Citation
Gold thin films produced from laser stimulated plasma reaction products

Material Information

Title:
Gold thin films produced from laser stimulated plasma reaction products
Creator:
Simon, Charles George, 1954-
Publication Date:
Language:
English
Physical Description:
ix, 235 leaves : ill. ; 28 cm.

Subjects

Subjects / Keywords:
Aluminum ( jstor )
Gases ( jstor )
Gold ( jstor )
Inlets ( jstor )
Ions ( jstor )
Laser beams ( jstor )
Lasers ( jstor )
Plasmas ( jstor )
Reaction products ( jstor )
Signals ( jstor )
Gold coatings ( lcsh )
Gold films ( lcsh )
Metallic films ( lcsh )
Thin films ( lcsh )
City of Orlando ( local )
Genre:
bibliography ( marcgt )
theses ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1988.
Bibliography:
Includes bibliographical references.
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by Charles George Simon.

Record Information

Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
Resource Identifier:
024965048 ( ALEPH )
AFM7016 ( NOTIS )
20177934 ( OCLC )
AA00004826_00001 ( sobekcm )

Downloads

This item has the following downloads:


Full Text









GOLD THIN FILMS PRODUCED FROM LASER
STIMULATED PLASMA REACTION PRODUCTS


By
CHARLES GEORGE SIMON


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY













UNIVERSITY OF FLORIDA

1988


OE _F LiBRARE




GOLD THIN FILMS PRODUCED FROM LASER
STIMULATED PLASMA REACTION PRODUCTS
By
CHARLES GEORGE SIMON
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1988
jj- iSE F LIBRARIES


To my wife, Diane,
to my parents, Sam and Bernice,
and
to Bobby Sammons.


ACKNOWLEDGEMENTS
The author wishes to express his gratitude to all who contributed
to this work and to his education at the University of Florida. In
particular, he wishes to express his appreciation for all of the effort
and guidance provided by his research director and committee chairman,
Samuel Colgate.
The author would like to thank his peers and the faculty and staff
members at the University of Florida (U.F.) and the University of South
Florida (U.S.F.) who contributed to this effort: at U.F., Mark Hail
and Roy King for quadrupole MS analyses, Mehdi Moini for FTICRMS
experiments, Dan Lesson for cluster beam TOFMS experiments, Paul
McCaslin and Jack Davis, Jr., for XPS analyses; at U.S.F., Alfred
D'Agostino and Carl Biver for XPS analyses, and Mike Ammons and Alicia
Slater for SEM/EDS analyses. Specials thanks are also extended to
Stephanie Boggess at U.F. for her invaluable assistance throughout the
course of this work, and to Bobby G. Sammons of Stone Container
Corporation, Port Wentworth, Georgia, for providing that special
impetus.
Finally, the author wishes to thank his committee members for
their contributions to this work, especially Martin Vala and John Eyler
who provided laboratory equipment and time, and The Florida High


Technology and Industry Council for their financial support (FHTIC
Grant #85092726).
IV


TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES vii
ABSTRACT viii
CHAPTERS
I INTRODUCTION 1
II EXPERIMENTAL 13
Production of Gas-Phase Gold Species: The Plasma
Reaction System 13
The Carbon Dioxide Laser, Optics, and
Operation 14
Gas Handling System and Procedures 18
The Plasma Reaction Chambers 28
The glass plasma reaction chamber 28
The aluminum plasma reaction chamber 34
The Product-Recovery/Substrate-Coating Systems. 40
Heated quartz tube 40
Staged cold traps 41
Substrate coating chambers 46
Heated substrate mount 50
Production of Gas-Phase Gold Species: Experimental
Conditions and Materials 51
Screening Study Experiments 51
Substrate Coating and Annealing Experiments.... 64
Product Volatility Study 75
Sublimation Experiments 76
Mass Spectrometer Experiments 77
Time of Flight MS Experiment 80
Gold Thin Film Characterization 83
Visible Absorption Spectroscopy 84
Optical Microreflectometry 85
X-Ray Photoelectron Spectroscopy 86
Scanning Electron Microscopy with Energy
Dispersive Spectroscopy 89
Electrical Resistance Measurements 90
v


Page
III RESULTS AND DISCUSSION 92
Production of Gas-Phase Gold Species 92
Screening Study Results 92
Substrate Coating and Annealing Results Ill
Product Volatility Study Results 115
Sublimation Experiments 115
Mass Spectrometer Experiments 116
Time of Flight MS Experiment 138
Gold Thin Film Characterization Results.. 151
Visible Absorption 151
Optical Microreflectrometry 153
X-Ray Photoelectron Spectroscopy 158
Scanning Electron Microscopy with Energy
Dispersive Spectroscopy 164
Electrical Resistance Measurements 193
IV SUMMARY AND CONCLUSIONS 210
Discussion of Plasma Reaction Product Formation 210
Conclusions 219
APPENDICES
A GLASS FIBER FILTER BLANKS 222
B ATOMIC ABSORPTION SPECTROMETER CALIBRATION 225
C STANDARD REFLECTANCE VALUES FOR SILICON CARBIDE 229
REFERENCES 230
BIOGRAPHICAL SKETCH 235
vi


LIST OF TABLES
Table Page
1. Gases Used in the Plasma Reaction Study 54
2. Screening Study Plasma Reaction Experiments 55
3. Substrate Coating Experiments 65
4. Substrate Annealing Conditions 69
5. Volatility Study Mass Spectrometer Experiments 77
6. Filter Catch Plasma Experiment Results 107
7. GC/MS Results from an Acetone Extract of H2C2H2/AU
Plasma Reaction Products 118
8. XPS Analytical Conditions and Results 161
9. Glass Fiber Filter Blanks 214
10. Repetitive Weighings on the Mettler Analytical
Balance 215
11. R(stnd) Values for SiC 220


Abstract of Dissertation Presented to the Graduate School of the
University of Florida in Partial Fulfillment of the Requirements
for the Degree of Doctor of Philosophy
GOLD THIN FILMS PRODUCED FROM LASER
STIMULATED PLASMA REACTION PRODUCTS
by
Charles George Simon
December 1988
Chairman: Samuel 0. Colgate
Major Department: Chemistry
Superfine particles of gold in the 100-400 nanometer size range
were produced in a plasma stimulated by 10.6 micron radiation from a
pulsed carbon dioxide laser. The production of the particles was shown
to be highly dependent on the types and pressures of the gases used in
the plasma, and the incident power density. The best conditions
determined for production of the particles were a partial pressure of
350 Pascals of methane gas mixed with hydrogen to a total pressure of
700-1400 Pascals, and an incident power density of 3 x 10^ watts/cm^.
The particles were used to coat tungsten, glass, and polymeric
substrates. The coated tungsten and glass substrates were subjected to
air and hydrogen anneals convectively at temperatures up to 600 K, and
by 10.6 and 0.532 micron laser radiation. Selected sample films were
then subjected to analyses by optical microreflectometry, X-ray
photoelectron spectroscopy, scanning electron microscopy, energy
dispersive spectroscopy, and electrical resistance.
The results of these analyses showed that the gold films had
highly variable properties depending on the substrate and annealing
vi i i


conditions. The average mass concentration of gold in the films was
95% (54 atomic %). High quality continuous gold lines could be written
on coated glass substrates using continuous wave 0.532 micron argon ion
laser radiation. Three distinct colors could be developed in the films
using thermal input. This property makes the product a viable
candidate for use as a multi-level optical encoding media.
Film collapse did not occur until 490 K and there were no other
contaminants in the films due to the containerless evaporation
technique. These properties indicate that the plasma reaction products
may be suitable high temperature replacements for gold blacks.
IX


CHAPTER I
INTRODUCTION
Methods for producing submicron gold film patterns are of current
interest to the microelectronic industry for use as interconnect
metallization as device sizes shrink in VLSI (very large scale
integration) circuitry. Interconnects provide communication routes
between single devices and each other, between single devices and the
outside world and between active regions within a single device. Since
propagation time delay along the interconnect is directly proportional
to film resistivity and inversely proportional to the film thickness,
as well as varying with the square of the length,1 it is important to
produce short and relatively thick (compared to the width) films with
good electrical properties in order to minimize operating times.
Current micron-size interconnects are patterned using aluminum, but
industry progression to submicron-size devices will eliminate aluminum
for this use because of electromigration problems. Gold is an ideal
substitute for aluminum because of its low resistivity, high
conductivity, and resistance to electromigration.
Chemical vapor deposition (CVD) is the only currently available
technique for producing gold thin films that met both the selective
deposition and high throughput requirements necessary for mass-
producing submicron patterns in VLSI circuits. Volatile gold compounds
are used in the CVD process to form the thin metal films by decomposing
1


2
on activated surfaces, leaving the metal atom on the surface and the
remaining molecular constituents in the gas phase. Thus, there is a
concurrent interest in high yield, cost effective methods for
synthesizing suitable compounds for use in gold CVD processes.
An alternative method to conventional solution based synthetic
chemistry that offers several advantages is the in situ gas phase
production of suitable gold compounds. This technique could be
integrated into a CVD system and produce volatile gold compounds on
demand, eliminating the need to store and handle such compounds, and
removing the processor's dependency on off-site precursor production.
The ideal system would use solid gold and non-toxic reactive gases to
form the volatile species upstream from the CVD chamber. After passing
through the CVD chamber, any unused gold compounds would be easily
recovered for recycle or gold reclamation. The following report
describes efforts to explore and understand novel chemical means which
might support the development of such a system based on production of
gas phase gold compounds in a pulsed laser stimulated plasma using a
solid gold target and non-toxic reactant gases.
A brief review of the physical properties and mechanisms of
currently available materials and methods utilized in interconnect
formation will illustrate the limitations that need to be overcome.
The advantages of using gold for interconnect metallization and the
effectiveness of CVD for submicron patterning will be described.
Evidence of the gas phase production of gold compounds using energetic
plasmas will also be presented. Finally, a brief description of the
proposed technique will be given, followed in Chapter II by a complete


3
description of all equipment and procedures and in Chapter III by a
discussion of the results.
Among the elements only gold, silver, copper, and aluminum have
high enough electrical conductivities at device operating temperatures
(> 300 K) to be considered for use in interconnect formation.3 Both
silver and copper are highly reactive and subject to catastrophic
oxidation. While aluminum is more stable to oxidation, it is far more
susceptible to electromigration than gold. Electromigration results
from mobility of the metal ions in the film driven by the friction
forces exerted by the flowing electrons. The ultimate result of
electromigration is the formation of a void large enough to cause a
discontinuity in the interconnect resulting in device failure.3 When
the factors responsible for electromigration are considered, the
advantages of gold over aluminum become clear.
In the polycrystalline thin metallic films which make up
interconnect lines, electromigration can be evaluated by considering
the total atomic flux, F, which can be expressed as the sum of the
atomic fluxes through the interior of the grain (equivalent to the flux
in the bulk metal) and the flux across the grain boundaries.
Huntington and Grone^ derived an expression for the flux in bulk
material, while Ho and d'Heurle^ did so for the added atomic flux
across grain boundaries. Both approaches are based on statistical
distribution of mobile atoms and adjacent vacancies in the crystal
lattice or grain boundaries. Combining their two expressions yields an
equation for F as a function of the current density J, the atomic
density N, the atomic diffusion coefficient D, the absolute temperature


4
T, the effective charge Z*q, the bulk conductivity cb, and the film
conductivity Cf:
F = NDZ*qJ/cbkT + (NDZ*qJ/cfkT)(s/d)
where k is the Boltzman constant, s is the average separation distance
between grain boundaries, and d is the average grain size. This model
is only an approximation since it ignores the geometrical orientation
of the grains and impurities adsorbed on the grain boundaries, and it
assumes that transport across grain boundaries occurs via channels
between the grains.
It is immediately apparent that the lower atomic density of gold,
0.098 moles/cm, compared to aluminum, 0.167 moles/cm, leads to a
lower F value for gold. Also, the lower effective nuclear charge of
the gold atom and the gold (+1) and (+3) ions (Z* = 0.65, 1.0, and 3.0,
respectively, using Slater's Rules) compared to the aluminum atom and
(+3) ion (Z* = 3.15 and 4.2, respectively, using Slater's Rules)7
results in a further lowering of the F value for gold.
Since movement of atoms within a crystal is highly restricted, and
the grain boundary area in these polycrystalline metal thin film
interconnects is many times greater than the external surface area, the
atomic flux within the thin film interconnect is dominated by diffusion
across the grain boundaries. Thus, the heavier, more bulky gold
atoms, possessing a lower relative charge than aluminum, but having a
similar net bulk resistivity of ca. 2.5 microohms/cm, are far less
prone to electromigration at high current densities. Typically,


5
current densities > 10 amp/cm^ cause serious electromigration problems
in aluminum and its alloys, while gold does not experience serious
problems until current densities exceed approximately 10^ amp/cm^.^
The next generation of electronic devices are expected to be of
submicron dimensions and operate at current densities up to 10
amp/cm^.l Thus gold appears to be a suitable material for
interconnect metallization in future devices. There are several
problems associated with the use of gold in silicon based circuitry.
Most notably, the high diffusivity of gold in silicon and silicon
dioxide necessitates the use of a barrier metal such as tungsten
between the two materials.^ While industrial methods for mass-
producing submicron patterns of tungsten based on CVD techniques
currently exist,there are no methods currently available for
mass-producing submicron patterns of gold. If an inexpensive, readily
available source of volatile gold species with low toxicity and good
deposition characteristics could be developed, it would greatly
facilitate efforts in this area.
A review of the methods available for producing gold thin films
reveals significant problems associated with the application of each
method to the mass-production of submicron patterning. There are seven
general categories of techniques currently employed to form gold films:
1) electroplating
2) sputtering (including reactive sputtering)
3) vacuum evaporation
4) ionized cluster deposition
5) superfine particle deposition


6
6) chemical vapor deposition (CVD)
7) direct write (including laser, electron, and ion beam
techniques).
Electroplating gold from solutions has been used extensively by
the electronic industry to form thin film devices and structures with
dimensions greater than several microns.However, the films produced
are typically porous and have significantly lower conductivities than
bulk gold. These plated films also contain alkali ion contaminants
that migrate in the electric fields and accumulate at junctions where
they change the device operating characteristics. There is also the
problem of dendritic growth experienced in electroplated gold films,
which can lead to formation of short circuits in adjacent conductors.*
A recent improvement in conventional electroplating was developed
by C. Patton using a laser-enhanced jet plating technique.This
method produced high quality gold spots and lines by directing a 25-
Watt continuous-wave argon ion laser beam through a focusing lens and
into a free-standing jet of electrolyte that acted as an optical wave
guide and a gold ion source. The laser energy and the fine jet stream
of electrolyte were directed onto a rastered cathode surface where
deposition rates as high as 30 microns/sec. were reported. The
inherently low throughput of this rastered system precludes its use as
a technique for mass-production of submicron gold patterns.
Sputtering is a physical vapor deposition (PVD) technique that
uses ionized gases (usually argon) to bombard a target composed of the
metal to be deposited. The energetic ion collisions dislodge surface
and near surface neutral metal atoms which then travel randomly to the


7
substrate where they are deposited. Masks and etching techniques are
used to form patterns. Several variations have been developed, such as
adding a reactive gas to the ambient, or heating and/or applying a
radio-frequency (rf) bias to the substrate. These modifications
improve step coverage on the substrate surface, and well-defined step
coverage is essential for small scale device and interconnect
formation.H20-23 Non-uniform step coverage results in "thin" areas
that lead to early device failure. The improvements have not
completely solved the step coverage problems for small dimensions, and
the methodology is still considered non-conformal.22 This major
disadvantage along with the non-selectivity of the deposition process
precludes the use of sputtering techniques for mass-production of
submicron gold patterns.
Vacuum evaporation is also a physical vapor deposition process.
Thermal convection, resistance heating, laser vaporization, or electron
gun vaporization is used to evaporate the metal in a vacuum. The atoms
then travel by line of sight to the substrate where they condense and
form a thin film.21 Masking and etching techniques are used to form
patterns. This methodology is limited by non-conformal step coverage
and non-selectivity of the deposited films.22 These limitations
exclude evaporation techniques from use in the mass-production of
submicron gold patterns.
Ionized cluster beam deposition is a recently developed technique
that utilizes ionized clusters of up to several thousand atoms to form
thin films.21*24 jhe clusters are formed by homogeneous or
heterogeneous nucleation either in the vapor phase in the plume exhaust


8
from a nozzle fitted onto a hot crucible containing the molten source
material, or on the side walls of the crucible itself before exiting
through the nozzle. The clusters are subsequently ionized by electron
bombardment with a current of several milliamps and energies in the 80-
100 eV range. They are then accelerated through a 1-10 KV potential
and directed to the substrate surface where they deposit non-
selectively with enough energy per atom (1-10 eV) to facilitate surface
mobility without inducing defect damage associated with higher impact
energies.
A recent study by Knauer and Poeschel showed that under optimum
conditions only about 1% of the total metal flux from a crucible filled
with molten gold or silver was in the form of clusters in the size
range of several hundred to several thousand atoms.25 Since only a few
percent of these clusters were ionized in the electron bombardment
step, the net efficiency of metal use was very low. This limitation,
together with the need for line of sight deposition (which implies non-
conformal step coverage) and the non-selectivity of the process,
preclude its use for mass-production of submicron gold film patterns.
Another recently developed technique for producing gold thin
films, also based on homogeneous and heterogeneous nucleation of
particles in the gas phase, involves the production of "ultra-fine"
particles in the 5-65 nanometer size range (10^-10^ atoms/particle)
that are subsequently deposited non-selectively on a substrate.25"2
Metal vapors are produced using a laser beam, arc discharge, or
electron beam in the presence of inert or reactive gases. At least one
group applied the technique to gold.28 The same limitations of non-


9
selectivity and non-conformal step coverage eliminate this method from
consideration as a viable procedure for submicron patterning of gold
films. However, investigators claim that high yields of metal
compounds can be formed by the activated clusters in reactive gas
streams.27 This is an interesting point which will be discussed
further below.
Chemical vapor deposition techniques do not depend on a flux of
condensible species reaching the substrate by direct line of sight and
hence are not subject to non-conformal step coverage problems.22
Substrates are surrounded by metal-bearing volatile species that do not
decompose without some form of additional energy input.20 In
principle, this allows close packing of the substrates in the
deposition chamber and selective deposition via selective energization
of pre-patterned barrier metal surfaces. There are many variations of
the basic CVD methodology designed to optimize performance of a
particular metal deposition system, but they all utilize a volatile
species that is forced to decompose on the substrate areas of interest
and leave behind a thin film of relatively pure metal.16,20-23
Chemical vapor deposition is the only category of currently
available metallization technology that meets the requirements of
selective deposition and high throughput necessary for mass-production
of submicron gold thin film patterns. To date, no reports of
simultaneous patterning of large arrays of submicron features with gold
have been published. Non-selective CVD of gold from triarylphosphine-
goldchlorides using thermal decomposition was demonstrated by Mann,
Wells, and Purdie in 1937.29 House and Colgate recently reported


10
similar results using the same compounds and rf stimulated thermal
decomposition.-^ There are other examples of non-selective CVD of gold
from organometal 1 ic compounds such as AuR(CNR'), and (R) PAuOSi(R),
where R and R' are methyl, ethyl, or phenyl groups.31,32 The most
recent compounds to be used for CVD of gold are dimethyl acetylaceto-
natogold(III) and its tri- and hexafluoro derivatives. Larson and Baum
reported the formation of high quality gold films from these compounds
by thermal decomposition at 300C.33 Films produced from the
fluorinated derivatives were relatively free from contamination and had
resistance values about twice that of bulk gold. This work represents
the current state of the art for gold CVD methods. While the compounds
used performed well, they are difficult to synthesize and have low
synthetic yields.34 These compounds are available commercially at a
cost of several hundred dollars per gram.35 Clearly a cheaper, more
readily available source of volatile gold species would be of benefit.
The only examples of submicron selective gold deposition reported
utilized various direct write methods, such as the laser-jet
electroplating technique described earlier,^ or ion beam pyrolysis of
solid (spun-on) organometal1ic films.36 Most groups have used focused
laser, ion, or electron beams to induce selective CVD of gold from
volatile compounds.37-44 Again, the fluorinated derivatives of
dimethyl acetylacetonatogold(111) formed the highest quality submicron
sized gold lines and spots. Despite the high quality of the gold films
produced by these methods, their inherently slow rate of throughput
precludes their economic use in mass-production scenarios.


11
As previously mentioned, one possible alternate source of
organogold compounds for use in CVD systems that offers the advantages
of low cost and availability on demand is the in situ production of
such compounds from solid gold and inocuous gases. Techniques exist
for producing gold oxides and halides from solid targets using sputter
gun evaporation in the presence of the reactive gases.^ Araya et al.
claim that goldcarbide superfine particles can be generated in the gas
phase from Nd:YAG pulsed laser stimulated plasmas using solid gold
targets in the presence of methane or Freon gases.^ There are also
examples of organogold ions formed in ion cyclotron resonance mass
spectrometer experiments using high-voltage spark and carbon dioxide
pulsed laser stimulated vaporization/ionization of solid targets in the
presence of aliphatic or aromatic hydrocarbons, alkylhalides, and
alcohols.46-49
In another related field of research, investigators have been
producing gold bearing plasma polymerized films using PVD sputtering or
evaporation techniques.50-58 These studies have shown that the metal
is incorporated in the films in the form of small particles that
drastically alter the optical and electrical properties of the
polymers.
Gold carbonyls and organogold compounds have been formed in matrix
isolation studies by cocondensation of gold atoms with carbon monoxide,
acetylene, ethylene, and propylene.59-62 These studies illustrate the
high reactivity of gold atoms with carbonaceous molecules, even at very
low temperatures.


12
Taking this evidence into consideration, it would seem possible to
develop a continuous process method for generating gaseous gold species
from solid gold and gaseous compounds in an energetic plasma. Such a
process could be incorporated in a CVD production line to provide
volatile gold compounds on demand. This technique would also eliminate
the need to store and handle synthetic compounds, a major economic and
safety factor advantage in itself.
Materials produced by the method would be evaluated by considering
the following criteria:
1) production rate
2) volatility
3) thermal stability
4) temperature of decomposition
5) film properties (resistance, purity, morphology, stability)
6) properties of by-products (should be non-contaminating to the
substrate and non-toxic)
7) ability to recycle or reclaim gold.
In addition to these considerations, the toxicity of the starting
materials would be a primary concern.
A plasma reaction system was designed and constructed to
investigate the feasibility of producing gas phase gold compounds in
large enough quantities to be used in mass-producing CVD submicron gold
patterns. The procedures and results of that investigation are
presented in the following chapters.


CHAPTER II
EXPERIMENTAL
The scope of this study was limited to the investigation of
reactions occurring between non-toxic or low-toxic gaseous species and
pulsed C02 laser stimulated gold vapors and plasmas. Particular
emphasis was placed on utilization of permanent carbonaceous gases.
The study consisted of three major parts: 1) production of gas phase
gold-bearing species in high yields in the plasma, 2) determination of
volatility of high-yield species, and 3) characterization of gold thin
films produced from the high-yield species. Detailed descriptions of
experimental equipment and procedures are presented together in this
chapter. Each major part of the study is treated autonomously.
Conditions leading to equipment or procedure modifications are
mentioned but are not discussed until the following chapter.
Production of Gas-Phase Gold Species:
The Plasma Reaction System
The plasma reaction system was composed of four sub-systems:
1) the pulsed carbon dioxide laser and associated optics
2) the gas handling system
3) the plasma reaction chambers
4) the product-recovery/substrate-coating systems.
13


14
Each sub-system is described in detail together with pertinent
operational procedures followed during the course of the study.
Carbon Dioxide Laser. Optics, and Operation
The foremost criterion for development of a successful method for
producing gaseous gold compounds for the intended use was a high
production rate. An energy source was needed that could provide both a
high flux of gold vapor and the additional energy needed to form a
reactive plasma from the volatilized gold and reactive gases. A
Lumonics pulsed TEA (transversely excited atmosphere) carbon dioxide
laser, model 101-1, that had previously demonstrated high
volatilization rates for refractory metals*^ was available for use in
this study. This laser was capable of producing an optical pulse
energy of 2.5 joules with a pulse halfwidth of 250 nanoseconds and a
power density of approximately 3 x 10^ watts/cm^ when optimally focused
through a 200 mm focal length lens. Maximum pulse repetition rate was
1 hz, giving the laser a duty time of approximately one millisecond per
hour. The emitted wavelength of 10.6 microns corresponds to the P(20)
line in the 001-100 band.
The laser's pulse energy could be varied by adjusting the nitrogen
gas pressure and flow rate to the spark gap trigger, by adjusting the
composition and flow rate of the helium/nitrogen/carbon-dioxide lasing
gas mixture, or by adjusting the operating voltage. During the course
of this study these parameters were maintained in a state that resulted
in maximum energy output.


15
The laser energy output was measured after major maintenance
events, such as disassembly and cleaning of the optics or electrodes,
using a Scientech 365 laser power/energy meter. During subsequent
operation, the laser output was monitored by exposing a piece of
thermal paper (Hewlett Packard #820-51A) to single pulses of the
unfocused, 28 mm dimeter beam and comparing the resultant discoloration
patterns to standard patterns that were produced under measured
conditions (see Figure 1).
The laser beam was directed into the plasma reaction chamber
through the optic path using a 5 cm square face coated silver mirror
during initial screening experiments. This mirror was subsequently
removed from the system and the laser was positioned in a direct line
of fire with the optics and the chamber at a distance of ca. 0.5 meters
in order to transmit as much energy as possible to the target.
An externally mounted 5 cm diameter germanium meniscus lens with a
200 mm focal length (Oriel model 4365) was used to focus the laser beam
during the first half of the study. A similar lens with a focal length
of 250 mm (11 VI, Inc., model 5-5741-1) replaced the initial lens for
the final half of the study. (This was necessary as a result of
physical damage sustained by the 200 mm lens during a cleaning
procedure accident.) Both lenses had an anti-reflection coating for
maximum transmission at 10.6 microns.
The lenses were held in a clamp mounted to an optical stand with
three degrees of freedom. This arrangement allowed the lens to be
positioned closer to the target than the optimum focal distance during
the course of an experimental run, thus distributing the laser energy


Figure 1. Thermal Paper Exposed to Single Pulses of the Carbon
Dioxide Laser
(a) Laser performing well (nominal)
(b) Laser performing poorly (gas mixture not
optimized for power level and pulse repetition
rate


17
(b)


18
over a larger surface area. This procedure was used in all experiments
where the effects of lower than maximum power densities were
investigated.
The optimum focal length for each lens was determined
experimentally by exposing thermal paper (in air) to the partially
focused beam at distances equivalent to 10, 60, 85, 135, and 195
percent of the expected focal lengths. The average spot diameters from
each point were plotted against the distance from the back edge of the
lens. The intersection of the two lines drawn through the points gave
the optimum focal length (Figure 2). The value determined for the two
lenses were 199 mm and 254 mm. These values were confirmed by
microscopic examination of target impact craters after exposure to the
highly focused beam.
After passing through the focusing lens, the beam entered the
reaction chamber through a 3.8 cm diameter zinc selenide window (II-VI,
Inc., #-746-7) which also had an anti-reflection coating for maximum
transmission at 10.6 microns. The distance between the lens and the
window was kept to a minimum in order to prevent damage of the latter
by interaction of the partially focused laser beam with surface
contaminants. This distance was ca. 0.5 cm for the 200 mm focal length
lens and ca. 2 cm for the 250 mm focal length lens.
Gas Handling System and Procedures
All of the gases used in this study, except one, were gaseous at
STP and were supplies from pressurized cylinders. Standard one and two
stage gas regulators and associated fittings were used to deliver these


Figure 2. Germanium Lens Focal Length Determination


30
20
10
0


21
gases to the mixing system through 0.635 cm o.d. polypropylene
tubing.
The one compound that was liquid at room temperature, dicyclo-
pentadiene, was placed in a 50 ml glass impinger and helium gas from
the gas handling system was bubbled through 30 ml of the liquid at 120
ml/min before entering the plasma chamber. This effectively saturated
the gas with the volatile liquid. Teflon tubing and fittings were used
to connect the impinger to the plasma chamber during this experiment
(Figure 3).
The gas mixing system used in all experiments, except the one
noted above, consisted of the following components:
1) three variable area flowmeters with built-in needle valves
(Cole-Parmer models J-3217-12 and J-3217-18), mounted together on an
aluminum plate,
2) a 120 ml acrylic gas drying column with 0-ring sealed aluminum
end caps (Altech Associates 100 psi model, sold by Cole-Parmer as model
J-1418-100) half filled with indicating drierite and half filled with
molecular sieves,
3) a 100 ml glass bubble-tube flowmeter,
4) a brass on/off plug valve with elastomeric O-ring seals (Nupro
model B-4P4T) and two brass fine metering valves (Nupro model B-SS4),
5) an oil-filled mechanical vacuum pump (Precision Scientific
model 25), and
6) a capacitance manometer (Baratron Type 220BA-01000A2B) with a
digital readout (MKS type (PDR-D-1).


Figure 3. Dicyclopentadiene Gas Delivery System


helium
gas in
dicyclopentadiene
i>


24
A diagram of the system components and the gas flow pattern is
presented in Figure 4.
Gases were supplied to the flowmeters at 69,000 Pascals (10 psi)
pressure and the flow rates adjusted using the variable area flowmeter
needle valves. Copper tubes (1/4 in o.d.) from the flowmeter exit
ports were teed together a few centimeters downstream using brass
compression fittings. The gases then passed through the drying column,
which also acted as a mixing chamber. Nominal total flow rates were
200-400 ml/min. After exiting the drying column the gases flowed
through a teflon tee. One arm of the tee went to the bubble-tube
flowmeter (which was vented to the atmosphere through the building hood
exhaust), and the other arm went to the plasma chamber on/off valve.
Thus, when the on/off valve was closed, the total gas flow passed
through the bubble-tube flowmeter. When the on/off valve was open,
part of the gas stream (about half) flowed through the plasma chamber
while the remainder was vented through the bubble-tube flowmeter. This
arrangement assured that no atmospheric gases were introduced into the
plasma reaction chamber through the gas handling system.
Flow rates were set using the flowmeter needle valves and measured
using the bubble-tube flowmeter and a stopwatch while the chamber
on/off valve was closed. When more than one gas was used for an
experiment, the flow rates were determined by addition, starting with
the lowest flow and ending with the highest flow. The bubble-tube
flowmeter was also used to monitor the excess gas flow to the
atmosphere during plasma reaction experiments. The variable area


Figure 4. Gas Mixing and Delivery System


flowmeters
wi th
metering
valves
O _
r//'r
//
LT
drying
column
gases
in
on/off
j=^)=v >
to
metering plasma
valves chamber
!=&=>
no
cr>


27
flowmeters were used to monitor the individual gas flows (comprising
the reaction mixtures) during experiments.
The gas flow to the plasma chamber was controlled by one or both
of the metering valves in most experiments. These valves were located
just downstream from the on/off valve and were used to separately
control the gas flow through two inlets into the plasma chamber. (One
inlet was located at the bottom of the chamber, beneath the target, and
the other inlet was located on the optic side arm adjacent to the zinc
selenide window. (See the plasma chamber description for further
details of the gas inlets.) In experiments where the chamber pressure
was 530 Pascals (4 torr) or greater, the gas flow was split equally
between the two inlets using the respective needle valves. In
experiments where the pressure was 133-533 Pascals (1-4 torr), one
needle valve and inlet were plugged and the entire gas flow was
directed through the optic side arm inlet. In experiments where the
chamber pressure was < 133 Pascals (< 1 torr), the Nupro metering
valves were replaced by an in-house fabricated, low-flow, 1000:1 taper
valve.
All experiments used the mechanical vacuum pump to provide the
driving force for gas flow through the system. The plasma chamber
pressure was monitored with the capacitance manometer which had a range
of 0-1000 torr in 0.1 torr increments (0-133,323 Pascals in 13 Pascal
increments). The manometer was calibrated using a standard mercury-
filled McLeod gauge.


28
The Plasma Reaction Chambers
Two plasma reaction chambers were used during the course of this
study. Their function was to provide a controlled environment for the
interaction of solid gold and gaseous compounds and elements. An
initial screening study was conducted using an all glass reaction
chamber. The remainder of the study was conducted using a more
versatile aluminum reaction chamber. A description of the all glass
chamber is presented first, followed by a description of the aluminum
chamber.
General features common to both chambers included a target
holder/manipulator for positioning the solid gold target, a zinc
selenide window for introducing the laser light, gas inlets for
introducing the reactant and inert gases, and a gas outlet for
delivering the reaction products and unreacted gases to the product
collection system and the vacuum pump. The major difference between
the two chambers was the design pressure rating. The glass chamber
used in the screening study was designed to operate in the pressure
range of 667-186,650 Pascals (5-1,400 torr), while the aluminum chamber
used throughout the rest of the study was designed to operate in the
pressure range of 0.133 to 93,000 Pascals (0.001 torr to 0.9
atmospheres).
The glass, plasma reaction chamber. This chamber was designed to
be utilized for initial screening of prospective gases and gas mixtures
for their effectiveness in producing and transporting gas phase gold-
bearing species. This involved the determination of optimum pressure


29
and laser energy density conditions for gases showing positive results.
The protocol also included the study of the interaction of the focused,
pulsed CO2 laser beam with several inert and reactive gases and gas
mixtures at pressures approaching 200,000 Pascals (ca. 2 atm.). The
transparent chamber facilitated the observation of gas breakdown. This
phenomenon resulted in absorption of most of the laser pulse energy by
the gases, leaving very little energy to vaporize the solid gold. (A
further discussion of this topic is presented in the following
chapter.)
A diagram of this plasma reaction chamber is presented in Figure
5. The two-piece borosilicate glass body was fabricated in the
Scientific Glass-Blowing Shop at the University of Florida and had a
total volume (including side arms) of 588 ml. Two 50 mm i.d. glass 0-
ring seal joints (Kimax No. 50) were used as the base structures. One
of the joints was modified by tapering the blank end and butt-sealing
it to a 12 mm o.d. by 9 mm i.d. by 4 cm long piece of glass tubing.
The overall length of the resultant bell-shaped structure was 20 cm. A
9 mm o.d. by 6 mm i.d. by 14 cm long piece of perforated teflon tubing
was press-fitted into the narrow end of the bell structure from the
inside. This tube extended about 1 cm into the 12 mm o.d. glass
extension tube. The rest of the teflon perf-tube extended through the
center of the bell structure and ended about 2 cm from the wide end. A
50 mm dia. by 2 mm thick teflon perforated plate was then attached to
the teflon tube by threading a stainless steel screw through the center
hold of the perf-plate and into the end of the teflon tube. This unit
comprised the main gas inlet to the plasma chamber. The perforated


Figure 5. The Glass Plasma Reaction Chamber


germanium lens


32
tube and plate distributed the gas flow evenly to the plasma reaction
zone. A length of copper tubing coming from one of the gas handling
system metering valves was attached to the narrow end of the glass,
gas-inlet structure with a brass, 0-ring sealed, quick-connect fitting.
The other 50 mm i.d. glass 0-ring joint was also tapered and butt-
sealed to a 12 mm o.d. by 4 cm long piece of glass tubing to form a 20
cm long bell-shaped structure. The narrow end was the plasma chamber
outlet and was attached to the product recovery system and a mercury
manometer using a brass quick-connect fitting. Another 12 mm o.d. by 4
cm long piece of glass tubing was sealed to the large diameter sidewall
of the bell structure 5 cm (on center) from the mouth and served as a
guide shaft for the sample holder. A 20 mm i.d. glass 0-ring joint
(Kimax No. 20) was sealed to the opposite sidewall 6 cm (on center)
from the mouth and served as the optic side arm attach point. The
offset center lines allowed the use of a large diameter target that was
rotated past the beam impact point.
The sample holder shaft was an aluminum rod 15 cm long by 9 mm
o.d. that was slip-fitted through the chamber side arm, as mentioned
above, and sealed by sliding a length of tightly fitted, 3 mm thick
silicon rubber tubing over the joint. The part of the aluminum shaft
that contacted the silicon rubber tube was coated with vacuum grease
(Dow Corning silicon high vacuum grease) to facilitate sealing during
shaft rotation. A 7 cm dia. aluminum cogwheel was attached to the
exterior end of the aluminum shaft and used to rotate the sample
manually. The other end of the shaft extended into the chamber and had
a threaded center hole that was used as a target attach point. The


33
shaft, and target, could be moved toward the beam input opening a
maximum of 3 cm in order to shorten the optic path.
The two piece optic side arm was constructed from glass and
aluminum. The piece closest to the plasma chamber was made from a 20
mm i.d. glass 0-ring joint butt-sealed to a 30 mm i.d. glass 0-ring
joint (Kimax No. 30). There were actually two such pieces fabricated.
One was 5 cm long and the other was 8 cm long. This provided different
path lengths between the zinc selenide window and the target surface.
By exchanging these pieces, and moving the target back and forth, the
optical path length between the backside of the window and the target
surface could be varied by 6 cm. This allowed adjustment of the
incident energy density of the laser beam while maintaining a minimum
distance between the external focusing lens and the window. (This
arrangement minimized the probability of damage to the window surface,
as previously mentioned.)
The aluminum window holder was machined to match the 30 mm i.d.
glass 0-ring joint on one end. The other end was machined to hold the
zinc selenide window described earlier. The window was sealed using a
rotary 0-ring gland that incorporated the window edge and the inside
circumference of the aluminum holder as sealing surfaces. Two teflon
rings with inside diameters 2 mm smaller than the window o.d. were used
as spacers on either side of the window. The window and spacers were
held in place using an aluminum ring with the same i.d. as the teflon
rings and an o.d. equal to that of the aluminum holder. This ring was
attached to the end of the holder with four screws. A brass swage
fitting (1/4 in. pipe thread to 1/4 in. tube) was located 1 cm (on


34
center) from the edge of the window seat on the side of the holder. A
1/4 in. copper tube coming from the gas handling system's other
metering valve was connected to this fitting and provided a sweep of
incoming gases across the window surface to help minimize contamination
of the surface.
Butadiene elastomeric 0-rings were used where required throughout
the system. Pinch clamps held the glass 0-ring joints together when
the system was not under low pressure. The rotary seal on the window
and the seal on the sample holder shaft had moderate leak rates and the
chamber could be pumped down only to 13 Pascals (0.1 torr). While this
operational parameter met the rough-vacuum design criterion, the affect
of the residual pressure of air on the proposed reactions was unknown.
Therefore, a study of the affect of increased levels of air in
successful gas mixtures was included in the screening study protocol.
The affect of very low concentrations of residual air in successful gas
mixtures was investigated using the aluminum reaction chamber.
The aluminum plasma reaction chamber. This chamber was fabricated
by the author from aluminum (Alcoa alloy 2024) using available
facilities in the Department of Chemistry at the University of Florida.
A diagram of the chamber, including the sample holder, optic side arm,
and observation ports is presented in Figure 6. The screening study
was completed, and all other experiments were conducted using this
chamber.


Figure 6. The Aluminum Plasma Reaction Chamber


capacitance
manometer
3
rotateable "
sample stand
gas from
mixing
system^011/f f
metering
valves
Hg>
-> to product recovery
system and vac. pump
laser
beam
stu
germanium
lens
CO
CT


37
The aluminum plasma reaction chamber consisted of five parts:
1) the main body, including two gas inlet inserts, a gas outlet
flange, and a capacitance manometer insert,
2) two glass observation ports and their flanges,
3) the baseplate,
4) the optic side arm, and
5) the sample holder.
All of the components were fabricated from aluminum except the glass
ports and the main body inserts and outlet flange (which were machined
from brass). Viton or butadiene elastomeric 0-rings were used for all
seals. All tubing, fittings, and inserts leading from the gas handling
system and capacitance manometer that were subject to vacuum were
either brazed or connected with 0-ring quick-couples.
The completed system was leak checked using a mass spectrometer
helium leak detector (Veeco Leak Indicator MS17) previously calibrated
with a standard leak (Veeco Sensitivity Calibrator Type SC-4). The
detector response indicated that the leak rate was < 2 x 10'^ cc-
atm/sec (air equivalent) at each union and overall under He flood
conditions.
The main body was machined from a single block of aluminum 9.5 cm
wide by 7.6 deep by 15.2 cm high. The reaction zone was formed by
boring a 5.1 cm dia. by 9.5 cm deep hole through the center of the
block, starting on the bottom face. The top of this cavity was tapered
30 and narrowed to 1.0 cm in two steps before exiting the center of
the top face of the block. Static face seal 0-ring glands and four-


38
hole bolt circles were machined around both holes for attachment of the
gas outlet flange and the chamber baseplate.
Several different outlet flanges were used to connect the plasma
chamber to the various product recovery systems. All of the flanges
were sealed to the chamber using the 0-ring face seal and connected to
the product recovery system by an 0-ring quick-connect type coupler. A
1.2 cm dia. hole was bored on one of the 9.5 cm wide sides 2 cm (on
center) from the bottom of the chamber. A 6 cm long insert with a
rotary 0-ring gland was inserted through this opening. The insert had
a 6 mm hole bored from the incoming end and turned 90 at the outlet
end. This design allowed the incoming gas to be directed toward or
away from the plasma reaction zone by rotating the insert. Another 1.2
cm dia. hole was bored in the same face 9 cm (on center) from the
bottom of the chamber. A 6 mm i.d. plug insert with a rotary 0-ring
gland was used to connect the plasma reaction zone with the capacitance
manometer via a 30 cm length of 1/4 in. o.d. tubing.
A 2.0 cm diameter hole was bored into one of the 7.6 cm wide faces
5.5 cm (on center) from the bottom of the chamber. The 0-ring gland
and four-hole bolt circle were machined around this opening. This was
the optic side arm attach point.
A 3.3 cm dia. hole was bored into the other 7.6 cm wide face 4.7
cm (on center) from the bottom of the chamber. The sample holder was
inserted through this opening. A rotary 0-ring gland was machined into
the circumference of the opening 3.0 mm from the outer edge. This
0-ring sealed the sample holder even when it was being rotated. A


39
four-hole bolt circle was machined around the port to secure the sample
holder with its 0-ring face seal.
Two 5.0 cm dia. ports were cut into the 9.5 cm wide sides directly
opposite from each other and 5.0 cm (on center) from the bottom of the
chamber. Static face seal 0-ring glands and four-hole bolt circles
were machined around each port. Two 1.0 cm thick port flanges with
matching 0-ring glands and bolt holes held and sealed 6.0 cm dia. by
6.0 mm thick lead glass windows over each port.
The baseplate was 12.7 cm square by 2.5 cm thick and had four bolt
holes that matched the bolt circle on the bottom face of the chamber.
In addition, the baseplate had four holes at the corners that were used
to attach the chamber assembly to a table. Block spacers were placed
under the baseplate to raise the chamber optic arm to the same height
as the laser beam.
The single piece, 3.0 cm i.d., optic side arm used the same type
of rotary 0-ring gland as described above to center the zinc selenide
window. An 0-ring face seal gland was cut into the aluminum holder and
used to form the primary vacuum seal against the face of the window. A
precisely machined teflon spacer, and an aluminum ring flange similar
to the one described above, provided the necessary squeeze to form the
seal without unduly stressing the window. A 6.0 mm dia. hole was bored
into the side arm 5.0 mm (on center) from the window face seal edge and
used as the sweep gas inlet. A brass insert with a rotary 0-ring gland
connected the inlet to one of the gas handling system metering valves.
The optic side arm was attached to the plasma chamber using the bolt
circle and face seal described earlier.


40
The sample stand was also made from a single piece of aluminum.
The sample attach point was a threaded hole in the end of a 1.4 cm dia.
by 2.3 long section of the stand. This section ended in a 3.3 cm dia.
by 1.5 cm long section that acted as the sealing surface for the rotary
seal in the chamber throat. The outer section of the one-piece stand
was 7.5 cm in diameter and 1.3 cm thick and acted as the flange. This
section contained a face seal 0-ring gland that formed the primary
vacuum seal, and a series of arced bolt slots that matched the bolt
circle on the chamber. The rotary seal allowed the sample to be
rotated manually while under vacuum by loosening the face seal bolts.
(Depending on target thickness, this was done once or twice an hour
during most experiments.) The bolts were retightened after the sample
rotation was completed. This was necessary because particles and
frictional wear frequently caused minor leaks in the rotary seal.
The Product-Recovery/Substrate-Coatinq Systems
There were several product-recovery/substrate-coating systems used
throughout the study. Many of the systems used common components
assembled in different sequences and maintained at different
temperatures. Many of these arrangements were designed to investigate
the volatility, or other physical properties, of the plasma reaction
products. The system descriptions are presented below along with their
respective operational parameters. Results are discussed in Chapter
III.
Heated quartz tube. A 2 mm i.d. by 4 mm o.d. by 50 cm long quartz
tube was attached directly to the glass plasma chamber outlet using a


41
Silicon rubber sleeve seal. The tube was placed in a Linberg tube
furnace with a 30 cm long high temperature zone. The furnace was
heated to 600-890 K during experiments in order to decompose any gold
bearing species that passed through. The gas flow rates were adjusted
to allow a residence time of 3-194 milliseconds in the hot zone. In
practice this resulted in visible deposits varying in color (from black
to purple to red to gold) and position along the tube. In some experi
ments the quartz tube was followed by a glass wool plug and/or a cold
finger (size 14/22 or 24/40) in a dry-ice/acetone bath (see Figure 7).
Staged cold traps. Several experiments used multiple cold traps
at progressively colder temperatures to observe product collection
characteristics. The various schemes used are pictured in Figure 8.
The first such scheme used a cold finger (CF) in water-ice (273 K)
followed by a second CF in dry-ice/acetone (195 K), and a third CF in
liquid nitrogen (77 K). Clogging of the CF in liquid nitrogen resulted
in its replacement with a second CF in dry-ice/acetone. The next
modification incorporated a glass wool plug before the cold traps.
This scheme was then modified by placing the glass wool between the
first CF, which was kept at room temperature, and a second cold trap
made from a 1/4 in. (6.35 mm) o.d. by 25 cm long glass U-tube kept in
crushed dry ice. Another scheme used a small test-tube inserted in the
gas stream at the plasma chamber outlet ahead of the U-tube in dry ice.
The test-tube was either maintained at ambient temperature or was
filled with dry ice. The flange which held this tube could also
accommodate a quartz window in place of the test-tube. Finally,


Figure 7. Heated Quartz Tube Product Recovery System


u-nng
seal
i>0
gas
i n
(M
u-nng
seal
i
w "?k
2 mm i.d. quartz tube
thermocouple
\ ^
-P*
CO
O C O'
r-t- to


Figure 8. Staged Cold Traps Used for Product Recovery
(a) Three cold fingers
(b) Cold finger with U-tube
(c) Test-tube with U-tube


45
-t>
gas
in
-£> to
pump
insert


46
the system was limited to the U-tube in crushed dry-ice (or dry-
ice/acetone) since this proved sufficient for trapping the plasma
reaction products for later use. A fresh trap was used for each
experiment. The 1/4 in. o.d. glass U-tubes were eventually replaced
with 3/8 in. (9.525 mm) o.d. glass U-tubes. One of these U-tube cold
traps was used in all subsequent experiments either alone or after a
substrate coating chamber.
Substrate coating chambers. Substrates were coated with the
plasma reaction products during experiments by sticking them to the
inside of the chamber windows (using Scotch clear adhesive tape), by
placing them in the connecting tubing leading to the U-tube cold trap,
or by placing them in one of the three coating chambers pictured in
Figure 9. The first two chambers were fabricated from glass in the
Scientific Glass Blowing Shop at the University of Florida. The third
chamber was constructed from aluminum by the author using available
facilities in the Department of Chemistry at the University of Florida.
All of the chambers were placed in line after the plasma chamber and
before the U-tube cold trap. The two glass coating chambers were
mounted perpendicular to the plasma chamber via an elbow quick-couple.
The aluminum coating chamber was connected directly to the top of the
plasma chamber using a straight quick-couple.
The first chamber was made by truncating a 20 mm i.d. glass 0-ring
seal joint (Kimax No. 20) 3 cm from the sealing end and attaching 1/4
in. o.d. by 5 cm long glass tubes on opposite sides, perpendicular to
the seal face. These tubes acted as the inlet and outlet. A 25 mm
dia. by 1 mm thick quartz window was placed on the 0-ring and held in


Figure 9. Substrate Coating Chambers
(a) Small glass chamber showing a ceramic feed
through in place
(b) Large glass chamber showing the 3-tier
sample rack


48
^ quartz window
(b)
hoider
gas
out
to heater controller


49
place by the system vacuum. Total volume of the chamber was 20 ml.
Substrates could be placed in this chamber and exposed to a 5 watt
Argon ion laser beam (Spectra Physics 165) while plasma reaction
products flowed through.
A second, larger coating chamber was constructed from two 40 mm
i.d. glass 0-ring seal joints (Kimax No. 40). The joints were tapered
and sealed to 1/4 in. tubing on the ends. The two halves were held
together with a pinch clamp when the system was not under vacuum. The
assembled unit was 20 cm long and had a total volume of 145 ml. A
three-tiered substrate holder rack was made by the author using three
38 mm dia. by 2 mm thick perforated aluminum plates connected by a
central stainless steel shaft. Substrates were placed on the different
rack plates in either equatorial or axial positions in order to observe
shadowing effects during coating.
A third, more versatile coating system was machined from aluminum
stock (Alcoa alloy 2024). This chamber was also a two-piece design and
had an 0-ring face seal between the halves. The bottom half started
with a 1/2 in. (12.7 mm) o.d. by 1.9 cm long inlet segment that sealed
directly to the top of the plasma chamber via a 1/2 in. brass quick-
couple. This section had an inside diameter of 1.0 cm. The next
segment of the bottom piece had an o.d. of 5.0 cm and an i.d. of 4.0 cm
and was 4.4 cm long. The final segment was 7.6 cm wide by 1.2 cm thick
and contained the 0-ring gland, a four-hole bolt circle, and a seat on
the inside diameter for a 4.0 mm wide by 3.0 mm thick teflon ring
spacer. This segment acted as a flange to connect the two pieces of
the chamber.


50
The top half started with a matching flange segment with a 3.0 mm
thick by 48 mm dia. teflon perforated plate press-fitted into the 4.0
mm wide seat on the inside diameter. This was followed by a 5.0 cm
o.d. by 4.0 cm i.d. by 1.9 cm long segment and a 1.0 cm i.d. by 1/2 in.
(12.7 mm) o.d. by 2.3 cm long outlet segment. The assembled chamber
was 13 cm long and had an internal volume of 87 ml.
The teflon perforated plate and spacer were used to hold a 47 mm
diameter borosilicate glass fiber filter that had a retention rating of
0.98 at 0.2 microns (Micro Filtration Systems GB 100 R47 mm). The
filter faced the gas flow and was backed by the perforated plate. The
teflon ring held the filter in place without damaging it. This
arrangement was used to trap particles that were produced in the plasma
chamber. Particles that were transported 20 cm up from the plasma
reaction zone, through the narrow plasma chamber outlet and up to the
filter, were very efficiently trapped. Other particles that impinged
on the plasma chamber sidewalls or fell to the bottom of the chamber
were not collected by the filter. Most large particles ("chunks" and
"flakes" tens of microns in size) that made it to the filter rebounded
on impact and were found in the bottom of the collection chamber.
Large particles that adhered to the filter were easily distinguished
using visual microscopy. Thus, the arrangement provided a semi-
quantitative method for comparing relative abundances and gold content
of particles entrained in the gas stream using gravimetric and atomic
absorption analyses, respectively.
Heated substrate mount. Several experiments were performed with
substrates attached to a heated mount shown in Figure 9. The 3.5 cm


51
dia. by 3.0 cm high mount consisted of a potted nichrone heating
element covered with a 2 mm thick aluminum plate that had a series of
threaded holes. Flat head screws were used to attach substrates to the
plate using the threaded holes. The mount was positioned in the top of
the aluminum collection chamber with the heated substrates facing the
gas flow. Three small ceramic posts minimized the area of contact
between the mount and the top of the collection chamber.
The heating element wires extended through the top of the chamber
through two glass inserts that were epoxy sealed (J. B. Weld Co.,
Sulphur Springs, TX) to the aluminum. Rubber septa and sealing putty
(Apiezon Q) were used to seal the wires at the exit of the glass
inserts. There was a small leak at this point, ca. 0.01 ml air/min
determined by differential pressure measurements. However, its
location downstream from the plasma reaction zone and the substrate
coating zone, and the results of earlier experiments that showed the
relative insensitivity of selective plasma reactions to air, minimized
concern over the leak.
Temperature control for the heated mount was provided by a 12 V dc
power convertor driven by a variable voltage auto-transformer.
Temperatures were controlled to 5% of the set point. A thermocouple
junction (type K) was implanted in the aluminum hot plate and connected
to a digital multi-meter (Kiethly 177 Microvolt DMM). The thermocouple
was calibrated using water ice and boiling deionized water.


52
Production of Gas-Phase Gold Species: Experimental
Conditions and Materials
Screening Study Experiments
The purpose of the screening study was to identify gases and/or
gas mixtures, operating pressures, and laser power density parameters
that resulted in the production of relatively large amounts of gas-
phase gold species. The screening study was continued throughout the
duration of the overall study. The product recovery systems described
above were used to separate the gold species from the gas stream.
Visual observation was used as an initial method of evaluation since
the relative abundances of gold species collected in individual
experiments varied drastically. Cold traps containing the recovered
products were sealed and heated in a bunsen burner and then opened to
the atmosphere and reheated. Observations of the relative quantities
of gold films formed on the glass surfaces were utilized to identify
successful operating conditions.
Glass fiber filter catches were determined gravimetrically using a
Mettler analytical balance. (Filter blank measurement methods and data
are presented in Appendix A). Quantitative measurements of the amounts
of gold collected in some of the cold traps, and on most of the glass
fiber filters, were performed using Atomic Absorption (AA) analyses
(Perkin Elmer Model 303 AA) and standard analytical techniques.
Samples were either extracted/ suspended in acetone, or dissolved in
aqua regia and diluted. Calibration data and response curves are
presented in Appendix C.


53
The initial gold target used in the screening study was formed by
melting and casting ca. 10 grams of Au wire (0.999 purity) into a 2-3
mm thick crescent shape. A machined graphite block was used as a mold
for the casting. A Canadian Maple Leaf 1 oz gold coin (0.999 purity)
was also used as a target during the screening study and in all
substrate coating experiments. This target required recasting after
extended use, but its total mass was never less than 23 grams, and its
thickness was never less than 3 mm. A 1.0 cm thick by 2.5 cm diameter
piece of graphite (mass = 23.7 grams) was used as a target in two
experiments and a 6 mm thick by 18 mm wide by 28 mm long OFHC copper
target (mass = 28.0 grams) was used in two other experiments.
Gases used in the study were obtained from several different
sources. The gases are listed in Table 1 along with their respective
vendor sources and purity ratings. No attempts were made to further
purify any of the gases beyond the removal of excess moisture in the
gas drying column already described, with one exception. The helium
gas used in test No. 861126B was passed through two liquid nitrogen
cold traps in order to remove traces of water which otherwise would
have reacted with the liquid dicyclopentadiene, causing it to
gelatinize.
Table 2 lists all of the experiments contained in the screening
study along with their respective experimental conditions. Each
experiment was given a six numeral identification number based on the
year, month, and day that it was performed. A letter was added to the
numerical code when more than one experiment was performed in the same
day. For example, "860602A" refers to the first experiment performed


54
Table 1. Gases Used in the Plasma Reaction Study
Gas
Vendor
Purity Rating
helium
Aireo
standard grade
argon
Aireo
standard grade
air
(laboratory ambient)
N/A
air
Aireo
breathing quality
hydrogen
Aireo
standard grade
Linde
standard grade
dicyclopentadiene
(liquid)
Aldrich Chemical
reagent grade
chlorodifluoro-
methane
Allied Chemical Corp.
refrigerant grade
dichlorodifluoro-
methane
Allied Chemical Corp.
refrigerant grade
hexafluoroethane
PCR, Inc.
99%
acetylene
Aireo
welder's grade
carbon monoxide
Matheson Specialty Gases
99.9%
methane
Matheson Specialty Gases
99.9% and 99%
natural gas
Gainesville Regional
Gas Company (through
laboratory lines)
commercial grade


Table 2. Screening Study Plasma Reaction Experiments
Expt. Gas
No. Mix
(target) (%)
Pressure *Flow Rate Through
(Pascal) Reaction Zone
ml/min cm/sec
(atm.)
CO2 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
860602A
He
161,500
N/A
N/A
optimum
0.20
none
(none)
(100)
156,100
N/A
N/A
optimum
0.20
141,500
N/A
N/A
optimum
0.20
134,800
N/A
N/A
optimum
0.20
128,100
N/A
N/A
optimum
0.20
121,500
N/A
N/A
optimum
0.20
114,800
N/A
N/A
optimum
0.20
107,900
N/A
N/A
optimum
0.20
101,500
N/A
N/A
optimum
0.20
94,790
N/A
N/A
optimum
0.20
88,130
N/A
N/A
optimum
0.20
72,130
N/A
N/A
optimum
0.20
58,800
N/A
N/A
optimum
0.20
36,130
N/A
N/A
optimum
0.20
26,800
N/A
N/A
optimum
0.20
18,800
N/A
N/A
optimum
0.20
860602B
Air
101,500
(open
to atm)
optimum
0.60
none
(none)
(100)
860530
H?
110,900
3500
162
optimum-5.6
2.70
none
(Au)
(100)
106,390
3500
169
optimum
1.80
860605
He/H?
13,870
40
15
optimum
2.20
790 K QT,
(Au)
(80/20)
194 msec
860606
He/H?
6,800
51
39
optimum
1.72
790 K QT,
(Au)
(75/25)
75 msec


Table 2 (continued)
Expt. Gas
No. Mix
(target) (%)
Pressure *Flow Rate Through
(Pascal) Reaction Zone
ml/min cm/sec
(atm.)
CO2 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
860612
He/Ho
800
54
346
optimum
6.36
790 K QT,
(Au)
(75/25)
8 msec
861022B
He
800
(54)
(346)
optimum
1.20
GWP, UT
(Au)
(100)
861124
He
1,330
125
484
optimum
16.20
UT
(Au)
(100)
870226
Ar/H?
1,390
(90)
(350)
optimum
3.60
300 K TT, UT
(Au)
(75/25)
670
(40)
(310)
optimum
7.68
(55/45)
750
(55)
(380)
optimum
6.96
860724
He/CO
4,930
315
330
optimum
0.30
GWP, two
(Au)
(77/23)
2,670
N/A
N/A
optimum
0.30
195 K CFs
1,600
N/A
N/A
optimum
0.60
1,200
22
95
optimum
12.90
861106
He/CO
UT
(Au)
(100/0)
1,600
N/A
N/A
optimum
0.06
(99/1.2)
1,600
N/A
N/A
optimum
0.09
(98/1.7)
1,600
N/A
N/A
optimum
0.09
(96/3.8)
1,600
N/A
N/A
optimum
0.09
(95/5.2)
1,470
N/A
N/A
optimum
0.06
(90/10)
1,600
N/A
N/A
optimum
0.06
4,000
N/A
N/A
optimum
0.06
(88/12)
9,070
N/A
N/A
optimum
1.50


Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate Through
Reaction Zone
ml/min cm/sec
(atm.)
C02 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
861110
(Au)
He/CO
(79/21)
1,530
210
707
optimum
14.40
195 K CF,
GWP, UT
861126B
(Au)
He (sat. 1,330
with dicyclopentadiene)
(125)
(484)
optimum
12.42
UT
861205
(Au)
He/C2H2
(81/19)
1,400
(125)
(460)
optimum
10.08
195 K TT,
861210
(Au)
He/C2H2
(98/2.5)
1,400
(130)
(490)
optimum
9.78
195 K TT,
870121
(Au)
h2/c2h2
(92/8.3)
1,360
(130)
(490)
optimum
11.04
300 K TT,
861022A
(Au)
ch4
(100)
1,200
(200)
(860)
optimum
3.96
GWP, UT
860701
(Au)
He/CH4
(77/23)
1,730
(300)
(890)
optimum
5.40
893 K QT,
3 msec,
195 K CF
860702
(Au)
He/CH4
(75/25)
1,600
(290)
(935)
optimum
7.02
573 K QT,
3 msec,
195 K CF
UT
UT
UT


Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate Through
Reaction Zone
ml/min cm/sec
(atm.)
C02 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
860704
(Au)
He/CH4
(75/25)
2,000
(330)
(850)
0.59
optimum
2.46
15.12
273 K CF,
195 K CF,
77 K CF
860722
(Au)
He/CH4
(75/25)
1,470
286
510
optimum
19.62
GWP, two
195 K CFs
861012
(Au)
He/CH4
(72/28)
2,130
(350)
(850)
optimum
19.62
GWP, UT
861023
(Au)
He/CH4
(70/30)
1,600
(220)
(710)
optimum
14.40
78 K CF,
GWP, UT
861022C
(carbon)
He/CH4
(75/25)
800
N/A
N/A
optimum
3.90
UT
861016
(Au)
He/CH4/air
(71/25/4)
1,200
(200)
(860)
optimum
6.90
GWP, UT
861017
(Au)
He/CH4/air
(75/21/4)
1,200
(200)
(860)
optimum
10.38
UT
861018
(Au)
He/CH4/air
(71/25/4)
1,600
(290)
(935)
optimum
6.78
300 K CF, UT
870109
(Au)
h2/ch4
(80/20)
1,310
(125)
(490)
optimum
15.00
195 K TT, UT


Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate Through
Reaction Zone
ml/min cm/sec
(atm.)
C02 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
870324
(Au)
h2/ch4
(84/16)
1,350
(130)
(500)
2.4
1.1
4.20
2.94
300 K TT,
UT
870313
(Au)
H2/Natural
Gas
(75/25)
1,420
(130)
(470)
optimum
10.20
300 K TT,
UT
880218
(Au)
Ar
(100)
1,390
75
278
optimum
29.82
GFF,UT
880222
(Au)
He
(100)
1,370
116
436
optimum
29.82
GFF, UT
880223
(Au)
h2/ch4
(76/24)
1,350
145
550
optimum
21.60
GFF, UT
880224
(Au)
h2/ch4
(74/26)
1,390
200
750
optimum
21.60
GFF, UT
880302
(Au)
h2/ch4
(74/26)
1,380
195
730
optimum
21.60
GFF, UT
880303
(Au)
h2/ch4
(74/26)
670
81
620
optimum
22.02
GFF, UT
880304
(Au)
h2/ch4
(74/20)
2,710
653
1,240
optimum
21.60
GFF, UT


Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate
Reaction
ml/min
(atm.)
Through
Zone
cm/sec
C02 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
880307
(Au)
ch4
(100)
1,470
(240)
(840)
optimum
21.60
GFF, UT
880309
(Au)
h2/ch4
(48/52)
670
72
550
optimum
21.60
GFF, UT
880311
(Au)
h2/co
(75/27)
1,390
(125)
(465)
optimum
19.98
GFF, UT
880317
(Au)
h2/co2
(75/25)
1,390
125
465
optimum
21.60
GFF, UT
880329
(Au)
He/CHClF2
(74/26)
1,470
145
510
optimum
3.66
GFF, UT
880415
(Au)
He/CHClF2
(76/24)
300
110
1,890
optimum
5.16
GFF, UT
880421
(Au)
He/CCl2F2
(76/24)
1,360
190
790
optimum
16.56
GFF, UT
880425
(Au)
He/CCl2F2/H2 1,370
(82/14/3.6)
175
660
optimum
20.70
GFF, UT
880427
(Au)
He/C2Fc
(73/27)
1,240
110
413
optimum
19.98
GFF, UT


Table 2 (continued)
Expt.
Gas
Pressure
*Flow Rate Through
CO? Laser Conditions
**Product
No.
Mix
(Pascal)
Reaction
Zone
Focal Point
Pulses
Recovery
(target)
(%)
ml/min
(atm.)
cm/sec
(mm dia.)
(x 1000)
System
880720
h?/ch4
1,350
200
760
optimum
9.77
GFF, UT
(carbon)
(74/26)
880723
h?/ch4
1,350
200
760
optimum
8.34
GFF, UT
(copper)
(74/26)
880724
H?/CHd
27
0
0
optimum
0.01
GFF, UT
(copper)
(74/26)
1,320
(195)
(760)
optimum
0.03
1,230
(185)
(780)
0.28
0.03
1,230
(185)
(780)
0.56
0.03
200
N/A
N/A
0.56
0.03
750
(80)
550
optimum
0.03
1,410
(210)
(770)
optimum
10.44
2,450
330
690
optimum
0.37
*Flowrate
values
in parentheses
are estimates
based on
measurements made
under similar
conditions.
**QT = quartz tube; GWP = glass wool plug; UT = 195 K U-tube; GFF = glass fiber filter; TT = test-tube;
CF = cold finger. See text for detailed descriptions.


62
on June 2, 1986. The gas mixtures, total pressures, and flow rates
through the plasma reaction system are also listed in this table. The
pulsed laser focal point diameter at target impact and the total number
of pulses for each experiment are included as well.
Volumetric flow rates were measured in ml/min at atmospheric
pressure using the bubble-tube flowmeter. Linear flow rates (L)
in cm/sec through the plasma reaction zone were calculated using the
following equation:
L = (F) (101,325/P)/7rr2
where F is the volumetric flow rate in ml/sec measured at atmospheric
pressure, P is the plasma reaction chamber pressure in Pascals, and r
is the radius of the reaction zone in cm. Some values (listed in
parentheses) were estimated from measurements made during similar
experiments utilizing the same nominal gas mixture and pressure and the
same settings on the variable-area flowmeters.
The diameter (d) for the laser beam at the target impact point was
calculated using the absolute value of the difference (x) between the
focal length of the lens (f) and the measured separation of the lens
and target, and the measured diameter (D) of the unfocused laser beam:
(d/2)/x = (D/2)/f
The impact point diameter was varied by moving the lens closer to or
farther away from the target.


63
The first experiment listed in Table 2 investigated the onset of
gas breakdown in helium under pressures ranging from 18,800 to 161,500
(Pascals (141-1211 torr). The second test listed demonstrated the same
effect in air at 101,500 Pascals (761.5 torr). In both of these
experiments the laser beam was focused into the center of the plasma
chamber. The target and target stand were removed from the system.
The third experiment listed demonstrated gas breakdown in hydrogen at
106,390 and 110,900 Pascals (798 and 832 torr) pressure when focusing
the laser on a gold target. The focusing lens was moved back 3 cm from
the optimum distance in order to observe the effect on the gas
breakdown. This same phenomenon was also observed in several other gas
mixtures at lower pressures during the course of the study.
Observations and results are discussed in the next chapter.
Gases were supplied to the chamber under pressure during segments
of the first and third experiments when reactor chamber pressures were
greater than the ambient pressure. Flow rates were controlled by a
metering valve at the chamber exit, upstream from the mechanical pump.
At lower pressures (< 101,500 Pascals) in these and all remaining
experiments, the pressures and gas flow rates were controlled using the
gas handling system described earlier and the metering valve before the
pump.
The last four experiments listed in Table 2 were attempts to
generate pure carbonaceous and copper-bearing species in the plasma
chamber using the carbon and copper targets, respectively, and a 3:1
H2CH4 gas mix. The remaining experiments listed in Table 2 were all
attempts to generate gold species that would remain entrained in the


64
gas stream and subsequently be trapped in the product recovery system.
The reader is directed to the table for a detailed presentation of the
experimental conditions. The results of each experiment are discussed
in Chapter III.
Substrate Coating and Annealing Experiments
Several different types of substrates were coated with the plasma
reaction products during the course of the study. Experiments that
produced the coated substrates are listed in Table 3 along with the
respective substrates and their physical positions in the plasma-
reaction or product-recovery systems during the coating process. In
all of the coating experiments the pulsed CO2 laser was operated at its
maximum voltage level (40 KV) and the focusing lens was adjusted to
provide an optimum focus at the target impact point. All coating
experiments were carried out at a nominal pressure of 1,330 Pascals (10
torr). A nominal gas mixture of 75% hydrogen and 25% methane was used
in all of these experiments with four exceptions. Two experiments were
performed using 100% helium, one test used 78% helium and 22% carbon
monoxide mixture, and one test used a mixture of 75% hydrogen and 25%
natural gas.
Eleven different types of substrates were coated with the plasma
reaction products:
1) glass plates cut from standard 1 mm thick microscope slides
(Corning No. 2947), varying in size from 5 mm by 10 mm to 25 mm by 40
mm,
2) quartz optical windows, 1 mm thick by 27 mm diameter,


65
Table 3. *Substrate Coating Experiments
Expt. Total # Substrates Position in
No. of Laser Coated System
Pulses
(x 1000)
861117 15.00
(78% He/22% CO)
W coated polycrystal -
line (pc) Si chip
placed in U-tube inlet
861124
(100% He)
16.20
glass plates
taped to plasma chamber
windows; placed in bottom
of plasma chamber
861126A
(100% He)
7.20
W coated pc Si chip
with an etched area;
patterned W on single
crystal (sc) SI; glass
pi ates
W/Si chips taped to glass
plates; glass plates taped
to windows and placed in
bottom of plasma chamber
870313 10.20
(75% H£/25% natural
W ribbon coil
gas)
placed in U-tube inlet, Ar
ion laser beam directed
through glass tube onto
leeward area
870326
12.60
W ribbon
placed in plasma chamber
outlet, Ar ion laser beam
directed through quartz
window onto W
870416
13.92
ceramic feedthrough
placed in small coating
chamber
870427
40.74
9 ceramic feedthroughs
placed in glass coating
chamber (GCC) on three
tiered rack
871106
27.66
glass plate
taped into GCC inlet
870721
63.12
W on pc and sc SI
chips; patterned A1
on sc Si chip
taped to first tier of
rack in GCC
870801
11.76
glass plate
taped into GCC inlet
870819
23.10
glass plate
taped into GCC inlet
870901
55.92
3 patterned W, 2 pat
terned A1 on sc SI
chips
taped onto glass plate
that was taped into GCC
inlet


66
Table 3 (continued)
Expt.
No.
Total #
of Laser
Pulses
(x 1000)
Substrates
Coated
Position in
System
880527
33.55
3 W on pc Si and
3 W on sc Si chips
taped to perf-plate in the
aluminum coating chamber
(ACC)
880602
31.32
7 W on pc Si and
5 W on sc Si chips
taped to perf-plate in ACC
880617
27.56
3 W on pc Si and
3 W on sc Si chips
clipped to 373 K hot plate
in ACC
880623
23.46
2 W on sc Si chips;
2 glass plates
clipped to 373 K hot plate
in ACC
880629
20.58
3 W on sc Si chips;
5 glass plates; strip
of Scotch tape, ad
hesive side up, with
an area of W thin film
stuck to the adhesive
taped to perf-plate in ACC
880708
6.41
2 charged aluminum
plates (+275 and -125)
volts dc potential)
pressed into center of
perf-plate
880711
9.98
Si chip with a central
strip of W on one side
charged with -125 volt
dc potential; two 2.5
cm dia. quartz optical
flats; 4 glass chips
placed near sidewall in
ACC
taped to plasma chamber
windows
*A11 experiments were conducted at a nominal pressure of 1,330 Pascals
using a nominal gas mixture of 75% H2 and 25% CH4, except where noted.


67
3) tungsten ribbon, 1.5 mm wide by 0.2 mm thick (H. Cross
Company),
4) ceramic electrical feedthroughs, 1 cm diameter surface,
5) blanket coated CVD tungsten (500-600 nm) on a silicon wafer
with one polycrystalline (pc) side and one single crystal (sc) side
(Harris Corporation) cut into 5 mm by 15 mm chips,
6) same as (5), with areas of tungsten etched away (1 M
K3Fe(CN)g:0.1 M ethylene diamene) to expose the silicon surface,
7) VLSI circuit patterned CVD tungsten on sc silicon with silicon
dioxide surfaces surrounding the 5-50 micron size tungsten features
(Harris Corporation), cut into 5 mm by 15 mm chips,
8) VLSI circuit patterned CVD aluminum on sc silicon with silicon
dioxide surfaces surrounding the 5-50 micron size features (Harris
Corporation), cut into 5 mm by 15 mm chips,
9) aluminum plates, 10 mm by 20 mm by 1 mm thick,
10) Scotch brand adhesive tape, and
11) Scotch brand black electrical tape.
All of the substrates, except the two polymeric tapes, were cleaned in
spectral grade acetone, rinsed in spectral grade methanol, placed in
clean glass petri dishes, and dried in a 383 K oven for at least one
hour. After carefully mounting the cooled substrates onto the plasma
chamber windows or in the substrate coating chamber using rolled Scotch
tape, they were rinsed off with dry nitrogen and placed in line.
Coated substrates were stored in air in glass petri dishes or plastic-
stoppered glass vials.


68
In most of the experiments the substrates were positioned in one
of the product-recovery/substrate-coating systems described earlier and
coated at room temperature (ca. 300 K). In one experiment a 5 cm long
piece of tungsten ribbon was coiled and placed in the inlet arm of the
glass U-tube cold trap and irradiated with an unfocused cw Argon ion
laser beam (4.5 watts, 514.5 nm). In another experiment a 1.5 cm long
piece of the tungsten ribbon was placed in the top of the plasma
reaction chamber at the exit union with the product recovery system
flange (see Figure 9) and exposed to the unfocused Ar ion laser beam
through a quartz window. This caused the ribbon to glow a dull red
when the chamber was under vacuum. When the system gas flow was turned
on the glow disappeared. In both experiments the laser beam was
impacting the leeward face of the ribbon. These were attempts to
observe thermal decomposition of gold species entrained in the gas
stream and subsequent deposition of gold along the thermal gradient
induced by the laser beam.
Two experiments utilized the hot plate described earlier to heat
glass plates and CVD tungsten coated pc and sc silicon chips to 373 + 5
K during the coating process. Problems associated with channeling of
the gas stream around the hot plate limited the efficiency of this
process, but several substrates were effectively coated in each
experiment and then subjected to spectral and microscopic analyses.
A list of the coated substrates that were annealed and the
respective annealing condisions is presented in Table 4. Some of the
tungsten coated and patterned chips, aluminum patterned chips, glass
plates, and quartz windows that had been coated with plasma reaction


69
Table 4. *Substrate Annealing Conditions
Expt.
Substrate
Annealing
Time
Temp.
No.
Method
(K)
861117
plasma chamber
pulsed C02 laser,
40 KV, unfocused
60 pulses
(78% He/
22% CO)
glass window
861126A
W on pc SI chip;
--radio frequency
10 sec
(100%)
patterned W on
(rf) coil (in
60 sec
sc Si chip
flowing air);
--rf coil in still
70 sec
dull red
air
870326
W ribbon
Ar ion laser, 4.5
211 min
watts, unfocused
(in situ)
870416
ceramic feed-
slow convective
141 min
(743)
through
heating (cv.h.)
in air while moni
toring electrical
resistance
(max.)
870427
ceramic feed-
same as above, ex-
57 min
(763)
through
cept under H2 flow
(max.)
870721
W on pc and sc Si;
cv.h. under H2 flow
18 hr
563
patterned A1 on sc
+ 1 hr
0 563
Si chips
+ 2 hr
0 723
870901
W and A1 on sc Si
chips
cv.h. under H2 flow
18 hr
563
880224
glass fiber
cv.h. in air
1 hr ca
. 400
filter (GFF)
+ 3 hr
873
880229
GFF
cv.h. in air
24 hr
420
+ 1 hr
573
880304
GFF
cv.h. in air
8 hr
505
880307
(100% CH4)
GFF
cv.h. in air
8 hr
505
880309
GFF
cv.h. in air
8 hr
505
(48% H2/
52% CH4)


70
Table 4 (continued)
Expt.
No.
Substrate
Annealing
Method
Time
Temp
(K)
880311
GFF
cv.h. in air
3 hr
515
(H2/C0)
880317
GFF
cv.h. in air
24 hr
515
(h2/co2)
880527
W on pc and sc
--cv.h. under H2 flow
18 hr
(533)
Si chips
--cv.h. in air
18 hr
(553)
W on pc and sc
--cv.h. under H2 flow
18 hr
(533)
Si chips
followed by cv.h.
in air
+19 hr
(603)
880602
W on pc and sc
--cv.h. in air
18 hr
373
Si chips
--cv.h. in air
--cv.h. in air
--cv.h. in air
--cv.h. under H2 flow
--cv.h. in air, fol
lowed by cv.h.
under H2
--cv.h. under H2,
followed by cv.h.
in air
18 hr
18 hr
18 hr
1 hr
18 hr
+ 1 hr
1 hr
+19 hr
(533)
(593)
(593)
(573)
(593)
(573)
(573)
(603)
880623
W on pc Si chip
glass plate
--rf coil in air
--drew lines with
focused Ar ion '
laser beam (3.5
watts)
3 sec
0.3 cm/sec
red hot
880629
W on pc Si chip
and glass plate
--rf coil, 0.013
Pascal
--cv.h. in air
--drew 1ines with
focused Ar ion laser
beam (3.5 watts)
(2.0 watts)
(1.0 watts)
1 min
85 min
0.5 cm/sec
0.5 cm/sec
0.5 cm/sec
(670)
880708
(-) dc potential
aluminum plate
cv.h. in air
90 sec
(875)


71
Table 4 (continued)
Expt.
No.
Substrate
Annealing
Method
Time
Temp.
(K)
880711
pieces of GFF
cv.h. in air
25 hr
383
23 hr
(473)
1 hr
(676)
90 sec
(875)
*A11 experiments were conducted at a nominal pressure of 1,330 Pascals
using a nominal gas mixture of 75% H2 and 25% CH4, except where noted.


72
products were annealed in air or hydrogen at temperatures ranging from
373-670 K for time intervals ranging from several seconds to several
hours. These anneals were performed in the tube furnace described
earlier. An annealing chamber was constructed from a 20 mm i.d. by 50
cm long borosilicate glass tube with 0-ring seal joints on both ends
(see Figure 10). The ends of this tube were connected to two matching
0-ring seal joints that had ends tapered to 1/4 in. o.d. tubing. Quick
couples were used to connect the chamber with the gas handling system
for delivery of hydrogen at ca. 400 ml/min. Anneals in air were
performed by disconnecting the chamber's gas inlet line and allowing
ambient air to be drawn through the system by convective flow. A brass
sample holder with a stainless steel insertion handle was used to place
and hold the substrates in the center of the tube furnace, adjacent to
the thermocouple.
Some glass fiber filters were also annealed in air at temperatures
ranging from 390-873 K by placing them in borosilicate glass petri
dishes and then into a laboratory drying oven or a muffle furnace.
This was done to observe the onset of a development process that
changed the color of the plasma reaction product coating from black to
purple to pink/red.
Several patterned and unpatterned CVD tungsten on silicon chips,
and one glass plate, were inserted into a radio frequency coil and
heated inductively. Either a 30-year-old ham radio with 100 watts of
power at 13.56 Mhz, or an ICOM All Solid State HF SSB tranceiver
feeding a Heath Kit tube-type linear amplifier at 14.000 Mhz and
delivering 250 watts of power, were used to power the 3 cm diameter 3


Figure 10. Substrate Annealing Chamber




75
I
turn coil. No temperature measurements were made in these tests, but
several samples were heated to a red glow. Exposure time to the rf
field was varied from 3-70 seconds. Some tests were performed in
ambient air with or without a fan blowing air past the sample, and
other samples were heated while under a pressure of 0.01 Pascals.
The unfocused pulsed CO2 laser beam was used to anneal a coated
chamber window and a coated quartz window. Exposures were varied from
1-100 pulses. The laser was operated at its maximum power level of 40
KV during all of these tests.
The Argon ion laser was used to write gold lines on coated
substrates by focusing the beam through a 75 mm focal length quartz
lens (Rolyn #11.0140) onto the coated surface. The laser was operated
at power levels of 3.5, 2.0, and 1.0 watts. Glass plates and CVD
tungsten on Si chips were taped to a carbon block and manually rastered
in front of the laser beam at the focal point. Pull rates were varied
from 0.3 cm/sec to 0.5 cm/sec. The focused beam was also fixed on
one spot on a CVD tungsten on sc SI chip for 10 seconds.
Product Volatility Study
The search for volatile gold compounds in the plasma reaction
products was divided into three categories, based on technique. The
first category of tests involved attempts to sublime gold compounds at
low pressure from the reaction products thermally and collect them in a
cold trap. The second category of tests utilized quadrupole and ion
cyclotron (ICR) mass spectrometers and several different methods of
sample delivery in an attempt to isolate and identify gold compounds.


76
compounds. The third category consisted of one series of experiments
using a time of flight mass spectrometer (TOFMS) to detect gold cluster
compounds formed in a Nd/YAG pulsed laser stimulated plasma using a
solid gold target and 1% methane in helium. Each experiment in the
volatility study is described below.
Sublimation Experiments
The two sublimation experiments that were performed used the
reaction products formed in a 75% He/25% CH4 plasma and isolated in the
product recovery system. The first experiment used the (195 K) U-tube
cold trap from 861018. This trap had been positioned after a 300 K
cold finger during the plasma reaction experiment. The second
sublimation experiment utilized the first cold finger trap (195 K), and
the glass wool plug contained in its outlet, from 861023. Both of
these cold traps contained milligram quantities of the dark-colored
plasma reaction products.
Both sublimation experiments were performed by attaching the
plasma containing cold traps (which had been sealed and stored at 195
K) to a fresh U-tube cold trap kept at 195 K. This trap was connected
to the mechanical vacuum pump, via a metering valve and a 195 K pump
trap, and the system was evacuated slowly to < 1 Pascal. In the first
test the products were warmed from 195-373 K over a period of four
hours. A second collection trap was exchanged for the first one when
the products reached 300 K. In the second test the plasma products
were warmed from 300 to 900 K over a period of 90 minutes. Only one
collection trap was used in this test. All of the collection traps,


77
and both of the product recovery traps, were sealed in air and heated
to 900 K in a bunsen burner. Color changes in the trap contents,
which indicated the presence of gold films, were observed visually.
Mass Spectrometer Experiments
Six experiments were performed using quadrupole or ICR mass
spectrometers to detect compounds in the plasma reaction products. All
of the instruments were located in the Department of Chemistry at the
University of Florida (U.F.). A synopsis of these experiments is
presented below in Table 5.
Table 5. Volatility Study Mass Spectrometer Experiments
Expt. Plasma Expt.
No. (Gas Mix)
Sample
Type
MS Type
Sample Introduction
Method
1 860704
(75% He/25% CH4)
target residue
quadrupole
solids probe,
heated to 670 K
2 870121
(93% H2/8% C2H2)
chamber wall
residue
GC/quad.MS
injected acetone
suspension/solution
3 870819
(75% H2/25% CH4)
U-tube cold
trap
quadrupole
connected to gas
inlet, heated to
680 K
4 860722
(75% He/25% CH4)
cold trap
after GWP
FTICR
connected to gas
inlet, heated to
380 K
5 870819
(75% H2/25% CH4)
coated glass
pi ate
FTICR
placed adjacent to
ICR cel 1; e-beam &
laser desorption
6 870819
(75% H2/25% CH4)
residue from
coated glass
pi ate
FTICR
solids probe,
heated to 450 K,
CID reactions


78
The first experiment was done in the laboratory of Prof. R.A. Yost
by Mr. M. Hail using a Finnigan/MAT 4515 quadrupole MS. Reaction
products were recovered from the gold target used in test 860704 (75%
He/25% CH4) by scraping the tar-like residue with a teflon spatula.
The sample was placed in a solids probe and heated to 673 K while
observing the mass response from 0-494 atomic mass units (a.m.u.). The
instrument's mass range was calibrated using perfluorotributylene.
The second experiment was done in the department's Analytical
Service Laboratory by Dr. R.W. King using a Finnigan/MAT 4500 gas
chromatograph/quadrupole mass spectrometer (GC/MS). A sample was
recovered from the plasma chamber sidewall after test 870121 (93% H2/8%
C2H2) by rinsing the sidewall with spectral grade acetone. The
extract/suspension was injected onto a 5 ft. x 1/4 in. glass
chromatography column packed with an inert support coated with 3%
SP2100 (an organo-si1ane polymer commonly used for hydrocarbon
separations). Helium carrier gas flow rate through the column was 30
ml/min. The column temperature was increased from 318-573 K at 10
degrees per minute while observing the mass response from 0-300 a.m.u.
This instrument was also calibrated using a standard hydrocarbon
mixture (FC 43).
The third experiment was performed in the laboratory of Prof. M.T.
Vala by the author using a Finnigan 3500 quadrupole MS. The U-tube
cold trap used in test 870819 (75% H2/25% CH4) was connected to the
instrument's solids probe inlet and heated to 680 K in a tube furnace
while observing the mass response from 0-500 a.m.u. The instrument
response was tested by placing a sample of triethylphosphine-gold


79
chloride (synthesized by Dr. E. Sczlick in the laboratory of G.J.
Palenik at U.F.) in the solids probe and heating it to 570 K.
The fourth, fifth, and sixth experiments were performed in the
laboratory of Prof. J.R. Eyler by Dr. M. Moini and the author. The
fourth one used a sample from test 860722 (75% He/25% CH4). The sample
was collected in a 195 K cold trap positioned after a glass wool plug
during the plasma experiment. This cold trap was connected to the gas
inlet of an ICRMS (Nicolet FTMS-1000 equipped with a 3.0 Tesla
superconducting magnet and described fully in the literature).*^ The
sample trap was then evacuated to 0.1 Pascals while still immersed in
dry ice. The valve to the MS was then opened and the mass response
from 0-1000 a.m.u. was observed using Fourier transform techniques
while the sample trap was slowly warmed to 380 K. The instrument
response was tested by placing a sample of triethylphosphine-gold
chloride in a solids probe and warming it to 450 K.
The fifth experiment used an inhouse fabricated ICRMS (equipped
with a Nicolet FTICR MS data station and a Varian Fieldial 1.0 Tesla
electromagnet) to examine plasma reaction products coated on a glass
plate in run 870819 (75% H2/25% CH4). The sample was mounted on a
solids probe and positioned in the vacuum chamber adjacent to the ICR
cell. The mass response from 0-400 a.m.u. was monitored using Fourier
transform methodology while the sample was exposed to a 500 nanoamp
electron beam for one hour. The sample was then irradiated with an
unfocused frequency doubled, 532 nm pulsed Nd:YAG laser (Quantel Model
YG 580) at power levels of 50-500 mJ/pulse in an attempt to desorb
compounds that would have then been ionized by co-desorbed potassium


80
ions. (The K+ ions came from the materials used to construct the ICR
cell. This was considered a "soft" ionization technique.) The mass
response was monitored for the next twenty minutes while the laser and
e-beam were on, and then for another ten minutes with the laser on and
the e-beam off.
The sixth experiment was performed in the Nicolet FTMS-1000 ICRMS
using a sample generated in run 870819 (75% H2/25% CH4). The sample
was placed in a capillary tube that was then inserted into the solids
probe and warmed to 450 K while the mass response from 0-1000 was
observed. Collision-induced ion dissociation (CID) experiments were
performed on compounds with mass numbers 44, 149, 195, 255, 334, and
348.
Time of Flight MS Plasma Experiment
This experiment was performed in the labortory of Prof. P.J.
Brucat in the Department of Chemistry at U.F. by Mr. D.E. Lessen and
the author. This laboratory was equipped with a cluster beam apparatus
linked to a time of flight mass spectrometer (see Figure 11) that is
described fully elsewhere.^ The cluster beam was produced by
irradiating a solid gold target with a focused pulsed Nd:YAG laser
(Quantel Model YG-580) beam at a power level of 1-2 mJ/pulse at target
impact (7 nsec pulses at 10 hz). Helium or helium/1% methane gas was
introduced to the target at a pressure of 1 atm. using a 1 msec
pulsed valve. The resultant plasma exited the target holder through a
2 mm dia. hole and was hypersonically expanded into a large vacuum
chamber maintained at a pressure of 0.01 Pascals. A skimmer in direct


Figure 11. Cluster Beam/TOFMS Apparatus


82
skimmer


83
line of sight with the plume exit allowed undeflected clusters to enter
a repeller grid where they were redirected down a three meter TOF tube
and into a multi-stage detector. A variable voltage horizontal
deflector (HD) located at the beginning of the TOF tube optimized the
transfer efficiency of various mass ranges of clusters.
During the course of the experiment the HD voltage was varied
between 50-120 volts. This allowed the observation of signals from
ionized gold clusters and cluster compounds from Au(l) to Au(7). At
each voltage setting the signals from positive ion clusters produced in
pure helium and in helium/1% methane plasmas were recorded.
Gold Thin Film Characterization
Six different techniques were utilized to characterize the plasma
reaction products formed in the 3:1 hydrogen/methane-gold plasmas.
Samples of the ultrafine particle product and coated substrates (both
annealed and unannealed) were subjected to analyses. Most samples were
in the form of thin films deposited on glass plates, ceramic
feedthroughs, and CVD tungsten or aluminum on silicon chips. A major
objective of these analyses was the determination of the relative
abundance, and the physical state, of the gold present in the soot-like
plasma reaction products. Film stoichiometry, structure, and
electrical properties were also investigated. The analytical
techniques utilized in this part of the study were
1) visible absorption spectroscopy,
2) optical microreflectometry (OMR),
3) x-ray photoelectron spectroscopy (XPS),


84
4) scanning electron microscopy (SEM) with
5) energy dispersive spectroscopy (EDS), and
6) electrical resistance (R)
The principle features of each technique are described briefly along
with the relevant parameters employed to analyze the sample films.
Detailed lists of the samples analyzed using each technique are
presented in Chapter III along with the respective analytical results
and a discussion of their meaning.
Visible Absorption Spectroscopy
A Hewlett-Packard Model 8450 diode array spectrometer was used by
the author to measure the absorption spectra (300-800 nm) of acetone
suspension/solutions of several samples recovered from the plasma
chamber sidewalls. Samples from CH4, He/CH4, and He/CO plasma
experiments were subjected to solvent dissolution tests using hexane,
toluene, acetone, diethyl-ether, 1:1 solutions of the preceding
solvents, water, hydrochloric acid, nitric acid, and aqua regia before
determining that pure acetone yielded the best results (discussed in
the next chapter). The absorption spectra of 10 ppm and 10,000 ppm Au
standards in acetone/water were also measured. These standards were
prepared by diluting 1 ml of the 1000 ppm and 10 ml of the 100,000 ppm
AA standards, respectively, to 100 ml with spectral grade acetone. All
of the sample and standard spectra were measured against an acetone
reference cell. All measurements were made in standard matched 1 cm
wide quartz cuvets.


85
The major objective of these analyses was the determination of the
presence or absence of the metallic absorption band for gold in the
550-600 nm region of the spectrum. This indicated the presence or
absence of gold particles large enough to exhibit metallic behavior.
Optical Microreflectometrv
An optical microreflectometer located in the laboratory of Prof.
P. Holloway in the Material Science Department at U.F. was used by the
author to measure the reflectance spectra of several samples. The
instrument consisted of a quartz halogen light source and focusing lens
assembly, a 1200 1/mm grating monochromator, a binocular microscope
with internal mirrors for directing reflected light to a GaAs
photomultiplier tube, and a Keithley autoranging picoammeter (Model
485). Reflectance curves were determined by comparing the sample
intensities to the intensities of a standard with known reflectivity in
air, R(std). The reflectance intensity of a SiC standard, I(std), was
measured at 10 nm intervals between 400 and 900 nm just prior to
measuring the intensity of each sample's reflectance, I(samp), at the
same wavelengths. The reflectance value for each sample point,
R(samp), was then calculated using the following equation:
R[samp] = [I(samp) DC] x [R(std)]/[I(std) DC]
where DC was the photomultiplier dark current. R(std) values for SiC
are listed in Appendix C.
Sample films were examined visually to determine a representative
area for reflectance measurements. The instrument analyzed an area 20
microns in diameter. The same spot on the SiC standard was measured


86
each time by aligning two small defects on the crystal surface with
points on the microscope measurement grid. Reflectance curves were
determined for annealed and unannealed films deposited on glass plate
and on CVD tungsten on Si chips, as-deposited films on the two
polymeric tapes, and the Harris Corp. standard sputtered Au film.
X-Ray Photoelectron Spectroscopy
X-ray photoelectron spectroscopy studies were carried out on
several CH4/H2/AU plasma reaction product coated and annealed W on Si
substrates. The XPS analyses had three major objectives: 1)
determination of the elemental surface composition of the film, 2)
determination of the binding energy (BE) of the Au 4f5/2 and 4f7/2
peaks and the C Is peak, and 3) determination of the gold and carbon
concentrations in the bulk of the film. The first objective was
achieved through the use of elemental survey scans from 0-1000 eV BE.
The second objective was accomplished using narrow scans (-10 eV) of
the respective Au and C peaks and observing the shift in BE and the
peak shapes and widths at half height (whh). The determination of
carbon and gold concentrations in the bulk of the films was
accomplished using narrow scans with variable photoelectron takeoff
angles and Ar+ ion etching. Spectra were recorded in a fixed analyzer
transmission mode, which allowed direct comparison of adjusted peak
areas for semiquantitative analyses. A detailed list of all samples
subjected to XPS analyses, along with the respective analytical
conditions and results, is presented in Chapter III together with a
detailed discussion of the results.


87
Two instruments were used to perform the analyses in these
studies. One instrument, a Kratos XSAM 800, was located in the
laboratory of Prof. V.Y. Young in the Department of Chemistry at U.F.
and was operated by Mr. P.C. McCaslin and Mr. J.G. Davis, Jr. The
instrument used a Mg anode (1254.6 eV Ka line) x-ray source operated at
15 kV accelerating potential. Samples were mounted to a grounded
holder using stainless steel screws that contacted the surface of the
sample films and the underlying W substrate near the edges. This
arrangement prevented charging of the thin film while it was being
exposed to the x-radiation and undergoing electron loss. Spectra were
recorded at photoelectron takeoff angles of 10 and 70 degrees. This
technique allowed observation and comparison of the signals produced
predominantly by near surface species (-1.5 nm sampling depth at 10
degree takeoff angle) and those produced predominantly by bulk species
(-7.5 nm, or three times the mean free path of 1.2 keV electrons in
gold,67,68 sampling depth at 70 degree takeoff angle). One sample was
also etched with Ar+ ions at 2.5 keV accelerating potential and 0.25 mA
sample current for a total of 60 minutes. Spectra were recorded before
the etch, after 15 minutes of etching and after 60 minutes of etching.
The second XPS instrument was a GCA/McPherson ESCA 36 located in
the laboratory of Prof. A.T. D'Agostino in the Department of Chemistry
at the University of South Florida and was operated by Mr. C. Biver.
This instrument used an A1 anode (1487.6 eV Ka line) x-ray source
operated at 15 kV potential. An initial set of samples that was
analyzed in this instrument was improperly grounded and thus did not
yield valid BE data. However, since the charging effect reached an


88
equilibrium status within the first few seconds of exposure to the
constant intensity x-ray beam,69 the total areas of the Au and C peaks
and the elemental survey scans provided useful information. One sample
film and one Harris Corp. standard sputter deposited Au film were
subjected to depth profiling using Ar+ ion etching (13 /A ion current
and 6.3 mA arc current). These two samples were grounded by pressing
copper foil over them, with an open area for analysis, and attaching
the foil securely to the grounded sample stand. All spectra were
recorded at a photoelectron takeoff angle of 75 degrees. Peak areas
were adjusted for elemental composition determinations using Scofield's
photoionization cross sections^ at 1254.6 and 1487.6 eV, respectively,
for the two instruments. Since only gold and carbon were detectable in
the films (the photoionization cross section for hydrogen is extremely
small, 0.0002 relative to carbon, and was not detectable with these
instruments), and the Scofield cross section value for the C Is peak is
taken as 1.00 relative (22,000 barns at 1254.6 eV, and 13,600 barns at
1487.6 eV), only the combined areas (XAu) of the Au 4f peaks were
adjusted. This was done using the following equation for the Mg Ka
source (1254.6 eV):
(XAu)/(7.68 + 9.79) = adjusted Au area
For the A1 Ka source (1487.6 eV), the following equation was used:
(XAu)/(7.54 + 9.58) = adjusted Au area


89
Once the adjusted Au areas (adjAu) were calculated they were compared
directly to the corresponding C Is peak areas to yield relative percent
atomic composition using the following equations:
(100)(adjAU)/(adjAu + C Is) = relative atomic % Au
(100)(C ls)/(adjAu + C Is) = relative atomic % C
Relative percent mass concentrations were then calculated using the
following equations, where ra%Au and ra%C are the relative atomic
percent concentrations of gold and carbon, respectively:
(ra%Au)(197)/[(ra%Au)(197) + (ra%C)(12.0)] = relative mass % Au
(ra%C)(12.0)/[(ra%Au)(197) + (ra%C)(12.0)] = relative mass % C
In some discussions of the results in the following chapter references
are made to the ratio of gold to carbon and vice versa. In all
instances these discussions are referring to the atomic ratios of the
two elements.
Scanning Electron Microscopy with Energy Dispersive Spectroscopy
The SEM/EDS analyses were carried out in order to determine 1) the
average grain or particle size and shape of the species comprising the
as deposited sample films and 2) the change in film structure
associated with various annealing regimes. These analyses were
performed in a JE0L SEM equipped with an EDS system located in the
laboratory of Prof. M. Ammons in the College of Engineering Center for


90
Electron Microscopy at the University of South Florida. The instrument
was operated by Prof. Ammons and Ms. A.S. Slater.
The optics in the EDS system precuded the observation of low Z
elements, thus hydrogen and carbon were not observable. The EDS was
used primarily to determine qualitatively the relative abundance of
gold in the surface being scanned by the SEM. By varying the electron
energy, and thus the mean free path in the sample film, a rough depth
profile could be observed. This facilitated the interpretation of the
signals produced by the underlying substrate. Plasma reaction products
coated on glass chips, W on sc and pc SI chips and Scotch tape were
examined along with the Harris Corp. standard sputtered Au film. Both
annealed and as-deposited samples were examined. A detailed list of
the samples analyzed is presented in the next chapter.
Electrical Resistance Measurements
Two methods of observing the electrical resistance properties of
the sample films were employed. The first technique consisted of
observing the resistance across a 3 mm wide ceramic junction in an
electrical feedthrough that had been heavily coated with plasma
reaction products. The feedthrough was inserted into the substrate
annealing chamber described earlier along with a thermocouple junction.
The resistance was monitored as the temperature was slowly increased
from 300-750 K. In one experiment hydrogen gas was flowed through the
system at 200 ml/min. In a second experiment the system was left open
to the ambient atmosphere. The purpose of these two tests was to
observe any minima in the resistance values versus the temperature as


Full Text
xml version 1.0 encoding UTF-8
REPORT xmlns http:www.fcla.edudlsmddaitss xmlns:xsi http:www.w3.org2001XMLSchema-instance xsi:schemaLocation http:www.fcla.edudlsmddaitssdaitssReport.xsd
INGEST IEID EIRHW638N_EJ7Y9K INGEST_TIME 2011-11-08T18:24:17Z PACKAGE AA00004826_00001
AGREEMENT_INFO ACCOUNT UF PROJECT UFDC
FILES



PAGE 1

*2/' 7+,1 ),/06 352'8&(' )520 /$6(5 67,08/$7(' 3/$60$ 5($&7,21 352'8&76 %\ &+$5/(6 *(25*( 6,021 $ ',66(57$7,21 35(6(17(' 72 7+( *5$'8$7( 6&+22/ 2) 7+( 81,9(56,7< 2) )/25,'$ ,1 3$57,$/ )8/),//0(17 2) 7+( 5(48,5(0(176 )25 7+( '(*5(( 2) '2&725 2) 3+,/2623+< 81,9(56,7< 2) )/25,'$ MM L6( ) /,%5$5,(6

PAGE 2

7R P\ ZLIH 'LDQH WR P\ SDUHQWV 6DP DQG %HUQLFH DQG WR %REE\ 6DPPRQV

PAGE 3

$&.12:/('*(0(176 7KH DXWKRU ZLVKHV WR H[SUHVV KLV JUDWLWXGH WR DOO ZKR FRQWULEXWHG WR WKLV ZRUN DQG WR KLV HGXFDWLRQ DW WKH 8QLYHUVLW\ RI )ORULGD ,Q SDUWLFXODU KH ZLVKHV WR H[SUHVV KLV DSSUHFLDWLRQ IRU DOO RI WKH HIIRUW DQG JXLGDQFH SURYLGHG E\ KLV UHVHDUFK GLUHFWRU DQG FRPPLWWHH FKDLUPDQ 6DPXHO &ROJDWH 7KH DXWKRU ZRXOG OLNH WR WKDQN KLV SHHUV DQG WKH IDFXOW\ DQG VWDII PHPEHUV DW WKH 8QLYHUVLW\ RI )ORULGD 8)f DQG WKH 8QLYHUVLW\ RI 6RXWK )ORULGD 86)f ZKR FRQWULEXWHG WR WKLV HIIRUW DW 8) 0DUN +DLO DQG 5R\ .LQJ IRU TXDGUXSROH 06 DQDO\VHV 0HKGL 0RLQL IRU )7,&506 H[SHULPHQWV 'DQ /HVVRQ IRU FOXVWHU EHDP 72)06 H[SHULPHQWV 3DXO 0F&DVOLQ DQG -DFN 'DYLV -U IRU ;36 DQDO\VHV DW 86) $OIUHG 'n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

PAGE 4

7HFKQRORJ\ DQG ,QGXVWU\ &RXQFLO IRU WKHLU ILQDQFLDO VXSSRUW )+7,& *UDQW f ,9

PAGE 5

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

PAGE 6

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

PAGE 7

/,67 2) 7$%/(6 7DEOH 3DJH *DVHV 8VHG LQ WKH 3ODVPD 5HDFWLRQ 6WXG\ 6FUHHQLQJ 6WXG\ 3ODVPD 5HDFWLRQ ([SHULPHQWV 6XEVWUDWH &RDWLQJ ([SHULPHQWV 6XEVWUDWH $QQHDOLQJ &RQGLWLRQV 9RODWLOLW\ 6WXG\ 0DVV 6SHFWURPHWHU ([SHULPHQWV )LOWHU &DWFK 3ODVPD ([SHULPHQW 5HVXOWV *&06 5HVXOWV IURP DQ $FHWRQH ([WUDFW RI +&+$8 3ODVPD 5HDFWLRQ 3URGXFWV ;36 $QDO\WLFDO &RQGLWLRQV DQG 5HVXOWV *ODVV )LEHU )LOWHU %ODQNV 5HSHWLWLYH :HLJKLQJV RQ WKH 0HWWOHU $QDO\WLFDO %DODQFH 5VWQGf 9DOXHV IRU 6L&

PAGE 8

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

PAGE 9

FRQGLWLRQV 7KH DYHUDJH PDVV FRQFHQWUDWLRQ RI JROG LQ WKH ILOPV ZDV b DWRPLF bf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

PAGE 10

&+$37(5 ,1752'8&7,21 0HWKRGV IRU SURGXFLQJ VXEPLFURQ JROG ILOP SDWWHUQV DUH RI FXUUHQW LQWHUHVW WR WKH PLFURHOHFWURQLF LQGXVWU\ IRU XVH DV LQWHUFRQQHFW PHWDOOL]DWLRQ DV GHYLFH VL]HV VKULQN LQ 9/6, YHU\ ODUJH VFDOH LQWHJUDWLRQf FLUFXLWU\ ,QWHUFRQQHFWV SURYLGH FRPPXQLFDWLRQ URXWHV EHWZHHQ VLQJOH GHYLFHV DQG HDFK RWKHU EHWZHHQ VLQJOH GHYLFHV DQG WKH RXWVLGH ZRUOG DQG EHWZHHQ DFWLYH UHJLRQV ZLWKLQ D VLQJOH GHYLFH 6LQFH SURSDJDWLRQ WLPH GHOD\ DORQJ WKH LQWHUFRQQHFW LV GLUHFWO\ SURSRUWLRQDO WR ILOP UHVLVWLYLW\ DQG LQYHUVHO\ SURSRUWLRQDO WR WKH ILOP WKLFNQHVV DV ZHOO DV YDU\LQJ ZLWK WKH VTXDUH RI WKH OHQJWK LW LV LPSRUWDQW WR SURGXFH VKRUW DQG UHODWLYHO\ WKLFN FRPSDUHG WR WKH ZLGWKf ILOPV ZLWK JRRG HOHFWULFDO SURSHUWLHV LQ RUGHU WR PLQLPL]H RSHUDWLQJ WLPHV &XUUHQW PLFURQVL]H LQWHUFRQQHFWV DUH SDWWHUQHG XVLQJ DOXPLQXP EXW LQGXVWU\ SURJUHVVLRQ WR VXEPLFURQVL]H GHYLFHV ZLOO HOLPLQDWH DOXPLQXP IRU WKLV XVH EHFDXVH RI HOHFWURPLJUDWLRQ SUREOHPV *ROG LV DQ LGHDO VXEVWLWXWH IRU DOXPLQXP EHFDXVH RI LWV ORZ UHVLVWLYLW\ KLJK FRQGXFWLYLW\ DQG UHVLVWDQFH WR HOHFWURPLJUDWLRQ &KHPLFDO YDSRU GHSRVLWLRQ &9'f LV WKH RQO\ FXUUHQWO\ DYDLODEOH WHFKQLTXH IRU SURGXFLQJ JROG WKLQ ILOPV WKDW PHW ERWK WKH VHOHFWLYH GHSRVLWLRQ DQG KLJK WKURXJKSXW UHTXLUHPHQWV QHFHVVDU\ IRU PDVV SURGXFLQJ VXEPLFURQ SDWWHUQV LQ 9/6, FLUFXLWV 9RODWLOH JROG FRPSRXQGV DUH XVHG LQ WKH &9' SURFHVV WR IRUP WKH WKLQ PHWDO ILOPV E\ GHFRPSRVLQJ

PAGE 11

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n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

PAGE 12

GHVFULSWLRQ RI DOO HTXLSPHQW DQG SURFHGXUHV DQG LQ &KDSWHU ,,, E\ D GLVFXVVLRQ RI WKH UHVXOWV $PRQJ WKH HOHPHQWV RQO\ JROG VLOYHU FRSSHU DQG DOXPLQXP KDYH KLJK HQRXJK HOHFWULFDO FRQGXFWLYLWLHV DW GHYLFH RSHUDWLQJ WHPSHUDWXUHV .f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f DQG WKH IOX[ DFURVV WKH JUDLQ ERXQGDULHV +XQWLQJWRQ DQG *URQHA GHULYHG DQ H[SUHVVLRQ IRU WKH IOX[ LQ EXON PDWHULDO ZKLOH +R DQG Gn+HXUOHA GLG VR IRU WKH DGGHG DWRPLF IOX[ DFURVV JUDLQ ERXQGDULHV %RWK DSSURDFKHV DUH EDVHG RQ VWDWLVWLFDO GLVWULEXWLRQ RI PRELOH DWRPV DQG DGMDFHQW YDFDQFLHV LQ WKH FU\VWDO ODWWLFH RU JUDLQ ERXQGDULHV &RPELQLQJ WKHLU WZR H[SUHVVLRQV \LHOGV DQ HTXDWLRQ IRU ) DV D IXQFWLRQ RI WKH FXUUHQW GHQVLW\ WKH DWRPLF GHQVLW\ 1 WKH DWRPLF GLIIXVLRQ FRHIILFLHQW WKH DEVROXWH WHPSHUDWXUH

PAGE 13

7 WKH HIIHFWLYH FKDUJH =rT WKH EXON FRQGXFWLYLW\ FE DQG WKH ILOP FRQGXFWLYLW\ &I ) 1'=rT-FEN7 1'=rT-FIN7fVGf ZKHUH N LV WKH %ROW]PDQ FRQVWDQW V LV WKH DYHUDJH VHSDUDWLRQ GLVWDQFH EHWZHHQ JUDLQ ERXQGDULHV DQG G LV WKH DYHUDJH JUDLQ VL]H 7KLV PRGHO LV RQO\ DQ DSSUR[LPDWLRQ VLQFH LW LJQRUHV WKH JHRPHWULFDO RULHQWDWLRQ RI WKH JUDLQV DQG LPSXULWLHV DGVRUEHG RQ WKH JUDLQ ERXQGDULHV DQG LW DVVXPHV WKDW WUDQVSRUW DFURVV JUDLQ ERXQGDULHV RFFXUV YLD FKDQQHOV EHWZHHQ WKH JUDLQV ,W LV LPPHGLDWHO\ DSSDUHQW WKDW WKH ORZHU DWRPLF GHQVLW\ RI JROG PROHVFPp FRPSDUHG WR DOXPLQXP PROHVFPpp OHDGV WR D ORZHU ) YDOXH IRU JROG $OVR WKH ORZHU HIIHFWLYH QXFOHDU FKDUJH RI WKH JROG DWRP DQG WKH JROG f DQG f LRQV =r DQG UHVSHFWLYHO\ XVLQJ 6ODWHUnV 5XOHVf FRPSDUHG WR WKH DOXPLQXP DWRP DQG f LRQ =r DQG UHVSHFWLYHO\ XVLQJ 6ODWHUnV 5XOHVf UHVXOWV LQ D IXUWKHU ORZHULQJ RI WKH ) YDOXH IRU JROG 6LQFH PRYHPHQW RI DWRPV ZLWKLQ D FU\VWDO LV KLJKO\ UHVWULFWHG DQG WKH JUDLQ ERXQGDU\ DUHD LQ WKHVH SRO\FU\VWDOOLQH PHWDO WKLQ ILOP LQWHUFRQQHFWV LV PDQ\ WLPHV JUHDWHU WKDQ WKH H[WHUQDO VXUIDFH DUHD WKH DWRPLF IOX[ ZLWKLQ WKH WKLQ ILOP LQWHUFRQQHFW LV GRPLQDWHG E\ GLIIXVLRQ DFURVV WKH JUDLQ ERXQGDULHVp 7KXV WKH KHDYLHU PRUH EXON\ JROG DWRPV SRVVHVVLQJ D ORZHU UHODWLYH FKDUJH WKDQ DOXPLQXP EXW KDYLQJ D VLPLODU QHW EXON UHVLVWLYLW\ RI FD PLFURRKPVFP DUH IDU OHVV SURQH WR HOHFWURPLJUDWLRQ DW KLJK FXUUHQW GHQVLWLHV 7\SLFDOO\

PAGE 14

FXUUHQW GHQVLWLHV p DPSFPA FDXVH VHULRXV HOHFWURPLJUDWLRQ SUREOHPV LQ DOXPLQXP DQG LWV DOOR\V ZKLOH JROG GRHV QRW H[SHULHQFH VHULRXV SUREOHPV XQWLO FXUUHQW GHQVLWLHV H[FHHG DSSUR[LPDWHO\ A DPSFPAA 7KH QH[W JHQHUDWLRQ RI HOHFWURQLF GHYLFHV DUH H[SHFWHG WR EH RI VXEPLFURQ GLPHQVLRQV DQG RSHUDWH DW FXUUHQW GHQVLWLHV XS WR p DPSFPAOp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f HOHFWURSODWLQJ f VSXWWHULQJ LQFOXGLQJ UHDFWLYH VSXWWHULQJf f YDFXXP HYDSRUDWLRQ f LRQL]HG FOXVWHU GHSRVLWLRQ f VXSHUILQH SDUWLFOH GHSRVLWLRQ

PAGE 15

f FKHPLFDO YDSRU GHSRVLWLRQ &9'f f GLUHFW ZULWH LQFOXGLQJ ODVHU HOHFWURQ DQG LRQ EHDP WHFKQLTXHVf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rp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f WHFKQLTXH WKDW XVHV LRQL]HG JDVHV XVXDOO\ DUJRQf WR ERPEDUG D WDUJHW FRPSRVHG RI WKH PHWDO WR EH GHSRVLWHG 7KH HQHUJHWLF LRQ FROOLVLRQV GLVORGJH VXUIDFH DQG QHDU VXUIDFH QHXWUDO PHWDO DWRPV ZKLFK WKHQ WUDYHO UDQGRPO\ WR WKH

PAGE 16

VXEVWUDWH ZKHUH WKH\ DUH GHSRVLWHG 0DVNV DQG HWFKLQJ WHFKQLTXHV DUH XVHG WR IRUP SDWWHUQV 6HYHUDO YDULDWLRQV KDYH EHHQ GHYHORSHG VXFK DV DGGLQJ D UHDFWLYH JDV WR WKH DPELHQW RU KHDWLQJ DQGRU DSSO\LQJ D UDGLRIUHTXHQF\ UIf ELDV WR WKH VXEVWUDWH 7KHVH PRGLILFDWLRQV LPSURYH VWHS FRYHUDJH RQ WKH VXEVWUDWH VXUIDFH DQG ZHOOGHILQHG VWHS FRYHUDJH LV HVVHQWLDO IRU VPDOO VFDOH GHYLFH DQG LQWHUFRQQHFW IRUPDWLRQ+}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r MKH FOXVWHUV DUH IRUPHG E\ KRPRJHQHRXV RU KHWHURJHQHRXV QXFOHDWLRQ HLWKHU LQ WKH YDSRU SKDVH LQ WKH SOXPH H[KDXVW

PAGE 17

IURP D QR]]OH ILWWHG RQWR D KRW FUXFLEOH FRQWDLQLQJ WKH PROWHQ VRXUFH PDWHULDO RU RQ WKH VLGH ZDOOV RI WKH FUXFLEOH LWVHOI EHIRUH H[LWLQJ WKURXJK WKH QR]]OH 7KH FOXVWHUV DUH VXEVHTXHQWO\ LRQL]HG E\ HOHFWURQ ERPEDUGPHQW ZLWK D FXUUHQW RI VHYHUDO PLOOLDPSV DQG HQHUJLHV LQ WKH H9 UDQJH 7KH\ DUH WKHQ DFFHOHUDWHG WKURXJK D .9 SRWHQWLDO DQG GLUHFWHG WR WKH VXEVWUDWH VXUIDFH ZKHUH WKH\ GHSRVLW QRQ VHOHFWLYHO\ ZLWK HQRXJK HQHUJ\ SHU DWRP H9f WR IDFLOLWDWH VXUIDFH PRELOLW\ ZLWKRXW LQGXFLQJ GHIHFW GDPDJH DVVRFLDWHG ZLWK KLJKHU LPSDFW HQHUJLHV $ UHFHQW VWXG\ E\ .QDXHU DQG 3RHVFKHO VKRZHG WKDW XQGHU RSWLPXP FRQGLWLRQV RQO\ DERXW b RI WKH WRWDO PHWDO IOX[ IURP D FUXFLEOH ILOOHG ZLWK PROWHQ JROG RU VLOYHU ZDV LQ WKH IRUP RI FOXVWHUV LQ WKH VL]H UDQJH RI VHYHUDO KXQGUHG WR VHYHUDO WKRXVDQG DWRPV 6LQFH RQO\ D IHZ SHUFHQW RI WKHVH FOXVWHUV ZHUH LRQL]HG LQ WKH HOHFWURQ ERPEDUGPHQW VWHS WKH QHW HIILFLHQF\ RI PHWDO XVH ZDV YHU\ ORZ 7KLV OLPLWDWLRQ WRJHWKHU ZLWK WKH QHHG IRU OLQH RI VLJKW GHSRVLWLRQ ZKLFK LPSOLHV QRQ FRQIRUPDO VWHS FRYHUDJHf DQG WKH QRQVHOHFWLYLW\ RI WKH SURFHVV SUHFOXGH LWV XVH IRU PDVVSURGXFWLRQ RI VXEPLFURQ JROG ILOP SDWWHUQV $QRWKHU UHFHQWO\ GHYHORSHG WHFKQLTXH IRU SURGXFLQJ JROG WKLQ ILOPV DOVR EDVHG RQ KRPRJHQHRXV DQG KHWHURJHQHRXV QXFOHDWLRQ RI SDUWLFOHV LQ WKH JDV SKDVH LQYROYHV WKH SURGXFWLRQ RI XOWUDILQH SDUWLFOHV LQ WKH QDQRPHWHU VL]H UDQJH AA DWRPVSDUWLFOHf WKDW DUH VXEVHTXHQWO\ GHSRVLWHG QRQVHOHFWLYHO\ RQ D VXEVWUDWHp 0HWDO YDSRUV DUH SURGXFHG XVLQJ D ODVHU EHDP DUF GLVFKDUJH RU HOHFWURQ EHDP LQ WKH SUHVHQFH RI LQHUW RU UHDFWLYH JDVHV $W OHDVW RQH JURXS DSSOLHG WKH WHFKQLTXH WR JROG 7KH VDPH OLPLWDWLRQV RI QRQ

PAGE 18

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

PAGE 19

VLPLODU UHVXOWV XVLQJ WKH VDPH FRPSRXQGV DQG UI VWLPXODWHG WKHUPDO GHFRPSRVLWLRQA 7KHUH DUH RWKHU H[DPSOHV RI QRQVHOHFWLYH &9' RI JROG IURP RUJDQRPHWDO LF FRPSRXQGV VXFK DV $X5&15nf DQG 5f 3$X26L5f ZKHUH 5 DQG 5n DUH PHWK\O HWK\O RU SKHQ\O JURXSV 7KH PRVW UHFHQW FRPSRXQGV WR EH XVHG IRU &9' RI JROG DUH GLPHWK\O DFHW\ODFHWR QDWRJROG,,,f DQG LWV WUL DQG KH[DIOXRUR GHULYDWLYHV /DUVRQ DQG %DXP UHSRUWHG WKH IRUPDWLRQ RI KLJK TXDOLW\ JROG ILOPV IURP WKHVH FRPSRXQGV E\ WKHUPDO GHFRPSRVLWLRQ DW r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f RUJDQRPHWDOLF ILOPV 0RVW JURXSV KDYH XVHG IRFXVHG ODVHU LRQ RU HOHFWURQ EHDPV WR LQGXFH VHOHFWLYH &9' RI JROG IURP YRODWLOH FRPSRXQGV $JDLQ WKH IOXRULQDWHG GHULYDWLYHV RI GLPHWK\O DFHW\ODFHWRQDWRJROGf IRUPHG WKH KLJKHVW TXDOLW\ VXEPLFURQ VL]HG JROG OLQHV DQG VSRWV 'HVSLWH WKH KLJK TXDOLW\ RI WKH JROG ILOPV SURGXFHG E\ WKHVH PHWKRGV WKHLU LQKHUHQWO\ VORZ UDWH RI WKURXJKSXW SUHFOXGHV WKHLU HFRQRPLF XVH LQ PDVVSURGXFWLRQ VFHQDULRV

PAGE 20

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

PAGE 21

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f SURGXFWLRQ UDWH f YRODWLOLW\ f WKHUPDO VWDELOLW\ f WHPSHUDWXUH RI GHFRPSRVLWLRQ f ILOP SURSHUWLHV UHVLVWDQFH SXULW\ PRUSKRORJ\ VWDELOLW\f f SURSHUWLHV RI E\SURGXFWV VKRXOG EH QRQFRQWDPLQDWLQJ WR WKH VXEVWUDWH DQG QRQWR[LFf f DELOLW\ WR UHF\FOH RU UHFODLP JROG ,Q DGGLWLRQ WR WKHVH FRQVLGHUDWLRQV WKH WR[LFLW\ RI WKH VWDUWLQJ PDWHULDOV ZRXOG EH D SULPDU\ FRQFHUQ $ SODVPD UHDFWLRQ V\VWHP ZDV GHVLJQHG DQG FRQVWUXFWHG WR LQYHVWLJDWH WKH IHDVLELOLW\ RI SURGXFLQJ JDV SKDVH JROG FRPSRXQGV LQ ODUJH HQRXJK TXDQWLWLHV WR EH XVHG LQ PDVVSURGXFLQJ &9' VXEPLFURQ JROG SDWWHUQV 7KH SURFHGXUHV DQG UHVXOWV RI WKDW LQYHVWLJDWLRQ DUH SUHVHQWHG LQ WKH IROORZLQJ FKDSWHUV

PAGE 22

&+$37(5 ,, (;3(5,0(17$/ 7KH VFRSH RI WKLV VWXG\ ZDV OLPLWHG WR WKH LQYHVWLJDWLRQ RI UHDFWLRQV RFFXUULQJ EHWZHHQ QRQWR[LF RU ORZWR[LF JDVHRXV VSHFLHV DQG SXOVHG & ODVHU VWLPXODWHG JROG YDSRUV DQG SODVPDV 3DUWLFXODU HPSKDVLV ZDV SODFHG RQ XWLOL]DWLRQ RI SHUPDQHQW FDUERQDFHRXV JDVHV 7KH VWXG\ FRQVLVWHG RI WKUHH PDMRU SDUWV f SURGXFWLRQ RI JDV SKDVH JROGEHDULQJ VSHFLHV LQ KLJK \LHOGV LQ WKH SODVPD f GHWHUPLQDWLRQ RI YRODWLOLW\ RI KLJK\LHOG VSHFLHV DQG f FKDUDFWHUL]DWLRQ RI JROG WKLQ ILOPV SURGXFHG IURP WKH KLJK\LHOG VSHFLHV 'HWDLOHG GHVFULSWLRQV RI H[SHULPHQWDO HTXLSPHQW DQG SURFHGXUHV DUH SUHVHQWHG WRJHWKHU LQ WKLV FKDSWHU (DFK PDMRU SDUW RI WKH VWXG\ LV WUHDWHG DXWRQRPRXVO\ &RQGLWLRQV OHDGLQJ WR HTXLSPHQW RU SURFHGXUH PRGLILFDWLRQV DUH PHQWLRQHG EXW DUH QRW GLVFXVVHG XQWLO WKH IROORZLQJ FKDSWHU 3URGXFWLRQ RI *DV3KDVH *ROG 6SHFLHV 7KH 3ODVPD 5HDFWLRQ 6\VWHP 7KH SODVPD UHDFWLRQ V\VWHP ZDV FRPSRVHG RI IRXU VXEV\VWHPV f WKH SXOVHG FDUERQ GLR[LGH ODVHU DQG DVVRFLDWHG RSWLFV f WKH JDV KDQGOLQJ V\VWHP f WKH SODVPD UHDFWLRQ FKDPEHUV f WKH SURGXFWUHFRYHU\VXEVWUDWHFRDWLQJ V\VWHPV

PAGE 23

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f FDUERQ GLR[LGH ODVHU PRGHO WKDW KDG SUHYLRXVO\ GHPRQVWUDWHG KLJK YRODWLOL]DWLRQ UDWHV IRU UHIUDFWRU\ PHWDOVrA ZDV DYDLODEOH IRU XVH LQ WKLV VWXG\ 7KLV ODVHU ZDV FDSDEOH RI SURGXFLQJ DQ RSWLFDO SXOVH HQHUJ\ RI MRXOHV ZLWK D SXOVH KDOIZLGWK RI QDQRVHFRQGV DQG D SRZHU GHQVLW\ RI DSSUR[LPDWHO\ [ A ZDWWVFPA ZKHQ RSWLPDOO\ IRFXVHG WKURXJK D PP IRFDO OHQJWK OHQV 0D[LPXP SXOVH UHSHWLWLRQ UDWH ZDV K] JLYLQJ WKH ODVHU D GXW\ WLPH RI DSSUR[LPDWHO\ RQH PLOOLVHFRQG SHU KRXU 7KH HPLWWHG ZDYHOHQJWK RI PLFURQV FRUUHVSRQGV WR WKH 3f OLQH LQ WKH EDQG 7KH ODVHUnV SXOVH HQHUJ\ FRXOG EH YDULHG E\ DGMXVWLQJ WKH QLWURJHQ JDV SUHVVXUH DQG IORZ UDWH WR WKH VSDUN JDS WULJJHU E\ DGMXVWLQJ WKH FRPSRVLWLRQ DQG IORZ UDWH RI WKH KHOLXPQLWURJHQFDUERQGLR[LGH ODVLQJ JDV PL[WXUH RU E\ DGMXVWLQJ WKH RSHUDWLQJ YROWDJH 'XULQJ WKH FRXUVH RI WKLV VWXG\ WKHVH SDUDPHWHUV ZHUH PDLQWDLQHG LQ D VWDWH WKDW UHVXOWHG LQ PD[LPXP HQHUJ\ RXWSXW

PAGE 24

7KH ODVHU HQHUJ\ RXWSXW ZDV PHDVXUHG DIWHU PDMRU PDLQWHQDQFH HYHQWV VXFK DV GLVDVVHPEO\ DQG FOHDQLQJ RI WKH RSWLFV RU HOHFWURGHV XVLQJ D 6FLHQWHFK ODVHU SRZHUHQHUJ\ PHWHU 'XULQJ VXEVHTXHQW RSHUDWLRQ WKH ODVHU RXWSXW ZDV PRQLWRUHG E\ H[SRVLQJ D SLHFH RI WKHUPDO SDSHU +HZOHWW 3DFNDUG $f WR VLQJOH SXOVHV RI WKH XQIRFXVHG PP GLPHWHU EHDP DQG FRPSDULQJ WKH UHVXOWDQW GLVFRORUDWLRQ SDWWHUQV WR VWDQGDUG SDWWHUQV WKDW ZHUH SURGXFHG XQGHU PHDVXUHG FRQGLWLRQV VHH )LJXUH f 7KH ODVHU EHDP ZDV GLUHFWHG LQWR WKH SODVPD UHDFWLRQ FKDPEHU WKURXJK WKH RSWLF SDWK XVLQJ D FP VTXDUH IDFH FRDWHG VLOYHU PLUURU GXULQJ LQLWLDO VFUHHQLQJ H[SHULPHQWV 7KLV PLUURU ZDV VXEVHTXHQWO\ UHPRYHG IURP WKH V\VWHP DQG WKH ODVHU ZDV SRVLWLRQHG LQ D GLUHFW OLQH RI ILUH ZLWK WKH RSWLFV DQG WKH FKDPEHU DW D GLVWDQFH RI FD PHWHUV LQ RUGHU WR WUDQVPLW DV PXFK HQHUJ\ DV SRVVLEOH WR WKH WDUJHW $Q H[WHUQDOO\ PRXQWHG FP GLDPHWHU JHUPDQLXP PHQLVFXV OHQV ZLWK D PP IRFDO OHQJWK 2ULHO PRGHO f ZDV XVHG WR IRFXV WKH ODVHU EHDP GXULQJ WKH ILUVW KDOI RI WKH VWXG\ $ VLPLODU OHQV ZLWK D IRFDO OHQJWK RI PP 9, ,QF PRGHO f UHSODFHG WKH LQLWLDO OHQV IRU WKH ILQDO KDOI RI WKH VWXG\ 7KLV ZDV QHFHVVDU\ DV D UHVXOW RI SK\VLFDO GDPDJH VXVWDLQHG E\ WKH PP OHQV GXULQJ D FOHDQLQJ SURFHGXUH DFFLGHQWf %RWK OHQVHV KDG DQ DQWLUHIOHFWLRQ FRDWLQJ IRU PD[LPXP WUDQVPLVVLRQ DW PLFURQV 7KH OHQVHV ZHUH KHOG LQ D FODPS PRXQWHG WR DQ RSWLFDO VWDQG ZLWK WKUHH GHJUHHV RI IUHHGRP 7KLV DUUDQJHPHQW DOORZHG WKH OHQV WR EH SRVLWLRQHG FORVHU WR WKH WDUJHW WKDQ WKH RSWLPXP IRFDO GLVWDQFH GXULQJ WKH FRXUVH RI DQ H[SHULPHQWDO UXQ WKXV GLVWULEXWLQJ WKH ODVHU HQHUJ\

PAGE 25

)LJXUH 7KHUPDO 3DSHU ([SRVHG WR 6LQJOH 3XOVHV RI WKH &DUERQ 'LR[LGH /DVHU Df /DVHU SHUIRUPLQJ ZHOO QRPLQDOf Ef /DVHU SHUIRUPLQJ SRRUO\ JDV PL[WXUH QRW RSWLPL]HG IRU SRZHU OHYHO DQG SXOVH UHSHWLWLRQ UDWH

PAGE 26

Ef

PAGE 27

RYHU D ODUJHU VXUIDFH DUHD 7KLV SURFHGXUH ZDV XVHG LQ DOO H[SHULPHQWV ZKHUH WKH HIIHFWV RI ORZHU WKDQ PD[LPXP SRZHU GHQVLWLHV ZHUH LQYHVWLJDWHG 7KH RSWLPXP IRFDO OHQJWK IRU HDFK OHQV ZDV GHWHUPLQHG H[SHULPHQWDOO\ E\ H[SRVLQJ WKHUPDO SDSHU LQ DLUf WR WKH SDUWLDOO\ IRFXVHG EHDP DW GLVWDQFHV HTXLYDOHQW WR DQG SHUFHQW RI WKH H[SHFWHG IRFDO OHQJWKV 7KH DYHUDJH VSRW GLDPHWHUV IURP HDFK SRLQW ZHUH SORWWHG DJDLQVW WKH GLVWDQFH IURP WKH EDFN HGJH RI WKH OHQV 7KH LQWHUVHFWLRQ RI WKH WZR OLQHV GUDZQ WKURXJK WKH SRLQWV JDYH WKH RSWLPXP IRFDO OHQJWK )LJXUH f 7KH YDOXH GHWHUPLQHG IRU WKH WZR OHQVHV ZHUH PP DQG PP 7KHVH YDOXHV ZHUH FRQILUPHG E\ PLFURVFRSLF H[DPLQDWLRQ RI WDUJHW LPSDFW FUDWHUV DIWHU H[SRVXUH WR WKH KLJKO\ IRFXVHG EHDP $IWHU SDVVLQJ WKURXJK WKH IRFXVLQJ OHQV WKH EHDP HQWHUHG WKH UHDFWLRQ FKDPEHU WKURXJK D FP GLDPHWHU ]LQF VHOHQLGH ZLQGRZ ,,9, ,QF f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

PAGE 28

)LJXUH *HUPDQLXP /HQV )RFDO /HQJWK 'HWHUPLQDWLRQ

PAGE 30

JDVHV WR WKH PL[LQJ V\VWHP WKURXJK FP RG SRO\SURS\OHQH WXELQJ 7KH RQH FRPSRXQG WKDW ZDV OLTXLG DW URRP WHPSHUDWXUH GLF\FOR SHQWDGLHQH ZDV SODFHG LQ D PO JODVV LPSLQJHU DQG KHOLXP JDV IURP WKH JDV KDQGOLQJ V\VWHP ZDV EXEEOHG WKURXJK PO RI WKH OLTXLG DW POPLQ EHIRUH HQWHULQJ WKH SODVPD FKDPEHU 7KLV HIIHFWLYHO\ VDWXUDWHG WKH JDV ZLWK WKH YRODWLOH OLTXLG 7HIORQ WXELQJ DQG ILWWLQJV ZHUH XVHG WR FRQQHFW WKH LPSLQJHU WR WKH SODVPD FKDPEHU GXULQJ WKLV H[SHULPHQW )LJXUH f 7KH JDV PL[LQJ V\VWHP XVHG LQ DOO H[SHULPHQWV H[FHSW WKH RQH QRWHG DERYH FRQVLVWHG RI WKH IROORZLQJ FRPSRQHQWV f WKUHH YDULDEOH DUHD IORZPHWHUV ZLWK EXLOWLQ QHHGOH YDOYHV &ROH3DUPHU PRGHOV DQG -f PRXQWHG WRJHWKHU RQ DQ DOXPLQXP SODWH f D PO DFU\OLF JDV GU\LQJ FROXPQ ZLWK ULQJ VHDOHG DOXPLQXP HQG FDSV $OWHFK $VVRFLDWHV SVL PRGHO VROG E\ &ROH3DUPHU DV PRGHO -f KDOI ILOOHG ZLWK LQGLFDWLQJ GULHULWH DQG KDOI ILOOHG ZLWK PROHFXODU VLHYHV f D PO JODVV EXEEOHWXEH IORZPHWHU f D EUDVV RQRII SOXJ YDOYH ZLWK HODVWRPHULF 2ULQJ VHDOV 1XSUR PRGHO %37f DQG WZR EUDVV ILQH PHWHULQJ YDOYHV 1XSUR PRGHO %66f f DQ RLOILOOHG PHFKDQLFDO YDFXXP SXPS 3UHFLVLRQ 6FLHQWLILF PRGHO f DQG f D FDSDFLWDQFH PDQRPHWHU %DUDWURQ 7\SH %$$%f ZLWK D GLJLWDO UHDGRXW 0.6 W\SH 3'5'f

PAGE 31

)LJXUH 'LF\FORSHQWDGLHQH *DV 'HOLYHU\ 6\VWHP

PAGE 32

KHOLXP JDV LQ GLF\FORSHQWDGLHQH L!

PAGE 33

$ GLDJUDP RI WKH V\VWHP FRPSRQHQWV DQG WKH JDV IORZ SDWWHUQ LV SUHVHQWHG LQ )LJXUH *DVHV ZHUH VXSSOLHG WR WKH IORZPHWHUV DW 3DVFDOV SVLf SUHVVXUH DQG WKH IORZ UDWHV DGMXVWHG XVLQJ WKH YDULDEOH DUHD IORZPHWHU QHHGOH YDOYHV &RSSHU WXEHV LQ RGf IURP WKH IORZPHWHU H[LW SRUWV ZHUH WHHG WRJHWKHU D IHZ FHQWLPHWHUV GRZQVWUHDP XVLQJ EUDVV FRPSUHVVLRQ ILWWLQJV 7KH JDVHV WKHQ SDVVHG WKURXJK WKH GU\LQJ FROXPQ ZKLFK DOVR DFWHG DV D PL[LQJ FKDPEHU 1RPLQDO WRWDO IORZ UDWHV ZHUH POPLQ $IWHU H[LWLQJ WKH GU\LQJ FROXPQ WKH JDVHV IORZHG WKURXJK D WHIORQ WHH 2QH DUP RI WKH WHH ZHQW WR WKH EXEEOHWXEH IORZPHWHU ZKLFK ZDV YHQWHG WR WKH DWPRVSKHUH WKURXJK WKH EXLOGLQJ KRRG H[KDXVWf DQG WKH RWKHU DUP ZHQW WR WKH SODVPD FKDPEHU RQRII YDOYH 7KXV ZKHQ WKH RQRII YDOYH ZDV FORVHG WKH WRWDO JDV IORZ SDVVHG WKURXJK WKH EXEEOHWXEH IORZPHWHU :KHQ WKH RQRII YDOYH ZDV RSHQ SDUW RI WKH JDV VWUHDP DERXW KDOIf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

PAGE 34

)LJXUH *DV 0L[LQJ DQG 'HOLYHU\ 6\VWHP

PAGE 35

IORZPHWHUV ZL WK PHWHULQJ YDOYHV 62 R 2 Bk UnU /7 GU\LQJ FROXPQ JDVHV LQ RQRII M Af Y WR PHWHULQJ SODVPD YDOYHV FKDPEHU t f§! QR FU!

PAGE 36

IORZPHWHUV ZHUH XVHG WR PRQLWRU WKH LQGLYLGXDO JDV IORZV FRPSULVLQJ WKH UHDFWLRQ PL[WXUHVf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f ,Q H[SHULPHQWV ZKHUH WKH FKDPEHU SUHVVXUH ZDV 3DVFDOV WRUUf RU JUHDWHU WKH JDV IORZ ZDV VSOLW HTXDOO\ EHWZHHQ WKH WZR LQOHWV XVLQJ WKH UHVSHFWLYH QHHGOH YDOYHV ,Q H[SHULPHQWV ZKHUH WKH SUHVVXUH ZDV 3DVFDOV WRUUf RQH QHHGOH YDOYH DQG LQOHW ZHUH SOXJJHG DQG WKH HQWLUH JDV IORZ ZDV GLUHFWHG WKURXJK WKH RSWLF VLGH DUP LQOHW ,Q H[SHULPHQWV ZKHUH WKH FKDPEHU SUHVVXUH ZDV 3DVFDOV WRUUf WKH 1XSUR PHWHULQJ YDOYHV ZHUH UHSODFHG E\ DQ LQKRXVH IDEULFDWHG ORZIORZ WDSHU YDOYH $OO H[SHULPHQWV XVHG WKH PHFKDQLFDO YDFXXP SXPS WR SURYLGH WKH GULYLQJ IRUFH IRU JDV IORZ WKURXJK WKH V\VWHP 7KH SODVPD FKDPEHU SUHVVXUH ZDV PRQLWRUHG ZLWK WKH FDSDFLWDQFH PDQRPHWHU ZKLFK KDG D UDQJH RI WRUU LQ WRUU LQFUHPHQWV 3DVFDOV LQ 3DVFDO LQFUHPHQWVf 7KH PDQRPHWHU ZDV FDOLEUDWHG XVLQJ D VWDQGDUG PHUFXU\ ILOOHG 0F/HRG JDXJH

PAGE 37

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f ZKLOH WKH DOXPLQXP FKDPEHU XVHG WKURXJKRXW WKH UHVW RI WKH VWXG\ ZDV GHVLJQHG WR RSHUDWH LQ WKH SUHVVXUH UDQJH RI WR 3DVFDOV WRUU WR DWPRVSKHUHVf 7KH JODVV SODVPD UHDFWLRQ FKDPEHU 7KLV FKDPEHU ZDV GHVLJQHG WR EH XWLOL]HG IRU LQLWLDO VFUHHQLQJ RI SURVSHFWLYH JDVHV DQG JDV PL[WXUHV IRU WKHLU HIIHFWLYHQHVV LQ SURGXFLQJ DQG WUDQVSRUWLQJ JDV SKDVH JROG EHDULQJ VSHFLHV 7KLV LQYROYHG WKH GHWHUPLQDWLRQ RI RSWLPXP SUHVVXUH

PAGE 38

DQG ODVHU HQHUJ\ GHQVLW\ FRQGLWLRQV IRU JDVHV VKRZLQJ SRVLWLYH UHVXOWV 7KH SURWRFRO DOVR LQFOXGHG WKH VWXG\ RI WKH LQWHUDFWLRQ RI WKH IRFXVHG SXOVHG &2 ODVHU EHDP ZLWK VHYHUDO LQHUW DQG UHDFWLYH JDVHV DQG JDV PL[WXUHV DW SUHVVXUHV DSSURDFKLQJ 3DVFDOV FD DWPf 7KH WUDQVSDUHQW FKDPEHU IDFLOLWDWHG WKH REVHUYDWLRQ RI JDV EUHDNGRZQ 7KLV SKHQRPHQRQ UHVXOWHG LQ DEVRUSWLRQ RI PRVW RI WKH ODVHU SXOVH HQHUJ\ E\ WKH JDVHV OHDYLQJ YHU\ OLWWOH HQHUJ\ WR YDSRUL]H WKH VROLG JROG $ IXUWKHU GLVFXVVLRQ RI WKLV WRSLF LV SUHVHQWHG LQ WKH IROORZLQJ FKDSWHUf $ GLDJUDP RI WKLV SODVPD UHDFWLRQ FKDPEHU LV SUHVHQWHG LQ )LJXUH 7KH WZRSLHFH ERURVLOLFDWH JODVV ERG\ ZDV IDEULFDWHG LQ WKH 6FLHQWLILF *ODVV%ORZLQJ 6KRS DW WKH 8QLYHUVLW\ RI )ORULGD DQG KDG D WRWDO YROXPH LQFOXGLQJ VLGH DUPVf RI PO 7ZR PP LG JODVV ULQJ VHDO MRLQWV .LPD[ 1R f ZHUH XVHG DV WKH EDVH VWUXFWXUHV 2QH RI WKH MRLQWV ZDV PRGLILHG E\ WDSHULQJ WKH EODQN HQG DQG EXWWVHDOLQJ LW WR D PP RG E\ PP LG E\ FP ORQJ SLHFH RI JODVV WXELQJ 7KH RYHUDOO OHQJWK RI WKH UHVXOWDQW EHOOVKDSHG VWUXFWXUH ZDV FP $ PP RG E\ PP LG E\ FP ORQJ SLHFH RI SHUIRUDWHG WHIORQ WXELQJ ZDV SUHVVILWWHG LQWR WKH QDUURZ HQG RI WKH EHOO VWUXFWXUH IURP WKH LQVLGH 7KLV WXEH H[WHQGHG DERXW FP LQWR WKH PP RG JODVV H[WHQVLRQ WXEH 7KH UHVW RI WKH WHIORQ SHUIWXEH H[WHQGHG WKURXJK WKH FHQWHU RI WKH EHOO VWUXFWXUH DQG HQGHG DERXW FP IURP WKH ZLGH HQG $ PP GLD E\ PP WKLFN WHIORQ SHUIRUDWHG SODWH ZDV WKHQ DWWDFKHG WR WKH WHIORQ WXEH E\ WKUHDGLQJ D VWDLQOHVV VWHHO VFUHZ WKURXJK WKH FHQWHU KROG RI WKH SHUISODWH DQG LQWR WKH HQG RI WKH WHIORQ WXEH 7KLV XQLW FRPSULVHG WKH PDLQ JDV LQOHW WR WKH SODVPD FKDPEHU 7KH SHUIRUDWHG

PAGE 39

)LJXUH 7KH *ODVV 3ODVPD 5HDFWLRQ &KDPEHU

PAGE 40

JHUPDQLXP OHQV

PAGE 41

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f IURP WKH PRXWK DQG VHUYHG DV D JXLGH VKDIW IRU WKH VDPSOH KROGHU $ PP LG JODVV ULQJ MRLQW .LPD[ 1R f ZDV VHDOHG WR WKH RSSRVLWH VLGHZDOO FP RQ FHQWHUf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f WR IDFLOLWDWH VHDOLQJ GXULQJ VKDIW URWDWLRQ $ FP GLD DOXPLQXP FRJZKHHO ZDV DWWDFKHG WR WKH H[WHULRU HQG RI WKH DOXPLQXP VKDIW DQG XVHG WR URWDWH WKH VDPSOH PDQXDOO\ 7KH RWKHU HQG RI WKH VKDIW H[WHQGHG LQWR WKH FKDPEHU DQG KDG D WKUHDGHG FHQWHU KROH WKDW ZDV XVHG DV D WDUJHW DWWDFK SRLQW 7KH

PAGE 42

VKDIW DQG WDUJHW FRXOG EH PRYHG WRZDUG WKH EHDP LQSXW RSHQLQJ D PD[LPXP RI FP LQ RUGHU WR VKRUWHQ WKH RSWLF SDWK 7KH WZR SLHFH RSWLF VLGH DUP ZDV FRQVWUXFWHG IURP JODVV DQG DOXPLQXP 7KH SLHFH FORVHVW WR WKH SODVPD FKDPEHU ZDV PDGH IURP D PP LG JODVV ULQJ MRLQW EXWWVHDOHG WR D PP LG JODVV ULQJ MRLQW .LPD[ 1R f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f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f ZDV ORFDWHG FP RQ

PAGE 43

FHQWHUf IURP WKH HGJH RI WKH ZLQGRZ VHDW RQ WKH VLGH RI WKH KROGHU $ LQ FRSSHU WXEH FRPLQJ IURP WKH JDV KDQGOLQJ V\VWHPnV RWKHU PHWHULQJ YDOYH ZDV FRQQHFWHG WR WKLV ILWWLQJ DQG SURYLGHG D VZHHS RI LQFRPLQJ JDVHV DFURVV WKH ZLQGRZ VXUIDFH WR KHOS PLQLPL]H FRQWDPLQDWLRQ RI WKH VXUIDFH %XWDGLHQH HODVWRPHULF ULQJV ZHUH XVHG ZKHUH UHTXLUHG WKURXJKRXW WKH V\VWHP 3LQFK FODPSV KHOG WKH JODVV ULQJ MRLQWV WRJHWKHU ZKHQ WKH V\VWHP ZDV QRW XQGHU ORZ SUHVVXUH 7KH URWDU\ VHDO RQ WKH ZLQGRZ DQG WKH VHDO RQ WKH VDPSOH KROGHU VKDIW KDG PRGHUDWH OHDN UDWHV DQG WKH FKDPEHU FRXOG EH SXPSHG GRZQ RQO\ WR 3DVFDOV WRUUf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f XVLQJ DYDLODEOH IDFLOLWLHV LQ WKH 'HSDUWPHQW RI &KHPLVWU\ DW WKH 8QLYHUVLW\ RI )ORULGD $ GLDJUDP RI WKH FKDPEHU LQFOXGLQJ WKH VDPSOH KROGHU RSWLF VLGH DUP DQG REVHUYDWLRQ SRUWV LV SUHVHQWHG LQ )LJXUH 7KH VFUHHQLQJ VWXG\ ZDV FRPSOHWHG DQG DOO RWKHU H[SHULPHQWV ZHUH FRQGXFWHG XVLQJ WKLV FKDPEHU

PAGE 44

)LJXUH 7KH $OXPLQXP 3ODVPD 5HDFWLRQ &KDPEHU

PAGE 45

FDSDFLWDQFH PDQRPHWHU URWDWHDEOH VDPSOH VWDQG JDV IURP PL[LQJ V\VWHPArI I PHWHULQJ YDOYHV +J! WR SURGXFW UHFRYHU\ V\VWHP DQG YDF SXPS ODVHU EHDP VWX JHUPDQLXP OHQV &2 &7}

PAGE 46

7KH DOXPLQXP SODVPD UHDFWLRQ FKDPEHU FRQVLVWHG RI ILYH SDUWV f WKH PDLQ ERG\ LQFOXGLQJ WZR JDV LQOHW LQVHUWV D JDV RXWOHW IODQJH DQG D FDSDFLWDQFH PDQRPHWHU LQVHUW f WZR JODVV REVHUYDWLRQ SRUWV DQG WKHLU IODQJHV f WKH EDVHSODWH f WKH RSWLF VLGH DUP DQG f WKH VDPSOH KROGHU $OO RI WKH FRPSRQHQWV ZHUH IDEULFDWHG IURP DOXPLQXP H[FHSW WKH JODVV SRUWV DQG WKH PDLQ ERG\ LQVHUWV DQG RXWOHW IODQJH ZKLFK ZHUH PDFKLQHG IURP EUDVVf 9LWRQ RU EXWDGLHQH HODVWRPHULF ULQJV ZHUH XVHG IRU DOO VHDOV $OO WXELQJ ILWWLQJV DQG LQVHUWV OHDGLQJ IURP WKH JDV KDQGOLQJ V\VWHP DQG FDSDFLWDQFH PDQRPHWHU WKDW ZHUH VXEMHFW WR YDFXXP ZHUH HLWKHU EUD]HG RU FRQQHFWHG ZLWK ULQJ TXLFNFRXSOHV 7KH FRPSOHWHG V\VWHP ZDV OHDN FKHFNHG XVLQJ D PDVV VSHFWURPHWHU KHOLXP OHDN GHWHFWRU 9HHFR /HDN ,QGLFDWRU 06f SUHYLRXVO\ FDOLEUDWHG ZLWK D VWDQGDUG OHDN 9HHFR 6HQVLWLYLW\ &DOLEUDWRU 7\SH 6&f 7KH GHWHFWRU UHVSRQVH LQGLFDWHG WKDW WKH OHDN UDWH ZDV [ nA FF DWPVHF DLU HTXLYDOHQWf DW HDFK XQLRQ DQG RYHUDOO XQGHU +H IORRG FRQGLWLRQV 7KH PDLQ ERG\ ZDV PDFKLQHG IURP D VLQJOH EORFN RI DOXPLQXP FP ZLGH E\ GHHS E\ FP KLJK 7KH UHDFWLRQ ]RQH ZDV IRUPHG E\ ERULQJ D FP GLD E\ FP GHHS KROH WKURXJK WKH FHQWHU RI WKH EORFN VWDUWLQJ RQ WKH ERWWRP IDFH 7KH WRS RI WKLV FDYLW\ ZDV WDSHUHG r DQG QDUURZHG WR FP LQ WZR VWHSV EHIRUH H[LWLQJ WKH FHQWHU RI WKH WRS IDFH RI WKH EORFN 6WDWLF IDFH VHDO ULQJ JODQGV DQG IRXU

PAGE 47

KROH EROW FLUFOHV ZHUH PDFKLQHG DURXQG ERWK KROHV IRU DWWDFKPHQW RI WKH JDV RXWOHW IODQJH DQG WKH FKDPEHU EDVHSODWH 6HYHUDO GLIIHUHQW RXWOHW IODQJHV ZHUH XVHG WR FRQQHFW WKH SODVPD FKDPEHU WR WKH YDULRXV SURGXFW UHFRYHU\ V\VWHPV $OO RI WKH IODQJHV ZHUH VHDOHG WR WKH FKDPEHU XVLQJ WKH ULQJ IDFH VHDO DQG FRQQHFWHG WR WKH SURGXFW UHFRYHU\ V\VWHP E\ DQ ULQJ TXLFNFRQQHFW W\SH FRXSOHU $ FP GLD KROH ZDV ERUHG RQ RQH RI WKH FP ZLGH VLGHV FP RQ FHQWHUf IURP WKH ERWWRP RI WKH FKDPEHU $ FP ORQJ LQVHUW ZLWK D URWDU\ ULQJ JODQG ZDV LQVHUWHG WKURXJK WKLV RSHQLQJ 7KH LQVHUW KDG D PP KROH ERUHG IURP WKH LQFRPLQJ HQG DQG WXUQHG r DW WKH RXWOHW HQG 7KLV GHVLJQ DOORZHG WKH LQFRPLQJ JDV WR EH GLUHFWHG WRZDUG RU DZD\ IURP WKH SODVPD UHDFWLRQ ]RQH E\ URWDWLQJ WKH LQVHUW $QRWKHU FP GLD KROH ZDV ERUHG LQ WKH VDPH IDFH FP RQ FHQWHUf IURP WKH ERWWRP RI WKH FKDPEHU $ PP LG SOXJ LQVHUW ZLWK D URWDU\ ULQJ JODQG ZDV XVHG WR FRQQHFW WKH SODVPD UHDFWLRQ ]RQH ZLWK WKH FDSDFLWDQFH PDQRPHWHU YLD D FP OHQJWK RI LQ RG WXELQJ $ FP GLDPHWHU KROH ZDV ERUHG LQWR RQH RI WKH FP ZLGH IDFHV FP RQ FHQWHUf IURP WKH ERWWRP RI WKH FKDPEHU 7KH ULQJ JODQG DQG IRXUKROH EROW FLUFOH ZHUH PDFKLQHG DURXQG WKLV RSHQLQJ 7KLV ZDV WKH RSWLF VLGH DUP DWWDFK SRLQW $ FP GLD KROH ZDV ERUHG LQWR WKH RWKHU FP ZLGH IDFH FP RQ FHQWHUf IURP WKH ERWWRP RI WKH FKDPEHU 7KH VDPSOH KROGHU ZDV LQVHUWHG WKURXJK WKLV RSHQLQJ $ URWDU\ ULQJ JODQG ZDV PDFKLQHG LQWR WKH FLUFXPIHUHQFH RI WKH RSHQLQJ PP IURP WKH RXWHU HGJH 7KLV ULQJ VHDOHG WKH VDPSOH KROGHU HYHQ ZKHQ LW ZDV EHLQJ URWDWHG $

PAGE 48

IRXUKROH EROW FLUFOH ZDV PDFKLQHG DURXQG WKH SRUW WR VHFXUH WKH VDPSOH KROGHU ZLWK LWV ULQJ IDFH VHDO 7ZR FP GLD SRUWV ZHUH FXW LQWR WKH FP ZLGH VLGHV GLUHFWO\ RSSRVLWH IURP HDFK RWKHU DQG FP RQ FHQWHUf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f IURP WKH ZLQGRZ IDFH VHDO HGJH DQG XVHG DV WKH VZHHS JDV LQOHW $ EUDVV LQVHUW ZLWK D URWDU\ ULQJ JODQG FRQQHFWHG WKH LQOHW WR RQH RI WKH JDV KDQGOLQJ V\VWHP PHWHULQJ YDOYHV 7KH RSWLF VLGH DUP ZDV DWWDFKHG WR WKH SODVPD FKDPEHU XVLQJ WKH EROW FLUFOH DQG IDFH VHDO GHVFULEHG HDUOLHU

PAGE 49

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f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

PAGE 50

6LOLFRQ UXEEHU VOHHYH VHDO 7KH WXEH ZDV SODFHG LQ D /LQEHUJ WXEH IXUQDFH ZLWK D FP ORQJ KLJK WHPSHUDWXUH ]RQH 7KH IXUQDFH ZDV KHDWHG WR GXULQJ H[SHULPHQWV LQ RUGHU WR GHFRPSRVH DQ\ JROG EHDULQJ VSHFLHV WKDW SDVVHG WKURXJK 7KH JDV IORZ UDWHV ZHUH DGMXVWHG WR DOORZ D UHVLGHQFH WLPH RI PLOOLVHFRQGV LQ WKH KRW ]RQH ,Q SUDFWLFH WKLV UHVXOWHG LQ YLVLEOH GHSRVLWV YDU\LQJ LQ FRORU IURP EODFN WR SXUSOH WR UHG WR JROGf DQG SRVLWLRQ DORQJ WKH WXEH ,Q VRPH H[SHULn PHQWV WKH TXDUW] WXEH ZDV IROORZHG E\ D JODVV ZRRO SOXJ DQGRU D FROG ILQJHU VL]H RU f LQ D GU\LFHDFHWRQH EDWK VHH )LJXUH f 6WDJHG FROG WUDSV 6HYHUDO H[SHULPHQWV XVHG PXOWLSOH FROG WUDSV DW SURJUHVVLYHO\ FROGHU WHPSHUDWXUHV WR REVHUYH SURGXFW FROOHFWLRQ FKDUDFWHULVWLFV 7KH YDULRXV VFKHPHV XVHG DUH SLFWXUHG LQ )LJXUH 7KH ILUVW VXFK VFKHPH XVHG D FROG ILQJHU &)f LQ ZDWHULFH .f IROORZHG E\ D VHFRQG &) LQ GU\LFHDFHWRQH .f DQG D WKLUG &) LQ OLTXLG QLWURJHQ .f &ORJJLQJ RI WKH &) LQ OLTXLG QLWURJHQ UHVXOWHG LQ LWV UHSODFHPHQW ZLWK D VHFRQG &) LQ GU\LFHDFHWRQH 7KH QH[W PRGLILFDWLRQ LQFRUSRUDWHG D JODVV ZRRO SOXJ EHIRUH WKH FROG WUDSV 7KLV VFKHPH ZDV WKHQ PRGLILHG E\ SODFLQJ WKH JODVV ZRRO EHWZHHQ WKH ILUVW &) ZKLFK ZDV NHSW DW URRP WHPSHUDWXUH DQG D VHFRQG FROG WUDS PDGH IURP D LQ PPf RG E\ FP ORQJ JODVV 8WXEH NHSW LQ FUXVKHG GU\ LFH $QRWKHU VFKHPH XVHG D VPDOO WHVWWXEH LQVHUWHG LQ WKH JDV VWUHDP DW WKH SODVPD FKDPEHU RXWOHW DKHDG RI WKH 8WXEH LQ GU\ LFH 7KH WHVWWXEH ZDV HLWKHU PDLQWDLQHG DW DPELHQW WHPSHUDWXUH RU ZDV ILOOHG ZLWK GU\ LFH 7KH IODQJH ZKLFK KHOG WKLV WXEH FRXOG DOVR DFFRPPRGDWH D TXDUW] ZLQGRZ LQ SODFH RI WKH WHVWWXEH )LQDOO\

PAGE 51

)LJXUH +HDWHG 4XDUW] 7XEH 3URGXFW 5HFRYHU\ 6\VWHP

PAGE 52

XQQJ VHDO ‘L! JDV L Q f0 XQQJ VHDO L Z "N PP LG TXDUW] WXEH WKHUPRFRXSOH ? A 3r &2 2 -' & 2n UW WR

PAGE 53

)LJXUH 6WDJHG &ROG 7UDSV 8VHG IRU 3URGXFW 5HFRYHU\ Df 7KUHH FROG ILQJHUV Ef &ROG ILQJHU ZLWK 8WXEH Ff 7HVWWXEH ZLWK 8WXEH

PAGE 54

W! JDV LQ e! WR SXPS LQVHUW

PAGE 55

WKH V\VWHP ZDV OLPLWHG WR WKH 8WXEH LQ FUXVKHG GU\LFH RU GU\ LFHDFHWRQHf VLQFH WKLV SURYHG VXIILFLHQW IRU WUDSSLQJ WKH SODVPD UHDFWLRQ SURGXFWV IRU ODWHU XVH $ IUHVK WUDS ZDV XVHG IRU HDFK H[SHULPHQW 7KH LQ RG JODVV 8WXEHV ZHUH HYHQWXDOO\ UHSODFHG ZLWK LQ PPf RG JODVV 8WXEHV 2QH RI WKHVH 8WXEH FROG WUDSV ZDV XVHG LQ DOO VXEVHTXHQW H[SHULPHQWV HLWKHU DORQH RU DIWHU D VXEVWUDWH FRDWLQJ FKDPEHU 6XEVWUDWH FRDWLQJ FKDPEHUV 6XEVWUDWHV ZHUH FRDWHG ZLWK WKH SODVPD UHDFWLRQ SURGXFWV GXULQJ H[SHULPHQWV E\ VWLFNLQJ WKHP WR WKH LQVLGH RI WKH FKDPEHU ZLQGRZV XVLQJ 6FRWFK FOHDU DGKHVLYH WDSHf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f FP IURP WKH VHDOLQJ HQG DQG DWWDFKLQJ LQ RG E\ FP ORQJ JODVV WXEHV RQ RSSRVLWH VLGHV SHUSHQGLFXODU WR WKH VHDO IDFH 7KHVH WXEHV DFWHG DV WKH LQOHW DQG RXWOHW $ PP GLD E\ PP WKLFN TXDUW] ZLQGRZ ZDV SODFHG RQ WKH ULQJ DQG KHOG LQ

PAGE 56

)LJXUH 6XEVWUDWH &RDWLQJ &KDPEHUV Df 6PDOO JODVV FKDPEHU VKRZLQJ D FHUDPLF IHHGn WKURXJK LQ SODFH Ef /DUJH JODVV FKDPEHU VKRZLQJ WKH WLHU VDPSOH UDFN

PAGE 57

A TXDUW] ZLQGRZ Ef KRLGHU JDV RXW WR KHDWHU FRQWUROOHU

PAGE 58

SODFH E\ WKH V\VWHP YDFXXP 7RWDO YROXPH RI WKH FKDPEHU ZDV PO 6XEVWUDWHV FRXOG EH SODFHG LQ WKLV FKDPEHU DQG H[SRVHG WR D ZDWW $UJRQ LRQ ODVHU EHDP 6SHFWUD 3K\VLFV f ZKLOH SODVPD UHDFWLRQ SURGXFWV IORZHG WKURXJK $ VHFRQG ODUJHU FRDWLQJ FKDPEHU ZDV FRQVWUXFWHG IURP WZR PP LG JODVV ULQJ VHDO MRLQWV .LPD[ 1R f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f 7KLV FKDPEHU ZDV DOVR D WZRSLHFH GHVLJQ DQG KDG DQ ULQJ IDFH VHDO EHWZHHQ WKH KDOYHV 7KH ERWWRP KDOI VWDUWHG ZLWK D LQ PPf RG E\ FP ORQJ LQOHW VHJPHQW WKDW VHDOHG GLUHFWO\ WR WKH WRS RI WKH SODVPD FKDPEHU YLD D LQ EUDVV TXLFN FRXSOH 7KLV VHFWLRQ KDG DQ LQVLGH GLDPHWHU RI FP 7KH QH[W VHJPHQW RI WKH ERWWRP SLHFH KDG DQ RG RI FP DQG DQ LG RI FP DQG ZDV FP ORQJ 7KH ILQDO VHJPHQW ZDV FP ZLGH E\ FP WKLFN DQG FRQWDLQHG WKH ULQJ JODQG D IRXUKROH EROW FLUFOH DQG D VHDW RQ WKH LQVLGH GLDPHWHU IRU D PP ZLGH E\ PP WKLFN WHIORQ ULQJ VSDFHU 7KLV VHJPHQW DFWHG DV D IODQJH WR FRQQHFW WKH WZR SLHFHV RI WKH FKDPEHU

PAGE 59

7KH WRS KDOI VWDUWHG ZLWK D PDWFKLQJ IODQJH VHJPHQW ZLWK D PP WKLFN E\ PP GLD WHIORQ SHUIRUDWHG SODWH SUHVVILWWHG LQWR WKH PP ZLGH VHDW RQ WKH LQVLGH GLDPHWHU 7KLV ZDV IROORZHG E\ D FP RG E\ FP LG E\ FP ORQJ VHJPHQW DQG D FP LG E\ LQ PPf RG E\ FP ORQJ RXWOHW VHJPHQW 7KH DVVHPEOHG FKDPEHU ZDV FP ORQJ DQG KDG DQ LQWHUQDO YROXPH RI PO 7KH WHIORQ SHUIRUDWHG SODWH DQG VSDFHU ZHUH XVHG WR KROG D PP GLDPHWHU ERURVLOLFDWH JODVV ILEHU ILOWHU WKDW KDG D UHWHQWLRQ UDWLQJ RI DW PLFURQV 0LFUR )LOWUDWLRQ 6\VWHPV *% 5 PPf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f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

PAGE 60

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f WR WKH DOXPLQXP 5XEEHU VHSWD DQG VHDOLQJ SXWW\ $SLH]RQ 4f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s b RI WKH VHW SRLQW $ WKHUPRFRXSOH MXQFWLRQ W\SH .f ZDV LPSODQWHG LQ WKH DOXPLQXP KRW SODWH DQG FRQQHFWHG WR D GLJLWDO PXOWLPHWHU .LHWKO\ 0LFURYROW '00f 7KH WKHUPRFRXSOH ZDV FDOLEUDWHG XVLQJ ZDWHU LFH DQG ERLOLQJ GHLRQL]HG ZDWHU

PAGE 61

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f 4XDQWLWDWLYH PHDVXUHPHQWV RI WKH DPRXQWV RI JROG FROOHFWHG LQ VRPH RI WKH FROG WUDSV DQG RQ PRVW RI WKH JODVV ILEHU ILOWHUV ZHUH SHUIRUPHG XVLQJ $WRPLF $EVRUSWLRQ $$f DQDO\VHV 3HUNLQ (OPHU 0RGHO $$f DQG VWDQGDUG DQDO\WLFDO WHFKQLTXHV 6DPSOHV ZHUH HLWKHU H[WUDFWHG VXVSHQGHG LQ DFHWRQH RU GLVVROYHG LQ DTXD UHJLD DQG GLOXWHG &DOLEUDWLRQ GDWD DQG UHVSRQVH FXUYHV DUH SUHVHQWHG LQ $SSHQGL[ &

PAGE 62

7KH LQLWLDO JROG WDUJHW XVHG LQ WKH VFUHHQLQJ VWXG\ ZDV IRUPHG E\ PHOWLQJ DQG FDVWLQJ FD JUDPV RI $X ZLUH SXULW\f LQWR D PP WKLFN FUHVFHQW VKDSH $ PDFKLQHG JUDSKLWH EORFN ZDV XVHG DV D PROG IRU WKH FDVWLQJ $ &DQDGLDQ 0DSOH /HDI R] JROG FRLQ SXULW\f ZDV DOVR XVHG DV D WDUJHW GXULQJ WKH VFUHHQLQJ VWXG\ DQG LQ DOO VXEVWUDWH FRDWLQJ H[SHULPHQWV 7KLV WDUJHW UHTXLUHG UHFDVWLQJ DIWHU H[WHQGHG XVH EXW LWV WRWDO PDVV ZDV QHYHU OHVV WKDQ JUDPV DQG LWV WKLFNQHVV ZDV QHYHU OHVV WKDQ PP $ FP WKLFN E\ FP GLDPHWHU SLHFH RI JUDSKLWH PDVV JUDPVf ZDV XVHG DV D WDUJHW LQ WZR H[SHULPHQWV DQG D PP WKLFN E\ PP ZLGH E\ PP ORQJ 2)+& FRSSHU WDUJHW PDVV JUDPVf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

PAGE 63

7DEOH *DVHV 8VHG LQ WKH 3ODVPD 5HDFWLRQ 6WXG\ *DV 9HQGRU 3XULW\ 5DWLQJ KHOLXP $LUHR VWDQGDUG JUDGH DUJRQ $LUHR VWDQGDUG JUDGH DLU ODERUDWRU\ DPELHQWf 1$ DLU $LUHR EUHDWKLQJ TXDOLW\ K\GURJHQ $LUHR VWDQGDUG JUDGH /LQGH VWDQGDUG JUDGH GLF\FORSHQWDGLHQH OLTXLGf $OGULFK &KHPLFDO UHDJHQW JUDGH FKORURGLIOXRUR PHWKDQH $OOLHG &KHPLFDO &RUS UHIULJHUDQW JUDGH GLFKORURGLIOXRUR PHWKDQH $OOLHG &KHPLFDO &RUS UHIULJHUDQW JUDGH KH[DIOXRURHWKDQH 3&5 ,QF b DFHW\OHQH $LUHR ZHOGHUnV JUDGH FDUERQ PRQR[LGH 0DWKHVRQ 6SHFLDOW\ *DVHV b PHWKDQH 0DWKHVRQ 6SHFLDOW\ *DVHV b DQG b QDWXUDO JDV *DLQHVYLOOH 5HJLRQDO *DV &RPSDQ\ WKURXJK ODERUDWRU\ OLQHVf FRPPHUFLDO JUDGH

PAGE 64

7DEOH 6FUHHQLQJ 6WXG\ 3ODVPD 5HDFWLRQ ([SHULPHQWV ([SW *DV 1R 0L[ WDUJHWf bf 3UHVVXUH r)ORZ 5DWH 7KURXJK 3DVFDOf 5HDFWLRQ =RQH POPLQ FPVHF DWPf &2 /DVHU &RQGLWLRQV )RFDO 3RLQW 3XOVHV PP GLDf [ f rr3URGXFW 5HFRYHU\ 6\VWHP $ +H 1$ 1$ RSWLPXP QRQH QRQHf f 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP % $LU RSHQ WR DWPf RSWLPXP QRQH QRQHf f +" RSWLPXP QRQH $Xf f RSWLPXP +H+" RSWLPXP 47 $Xf f PVHF +H+" RSWLPXP 47 $Xf f PVHF

PAGE 65

7DEOH FRQWLQXHGf ([SW *DV 1R 0L[ WDUJHWf bf 3UHVVXUH r)ORZ 5DWH 7KURXJK 3DVFDOf 5HDFWLRQ =RQH POPLQ FPVHF DWPf &2 /DVHU &RQGLWLRQV )RFDO 3RLQW 3XOVHV PP GLDf [ f rr3URGXFW 5HFRYHU\ 6\VWHP +H+R RSWLPXP 47 $Xf f PVHF % +H f f RSWLPXP *:3 87 $Xf f +H RSWLPXP 87 $Xf f $U+" f f RSWLPXP 77 87 $Xf f f f RSWLPXP f f f RSWLPXP +H&2 RSWLPXP *:3 WZR $Xf f 1$ 1$ RSWLPXP &)V 1$ 1$ RSWLPXP RSWLPXP +H&2 87 $Xf f 1$ 1$ RSWLPXP f 1$ 1$ RSWLPXP f 1$ 1$ RSWLPXP f 1$ 1$ RSWLPXP f 1$ 1$ RSWLPXP f 1$ 1$ RSWLPXP 1$ 1$ RSWLPXP f 1$ 1$ RSWLPXP

PAGE 66

7DEOH FRQWLQXHGf ([SW 1R WDUJHWf *DV 0L[ bf 3UHVVXUH 3DVFDOf r)ORZ 5DWH 7KURXJK 5HDFWLRQ =RQH POPLQ FPVHF DWPf & /DVHU &RQGLWLRQV )RFDO 3RLQW 3XOVHV PP GLDf [ f rr3URGXFW 5HFRYHU\ 6\VWHP $Xf +H&2 f RSWLPXP &) *:3 87 % $Xf +H VDW ZLWK GLF\FORSHQWDGLHQHf f f RSWLPXP 87 $Xf +H&+ f f f RSWLPXP 77 $Xf +H&+ f f f RSWLPXP 77 $Xf KFK f f f RSWLPXP 77 $ $Xf FK f f f RSWLPXP *:3 87 $Xf +H&+ f f f RSWLPXP 47 PVHF &) $Xf +H&+ f f f RSWLPXP 47 PVHF &) 87 87 87

PAGE 67

7DEOH FRQWLQXHGf ([SW 1R WDUJHWf *DV 0L[ bf 3UHVVXUH 3DVFDOf r)ORZ 5DWH 7KURXJK 5HDFWLRQ =RQH POPLQ FPVHF DWPf & /DVHU &RQGLWLRQV )RFDO 3RLQW 3XOVHV PP GLDf [ f rr3URGXFW 5HFRYHU\ 6\VWHP $Xf +H&+ f f f RSWLPXP &) &) &) $Xf +H&+ f RSWLPXP *:3 WZR &)V $Xf +H&+ f f f RSWLPXP *:3 87 $Xf +H&+ f f f RSWLPXP &) *:3 87 & FDUERQf +H&+ f 1$ 1$ RSWLPXP 87 $Xf +H&+DLU f f f RSWLPXP *:3 87 $Xf +H&+DLU f f f RSWLPXP 87 $Xf +H&+DLU f f f RSWLPXP &) 87 $Xf KFK f f f RSWLPXP 77 87

PAGE 68

7DEOH FRQWLQXHGf ([SW 1R WDUJHWf *DV 0L[ bf 3UHVVXUH 3DVFDOf r)ORZ 5DWH 7KURXJK 5HDFWLRQ =RQH POPLQ FPVHF DWPf & /DVHU &RQGLWLRQV )RFDO 3RLQW 3XOVHV PP GLDf [ f rr3URGXFW 5HFRYHU\ 6\VWHP $Xf KFK f f f 77 87 $Xf +1DWXUDO *DV f f f RSWLPXP 77 87 $Xf $U f RSWLPXP *))87 $Xf +H f RSWLPXP *)) 87 $Xf KFK f RSWLPXP *)) 87 $Xf KFK f RSWLPXP *)) 87 $Xf KFK f RSWLPXP *)) 87 $Xf KFK f RSWLPXP *)) 87 $Xf KFK f RSWLPXP *)) 87

PAGE 69

7DEOH FRQWLQXHGf ([SW 1R WDUJHWf *DV 0L[ bf 3UHVVXUH 3DVFDOf r)ORZ 5DWH 5HDFWLRQ POPLQ DWPf 7KURXJK =RQH FPVHF & /DVHU &RQGLWLRQV )RFDO 3RLQW 3XOVHV PP GLDf [ f rr3URGXFW 5HFRYHU\ 6\VWHP $Xf FK f f f RSWLPXP *)) 87 $Xf KFK f RSWLPXP *)) 87 $Xf KFR f f f RSWLPXP *)) 87 $Xf KFR f RSWLPXP *)) 87 $Xf +H&+&O) f RSWLPXP *)) 87 $Xf +H&+&O) f RSWLPXP *)) 87 $Xf +H&&O) f RSWLPXP *)) 87 $Xf +H&&O)+ f RSWLPXP *)) 87 $Xf +H&)F f RSWLPXP *)) 87

PAGE 70

7DEOH FRQWLQXHGf ([SW *DV 3UHVVXUH r)ORZ 5DWH 7KURXJK &2" /DVHU &RQGLWLRQV rr3URGXFW 1R 0L[ 3DVFDOf 5HDFWLRQ =RQH )RFDO 3RLQW 3XOVHV 5HFRYHU\ WDUJHWf bf POPLQ DWPf FPVHF PP GLDf [ f 6\VWHP K"FK RSWLPXP *)) 87 FDUERQf f K"FK RSWLPXP *)) 87 FRSSHUf f +"&+G RSWLPXP *)) 87 FRSSHUf f f f RSWLPXP f f f f 1$ 1$ f RSWLPXP f f RSWLPXP RSWLPXP r)ORZUDWH YDOXHV LQ SDUHQWKHVHV DUH HVWLPDWHV EDVHG RQ PHDVXUHPHQWV PDGH XQGHU VLPLODU FRQGLWLRQV rr47 TXDUW] WXEH *:3 JODVV ZRRO SOXJ 87 8WXEH *)) JODVV ILEHU ILOWHU 77 WHVWWXEH &) FROG ILQJHU 6HH WH[W IRU GHWDLOHG GHVFULSWLRQV

PAGE 71

RQ -XQH 7KH JDV PL[WXUHV WRWDO SUHVVXUHV DQG IORZ UDWHV WKURXJK WKH SODVPD UHDFWLRQ V\VWHP DUH DOVR OLVWHG LQ WKLV WDEOH 7KH SXOVHG ODVHU IRFDO SRLQW GLDPHWHU DW WDUJHW LPSDFW DQG WKH WRWDO QXPEHU RI SXOVHV IRU HDFK H[SHULPHQW DUH LQFOXGHG DV ZHOO 9ROXPHWULF IORZ UDWHV ZHUH PHDVXUHG LQ POPLQ DW DWPRVSKHULF SUHVVXUH XVLQJ WKH EXEEOHWXEH IORZPHWHU /LQHDU IORZ UDWHV /f LQ FPVHF WKURXJK WKH SODVPD UHDFWLRQ ]RQH ZHUH FDOFXODWHG XVLQJ WKH IROORZLQJ HTXDWLRQ / )f 3fUU ZKHUH ) LV WKH YROXPHWULF IORZ UDWH LQ POVHF PHDVXUHG DW DWPRVSKHULF SUHVVXUH 3 LV WKH SODVPD UHDFWLRQ FKDPEHU SUHVVXUH LQ 3DVFDOV DQG U LV WKH UDGLXV RI WKH UHDFWLRQ ]RQH LQ FP 6RPH YDOXHV OLVWHG LQ SDUHQWKHVHVf ZHUH HVWLPDWHG IURP PHDVXUHPHQWV PDGH GXULQJ VLPLODU H[SHULPHQWV XWLOL]LQJ WKH VDPH QRPLQDO JDV PL[WXUH DQG SUHVVXUH DQG WKH VDPH VHWWLQJV RQ WKH YDULDEOHDUHD IORZPHWHUV 7KH GLDPHWHU Gf IRU WKH ODVHU EHDP DW WKH WDUJHW LPSDFW SRLQW ZDV FDOFXODWHG XVLQJ WKH DEVROXWH YDOXH RI WKH GLIIHUHQFH [f EHWZHHQ WKH IRFDO OHQJWK RI WKH OHQV If DQG WKH PHDVXUHG VHSDUDWLRQ RI WKH OHQV DQG WDUJHW DQG WKH PHDVXUHG GLDPHWHU 'f RI WKH XQIRFXVHG ODVHU EHDP Gf[ 'fI 7KH LPSDFW SRLQW GLDPHWHU ZDV YDULHG E\ PRYLQJ WKH OHQV FORVHU WR RU IDUWKHU DZD\ IURP WKH WDUJHW

PAGE 72

7KH ILUVW H[SHULPHQW OLVWHG LQ 7DEOH LQYHVWLJDWHG WKH RQVHW RI JDV EUHDNGRZQ LQ KHOLXP XQGHU SUHVVXUHV UDQJLQJ IURP WR 3DVFDOV WRUUf 7KH VHFRQG WHVW OLVWHG GHPRQVWUDWHG WKH VDPH HIIHFW LQ DLU DW 3DVFDOV WRUUf ,Q ERWK RI WKHVH H[SHULPHQWV WKH ODVHU EHDP ZDV IRFXVHG LQWR WKH FHQWHU RI WKH SODVPD FKDPEHU 7KH WDUJHW DQG WDUJHW VWDQG ZHUH UHPRYHG IURP WKH V\VWHP 7KH WKLUG H[SHULPHQW OLVWHG GHPRQVWUDWHG JDV EUHDNGRZQ LQ K\GURJHQ DW DQG 3DVFDOV DQG WRUUf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f LQ WKHVH DQG DOO UHPDLQLQJ H[SHULPHQWV WKH SUHVVXUHV DQG JDV IORZ UDWHV ZHUH FRQWUROOHG XVLQJ WKH JDV KDQGOLQJ V\VWHP GHVFULEHG HDUOLHU DQG WKH PHWHULQJ YDOYH EHIRUH WKH SXPS 7KH ODVW IRXU H[SHULPHQWV OLVWHG LQ 7DEOH ZHUH DWWHPSWV WR JHQHUDWH SXUH FDUERQDFHRXV DQG FRSSHUEHDULQJ VSHFLHV LQ WKH SODVPD FKDPEHU XVLQJ WKH FDUERQ DQG FRSSHU WDUJHWV UHVSHFWLYHO\ DQG D +&+ JDV PL[ 7KH UHPDLQLQJ H[SHULPHQWV OLVWHG LQ 7DEOH ZHUH DOO DWWHPSWV WR JHQHUDWH JROG VSHFLHV WKDW ZRXOG UHPDLQ HQWUDLQHG LQ WKH

PAGE 73

JDV VWUHDP DQG VXEVHTXHQWO\ EH WUDSSHG LQ WKH SURGXFW UHFRYHU\ V\VWHP 7KH UHDGHU LV GLUHFWHG WR WKH WDEOH IRU D GHWDLOHG SUHVHQWDWLRQ RI WKH H[SHULPHQWDO FRQGLWLRQV 7KH UHVXOWV RI HDFK H[SHULPHQW DUH GLVFXVVHG LQ &KDSWHU ,,, 6XEVWUDWH &RDWLQJ DQG $QQHDOLQJ ([SHULPHQWV 6HYHUDO GLIIHUHQW W\SHV RI VXEVWUDWHV ZHUH FRDWHG ZLWK WKH SODVPD UHDFWLRQ SURGXFWV GXULQJ WKH FRXUVH RI WKH VWXG\ ([SHULPHQWV WKDW SURGXFHG WKH FRDWHG VXEVWUDWHV DUH OLVWHG LQ 7DEOH DORQJ ZLWK WKH UHVSHFWLYH VXEVWUDWHV DQG WKHLU SK\VLFDO SRVLWLRQV LQ WKH SODVPD UHDFWLRQ RU SURGXFWUHFRYHU\ V\VWHPV GXULQJ WKH FRDWLQJ SURFHVV ,Q DOO RI WKH FRDWLQJ H[SHULPHQWV WKH SXOVHG &2 ODVHU ZDV RSHUDWHG DW LWV PD[LPXP YROWDJH OHYHO .9f DQG WKH IRFXVLQJ OHQV ZDV DGMXVWHG WR SURYLGH DQ RSWLPXP IRFXV DW WKH WDUJHW LPSDFW SRLQW $OO FRDWLQJ H[SHULPHQWV ZHUH FDUULHG RXW DW D QRPLQDO SUHVVXUH RI 3DVFDOV WRUUf $ QRPLQDO JDV PL[WXUH RI b K\GURJHQ DQG b PHWKDQH ZDV XVHG LQ DOO RI WKHVH H[SHULPHQWV ZLWK IRXU H[FHSWLRQV 7ZR H[SHULPHQWV ZHUH SHUIRUPHG XVLQJ b KHOLXP RQH WHVW XVHG b KHOLXP DQG b FDUERQ PRQR[LGH PL[WXUH DQG RQH WHVW XVHG D PL[WXUH RI b K\GURJHQ DQG b QDWXUDO JDV (OHYHQ GLIIHUHQW W\SHV RI VXEVWUDWHV ZHUH FRDWHG ZLWK WKH SODVPD UHDFWLRQ SURGXFWV f JODVV SODWHV FXW IURP VWDQGDUG PP WKLFN PLFURVFRSH VOLGHV &RUQLQJ 1R f YDU\LQJ LQ VL]H IURP PP E\ PP WR PP E\ PP f TXDUW] RSWLFDO ZLQGRZV PP WKLFN E\ PP GLDPHWHU

PAGE 74

7DEOH r6XEVWUDWH &RDWLQJ ([SHULPHQWV ([SW 7RWDO 6XEVWUDWHV 3RVLWLRQ LQ 1R RI /DVHU &RDWHG 6\VWHP 3XOVHV [ f b +Hb &2f : FRDWHG SRO\FU\VWDO OLQH SFf 6L FKLS SODFHG LQ 8WXEH LQOHW b +Hf JODVV SODWHV WDSHG WR SODVPD FKDPEHU ZLQGRZV SODFHG LQ ERWWRP RI SODVPD FKDPEHU $ b +Hf : FRDWHG SF 6L FKLS ZLWK DQ HWFKHG DUHD SDWWHUQHG : RQ VLQJOH FU\VWDO VFf 6, JODVV SL DWHV :6L FKLSV WDSHG WR JODVV SODWHV JODVV SODWHV WDSHG WR ZLQGRZV DQG SODFHG LQ ERWWRP RI SODVPD FKDPEHU b +eb QDWXUDO : ULEERQ FRLO JDVf SODFHG LQ 8WXEH LQOHW $U LRQ ODVHU EHDP GLUHFWHG WKURXJK JODVV WXEH RQWR OHHZDUG DUHD : ULEERQ SODFHG LQ SODVPD FKDPEHU RXWOHW $U LRQ ODVHU EHDP GLUHFWHG WKURXJK TXDUW] ZLQGRZ RQWR : FHUDPLF IHHGWKURXJK SODFHG LQ VPDOO FRDWLQJ FKDPEHU FHUDPLF IHHGWKURXJKV SODFHG LQ JODVV FRDWLQJ FKDPEHU *&&f RQ WKUHHn WLHUHG UDFN JODVV SODWH WDSHG LQWR *&& LQOHW : RQ SF DQG VF 6, FKLSV SDWWHUQHG $ RQ VF 6L FKLS WDSHG WR ILUVW WLHU RI UDFN LQ *&& JODVV SODWH WDSHG LQWR *&& LQOHW JODVV SODWH WDSHG LQWR *&& LQOHW SDWWHUQHG : SDWn WHUQHG $ RQ VF 6, FKLSV WDSHG RQWR JODVV SODWH WKDW ZDV WDSHG LQWR *&& LQOHW

PAGE 75

7DEOH FRQWLQXHGf ([SW 1R 7RWDO RI /DVHU 3XOVHV [ f 6XEVWUDWHV &RDWHG 3RVLWLRQ LQ 6\VWHP : RQ SF 6L DQG : RQ VF 6L FKLSV WDSHG WR SHUISODWH LQ WKH DOXPLQXP FRDWLQJ FKDPEHU $&&f : RQ SF 6L DQG : RQ VF 6L FKLSV WDSHG WR SHUISODWH LQ $&& : RQ SF 6L DQG : RQ VF 6L FKLSV FOLSSHG WR KRW SODWH LQ $&& : RQ VF 6L FKLSV JODVV SODWHV FOLSSHG WR KRW SODWH LQ $&& : RQ VF 6L FKLSV JODVV SODWHV VWULS RI 6FRWFK WDSH DGn KHVLYH VLGH XS ZLWK DQ DUHD RI : WKLQ ILOP VWXFN WR WKH DGKHVLYH WDSHG WR SHUISODWH LQ $&& FKDUJHG DOXPLQXP SODWHV DQG f YROWV GF SRWHQWLDOf SUHVVHG LQWR FHQWHU RI SHUISODWH 6L FKLS ZLWK D FHQWUDO VWULS RI : RQ RQH VLGH FKDUJHG ZLWK YROW GF SRWHQWLDO WZR FP GLD TXDUW] RSWLFDO IODWV JODVV FKLSV SODFHG QHDU VLGHZDOO LQ $&& WDSHG WR SODVPD FKDPEHU ZLQGRZV r$ H[SHULPHQWV ZHUH FRQGXFWHG DW D QRPLQDO SUHVVXUH RI 3DVFDOV XVLQJ D QRPLQDO JDV PL[WXUH RI b + DQG b &+ H[FHSW ZKHUH QRWHG

PAGE 76

f WXQJVWHQ ULEERQ PP ZLGH E\ PP WKLFN + &URVV &RPSDQ\f f FHUDPLF HOHFWULFDO IHHGWKURXJKV FP GLDPHWHU VXUIDFH f EODQNHW FRDWHG &9' WXQJVWHQ QPf RQ D VLOLFRQ ZDIHU ZLWK RQH SRO\FU\VWDOOLQH SFf VLGH DQG RQH VLQJOH FU\VWDO VFf VLGH +DUULV &RUSRUDWLRQf FXW LQWR PP E\ PP FKLSV f VDPH DV f ZLWK DUHDV RI WXQJVWHQ HWFKHG DZD\ 0 .)H&1fJ 0 HWK\OHQH GLDPHQHf WR H[SRVH WKH VLOLFRQ VXUIDFH f 9/6, FLUFXLW SDWWHUQHG &9' WXQJVWHQ RQ VF VLOLFRQ ZLWK VLOLFRQ GLR[LGH VXUIDFHV VXUURXQGLQJ WKH PLFURQ VL]H WXQJVWHQ IHDWXUHV +DUULV &RUSRUDWLRQf FXW LQWR PP E\ PP FKLSV f 9/6, FLUFXLW SDWWHUQHG &9' DOXPLQXP RQ VF VLOLFRQ ZLWK VLOLFRQ GLR[LGH VXUIDFHV VXUURXQGLQJ WKH PLFURQ VL]H IHDWXUHV +DUULV &RUSRUDWLRQf FXW LQWR PP E\ PP FKLSV f DOXPLQXP SODWHV PP E\ PP E\ PP WKLFN f 6FRWFK EUDQG DGKHVLYH WDSH DQG f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

PAGE 77

,Q PRVW RI WKH H[SHULPHQWV WKH VXEVWUDWHV ZHUH SRVLWLRQHG LQ RQH RI WKH SURGXFWUHFRYHU\VXEVWUDWHFRDWLQJ V\VWHPV GHVFULEHG HDUOLHU DQG FRDWHG DW URRP WHPSHUDWXUH FD .f ,Q RQH H[SHULPHQW D FP ORQJ SLHFH RI WXQJVWHQ ULEERQ ZDV FRLOHG DQG SODFHG LQ WKH LQOHW DUP RI WKH JODVV 8WXEH FROG WUDS DQG LUUDGLDWHG ZLWK DQ XQIRFXVHG FZ $UJRQ LRQ ODVHU EHDP ZDWWV QPf ,Q DQRWKHU H[SHULPHQW D FP ORQJ SLHFH RI WKH WXQJVWHQ ULEERQ ZDV SODFHG LQ WKH WRS RI WKH SODVPD UHDFWLRQ FKDPEHU DW WKH H[LW XQLRQ ZLWK WKH SURGXFW UHFRYHU\ V\VWHP IODQJH VHH )LJXUH f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

PAGE 78

7DEOH r6XEVWUDWH $QQHDOLQJ &RQGLWLRQV ([SW 6XEVWUDWH $QQHDOLQJ 7LPH 7HPS 1R 0HWKRG .f SODVPD FKDPEHU SXOVHG & ODVHU .9 XQIRFXVHG SXOVHV b +H b &2f JODVV ZLQGRZ $ : RQ SF 6, FKLS UDGLR IUHTXHQF\ VHF bf SDWWHUQHG : RQ UIf FRLO LQ VHF VF 6L FKLS IORZLQJ DLUf UI FRLO LQ VWLOO VHF GXOO UHG DLU : ULEERQ $U LRQ ODVHU PLQ ZDWWV XQIRFXVHG LQ VLWXf FHUDPLF IHHG VORZ FRQYHFWLYH PLQ f WKURXJK KHDWLQJ FYKf LQ DLU ZKLOH PRQLn WRULQJ HOHFWULFDO UHVLVWDQFH PD[f FHUDPLF IHHG VDPH DV DERYH H[ PLQ f WKURXJK FHSW XQGHU + IORZ PD[f : RQ SF DQG VF 6L FYK XQGHU + IORZ KU SDWWHUQHG $ RQ VF KU 6L FKLSV KU : DQG $ RQ VF 6L FKLSV FYK XQGHU + IORZ KU JODVV ILEHU FYK LQ DLU KU FD ILOWHU *))f KU *)) FYK LQ DLU KU KU *)) FYK LQ DLU KU b &+f *)) FYK LQ DLU KU *)) FYK LQ DLU KU b + b &+f

PAGE 79

7DEOH FRQWLQXHGf ([SW 1R 6XEVWUDWH $QQHDOLQJ 0HWKRG 7LPH 7HPS .f *)) FYK LQ DLU KU +&f *)) FYK LQ DLU KU KFRf : RQ SF DQG VF FYK XQGHU + IORZ KU f 6L FKLSV FYK LQ DLU KU f : RQ SF DQG VF FYK XQGHU + IORZ KU f 6L FKLSV IROORZHG E\ FYK LQ DLU KU f : RQ SF DQG VF FYK LQ DLU KU 6L FKLSV FYK LQ DLU FYK LQ DLU FYK LQ DLU FYK XQGHU + IORZ FYK LQ DLU IROn ORZHG E\ FYK XQGHU + FYK XQGHU + IROORZHG E\ FYK LQ DLU KU KU KU KU KU KU KU KU f f f f f f f f : RQ SF 6L FKLS JODVV SODWH UI FRLO LQ DLU GUHZ OLQHV ZLWK IRFXVHG $U LRQ n ODVHU EHDP ZDWWVf VHF FPVHF UHG KRW : RQ SF 6L FKLS DQG JODVV SODWH UI FRLO 3DVFDO FYK LQ DLU GUHZ LQHV ZLWK IRFXVHG $U LRQ ODVHU EHDP ZDWWVf ZDWWVf ZDWWVf PLQ PLQ FPVHF FPVHF FPVHF f f GF SRWHQWLDO DOXPLQXP SODWH FYK LQ DLU VHF f

PAGE 80

7DEOH FRQWLQXHGf ([SW 1R 6XEVWUDWH $QQHDOLQJ 0HWKRG 7LPH 7HPS .f SLHFHV RI *)) FYK LQ DLU KU KU f KU f VHF f r$ H[SHULPHQWV ZHUH FRQGXFWHG DW D QRPLQDO SUHVVXUH RI 3DVFDOV XVLQJ D QRPLQDO JDV PL[WXUH RI b + DQG b &+ H[FHSW ZKHUH QRWHG

PAGE 81

SURGXFWV ZHUH DQQHDOHG LQ DLU RU K\GURJHQ DW WHPSHUDWXUHV UDQJLQJ IURP IRU WLPH LQWHUYDOV UDQJLQJ IURP VHYHUDO VHFRQGV WR VHYHUDO KRXUV 7KHVH DQQHDOV ZHUH SHUIRUPHG LQ WKH WXEH IXUQDFH GHVFULEHG HDUOLHU $Q DQQHDOLQJ FKDPEHU ZDV FRQVWUXFWHG IURP D PP LG E\ FP ORQJ ERURVLOLFDWH JODVV WXEH ZLWK ULQJ VHDO MRLQWV RQ ERWK HQGV VHH )LJXUH f 7KH HQGV RI WKLV WXEH ZHUH FRQQHFWHG WR WZR PDWFKLQJ ULQJ VHDO MRLQWV WKDW KDG HQGV WDSHUHG WR LQ RG WXELQJ 4XLFN FRXSOHV ZHUH XVHG WR FRQQHFW WKH FKDPEHU ZLWK WKH JDV KDQGOLQJ V\VWHP IRU GHOLYHU\ RI K\GURJHQ DW FD POPLQ $QQHDOV LQ DLU ZHUH SHUIRUPHG E\ GLVFRQQHFWLQJ WKH FKDPEHUn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

PAGE 82

)LJXUH 6XEVWUDWH $QQHDOLQJ &KDPEHU

PAGE 84

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f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f PDVV VSHFWURPHWHUV DQG VHYHUDO GLIIHUHQW PHWKRGV RI VDPSOH GHOLYHU\ LQ DQ DWWHPSW WR LVRODWH DQG LGHQWLI\ JROG FRPSRXQGV

PAGE 85

FRPSRXQGV 7KH WKLUG FDWHJRU\ FRQVLVWHG RI RQH VHULHV RI H[SHULPHQWV XVLQJ D WLPH RI IOLJKW PDVV VSHFWURPHWHU 72)06f WR GHWHFW JROG FOXVWHU FRPSRXQGV IRUPHG LQ D 1G<$* SXOVHG ODVHU VWLPXODWHG SODVPD XVLQJ D VROLG JROG WDUJHW DQG b PHWKDQH LQ KHOLXP (DFK H[SHULPHQW LQ WKH YRODWLOLW\ VWXG\ LV GHVFULEHG EHORZ 6XEOLPDWLRQ ([SHULPHQWV 7KH WZR VXEOLPDWLRQ H[SHULPHQWV WKDW ZHUH SHUIRUPHG XVHG WKH UHDFWLRQ SURGXFWV IRUPHG LQ D b +Hb &+ SODVPD DQG LVRODWHG LQ WKH SURGXFW UHFRYHU\ V\VWHP 7KH ILUVW H[SHULPHQW XVHG WKH .f 8WXEH FROG WUDS IURP 7KLV WUDS KDG EHHQ SRVLWLRQHG DIWHU D FROG ILQJHU GXULQJ WKH SODVPD UHDFWLRQ H[SHULPHQW 7KH VHFRQG VXEOLPDWLRQ H[SHULPHQW XWLOL]HG WKH ILUVW FROG ILQJHU WUDS .f DQG WKH JODVV ZRRO SOXJ FRQWDLQHG LQ LWV RXWOHW IURP %RWK RI WKHVH FROG WUDSV FRQWDLQHG PLOOLJUDP TXDQWLWLHV RI WKH GDUNFRORUHG SODVPD UHDFWLRQ SURGXFWV %RWK VXEOLPDWLRQ H[SHULPHQWV ZHUH SHUIRUPHG E\ DWWDFKLQJ WKH SODVPD FRQWDLQLQJ FROG WUDSV ZKLFK KDG EHHQ VHDOHG DQG VWRUHG DW .f WR D IUHVK 8WXEH FROG WUDS NHSW DW 7KLV WUDS ZDV FRQQHFWHG WR WKH PHFKDQLFDO YDFXXP SXPS YLD D PHWHULQJ YDOYH DQG D SXPS WUDS DQG WKH V\VWHP ZDV HYDFXDWHG VORZO\ WR 3DVFDO ,Q WKH ILUVW WHVW WKH SURGXFWV ZHUH ZDUPHG IURP RYHU D SHULRG RI IRXU KRXUV $ VHFRQG FROOHFWLRQ WUDS ZDV H[FKDQJHG IRU WKH ILUVW RQH ZKHQ WKH SURGXFWV UHDFKHG ,Q WKH VHFRQG WHVW WKH SODVPD SURGXFWV ZHUH ZDUPHG IURP WR RYHU D SHULRG RI PLQXWHV 2QO\ RQH FROOHFWLRQ WUDS ZDV XVHG LQ WKLV WHVW $OO RI WKH FROOHFWLRQ WUDSV

PAGE 86

DQG ERWK RI WKH SURGXFW UHFRYHU\ WUDSV ZHUH VHDOHG LQ DLU DQG KHDWHG WR LQ D EXQVHQ EXUQHU &RORU FKDQJHV LQ WKH WUDS FRQWHQWV ZKLFK LQGLFDWHG WKH SUHVHQFH RI JROG ILOPV ZHUH REVHUYHG YLVXDOO\ 0DVV 6SHFWURPHWHU ([SHULPHQWV 6L[ H[SHULPHQWV ZHUH SHUIRUPHG XVLQJ TXDGUXSROH RU ,&5 PDVV VSHFWURPHWHUV WR GHWHFW FRPSRXQGV LQ WKH SODVPD UHDFWLRQ SURGXFWV $OO RI WKH LQVWUXPHQWV ZHUH ORFDWHG LQ WKH 'HSDUWPHQW RI &KHPLVWU\ DW WKH 8QLYHUVLW\ RI )ORULGD 8)f $ V\QRSVLV RI WKHVH H[SHULPHQWV LV SUHVHQWHG EHORZ LQ 7DEOH 7DEOH 9RODWLOLW\ 6WXG\ 0DVV 6SHFWURPHWHU ([SHULPHQWV ([SW 3ODVPD ([SW 1R *DV 0L[f 6DPSOH 7\SH 06 7\SH 6DPSOH ,QWURGXFWLRQ 0HWKRG b +Hb &+f WDUJHW UHVLGXH TXDGUXSROH VROLGV SUREH KHDWHG WR b +b &+f FKDPEHU ZDOO UHVLGXH *&TXDG06 LQMHFWHG DFHWRQH VXVSHQVLRQVROXWLRQ b +b &+f 8WXEH FROG WUDS TXDGUXSROH FRQQHFWHG WR JDV LQOHW KHDWHG WR b +Hb &+f FROG WUDS DIWHU *:3 )7,&5 FRQQHFWHG WR JDV LQOHW KHDWHG WR b +b &+f FRDWHG JODVV SL DWH )7,&5 SODFHG DGMDFHQW WR ,&5 FHO HEHDP t ODVHU GHVRUSWLRQ b +b &+f UHVLGXH IURP FRDWHG JODVV SL DWH )7,&5 VROLGV SUREH KHDWHG WR &,' UHDFWLRQV

PAGE 87

7KH ILUVW H[SHULPHQW ZDV GRQH LQ WKH ODERUDWRU\ RI 3URI 5$
PAGE 88

FKORULGH V\QWKHVL]HG E\ 'U ( 6F]OLFN LQ WKH ODERUDWRU\ RI *3DOHQLN DW 8)f LQ WKH VROLGV SUREH DQG KHDWLQJ LW WR 7KH IRXUWK ILIWK DQG VL[WK H[SHULPHQWV ZHUH SHUIRUPHG LQ WKH ODERUDWRU\ RI 3URI -5 (\OHU E\ 'U 0 0RLQL DQG WKH DXWKRU 7KH IRXUWK RQH XVHG D VDPSOH IURP WHVW b +Hb &+f 7KH VDPSOH ZDV FROOHFWHG LQ D FROG WUDS SRVLWLRQHG DIWHU D JODVV ZRRO SOXJ GXULQJ WKH SODVPD H[SHULPHQW 7KLV FROG WUDS ZDV FRQQHFWHG WR WKH JDV LQOHW RI DQ ,&506 1LFROHW )706 HTXLSSHG ZLWK D 7HVOD VXSHUFRQGXFWLQJ PDJQHW DQG GHVFULEHG IXOO\ LQ WKH OLWHUDWXUHfr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f WR H[DPLQH SODVPD UHDFWLRQ SURGXFWV FRDWHG RQ D JODVV SODWH LQ UXQ b +b &+f 7KH VDPSOH ZDV PRXQWHG RQ D VROLGV SUREH DQG SRVLWLRQHG LQ WKH YDFXXP FKDPEHU DGMDFHQW WR WKH ,&5 FHOO 7KH PDVV UHVSRQVH IURP DPX ZDV PRQLWRUHG XVLQJ )RXULHU WUDQVIRUP PHWKRGRORJ\ ZKLOH WKH VDPSOH ZDV H[SRVHG WR D QDQRDPS HOHFWURQ EHDP IRU RQH KRXU 7KH VDPSOH ZDV WKHQ LUUDGLDWHG ZLWK DQ XQIRFXVHG IUHTXHQF\ GRXEOHG QP SXOVHG 1G<$* ODVHU 4XDQWHO 0RGHO <* f DW SRZHU OHYHOV RI P-SXOVH LQ DQ DWWHPSW WR GHVRUE FRPSRXQGV WKDW ZRXOG KDYH WKHQ EHHQ LRQL]HG E\ FRGHVRUEHG SRWDVVLXP

PAGE 89

LRQV 7KH LRQV FDPH IURP WKH PDWHULDOV XVHG WR FRQVWUXFW WKH ,&5 FHOO 7KLV ZDV FRQVLGHUHG D VRIW LRQL]DWLRQ WHFKQLTXHf 7KH PDVV UHVSRQVH ZDV PRQLWRUHG IRU WKH QH[W WZHQW\ PLQXWHV ZKLOH WKH ODVHU DQG HEHDP ZHUH RQ DQG WKHQ IRU DQRWKHU WHQ PLQXWHV ZLWK WKH ODVHU RQ DQG WKH HEHDP RII 7KH VL[WK H[SHULPHQW ZDV SHUIRUPHG LQ WKH 1LFROHW )706 ,&506 XVLQJ D VDPSOH JHQHUDWHG LQ UXQ b +b &+f 7KH VDPSOH ZDV SODFHG LQ D FDSLOODU\ WXEH WKDW ZDV WKHQ LQVHUWHG LQWR WKH VROLGV SUREH DQG ZDUPHG WR ZKLOH WKH PDVV UHVSRQVH IURP ZDV REVHUYHG &ROOLVLRQLQGXFHG LRQ GLVVRFLDWLRQ &,'f H[SHULPHQWV ZHUH SHUIRUPHG RQ FRPSRXQGV ZLWK PDVV QXPEHUV DQG 7LPH RI )OLJKW 06 3ODVPD ([SHULPHQW 7KLV H[SHULPHQW ZDV SHUIRUPHG LQ WKH ODERUWRU\ RI 3URI 3%UXFDW LQ WKH 'HSDUWPHQW RI &KHPLVWU\ DW 8) E\ 0U '( /HVVHQ DQG WKH DXWKRU 7KLV ODERUDWRU\ ZDV HTXLSSHG ZLWK D FOXVWHU EHDP DSSDUDWXV OLQNHG WR D WLPH RI IOLJKW PDVV VSHFWURPHWHU VHH )LJXUH f WKDW LV GHVFULEHG IXOO\ HOVHZKHUHA 7KH FOXVWHU EHDP ZDV SURGXFHG E\ LUUDGLDWLQJ D VROLG JROG WDUJHW ZLWK D IRFXVHG SXOVHG 1G<$* ODVHU 4XDQWHO 0RGHO <*f EHDP DW D SRZHU OHYHO RI P-SXOVH DW WDUJHW LPSDFW QVHF SXOVHV DW K]f +HOLXP RU KHOLXPb PHWKDQH JDV ZDV LQWURGXFHG WR WKH WDUJHW DW D SUHVVXUH RI DWP XVLQJ D PVHF SXOVHG YDOYH 7KH UHVXOWDQW SODVPD H[LWHG WKH WDUJHW KROGHU WKURXJK D PP GLD KROH DQG ZDV K\SHUVRQLFDOO\ H[SDQGHG LQWR D ODUJH YDFXXP FKDPEHU PDLQWDLQHG DW D SUHVVXUH RI 3DVFDOV $ VNLPPHU LQ GLUHFW

PAGE 90

)LJXUH &OXVWHU %HDP72)06 $SSDUDWXV

PAGE 91

VNLPPHU

PAGE 92

OLQH RI VLJKW ZLWK WKH SOXPH H[LW DOORZHG XQGHIOHFWHG FOXVWHUV WR HQWHU D UHSHOOHU JULG ZKHUH WKH\ ZHUH UHGLUHFWHG GRZQ D WKUHH PHWHU 72) WXEH DQG LQWR D PXOWLVWDJH GHWHFWRU $ YDULDEOH YROWDJH KRUL]RQWDO GHIOHFWRU +'f ORFDWHG DW WKH EHJLQQLQJ RI WKH 72) WXEH RSWLPL]HG WKH WUDQVIHU HIILFLHQF\ RI YDULRXV PDVV UDQJHV RI FOXVWHUV 'XULQJ WKH FRXUVH RI WKH H[SHULPHQW WKH +' YROWDJH ZDV YDULHG EHWZHHQ YROWV 7KLV DOORZHG WKH REVHUYDWLRQ RI VLJQDOV IURP LRQL]HG JROG FOXVWHUV DQG FOXVWHU FRPSRXQGV IURP $XOf WR $Xf $W HDFK YROWDJH VHWWLQJ WKH VLJQDOV IURP SRVLWLYH LRQ FOXVWHUV SURGXFHG LQ SXUH KHOLXP DQG LQ KHOLXPb PHWKDQH SODVPDV ZHUH UHFRUGHG *ROG 7KLQ )LOP &KDUDFWHUL]DWLRQ 6L[ GLIIHUHQW WHFKQLTXHV ZHUH XWLOL]HG WR FKDUDFWHUL]H WKH SODVPD UHDFWLRQ SURGXFWV IRUPHG LQ WKH K\GURJHQPHWKDQHJROG SODVPDV 6DPSOHV RI WKH XOWUDILQH SDUWLFOH SURGXFW DQG FRDWHG VXEVWUDWHV ERWK DQQHDOHG DQG XQDQQHDOHGf ZHUH VXEMHFWHG WR DQDO\VHV 0RVW VDPSOHV ZHUH LQ WKH IRUP RI WKLQ ILOPV GHSRVLWHG RQ JODVV SODWHV FHUDPLF IHHGWKURXJKV DQG &9' WXQJVWHQ RU DOXPLQXP RQ VLOLFRQ FKLSV $ PDMRU REMHFWLYH RI WKHVH DQDO\VHV ZDV WKH GHWHUPLQDWLRQ RI WKH UHODWLYH DEXQGDQFH DQG WKH SK\VLFDO VWDWH RI WKH JROG SUHVHQW LQ WKH VRRWOLNH SODVPD UHDFWLRQ SURGXFWV )LOP VWRLFKLRPHWU\ VWUXFWXUH DQG HOHFWULFDO SURSHUWLHV ZHUH DOVR LQYHVWLJDWHG 7KH DQDO\WLFDO WHFKQLTXHV XWLOL]HG LQ WKLV SDUW RI WKH VWXG\ ZHUH f YLVLEOH DEVRUSWLRQ VSHFWURVFRS\ f RSWLFDO PLFURUHIOHFWRPHWU\ 205f f [UD\ SKRWRHOHFWURQ VSHFWURVFRS\ ;36f

PAGE 93

f VFDQQLQJ HOHFWURQ PLFURVFRS\ 6(0f ZLWK f HQHUJ\ GLVSHUVLYH VSHFWURVFRS\ ('6f DQG f HOHFWULFDO UHVLVWDQFH 5f 7KH SULQFLSOH IHDWXUHV RI HDFK WHFKQLTXH DUH GHVFULEHG EULHIO\ DORQJ ZLWK WKH UHOHYDQW SDUDPHWHUV HPSOR\HG WR DQDO\]H WKH VDPSOH ILOPV 'HWDLOHG OLVWV RI WKH VDPSOHV DQDO\]HG XVLQJ HDFK WHFKQLTXH DUH SUHVHQWHG LQ &KDSWHU ,,, DORQJ ZLWK WKH UHVSHFWLYH DQDO\WLFDO UHVXOWV DQG D GLVFXVVLRQ RI WKHLU PHDQLQJ 9LVLEOH $EVRUSWLRQ 6SHFWURVFRS\ $ +HZOHWW3DFNDUG 0RGHO GLRGH DUUD\ VSHFWURPHWHU ZDV XVHG E\ WKH DXWKRU WR PHDVXUH WKH DEVRUSWLRQ VSHFWUD QPf RI DFHWRQH VXVSHQVLRQVROXWLRQV RI VHYHUDO VDPSOHV UHFRYHUHG IURP WKH SODVPD FKDPEHU VLGHZDOOV 6DPSOHV IURP &+ +H&+ DQG +H&2 SODVPD H[SHULPHQWV ZHUH VXEMHFWHG WR VROYHQW GLVVROXWLRQ WHVWV XVLQJ KH[DQH WROXHQH DFHWRQH GLHWK\OHWKHU VROXWLRQV RI WKH SUHFHGLQJ VROYHQWV ZDWHU K\GURFKORULF DFLG QLWULF DFLG DQG DTXD UHJLD EHIRUH GHWHUPLQLQJ WKDW SXUH DFHWRQH \LHOGHG WKH EHVW UHVXOWV GLVFXVVHG LQ WKH QH[W FKDSWHUf 7KH DEVRUSWLRQ VSHFWUD RI SSP DQG SSP $X VWDQGDUGV LQ DFHWRQHZDWHU ZHUH DOVR PHDVXUHG 7KHVH VWDQGDUGV ZHUH SUHSDUHG E\ GLOXWLQJ PO RI WKH SSP DQG PO RI WKH SSP $$ VWDQGDUGV UHVSHFWLYHO\ WR PO ZLWK VSHFWUDO JUDGH DFHWRQH $OO RI WKH VDPSOH DQG VWDQGDUG VSHFWUD ZHUH PHDVXUHG DJDLQVW DQ DFHWRQH UHIHUHQFH FHOO $OO PHDVXUHPHQWV ZHUH PDGH LQ VWDQGDUG PDWFKHG FP ZLGH TXDUW] FXYHWV

PAGE 94

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f 5HIOHFWDQFH FXUYHV ZHUH GHWHUPLQHG E\ FRPSDULQJ WKH VDPSOH LQWHQVLWLHV WR WKH LQWHQVLWLHV RI D VWDQGDUG ZLWK NQRZQ UHIOHFWLYLW\ LQ DLU 5VWGf 7KH UHIOHFWDQFH LQWHQVLW\ RI D 6L& VWDQGDUG ,VWGf ZDV PHDVXUHG DW QP LQWHUYDOV EHWZHHQ DQG QP MXVW SULRU WR PHDVXULQJ WKH LQWHQVLW\ RI HDFK VDPSOHnV UHIOHFWDQFH ,VDPSf DW WKH VDPH ZDYHOHQJWKV 7KH UHIOHFWDQFH YDOXH IRU HDFK VDPSOH SRLQW 5VDPSf ZDV WKHQ FDOFXODWHG XVLQJ WKH IROORZLQJ HTXDWLRQ 5>VDPS@ >,VDPSf '&@ [ >5VWGf@>,VWGf '&@ ZKHUH '& ZDV WKH SKRWRPXOWLSOLHU GDUN FXUUHQW 5VWGf YDOXHV IRU 6L& DUH OLVWHG LQ $SSHQGL[ & 6DPSOH ILOPV ZHUH H[DPLQHG YLVXDOO\ WR GHWHUPLQH D UHSUHVHQWDWLYH DUHD IRU UHIOHFWDQFH PHDVXUHPHQWV 7KH LQVWUXPHQW DQDO\]HG DQ DUHD PLFURQV LQ GLDPHWHU 7KH VDPH VSRW RQ WKH 6L& VWDQGDUG ZDV PHDVXUHG

PAGE 95

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f GHWHUPLQDWLRQ RI WKH HOHPHQWDO VXUIDFH FRPSRVLWLRQ RI WKH ILOP f GHWHUPLQDWLRQ RI WKH ELQGLQJ HQHUJ\ %(f RI WKH $X I DQG I SHDNV DQG WKH & ,V SHDN DQG f GHWHUPLQDWLRQ RI WKH JROG DQG FDUERQ FRQFHQWUDWLRQV LQ WKH EXON RI WKH ILOP 7KH ILUVW REMHFWLYH ZDV DFKLHYHG WKURXJK WKH XVH RI HOHPHQWDO VXUYH\ VFDQV IURP H9 %( 7KH VHFRQG REMHFWLYH ZDV DFFRPSOLVKHG XVLQJ QDUURZ VFDQV H9f RI WKH UHVSHFWLYH $X DQG & SHDNV DQG REVHUYLQJ WKH VKLIW LQ %( DQG WKH SHDN VKDSHV DQG ZLGWKV DW KDOI KHLJKW ZKKf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

PAGE 96

7ZR LQVWUXPHQWV ZHUH XVHG WR SHUIRUP WKH DQDO\VHV LQ WKHVH VWXGLHV 2QH LQVWUXPHQW D .UDWRV ;6$0 ZDV ORFDWHG LQ WKH ODERUDWRU\ RI 3URI 9<
PAGE 97

HTXLOLEULXP VWDWXV ZLWKLQ WKH ILUVW IHZ VHFRQGV RI H[SRVXUH WR WKH FRQVWDQW LQWHQVLW\ [UD\ EHDP WKH WRWDO DUHDV RI WKH $X DQG & SHDNV DQG WKH HOHPHQWDO VXUYH\ VFDQV SURYLGHG XVHIXO LQIRUPDWLRQ 2QH VDPSOH ILOP DQG RQH +DUULV &RUS VWDQGDUG VSXWWHU GHSRVLWHG $X ILOP ZHUH VXEMHFWHG WR GHSWK SURILOLQJ XVLQJ $U LRQ HWFKLQJ $ LRQ FXUUHQW DQG P$ DUF FXUUHQWf 7KHVH WZR VDPSOHV ZHUH JURXQGHG E\ SUHVVLQJ FRSSHU IRLO RYHU WKHP ZLWK DQ RSHQ DUHD IRU DQDO\VLV DQG DWWDFKLQJ WKH IRLO VHFXUHO\ WR WKH JURXQGHG VDPSOH VWDQG $OO VSHFWUD ZHUH UHFRUGHG DW D SKRWRHOHFWURQ WDNHRII DQJOH RI GHJUHHV 3HDN DUHDV ZHUH DGMXVWHG IRU HOHPHQWDO FRPSRVLWLRQ GHWHUPLQDWLRQV XVLQJ 6FRILHOGnV SKRWRLRQL]DWLRQ FURVV VHFWLRQVA DW DQG H9 UHVSHFWLYHO\ IRU WKH WZR LQVWUXPHQWV 6LQFH RQO\ JROG DQG FDUERQ ZHUH GHWHFWDEOH LQ WKH ILOPV WKH SKRWRLRQL]DWLRQ FURVV VHFWLRQ IRU K\GURJHQ LV H[WUHPHO\ VPDOO UHODWLYH WR FDUERQ DQG ZDV QRW GHWHFWDEOH ZLWK WKHVH LQVWUXPHQWVf DQG WKH 6FRILHOG FURVV VHFWLRQ YDOXH IRU WKH & ,V SHDN LV WDNHQ DV UHODWLYH EDUQV DW H9 DQG EDUQV DW H9f RQO\ WKH FRPELQHG DUHDV ;$Xf RI WKH $X I SHDNV ZHUH DGMXVWHG 7KLV ZDV GRQH XVLQJ WKH IROORZLQJ HTXDWLRQ IRU WKH 0J .D VRXUFH H9f ;$Xf f DGMXVWHG $X DUHD )RU WKH $ .D VRXUFH H9f WKH IROORZLQJ HTXDWLRQ ZDV XVHG ;$Xf f DGMXVWHG $X DUHD

PAGE 98

2QFH WKH DGMXVWHG $X DUHDV DGM$Xf ZHUH FDOFXODWHG WKH\ ZHUH FRPSDUHG GLUHFWO\ WR WKH FRUUHVSRQGLQJ & ,V SHDN DUHDV WR \LHOG UHODWLYH SHUFHQW DWRPLF FRPSRVLWLRQ XVLQJ WKH IROORZLQJ HTXDWLRQV fDGM$8fDGM$X & ,Vf UHODWLYH DWRPLF b $X f& OVfDGM$X & ,Vf UHODWLYH DWRPLF b & 5HODWLYH SHUFHQW PDVV FRQFHQWUDWLRQV ZHUH WKHQ FDOFXODWHG XVLQJ WKH IROORZLQJ HTXDWLRQV ZKHUH UDb$X DQG UDb& DUH WKH UHODWLYH DWRPLF SHUFHQW FRQFHQWUDWLRQV RI JROG DQG FDUERQ UHVSHFWLYHO\ UDb$Xff>UDb$Xff UDb&ff@ UHODWLYH PDVV b $X UDb&ff>UDb$Xff UDb&ff@ UHODWLYH PDVV b & ,Q VRPH GLVFXVVLRQV RI WKH UHVXOWV LQ WKH IROORZLQJ FKDSWHU UHIHUHQFHV DUH PDGH WR WKH UDWLR RI JROG WR FDUERQ DQG YLFH YHUVD ,Q DOO LQVWDQFHV WKHVH GLVFXVVLRQV DUH UHIHUULQJ WR WKH DWRPLF UDWLRV RI WKH WZR HOHPHQWV 6FDQQLQJ (OHFWURQ 0LFURVFRS\ ZLWK (QHUJ\ 'LVSHUVLYH 6SHFWURVFRS\ 7KH 6(0('6 DQDO\VHV ZHUH FDUULHG RXW LQ RUGHU WR GHWHUPLQH f WKH DYHUDJH JUDLQ RU SDUWLFOH VL]H DQG VKDSH RI WKH VSHFLHV FRPSULVLQJ WKH DV GHSRVLWHG VDPSOH ILOPV DQG f WKH FKDQJH LQ ILOP VWUXFWXUH DVVRFLDWHG ZLWK YDULRXV DQQHDOLQJ UHJLPHV 7KHVH DQDO\VHV ZHUH SHUIRUPHG LQ D -(/ 6(0 HTXLSSHG ZLWK DQ ('6 V\VWHP ORFDWHG LQ WKH ODERUDWRU\ RI 3URI 0 $PPRQV LQ WKH &ROOHJH RI (QJLQHHULQJ &HQWHU IRU

PAGE 99

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

PAGE 100

WKH UHDFWLRQ SURGXFW ILOP FRQQHFWLQJ WKH HOHFWURGHV ZDV KHDWHG XQGHU K\GURJHQ DQG XQGHU DLU 7KH VHFRQG UHVLVWDQFH PHDVXUHPHQW PHWKRG XVHG D SRLQW SUREH WHFKQLTXH GHVFULEHG LQ GHWDLO E\ /% 9DOGHVWR GHWHUPLQH WKH VKHHW UHVLVWDQFH 5V LQ RKPVVTXDUH RI VDPSOH ILOPV FRDWHG RQ QRQFRQGXFWRUV JODVV TXDUW] 6FRWFK WDSHVf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ff 7KH FRUUHFWLRQ IDFWRU LV EDVHG RQ D SUREH VSDFLQJ HTXDO WR b RI WKH DYHUDJH VSHFLPHQ GLDPHWHU 6LQFH WKH SUREH VSDFLQJ ZDV PP DQG WKH DYHUDJH VDPSOH ILOP GLPHQVLRQV ZHUH QRW GLVFHUQLEOH GXH WR WKH PLFURVFRSLF GLVFRQWLQXLWLHV LQKHUHQW LQ WKH ILOPV WKH VKHHW UHVLVWDQFH YDOXHV FDQ EH YLHZHG RQO\ LQ UHODWLRQ WR HDFK RWKHU DQG WR WKH VWDQGDUG VSXWWHUHG $X ILOP VKHHW UHVLVWDQFH

PAGE 101

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

PAGE 102

WKH QH[W JURXS RI VFUHHQLQJ VWXG\ H[SHULPHQWV ZKLFK LQYHVWLJDWHG WKH XVH RI FDUERQDFHRXV JDVHV >&2 &2 &+ &+} &+f@ PL[HG ZLWK KHOLXP RU K\GURJHQ LQ WKH SURGXFWLRQ V\VWHP 7KH PRVW VXFFHVVIXO FDQGLGDWHV IURP WKLV JURXS RI H[SHULPHQWV DORQJ ZLWK VHYHUDO FKORURIOXRURFDUERQ+H JDV PL[WXUHV &+&,) &&A} DQFr Af ZHUH WKHQ VXEMHFWHG WR D VHULHV RI VHPLTXDQWLWDWLYH ILOWHU FDWFK UXQV LQ RUGHU WR GHWHUPLQH WKH RSWLPXP FRQGLWLRQV IRU $X WUDQVSRUW LQ WKH JDV VWUHDP )LQDOO\ WKH PRVW VXFFHVVIXO FRQGLWLRQV b +b &+ DW 3DVFDOVf ZHUH XWLOL]HG LQ WKH VXEVWUDWH FRDWLQJ DQG DQQHDOLQJ H[SHULPHQWV GHVFULEHG LQ WKH QH[W VHFWLRQ 7KH RQVHW RI JDV EUHDNGRZQ DQG VXEVHTXHQW HQHUJ\ ORVV LQ WKH JDVHRXV SODVPD SULRU WR WDUJHW LPSDFW ZDV WKH ILUVW SDUDPHWHU LQYHVWLJDWHG 6LQFH $UD\D HW DO KDG UHSRUWHG D SHDN LQ WKH SURGXFWLRQ UDWH RI XOWUDILQH PHWDO 7L )H 1L $O DQG 0Rf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

PAGE 103

DV WKH SKRWRLRQL]DWLRQ FURVVVHFWLRQV DQG WKH LRQL]DWLRQ SRWHQWLDOV 73 +XJKHV RIIHUV DQ H[FHOOHQW UHYLHZ RI ERWK WKHRU\ DQG H[SHULPHQWV GHDOLQJ ZLWK WKLV SKHQRPHQRQf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f WKH WDUJHW ZDV UHPRYHG DQG VWDQGDUG JUDGH KHOLXP ZDV VXSSOLHG WR WKH SODVPD FKDPEHU DW SUHVVXUHV UDQJLQJ IURP 3DVFDOV ZKLOH WKH ODVHU EHDP ZDV IRFXVHG LQWR WKH FHQWHU RI WKH FKDPEHU $W SUHVVXUHV JUHDWHU WKDQ 3DVFDOV DOO RI WKH ODVHU SXOVHV UHVXOWHG LQ JDV EUHDNGRZQ SODVPD IRUPDWLRQ $W 3D b RI WKH SXOVHV UHVXOWHG LQ JDV EUHDNGRZQ

PAGE 104

DW 3D b RI WKH SXOVHV UHVXOWHG LQ EUHDNGRZQ DQG DW 3D QR EUHDNGRZQ ZDV REVHUYHG VHH )LJXUH f $ VLPLODU H[SHULPHQW % ZDV SHUIRUPHG ZLWK WKH V\VWHP RSHQ WR WKH DWPRVSKHUH 3Df 7KH ILUVW IHZ SXOVHV GLG QRW LQLWLDWH JDV EUHDNGRZQ DV KDG RFFXUUHG LQ WKH LQLWLDO SODVPD FKDPEHU VWDUWXS WHVW DQG LQ H[SHULPHQW ZKHQ WKH JROG WDUJHW ZDV LQ SODFH +RZHYHU VXEVHTXHQW ODVHU SXOVHV LQWR WKH WDUJHWOHVV FKDPEHU FDXVHG JDV EUHDNGRZQ WR RFFXU b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n WR n VHFRQGV DQG WKH GXUDWLRQ RI WKH ODVHU SXOVH ZDV QVHF 7KXV WKHUH ZDV DPSOH WLPH IRU KHDWLQJ DQG YDSRUL]DWLRQ RI VRPH RI WKH $X GXULQJ WKH HDUO\ VWDJHV RI WKH LQFRPLQJ SXOVH 7KLV PHWDO YDSRU ZDV WKHQ HMHFWHG LQWR WKH DWPRVSKHUH LQ WKH SDWK RI WKH ODVHU EHDP 7KLV LQFUHDVHG WKH RSWLFDO GHQVLW\ RI WKH JDV DQG LQLWLDWHG WKH JDV EUHDNGRZQ REVHUYHG :KHQ WKH DPELHQW JDV SUHVVXUH ZDV ORZHUHG HQRXJK LQ VXEVHTXHQW H[SHULPHQWVf WKH HIIHFW RI WKH PHWDO YDSRU ZDV QRW JUHDW HQRXJK WR LQLWLDWH WKH LRQL]DWLRQ FDVFDGH OHDGLQJ WR JDV EUHDNGRZQ

PAGE 105

)LJXUH 3HUFHQW RI &2A /DVHU 3XOVHV 5HVXOWLQJ LQ +HOLXP *DV %UHDNGRZQ 9HUVXV 3UHVVXUH

PAGE 106

b RI 3XOVHV 5HVXOWLQJ LQ *DV %UHDNGRZQ FQ R R R 

PAGE 107

:KHQ WKH WDUJHW ZDV UHPRYHG DQG WKH V\VWHP ZDV OHIW RSHQ WR WKH DWPRVSKHUH QR JDV IORZf WKH ILUVW IHZ ODVHU SXOVHV LPSDFWHG RQ WKH FKDPEHU EDFN ZDOO DQG QR JDV EUHDNGRZQ RFFXUUHG +RZHYHU LW ZDV DSSDUHQW IURP WKH YLVLEOH LQWHUDFWLRQ RI WKH ODVHU EHDP ZLWK WKH JODVV VXUIDFH WKDW PDWHULDO SUREDEO\ K\GURFDUERQ FRQWDPLQDQWVf ZDV EHLQJ YDSRUL]HG DQG LQWURGXFHG LQWR WKH FKDPEHU DPELHQW ,W ZDV VSHFXODWHG WKDW VRPH RI WKLV PDWHULDO LQ WKH IRUP RI VPDOO SDUWLFOHV UDQGRPO\ GLIIXVHG WR ORFDWLRQV QHDU HQRXJK WR WKH EHDP IRFDO SRLQW WR EH YDSRUL]HG DQG LQFUHDVH WKH RSWLFDO GHQVLW\ RI WKH ORFDO JDV WR D SRLQW JUHDW HQRXJK WR LQLWLDWH JDV EUHDNGRZQ 3XOVHV WKDW GLG QRW FDXVH EUHDNGRZQ VWUXFN WKH EDFN ZDOO DQG LQWURGXFHG PRUH SDUWLFOHV LQWR WKH FKDPEHU 7KH XQSUHGLFWDEOH DSSHDUDQFH RI WKH JDV SODVPD GXULQJ WKH SDUW RI WKH H[SHULPHQW IROORZLQJ WKH ILUVW IHZ SXOVHV FRUUHODWHG ZHOO ZLWK WKLV H[SODQDWLRQ $V D UHVXOW RI WKHVH REVHUYDWLRQV DOO VXEVHTXHQW VFUHHQLQJ VWXG\ H[SHULPHQWV ZHUH SHUIRUPHG DW SUHVVXUHV 3D 9LVXDO LQVSHFWLRQ RI WKH SURGXFW UHFRYHU\ V\VWHPV DV GHVFULEHG HDUOLHU ZDV XVHG WR LQGLFDWH SRVLWLYH RU QHJDWLYH UHVXOWV LQ WKLV SKDVH RI WKH VWXG\ 5HIHUULQJ WR 7DEOH D +H+ JDV PL[WXUH ZDV WULHG DW SUHVVXUHV RI DQG 3DVFDOV ZLWK QHJDWLYH UHVXOWV +HOLXP ZDV WKHQ XVHG DORQH DW DQG 3D DOVR ZLWK QHJDWLYH UHVXOWV $UJRQ DW 3D DOVR \LHOGHG QHJDWLYH UHVXOWV DV GLG D PL[WXUH RI $U+ DW DQG 3D DQG D PL[WXUH DW 3D /DWHU LQ WKH VWXG\ DUJRQ DQG KHOLXP ZHUH VXEMHFWHG LQGLYLGXDOO\ WR VHPLTXDQWLWDWLYH JODVV ILEHU ILOWHU FDWFK H[SHULPHQWV DW 3D GLVFXVVHG EHORZf

PAGE 108

,Q DOO RI WKHVH H[SHULPHQWV H[FHSW WKH b $U UXQV WKH WDUJHW ZDV GHHSO\ FUDWHUHG DQG WKHUH ZHUH SLHFHV RI $X LQ WKH ERWWRP RI WKH FKDPEHU :KHQ b $U ZDV XVHG WKH WDUJHW LPSDFW SRLQW ZDV D VKDOORZ FUDWHU DQG WKHUH ZDV OLWWOH $X GHEULV LQ WKH FKDPEHU 7KH FROLQHDU VKDSH RI WKH SOXPH LQ WKH $U UXQV FRPSDUHG WR WKH PRUH VSKHULFDO SOXPHV ZLWK WKH RWKHU JDVHV LQGLFDWHG WKDW WKHUH ZDV VRPH SDUWLDO JDV EUHDNGRZQ RFFXUULQJ 7KLV REVHUYDWLRQ OHDG WR WKH VHOHFWLRQ RI +H IRU XVH DV WKH LQHUW GLOXHQW JDV LQ WKH UHPDLQGHU RI WKH VFUHHQLQJ VWXG\ 7KH QH[W H[SHULPHQW OLVWHG LQ 7DEOH XVHG D PL[WXUH RI KHOLXP DQG FDUERQ PRQR[LGH DW DQG 3D H[SW f *DV EUHDNGRZQ RFFXUUHG VHYHUDO FHQWLPHWHUV LQ IURQW RI WKH WDUJHW DW SUHVVXUHV DERYH 3D $W 3D WKH HQWLUH FKDPEHU SXOVHG D EULJKW ZKLWH 7KH SUHVVXUH ZDV ORZHUHG WR 3D DQG WKH V\VWHP ZDV DOORZHG WR UXQ IRU ODVHU SXOVHV %\ WKH HQG RI WKH H[SHULPHQW D EODFN VRRWOLNH VXEVWDQFH KDG WKLFNO\ FRDWHG WKH JODVV SODVPD FKDPEHU DQG FROOHFWHG LQ WKH JODVV ZRRO SOXJ LQ WKH SURGXFW UHFRYHU\ V\VWHP 7KH QH[W H[SHULPHQW OLVWHG f VWDUWHG ZLWK b KHOLXP DQG WKHQ &2 ZDV DGGHG LQFUHPHQWDOO\ ZKLOH PDLQWDLQLQJ WKH WRWDO SUHVVXUH DW 3D 6RPH VRRW IRUPDWLRQ ZDV REVHUYHG ZKHQ WKH &2 FRQFHQWUDWLRQ UHDFKHG b $V WKH FRQFHQWUDWLRQ ZDV LQFUHDVHG WR b DQG b WKH SURGXFWLRQ UDWH RI WKH VRRW LQFUHDVHG YLVLEO\ :KHQ WKH SUHVVXUH ZDV LQFUHDVHG WR 3D ZLWK WKH b PL[WXUH QR IXUWKHU SURGXFWLRQ RI VRRW ZDV QRWHG )LQDOO\ WKH &2 FRQFHQWUDWLRQ ZDV LQFUHDVHG WR b DQG WKH SUHVVXUH ZDV LQFUHDVHG WR 3D IRU D &2 SDUWLDO SUHVVXUH RI 3D $JDLQ QR IXUWKHU VRRW SURGXFWLRQ ZDV QRWHG

PAGE 109

7KH QH[W H[SHULPHQW OLVWHG f XVHG D PL[ RI +H&2 DW 3D DQG UDQ IRU SXOVHV $ FRSLRXV DPRXQW RI VRRW ZDV GHSRVLWHG RQ WKH SODVPD FKDPEHU ZDOOV DQG WUDSSHG RQ WKH JODVV ZRRO SOXJ *:3f LQ WKH SURGXFW UHFRYHU\ V\VWHP 7KHUH ZHUH QR YLVLEOH GHSRVLWV LQ WKH JODVV FROG WUDS DIWHU WKH *:3 7KLV WUDS ZDV VHDOHG DQG KHDWHG LQ D IODPH WR DQG WKHQ FRROHG ZLWK QR UHVXOWDQW YLVLEOH FKDQJH LQ DSSHDUDQFH LH FRORU FKDQJHf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b &+ DW 3D DQG ODVHU SXOVHV 7KH SURGXFW UHFRYHU\ V\VWHP XVHG LQ WKHVH H[SHULPHQWV KDG D WHVW WXEH SODFHG LQ WKH JDV VWUHDP DV LW H[LWHG WKH FKDPEHU VHH )LJXUH f ,Q WZR UXQV b DQG b &+f WKLV WXEH ZDV FRROHG WR ZLWK

PAGE 110

GU\LFH DQG LQ WKH WKLUG UXQ LW ZDV DW URRP WHPSHUDWXUH $ YHU\ OLJKW DPRXQW RI GHHS SXUSOHEODFN VRRW ZDV GHSRVLWHG RQ WKLV WHVW WXEH DQG LQ WKH FROG WUDS LQ WKH b &+ UXQ D YHU\ KHDY\ FRDWLQJ RI EODFN VRRW UHVXOWHG IURP WKH b UXQ DQG D PRGHUDWH DPRXQW RI EODFN VRRW ZDV FROOHFWHG LQ WKH b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

PAGE 111

)LJXUH $$ 6SHFWUXP RI &ROG 7UDS $FHWRQH ([WUDFW 6KRZLQJ (QKDQFHG $X 6LJQDO IURP 3DUWLFOHV

PAGE 112

7LPH PLQf R Sr R R

PAGE 113

WUDS ZDV VHDOHG DQG KHDWHG LQ D IODPH DV GHVFULEHG DERYH 7KH GDUN GHSRVLW GLG QRW FKDQJH VLJQLILFDQWO\ LQ DSSHDUDQFH XQWLO WKH WXEH ZDV XQVHDOHG DQG UHKHDWHG LQ DLU 7KH GDUN GHSRVLWV VHHPHG WR EXUQ RII DQG OHIW EHKLQG D WKLQ DUHD RI SLQN FRORUHG ILOP DVVRFLDWHG ZLWK WKH KHDYLHVW GHSRVLWV LQ WKH WUDS WKHVH ZHUH ORFDWHG DW WKH FROG OLQH RQ WKH LQOHW VLGHf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

PAGE 114

HIIHFWLYHO\ GHFUHDVLQJ WKH SRZHU GHQVLW\ IURP [ A WR [ A ZDWWVFPA 7KH WHVW ZDV UXQ IRU SXOVHV DW WKH ORZHU SRZHU GHQVLW\ ZLWK QHJDWLYH UHVXOWV 7KH IRFXV ZDV WKHQ RSWLPL]HG DQG ZLWKLQ D IHZ KXQGUHG SXOVHV YLVLEOH GHSRVLWV KDG DSSHDUHG LQ WKH ILUVW WZR FROG WUDSV DQG .f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f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

PAGE 115

DEXQGDQFH RI WKH $X ILOPV LQ UHODWLRQ WR WKH VRRW GHSRVLWV DSSHDUHG WR EH OHVV 7KHVH WHVWV DQG f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f DW 3D IRU D GXUDWLRQ RI SXOVHV 7KH UHVXOWV ZHUH SRVLWLYH EXW WKH UHODWLYH SURSRUWLRQ RI $X ILOP OHIW LQ WKH FROG WUDS DIWHU KHDWLQJ WKH EODFN GHSRVLWV ZDV OHVV WKDQ WKH DPRXQWV REVHUYHG LQ WKH +&+ H[SHULPHQWV 7KLV FRQFOXGHG WKH VFUHHQLQJ VWXG\ H[SHULPHQWV WKDW XVHG YLVXDO REVHUYDWLRQV WR HYDOXDWH UHVXOWV 7KH ILQDO VHULHV RI VFUHHQLQJ VWXG\ WHVWV ZHUH SHUIRUPHG XVLQJ WKH JODVV ILEHU ILOWHUV *))f DQG KROGHU GHVFULEHG LQ WKH ODVW FKDSWHU 7KHVH WHVWV SURYLGHG D VHPL TXDQWLWDWLYH PHDVXUH RI WKH DPRXQW RI $X WUDQVSRUWHG IURP WKH SODVPD

PAGE 116

]RQH WR WKH ILOWHU 7KH PDMRULW\ RI WKHVH WHVWV ODVWHG RYHU ODVHU SXOVHV 7KH WHVWV LQYROYLQJ WKH FKORURIOXRURFDUERQ JDV &+&,) ODVWHG DQG SXOVHV DQG WKH WHVWV LQYROYLQJ JUDSKLWH DQG FRSSHU WDUJHWV ODVWHG SXOVHV UHIHU WR 7DEOH IRU SXOVH YDOXHVf 7DEOH OLVWV WKH *)) UXQV ZLWK WKH JUDYLPHWULF DQG $$ UHVXOWV OLVWHG LQ ZHLJKW SHU SXOVHV 7KH *)) FDWFKHV WKDW FRQVLVWHG PDLQO\ RI ODUJH SDUWLFOHV WKRVH GLVFHUQLEOH XQGHU YLVXDO PLFURVFRS\f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f SUHVVXUH LQ WKHLU SXOVHG 1G<$* VWLPXODWHG SODVPD UHDFWLRQ V\VWHP DOWKRXJK WKHLU SHDN SURGXFWLRQ UDWH RFFXUUHG DW 3DVFDOV 7KH FRQFHQWUDWLRQ RI $X LQ WKH PDWHULDO SURGXFHG LQ WKHVH WHVWV UDQJHG IURP b ZLWK RQH RXWO\LQJ YDOXH RI b H[SW f 7KH WDUJHW ZDV URWDWHG RQO\ HYHU\ KRXUV LQ WKLV H[SHULPHQW DV RSSRVHG WR HYHU\ PLQXWHV LQ WKH RWKHU H[SHULPHQWV 7KH GHHS DQG YDULDEOH FUDWHULQJ RI WKH $X WDUJHW SURGXFHG YDU\LQJ QR]]OH FRQILJXUDWLRQV IRU WKH SOXPH H[SDQVLRQ GXULQJ WKH WHVW WLPH DQG DSSDUHQWO\ DIIHFWHG WKH DPRXQW RI FDUERQDFHRXV PDWHULDO LQFRUSRUDWHG LQ

PAGE 117

7DEOH )LOWHU &DWFK 3ODVPD ([SHULPHQW 5HVXOWV ([SW 1R *DV 0L[ 7DUJHW 7RWDO 3UHV 3Df &DUERQDFHRXV *DV 3UHV 3Df )LOWHU &DWFK LJ SXOVHVf 7RWDO JUDYf *ROG $$f *ROG $U $X +H $X FKK $X &++ $X &++ $X &++ $X N &++ $X FK $X &++ $X FRK $X &"+" $X &+&)+H $X &+&)+H $X &&")"+H $X r &&")"+H+" $X &R)J+H $X r &++ *UDSKLWH &++ &RSSHU &++ &RSSHU r f f r1HDUO\ DOO RI WKH PDWHULDO ZDV LQ WKH IRUP RI ODUJH SDUWLFOHV

PAGE 118

)LJXUH :HLJKW RI $X &ROOHFWHG E\ WKH *)) 9HUVXV &+A DQG &2 3DUWLDO 3UHVVXUHV

PAGE 119

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r 7KHVH FRPSRXQGV ZHUH QRW LQYHVWLJDWHG IXUWKHU GXH WR WKHLU SRWHQWLDO IRU FRQWDPLQDWLQJ WKH 9/6, PLFURFLUFXLWU\ ZLWK &O DQG ) DQG WKHLU ORZ LQFRUSRUDWLRQ RI $X DV HYLGHQFHG E\ WKH WDUJHW LPSDFWf 7KH RQH WHVW WKDW XVHG D JUDSKLWH WDUJHW DQG WKH +&+ JDV PL[WXUH DW 3D YHULILHG HDUOLHU REVHUYDWLRQV RI QR VRRW SURGXFWLRQ E\ SODVPDV XQGHU WKHVH FRQGLWLRQV 7KH WDUJHW ZDV GHHSO\ SLWWHG DIWHU SXOVHV DQG WKHUH ZDV D ODUJH DPRXQW RI SDUWLFXODWH GHEULV LQ WKH ERWWRP RI WKH FKDPEHU EXW WKH *)) ZDV HVVHQWLDOO\ FOHDQ 7KLV LQGLFDWHG WKDW WKH $X ZDV QHFHVVDU\ IRU WKH IRUPDWLRQ RI WKH

PAGE 120

,OO FDUERQDFHRXV PDWHULDO WKDW ZDV WUDQVSRUWHG WR WKH *)) DORQJ ZLWK WKH VXSHUILQH $X SDUWLFOHV 7KH WZR WHVWV WKDW XVHG D FRSSHU WDUJHW DQG WKH +&+ JDV PL[ DW 3D \LHOGHG QHJDWLYH UHVXOWV LQ WHUPV RI VXSHUILQH SDUWLFOH SURGXFWLRQ ,QVSHFWLRQ RI WKH WDUJHW DIWHU SXOVHV LQ WKH ILUVW WHVW UHYHDOHG YHU\ OLWWOH &X UHPRYDO LQ WKH PP GLD LPSDFW VSRW GHVSLWH RSHUDWLQJ DW WKH RSWLPXP OHQV IRFDO GLVWDQFH ,Q WKH VHFRQG H[SHULPHQW ZLWK WKH &X WDUJHW f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

PAGE 121

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a FP IURP WKH WDUJHW LPSDFW DQG H[SRVHG WR WKH SODVPD SURGXFHG LQ b +H DW 3D $IWHU ODVHU SXOVHV WKHVH SODWHV KDG D VKLQ\ PHWDOOLF $X FRDWLQJ VLPLODU WR WKRVH SURGXFHG LQ $X HYDSRUDWLRQ V\VWHPV 7KHUH ZDV QR FDUU\RYHU RI $X LQWR WKH UHFRYHU\ V\VWHP DQG WKH f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

PAGE 122

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

PAGE 123

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f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

PAGE 124

7KH VDPH W\SH RI VXEVWUDWH ZDV VXEMHFWHG WR SXOVHG UI KHDWLQJ XQGHU D YDFXXP 3Df DQG ORRNHG VLPLODU WR FRQYHFWLYHO\ KHDWHG VDPSOHV $ FRDWHG JODVV VXEVWUDWH DQQHDOHG XQGHU WKH VDPH FRQGLWLRQV GLG QRW H[KLELW D FRORU FKDQJH 7KHVH REVHUYDWLRQV LQGLFDWHG WKDW WKH DQQHDOLQJ HIIHFW RQ WKH : FRDWHG FKLS ZDV GXH WR WKH KHDWLQJ RI WKH : OD\HU DQG QRW WKH $X SODVPD SURGXFW WKLQ ILOP 7KH FRDWHG : RQ 6L VXEVWUDWHV WKDW ZHUH KHDWHG ZLWK WKH IRFXVHG DUJRQ LRQ ODVHU EHDP LQ DLU VKRZHG D YHU\ OLJKW WKLQ OLQH RI GLVFRORUDWLRQ GDUN EURZQf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

PAGE 125

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b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

PAGE 126

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b +b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b +Hb &+$8 SODVPD H[SHULPHQWV 7KHVH FRPSRXQGV DUH UHIHUUHG WR DV 353 WKURXJKRXW WKH UHPDLQGHU RI WKH WH[W DQG ILJXUH KHDGLQJV $Q\ GLIIHUHQW FRQGLWLRQV DUH QRWHG H[SOLFLWO\

PAGE 127

Q DPX )LJXUH 7RWDO ,RQ &RXQW 0DVV 6SHFWUD RI 7DUJHW 5HVLGXH

PAGE 128

7DEOH *&06 5HVXOWV IURP DQ $FHWRQH ([WUDFW RI +&+$8 3ODVPD 5HDFWLRQ 3URGXFWV 0HDVXUHG 0DVV 1R 3RLQWV $EVROXWH ,QWHQVLW\ b ,QW %DVH I r r r r

PAGE 129

,Q WKH WKLUG H[SHULPHQW D FROG WUDS FRDWHG ZLWK WKH 353 ZDV FRQQHFWHG WR WKH VROLGV SUREH LQOHW DQG KHDWHG WR ZKLOH REVHUYLQJ WKH PDVV UHVSRQVH IURP DPX 7KH UHVXOWV RI WKLV WHVW ZHUH VLPLODU WR WKH ILUVW 06 WHVW ZLWK WKH PRVW SURPLQHQW SHDNV RFFXUULQJ DW DQG DPX UHVXOWV QRW VKRZQf 1R VLJQLILFDQW SHDNV DSSHDUHG RYHU PDVV XQLWV ZKLOH D SUHSRQGHUDQFH RI WKH SHDNV DSSHDUHG EHORZ DPX 7KH IRXUWK H[SHULPHQW XWLOL]HG WKH 1LFROHW ,&506 WR ORRN DW D VDPSOH RI WKH FROG WUDS FRQWHQWV FROOHFWHG DIWHU D JODVV ZRRO SOXJ GXULQJ D 353 SURGXFWLRQ H[SHULPHQW 7KH PRVW SURPLQHQW SHDN ZDV DW PDVV DQG WKH UHPDLQGHU RI WKH SHDNV ZHUH EHORZ DPX UHVXOWV QRW VKRZQf $ VDPSOH RI WULHWK\OSKRVSKLQHJROG FKORULGH 7(3*&f ZDV SODFHG LQ WKH VROLGV SUREH IROORZLQJ WKLV DQDO\VLV DQG WKH UHVXOWDQW VSHFWUD RI WKH YRODWLOH $X FRPSRXQG )LJXUH f FRQILUPHG WKH LQVWUXPHQWnV UHVSRQVH 7KH SDUHQW LRQ SHDN PLQXV RQH +f DSSHDUHG DW DPX DQG WKH SDUHQW LRQ PLQXV &O DSSHDUV DW DPX ,Q WKH ILIWK 06 H[SHULPHQW D JODVV SODWH FRDWHG ZLWK 353 ZDV SODFHG LQ WKH LQKRXVH IDEULFDWHG ,&506 DGMDFHQW WR WKH ,&5 FHOO DQG REVHUYHG DV LW URVH WR r& RYHU RQH KRXU )LJXUH VKRZV WKH ODUJH DPRXQW RI ORZ PDVV SHDNV WKDW DSSHDUHG DW WZR PLQXWHV $IWHU PLQXWHV PDVV ZDV WKH PRVW SURPLQHQW SHDN )LJXUH f DQG PDVV ZDV VWDUWLQJ WR JURZ LQ %\ PLQXWHV PDVV KDG EHFRPH YHU\ SURPLQHQW PDVV ZDV SUHYDOHQW DQG PDVV ZDV VWLOO WKH KLJKHVW SHDN )LJXUH f $IWHU PLQXWHV WKH PDVV VLJQDO KDG GHFUHDVHG VXEVWDQWLDOO\ DQG PDVV ZDV WKH KLJKHVW SHDN ZKLOH PDVV KDG DOVR LQFUHDVHG )LJXUH f

PAGE 130

5(/$7,9( ,17(16,7< )LJXUH ,&506 RI 7ULHWK\OSKRVSKLQH *ROG &KORULGH

PAGE 131

)LJXUH ,&506 DPXf RI 353 0LQXWHV

PAGE 132

5(/$7,9( ,17(16,7< )LJXUH ,&506 DPXf RI 353 0LQXWHV

PAGE 133

5(/$7,9( ,17(16,7< )LJXUH ,&506 DPXf RI 353 0LQXWHV

PAGE 134

5(/$7,9( ,17(16,7< )LJXUH ,&506 DPXf RI 353 0LQXWHV

PAGE 135

$W WKLV SRLQW WKH SXOVHG 1G<$* ODVHU ZDV XVHG WR LUUDGLDWH WKH VDPSOH DQG WKH PDVV VLJQDO LQFUHDVHG GUDPDWLFDOO\ )LJXUH f (YHQ DIWHU PLQXWHV RI FRQWLQXRXV SXOVLQJ ZLWK WKH ODVHU WKH PDVV VLJQDO VWLOO GRPLQDWHG WKH VSHFWUXP )LJXUH f 1H[W WKH HOHFWURQ EHDP ZDV WXUQHG RII DQG WKH VSHFWUXP ZDV UHFRUGHG ZKLOH WKH ODVHU ZDV VWLOO SXOVLQJ )LJXUH VKRZV WKH UHVXOWDQW PDVV VSHFWUD ZLWK QR SHDNV RYHU DPX VLJQLILFDQWO\ VWURQJHU WKDQ WKH EDFNJURXQG 7KLV H[SHULPHQW ZDV UHSHDWHG LQ WKH 1LFROHW ,&506 DQG VSHFWUD ZHUH UHFRUGHG DW WHPSHUDWXUHV RI ar& )LJXUHV DQG f r& )LJXUH f DQG r& )LJXUHV DQG f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f &,' UHDFWLRQV ZHUH UXQ RQ WKH KLJK PDVV SHDNV DQG )LJXUHV DQG VKRZ WKH UHVXOWV RI &,' RQ PDVV DW FROOLVLRQ WLPH DQG DIWHU PVHF RI FROOLVLRQ WLPH UHVSHFWLYHO\ 7KH PDMRU SURGXFW DSSHDUHG DW PDVV 7KH &,' RQ PDVV XQGHU WKH VDPH FRQGLWLRQV LV VKRZQ LQ )LJXUHV DQG 6RPH LQFUHDVH LQ PDVV VLJQDO DQG WKH DSSHDUDQFH RI D PRGHUDWH VLJQDO DW DPX ZHUH WKH RQO\ FKDQJHV QRWHG 7KH &,' UHDFWLRQV RQ WKH UHPDLQLQJ FRPSRXQGV

PAGE 136

5(/$7,9( ,17(16,7< )LJXUH ,&506 DPXf RI 353 0LQXWHV /DVHU 2Q

PAGE 137

5(/$7,9( ,17(16,7< )LJXUH ,&506 DPXf RI 353 0LQXWHV /DVHU 2Q

PAGE 138

)LJXUH ,&506 DPXf RI 353 /DVHU 2Q H%HDP 2II 5(/$7,9( ,17(16,7<

PAGE 139

)LJXUH ,&506 DPXf RI 353 DW Ar&

PAGE 140

5(/$7,9( ,17(16( )LJXUH ,&506 DPXf RI 353 DW rr&

PAGE 141

)LJXUH ,&506 5HODWLYH ,QWHQVLW\ ==O

PAGE 142

)LJXUH ,&506 DPXf RI 353 DW r&

PAGE 143

5HODWLYH ,QWHQVLW\ )LJXUH ,&506 DPXf RI 353 DW r&

PAGE 144

*2 HQ )LJXUH ,&506 RI &,' RI 0DVV 1R &ROOLVVLRQ 7LPH

PAGE 145

)LJXUH ,&506 RI &,' RI 0DVV PVHF &ROOLVLRQ 7LPH

PAGE 146

5HODWLYH ,QWHQVLW\ &2 )LJXUH ,&506 RI &,' RI 0DVV 1R &ROOLVLRQ 7LPH

PAGE 147

5HODWLYH ,QWHQVLW\ )LJXUH ,&506 RI &,' RI 0DVV PVHF &ROOLVLRQ 7LPH

PAGE 148

PHQWLRQHG ZHUH DOO QHJDWLYH ZLWK UHVSHFW WR WKH DSSHDUDQFH RI $X LRQ 0DVV ZDV LGHQWLILHG DV &2 E\ D FKDUJH WUDQVIHU UHDFWLRQ ZLWK ZDWHU 7KXV WKH SUHVHQFH RI YRODWLOH $X FRPSRXQGV FRXOG QRW EH HVWDEOLVKHG E\ WKH 06 VWXG\ UHVXOWV 7KH LGHQWLILFDWLRQ RI &2 DQG WKH XELTXLWRXV SUHVHQFH RI D FRPSRXQG ZLWK D FKDUJH WR PDVV UDWLR RI RU ZDV ILUPO\ HVWDEOLVKHG DV ZDV WKH SUHVHQFH RI PDQ\ ORZ PDVV FRPSRXQGV DPXf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f E\ DGGLQJ &+ WR WKH +H JDV QRUPDOO\ XVHG LQ WKH FOXVWHU EHDP DSSDUDWXV 7KH UHVXOWV FRQILUPHG WKDW WKLV ZDV SRVVLEOH 5HFDOO WKDW WKH KRUL]RQWDO GHIOHFWRU +'f YROWDJH GLUHFWO\ DIIHFWHG WKH LRQ VLJQDOV DV SUHYLRXVO\ GLVFXVVHG 7KXV ZKHQ D VSHFWUD VFDQQLQJ VHYHUDO KXQGUHG DPX ZDV UHFRUGHG WKH JUHDWHVW VHQVLWLYLW\ ZDV IRU WKH FHQWUDO PDVV UHJLRQ 7KLV OLPLWDWLRQ GLG QRW DSSO\ WR WKH QDUURZ UDQJH VFDQV DPXf $OO RI WKH FRPSDUDWLYH VSHFWUD RI VSHFLHV IRUPHG LQ +H DQG +H&+ SODVPDV ZHUH UHFRUGHG DW WKH VDPH +' YROWDJHV

PAGE 149

,W VKRXOG DOVR EH QRWHG WKDW WKHUH DUH VHYHUDO SRVVLEOH PHFKDQLVPV UHVSRQVLEOH IRU WKH REVHUYHG FKDQJHV LQ WKH SRVLWLYH LRQ VSHFWUD ZKHQ WKH &+ JDV ZDV DGGHG WR WKH SODVPD 7KH WKUHH PDMRU PHFKDQLVPV DUH f QHXWUDOL]DWLRQ $XQf 5f $XQf 5 f FRPELQDWLRQGLVVRFLDWLRQ $XQf $X $XQf f LRQ SURGXFW UHDFWLRQV $XQf 5 +H $XQf5 +Hr $XQf 5 +H $XQf5 +Hr $XQf5 +Hr $XQf5 +H Hn $XQf5 $X +H $XQf5 +Hr ZKHUH WKH r GHQRWHV D WUDQVDWLRQDOO\ KRW VSHFLHV 1R DWWHPSW ZDV PDGH WR LGHQWLI\ DQ\ RI WKHVH RU DQ\ RWKHU PHFKDQLVPV DV WKH RQHVf UHVSRQVLEOH IRU WKH FKDQJHV LQ LRQ VLJQDOV REVHUYHG )LJXUH VKRZV WKH $X WR $8 LRQ VLJQDOV DORQJ ZLWK UHVSHFWLYH ILUVW DQG VHFRQG R[LGH SHDNV ZKLFK ZHUH IRUPHG LQ WKH +H SODVPD 7KH R[LGH SHDNV ZHUH XELTXLWRXV LQ WKLV DSSDUDWXV DQG PRVW OLNHO\ ZHUH IRUPHG IURP UHVLGXDO PRLVWXUH LQ WKH WDUJHW DQG KROGHUf :KHQ b &+ ZDV DGGHG WR WKH +H JDV VWUHDP D GUDPDWLF FKDQJH LQ WKH LRQ VSHFWUD RFFXUUHG )LJXUH f 7KH $X DQG $Xe VLJQDOV GHFUHDVHG E\ QHDUO\ WZR RUGHUV RI PDJQLWXGH WKH $8 VLJQDO GHFUHDVHG E\ D IDFWRU RI WKUHH WKH $8 VLJQDO GHFUHDVHG E\ D IDFWRU RI VHYHQ DQG WKH $8 VLJQDO LQFUHDVHG

PAGE 150

,QWHQVLW\ YROWVf

PAGE 151

Lf§ 7KRXVDQGV DPX )LJXUH 72)06 RI $X WR $XA &OXVWHUV )RUPHG LQ b &+A+H 3ODVPD

PAGE 152

E\ RQH RUGHU RI PDJQLWXGH 7KHUH ZDV DOVR D SOHWKRUD RI QHZ SHDNV ZKLFK DSSHDUHG DW VWDJJHUHG LQWHUYDOV DIWHU HDFK $X FOXVWHU SHDN 6LPLODU VFDQV RI WKH $8 WR $8 UHJLRQ )LJXUHV DQG f VKRZHG WKH VDPH HIIHFW RI DGGLWLRQDO SHDNV DSSHDULQJ ZKHQ &+ ZDV DGGHG WR WKH SODVPD 7KHVH VSHFWUD DOVR VKRZ WKH ODUJH LQFUHDVH LQ WKH $8 VLJQDO DQG LWV R[LGHVf DV ZHOO DV PRGHUDWH LQFUHDVHV LQ WKH $XJ DQG $8 VLJQDOV 2QFH DJDLQ WKH $8 VLJQDO DSSHDUHG WR EH UHODWLYHO\ LQVHQVLWLYH WR WKH DGGLWLRQ RI &+ WR WKH SODVPD 7KH H[SHULPHQW ZDV UHSHDWHG ZLWK WKH +' VHW WR RSWLPL]H WKH $X VLJQDO )LJXUHV DQG VKRZ WKH VSHFWUD IURP VSHFLHV SURGXFHG LQ WKH KHOLXP DQG KHOLXPPHWKDQH SODVPDV UHVSHFWLYHO\ 7KHVH VSHFWUD LQGLFDWH WKH KLJK VHQVLWLYLW\ RI WKH $X $X2 DQG $X2e VLJQDOV WR WKH SODVPD FRQGLWLRQV 7KH PRVW SURPLQHQW QHZ SHDNV RFFXUUHG DW DQG PDVV XQLWV DERYH WKH $X PDVVf 7KHVH SHDNV ZHUH HYLGHQWO\ GXH WR WKH DGGLWLRQ RI FDUERQ DQG K\GURJHQ WR WKH $X DQG $X2 VSHFLHV )RU H[DPSOH WKH ODUJHVW SHDN DW PDVV XQLWV FRXOG KDYH EHHQ GXH WR HLWKHU $8&+ RU $82& DPRQJ RWKHU SRVVLELOLWLHV 7KH $X UHJLRQ ZDV REVHUYHG LQ WKH QH[W H[SHULPHQW DQG WKH VSHFWUD DUH SUHVHQWHG LQ )LJXUHV DQG 7KH SDWWHUQ RI DGGLWLRQDO SHDNV ZDV HYHQ PRUH SURQRXQFHG LQ WKLV WHVW 7KH\ DSSHDUHG DW DQG PDVV XQLWV DERYH WKH $Xe VLJQDO DW DPX 7KLV ZDV VWURQJO\ VXJJHVWLYH RI WKH RUGHUHG DGGLWLRQ RI & &+ &+ &+ &+ &+ &J+ &+ &J+ &J&+ DQG &MRK WR WKH $X GLPHU 7KH VLJQDOV DW DQG GRPLQDWHG WKH QHZ SHDNV 9HU\ VLPLODU UHVXOWV ZHUH REVHUYHG LQ WKH $8 VSHFWUXP ZKHQ &+ ZDV DGGHG WR WKH SODVPD 7KH EHIRUH DQG DIWHU VSHFWUD SUHVHQWHG LQ

PAGE 153

,QWHQVLW\ YROWVf > U Ua 7KRXVDQGV DPX )LJXUH 72)06 RI $XA WR $XJ )RUPHG LQ +HOLXP 3ODVPD DFWR\UL mQLO

PAGE 154

)LJXUH 72)06 RI $XA WR $XJ )RUPHG LQ b &+A+H 3ODVPD

PAGE 155

,QWHQVLW\ YROWVf $X ?$D$W $X2 $X2 :O U&7! DPX )LJXUH 72)06 ([SDQGHG $X 5HJLRQ IURP +HOLXP 3ODVPDf

PAGE 156

R !! Ff F FX F $X $X2+ $X+ $X2 $X2 n9AO9 nQ Y :? \ 99YB$Y n‘ aU 7 m2 DPX )LJXUH 72)06 ([SDQGHG $X 5HJLRQ IURP b &++H 3ODVPDf 3r

PAGE 159

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

PAGE 160

)LJXUH 72)06 ([SDQGHG $XA 5HJLRQ IURP +H 3ODVPDf

PAGE 161

)LJXUH 72)06 ([SDQGHG $XA 5HJLRQ IURP b &+A+H 3ODVPDf

PAGE 162

VXEMHFWHG WR IXUWKHU DQDO\VHV WR GHWHUPLQH VRPH RI WKHLU SURSHUWLHV 7KHVH DQDO\VHV ZHUH DOVR LQWHQGHG WR GHWHUPLQH WKH VWDWH RI WKH $X LQ WKH 353 *ROG 7KLQ )LOP &KDUDFWHUL]DWLRQ 5HVXOWV 9LVLEOH $EVRUSWLRQ 6SHFWURVFRS\ )LJXUH VKRZV WKH UHVXOWV RI YLVLEOH DEVRUSWLRQ VSHFWUD QPf RI DFHWRQH H[WUDFWVXVSHQVLRQV RI 353 IRUPHG LQ SXUH &+ +H&2 DQG +H&+DLU SODVPDV 7KH VSHFWUD RI QJ $XPO ZDWHUf DQG QJ $XPO DFHWRQHf DUH DOVR LQFOXGHG LQ WKLV ILJXUH 7KH PRVW VLJQLILFDQW IHDWXUH RI WKHVH VSHFWUD LV WKH SUHVHQFH RI WKH $X PHWDOOLF DEVRUSWLRQ EDQG FHQWHUHG DW QP LQ WKH +H&2 DQG +H&+DLU 353 H[WUDFWVXVSHQVLRQV GHQRWLQJ WKH SUHVHQFH RI VXVSHQGHG $X SDUWLFOHV 7KH FRQVSLFXRXV DEVHQFH RI WKLV EDQG LQ WKH &+ 353 H[WUDFWVXVSHQVLRQ DJUHHG ZLWK HDUOLHU REVHUYDWLRQV LQ WKH VFUHHQLQJ VWXG\ 2SWLFDO 0LFURUHIOHFWRPHWU\ 5HIOHFWDQFH VSHFWUD QP ZHUH UHFRUGHG IRU WKH +DUULV 6WDQGDUG VSXWWHUHG $X ILOP )LJXUH f 353 FRDWHG :6L )LJXUH f 353 FRDWHG JODVV )LJXUH f DQG 353 FRDWHG 6FRWFK EUDQG EODFN HOHFWULFDO WDSH DQG WUDQVSDUHQW WDSH )LJXUH f 7KH PDMRU FRPSDUDWLYH IHDWXUHV LQ WKHVH VSHFWUD DUH WKH VKDUS LQFUHDVH LQ UHIOHFWLRQ RI $X EHWZHHQ DQG QP DQG WKH UHODWLYHO\ KLJK UHIOHFWLYLW\ RI $X IURP QP VHH )LJXUH f

PAGE 163

$EVRUEDQFH R :DYHOHQJWK QPf )LJXUH 9LVLEOH $EVRUEDQFH 6SHFWUD RI $FHWRQH ([WUDFWV RI 5HDFWLRQ 3URGXFWV IURP &+A$X +H&2$X DQG +H&+A$LU$X 3ODVPDV

PAGE 164

 L :DYHOHQJWK QPf )LJXUH 9LVLEOH 5HIOHFWDQFH 6SHFWUD RI +DUULV 6WQG 6SXWWHUHG $X )LOP

PAGE 165

:DYHOHQJWK QPf 9LVLEOH 5HIOHFWDQFH 6SHFWUD RI 353 RQ :6L f§rf§ $V 'HSRVLWHG ffff $QQHDOHG LQ +J r& KU &&7! UH $QQHDOHG LQ $LU r& KUV (WFKHG 6SRW RQ $LU $QQHDO 6DPSOH

PAGE 166

HQ A ZR B@ :DYHOHQJWK QPf UH 9LVLEOH 5HIOHFWDQFH 6SHFWUD RI 353 RQ *ODVV $f r& 'HSRVLWLRQ %f $IWHU r& KU +" $QQHDO DQG &f r& 'HSRVLWLRQ

PAGE 167

HQ f§, :DYHOHQJWK QPf IH UH 9LVLEOH 5HIOHFWLRQ 6SHFWUD RI 353 RQ $f $GKHVLYH 6LGH 6FRWFK %UDQG 7UDQVSDUHQW 7DSH %f %DFN 6LGH 6FRWFK %UDQG %ODFN (OHFWULFDO 7DSH

PAGE 168

,Q )LJXUH WKH UHIOHFWDQFH VSHFWUD IRU WKH 353 RQ :6L DUH FRPSDUHG IRU IRXU GLIIHUHQW VDPSOHV $VGHSRVLWHG DLUDQQHDOHG DQG K\GURJHQDQQHDOHG VDPSOHV DOO KDG VLPLODU VSHFWUD ZLWK QR VKDUS LQFUHDVH LQ UHIOHFWLYLW\ DQG RYHUDOO ORZ UHIOHFWLYLW\ EHORZ QP 7KLV ZDV LQGLFDWLYH RI KLJKO\ FDUERQ FRQWDPLQDWHG ILOPV 7KH VDPSOH WKDW ZDV VXEMHFWHG WR DUJRQ LRQ HWFKLQJ GLVSOD\HG WKH : UHIOHFWLRQ VSHFWUXP LQGLFDWLQJ UHPRYDO RI WKH DQQHDOHG 353 ILOP E\ WKH HWFKLQJ SURFHVV 7KH FRDWHG JODVV VXEVWUDWHV GLVSOD\HG WKH PRVW YDULDEOH VSHFWUD 7KH DVGHSRVLWHG VDPSOH VSHFWUXP ZDV VLPLODU WR WKH FRDWHG :6L VSHFWUD ZKLOH WKH DLUDQQHDOHG VDPSOH RQ JODVV GLVSOD\HG WKH VKDUS WUDQVLWLRQ DW QP EXW ZDV QRW KLJKO\ UHIOHFWLYH XQWLO QP 7KH JODVV SODWH WKDW ZDV FRDWHG ZLWK 353 DW r& ZDV WKH PRVW VLPLODU WR WKH $X VWDQGDUG LQ LWV UHIOHFWDQFH SURSHUWLHV ZLWK WKH VKDUS WUDQVLWLRQ RFFXUULQJ DW QP DQG KLJK UHIOHFWLYLW\ ODVWLQJ WR QP 7KH WZR WDSH VDPSOHV DOVR GLVSOD\HG VKDUS WUDQVLWLRQV DW QP LQGLFDWLQJ WKDW WKH 353 ILOP ZDV KLJKO\ UHIOHFWLYH DV GHSRVLWHG RQ WKHVH VXEVWUDWHV 7KH FRDWHG DGKHVLYH VLGH RI WKH WUDQVSDUHQW WDSH ZDV SDUWLFXODUO\ UHIOHFWLYH DV LWV VSHFWUXP VKRZV )LJXUH f 7KHVH VSHFWUD SURYLGHG D PHDVXUH RI WKH 353 UHIOHFWDQFH SURSHUWLHV RQ WKH GLIIHUHQW VXEVWUDWHV 7KH\ DOVR LQGLFDWHG WKH ORZ UHIOHFWLYLW\ RI WKH GDUN FRORUHG ILOPV RQ :6L VXEVWUDWHV DQG WKH KLJKO\ UHIOHFWLYH PHWDOOLF ORRNLQJ ILOP RQ WKH WUDQVSDUHQW WDSH r& GHSRVLWLRQf DQG WKH r& GHSRVLWHG ILOP RQ JODVV

PAGE 169

;5D\ 3KRWRHOHFWURQ 6SHFWURVFRS\ 7KH ;36 VWXGLHV GHWHUPLQHG WKH 353 ILOP FRPSRVLWLRQV DQG WKH ELQGLQJ HQHUJ\ RI WKH $X LQ WKH ILOPV 7KUHH W\SHV RI 353 VDPSOHV FRDWHG RQ :6L ZHUH DQDO\]HG DORQJ ZLWK WKH +DUULV VWDQGDUG $X ILOP DV GHSRVLWHG DQQHDOHG LQ DLU DW r& RU r& IRU KRXUV DQG DQQHDOHG LQ + DW r& IRU KRXUV DQG r& IRU RQH KRXU 7KH +DUULV VWDQGDUG DQG RQH HDFK RI WKH DLU DQG + DQQHDOHG VDPSOHV ZHUH VXEMHFWHG WR $U LRQ HWFKLQJ DV GHVFULEHG HDUOLHU 7KH SKRWRHOHFWURQ WDNHRII DQJOH 7KHWDf ZDV UHODWLYHO\ ORZ rf LQ WKH ILUVW WZR HWFK UXQV OLVWHG 7KH WKLUG HWFKHG VDPSOH ZDV DOVR VXEMHFWHG WR LQLWLDO DQDO\VHV DW 7KHWD HTXDO WR r DQG r 7KH RWKHU VDPSOHV ZHUH VXEMHFWHG WR VXUIDFH DQDO\VHV DW D KLJK 7KHWD RI r 7KH ;36 DQD\WLFDO FRQGLWLRQV DQG UHVXOWV DUH OLVWHG LQ 7DEOH 7KH KHDY\ DWRPLF FRQFHQWUDWLRQ RI & RQ WKH VXUIDFH bf RI WKH VWDQGDUG $X ILOP ZDV LQGLFDWLYH RI WKH KDQGOLQJ WKDW WKH VDPSOH H[SHULHQFHG EHIRUH DQDO\VLV 7KH & FRQFHQWUDWLRQ IHOO WR RI LWV VWDUWLQJ FRQFHQWUDWLRQ DIWHU PLQXWHV RI HWFKLQJ $IWHU RQH KRXU RI HWFKLQJ WKH & PDVV FRQFHQWUDWLRQ ZDV VWDEOH DW b 7KH DWRPLF FRQFHQWUDWLRQ RI WKH $X LQ WKH EXON LH DIWHU RQH KRXU RI HWFKLQJf ZDV b RU b PDVV FRQFHQWUDWLRQ 7KH 353 ILOP VDPSOH IURP H[SHULPHQW WKDW KDG EHHQ DQQHDOHG LQ DLU DQG VXEMHFWHG WR SURILOH DQDO\VLV VKRZHG D PD[LPXP JROG PDVV FRQFHQWUDWLRQ RI b DIWHU PLQXWHV RI HWFKLQJ $IWHU PLQXWHV RI HWFKLQJ WKH $X FRQFHQWUDWLRQ GURSSHG WR PDVV SHUFHQW DQG

PAGE 170

7DEOH ;36 $QDO\WLFDO &RQGLWLRQV DQG 5HVXOWV ,QVWUXn PHQW 6DPSOH $QJOH $X I $X & ,V & (WFK 7LPH PLQf %( H9f :LGWK H9f $WRPLF b 0DVV b %( H9f :LGWK H9f $WRPLF b 0DVV b 5HODWLYH b *&$ +DUULV 6WQG r f§ r r *&$ $LU r& KU .UDWRV B B + r& KU .UDWRV +DUULV 6WQG .UDWRV + r& KU .UDWRV $LU r& KU .UDWRV DV GHSRVLWHG r6DPSOH QRW JURXQGHG SURSHUO\ A8VHG DV FDOLEUDWLRQ VWDQGDUG WR DGMXVW LQVWUXPHQW VFDOH

PAGE 171

LW ZDV REYLRXV IURP YLVXDO LQVSHFWLRQ DIWHU WKH UXQ WKDW WKH ILOP ZDV QHDUO\ HWFKHG DZD\ 7KH VHFRQG VDPSOH 353 ILOP WKDW ZDV VXEMHFWHG WR GHSWK SURILOH DQDO\VLV ZDV DQ DLU DQQHDOHG ILOP IURP H[SHULPHQW 7KLV ILOP KDG D QHDU VXUIDFH & DWRPLF FRQFHQWUDWLRQ RI b GHWHUPLQHG E\ D 7KHWD r LQLWLDO VFDQ $ 7KHWD r LQLWLDO VFDQ VKRZHG D & DWRPLF FRQFHQWUDWLRQ RI b LQGLFDWLQJ WKH QHDU VXUIDFH QDWXUH RI WKH FDUERQ 7KH $X FRQFHQWUDWLRQ ZDV DWRPLF SHUFHQW b PDVVf XQGHU WKH VDPH FRQGLWLRQV $IWHU PLQXWHV RI HWFKLQJ WKH $X FRQFHQWUDWLRQ ZDV DWRPLF SHUFHQW b PDVVf $IWHU RQH KRXU RI HWFKLQJ WKH EXON $X DWRPLF FRQFHQWUDWLRQ LQ WKLV ILOP ZDV GHWHUPLQHG WR EH b RU b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bf VXUIDFH DQDO\VHV LQ RUGHU WR REVHUYH ELQGLQJ HQHUJ\ %(f VKLIWV KDG $X DWRPLF FRQFHQWUDWLRQV RI b +DUULV VWGf b + DQQHDOf b DLU DQQHDOf DQG b DV GHSRVLWHGf 7KHVH FRQFHQWUDWLRQV ZHUH FRQVLVWHQW ZLWK WKH RWKHU DQDO\VHV DQG VKRZHG WKDW WKH $X& UDWLRV ZHUH PRUH GHSHQGHQW RQ WKH VDPSOH VRXUFH WKDQ RQ WKH

PAGE 172

,QWHQVLW\ &RXQWVf

PAGE 173

,QWHQVLW\ &RXQWVf )LJXUH ;36 6FDQ RI $X I 3HDNV DW +LJK DQG /RZ 3KRWRHOHFWURQ 7DNHRII $QJOHV

PAGE 174

,QWHQVLW\ &RXQWVf )LJXUH ;36 6FDQ RI & 3HDN DW +LJK DQG /RZ 3KRWRHOHFWURQ 7DNHRII $QJOHV

PAGE 175

DQQHDOLQJ FRQGLWLRQV %RWK WKH + DQG DLU DQQHDOHG VDPSOHV IURP KDG WKH VDPH EXON $X PDVV FRQFHQWUDWLRQ RI b (YHQ WKH XQDQQHDOHG VDPSOH IURP KDG WKH VDPH EXON $X PDVV FRQFHQWUDWLRQ DV LWV DLU DQQHDOHG FRXQWHUSDUW bf 7KHVH UHVXOWV ZHUH DOVR FRQVLVWHQW ZLWK WKH UHVXOWV RI WKH JUDYLPHWULF$$ VWXG\ ZKLFK LQGLFDWHG D UDQJH RI b $X PDVV FRQFHQWUDWLRQ LQ WKH DV GHSRVLWHG ILOPV ZLWK DQ DYHUDJH YDOXH RI b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nrp 6FDQQLQJ (OHFWURQ 6SHFWURVFRS\ ZLWK (QHUJ\ 'LVSHUVLYH 6SHFWURVFRS\ 7KH 6(0('6 DQDO\VHV ZHUH SHUIRUPHG RQ WKH VWDQGDUG $X ILOP DQG 353 FRDWHG VF :6L JODVV DQG SRO\PHULF WDSH VXEVWUDWHV LQ RUGHU WR GHWHUPLQH JUDLQ VL]H DQG ILOP PRUSKRORJ\ 7KH +DUULV VWDQGDUG VSXWWHU GHSRVLWHG $X ILOP ZDV SKRWRJUDSKHG DV UHFHLYHG DQG DIWHU XQGHUJRLQJ RQH KRXU RI $U LRQ HWFKLQJ LQ WKH ;36 VWXG\ )LJXUHV DQG f 7KH SHEEOHOLNH ILOP KDG D VXUIDFH JUDLQ VL]H RI QP DQG ZDV IDLUO\ XQLIRUP LQ DSSHDUDQFH 7KLV LV D W\SLFDO VWUXFWXUH IRU D VSXWWHU GHSRVLWHG $X ILOP DQG LV LQGLFDWLYH RI WKUHH GLPHQVLRQDO KLOORFN JURZWK

PAGE 176

)LJXUH 6(0 3KRWRJUDSK RI +DUULV 6WQG 6SXWWHUHG $X )L

PAGE 177

*&

PAGE 178

)LJXUH 6(0 3KRWRJUDSK RI +DUULV 6WQG 6SXWWHUHG $X )LOP $IWHU +RXU RI $UJRQ ,RQ (WFKLQJ

PAGE 180

RQ LVODQGV 7KLV ZDV YHULILHG E\ WKH 6(0 RI WKH VDPH ILOP DIWHU HWFKLQJ ZKLFK UHYHDOHG WKH XQGHUO\LQJ $X LVODQG VWUXFWXUH 7KH HDUO\ VWDJHV RI WKH KLOORFN IRUPDWLRQ DUH YLVLEOH RQ WKH ODUJHU LVODQG VWUXFWXUHV )LJXUH f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f 7KH 6(0 YLHZ RI WKLV VDPSOH ZDV QRW UHYHDOLQJ GXH WR WKH PRXQWLQJ WHFKQLTXH +RZHYHU WKH DV GHSRVLWHG 353 ILOP RQ VF :6L FOHDUO\ VKRZHG D XQLIRUP JUDLQ RI $QJVWURPV )LJXUH f 7KH .9 ('6 VSHFWUXP RI WKLV VXUIDFH )LJXUH f LQGLFDWHG WKDW WKH $X& ILOP ZDV YHU\ WKLQ $ ORZHU HQHUJ\ VSHFWUXP ZDV QRW UHFRUGHG IRU WKLV VDPSOH 7KH 6(0 SKRWRJUDSK RI WKH DLU DQQHDOHG 353 ILOP RQ VF :6L )LJXUH f VKRZV D VLPLODU XQLIRUP JUDLQ VL]H EXW WKH VWUXFWXUH LV DOWHUHG VLJQLILFDQWO\ 7KH $X SDUWLFXOHV DSSHDU WR KDYH MRLQHG WR IRUP D FKDLQPDLO W\SH RI VWUXFWXUH ZLWK WKH FDUERQDFHRXV PDWHULDO ORFDWHG LQ WKH LQWHUVWLWLDO DUHDV 7KH DQG .9 ('6 VSHFWUD RI WKLV VXUIDFH DUH SUHVHQWHG LQ )LJXUHV DQG 7KH VWURQJ $X VLJQDO LQ WKH IRUPHU VSHFWUXP YHUVXV WKH KLJKHU HQHUJ\ VSHFWUXP DJDLQ LOOXVWUDWHV WKH

PAGE 181

,QWHQVLW\ FRXQWVf r9) H9 QR )LJXUH ('6 RI +DUULV 6WQG 6SXWWHUHG $X )LOP RQ 6L .9 r9HUWLFDO )XOO6FDOH &RXQWV

PAGE 182

,QWHQVLW\ FRXQWVf ,I + L M 5  /, 5 8 8 M n  OLW L M 997nM f777UUYA M QLAL //Of§// r9)6 H 9 )LJXUH ('6 RI +A&+A$X 3ODVPD 5HDFWLRQ 3URGXFW 353f .9 r9HUWLFDO )XOO6FDOH &RXQWV

PAGE 183

)LJXUH 6(0 3KRWRJUDSK RI 353 RQ :6L

PAGE 185

,QWHQVLW\ FRXQWVf )LJXUH ('6 RI 353 RQ :6L .9 r9HUWLFDO )XOO6FDOH &RXQWV

PAGE 186

)LJXUH 6(0 3KRWRJUDSK RI 353 RQ :6L $IWHU r& +RXU $QQHDO LQ $LU

PAGE 188

,QWHQVLW\ FRXQWVf r9)6 H9 )LJXUH ('6 RI 353 RQ :6L $IWHU r& +RXU $QQHDO LQ $LU .9 r9HUWLFDO )XOO6FDOH &RXQWV

PAGE 189

,QWHQVLW\ FRXQWVf )LJXUH ('6 RI 353 RQ :6L $IWHU r& +RXU $QQHDO LQ $LU .9 &2 R A9HUWLFDO )XOO6FDOH &RXQWV

PAGE 190

WKLQQHVV RI WKH ILOP DQG YHULILHV WKDW WKH SKRWRJUDSKHG VXUIDFH LV FRPSRVHG RI WKH $X& V\VWHP 7KH 6(0('6 DQDO\VLV RI D K\GURJHQ DQQHDOHG 353 ILOP \LHOGHG UHVXOWV VLPLODU WR WKH DLU DQQHDOHG VDPSOH 7KH 6(0 SKRWRJUDSK VKRZV WKH VDPH FKDLQPDLO VWUXFWXUH EXW KDV OHVV FRQWUDVW EHWZHHQ WKH $X DQG & DUHDV )LJXUH f 7KLV PD\ EH GXH WR WKH SUHVHQFH RI D VXUIDFH K\GURFDUERQ ILOP DV ZDV LQGLFDWHG E\ WKH ;36 UHVXOWV 2QO\ WKH KLJK HQHUJ\ ('6 VSHFWUXP ZDV UHFRUGHG IRU WKLV VDPSOH )LJXUH f DQG LW YHULILHV WKH SUHVHQFH RI D WKLQ $X VXUIDFH ILOP 7KH 6(0 SKRWRJUDSK RI D 353 ILOP RQ VF :6L WKDW ZDV GHSRVLWHG DW r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f ZHUH VLPLODU WR WKH RWKHU VDPSOHV ZLWK

PAGE 191

)LJXUH 6(0 3KRWRJUDSK RI 353 RQ :6L $IWHU r& +RXU $QQHDO LQ +\GURJHQ

PAGE 193

,QWHQVLW\ FRXQWVf Z f ( M LV 1 -L M VU M ,N : f§UYWn&79 r 9)6 H9 )LJXUH ('6 RI 353 RQ :6L $IWHU r& +RXU $QQHDO LQ +\GURJHQ .9 r9HUWLFD )XOO6FDOH &RXQWV

PAGE 194

)LJXUH 6(0 3KRWRJUDSK RI 353 RQ :6L r& 'HSRVLWLRQ

PAGE 196

,QWHQVLW\ FRXQWVf L L L L )LJXUH ('6 RI 353 RQ :6 r& 'HSRVLWLRQ .9 ‘A9HUWLFDO )XOO6FDOH &RXQWV

PAGE 197

,QWHQVLW\ FRXQWVf Z L M L LQ 1 M fn8 / ,9 Z r9)6 H9 )LJXUH ('6 RI 353 RQ :6L r& 'HSRVLWLRQ .9 r9HUWLFDO )XOO6FDOH &RXQWV

PAGE 198

)LJXUH 6(0 3KRWRJUDSK RI 353 RQ *ODVV $IWHU r& +RXU $QQHDO LQ $LU

PAGE 200

,QWHQVLW\ FRXQWVf W -0 5 5 U L /, 9YU 9 / 5 $ W f§f r9) H9 )LJXUH ('6 RI 353 RQ *ODVV $IWHU r& +RXU $QQHDO LQ $LU .9 r9HUWLFDO )XOO6FDOH &RXQWV

PAGE 201

,QWHQVLW\ FRXQWVf r 9)6  H9 )LJXUH ('6 RI 353 RQ *ODVV $IWHU r& +RXU $QQHDO LQ $LU .9 A9HUWLFDO )XOO6FDOH &RXQWV

PAGE 202

UHVSHFW WR WKH VWURQJ VXEVWUDWH VLJQDO IURP 6L LQ WKLV FDVHf LQGLFDWLQJ WKH WKLQQHVV RI WKH $X ILOP 7KH 6(0 SKRWRJUDSK RI D 353 VDPSOH GHSRVLWHG RQ JODVV DW r& VKRZHG DQ HYHQ PRUH XQLIRUP JUDLQOHVV VWUXFWXUH )LJXUH f $JDLQ WKH ILOP ZDV YLHZHG XQGHU PXFK KLJKHU PDJQLILFDWLRQ WKDQ SLFWXUHG ZLWKRXW REWDLQLQJ DGGLWLRQDO VWUXFWXUDO LQIRUPDWLRQ 7KH ORZ DQG KLJK HQHUJ\ ('6 VSHFWUD IRU WKLV VXUIDFH )LJXUHV DQG f LQGLFDWHG WKDW WKLV ZDV DOVR D YHU\ WKLQ ILOP 7KH 353 GHSRVLWHG RQ WKH DGKHVLYH VLGH RI 6FRWFK EUDQG WUDQVSDUHQW WDSH DQG VXEMHFWHG WR 6(0 DQDO\VLV LV SLFWXUHG LQ )LJXUH $ XQLIRUP GLVSHUVLRQ RI $QJVWURP VL]H JUDLQV LV YLVLEOH RQ WKH HYHQ ILQHU JUDLQHG EDFNJURXQG 7KH ('6 VSHFWUXP )LJXUH f YHULILHG WKH SUHVHQFH RI $X RQ WKLV VXUIDFH 7KH ODVW WKUHH 6(0 SKRWRJUDSKV LQFOXGHG LQ WKLV VHFWLRQ )LJXUHV DQG f VKRZ WKH ODVHU DQQHDOHG 353 FRDWHG VF :6L VXUIDFH GHVFULEHG HDUOLHU )LJXUH FOHDUO\ VKRZV WKH GLVVLSDWLRQ IURQW RI WKH KHDW ZDYH JHQHUDWHG E\ WKH ODVHU EHDP 7KH WDUJHW VSRW LV QHDU WKH FHQWHU RI WKH SKRWRJUDSK )LJXUHV DQG VKRZ WKH HIIHFW RI WKH KHDW GHVFULEHG HDUOLHU 7KH LQFUHDVHG RSHQQHVV RI WKH JUDLQ VWUXFWXUH LV FOHDUO\ HYLGHQW LQ WKHVH VKRWV WDNHQ DW D r DQJOH (OHFWULFDO 5HVLVWDQFH 0HDVXUHPHQWV 7KH HOHFWULFDO IHHGWKURXJKV WKDW ZHUH VXEMHFWHG WR DLU DQG K\GURJHQ DQQHDOV ZKLOH REVHUYLQJ WKH UHVLVWDQFH DFURVV D 353 FRDWHG VXUIDFH H[SHULHQFHG SUREOHPV ZLWK WKH HOHFWURGH FRQWDFWV 7KH HOHFWURGHV ZHUH FRDWHG ZLWK D ORZ PHOWLQJ DOOR\ WKDW ZDV DSSDUHQWO\

PAGE 203

)LJXUH 6(0 3KRWRJUDSK RI 353 RQ *ODVV r& 'HSRVLWLRQ

PAGE 204

VV ;M O0Q 8'

PAGE 205

,QWHQVLW\ FRXQWVf r9)6 H9 &7! )LJXUH ('6 RI 353 RQ *ODVV r& 'HSRVLWLRQ .9 A9HUWLFDO )XOO6FDOH &RXQWV

PAGE 206

,QWHQVLW\ FRXQWVf H9 )LJXUH ('6 RI 353 RQ *ODVV r& 'HSRVLWLRQ .9 r9HUWLFDO )XOO6FDOH &RXQWV

PAGE 207

)LJXUH 6(0 3KRWRJUDSK RI 353 RQ $GKHVLYH 6LGH RI 6FRWFK %UDQG 7UDQVSDUHQW 7DSH

PAGE 209

e= =R X &2 F FX 8 FU L L $f L & / ? ‘L7DYU\A InLOK ‘WX
PAGE 210

)LJXUH 6(0 3KRWRJUDSK RI /DVHU $QQHDOHG $UHD RI 353 RQ :6L

PAGE 212

)LJXUH 6(0 3KRWRJUDSK RI 8QDQQHDOHG 353 RQ :6L

PAGE 214

)LJXUH 6(0 3KRWRJUDSK RI /DVHU $QQHDOHG 6SRW RI 353 RQ :6L

PAGE 216

PHDQW WR IDFLOLWDWH VROGHULQJ 7KLV ILOP PHOWHG DQG EURNH WKH FRQWDFW LQ WKH ILUVW WHVW DLU DQQHDOHG VDPSOHf 7KH IHHGWKURXJK XVHG LQ WKH VHFRQG WHVW + DQQHDOf ZDV HWFKHG LQ FRQ +& DQG EDNHG DW r& IRU KRXUV EHIRUH EHLQJ FRDWHG ZLWK WKH 353 7KH UHVXOWV RI WKLV WHVW DUH SUHVHQWHG LQ )LJXUH )LJXUH LOOXVWUDWHV WKH HOHFWULFDO SURSHUWLHV RI D IRUPLQJ $X ILOP 7KH HDUO\ FRQGXFWDQFH ORZ UHVLVWDQFHf RI WKH ILOP LQGLFDWHG WKDW WKH FORVHO\ SDFNHG SDUWLFOHV KDG HQRXJK FRQWDFW WR FRPSOHWH WKH FLUFXLW $V WKH WHPSHUDWXUH ZDV LQFUHDVHG WKH SDUWLFOHV FRDOHVFHG LQWR VHSDUDWHG LVODQGV DQG ORVW FRQWDFW ZLWK RQH DQRWKHU $V WKH WHPSHUDWXUH URVH WR RYHU r& WKH $X LVODQGV EHJDQ PHUJLQJ DQG HYHQWXDOO\ FRPSOHWHG WKH FLUFXLW DJDLQ 7KLV LVODQG IRUPDWLRQ DQG FRDOHVFHQFH KDV EHHQ REVHUYHG E\ RWKHU LQYHVWLJDWRUV DQG LV W\SLFDO RI $X ILOP JURZWK! )RXU SRLQW SUREH UHVLVWDQFH PHDVXUHPHQWV VKRZHG D VKHHW UHVLVWDQFH YDOXH 5Vf RI 2KPV SHU VTXDUH PP IRU WKH +DUULV VWDQGDUG $X ILOP 7KH WZR FRDWHG JODVV SODWHV WKDW ZHUH DQDO\]HG E\ 6(0('6 VKRZHG LQILQLWH UHVLVWDQFH DW DOO LQSXW VHWWLQJV LQGLFDWLQJ WKH GLVFRQWLQXLW\ RI WKH ILOPV 7KH VDPH UHVXOWV ZHUH REVHUYHG ZLWK WKH FRDWHG EODFN HOHFWULFDO WDSH WKH FRDWHG WUDQVSDUHQW WDSH DQG DQ DLU DQQHDOHG FRDWHG *)) VDPSOH 7KH JODVV SODWH FRDWHG ZLWK $X IURP +H SODVPD E\ OLQH RI VLJKW GHSRVLWLRQf KDG D 5V YDOXH RI 2KPVPP DQG D TXDUW] ZLQGRZ WKLFNO\ FRDWHG ZLWK 353 KDG D 5V YDOXH RI 2KPVPP 7KHVH WZR VDPSOHV LQGLFDWHG WKH HIIHFWLYHQHVV RI WKH +H SODVPD IRU SURGXFLQJ FRQGXFWLYH

PAGE 217

UR 2 &2 / 7HPSHUDWXUH r&f )LJXUH (OHFWULFDO 5HVLVWDQFH YV 7HPSHUDWXUH IRU D 353 &RDWHG )HHGWKURXJK

PAGE 218

$X ILOPV LQ FORVH SUR[LPLW\ WR WKH SODVPD ]RQH DQG WKH FRQGXFWLYLW\ SRVVLEOH ZLWK D WKLFN OD\HU RI WKH 353 SUHVXPDEO\ GXH WR WKH FORVH SUR[LPLW\ RI WKH $X SDUWLFOHV WR HDFK RWKHU DQG WKH OLPLWHG FRQGXFWLYLW\ RI WKH FDUERQDFHRXV PDWHULDO

PAGE 219

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f 7KH ILUVW SKRWRQV LQ WKH QDQRVHFRQG SXOVH WR UHDFK WKH JROG VXUIDFH ZHUH SDUWLDOO\ UHIOHFWHG DQG SDUWLDOO\ DEVRUEHG E\ FRQGXFWLRQ EDQG HOHFWURQV YLD DQ LQWHUQDO SKRWRHOHFWULF HIIHFW (OHFWURQSKRQRQ FROOLVLRQV ZKLFK RFFXU RQ D WLPH VFDOH RI a WR VHF MQ JG FRQGXFWRUV FKDQJHG WKH HQHUJ\ LQSXW LQWR KHDW DQG FDXVHG UDSLG YDSRUL]DWLRQ RI VRPH RI WKH PHWDO%HFDXVH RI WKH VSHHG

PAGE 220

RI WKLV SURFHVV WKH YDSRU IURQW ZDV LQLWLDOO\ WKH VDPH GHQVLW\ DV WKH VROLG SKDVH DQG ZDV KLJKO\ LRQL]HG GXH WR LWV KLJK WHPSHUDWXUHA f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r DWRPVSXOVHf f 7KH DGYDQFH RI WKH LRQL]HG SOXPH ZDV SUHFHGHG E\ KRW HOHFWURQV ZKLFK H[FLWHG WKH DPELHQW JDV EHIRUH WKH JROG DUULYHG 7KLV UHVXOWHG IURP WKH SURGXFWLRQ RI KLJK HQHUJ\ HOHFWURQV GXULQJ VWHS f WKDW KDG D PRVW SUREDEOH WKHUPDO YHORFLW\ 9S N7PfAA DQG H[SDQGHG IURP WKH VXUIDFH LQ DOO GLUHFWLRQV EXW ZLWK D GLVWULEXWLRQ WKDW IDYRUHG FRD[LDO GLVSHUVLRQ RI WKH KLJKHVW HQHUJ\ HOHFWURQV 7KHVH HOHFWURQV FDXVHG D UDSLG LQFUHDVH LQ WKH RSWLFDO GHQVLW\ RI WKH DPELHQW JDV YLD LQYHUVH

PAGE 221

EUHPVVWUDKOXQJf ZKLFK OHG WR IXUWKHU H[FLWDWLRQ RI WKH VSHFLHV SUHVHQW LQ D PDQQHU DQDORJRXV WR WKH JDV EUHDNGRZQ SKHQRPHQD GHVFULEHG HDUOLHU 7KLV HIIHFW DOVR OLPLWHG WKH DPRXQW RI LQFRPLQJ ODVHU HQHUJ\ WKDW UHDFKHG WKH VXUIDFH RI WKH WDUJHW 6LQFH HOHFWURQ WHPSHUDWXUHV DUH W\SLFDOO\ DQ RUGHU RI PDJQLWXGH KLJKHU WKDQ LRQ WHPSHUDWXUHV LQ WKLV UHJLPHn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r :FP \LHOGV D 9L RI [ FPVHF 7KH H[SHULPHQWDO HYLGHQFH SUHVHQWHG E\ 7DQ HW DO VKRZHG WKDW RYHU b RI WKH LRQV KDYH YHORFLWLHV LQ H[FHVV RI 9L 7KLV FDOFXODWHG YDOXH LV LQ UHDVRQDEO\ FORVH DJUHHPHQW ZLWK WKH H[SHULPHQWDOO\ GHWHUPLQHG YDOXH RI [ A FPVHF IRU DOXPLQXP LRQ YHORFLWLHV LQ VLPLODU SODVPDV ZLWK ,S [ :FP UHSRUWHG E\ '\HU HW DO 1RWH WKDW 7DQ HW DOnV HPSLULFDO UHODWLRQVKLS SUHGLFWV D 9L RI [ A FPVHF IRU WKLV FDVHf 7KXV DQ XSSHU OLPLW IRU WKH WRWDO GLVWDQFH WUDYHOHG E\ WKH LRQL]HG SODVPD IURQW GXULQJ WKH QV ODVHU SXOVH LV JLYHQ E\

PAGE 222

[ VHFf [ [ FPVHFf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f 7KH KLJK WHPSHUDWXUH OLJKW HPLWWLQJ SRUWLRQf SODVPD JHQHUDWHG LQ WKLV VWXG\ H[WHQGHG DSSUR[LPDWHO\ FP IURP WKH WDUJHW VXUIDFH DQG ZDV URXJKO\ VSKHULFDO LQLWLDOO\ 7KH SODVPD VKDSH EHFDPH PRUH SURODWH DV WDUJHW FUDWHULQJ SURJUHVVHG DQG WRRN RQ WKH FODVVLF VKDSH RI D FDQGOH IODPH DIWHU VHYHUDO PLQXWHV RI SXOVLQJ RQ WKH VDPH VSRW )LJXUH f 7KH FRD[LDO FRUH RI WKH SODVPD ZDV ZKLWH LQGLFDWLQJ KLJK WHPSHUDWXUH EURDGEDQG HPLVVLRQ DQG H[WHQGHG IURP WKH WDUJHW VXUIDFH WR DERXW RI WKH GLVWDQFH WR WKH HGJH RI WKH OLJKW HPLWWLQJ ]RQH 7KLV KRW FRUH ZDV RQO\ D IHZ PLOOLPHWHUV LQ GLDPHWHU DQG LW ZDV DSSDUHQW IURP SKRWRJUDSKV WKDW WKH SODVPD ZDV UDGLDOO\ V\PPHWULF DQG WKH EULJKWHVW HPLVVLRQ ZDV IURP D KHPLVSKHULFDO SOXPH PP LQ GLDPHWHU WKDW RULJLQDWHG DW WKH JDUJHW LPSDFW SRLQW

PAGE 223

$FWXDO 6L]H 3LFWXUHGf )LJXUH 7\SLFDO 3ODVPD 3URGXFHG E\ WKH 3XOVHG &2S /DVHU ,QFLGHQW RQ D 6ROLG *ROG 7DUJHW LQ 3D RI +&+

PAGE 224

f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pA 1R VXFK VKLIWV ZHUH REVHUYHG LQ WKH VSHFWUD +LJK DQJOH ;36 VWXGLHV RI XQDQQHDOHG DQG DLU DQQHDOHG SDUWLFOH ILOPV IRUPHG GXULQJ WKH VDPH SODVPD H[SHULPHQW VKRZHG RQO\ D VPDOO GHFUHDVH LQ WKH &$X UDWLR IURP WR 3URILOH ;36 VWXGLHV RI DQ DLU DQQHDOHG DQG D K\GURJHQ DQQHDOHG VDPSOH IURP GLIIHUHQW SODVPD H[SHULPHQWVf VKRZHG &$X UDWLRV LQ WKH ILOP EXON RI DQG UHVSHFWLYHO\ 7KLV FRPSDUHV WR D &$X UDWLR RI LQ WKH +DUULV VWDQGDUG $X ILOP EXONf +RZHYHU WKH FRQGXFWLYLW\ WHVWV WKH UHIOHFWDQFH VSHFWUD WKH 06 VWXGLHV DQG WKH REVHUYDWLRQ RI YLVLEOH FORXGV ULVLQJ IURP WKH VXUIDFH RI ILOPV GXULQJ ODVHU DQQHDOV DOO LQGLFDWHG WKDW FDUERQ FRPSRXQGV ZHUH DVVRFLDWHG ZLWK WKH H[WHULRU VXUIDFHV RI WKH SDUWLFOHV 7KXV WKHUH LV HYLGHQFH WKDW WKH FDUERQ LV SUHVHQW RQ WKH H[WHULRU RI WKH SDUWLFOHV DQG WKDW LV PD\ DOVR EH SUHVHQW LQ WKH LQWHULRU RI

PAGE 225

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f ZDV D FULWLFDO SDUDPHWHU 7KH IRUPDWLRQ RI 353 XVLQJ &2 DQG &2 LQ SODFH RI &+ LQGLFDWHG WKDW FDUERQ UDWKHU WKDQ VRPH XQLTXH K\GURFDUERQ ZDV WKH GRPLQDQW DORQJ ZLWK JROGf VSHFLHV LQYROYHG LQ WKH 353 IRUPDWLRQ $ PRUH H[KDXVWLYH VWXG\ RI WKH SUHVVXUH GHSHQGHQF\ RQ WKHVH WKUHH JDVHV ZRXOG \LHOG IXUWKHU LQVLJKW LQWR WKH PHFKDQLVP RI & LQFOXVLRQ f ,W VHHPV SUREDEOH WKDW WKH $X XQGHUZHQW KRPRJHQHRXV QXFOHDWLRQ LQ WKH H[SDQGLQJ FRROLQJ SODVPD IURQW DQG IRUPHG $X SDUWLFOHV ODUJHU WKDQ $ ZKLFK WKHQ FRQWDFWHG WKH FDUERQDFHRXV VSHFLHV DQG EHFDPH

PAGE 226

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f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f 6R ZKLOH D OLPLWHG DPRXQW RI & PD\ EH LQFRUSRUDWHG DORQJ ZLWK $X RQ WRS RI D SXUH $X FRUH LQ WKH JURZLQJ SDUWLFOH LW VHHPV OLNHO\ WKDW WKH PDMRULW\ RI WKH & LV DGGHG WR WKH H[WHULRU RI WKH $X FRUH $JJORPHUDWLRQ RI WKHVH & FRDWHG SDUWLFOHV LQ WKH JDV SKDVH PD\ DFFRXQW IRU WKHLU HQWUDLQPHQW LQ WKH JDV SKDVH RU WKH JURZWK PHFKDQLVP RI WKH

PAGE 227

3DUWLFOH 'LDPHWHU $QJVWURPVf )LJXUH 3DUWLFOH 'LDPHWHU 9HUVXV 5DWLR RI &DUERQ $WRPV 5HTXLUHG WR )RUP D 0RQROD\HU RQ WKH 6XUIDFH WR *ROG $WRPV LQ WKH 3DUWLFOH

PAGE 228

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f 7KH ;36 DQDO\VHV VKRZHG WKDW WKH $X ZDV SUHVHQW LQ WKH PHWDOOLF VWDWH LQ WKH UHDFWLRQ SURGXFW 7KH QXFOHDWLRQ DQG JURZWK RI WKLQ $X ILOPV IURP WKH SURGXFWV UHVHPEOHG RWKHU $X ILOP JURZWK VFHQDULRV IURP HYDSRUDWLRQ DQG VSXWWHU

PAGE 229

VRXUFHV ZLWK WKH H[FHSWLRQ RI WKH LQFOXVLRQ RI VXEVWDQWLDO DPRXQWV RI FDUERQ DWRP bf $OWKRXJK WKH SODVPD SURGXFWV JDYH QR LQGLFDWLRQV RI EHLQJ VXLWDEOH IRU XVH LQ PLFURHOHFWURQLF LQWHUFRQQHFW IRUPDWLRQ WKH RSWLFDO SURSHUWLHV RI WKH WKLQ $X FOXVWHU ILOPV ZHUH QRW WKRURXJKO\ LQYHVWLJDWHG 3UHOLPLQDU\ LQIUDUHG UHIOHFWLRQ DQG WUDQVPLVVLRQ PHDVXUHPHQWV QRW UHSRUWHG LQ WKH WH[W GXH WR WKH FXUVRU\ QDWXUH RI WKH DQDO\VHVf LQGLFDWHG YHU\ KLJK EURDGEDQG DEVRUSWLRQ 7KHVH SURSHUWLHV PD\ EH RI LQWHUHVW WR WKH HOHFWURQLF LQGXVWU\ IRU XVH LQ ERORPHWHUV RU RWKHU GHYLFHV UHTXLULQJ LQIUDUHG DEVRUEHUV RI ORZ WKHUPDO PDVV *ROG EODFNV KDYH KLVWRULFDOO\ EHHQ XVHG IRU WKLV SXUSRVHn EXW WKHUH LV DQ RSHUDWLRQDO XSSHU WHPSHUDWXUH OLPLW RI r& $ERYH WKHVH WHPSHUDWXUHV WKH JROG EODFN ILOPV ZKLFK DUH FRPSRVHG RI DJJORPHUDWHV RI WR QP GLDPHWHU $X SDUWLFOHV ORRVHO\ SDFNHG LQ D KLJK SRURVLW\ PDWUL[ FROODSVH DQG ORVH WKHLU KLJK DEVRUSWLRQ FKDUDFWHULVWLFV 7KHVH ILOPV DOVR DUH VXEMHFW WR FRQWDPLQDWLRQ IURP WKH FUXFLEOH DQGRU KHDWLQJ HOHPHQW PDWHULDOV WKDW DUH XVHG LQ WKH IRUPDWLRQ SURFHVV HYDSRUDWLRQ RI $X LQ WKH SUHVHQFH RI WR 3D RI 1 + RU DLUf 7KH 353 UHSRUWHG RQ LQ WKLV WH[W KDV WKH DGYDQWDJHV RI EHLQJ IUHH IURP PHWDOOLF R[LGH LPSXULWLHV DQG EHLQJ UHVLVWDQW WR FROODSVH DV LQGLFDWHG E\ D VKDUS FRORU FKDQJH LQ WKH ILOPf DW WHPSHUDWXUHV LQ H[FHVV RI r& SUHVXPDEO\ GXH WR WKH WKLQ FDUERQDFHRXV FRDWLQJ RQ WKH $X SDUWLFOHV ,Q DGGLWLRQ WR WKH LQIUDUHG FKDUDFWHULVWLFV RI WKH 353 ILOPV WKH YLVLEOH SURSHUWLHV FRXOG DOVR EH RI JUHDW LQWHUHVW WR WKH HOHFWURQLF LQGXVWU\ 7KHUH ZHUH WKUHH GLVWLQFW FRORUV WKDW FRXOG EH

PAGE 230

SURGXFHG LQ WKH 353 ILOPV GHSHQGLQJ RQ DQQHDOLQJ FRQGLWLRQV DQG WKXV RQ WKH DPRXQW DQG ORFDWLRQ RI FDUERQ LQFOXVLRQf EODFN SXUSOH DQG UHG\HOORZ 6LQFH LW ZDV VKRZQ WKDW DQ $U LRQ ODVHU FRXOG FDXVH ORFDO DQQHDOLQJ WKLV PDWHULDO FRXOG EH XWLOL]HG DV D PXOWLOHYHO PLFUR RSWLFDO HQFRGLQJ PHGLXP 7KHVH SURSHUWLHV ZDUUDQW D IXUWKHU LQYHVWLJDWLRQ RI WKH 353 IRUPDWLRQ PHFKDQLVP DQG IXUWKHU FKDUDFWHUL]DWLRQ RI LWV RSWLFDO SURSHUWLHV

PAGE 231

$33(1',; $ */$66 ),%(5 ),/7(5 %/$1.6 7KUHH ERURVLOLFDWH JODVV ILEHU ILOWHUV RI WKH W\SH XVHG LQ WKH VWXG\ 0LFUR )LOWUDWLRQV 6\VWHPV *%5 PPf ZHUH FKRVHQ UDQGRPO\ IURP WKH ER[ DQG VXEMHFWHG WR EODQN JUDYLPHWULF DQDO\VHV XVLQJ WKH 0HWWOHU DQDO\WLFDO EDODQFH 7KH ILOWHUV ZHUH SODFHG LQ JODVV SHWUL GLVKHV DQG GULHG RYHUQLJKW LQ D RYHQ 7KH\ ZHUH WKHQ UHPRYHG IURP WKH RYHQ DQG DOORZHG WR FRPH WR URRP WHPSHUDWXUH LQ D GHVLFFDWRU EHIRUH EHLQJ ZHLJKHG (DFK ILOWHU ZDV ZHLJKHG VHSDUDWHO\ LQ WKH ERWWRP KDOI RI WKH JODVV SHWUL GLVK DQG WKHQ WUDQVIHUUHG WR WKH ILOWHU KROGHU DQG LQVWDOOHG LQ WKH SODVPD UHDFWLRQ V\VWHP 7KH SHWUL GLVK ZDV WKHQ ZHLJKHG DQG UHWXUQHG WR WKH GHVLFFDWRU 7KH LQLWLDO ILOWHU ZHLJKWV ZHUH GHWHUPLQHG E\ GLIIHUHQFH XVLQJ WKLV PHWKRG 7KH ILOWHUV ZHUH VXEMHFWHG WR EODQN UXQV E\ HYDFXDWLQJ WKH SODVPD UHDFWLRQ V\VWHP DQG WKHQ SXOOLQJ D PL[WXUH RI b +b &+ JDV WKURXJK WKH V\VWHP DW D QRPLQDO DWPRVSKHULFf IORZ UDWH RI POPLQ DQG D QRPLQDO SUHVVXUH RI 3DVFDOV WRUUf IRU PLQXWHV 7KH V\VWHP ZDV WKHQ ILOOHG WR DWPRVSKHULF SUHVVXUH ZLWK WKH JDV PL[WXUH DQG WKH ILOWHU KROGHU ZDV UHPRYHG 7KH ILOWHU ZDV WKHQ UHPRYHG IURP WKH KROGHU DQG SODFHG LQWR D SUHZHLJKHG SHWUL GLVK WKDW ZDV DOUHDG\ RQ WKH EDODQFH )LQDO ILOWHU ZHLJKWV ZHUH GHWHUPLQHG E\ GLIIHUHQFH XVLQJ WKLV WHFKQLTXH

PAGE 232

$OO ZHLJKWV ZHUH UHFRUGHG WR WKH QHDUHVW PJ *UHDW FDUH ZDV WDNHQ WR DVVXUH WKDW QR SDUWLFOHV RU IODNHV ZHUH SURGXFHG GXULQJ WKH KDQGOLQJ RI WKH GHOLFDWH ILOWHUV DV ZDV WKH SUDFWLFH GXULQJ SURGXFWLRQ UXQV 7KH LQLWLDO DQG ILQDO ILOWHU ZHLJKWV DQG WKH GLIIHUHQFHV 'f DUH OLVWHG LQ 7DEOH 7KH VWDQGDUG GHLYDWLRQ 6f RI WKH EODQN ILOWHU ZHLJKWV ZDV FDOFXODWHG XVLQJ WKH IROORZLQJ HTXDWLRQ 6 &>('f@` 7KH YDOXH RI 6 IRU WKH WKUHH ILOWHUV ZDV GHWHUPLQHG WR EH PJ 7DEOH *ODVV )LEHUn)LOWHU %ODQN :HLJKWV )LOWHU ,QLWLDO :HLJKW PJf )LQDO :HLJKW PJf 'LIIHUHQFH PJf ,Q RUGHU WR GHWHUPLQH WKH FRQWULEXWLRQ RI WKH QRUPDO VWDQGDUG GHYLDWLRQ RI WKH EDODQFH WR WKH VWDQGDUG GHYLDWLRQ RI WKH ILOWHU EODQN ZHLJKWV ILYH FRSSHU SHQQ\ ZHLJKWV ZHUH HDFK ZHLJKHG WKUHH WLPHV VHH 7DEOH f 7KH VDPSOH VWDQGDUG GHYLDWLRQ Vf IRU HDFK SHQQ\ ZHLJKW ZDV FDOFXODWHG XVLQJ WKH IROORZLQJ HTXDWLRQ V >(P [f@`?

PAGE 233

ZKHUH P LV WKH DYHUDJH RI WKH WKUHH ZHLJKWV DQG [ LV WKH LQGLYLGXDO ZHLJKW YDOXH 7KH PHDQ YDOXH IRU V IRU DOO ILYH ZHLJKWV ZDV GHWHUPLQHG WR EH PJ 7DEOH 5HSHWLWLYH :HLJKLQJV RQ WKH 0HWWOHU $QDO\WLFDO %DODQFH 3HQQ\ :HLJKW PJf $YHUDJH 6WDQGDUG 'HYLDWLRQ f f f

PAGE 234

$33(1',; % $720,& $%62537,21 63(&7520(7(5 &$/,%5$7,21 7KH 3HUNLQ (OPHU 0RGHO $$ VSHFWURPHWHU ZDV ILWWHG ZLWK D )LVKHU 6FLHQWLILF $X KROORZ FDWKRGH WXEH DQG WXQHG WR WKH QP OLQH 7KH ODPS ZDV RSHUDWHG DW PDPS $ VWRFN VROXWLRQ RI FRQFHQWUDWHG $X VWDQGDUG ZDV SUHSDUHG E\ GLVVROYLQJ JUDPV RI b SXUH $X ZLUH LQ PO RI DTXD UHJLD 7KLV VROXWLRQ ZDV WKHQ GLOXWHG WR PO LQ D YROXPHWULF IODVN DQG VHDOHG 6HULDO GLOXWLRQ LQ HLWKHU GHLRQL]HG ZDWHU RU VSHFWUDO JUDGH DFHWRQH ZDV XVHG WR SUHSDUH SSP JUDPV SHU PLOOLRQ POf ZRUNLQJ VWDQGDUGV DW WKH EHJLQQLQJ RI HDFK GD\ WKDW DQDO\VHV ZHUH SHUIRUPHG 7KH LQVWUXPHQWnV EXUQHU IODPH DFHW\OHQHDLUf ZDV DGMXVWHG WR JLYH WKH JUHDWHVW OLQHDU UHVSRQVH UDQJH IRU HDFK W\SH RI VROYHQW ,Q SUDFWLFH WKLV FRQVLVWHG RI OHDQLQJ WKH JDV PL[WXUH VXEVWDQWLDOO\ ZKHQ UXQQLQJ VDPSOHV DQG VWDQGDUGV GLVVROYHG RU VXVSHQGHGf LQ DFHWRQH FRPSDUHG WR WKRVH GLVVROYHG LQ ZDWHU 7KH LQVWUXPHQW UHVSRQVH ZDV UHFRUGHG DV SHUFHQW DEVRUSWLRQ WR WKH QHDUHVW b RQ D VWULSFKDUW UHFRUGHU VHH )LJXUH f 6WUDLJKW OLQH FDOLEUDWLRQ SORWV RI DEVRUEDQFH $f YHUVXV FRQFHQWUDWLRQ ZHUH SUHSDUHG IURP WKH WUDQVPLVVLRQ GDWD XVLQJ WKH /DPEHUW%HHU UHODWLRQVKLS ZKHUH 7 b DEVRUSWLRQf ORJ 7 $

PAGE 235

)LJXUH VKRZV D W\SLFDO FDOLEUDWLRQ SORW IRU WKH LQVWUXPHQW 1R VLJQLILFDQW GLIIHUHQFHV LQ LQVWUXPHQW SHUIRUPDQFH ZHUH QRWHG RQFH WKH IODPH FRQGLWLRQV ZHUH RSWLPL]HG ZKHQ XVLQJ DFHWRQH VROYHQW YHUVXV ZDWHU VROYHQW

PAGE 236

)LJXUH 7\SLFDO $$ &DOLEUDWLRQ 3ORW RI $EVRUEDQFH YV $X &RQFHQWUDWLRQ

PAGE 237

\J $XPO 0'6RU'DQFH R R R f r f

PAGE 238

$33(1',; & 67$1'$5' 5()/(&7$1&( 9$/8(6 )25 6,/,&21 &$5%,'( 5VWQGf IRU VLQJOH FU\VWDO 6L& XVHG WR FDOFXODWH UHIOHFWDQFH FXUYHV IRU PLFURUHIOHFWRPHWU\ DQDO\VHV DUH OLVWHG EHORZ 7DEOH 5VWQGf 9DOXHV IRU 6L& :DYHOHQJWK QPf 5VWQGf bf :DYHOHQJWK QPf 5VWQGf bf

PAGE 239

5()(5(1&(6 6LPRQ 6 &RKHQ 9/6, (OHFWURQLFV 0LFURVWUXFWXUH 6FLHQFH 9RO 9/6, 0HWDOOL]DWLRQ 1* (LQVSUXFK 66 &RKHQ DQG *6 *LOGHQEODW HGV $FDGHPLF 3UHVV ,QF 2UODQGR )/ f &KDS %0 :HOFK '$ 1HOVRQ <' 6KHQ DQG 5 9HQNDWDUDPDQ 9/6, (OHFWURQLFV 0LFURVWUXFWXUH 6FLHQFH 9RO 9/6, 0HWDOOL]DWLRQ 1* (LQVSUXFK 66 &RKHQ DQG *6 *LOGHQEODW HGV $FDGHPLF 3UHVV ,QF 2UODQGR )/ f &KDS %OHFK + 6HOOR DQG /9 *UHJRU +DQGERRN RI 7KLQ )LOP 7HFKQRORJ\ /, 0DLVVHO DQG 5 *ODQJ HGV 0F*UDZ+LOO %RRN &RPSDQ\ ,QF 1HZ
PAGE 240

6 :ROI DQG 51 7DXEHU 6LOLFRQ 3URFHVVLQJ IRU WKH 9/6, (UD 9RO 3URFHVV 7HFKQRORJ\ /DWWLFH 3UHVV 6XQVHW %HDFK &$ f (. %URDGEHQW 86 3DWHQW f -/ %HDXFKDPS DQG 30 *HRUJH 86 3DWHQW f 6& %DEHU DQG 95 3RUWHU 86 3DWHQW f 0) 5XEQHU DQG 3 &XNRU 86 3DWHQW f 3% *KDWH 7KLQ 6ROLG )LOPV f '6 &DPEHOO +DQGERRN RI 7KLQ )LOP 7HFKQRORJ\ /, 0DLVVHO DQG 5 *ODQJ HGV 0F*UDZ+LOO %RRN &RPSDQ\ ,QF 1HZ
PAGE 241

$ 6KLRWDQL DQG + 6FKPLGEDXU $PHU &KHP 6RF f &( /DUVRQ 7+ %DXP DQG 5/ -DFNVRQ (OHFWURFKHP 6RF fW f + 6FKPLGEDXU *PHOLQ +DQGEXFK GHU $QRUTDQLVFKH &KHPLH *ROG 2UJDQLF &RPSRXQGV 6SULQJHU9HUODJ %HUOLQ f &\DQRSXUH &RUSRUDWLRQ 3URGXFW %XOOHWLQ f 5< -DQ DQG 6' $OOHQ 63,( f 7+ %DXP DQG &5 -RQHV $SSO 3K\V /HWW f f 7+ %DXP DQG &5 -RQHV 9DF 6FL 7HFK % f f 7+ %DXP (( 0DULQHUR DQG &5 -RQHV $SSO 3K\V /HWW f f 77 .RGDV 7+ %DXP DQG 3% &RPLWD $SSO 3K\V f f 7+ %DXP (OHFWURFKHP 6RF f f *0 6KHGG + /H]HF $' 'XEQHU DQG 0HOQJDLOLV $SSO 3K\V /HWW f f *DPR 1 7DNDNXUD 1 6DPRWR 5 6KLPX]X DQG 6 1DPED -DS $SSO 3K\V f f +:3 .RRSV 5 :HLG '3 .HUQ DQG 7+ %DXP 9DF 6FL 7HFK % f f (' :ROOH\ 86 3DWHQW f :/ *UDG\ DQG 00 %XUVH\ ,QW 0DVV 6SHFWURP ,RQ 3K\V f :/ *UDG\ DQG 00 %XUVH\ ,QW 0DVV 6SHFWURP ,RQ 3K\V f $. &KRZGKXU\ DQG &/ :LONLQV $P &KHP 6RF f f '$ :HLO DQG &/ :LONLQV $P &KHP 6RF f ( .D\ $ 'LONV DQG 8 +HW]OHU 0DFURPRO 6FL&KHP $ f f n n 7 ( .D\ DQG $ 'LONV 7KLQ 6ROLG )LOPV f

PAGE 242

+ %LHGHUPDQ DQG / +ROODQG 1XFO ,QVWUXP 0HWKRGV f 5$ 5R\ 5 0HLVVLHU DQG 69 .ULVKQDVZDP\ 7KLQ 6ROLG )LOPV f ( .D\ DQG 0 +HFT $SSO 3K\V f f + %LHGHUPDQ 9DFXXP f f / 0DUWLQX 7KLQ 6ROLG )LOPV f / 0DUWLQX 6RODU (QHUJ\ 0DWHU f 6$< $O,VPDLO DQG &$ +RJDUWK 3K\V ( 6FL ,QVWUXP f 0F,QWRVK DQG *$ 2]LQ ,QRUJ &KHP f f 3+ .DVDL DQG 30 -RQHV $P &KHP 6RF f f 3+ .DVDL $P &KHP 6RF f f 3+ .DVDL $P &KHP 6RF +f f *0 6FKUDJJ 'RFWRUDO 'LVVHUWDWLRQ 8QLYHUVLW\ RI )ORULGD f + .KDOLID 6XHKOD DQG / (UGH\ 7DODQWD f -5 (\OHU 75$& f f /HVVRQ DQG 3%UXFDW -&3 VXEPLWWHG 'HFHPEHU 0 .ODVVRQ +HGPDQ $ %HUQGWVVRQ 5 1LOVVRQ DQG & 1RUGOLQJ 3K\VLFD 6FULSWD f %/ +HQNH 3K\V 5HY $ f f .UDWRV ,QF ;6$0 2SHUDWRUV +DQGERRN f -+ 6FRILHOG (OHFWURQ 6SHFWURV f /% 9DOGHV 3URF ,5( f 73 +XJKHVW 3ODVPDV DQG /DVHU /LJKW :LOH\ DQG 6RQV 1HZ
PAGE 243

1) 0RWW DQG + -RQHV 7KH 7KHRU\ RI WKH 3URSHUWLHV RI 0HWDOV DQG $OOR\V 'RYHU 3XEOLFDWLRQV ,QF 1HZ
PAGE 244

%,2*5$3+,&$/ 6.(7&+ &KDUOHV *HRUJH 6LPRQ ZDV ERUQ LQ :HVW 3DOP %HDFK )ORULGD RQ $XJXVW +H UHFHLYHG WKH %DFKHORU RI 6FLHQFH GHJUHH LQ FKHPLVWU\ XQGHU WKH JXLGDQFH RI 3URI 1HDO %RHKQNH IURP -DFNVRQYLOOH 8QLYHUVLW\ LQ -DFNVRQYLOOH )ORULGD LQ +H WKHQ HQWHUHG WKH *UDGXDWH 6FKRRO DW WKH 8QLYHUVLW\ RI 6RXWK &DUROLQD 86&f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

PAGE 245

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

PAGE 246

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

PAGE 247

m56n79 2) )/25,'$ +8 OLOL


R.S'TV OF FLORIDA
3 4 HU lili I
1262 08556 7781


GOLD THIN FILMS PRODUCED FROM LASER
STIMULATED PLASMA REACTION PRODUCTS
By
CHARLES GEORGE SIMON
A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF
THE UNIVERSITY OF FLORIDA
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
UNIVERSITY OF FLORIDA
1988
jj- iM F LIBRARIES

To my wife, Diane,
to my parents, Sam and Bernice,
and
to Bobby Sammons.

ACKNOWLEDGEMENTS
The author wishes to express his gratitude to all who contributed
to this work and to his education at the University of Florida. In
particular, he wishes to express his appreciation for all of the effort
and guidance provided by his research director and committee chairman,
Samuel Colgate.
The author would like to thank his peers and the faculty and staff
members at the University of Florida (U.F.) and the University of South
Florida (U.S.F.) who contributed to this effort: at U.F., Mark Hail
and Roy King for quadrupole MS analyses, Mehdi Moini for FTICRMS
experiments, Dan Lesson for cluster beam TOFMS experiments, Paul
McCaslin and Jack Davis, Jr., for XPS analyses; at U.S.F., Alfred
D'Agostino and Carl Biver for XPS analyses, and Mike Ammons and Alicia
Slater for SEM/EDS analyses. Specials thanks are also extended to
Stephanie Boggess at U.F. for her invaluable assistance throughout the
course of this work, and to Bobby G. Sammons of Stone Container
Corporation, Port Wentworth, Georgia, for providing that special
impetus.
Finally, the author wishes to thank his committee members for
their contributions to this work, especially Martin Vala and John Eyler
who provided laboratory equipment and time, and The Florida High

Technology and Industry Council for their financial support (FHTIC
Grant #85092726).
IV

TABLE OF CONTENTS
Page
ACKNOWLEDGEMENTS iii
LIST OF TABLES vii
ABSTRACT viii
CHAPTERS
I INTRODUCTION 1
II EXPERIMENTAL 13
Production of Gas-Phase Gold Species: The Plasma
Reaction System 13
The Carbon Dioxide Laser, Optics, and
Operation 14
Gas Handling System and Procedures 18
The Plasma Reaction Chambers 28
The glass plasma reaction chamber 28
The aluminum plasma reaction chamber 34
The Product-Recovery/Substrate-Coating Systems. 40
Heated quartz tube 40
Staged cold traps 41
Substrate coating chambers 46
Heated substrate mount 50
Production of Gas-Phase Gold Species: Experimental
Conditions and Materials 51
Screening Study Experiments 51
Substrate Coating and Annealing Experiments.... 64
Product Volatility Study 75
Sublimation Experiments 76
Mass Spectrometer Experiments 77
Time of Flight MS Experiment 80
Gold Thin Film Characterization 83
Visible Absorption Spectroscopy 84
Optical Microreflectometry 85
X-Ray Photoelectron Spectroscopy 86
Scanning Electron Microscopy with Energy
Dispersive Spectroscopy 89
Electrical Resistance Measurements 90
v

Page
III RESULTS AND DISCUSSION 92
Production of Gas-Phase Gold Species 92
Screening Study Results 92
Substrate Coating and Annealing Results Ill
Product Volatility Study Results 115
Sublimation Experiments 115
Mass Spectrometer Experiments 116
Time of Flight MS Experiment 138
Gold Thin Film Characterization Results.. 151
Visible Absorption 151
Optical Microreflectrometry 153
X-Ray Photoelectron Spectroscopy 158
Scanning Electron Microscopy with Energy
Dispersive Spectroscopy 164
Electrical Resistance Measurements 193
IV SUMMARY AND CONCLUSIONS 210
Discussion of Plasma Reaction Product Formation 210
Conclusions 219
APPENDICES
A GLASS FIBER FILTER BLANKS 222
B ATOMIC ABSORPTION SPECTROMETER CALIBRATION 225
C STANDARD REFLECTANCE VALUES FOR SILICON CARBIDE 229
REFERENCES 230
BIOGRAPHICAL SKETCH 235
vi

LIST OF TABLES
Table Page
1. Gases Used in the Plasma Reaction Study 54
2. Screening Study Plasma Reaction Experiments 55
3. Substrate Coating Experiments 65
4. Substrate Annealing Conditions 69
5. Volatility Study Mass Spectrometer Experiments 77
6. Filter Catch Plasma Experiment Results 107
7. GC/MS Results from an Acetone Extract of H2C2H2/AU
Plasma Reaction Products 118
8. XPS Analytical Conditions and Results 161
9. Glass Fiber Filter Blanks 214
10. Repetitive Weighings on the Mettler Analytical
Balance 215
11. R(stnd) Values for SiC 220

Abstract of Dissertation Presented to the Graduate School of the
University of Florida in Partial Fulfillment of the Requirements
for the Degree of Doctor of Philosophy
GOLD THIN FILMS PRODUCED FROM LASER
STIMULATED PLASMA REACTION PRODUCTS
by
Charles George Simon
December 1988
Chairman: Samuel 0. Colgate
Major Department: Chemistry
Superfine particles of gold in the 100-400 nanometer size range
were produced in a plasma stimulated by 10.6 micron radiation from a
pulsed carbon dioxide laser. The production of the particles was shown
to be highly dependent on the types and pressures of the gases used in
the plasma, and the incident power density. The best conditions
determined for production of the particles were a partial pressure of
350 Pascals of methane gas mixed with hydrogen to a total pressure of
700-1400 Pascals, and an incident power density of 3 x 10^ watts/cm^.
The particles were used to coat tungsten, glass, and polymeric
substrates. The coated tungsten and glass substrates were subjected to
air and hydrogen anneals convectively at temperatures up to 600 K, and
by 10.6 and 0.532 micron laser radiation. Selected sample films were
then subjected to analyses by optical microreflectometry, X-ray
photoelectron spectroscopy, scanning electron microscopy, energy
dispersive spectroscopy, and electrical resistance.
The results of these analyses showed that the gold films had
highly variable properties depending on the substrate and annealing
vi i i

conditions. The average mass concentration of gold in the films was
95% (54 atomic %). High quality continuous gold lines could be written
on coated glass substrates using continuous wave 0.532 micron argon ion
laser radiation. Three distinct colors could be developed in the films
using thermal input. This property makes the product a viable
candidate for use as a multi-level optical encoding media.
Film collapse did not occur until 490 K and there were no other
contaminants in the films due to the containerless evaporation
technique. These properties indicate that the plasma reaction products
may be suitable high temperature replacements for gold blacks.
IX

CHAPTER I
INTRODUCTION
Methods for producing submicron gold film patterns are of current
interest to the microelectronic industry for use as interconnect
metallization as device sizes shrink in VLSI (very large scale
integration) circuitry. Interconnects provide communication routes
between single devices and each other, between single devices and the
outside world and between active regions within a single device. Since
propagation time delay along the interconnect is directly proportional
to film resistivity and inversely proportional to the film thickness,
as well as varying with the square of the length,1 it is important to
produce short and relatively thick (compared to the width) films with
good electrical properties in order to minimize operating times.
Current micron-size interconnects are patterned using aluminum, but
industry progression to submicron-size devices will eliminate aluminum
for this use because of electromigration problems. Gold is an ideal
substitute for aluminum because of its low resistivity, high
conductivity, and resistance to electromigration.
Chemical vapor deposition (CVD) is the only currently available
technique for producing gold thin films that met both the selective
deposition and high throughput requirements necessary for mass-
producing submicron patterns in VLSI circuits. Volatile gold compounds
are used in the CVD process to form the thin metal films by decomposing
1

2
on activated surfaces, leaving the metal atom on the surface and the
remaining molecular constituents in the gas phase. Thus, there is a
concurrent interest in high yield, cost effective methods for
synthesizing suitable compounds for use in gold CVD processes.
An alternative method to conventional solution based synthetic
chemistry that offers several advantages is the in situ gas phase
production of suitable gold compounds. This technique could be
integrated into a CVD system and produce volatile gold compounds on
demand, eliminating the need to store and handle such compounds, and
removing the processor's dependency on off-site precursor production.
The ideal system would use solid gold and non-toxic reactive gases to
form the volatile species upstream from the CVD chamber. After passing
through the CVD chamber, any unused gold compounds would be easily
recovered for recycle or gold reclamation. The following report
describes efforts to explore and understand novel chemical means which
might support the development of such a system based on production of
gas phase gold compounds in a pulsed laser stimulated plasma using a
solid gold target and non-toxic reactant gases.
A brief review of the physical properties and mechanisms of
currently available materials and methods utilized in interconnect
formation will illustrate the limitations that need to be overcome.
The advantages of using gold for interconnect metallization and the
effectiveness of CVD for submicron patterning will be described.
Evidence of the gas phase production of gold compounds using energetic
plasmas will also be presented. Finally, a brief description of the
proposed technique will be given, followed in Chapter II by a complete

3
description of all equipment and procedures and in Chapter III by a
discussion of the results.
Among the elements only gold, silver, copper, and aluminum have
high enough electrical conductivities at device operating temperatures
(> 300 K) to be considered for use in interconnect formation.2 Both
silver and copper are highly reactive and subject to catastrophic
oxidation. While aluminum is more stable to oxidation, it is far more
susceptible to electromigration than gold. Electromigration results
from mobility of the metal ions in the film driven by the friction
forces exerted by the flowing electrons. The ultimate result of
electromigration is the formation of a void large enough to cause a
discontinuity in the interconnect resulting in device failure.3 When
the factors responsible for electromigration are considered, the
advantages of gold over aluminum become clear.
In the polycrystalline thin metallic films which make up
interconnect lines, electromigration can be evaluated by considering
the total atomic flux, F, which can be expressed as the sum of the
atomic fluxes through the interior of the grain (equivalent to the flux
in the bulk metal) and the flux across the grain boundaries.
Huntington and Grone^ derived an expression for the flux in bulk
material, while Ho and d'Heurle^ did so for the added atomic flux
across grain boundaries. Both approaches are based on statistical
distribution of mobile atoms and adjacent vacancies in the crystal
lattice or grain boundaries. Combining their two expressions yields an
equation for F as a function of the current density J, the atomic
density N, the atomic diffusion coefficient D, the absolute temperature

4
T, the effective charge Z*q, the bulk conductivity cb, and the film
conductivity Cf:
F = NDZ*qJ/cbkT + (NDZ*qJ/cfkT)(s/d)
where k is the Boltzman constant, s is the average separation distance
between grain boundaries, and d is the average grain size. This model
is only an approximation since it ignores the geometrical orientation
of the grains and impurities adsorbed on the grain boundaries, and it
assumes that transport across grain boundaries occurs via channels
between the grains.
It is immediately apparent that the lower atomic density of gold,
0.098 moles/cm®, compared to aluminum, 0.167 moles/cm®,® leads to a
lower F value for gold. Also, the lower effective nuclear charge of
the gold atom and the gold (+1) and (+3) ions (Z* = 0.65, 1.0, and 3.0,
respectively, using Slater's Rules) compared to the aluminum atom and
(+3) ion (Z* = 3.15 and 4.2, respectively, using Slater's Rules)7
results in a further lowering of the F value for gold.
Since movement of atoms within a crystal is highly restricted, and
the grain boundary area in these polycrystalline metal thin film
interconnects is many times greater than the external surface area, the
atomic flux within the thin film interconnect is dominated by diffusion
across the grain boundaries.® Thus, the heavier, more bulky gold
atoms, possessing a lower relative charge than aluminum, but having a
similar net bulk resistivity of ca. 2.5 microohms/cm, are far less
prone to electromigration at high current densities. Typically,

5
current densities > 10® amp/cm^ cause serious electromigration problems
in aluminum and its alloys, while gold does not experience serious
problems until current densities exceed approximately 10^ amp/cm^.^
The next generation of electronic devices are expected to be of
submicron dimensions and operate at current densities up to 10®
amp/cm^.l® Thus gold appears to be a suitable material for
interconnect metallization in future devices. There are several
problems associated with the use of gold in silicon based circuitry.
Most notably, the high diffusivity of gold in silicon and silicon
dioxide necessitates the use of a barrier metal such as tungsten
between the two materials.^ While industrial methods for mass-
producing submicron patterns of tungsten based on CVD techniques
currently exist,there are no methods currently available for
mass-producing submicron patterns of gold. If an inexpensive, readily
available source of volatile gold species with low toxicity and good
deposition characteristics could be developed, it would greatly
facilitate efforts in this area.
A review of the methods available for producing gold thin films
reveals significant problems associated with the application of each
method to the mass-production of submicron patterning. There are seven
general categories of techniques currently employed to form gold films:
1) electroplating
2) sputtering (including reactive sputtering)
3) vacuum evaporation
4) ionized cluster deposition
5) superfine particle deposition

6
6) chemical vapor deposition (CVD)
7) direct write (including laser, electron, and ion beam
techniques).
Electroplating gold from solutions has been used extensively by
the electronic industry to form thin film devices and structures with
dimensions greater than several microns.However, the films produced
are typically porous and have significantly lower conductivities than
bulk gold. These plated films also contain alkali ion contaminants
that migrate in the electric fields and accumulate at junctions where
they change the device operating characteristics. There is also the
problem of dendritic growth experienced in electroplated gold films,
which can lead to formation of short circuits in adjacent conductors.*®
A recent improvement in conventional electroplating was developed
by C. Patton using a laser-enhanced jet plating technique.This
method produced high quality gold spots and lines by directing a 25-
Watt continuous-wave argon ion laser beam through a focusing lens and
into a free-standing jet of electrolyte that acted as an optical wave
guide and a gold ion source. The laser energy and the fine jet stream
of electrolyte were directed onto a rastered cathode surface where
deposition rates as high as 30 microns/sec. were reported. The
inherently low throughput of this rastered system precludes its use as
a technique for mass-production of submicron gold patterns.
Sputtering is a physical vapor deposition (PVD) technique that
uses ionized gases (usually argon) to bombard a target composed of the
metal to be deposited. The energetic ion collisions dislodge surface
and near surface neutral metal atoms which then travel randomly to the

7
substrate where they are deposited. Masks and etching techniques are
used to form patterns. Several variations have been developed, such as
adding a reactive gas to the ambient, or heating and/or applying a
radio-frequency (rf) bias to the substrate. These modifications
improve step coverage on the substrate surface, and well-defined step
coverage is essential for small scale device and interconnect
formation.H»20-23 Non-uniform step coverage results in "thin" areas
that lead to early device failure. The improvements have not
completely solved the step coverage problems for small dimensions, and
the methodology is still considered non-conformal.22 This major
disadvantage along with the non-selectivity of the deposition process
precludes the use of sputtering techniques for mass-production of
submicron gold patterns.
Vacuum evaporation is also a physical vapor deposition process.
Thermal convection, resistance heating, laser vaporization, or electron
gun vaporization is used to evaporate the metal in a vacuum. The atoms
then travel by line of sight to the substrate where they condense and
form a thin film.21 Masking and etching techniques are used to form
patterns. This methodology is limited by non-conformal step coverage
and non-selectivity of the deposited films.22 These limitations
exclude evaporation techniques from use in the mass-production of
submicron gold patterns.
Ionized cluster beam deposition is a recently developed technique
that utilizes ionized clusters of up to several thousand atoms to form
thin films.21*24 jhe clusters are formed by homogeneous or
heterogeneous nucleation either in the vapor phase in the plume exhaust

8
from a nozzle fitted onto a hot crucible containing the molten source
material, or on the side walls of the crucible itself before exiting
through the nozzle. The clusters are subsequently ionized by electron
bombardment with a current of several milliamps and energies in the 80-
100 eV range. They are then accelerated through a 1-10 KV potential
and directed to the substrate surface where they deposit non-
selectively with enough energy per atom (1-10 eV) to facilitate surface
mobility without inducing defect damage associated with higher impact
energies.
A recent study by Knauer and Poeschel showed that under optimum
conditions only about 1% of the total metal flux from a crucible filled
with molten gold or silver was in the form of clusters in the size
range of several hundred to several thousand atoms.25 Since only a few
percent of these clusters were ionized in the electron bombardment
step, the net efficiency of metal use was very low. This limitation,
together with the need for line of sight deposition (which implies non-
conformal step coverage) and the non-selectivity of the process,
preclude its use for mass-production of submicron gold film patterns.
Another recently developed technique for producing gold thin
films, also based on homogeneous and heterogeneous nucleation of
particles in the gas phase, involves the production of "ultra-fine"
particles in the 5-65 nanometer size range (10^-10^ atoms/particle)
that are subsequently deposited non-selectively on a substrate.25"2®
Metal vapors are produced using a laser beam, arc discharge, or
electron beam in the presence of inert or reactive gases. At least one
group applied the technique to gold.28 The same limitations of non-

9
selectivity and non-conformal step coverage eliminate this method from
consideration as a viable procedure for submicron patterning of gold
films. However, investigators claim that high yields of metal
compounds can be formed by the activated clusters in reactive gas
streams.27 This is an interesting point which will be discussed
further below.
Chemical vapor deposition techniques do not depend on a flux of
condensible species reaching the substrate by direct line of sight and
hence are not subject to non-conformal step coverage problems.22
Substrates are surrounded by metal-bearing volatile species that do not
decompose without some form of additional energy input.20 In
principle, this allows close packing of the substrates in the
deposition chamber and selective deposition via selective energization
of pre-patterned barrier metal surfaces. There are many variations of
the basic CVD methodology designed to optimize performance of a
particular metal deposition system, but they all utilize a volatile
species that is forced to decompose on the substrate areas of interest
and leave behind a thin film of relatively pure metal.16,20-23
Chemical vapor deposition is the only category of currently
available metallization technology that meets the requirements of
selective deposition and high throughput necessary for mass-production
of submicron gold thin film patterns. To date, no reports of
simultaneous patterning of large arrays of submicron features with gold
have been published. Non-selective CVD of gold from triarylphosphine-
goldchlorides using thermal decomposition was demonstrated by Mann,
Wells, and Purdie in 1937.29 House and Colgate recently reported

10
similar results using the same compounds and rf stimulated thermal
decomposition.-^ There are other examples of non-selective CVD of gold
from organometal 1 ic compounds such as AuR(CNR'), and (R) PAuOSi(R),
where R and R' are methyl, ethyl, or phenyl groups.31,32 The most
recent compounds to be used for CVD of gold are dimethyl acetylaceto-
natogold(III) and its tri- and hexafluoro derivatives. Larson and Baum
reported the formation of high quality gold films from these compounds
by thermal decomposition at 300°C.33 Films produced from the
fluorinated derivatives were relatively free from contamination and had
resistance values about twice that of bulk gold. This work represents
the current state of the art for gold CVD methods. While the compounds
used performed well, they are difficult to synthesize and have low
synthetic yields.34 These compounds are available commercially at a
cost of several hundred dollars per gram.35 Clearly a cheaper, more
readily available source of volatile gold species would be of benefit.
The only examples of submicron selective gold deposition reported
utilized various direct write methods, such as the laser-jet
electroplating technique described earlier,^ or ion beam pyrolysis of
solid (spun-on) organometallic films.36 Most groups have used focused
laser, ion, or electron beams to induce selective CVD of gold from
volatile compounds.37-44 Again, the fluorinated derivatives of
dimethyl acetylacetonatogold(111) formed the highest quality submicron
sized gold lines and spots. Despite the high quality of the gold films
produced by these methods, their inherently slow rate of throughput
precludes their economic use in mass-production scenarios.

11
As previously mentioned, one possible alternate source of
organogold compounds for use in CVD systems that offers the advantages
of low cost and availability on demand is the in situ production of
such compounds from solid gold and inocuous gases. Techniques exist
for producing gold oxides and halides from solid targets using sputter
gun evaporation in the presence of the reactive gases.^ Araya et al.
claim that goldcarbide superfine particles can be generated in the gas
phase from Nd:YAG pulsed laser stimulated plasmas using solid gold
targets in the presence of methane or Freon gases.^ There are also
examples of organogold ions formed in ion cyclotron resonance mass
spectrometer experiments using high-voltage spark and carbon dioxide
pulsed laser stimulated vaporization/ionization of solid targets in the
presence of aliphatic or aromatic hydrocarbons, alkylhalides, and
alcohols.46-49
In another related field of research, investigators have been
producing gold bearing plasma polymerized films using PVD sputtering or
evaporation techniques.50-58 These studies have shown that the metal
is incorporated in the films in the form of small particles that
drastically alter the optical and electrical properties of the
polymers.
Gold carbonyls and organogold compounds have been formed in matrix
isolation studies by cocondensation of gold atoms with carbon monoxide,
acetylene, ethylene, and propyl ene.59-62 These studies illustrate the
high reactivity of gold atoms with carbonaceous molecules, even at very
low temperatures.

12
Taking this evidence into consideration, it would seem possible to
develop a continuous process method for generating gaseous gold species
from solid gold and gaseous compounds in an energetic plasma. Such a
process could be incorporated in a CVD production line to provide
volatile gold compounds on demand. This technique would also eliminate
the need to store and handle synthetic compounds, a major economic and
safety factor advantage in itself.
Materials produced by the method would be evaluated by considering
the following criteria:
1) production rate
2) volatility
3) thermal stability
4) temperature of decomposition
5) film properties (resistance, purity, morphology, stability)
6) properties of by-products (should be non-contaminating to the
substrate and non-toxic)
7) ability to recycle or reclaim gold.
In addition to these considerations, the toxicity of the starting
materials would be a primary concern.
A plasma reaction system was designed and constructed to
investigate the feasibility of producing gas phase gold compounds in
large enough quantities to be used in mass-producing CVD submicron gold
patterns. The procedures and results of that investigation are
presented in the following chapters.

CHAPTER II
EXPERIMENTAL
The scope of this study was limited to the investigation of
reactions occurring between non-toxic or low-toxic gaseous species and
pulsed C02 laser stimulated gold vapors and plasmas. Particular
emphasis was placed on utilization of permanent carbonaceous gases.
The study consisted of three major parts: 1) production of gas phase
gold-bearing species in high yields in the plasma, 2) determination of
volatility of high-yield species, and 3) characterization of gold thin
films produced from the high-yield species. Detailed descriptions of
experimental equipment and procedures are presented together in this
chapter. Each major part of the study is treated autonomously.
Conditions leading to equipment or procedure modifications are
mentioned but are not discussed until the following chapter.
Production of Gas-Phase Gold Species:
The Plasma Reaction System
The plasma reaction system was composed of four sub-systems:
1) the pulsed carbon dioxide laser and associated optics
2) the gas handling system
3) the plasma reaction chambers
4) the product-recovery/substrate-coating systems.
13

14
Each sub-system is described in detail together with pertinent
operational procedures followed during the course of the study.
Carbon Dioxide Laser. Optics, and Operation
The foremost criterion for development of a successful method for
producing gaseous gold compounds for the intended use was a high
production rate. An energy source was needed that could provide both a
high flux of gold vapor and the additional energy needed to form a
reactive plasma from the volatilized gold and reactive gases. A
Lumonics pulsed TEA (transversely excited atmosphere) carbon dioxide
laser, model 101-1, that had previously demonstrated high
volatilization rates for refractory metals*^ was available for use in
this study. This laser was capable of producing an optical pulse
energy of 2.5 joules with a pulse halfwidth of 250 nanoseconds and a
power density of approximately 3 x 10^ watts/cm^ when optimally focused
through a 200 mm focal length lens. Maximum pulse repetition rate was
1 hz, giving the laser a duty time of approximately one millisecond per
hour. The emitted wavelength of 10.6 microns corresponds to the P(20)
line in the 001-100 band.
The laser's pulse energy could be varied by adjusting the nitrogen
gas pressure and flow rate to the spark gap trigger, by adjusting the
composition and flow rate of the helium/nitrogen/carbon-dioxide lasing
gas mixture, or by adjusting the operating voltage. During the course
of this study these parameters were maintained in a state that resulted
in maximum energy output.

15
The laser energy output was measured after major maintenance
events, such as disassembly and cleaning of the optics or electrodes,
using a Scientech 365 laser power/energy meter. During subsequent
operation, the laser output was monitored by exposing a piece of
thermal paper (Hewlett Packard #820-51A) to single pulses of the
unfocused, 28 mm dimeter beam and comparing the resultant discoloration
patterns to standard patterns that were produced under measured
conditions (see Figure 1).
The laser beam was directed into the plasma reaction chamber
through the optic path using a 5 cm square face coated silver mirror
during initial screening experiments. This mirror was subsequently
removed from the system and the laser was positioned in a direct line
of fire with the optics and the chamber at a distance of ca. 0.5 meters
in order to transmit as much energy as possible to the target.
An externally mounted 5 cm diameter germanium meniscus lens with a
200 mm focal length (Oriel model 4365) was used to focus the laser beam
during the first half of the study. A similar lens with a focal length
of 250 mm (11 - VI, Inc., model 5-5741-1) replaced the initial lens for
the final half of the study. (This was necessary as a result of
physical damage sustained by the 200 mm lens during a cleaning
procedure accident.) Both lenses had an anti-reflection coating for
maximum transmission at 10.6 microns.
The lenses were held in a clamp mounted to an optical stand with
three degrees of freedom. This arrangement allowed the lens to be
positioned closer to the target than the optimum focal distance during
the course of an experimental run, thus distributing the laser energy

Figure 1. Thermal Paper Exposed to Single Pulses of the Carbon
Dioxide Laser
(a) Laser performing well (nominal)
(b) Laser performing poorly (gas mixture not
optimized for power level and pulse repetition
rate

17
(b)

18
over a larger surface area. This procedure was used in all experiments
where the effects of lower than maximum power densities were
investigated.
The optimum focal length for each lens was determined
experimentally by exposing thermal paper (in air) to the partially
focused beam at distances equivalent to 10, 60, 85, 135, and 195
percent of the expected focal lengths. The average spot diameters from
each point were plotted against the distance from the back edge of the
lens. The intersection of the two lines drawn through the points gave
the optimum focal length (Figure 2). The value determined for the two
lenses were 199 mm and 254 mm. These values were confirmed by
microscopic examination of target impact craters after exposure to the
highly focused beam.
After passing through the focusing lens, the beam entered the
reaction chamber through a 3.8 cm diameter zinc selenide window (II-VI,
Inc., #-746-7) which also had an anti-reflection coating for maximum
transmission at 10.6 microns. The distance between the lens and the
window was kept to a minimum in order to prevent damage of the latter
by interaction of the partially focused laser beam with surface
contaminants. This distance was ca. 0.5 cm for the 200 mm focal length
lens and ca. 2 cm for the 250 mm focal length lens.
Gas Handling System and Procedures
All of the gases used in this study, except one, were gaseous at
STP and were supplies from pressurized cylinders. Standard one and two
stage gas regulators and associated fittings were used to deliver these

Figure 2. Germanium Lens Focal Length Determination

30
20
10
0

21
gases to the mixing system through 0.635 cm o.d. polypropylene
tubing.
The one compound that was liquid at room temperature, dicyclo-
pentadiene, was placed in a 50 ml glass impinger and helium gas from
the gas handling system was bubbled through 30 ml of the liquid at 120
ml/min before entering the plasma chamber. This effectively saturated
the gas with the volatile liquid. Teflon tubing and fittings were used
to connect the impinger to the plasma chamber during this experiment
(Figure 3).
The gas mixing system used in all experiments, except the one
noted above, consisted of the following components:
1) three variable area flowmeters with built-in needle valves
(Cole-Parmer models J-3217-12 and J-3217-18), mounted together on an
aluminum plate,
2) a 120 ml acrylic gas drying column with 0-ring sealed aluminum
end caps (Altech Associates 100 psi model, sold by Cole-Parmer as model
J-1418-100) half filled with indicating drierite and half filled with
molecular sieves,
3) a 100 ml glass bubble-tube flowmeter,
4) a brass on/off plug valve with elastomeric O-ring seals (Nupro
model B-4P4T) and two brass fine metering valves (Nupro model B-SS4),
5) an oil-filled mechanical vacuum pump (Precision Scientific
model 25), and
6) a capacitance manometer (Baratron Type 220BA-01000A2B) with a
digital readout (MKS type (PDR-D-1).

Figure 3. Dicyclopentadiene Gas Delivery System

helium
gas in
dicyclopentadiene

24
A diagram of the system components and the gas flow pattern is
presented in Figure 4.
Gases were supplied to the flowmeters at 69,000 Pascals (10 psi)
pressure and the flow rates adjusted using the variable area flowmeter
needle valves. Copper tubes (1/4 in o.d.) from the flowmeter exit
ports were teed together a few centimeters downstream using brass
compression fittings. The gases then passed through the drying column,
which also acted as a mixing chamber. Nominal total flow rates were
200-400 ml/min. After exiting the drying column the gases flowed
through a teflon tee. One arm of the tee went to the bubble-tube
flowmeter (which was vented to the atmosphere through the building hood
exhaust), and the other arm went to the plasma chamber on/off valve.
Thus, when the on/off valve was closed, the total gas flow passed
through the bubble-tube flowmeter. When the on/off valve was open,
part of the gas stream (about half) flowed through the plasma chamber
while the remainder was vented through the bubble-tube flowmeter. This
arrangement assured that no atmospheric gases were introduced into the
plasma reaction chamber through the gas handling system.
Flow rates were set using the flowmeter needle valves and measured
using the bubble-tube flowmeter and a stopwatch while the chamber
on/off valve was closed. When more than one gas was used for an
experiment, the flow rates were determined by addition, starting with
the lowest flow and ending with the highest flow. The bubble-tube
flowmeter was also used to monitor the excess gas flow to the
atmosphere during plasma reaction experiments. The variable area

Figure 4. Gas Mixing and Delivery System

f lowrneters
wi th
metering
valves
° «
»o I
OOo
O
*?>/
//
LT
drying
column
gases
in
on/off
>
to
metering plasma
valves chamber
!=&=>—>
no
cr>

27
flowmeters were used to monitor the individual gas flows (comprising
the reaction mixtures) during experiments.
The gas flow to the plasma chamber was controlled by one or both
of the metering valves in most experiments. These valves were located
just downstream from the on/off valve and were used to separately
control the gas flow through two inlets into the plasma chamber. (One
inlet was located at the bottom of the chamber, beneath the target, and
the other inlet was located on the optic side arm adjacent to the zinc
selenide window. (See the plasma chamber description for further
details of the gas inlets.) In experiments where the chamber pressure
was 530 Pascals (4 torr) or greater, the gas flow was split equally
between the two inlets using the respective needle valves. In
experiments where the pressure was 133-533 Pascals (1-4 torr), one
needle valve and inlet were plugged and the entire gas flow was
directed through the optic side arm inlet. In experiments where the
chamber pressure was < 133 Pascals (< 1 torr), the Nupro metering
valves were replaced by an in-house fabricated, low-flow, 1000:1 taper
valve.
All experiments used the mechanical vacuum pump to provide the
driving force for gas flow through the system. The plasma chamber
pressure was monitored with the capacitance manometer which had a range
of 0-1000 torr in 0.1 torr increments (0-133,323 Pascals in 13 Pascal
increments). The manometer was calibrated using a standard mercury-
filled McLeod gauge.

28
The Plasma Reaction Chambers
Two plasma reaction chambers were used during the course of this
study. Their function was to provide a controlled environment for the
interaction of solid gold and gaseous compounds and elements. An
initial screening study was conducted using an all glass reaction
chamber. The remainder of the study was conducted using a more
versatile aluminum reaction chamber. A description of the all glass
chamber is presented first, followed by a description of the aluminum
chamber.
General features common to both chambers included a target
holder/manipulator for positioning the solid gold target, a zinc
selenide window for introducing the laser light, gas inlets for
introducing the reactant and inert gases, and a gas outlet for
delivering the reaction products and unreacted gases to the product
collection system and the vacuum pump. The major difference between
the two chambers was the design pressure rating. The glass chamber
used in the screening study was designed to operate in the pressure
range of 667-186,650 Pascals (5-1,400 torr), while the aluminum chamber
used throughout the rest of the study was designed to operate in the
pressure range of 0.133 to 93,000 Pascals (0.001 torr to - 0.9
atmospheres).
The glass, plasma reaction chamber. This chamber was designed to
be utilized for initial screening of prospective gases and gas mixtures
for their effectiveness in producing and transporting gas phase gold-
bearing species. This involved the determination of optimum pressure

29
and laser energy density conditions for gases showing positive results.
The protocol also included the study of the interaction of the focused,
pulsed CO2 laser beam with several inert and reactive gases and gas
mixtures at pressures approaching 200,000 Pascals (ca. 2 atm.). The
transparent chamber facilitated the observation of gas breakdown. This
phenomenon resulted in absorption of most of the laser pulse energy by
the gases, leaving very little energy to vaporize the solid gold. (A
further discussion of this topic is presented in the following
chapter.)
A diagram of this plasma reaction chamber is presented in Figure
5. The two-piece borosilicate glass body was fabricated in the
Scientific Glass-Blowing Shop at the University of Florida and had a
total volume (including side arms) of 588 ml. Two 50 mm i.d. glass 0-
ring seal joints (Kimax No. 50) were used as the base structures. One
of the joints was modified by tapering the blank end and butt-sealing
it to a 12 mm o.d. by 9 mm i.d. by 4 cm long piece of glass tubing.
The overall length of the resultant bell-shaped structure was 20 cm. A
9 mm o.d. by 6 mm i.d. by 14 cm long piece of perforated teflon tubing
was press-fitted into the narrow end of the bell structure from the
inside. This tube extended about 1 cm into the 12 mm o.d. glass
extension tube. The rest of the teflon perf-tube extended through the
center of the bell structure and ended about 2 cm from the wide end. A
50 mm dia. by 2 mm thick teflon perforated plate was then attached to
the teflon tube by threading a stainless steel screw through the center
hold of the perf-plate and into the end of the teflon tube. This unit
comprised the main gas inlet to the plasma chamber. The perforated

Figure 5. The Glass Plasma Reaction Chamber

germanium lens

32
tube and plate distributed the gas flow evenly to the plasma reaction
zone. A length of copper tubing coming from one of the gas handling
system metering valves was attached to the narrow end of the glass,
gas-inlet structure with a brass, 0-ring sealed, quick-connect fitting.
The other 50 mm i.d. glass 0-ring joint was also tapered and butt-
sealed to a 12 mm o.d. by 4 cm long piece of glass tubing to form a 20
cm long bell-shaped structure. The narrow end was the plasma chamber
outlet and was attached to the product recovery system and a mercury
manometer using a brass quick-connect fitting. Another 12 mm o.d. by 4
cm long piece of glass tubing was sealed to the large diameter sidewall
of the bell structure 5 cm (on center) from the mouth and served as a
guide shaft for the sample holder. A 20 mm i.d. glass 0-ring joint
(Kimax No. 20) was sealed to the opposite sidewall 6 cm (on center)
from the mouth and served as the optic side arm attach point. The
offset center lines allowed the use of a large diameter target that was
rotated past the beam impact point.
The sample holder shaft was an aluminum rod 15 cm long by 9 mm
o.d. that was slip-fitted through the chamber side arm, as mentioned
above, and sealed by sliding a length of tightly fitted, 3 mm thick
silicon rubber tubing over the joint. The part of the aluminum shaft
that contacted the silicon rubber tube was coated with vacuum grease
(Dow Corning silicon high vacuum grease) to facilitate sealing during
shaft rotation. A 7 cm dia. aluminum cogwheel was attached to the
exterior end of the aluminum shaft and used to rotate the sample
manually. The other end of the shaft extended into the chamber and had
a threaded center hole that was used as a target attach point. The

33
shaft, and target, could be moved toward the beam input opening a
maximum of 3 cm in order to shorten the optic path.
The two piece optic side arm was constructed from glass and
aluminum. The piece closest to the plasma chamber was made from a 20
mm i.d. glass 0-ring joint butt-sealed to a 30 mm i.d. glass 0-ring
joint (Kimax No. 30). There were actually two such pieces fabricated.
One was 5 cm long and the other was 8 cm long. This provided different
path lengths between the zinc selenide window and the target surface.
By exchanging these pieces, and moving the target back and forth, the
optical path length between the backside of the window and the target
surface could be varied by 6 cm. This allowed adjustment of the
incident energy density of the laser beam while maintaining a minimum
distance between the external focusing lens and the window. (This
arrangement minimized the probability of damage to the window surface,
as previously mentioned.)
The aluminum window holder was machined to match the 30 mm i.d.
glass 0-ring joint on one end. The other end was machined to hold the
zinc selenide window described earlier. The window was sealed using a
rotary 0-ring gland that incorporated the window edge and the inside
circumference of the aluminum holder as sealing surfaces. Two teflon
rings with inside diameters 2 mm smaller than the window o.d. were used
as spacers on either side of the window. The window and spacers were
held in place using an aluminum ring with the same i.d. as the teflon
rings and an o.d. equal to that of the aluminum holder. This ring was
attached to the end of the holder with four screws. A brass swage
fitting (1/4 in. pipe thread to 1/4 in. tube) was located 1 cm (on

34
center) from the edge of the window seat on the side of the holder. A
1/4 in. copper tube coming from the gas handling system's other
metering valve was connected to this fitting and provided a sweep of
incoming gases across the window surface to help minimize contamination
of the surface.
Butadiene elastomeric 0-rings were used where required throughout
the system. Pinch clamps held the glass 0-ring joints together when
the system was not under low pressure. The rotary seal on the window
and the seal on the sample holder shaft had moderate leak rates and the
chamber could be pumped down only to 13 Pascals (0.1 torr). While this
operational parameter met the rough-vacuum design criterion, the affect
of the residual pressure of air on the proposed reactions was unknown.
Therefore, a study of the affect of increased levels of air in
successful gas mixtures was included in the screening study protocol.
The affect of very low concentrations of residual air in successful gas
mixtures was investigated using the aluminum reaction chamber.
The aluminum plasma reaction chamber. This chamber was fabricated
by the author from aluminum (Alcoa alloy 2024) using available
facilities in the Department of Chemistry at the University of Florida.
A diagram of the chamber, including the sample holder, optic side arm,
and observation ports is presented in Figure 6. The screening study
was completed, and all other experiments were conducted using this
chamber.

Figure 6. The Aluminum Plasma Reaction Chamber

capacitance
manometer
3
rotateable "
sample stand
gas from
mixing
system^011/°f f
metering
valves
Hg>
-> to product recovery
system and vac. pump
laser
beam
stti
germanium
lens
CO
CT>

37
The aluminum plasma reaction chamber consisted of five parts:
1) the main body, including two gas inlet inserts, a gas outlet
flange, and a capacitance manometer insert,
2) two glass observation ports and their flanges,
3) the baseplate,
4) the optic side arm, and
5) the sample holder.
All of the components were fabricated from aluminum except the glass
ports and the main body inserts and outlet flange (which were machined
from brass). Viton or butadiene elastomeric 0-rings were used for all
seals. All tubing, fittings, and inserts leading from the gas handling
system and capacitance manometer that were subject to vacuum were
either brazed or connected with 0-ring quick-couples.
The completed system was leak checked using a mass spectrometer
helium leak detector (Veeco Leak Indicator MS17) previously calibrated
with a standard leak (Veeco Sensitivity Calibrator Type SC-4). The
detector response indicated that the leak rate was < 2 x 10'^ cc-
atm/sec (air equivalent) at each union and overall under He flood
conditions.
The main body was machined from a single block of aluminum 9.5 cm
wide by 7.6 deep by 15.2 cm high. The reaction zone was formed by
boring a 5.1 cm dia. by 9.5 cm deep hole through the center of the
block, starting on the bottom face. The top of this cavity was tapered
30° and narrowed to 1.0 cm in two steps before exiting the center of
the top face of the block. Static face seal 0-ring glands and four-

38
hole bolt circles were machined around both holes for attachment of the
gas outlet flange and the chamber baseplate.
Several different outlet flanges were used to connect the plasma
chamber to the various product recovery systems. All of the flanges
were sealed to the chamber using the 0-ring face seal and connected to
the product recovery system by an 0-ring quick-connect type coupler. A
1.2 cm dia. hole was bored on one of the 9.5 cm wide sides 2 cm (on
center) from the bottom of the chamber. A 6 cm long insert with a
rotary 0-ring gland was inserted through this opening. The insert had
a 6 mm hole bored from the incoming end and turned 90° at the outlet
end. This design allowed the incoming gas to be directed toward or
away from the plasma reaction zone by rotating the insert. Another 1.2
cm dia. hole was bored in the same face 9 cm (on center) from the
bottom of the chamber. A 6 mm i.d. plug insert with a rotary 0-ring
gland was used to connect the plasma reaction zone with the capacitance
manometer via a 30 cm length of 1/4 in. o.d. tubing.
A 2.0 cm diameter hole was bored into one of the 7.6 cm wide faces
5.5 cm (on center) from the bottom of the chamber. The 0-ring gland
and four-hole bolt circle were machined around this opening. This was
the optic side arm attach point.
A 3.3 cm dia. hole was bored into the other 7.6 cm wide face 4.7
cm (on center) from the bottom of the chamber. The sample holder was
inserted through this opening. A rotary 0-ring gland was machined into
the circumference of the opening 3.0 mm from the outer edge. This
0-ring sealed the sample holder even when it was being rotated. A

39
four-hole bolt circle was machined around the port to secure the sample
holder with its 0-ring face seal.
Two 5.0 cm dia. ports were cut into the 9.5 cm wide sides directly
opposite from each other and 5.0 cm (on center) from the bottom of the
chamber. Static face seal 0-ring glands and four-hole bolt circles
were machined around each port. Two 1.0 cm thick port flanges with
matching 0-ring glands and bolt holes held and sealed 6.0 cm dia. by
6.0 mm thick lead glass windows over each port.
The baseplate was 12.7 cm square by 2.5 cm thick and had four bolt
holes that matched the bolt circle on the bottom face of the chamber.
In addition, the baseplate had four holes at the corners that were used
to attach the chamber assembly to a table. Block spacers were placed
under the baseplate to raise the chamber optic arm to the same height
as the laser beam.
The single piece, 3.0 cm i.d., optic side arm used the same type
of rotary 0-ring gland as described above to center the zinc selenide
window. An 0-ring face seal gland was cut into the aluminum holder and
used to form the primary vacuum seal against the face of the window. A
precisely machined teflon spacer, and an aluminum ring flange similar
to the one described above, provided the necessary squeeze to form the
seal without unduly stressing the window. A 6.0 mm dia. hole was bored
into the side arm 5.0 mm (on center) from the window face seal edge and
used as the sweep gas inlet. A brass insert with a rotary 0-ring gland
connected the inlet to one of the gas handling system metering valves.
The optic side arm was attached to the plasma chamber using the bolt
circle and face seal described earlier.

40
The sample stand was also made from a single piece of aluminum.
The sample attach point was a threaded hole in the end of a 1.4 cm dia.
by 2.3 long section of the stand. This section ended in a 3.3 cm dia.
by 1.5 cm long section that acted as the sealing surface for the rotary
seal in the chamber throat. The outer section of the one-piece stand
was 7.5 cm in diameter and 1.3 cm thick and acted as the flange. This
section contained a face seal 0-ring gland that formed the primary
vacuum seal, and a series of arced bolt slots that matched the bolt
circle on the chamber. The rotary seal allowed the sample to be
rotated manually while under vacuum by loosening the face seal bolts.
(Depending on target thickness, this was done once or twice an hour
during most experiments.) The bolts were retightened after the sample
rotation was completed. This was necessary because particles and
frictional wear frequently caused minor leaks in the rotary seal.
The Product-Recovery/Substrate-Coatinq Systems
There were several product-recovery/substrate-coating systems used
throughout the study. Many of the systems used common components
assembled in different sequences and maintained at different
temperatures. Many of these arrangements were designed to investigate
the volatility, or other physical properties, of the plasma reaction
products. The system descriptions are presented below along with their
respective operational parameters. Results are discussed in Chapter
III.
Heated quartz tube. A 2 mm i.d. by 4 mm o.d. by 50 cm long quartz
tube was attached directly to the glass plasma chamber outlet using a

41
Silicon rubber sleeve seal. The tube was placed in a Linberg tube
furnace with a 30 cm long high temperature zone. The furnace was
heated to 600-890 K during experiments in order to decompose any gold
bearing species that passed through. The gas flow rates were adjusted
to allow a residence time of 3-194 milliseconds in the hot zone. In
practice this resulted in visible deposits varying in color (from black
to purple to red to gold) and position along the tube. In some experi¬
ments the quartz tube was followed by a glass wool plug and/or a cold
finger (size 14/22 or 24/40) in a dry-ice/acetone bath (see Figure 7).
Staged cold traps. Several experiments used multiple cold traps
at progressively colder temperatures to observe product collection
characteristics. The various schemes used are pictured in Figure 8.
The first such scheme used a cold finger (CF) in water-ice (273 K)
followed by a second CF in dry-ice/acetone (195 K), and a third CF in
liquid nitrogen (77 K). Clogging of the CF in liquid nitrogen resulted
in its replacement with a second CF in dry-ice/acetone. The next
modification incorporated a glass wool plug before the cold traps.
This scheme was then modified by placing the glass wool between the
first CF, which was kept at room temperature, and a second cold trap
made from a 1/4 in. (6.35 mm) o.d. by 25 cm long glass U-tube kept in
crushed dry ice. Another scheme used a small test-tube inserted in the
gas stream at the plasma chamber outlet ahead of the U-tube in dry ice.
The test-tube was either maintained at ambient temperature or was
filled with dry ice. The flange which held this tube could also
accommodate a quartz window in place of the test-tube. Finally,

Figure 7. Heated Quartz Tube Product Recovery System

gas
out
-p»
GO

Figure 8. Staged Cold Traps Used for Product Recovery
(a) Three cold fingers
(b) Cold finger with U-tube
(c) Test-tube with U-tube

45
-t>
gas
in
-£> to
pump
insert

46
the system was limited to the U-tube in crushed dry-ice (or dry-
ice/acetone) since this proved sufficient for trapping the plasma
reaction products for later use. A fresh trap was used for each
experiment. The 1/4 in. o.d. glass U-tubes were eventually replaced
with 3/8 in. (9.525 mm) o.d. glass U-tubes. One of these U-tube cold
traps was used in all subsequent experiments either alone or after a
substrate coating chamber.
Substrate coating chambers. Substrates were coated with the
plasma reaction products during experiments by sticking them to the
inside of the chamber windows (using Scotch clear adhesive tape), by
placing them in the connecting tubing leading to the U-tube cold trap,
or by placing them in one of the three coating chambers pictured in
Figure 9. The first two chambers were fabricated from glass in the
Scientific Glass Blowing Shop at the University of Florida. The third
chamber was constructed from aluminum by the author using available
facilities in the Department of Chemistry at the University of Florida.
All of the chambers were placed in line after the plasma chamber and
before the U-tube cold trap. The two glass coating chambers were
mounted perpendicular to the plasma chamber via an elbow quick-couple.
The aluminum coating chamber was connected directly to the top of the
plasma chamber using a straight quick-couple.
The first chamber was made by truncating a 20 mm i.d. glass 0-ring
seal joint (Kimax No. 20) 3 cm from the sealing end and attaching 1/4
in. o.d. by 5 cm long glass tubes on opposite sides, perpendicular to
the seal face. These tubes acted as the inlet and outlet. A 25 mm
dia. by 1 mm thick quartz window was placed on the 0-ring and held in

Figure 9. Substrate Coating Chambers
(a) Small glass chamber showing a ceramic feed¬
through in place
(b) Large glass chamber showing the 3-tier
sample rack

48
^ quartz window
(b)
hoider
gas
out
to heater controller

49
place by the system vacuum. Total volume of the chamber was 20 ml.
Substrates could be placed in this chamber and exposed to a 5 watt
Argon ion laser beam (Spectra Physics 165) while plasma reaction
products flowed through.
A second, larger coating chamber was constructed from two 40 mm
i.d. glass 0-ring seal joints (Kimax No. 40). The joints were tapered
and sealed to 1/4 in. tubing on the ends. The two halves were held
together with a pinch clamp when the system was not under vacuum. The
assembled unit was 20 cm long and had a total volume of 145 ml. A
three-tiered substrate holder rack was made by the author using three
38 mm dia. by 2 mm thick perforated aluminum plates connected by a
central stainless steel shaft. Substrates were placed on the different
rack plates in either equatorial or axial positions in order to observe
shadowing effects during coating.
A third, more versatile coating system was machined from aluminum
stock (Alcoa alloy 2024). This chamber was also a two-piece design and
had an 0-ring face seal between the halves. The bottom half started
with a 1/2 in. (12.7 mm) o.d. by 1.9 cm long inlet segment that sealed
directly to the top of the plasma chamber via a 1/2 in. brass quick-
couple. This section had an inside diameter of 1.0 cm. The next
segment of the bottom piece had an o.d. of 5.0 cm and an i.d. of 4.0 cm
and was 4.4 cm long. The final segment was 7.6 cm wide by 1.2 cm thick
and contained the 0-ring gland, a four-hole bolt circle, and a seat on
the inside diameter for a 4.0 mm wide by 3.0 mm thick teflon ring
spacer. This segment acted as a flange to connect the two pieces of
the chamber.

50
The top half started with a matching flange segment with a 3.0 mm
thick by 48 mm dia. teflon perforated plate press-fitted into the 4.0
mm wide seat on the inside diameter. This was followed by a 5.0 cm
o.d. by 4.0 cm i.d. by 1.9 cm long segment and a 1.0 cm i.d. by 1/2 in.
(12.7 mm) o.d. by 2.3 cm long outlet segment. The assembled chamber
was 13 cm long and had an internal volume of 87 ml.
The teflon perforated plate and spacer were used to hold a 47 mm
diameter borosilicate glass fiber filter that had a retention rating of
0.98 at 0.2 microns (Micro Filtration Systems GB 100 R47 mm). The
filter faced the gas flow and was backed by the perforated plate. The
teflon ring held the filter in place without damaging it. This
arrangement was used to trap particles that were produced in the plasma
chamber. Particles that were transported 20 cm up from the plasma
reaction zone, through the narrow plasma chamber outlet and up to the
filter, were very efficiently trapped. Other particles that impinged
on the plasma chamber sidewalls or fell to the bottom of the chamber
were not collected by the filter. Most large particles ("chunks" and
"flakes" tens of microns in size) that made it to the filter rebounded
on impact and were found in the bottom of the collection chamber.
Large particles that adhered to the filter were easily distinguished
using visual microscopy. Thus, the arrangement provided a semi-
quantitative method for comparing relative abundances and gold content
of particles entrained in the gas stream using gravimetric and atomic
absorption analyses, respectively.
Heated substrate mount. Several experiments were performed with
substrates attached to a heated mount shown in Figure 9. The 3.5 cm

51
dia. by 3.0 cm high mount consisted of a potted nichrone heating
element covered with a 2 mm thick aluminum plate that had a series of
threaded holes. Flat head screws were used to attach substrates to the
plate using the threaded holes. The mount was positioned in the top of
the aluminum collection chamber with the heated substrates facing the
gas flow. Three small ceramic posts minimized the area of contact
between the mount and the top of the collection chamber.
The heating element wires extended through the top of the chamber
through two glass inserts that were epoxy sealed (J. B. Weld Co.,
Sulphur Springs, TX) to the aluminum. Rubber septa and sealing putty
(Apiezon Q) were used to seal the wires at the exit of the glass
inserts. There was a small leak at this point, ca. 0.01 ml air/min
determined by differential pressure measurements. However, its
location downstream from the plasma reaction zone and the substrate
coating zone, and the results of earlier experiments that showed the
relative insensitivity of selective plasma reactions to air, minimized
concern over the leak.
Temperature control for the heated mount was provided by a 12 V dc
power convertor driven by a variable voltage auto-transformer.
Temperatures were controlled to + 5% of the set point. A thermocouple
junction (type K) was implanted in the aluminum hot plate and connected
to a digital multi-meter (Kiethly 177 Microvolt DMM). The thermocouple
was calibrated using water ice and boiling deionized water.

52
Production of Gas-Phase Gold Species: Experimental
Conditions and Materials
Screening Study Experiments
The purpose of the screening study was to identify gases and/or
gas mixtures, operating pressures, and laser power density parameters
that resulted in the production of relatively large amounts of gas-
phase gold species. The screening study was continued throughout the
duration of the overall study. The product recovery systems described
above were used to separate the gold species from the gas stream.
Visual observation was used as an initial method of evaluation since
the relative abundances of gold species collected in individual
experiments varied drastically. Cold traps containing the recovered
products were sealed and heated in a bunsen burner and then opened to
the atmosphere and reheated. Observations of the relative quantities
of gold films formed on the glass surfaces were utilized to identify
successful operating conditions.
Glass fiber filter catches were determined gravimetrically using a
Mettler analytical balance. (Filter blank measurement methods and data
are presented in Appendix A). Quantitative measurements of the amounts
of gold collected in some of the cold traps, and on most of the glass
fiber filters, were performed using Atomic Absorption (AA) analyses
(Perkin Elmer Model 303 AA) and standard analytical techniques.
Samples were either extracted/ suspended in acetone, or dissolved in
aqua regia and diluted. Calibration data and response curves are
presented in Appendix C.

53
The initial gold target used in the screening study was formed by
melting and casting ca. 10 grams of Au wire (0.999 purity) into a 2-3
mm thick crescent shape. A machined graphite block was used as a mold
for the casting. A Canadian Maple Leaf 1 oz gold coin (0.999 purity)
was also used as a target during the screening study and in all
substrate coating experiments. This target required recasting after
extended use, but its total mass was never less than 23 grams, and its
thickness was never less than 3 mm. A 1.0 cm thick by 2.5 cm diameter
piece of graphite (mass = 23.7 grams) was used as a target in two
experiments and a 6 mm thick by 18 mm wide by 28 mm long OFHC copper
target (mass = 28.0 grams) was used in two other experiments.
Gases used in the study were obtained from several different
sources. The gases are listed in Table 1 along with their respective
vendor sources and purity ratings. No attempts were made to further
purify any of the gases beyond the removal of excess moisture in the
gas drying column already described, with one exception. The helium
gas used in test No. 861126B was passed through two liquid nitrogen
cold traps in order to remove traces of water which otherwise would
have reacted with the liquid dicyclopentadiene, causing it to
gelatinize.
Table 2 lists all of the experiments contained in the screening
study along with their respective experimental conditions. Each
experiment was given a six numeral identification number based on the
year, month, and day that it was performed. A letter was added to the
numerical code when more than one experiment was performed in the same
day. For example, "860602A" refers to the first experiment performed

54
Table 1. Gases Used in the Plasma Reaction Study
Gas
Vendor
Purity Rating
helium
Aireo
standard grade
argon
Aireo
standard grade
air
(laboratory ambient)
N/A
air
Aireo
breathing quality
hydrogen
Aireo
standard grade
Linde
standard grade
dicyclopentadiene
(liquid)
Aldrich Chemical
reagent grade
chlorodifluoro-
methane
Allied Chemical Corp.
refrigerant grade
dichlorodifluoro-
methane
Allied Chemical Corp.
refrigerant grade
hexafluoroethane
PCR, Inc.
99%
acetylene
Aireo
welder's grade
carbon monoxide
Matheson Specialty Gases
99.9%
methane
Matheson Specialty Gases
99.9% and 99%
natural gas
Gainesville Regional
Gas Company (through
laboratory lines)
commercial grade

Table 2. Screening Study Plasma Reaction Experiments
Expt. Gas
No. Mix
(target) (%)
Pressure *Flow Rate Through
(Pascal) Reaction Zone
ml/min cm/sec
(atm.)
CO2 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
860602A
He
161,500
N/A
N/A
optimum
0.20
none
(none)
(100)
156,100
N/A
N/A
optimum
0.20
141,500
N/A
N/A
optimum
0.20
134,800
N/A
N/A
optimum
0.20
128,100
N/A
N/A
optimum
0.20
121,500
N/A
N/A
optimum
0.20
114,800
N/A
N/A
optimum
0.20
107,900
N/A
N/A
optimum
0.20
101,500
N/A
N/A
optimum
0.20
94,790
N/A
N/A
optimum
0.20
88,130
N/A
N/A
optimum
0.20
72,130
N/A
N/A
optimum
0.20
58,800
N/A
N/A
optimum
0.20
36,130
N/A
N/A
optimum
0.20
26,800
N/A
N/A
optimum
0.20
18,800
N/A
N/A
optimum
0.20
860602B
Air
101,500
(open
to atm)
optimum
0.60
none
(none)
(100)
860530
h2
110,900
3500
162
optimum-5.6
2.70
none
(Au)
(100)
106,390
3500
169
optimum
1.80
860605
He/Ho
13,870
40
15
optimum
2.20
790 K QT,
(Au)
(80/20)
194 msec
860606
He/H?
6,800
51
39
optimum
1.72
790 K QT,
(Au)
(75/25)
75 msec

Table 2 (continued)
Expt. Gas
No. Mix
(target) (%)
Pressure *Flow Rate Through
(Pascal) Reaction Zone
ml/min cm/sec
(atm.)
CO2 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
860612
He/Ho
800
54
346
optimum
6.36
790 K QT,
(Au)
(75/25)
8 msec
861022B
He
800
(54)
(346)
optimum
1.20
GWP, UT
(Au)
(100)
861124
He
1,330
125
484
optimum
16.20
UT
(Au)
(100)
870226
Ar/H?
1,390
(90)
(350)
optimum
3.60
300 K TT, UT
(Au)
(75/25)
670
(40)
(310)
optimum
7.68
(55/45)
750
(55)
(380)
optimum
6.96
860724
He/CO
4,930
315
330
optimum
0.30
GWP, two
(Au)
(77/23)
2,670
N/A
N/A
optimum
0.30
195 K CFs
1,600
N/A
N/A
optimum
0.60
1,200
22
95
optimum
12.90
861106
He/CO
UT
(Au)
(100/0)
1,600
N/A
N/A
optimum
0.06
(99/1.2)
1,600
N/A
N/A
optimum
0.09
(98/1.7)
1,600
N/A
N/A
optimum
0.09
(96/3.8)
1,600
N/A
N/A
optimum
0.09
(95/5.2)
1,470
N/A
N/A
optimum
0.06
(90/10)
1,600
N/A
N/A
optimum
0.06
4,000
N/A
N/A
optimum
0.06
(88/12)
9,070
N/A
N/A
optimum
1.50

Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate Through
Reaction Zone
ml/min cm/sec
(atm.)
C02 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
861110
(Au)
He/CO
(79/21)
1,530
210
707
optimum
14.40
195 K CF,
GWP, UT
861126B
(Au)
He (sat. 1,330
with dicyclopentadiene)
(125)
(484)
optimum
12.42
UT
861205
(Au)
He/C2H2
(81/19)
1,400
(125)
(460)
optimum
10.08
195 K TT,
861210
(Au)
He/C2H2
(98/2.5)
1,400
(130)
(490)
optimum
9.78
195 K TT,
870121
(Au)
h2/c2h2
(92/8.3)
1,360
(130)
(490)
optimum
11.04
300 K TT,
861022A
(Au)
ch4
(100)
1,200
(200)
(860)
optimum
3.96
GWP, UT
860701
(Au)
He/CH4
(77/23)
1,730
(300)
(890)
optimum
5.40
893 K QT,
3 msec,
195 K CF
860702
(Au)
He/CH4
(75/25)
1,600
(290)
(935)
optimum
7.02
573 K QT,
3 msec,
195 K CF
UT
UT
UT

Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate Through
Reaction Zone
ml/min cm/sec
(atm.)
C02 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
860704
(Au)
He/CH4
(75/25)
2,000
(330)
(850)
0.59
optimum
2.46
15.12
273 K CF,
195 K CF,
77 K CF
860722
(Au)
He/CH4
(75/25)
1,470
286
510
optimum
19.62
GWP, two
195 K CFs
861012
(Au)
He/CH4
(72/28)
2,130
(350)
(850)
optimum
19.62
GWP, UT
861023
(Au)
He/CH4
(70/30)
1,600
(220)
(710)
optimum
14.40
78 K CF,
GWP, UT
861022C
(carbon)
He/CH4
(75/25)
800
N/A
N/A
optimum
3.90
UT
861016
(Au)
He/CH4/air
(71/25/4)
1,200
(200)
(860)
optimum
6.90
GWP, UT
861017
(Au)
He/CH4/air
(75/21/4)
1,200
(200)
(860)
optimum
10.38
UT
861018
(Au)
He/CH4/air
(71/25/4)
1,600
(290)
(935)
optimum
6.78
300 K CF, UT
870109
(Au)
h2/ch4
(80/20)
1,310
(125)
(490)
optimum
15.00
195 K TT, UT

Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate Through
Reaction Zone
ml/min cm/sec
(atm.)
CO2 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
870324
(Au)
H?/CH4
(84/16)
1,350
(130)
(500)
2.4
1.1
4.20
2.94
300 K TT,
UT
870313
(Au)
^/Natural
Gas
(75/25)
1,420
(130)
(470)
optimum
10.20
300 K TT,
UT
880218
(Au)
Ar
(100)
1,390
75
278
optimum
29.82
GFF,UT
880222
(Au)
He
(100)
1,370
116
436
optimum
29.82
GFF, UT
880223
(Au)
H9/CH4
(76/24)
1,350
145
550
optimum
21.60
GFF, UT
880224
(Au)
H0/CH4
(74/26)
1,390
200
750
optimum
21.60
GFF, UT
880302
(Au)
H7/CH4
(74/26)
1,380
195
730
optimum
21.60
GFF, UT
880303
(Au)
H9/CH4
(74/26)
670
81
620
optimum
22.02
GFF, UT
880304
(Au)
H0/CH4
(74/20)
2,710
653
1,240
optimum
21.60
GFF, UT

Table 2 (continued)
Expt.
No.
(target)
Gas
Mix
(%)
Pressure
(Pascal)
*Flow Rate
Reaction
ml/min
(atm.)
Through
Zone
cm/sec
C02 Laser Conditions
Focal Point Pulses
(mm dia.) (x 1000)
**Product
Recovery
System
880307
(Au)
ch4
(100)
1,470
(240)
(840)
optimum
21.60
GFF, UT
880309
(Au)
h2/ch4
(48/52)
670
72
550
optimum
21.60
GFF, UT
880311
(Au)
h2/co
(75/27)
1,390
(125)
(465)
optimum
19.98
GFF, UT
880317
(Au)
h2/co2
(75/25)
1,390
125
465
optimum
21.60
GFF, UT
880329
(Au)
He/CHClF2
(74/26)
1,470
145
510
optimum
3.66
GFF, UT
880415
(Au)
He/CHClF2
(76/24)
300
110
1,890
optimum
5.16
GFF, UT
880421
(Au)
He/CCl2F2
(76/24)
1,360
190
790
optimum
16.56
GFF, UT
880425
(Au)
He/CCl2F2/H2 1,370
(82/14/3.6)
175
660
optimum
20.70
GFF, UT
880427
(Au)
He/C2Fc
(73/27)
1,240
110
413
optimum
19.98
GFF, UT

Table 2 (continued)
Expt.
Gas
Pressure
*Flow Rate Through
CO? Laser Conditions
**Product
No.
Mix
(Pascal)
Reaction
Zone
Focal Point
Pulses
Recovery
(target)
(%)
ml/min
(atm.)
cm/sec
(mm dia.)
(x 1000)
System
880720
h?/ch4
1,350
200
760
optimum
9.77
GFF, UT
(carbon)
(74/26)
880723
h?/ch4
1,350
200
760
optimum
8.34
GFF, UT
(copper)
(74/26)
880724
H?/CHd
27
0
0
optimum
0.01
GFF, UT
(copper)
(74/26)
1,320
(195)
(760)
optimum
0.03
1,230
(185)
(780)
0.28
0.03
1,230
(185)
(780)
0.56
0.03
200
N/A
N/A
0.56
0.03
750
(80)
550
optimum
0.03
1,410
(210)
(770)
optimum
10.44
2,450
330
690
optimum
0.37
*Flowrate
values
in parentheses
are estimates
based on
measurements made
under similar
conditions.
**QT = quartz tube; GWP = glass wool plug; UT = 195 K U-tube; GFF = glass fiber filter; TT = test-tube;
CF = cold finger. See text for detailed descriptions.

62
on June 2, 1986. The gas mixtures, total pressures, and flow rates
through the plasma reaction system are also listed in this table. The
pulsed laser focal point diameter at target impact and the total number
of pulses for each experiment are included as well.
Volumetric flow rates were measured in ml/min at atmospheric
pressure using the bubble-tube flowmeter. Linear flow rates (L)
in cm/sec through the plasma reaction zone were calculated using the
following equation:
L = (F) (101,325/P)/7rr2
where F is the volumetric flow rate in ml/sec measured at atmospheric
pressure, P is the plasma reaction chamber pressure in Pascals, and r
is the radius of the reaction zone in cm. Some values (listed in
parentheses) were estimated from measurements made during similar
experiments utilizing the same nominal gas mixture and pressure and the
same settings on the variable-area flowmeters.
The diameter (d) for the laser beam at the target impact point was
calculated using the absolute value of the difference (x) between the
focal length of the lens (f) and the measured separation of the lens
and target, and the measured diameter (D) of the unfocused laser beam:
(d/2)/x = (D/2)/f
The impact point diameter was varied by moving the lens closer to or
farther away from the target.

63
The first experiment listed in Table 2 investigated the onset of
gas breakdown in helium under pressures ranging from 18,800 to 161,500
(Pascals (141-1211 torr). The second test listed demonstrated the same
effect in air at 101,500 Pascals (761.5 torr). In both of these
experiments the laser beam was focused into the center of the plasma
chamber. The target and target stand were removed from the system.
The third experiment listed demonstrated gas breakdown in hydrogen at
106,390 and 110,900 Pascals (798 and 832 torr) pressure when focusing
the laser on a gold target. The focusing lens was moved back 3 cm from
the optimum distance in order to observe the effect on the gas
breakdown. This same phenomenon was also observed in several other gas
mixtures at lower pressures during the course of the study.
Observations and results are discussed in the next chapter.
Gases were supplied to the chamber under pressure during segments
of the first and third experiments when reactor chamber pressures were
greater than the ambient pressure. Flow rates were controlled by a
metering valve at the chamber exit, upstream from the mechanical pump.
At lower pressures (< 101,500 Pascals) in these and all remaining
experiments, the pressures and gas flow rates were controlled using the
gas handling system described earlier and the metering valve before the
pump.
The last four experiments listed in Table 2 were attempts to
generate pure carbonaceous and copper-bearing species in the plasma
chamber using the carbon and copper targets, respectively, and a 3:1
H2CH4 gas mix. The remaining experiments listed in Table 2 were all
attempts to generate gold species that would remain entrained in the

64
gas stream and subsequently be trapped in the product recovery system.
The reader is directed to the table for a detailed presentation of the
experimental conditions. The results of each experiment are discussed
in Chapter III.
Substrate Coating and Annealing Experiments
Several different types of substrates were coated with the plasma
reaction products during the course of the study. Experiments that
produced the coated substrates are listed in Table 3 along with the
respective substrates and their physical positions in the plasma-
reaction or product-recovery systems during the coating process. In
all of the coating experiments the pulsed CO2 laser was operated at its
maximum voltage level (40 KV) and the focusing lens was adjusted to
provide an optimum focus at the target impact point. All coating
experiments were carried out at a nominal pressure of 1,330 Pascals (10
torr). A nominal gas mixture of 75% hydrogen and 25% methane was used
in all of these experiments with four exceptions. Two experiments were
performed using 100% helium, one test used 78% helium and 22% carbon
monoxide mixture, and one test used a mixture of 75% hydrogen and 25%
natural gas.
Eleven different types of substrates were coated with the plasma
reaction products:
1) glass plates cut from standard 1 mm thick microscope slides
(Corning No. 2947), varying in size from 5 mm by 10 mm to 25 mm by 40
mm,
2) quartz optical windows, 1 mm thick by 27 mm diameter,

65
Table 3. *Substrate Coating Experiments
Expt. Total # Substrates Position in
No. of Laser Coated System
Pulses
(x 1000)
861117 15.00
(78% He/22% CO)
W coated polycrystal -
line (pc) Si chip
placed in U-tube inlet
861124
(100% He)
16.20
glass plates
taped to plasma chamber
windows; placed in bottom
of plasma chamber
861126A
(100% He)
7.20
W coated pc Si chip
with an etched area;
patterned W on single
crystal (sc) SI; glass
pi ates
W/Si chips taped to glass
plates; glass plates taped
to windows and placed in
bottom of plasma chamber
870313 10.20
(75% H£/25% natural
W ribbon coil
gas)
placed in U-tube inlet, Ar
ion laser beam directed
through glass tube onto
leeward area
870326
12.60
W ribbon
placed in plasma chamber
outlet, Ar ion laser beam
directed through quartz
window onto W
870416
13.92
ceramic feedthrough
placed in small coating
chamber
870427
40.74
9 ceramic feedthroughs
placed in glass coating
chamber (GCC) on three¬
tiered rack
871106
27.66
glass plate
taped into GCC inlet
870721
63.12
W on pc and sc SI
chips; patterned A1
on sc Si chip
taped to first tier of
rack in GCC
870801
11.76
glass plate
taped into GCC inlet
870819
23.10
glass plate
taped into GCC inlet
870901
55.92
3 patterned W, 2 pat¬
terned A1 on sc SI
chips
taped onto glass plate
that was taped into GCC
inlet

66
Table 3 (continued)
Expt.
No.
Total #
of Laser
Pulses
(x 1000)
Substrates
Coated
Position in
System
880527
33.55
3 W on pc Si and
3 W on sc Si chips
taped to perf-plate in the
aluminum coating chamber
(ACC)
880602
31.32
7 W on pc Si and
5 W on sc Si chips
taped to perf-plate in ACC
880617
27.56
3 W on pc Si and
3 W on sc Si chips
clipped to 373 K hot plate
in ACC
880623
23.46
2 W on sc Si chips;
2 glass plates
clipped to 373 K hot plate
in ACC
880629
20.58
3 W on sc Si chips;
5 glass plates; strip
of Scotch tape, ad¬
hesive side up, with
an area of W thin film
stuck to the adhesive
taped to perf-plate in ACC
880708
6.41
2 charged aluminum
plates (+275 and -125)
volts dc potential)
pressed into center of
perf-plate
880711
9.98
Si chip with a central
strip of W on one side
charged with -125 volt
dc potential; two 2.5
cm dia. quartz optical
flats; 4 glass chips
placed near sidewall in
ACC
taped to plasma chamber
windows
*A11 experiments were conducted at a nominal pressure of 1,330 Pascals
using a nominal gas mixture of 75% H2 and 25% CH4, except where noted.

67
3) tungsten ribbon, 1.5 mm wide by 0.2 mm thick (H. Cross
Company),
4) ceramic electrical feedthroughs, 1 cm diameter surface,
5) blanket coated CVD tungsten (500-600 nm) on a silicon wafer
with one polycrystalline (pc) side and one single crystal (sc) side
(Harris Corporation) cut into 5 mm by 15 mm chips,
6) same as (5), with areas of tungsten etched away (1 M
K3Fe(CN)g:0.1 M ethylene diamene) to expose the silicon surface,
7) VLSI circuit patterned CVD tungsten on sc silicon with silicon
dioxide surfaces surrounding the 5-50 micron size tungsten features
(Harris Corporation), cut into 5 mm by 15 mm chips,
8) VLSI circuit patterned CVD aluminum on sc silicon with silicon
dioxide surfaces surrounding the 5-50 micron size features (Harris
Corporation), cut into 5 mm by 15 mm chips,
9) aluminum plates, 10 mm by 20 mm by 1 mm thick,
10) Scotch brand adhesive tape, and
11) Scotch brand black electrical tape.
All of the substrates, except the two polymeric tapes, were cleaned in
spectral grade acetone, rinsed in spectral grade methanol, placed in
clean glass petri dishes, and dried in a 383 K oven for at least one
hour. After carefully mounting the cooled substrates onto the plasma
chamber windows or in the substrate coating chamber using rolled Scotch
tape, they were rinsed off with dry nitrogen and placed in line.
Coated substrates were stored in air in glass petri dishes or plastic-
stoppered glass vials.

68
In most of the experiments the substrates were positioned in one
of the product-recovery/substrate-coating systems described earlier and
coated at room temperature (ca. 300 K). In one experiment a 5 cm long
piece of tungsten ribbon was coiled and placed in the inlet arm of the
glass U-tube cold trap and irradiated with an unfocused cw Argon ion
laser beam (4.5 watts, 514.5 nm). In another experiment a 1.5 cm long
piece of the tungsten ribbon was placed in the top of the plasma
reaction chamber at the exit union with the product recovery system
flange (see Figure 9) and exposed to the unfocused Ar ion laser beam
through a quartz window. This caused the ribbon to glow a dull red
when the chamber was under vacuum. When the system gas flow was turned
on the glow disappeared. In both experiments the laser beam was
impacting the leeward face of the ribbon. These were attempts to
observe thermal decomposition of gold species entrained in the gas
stream and subsequent deposition of gold along the thermal gradient
induced by the laser beam.
Two experiments utilized the hot plate described earlier to heat
glass plates and CVD tungsten coated pc and sc silicon chips to 373 ± 5
K during the coating process. Problems associated with channeling of
the gas stream around the hot plate limited the efficiency of this
process, but several substrates were effectively coated in each
experiment and then subjected to spectral and microscopic analyses.
A list of the coated substrates that were annealed and the
respective annealing condisions is presented in Table 4. Some of the
tungsten coated and patterned chips, aluminum patterned chips, glass
plates, and quartz windows that had been coated with plasma reaction

69
Table 4. *Substrate Annealing Conditions
Expt.
Substrate
Annealing
Time
Temp.
No.
Method
(K)
861117
plasma chamber
pulsed C02 laser,
40 KV, unfocused
60 pulses
(78% He/
22% CO)
glass window
861126A
W on pc SI chip;
--radio frequency
10 sec
(100%)
patterned W on
(rf) coil (in
60 sec
sc Si chip
flowing air);
--rf coil in still
70 sec
dull red
air
870326
W ribbon
Ar ion laser, 4.5
211 min
watts, unfocused
(in situ)
870416
ceramic feed-
slow convective
141 min
(743)
through
heating (cv.h.)
in air while moni¬
toring electrical
resistance
(max.)
870427
ceramic feed-
same as above, ex-
57 min
(763)
through
cept under H2 flow
(max.)
870721
W on pc and sc Si;
cv.h. under H2 flow
18 hr
563
patterned A1 on sc
+ 1 hr
0 563
Si chips
+ 2 hr
0 723
870901
W and A1 on sc Si
chips
cv.h. under H2 flow
18 hr
563
880224
glass fiber
cv.h. in air
1 hr ca
. 400
filter (GFF)
+ 3 hr
873
880229
GFF
cv.h. in air
24 hr
420
+ 1 hr
573
880304
GFF
cv.h. in air
8 hr
505
880307
(100% CH4)
GFF
cv.h. in air
8 hr
505
880309
GFF
cv.h. in air
8 hr
505
(48% H2/
52% CH4)

70
Table 4 (continued)
Expt.
No.
Substrate
Annealing
Method
Time
Temp
(K)
880311
GFF
cv.h. in air
3 hr
515
(H2/C0)
880317
GFF
cv.h. in air
24 hr
515
(h2/co2)
880527
W on pc and sc
--cv.h. under H2 flow
18 hr
(533)
Si chips
--cv.h. in air
18 hr
(553)
W on pc and sc
--cv.h. under H2 flow
18 hr
(533)
Si chips
followed by cv.h.
in air
+19 hr
(603)
880602
W on pc and sc
--cv.h. in air
18 hr
373
Si chips
--cv.h. in air
--cv.h. in air
--cv.h. in air
--cv.h. under H2 flow
--cv.h. in air, fol¬
lowed by cv.h.
under H2
--cv.h. under H2,
followed by cv.h.
in air
18 hr
18 hr
18 hr
1 hr
18 hr
+ 1 hr
1 hr
+19 hr
(533)
(593)
(593)
(573)
(593)
(573)
(573)
(603)
880623
W on pc Si chip
glass plate
--rf coil in air
--drew lines with
focused Ar ion '
laser beam (3.5
watts)
3 sec
0.3 cm/sec
red hot
880629
W on pc Si chip
and glass plate
--rf coil, 0.013
Pascal
--cv.h. in air
--drew 1ines with
focused Ar ion laser
beam (3.5 watts)
(2.0 watts)
(1.0 watts)
1 min
85 min
0.5 cm/sec
0.5 cm/sec
0.5 cm/sec
(670)
880708
(-) dc potential
aluminum plate
cv.h. in air
90 sec
(875)

71
Table 4 (continued)
Expt.
No.
Substrate
Annealing
Method
Time
Temp.
(K)
880711
pieces of GFF
cv.h. in air
25 hr
383
23 hr
(473)
1 hr
(676)
90 sec
(875)
*A11 experiments were conducted at a nominal pressure of 1,330 Pascals
using a nominal gas mixture of 75% H2 and 25% CH4, except where noted.

72
products were annealed in air or hydrogen at temperatures ranging from
373-670 K for time intervals ranging from several seconds to several
hours. These anneals were performed in the tube furnace described
earlier. An annealing chamber was constructed from a 20 mm i.d. by 50
cm long borosilicate glass tube with 0-ring seal joints on both ends
(see Figure 10). The ends of this tube were connected to two matching
0-ring seal joints that had ends tapered to 1/4 in. o.d. tubing. Quick
couples were used to connect the chamber with the gas handling system
for delivery of hydrogen at ca. 400 ml/min. Anneals in air were
performed by disconnecting the chamber's gas inlet line and allowing
ambient air to be drawn through the system by convective flow. A brass
sample holder with a stainless steel insertion handle was used to place
and hold the substrates in the center of the tube furnace, adjacent to
the thermocouple.
Some glass fiber filters were also annealed in air at temperatures
ranging from 390-873 K by placing them in borosilicate glass petri
dishes and then into a laboratory drying oven or a muffle furnace.
This was done to observe the onset of a development process that
changed the color of the plasma reaction product coating from black to
purple to pink/red.
Several patterned and unpatterned CVD tungsten on silicon chips,
and one glass plate, were inserted into a radio frequency coil and
heated inductively. Either a 30-year-old ham radio with - 100 watts of
power at 13.56 Mhz, or an ICOM All Solid State HF SSB tranceiver
feeding a Heath Kit tube-type linear amplifier at 14.000 Mhz and
delivering - 250 watts of power, were used to power the 3 cm diameter 3

Figure 10. Substrate Annealing Chamber


75
I
turn coil. No temperature measurements were made in these tests, but
several samples were heated to a red glow. Exposure time to the rf
field was varied from 3-70 seconds. Some tests were performed in
ambient air with or without a fan blowing air past the sample, and
other samples were heated while under a pressure of 0.01 Pascals.
The unfocused pulsed CO2 laser beam was used to anneal a coated
chamber window and a coated quartz window. Exposures were varied from
1-100 pulses. The laser was operated at its maximum power level of 40
KV during all of these tests.
The Argon ion laser was used to write gold lines on coated
substrates by focusing the beam through a 75 mm focal length quartz
lens (Rolyn #11.0140) onto the coated surface. The laser was operated
at power levels of 3.5, 2.0, and 1.0 watts. Glass plates and CVD
tungsten on Si chips were taped to a carbon block and manually rastered
in front of the laser beam at the focal point. Pull rates were varied
from - 0.3 cm/sec to - 0.5 cm/sec. The focused beam was also fixed on
one spot on a CVD tungsten on sc SI chip for 10 seconds.
Product Volatility Study
The search for volatile gold compounds in the plasma reaction
products was divided into three categories, based on technique. The
first category of tests involved attempts to sublime gold compounds at
low pressure from the reaction products thermally and collect them in a
cold trap. The second category of tests utilized quadrupole and ion
cyclotron (ICR) mass spectrometers and several different methods of
sample delivery in an attempt to isolate and identify gold compounds.

76
compounds. The third category consisted of one series of experiments
using a time of flight mass spectrometer (TOFMS) to detect gold cluster
compounds formed in a Nd/YAG pulsed laser stimulated plasma using a
solid gold target and 1% methane in helium. Each experiment in the
volatility study is described below.
Sublimation Experiments
The two sublimation experiments that were performed used the
reaction products formed in a 75% He/25% CH4 plasma and isolated in the
product recovery system. The first experiment used the (195 K) U-tube
cold trap from 861018. This trap had been positioned after a 300 K
cold finger during the plasma reaction experiment. The second
sublimation experiment utilized the first cold finger trap (195 K), and
the glass wool plug contained in its outlet, from 861023. Both of
these cold traps contained milligram quantities of the dark-colored
plasma reaction products.
Both sublimation experiments were performed by attaching the
plasma containing cold traps (which had been sealed and stored at 195
K) to a fresh U-tube cold trap kept at 195 K. This trap was connected
to the mechanical vacuum pump, via a metering valve and a 195 K pump
trap, and the system was evacuated slowly to < 1 Pascal. In the first
test the products were warmed from 195-373 K over a period of four
hours. A second collection trap was exchanged for the first one when
the products reached 300 K. In the second test the plasma products
were warmed from 300 to - 900 K over a period of 90 minutes. Only one
collection trap was used in this test. All of the collection traps,

77
and both of the product recovery traps, were sealed in air and heated
to - 900 K in a bunsen burner. Color changes in the trap contents,
which indicated the presence of gold films, were observed visually.
Mass Spectrometer Experiments
Six experiments were performed using quadrupole or ICR mass
spectrometers to detect compounds in the plasma reaction products. All
of the instruments were located in the Department of Chemistry at the
University of Florida (U.F.). A synopsis of these experiments is
presented below in Table 5.
Table 5. Volatility Study Mass Spectrometer Experiments
Expt. Plasma Expt.
No. (Gas Mix)
Sample
Type
MS Type
Sample Introduction
Method
1 860704
(75% He/25% CH4)
target residue
quadrupole
solids probe,
heated to 670 K
2 870121
(93% H2/8% C2H2)
chamber wall
residue
GC/quad.MS
injected acetone
suspension/solution
3 870819
(75% H2/25% CH4)
U-tube cold
trap
quadrupole
connected to gas
inlet, heated to
680 K
4 860722
(75% He/25% CH4)
cold trap
after GWP
FTICR
connected to gas
inlet, heated to
380 K
5 870819
(75% H2/25% CH4)
coated glass
pi ate
FTICR
placed adjacent to
ICR cel 1; e-beam &
laser desorption
6 870819
(75% H2/25% CH4)
residue from
coated glass
pi ate
FTICR
solids probe,
heated to 450 K,
CID reactions

78
The first experiment was done in the laboratory of Prof. R.A. Yost
by Mr. M. Hail using a Finnigan/MAT 4515 quadrupole MS. Reaction
products were recovered from the gold target used in test 860704 (75%
He/25% CH4) by scraping the tar-like residue with a teflon spatula.
The sample was placed in a solids probe and heated to 673 K while
observing the mass response from 0-494 atomic mass units (a.m.u.). The
instrument's mass range was calibrated using perfluorotributylene.
The second experiment was done in the department's Analytical
Service Laboratory by Dr. R.W. King using a Finnigan/MAT 4500 gas
chromatograph/quadrupole mass spectrometer (GC/MS). A sample was
recovered from the plasma chamber sidewall after test 870121 (93% H2/8%
C2H2) by rinsing the sidewall with spectral grade acetone. The
extract/suspension was injected onto a 5 ft. x 1/4 in. glass
chromatography column packed with an inert support coated with 3%
SP2100 (an organo-si1ane polymer commonly used for hydrocarbon
separations). Helium carrier gas flow rate through the column was 30
ml/min. The column temperature was increased from 318-573 K at 10
degrees per minute while observing the mass response from 0-300 a.m.u.
This instrument was also calibrated using a standard hydrocarbon
mixture (FC 43).
The third experiment was performed in the laboratory of Prof. M.T.
Vala by the author using a Finnigan 3500 quadrupole MS. The U-tube
cold trap used in test 870819 (75% H2/25% CH4) was connected to the
instrument's solids probe inlet and heated to 680 K in a tube furnace
while observing the mass response from 0-500 a.m.u. The instrument
response was tested by placing a sample of triethylphosphine-gold

79
chloride (synthesized by Dr. E. Sczlick in the laboratory of G.J.
Palenik at U.F.) in the solids probe and heating it to 570 K.
The fourth, fifth, and sixth experiments were performed in the
laboratory of Prof. J.R. Eyler by Dr. M. Moini and the author. The
fourth one used a sample from test 860722 (75% He/25% CH4). The sample
was collected in a 195 K cold trap positioned after a glass wool plug
during the plasma experiment. This cold trap was connected to the gas
inlet of an ICRMS (Nicolet FTMS-1000 equipped with a 3.0 Tesla
superconducting magnet and described fully in the literature).*^ The
sample trap was then evacuated to 0.1 Pascals while still immersed in
dry ice. The valve to the MS was then opened and the mass response
from 0-1000 a.m.u. was observed using Fourier transform techniques
while the sample trap was slowly warmed to - 380 K. The instrument
response was tested by placing a sample of triethylphosphine-gold
chloride in a solids probe and warming it to - 450 K.
The fifth experiment used an inhouse fabricated ICRMS (equipped
with a Nicolet FTICR MS data station and a Varian Fieldial 1.0 Tesla
electromagnet) to examine plasma reaction products coated on a glass
plate in run 870819 (75% H2/25% CH4). The sample was mounted on a
solids probe and positioned in the vacuum chamber adjacent to the ICR
cell. The mass response from 0-400 a.m.u. was monitored using Fourier
transform methodology while the sample was exposed to a 500 nanoamp
electron beam for one hour. The sample was then irradiated with an
unfocused frequency doubled, 532 nm pulsed Nd:YAG laser (Quantel Model
YG 580) at power levels of 50-500 mJ/pulse in an attempt to desorb
compounds that would have then been ionized by co-desorbed potassium

80
ions. (The K+ ions came from the materials used to construct the ICR
cell. This was considered a "soft" ionization technique.) The mass
response was monitored for the next twenty minutes while the laser and
e-beam were on, and then for another ten minutes with the laser on and
the e-beam off.
The sixth experiment was performed in the Nicolet FTMS-1000 ICRMS
using a sample generated in run 870819 (75% H2/25% CH4). The sample
was placed in a capillary tube that was then inserted into the solids
probe and warmed to - 450 K while the mass response from 0-1000 was
observed. Collision-induced ion dissociation (CID) experiments were
performed on compounds with mass numbers 44, 149, 195, 255, 334, and
348.
Time of Flight MS Plasma Experiment
This experiment was performed in the labortory of Prof. P.J.
Brucat in the Department of Chemistry at U.F. by Mr. D.E. Lessen and
the author. This laboratory was equipped with a cluster beam apparatus
linked to a time of flight mass spectrometer (see Figure 11) that is
described fully elsewhere.^ The cluster beam was produced by
irradiating a solid gold target with a focused pulsed Nd:YAG laser
(Quantel Model YG-580) beam at a power level of 1-2 mJ/pulse at target
impact (7 nsec pulses at 10 hz). Helium or helium/1% methane gas was
introduced to the target at a pressure of - 1 atm. using a 1 msec
pulsed valve. The resultant plasma exited the target holder through a
2 mm dia. hole and was hypersonically expanded into a large vacuum
chamber maintained at a pressure of 0.01 Pascals. A skimmer in direct

Figure 11. Cluster Beam/TOFMS Apparatus

82
skimmer

83
line of sight with the plume exit allowed undeflected clusters to enter
a repeller grid where they were redirected down a three meter TOF tube
and into a multi-stage detector. A variable voltage horizontal
deflector (HD) located at the beginning of the TOF tube optimized the
transfer efficiency of various mass ranges of clusters.
During the course of the experiment the HD voltage was varied
between 50-120 volts. This allowed the observation of signals from
ionized gold clusters and cluster compounds from Au(l) to Au(7). At
each voltage setting the signals from positive ion clusters produced in
pure helium and in helium/1% methane plasmas were recorded.
Gold Thin Film Characterization
Six different techniques were utilized to characterize the plasma
reaction products formed in the 3:1 hydrogen/methane-gold plasmas.
Samples of the ultrafine particle product and coated substrates (both
annealed and unannealed) were subjected to analyses. Most samples were
in the form of thin films deposited on glass plates, ceramic
feedthroughs, and CVD tungsten or aluminum on silicon chips. A major
objective of these analyses was the determination of the relative
abundance, and the physical state, of the gold present in the soot-like
plasma reaction products. Film stoichiometry, structure, and
electrical properties were also investigated. The analytical
techniques utilized in this part of the study were
1) visible absorption spectroscopy,
2) optical microreflectometry (OMR),
3) x-ray photoelectron spectroscopy (XPS),

84
4) scanning electron microscopy (SEM) with
5) energy dispersive spectroscopy (EDS), and
6) electrical resistance (R)
The principle features of each technique are described briefly along
with the relevant parameters employed to analyze the sample films.
Detailed lists of the samples analyzed using each technique are
presented in Chapter III along with the respective analytical results
and a discussion of their meaning.
Visible Absorption Spectroscopy
A Hewlett-Packard Model 8450 diode array spectrometer was used by
the author to measure the absorption spectra (300-800 nm) of acetone
suspension/solutions of several samples recovered from the plasma
chamber sidewalls. Samples from CH4, He/CH4, and He/CO plasma
experiments were subjected to solvent dissolution tests using hexane,
toluene, acetone, diethyl-ether, 1:1 solutions of the preceding
solvents, water, hydrochloric acid, nitric acid, and aqua regia before
determining that pure acetone yielded the best results (discussed in
the next chapter). The absorption spectra of 10 ppm and 10,000 ppm Au
standards in acetone/water were also measured. These standards were
prepared by diluting 1 ml of the 1000 ppm and 10 ml of the 100,000 ppm
AA standards, respectively, to 100 ml with spectral grade acetone. All
of the sample and standard spectra were measured against an acetone
reference cell. All measurements were made in standard matched 1 cm
wide quartz cuvets.

85
The major objective of these analyses was the determination of the
presence or absence of the metallic absorption band for gold in the
550-600 nm region of the spectrum. This indicated the presence or
absence of gold particles large enough to exhibit metallic behavior.
Optical Microreflectometrv
An optical microreflectometer located in the laboratory of Prof.
P. Holloway in the Material Science Department at U.F. was used by the
author to measure the reflectance spectra of several samples. The
instrument consisted of a quartz halogen light source and focusing lens
assembly, a 1200 1/mm grating monochromator, a binocular microscope
with internal mirrors for directing reflected light to a GaAs
photomultiplier tube, and a Keithley autoranging picoammeter (Model
485). Reflectance curves were determined by comparing the sample
intensities to the intensities of a standard with known reflectivity in
air, R(std). The reflectance intensity of a SiC standard, I(std), was
measured at 10 nm intervals between 400 and 900 nm just prior to
measuring the intensity of each sample's reflectance, I(samp), at the
same wavelengths. The reflectance value for each sample point,
R(samp), was then calculated using the following equation:
R[samp] = [I(samp) - DC] x [R(std)]/[I(std) - DC]
where DC was the photomultiplier dark current. R(std) values for SiC
are listed in Appendix C.
Sample films were examined visually to determine a representative
area for reflectance measurements. The instrument analyzed an area 20
microns in diameter. The same spot on the SiC standard was measured

86
each time by aligning two small defects on the crystal surface with
points on the microscope measurement grid. Reflectance curves were
determined for annealed and unannealed films deposited on glass plate
and on CVD tungsten on Si chips, as-deposited films on the two
polymeric tapes, and the Harris Corp. standard sputtered Au film.
X-Ray Photoelectron Spectroscopy
X-ray photoelectron spectroscopy studies were carried out on
several CH4/H2/AU plasma reaction product coated and annealed W on Si
substrates. The XPS analyses had three major objectives: 1)
determination of the elemental surface composition of the film, 2)
determination of the binding energy (BE) of the Au 4f5/2 and 4f7/2
peaks and the C Is peak, and 3) determination of the gold and carbon
concentrations in the bulk of the film. The first objective was
achieved through the use of elemental survey scans from 0-1000 eV BE.
The second objective was accomplished using narrow scans (-10 eV) of
the respective Au and C peaks and observing the shift in BE and the
peak shapes and widths at half height (whh). The determination of
carbon and gold concentrations in the bulk of the films was
accomplished using narrow scans with variable photoelectron takeoff
angles and Ar+ ion etching. Spectra were recorded in a fixed analyzer
transmission mode, which allowed direct comparison of adjusted peak
areas for semiquantitative analyses. A detailed list of all samples
subjected to XPS analyses, along with the respective analytical
conditions and results, is presented in Chapter III together with a
detailed discussion of the results.

87
Two instruments were used to perform the analyses in these
studies. One instrument, a Kratos XSAM 800, was located in the
laboratory of Prof. V.Y. Young in the Department of Chemistry at U.F.
and was operated by Mr. P.C. McCaslin and Mr. J.G. Davis, Jr. The
instrument used a Mg anode (1254.6 eV Ka line) x-ray source operated at
15 kV accelerating potential. Samples were mounted to a grounded
holder using stainless steel screws that contacted the surface of the
sample films and the underlying W substrate near the edges. This
arrangement prevented charging of the thin film while it was being
exposed to the x-radiation and undergoing electron loss. Spectra were
recorded at photoelectron takeoff angles of 10 and 70 degrees. This
technique allowed observation and comparison of the signals produced
predominantly by near surface species (-1.5 nm sampling depth at 10
degree takeoff angle) and those produced predominantly by bulk species
(-7.5 nm, or three times the mean free path of 1.2 keV electrons in
gold,67’68 sampling depth at 70 degree takeoff angle). One sample was
also etched with Ar+ ions at 2.5 keV accelerating potential and 0.25 mA
sample current for a total of 60 minutes. Spectra were recorded before
the etch, after 15 minutes of etching and after 60 minutes of etching.
The second XPS instrument was a GCA/McPherson ESCA 36 located in
the laboratory of Prof. A.T. D'Agostino in the Department of Chemistry
at the University of South Florida and was operated by Mr. C. Biver.
This instrument used an A1 anode (1487.6 eV Ka line) x-ray source
operated at 15 kV potential. An initial set of samples that was
analyzed in this instrument was improperly grounded and thus did not
yield valid BE data. However, since the charging effect reached an

88
equilibrium status within the first few seconds of exposure to the
constant intensity x-ray beam,69 the total areas of the Au and C peaks
and the elemental survey scans provided useful information. One sample
film and one Harris Corp. standard sputter deposited Au film were
subjected to depth profiling using Ar+ ion etching (13 /¿A ion current
and 6.3 mA arc current). These two samples were grounded by pressing
copper foil over them, with an open area for analysis, and attaching
the foil securely to the grounded sample stand. All spectra were
recorded at a photoelectron takeoff angle of 75 degrees. Peak areas
were adjusted for elemental composition determinations using Scofield's
photoionization cross sections^ at 1254.6 and 1487.6 eV, respectively,
for the two instruments. Since only gold and carbon were detectable in
the films (the photoionization cross section for hydrogen is extremely
small, 0.0002 relative to carbon, and was not detectable with these
instruments), and the Scofield cross section value for the C Is peak is
taken as 1.00 relative (22,000 barns at 1254.6 eV, and 13,600 barns at
1487.6 eV), only the combined areas (XAu) of the Au 4f peaks were
adjusted. This was done using the following equation for the Mg Ka
source (1254.6 eV):
(XAu)/(7.68 + 9.79) = adjusted Au area
For the A1 Ka source (1487.6 eV), the following equation was used:
(XAu)/(7.54 + 9.58) = adjusted Au area

89
Once the adjusted Au areas (adjAu) were calculated they were compared
directly to the corresponding C Is peak areas to yield relative percent
atomic composition using the following equations:
(100)(adjAU)/(adjAu + C Is) = relative atomic % Au
(100)(C ls)/(adjAu + C Is) = relative atomic % C
Relative percent mass concentrations were then calculated using the
following equations, where ra%Au and ra%C are the relative atomic
percent concentrations of gold and carbon, respectively:
(ra%Au)(197)/[(ra%Au)(197) + (ra%C)(12.0)] = relative mass % Au
(ra%C)(12.0)/[(ra%Au)(197) + (ra%C)(12.0)] = relative mass % C
In some discussions of the results in the following chapter references
are made to the ratio of gold to carbon and vice versa. In all
instances these discussions are referring to the atomic ratios of the
two elements.
Scanning Electron Microscopy with Energy Dispersive Spectroscopy
The SEM/EDS analyses were carried out in order to determine 1) the
average grain or particle size and shape of the species comprising the
as deposited sample films and 2) the change in film structure
associated with various annealing regimes. These analyses were
performed in a JE0L SEM equipped with an EDS system located in the
laboratory of Prof. M. Ammons in the College of Engineering Center for

90
Electron Microscopy at the University of South Florida. The instrument
was operated by Prof. Ammons and Ms. A.S. Slater.
The optics in the EDS system precuded the observation of low Z
elements, thus hydrogen and carbon were not observable. The EDS was
used primarily to determine qualitatively the relative abundance of
gold in the surface being scanned by the SEM. By varying the electron
energy, and thus the mean free path in the sample film, a rough depth
profile could be observed. This facilitated the interpretation of the
signals produced by the underlying substrate. Plasma reaction products
coated on glass chips, W on sc and pc SI chips and Scotch tape were
examined along with the Harris Corp. standard sputtered Au film. Both
annealed and as-deposited samples were examined. A detailed list of
the samples analyzed is presented in the next chapter.
Electrical Resistance Measurements
Two methods of observing the electrical resistance properties of
the sample films were employed. The first technique consisted of
observing the resistance across a 3 mm wide ceramic junction in an
electrical feedthrough that had been heavily coated with plasma
reaction products. The feedthrough was inserted into the substrate
annealing chamber described earlier along with a thermocouple junction.
The resistance was monitored as the temperature was slowly increased
from 300-750 K. In one experiment hydrogen gas was flowed through the
system at 200 ml/min. In a second experiment the system was left open
to the ambient atmosphere. The purpose of these two tests was to
observe any minima in the resistance values versus the temperature as

91
the reaction product film connecting the electrodes was heated under
hydrogen and under air.
The second resistance measurement method used a 4-point probe
technique, described in detail by L.B. Valdes,to determine the sheet
resistance, Rs, in ohms/square, of sample films coated on nonconductors
(glass, quartz, Scotch tapes). An Alessi CPA/1 Resistivity Test
Fixture with a 4-point osmium head was available for use in the
laboratory of Prof. P. Holloway. Since the sample films were unevenly
coated, and thickness determinations of the delicate films was not
obtainable with available instrumentation, the main objective of these
measurements was the determination of relative sheet resistance values
for various areas on the samples.
Measurements were made by adjusting the input current to an
appropriate level, measured in amps, and reading the voltage drop
between the two outer probes and the two inner probes. The sheet
resistance was then calculated using the relationship:
Rs = (V/I)(4.2)
The correction factor, 4.2, is based on a probe spacing equal to -10%
of the average specimen diameter. Since the probe spacing was 1 mm and
the average sample film dimensions were not discernible due to the
microscopic discontinuities inherent in the films, the sheet resistance
values can be viewed only in relation to each other and to the standard
sputtered Au film sheet resistance.

CHAPTER III
RESULTS AND DISCUSSION
In this chapter the experimental results are presented along with
interpretive discussions relating the observations to known theories
appropriate to each subject. The three phases of the study are treated
separately, as in the preceding chapter, with one exception. A
probable mechanism of formation of the gas-phase gold bearing species
in the pulsed laser stimulated plasma is not presented until the final
section of this chapter, after all of the experimental evidence has
been presented.
Production of Gas-Phase Gold Species
Screening Study Results
As mentioned earlier, the purpose of the screening study was to
identify gases and/or gas mixtures, operating pressures, and laser
power density parameters that would result in the production of copious
amounts of gas-phase gold species. Several parameters had to be
considered simultaneously. Thus, the first experiments addressed the
operational limits of the plasma reaction system with respect to gas
pressure and laser power density levels. The next group of experiments
investigated the use of He, Ar, H2, and mixtures of He/H2 and Ar/H2 in
the production system. Negative results with these mixtures led to the
92

93
the next group of screening study experiments which investigated the
use of carbonaceous gases [CO, CO2, CH4, C2H2» (C5H5)2] mixed with
helium or hydrogen in the production system. The most successful
candidates from this group of experiments, along with several
chlorofluorocarbon/He gas mixtures (CHCIF2, CC12^2» anc* ^Fg) were then
subjected to a series of semi-quantitative filter catch runs in order
to determine the optimum conditions for Au transport in the gas stream.
Finally, the most successful conditions (75% H2/25% CH4 at 1,330
Pascals) were utilized in the substrate coating and annealing
experiments described in the next section.
The onset of gas breakdown and subsequent energy loss in the
gaseous plasma prior to target impact was the first parameter
investigated. Since Araya et al. had reported a peak in the production
rate of ultrafine metal (Ti, Fe, Ni, Al, and Mo) particles from pulsed,
Nd:YAG laser stimulated plasmas at air pressures of -100,000 Pascals
and power densities of 104-107 watts/cm2,27 the first experiments in
this study attempted to duplicate this result using the pulsed CO2
laser and a gold target. However, on observing the first few pulses of
the focused CO2 laser beam in air at atmospheric pressure in front of
the Au target, it was apparent that gas breakdown could be initiated
under these conditions. This phenomenon results from multiphoton
ionization of the gases by the leading photons in the pulse, followed
by a cascade of ionization when the free carrier density reaches a
critical value. The change in density of free carriers is proportional
to the density of the atoms and/or molecules and the spectral
irradiance, as well as the physical properties of the gas species, such

94
as the photoionization crosssections and the ionization potentials.
(T.P. Hughes offers an excellent review of both theory and experiments
dealing with this phenomenon.)^ when the effects of Bremsstrahlung
radiation are considered, most notably the continuum spectrum produced
by electron-neutral atom collisions in the initial stages of gas
breakdown, the cascade effect and subsequent gas plasma formation is
not surprising. The high density of continuum radiation produces a
correspondingly high density of free carriers, ions, atoms, and
molecules in a multitude of energy states. This scenario leads to a
rapid increase in absorption of the incoming laser photons by the
gaseous species, resulting in low irradiance of the target.
Thus, it was necessary to define the pressure limits for gas
breakdown occurrence in the plasma production system. In experiment
860530 H2 was supplied to the chamber at 110,900 Pa and the laser
energy density at the target surface was varied by moving the focusing
lens back 3 cm. Gas breakdown was observed in the form of a gas plasma
located about 2 cm in front of the target impact point. As the lens
was moved away from the target, the gas plasma moved synchronously,
always remaining approximately 18 cm from the back side of the 20 cm
focal length lens.
In experiment 86062A (see Table 2) the target was removed and
standard grade helium was supplied to the plasma chamber at pressures
ranging from 18,800-161,500 Pascals while the laser beam was focused
into the center of the chamber. At pressures greater than 88,000
Pascals all of the laser pulses resulted in gas breakdown plasma
formation. At 72,000 Pa -95% of the pulses resulted in gas breakdown;

95
at 58,800 Pa -70% of the pulses resulted in breakdown and at 18,800 Pa
no breakdown was observed (see Figure 12).
A similar experiment, 880602B, was performed with the system open
to the atmosphere (101,500 Pa). The first few pulses did not initiate
gas breakdown, as had occurred in the initial plasma chamber start-up
test and in experiment 860530, when the gold target was in place.
However, subsequent laser pulses into the targetless chamber caused gas
breakdown to occur 20-50% of the time. These observations could be
explained by considering the laser/solid interactions that took place
on the surface of the Au target and on the surface of the glass chamber
back wall.
As the incoming photons struck the solid gold target surface some
were reflected and some were absorbed by conduction band electrons that
were then raised to higher energy states. Heat was generated in the
metal by collisions of these excited electrons with phonons. The mean
relaxation time in the highly conducting Au solid is on the order of
10'12 to 10'13 seconds73 and the duration of the laser pulse was > 250
nsec. Thus, there was ample time for heating and vaporization of some
of the Au during the early stages of the incoming pulse. This metal
vapor was then ejected into the atmosphere in the path of the laser
beam. This increased the optical density of the gas and initiated the
gas breakdown observed. When the ambient gas pressure was lowered
enough (in subsequent experiments), the effect of the metal vapor was
not great enough to initiate the ionization cascade leading to gas
breakdown.

Figure 12. Percent of CO^ Laser Pulses Resulting in
Helium Gas Breakdown Versus Pressure

% of Pulses Resulting in Gas Breakdown
cn o
o o
¿6

98
When the target was removed and the system was left open to the
atmosphere (no gas flow), the first few laser pulses impacted on the
chamber back wall and no gas breakdown occurred. However, it was
apparent from the visible interaction of the laser beam with the glass
surface that material (probably hydrocarbon contaminants) was being
vaporized and introduced into the chamber ambient. It was speculated
that some of this material, in the form of small particles, randomly
diffused to locations near enough to the beam focal point to be
vaporized and increase the optical density of the local gas to a point
great enough to initiate gas breakdown. Pulses that did not cause
breakdown struck the back wall and introduced more particles into the
chamber. The unpredictable appearance of the gas plasma during the
part of the experiment following the first few pulses correlated well
with this explanation.
As a result of these observations, all subsequent screening study
experiments were performed at pressures < 18,000 Pa. Visual inspection
of the product recovery systems, as described earlier, was used to
indicate positive or negative results in this phase of the study.
Referring to Table 2, a He/H2 -3:1 gas mixture was tried at pressures
of 13,870, 6800, and 800 Pascals with negative results. Helium was
then used alone at 800 and 1330 Pa, also with negative results. Argon
at 1390 Pa also yielded negative results, as did a 3:1 mixture of Ar/H2
at 1390 and 670 Pa, and a -1:1 mixture at 750 Pa. Later in the study
argon and helium were subjected individually to semiquantitative glass
fiber filter catch experiments at -1400 Pa (discussed below).

99
In all of these experiments, except the 100% Ar runs, the target
was deeply cratered and there were pieces of Au in the bottom of the
chamber. When 100% Ar was used the target impact point was a shallow
crater and there was little Au debris in the chamber. The colinear
shape of the plume in the Ar runs, compared to the more spherical
plumes with the other gases, indicated that there was some partial gas
breakdown occurring. This observation lead to the selection of He for
use as the inert diluent gas in the remainder of the screening study.
The next experiment listed in Table 2 used a 3:1 mixture of helium
and carbon monoxide at 4930, 2670, 1600, and 1200 Pa (expt. 860724).
Gas breakdown occurred several centimeters in front of the target at
pressures above -2000 Pa. At 1600 Pa the entire chamber pulsed a
bright white. The pressure was lowered to 1200 Pa and the system was
allowed to run for -13,000 laser pulses. By the end of the experiment
a black, soot-like substance had thickly coated the glass plasma
chamber and collected in the glass wool plug in the product recovery
system. The next experiment listed (861106) started with 100% helium
and then CO was added incrementally while maintaining the total
pressure at 1600 Pa. Some soot formation was observed when the CO
concentration reached 3.8%. As the concentration was increased to 5.2%
and 10%, the production rate of the soot increased visibly. When the
pressure was increased to 4000 Pa with the 10% mixture, no further
production of soot was noted. Finally the CO concentration was
increased to 12% and the pressure was increased to 9070 Pa (for a CO
partial pressure of 1090 Pa. Again, no further soot production was
noted.

100
The next experiment listed (861110) used a 4:1 mix of He/CO at
1530 Pa and ran for 14,400 pulses. A copious amount of soot was
deposited on the plasma chamber walls and trapped on the glass wool
plug (GWP) in the product recovery system. There were no visible
deposits in the glass cold trap after the GWP. This trap was sealed
and heated in a flame to -900 K and then cooled with no resultant
visible change in appearance (i.e., color change).
Extracts of the soot were prepared by placing pieces of the GWP in
separate glass vials with hexane, toluene, acetone, water, and aqua
regia and gently agitating them. There was no change in appearance of
the systems containing hexane, toluene, or water, but the acetone
extract took on a light purple color and the soot particles were
visibly loosened from the glass fibers. The vial containing aqua regia
showed complete dissolution of the soot. The extracts were then
subjected to ultrasonic agitation for 30 minutes and allowed to stand
for several days and were then analyzed by AA. Results indicated that
the acetone extract contained Au in the bulk of the solution and
associated with fine black particles that had settled to the bottom of
the vial. There was no indication of Au in the other solvents that was
not associated with the particles, except for aqua regia which had
dissolved the particles.
The next series of experiments used mixtures of acetylene and
helium containing 2.5, 8.3, and 19% C2H2 at 1400 Pa and -10,000 laser
pulses. The product recovery system used in these experiments had a
test tube placed in the gas stream as it exited the chamber (see Figure
8). In two runs (19% and 2.5% C2H2) this tube was cooled to 195 K with

101
dry-ice and in the third run it was at room temperature. A very light
amount of deep purple/black soot was deposited on this test tube and in
the cold trap in the 2.5% run5 a ver\y heavy coating of black soot
resulted from the 8.3% run; and a moderate amount of black soot was
collected in the 19% run.
The cold trap contents of the second run were subjected to the
solvent extraction test described above with the same results. Figure
13 shows an example of the increase in the Au AA signal when the
instruments sampling tube was placed in the bottom of the acetone
extract vial. It was apparent that the Au particles were small enough
to atomize in the instruments air/acetylene flame.
The remaining cold traps and all three coated test tubes were
heated in a bunsen burner flame and yielded pink to red colored thin
films indicating the presence of gold.74 The thicker areas of the
films on the test tubes and at the cold lines on the inlet sides of the
cold traps were metallic yellow in color. The original black color
film that coated the glassware changed to deep purple and then
disappeared within a few seconds after heating to yield the red and
yellow films which persisted. These tests were considered positive
because of the relatively large amount of Au transported from the
plasma zone to the cold trap, and CO was selected for further
evaluation despite its moderate toxicity.
Experiment 861126 utilized the mixture of helium gas saturated
with dicyclopentadiene described earlier. This test was run for 3660
laser pulses and produced a very heavy, sticky black soot-like residue
that deposited on the chamber walls and in the cold trap. The cold

Figure 13. AA Spectrum of Cold Trap Acetone Extract
Showing Enhanced Au Signal from Particles

Time (min)
o
-p*
o
00
o
>
b>
L
L
• . .
■ •
: 1
, ,
| , j ;
—
!
-
luiu trap
arotnno ovtv’art
1 1 Í i
. ¡ !
.
- - •—
———
-
—-
—
—
icles
from b<
tí——
Dttom
1
)f exti
o
———
r
(
j
c
s\
part
¿T
'’act ti
L. ' ' l
ibe
o'
—
.—
! i
L
: i 1
. , ,
i i • ;
I
i ' :
! ;
861012
extract
â–  i : 1.
1 ! • 1
decant
. i ! ;
• ! ■ i
•
—*—
—
. i ' j
|
—
—
—
..
r —
-
—
—
! , j
—
—
...
-
1 : ! ;
o ppm hu
standard
: ; i j
i j i
| ; . .
â–  ;
j
cl
j
(.
n
c
!)
N
â– j
c
D
J
0
rv—c
J
1
1
1
o
CO

104
trap was sealed and heated in a flame as described above. The dark
deposit did not change significantly in appearance until the tube was
unsealed and reheated in air. The dark deposits seemed to burn off and
left behind a thin area of pink colored film associated with the
heaviest deposits in the trap (these were located at the cold line on
the inlet side). Thus, this test was considered negative.
Pure methane gas was used in experiment 861022A which was run for
-4000 laser pulses. Some light gray deposits were noted in the cold
trap. Some grains of Au were also present in the bottom of the plasma
chamber. The cold trap was heated in air as described above and
yielded a very light pink film in the areas of heaviest deposition.
This test was considered negative.
The next series of experiments listed in Table 2 utilized -3:1
mixtures of CH^He at pressures between 1470 and 2000 Pa. The first
two tests in this series, 860701 and 860702, used the heated quartz
tube recovery system with a gas residence time of 3 msec and operated
at temperatures of 893 and 573 K, respectively. In the first test,
which lasted for 5400 laser pulses, a light purple residue was found in
the middle of the heated tube and a dark purple to gold colored residue
was found in the exit end of the tube. No colored deposits were
collected in the cold trap after the heated tube. The second test was
run for 7020 pulses and yielded similar results except all films were
darker and some purple deposits were found in the cold trap. These
tests were considered positive.
In the next experiment in this series, 860704, the focal point
diameter at target impact was increased from the optimum to 1.2 mm,

105
effectively decreasing the power density from 3 x 10^ to 9 x 10^
watts/cm^. The test was run for 2460 pulses at the lower power density
with negative results. The focus was then optimized and within a few
hundred pulses visible deposits had appeared in the first two cold
traps (273 and 195 K). At the end of the run a moderate amount of
product was present in the first trap and the remainder was in the
second trap. No visible deposits were present in the third cold trap.
This completed the experiments performed in the glass plasma reaction
chamber. The aluminum chamber was used in the remainder of the study.
Two more experiments in the above series, 861012 and 861023,
showed that the Au was associated with the soot-like product particles
and could be isolated in the GWP. The cold traps after the GWP had
clear deposits that turned yellow on warming to room temperature and
then turned black when heated in the flame under He. The black
deposits disappeared in a few seconds when the traps were reheated in
air, leaving the glass clear.
At this point in the study a "blank" run was performed (861022C)
using the same gas mixture at 800 Pa and a graphite target. No dark
deposits were observed, but a clear condensate was found in the cold
trap. This material behaved identically to the cold trap contents
after the GWP in the last two runs. It was assumed that this material
was a mixture of various unsaturated hydrocarbons that polymerized on
heating in He and combusted on heating in air.
The next series of experiments utilized a mixture of -18:6:1
He/CH4/air at 1200 and 1600 Pa and -7000-10,000 laser pulses. Results
were similar to earlier He/CH4 runs with one exception. The relative

106
abundance of the Au films in relation to the soot deposits appeared to
be less. These tests (861016, 861017, and 861018) were considered
positive.
The next two experiments, 870109 and 870324, used a -4:1 mix of
hydrogen and methane at -1300 Pa. The first test gave the best results
in the study up to that point. The dark purple deposits in the cold
trap yielded the heaviest Au film observed up to that point and this
gas mixture was selected for further investigation.
In experiment 870324 two focal point diameters larger than the
optimum were investigated: 2.4 mm, corresponding to a power density of
2 x 10^ watts/cm^; and 1.1 mm, corresponding to a power level of 1 x
10^ watts/cm^. The plasma was very small with the lower power
density and no deposits were observed in the cold trap after 4200 laser
pulses. The plasma was somewhat larger with the 1.1 mm dia. focal
point but only a light deposit was collected in the cold trap after
-3000 laser pulses. These tests were considered negative.
One experiment was performed using a 3:1 mixture of hydrogen and
natural gas (870313) at 1420 Pa for a duration of 10,200 pulses. The
results were positive, but the relative proportion of Au film left in
the cold trap after heating the black deposits was less than the
amounts observed in the H2/CH4 experiments.
This concluded the screening study experiments that used visual
observations to evaluate results. The final series of screening study
tests were performed using the glass fiber filters (GFF) and holder
described in the last chapter. These tests provided a semi-
quantitative measure of the amount of Au transported from the plasma

107
zone to the filter. The majority of these tests lasted over 20,000
laser pulses. The tests involving the chlorofluorocarbon gas CHCIF2
lasted 3660 and 5160 pulses and the tests involving graphite and copper
targets lasted -10,000 pulses (refer to Table 2 for pulse values).
Table 6 lists the GFF runs with the gravimetric and AA results listed
in weight per 1000 pulses. The GFF catches that consisted mainly of
large particles (those discernible under visual microscopy) are
asterisked. The bulk of the mass collected on the remaining filters
was in the form of the superfine particles observed in earlier
experiments.
The effectiveness of CH4 and CO in transporting Au in the form of
the superfine soot-like material was verified in these experiments. A
strong dependency on the partial pressure of the carbonaceous gas in
hydrogen was exhibited in these tests. Figure 14 shows a plot of this
relationship for CH4 and CO and indicates the optimum production rate
occurred at -350 Pa. Araya et al. also observed a strong dependency of
the production of superfine Ti particles on the gas (air) pressure in
their pulsed Nd:YAG stimulated plasma reaction system, although their
peak production rate occurred at -100,000 Pascals.27
The concentration of Au in the material produced in these tests
ranged from 82-99%, with one outlying value of 37% (expt. 880224). The
target was rotated only every 1.5-2.0 hours in this experiment, as
opposed to every 30 minutes in the other experiments. The deep and
variable cratering of the Au target produced varying nozzle
configurations for the plume expansion during the test time and
apparently affected the amount of carbonaceous material incorporated in

Table 6. Filter Catch Plasma Experiment Results
Expt. No.
Gas Mix
Target
Total
Pres. (Pa)
Carbonaceous
Gas
Pres. (Pa)
Filter Catch
(/ig/1000 pulses)
Total (grav.) Gold (AA)
Gold
880218
Ar
Au
1390
0
0.9
880222
He
Au
1370
0
27
0.7
2.6
880223
ch4/h2
Au
1350
324
264
217
82
880224
CH4/H2
Au
1390
360
782
291
37
880302
CH4/H2
Au
1380
261
347
343
99
880303
CH4/H2
Au
670
174
68
"k
61
90
880304
CH4/H2
Au
2710
705
92
★
43
47
880307
ch4
Au
1470
1470
226
★
26
12
880309
CH4/H2
Au
670
348
348
285
82
880311
co/h2
Au
1390
375
216
205
95
880317
C0?/H?
Au
1390
348
58
56
96
880239
CHC1F2/He
Au
1470
382
4830
880415
CHC1F2/He
Au
300
72
607
880421
CC1?F?/He
Au
1360
326
866
*
880425
CC1?F?/He/H?
Au
1370
192
1307
880427
CoFg/Re
Au
1240
335
225
*
880720
CH4/H2
Graphite
1350
351
<20
*
880723
CH4/H2
Copper
1350
351
163
★
--
880724
CH4/H2
Copper
1410
367
174
*
“ -
“ -
*Nearly all of the material was in the form of large particles.

109
Figure 14. Weight of Au Collected by the GFF Versus CH^ and CO
Partial Pressures

110
the material. This apparent nozzle configuration dependency was also
observed by Hagena and Obert when forming clusters from CO2 in
expanding supersonic jets.^S
The three halogenated species examined also exhibited some
pressure dependency on the production rate of particulate material
collected on the GFF. This material ranged in color from light brown
to black and was not wetted by aqua regia. In this respect it behaved
very similarly to teflon. This was in sharp contrast to the immediate
dissolution in aqua regia of the material produced by CH4, CO, and CO2.
The Au target in all of the halogenated gas experiments was only
slightly pitted with a shallow crater, indicating very little Au mass
removal. This result was similar to that observed in other experiments
where gas breakdown had occurred, but the gas plume before the target
was not observed in these tests. There was also an indication that the
presence of hydrogen enhanced the production rate of fine particulate
material from the saturated chlorofluorocarbon, CC12F2* These
compounds were not investigated further due to their potential for
contaminating the VLSI microcircuitry with Cl and F and their low
incorporation of Au (as evidenced by the target impact).
The one test that used a graphite target and the 3:1 H2/CH4 gas
mixture at 1350 Pa verified earlier observations of no soot production
by plasmas under these conditions. The target was deeply pitted after
10,000 pulses and there was a large amount of particulate debris in the
bottom of the chamber, but the GFF was essentially clean. This
indicated that the Au was necessary for the formation of the

Ill
carbonaceous material that was transported to the GFF along with the
superfine Au particles.
The two tests that used a copper target and the 3:1 H2/CH4 gas mix
at -1400 Pa yielded negative results in terms of superfine particle
production. Inspection of the target after -9000 pulses in the first
test revealed very little Cu removal in the 1.5 mm dia. impact spot,
despite operating at the optimum lens focal distance. In the second
experiment with the Cu target (880724) the lens was moved 10 mm closer
to and farther away from the target while the chamber pressure was at
200 Pa. The target was removed and inspected under the microscope
after several hundred laser pulses at each focal distance adjustment.
The greatest degree of cratering occurred at the optimum focal
distance. The test was continued for -10,000 pulses at 1410 Pa
pressure and the optimum focal distance and again yielded negative
results.
During these two experiments some gas breakdown was observed in
the first few pulses. The metal surface at the impact point appeared
to melt during these pulses and then became highly reflective to the
laser beam as evidenced by reflected impacts on the plasma chamber
wall. This phenomenon had not been observed previously in the study.
This point is discussed further in the final section of this chapter.
From the results of the screening study the 3:1 H2/CH4 gas mixture
at 1350 Pa was identified as the best conditions for production of the
Au bearing species which appeared as superfine particles. The state of
the Au in these particles was not known at this point, but the copious
amounts produced in the plasma reaction system and the apparent ease of

112
formation of Au films on the glassware that had been coated with the
product warranted further investigation of this material. Although CO
appeared to produce similar products under the same conditions, its
higher toxicity excluded it from further investigation.
Substrate Coating and Annealing Results
The substrates that were coated are listed in Table 3 in the
experimental section. All coating experiments were performed at 1330
Pa and most utilized the 3:1 H2/CH4 gas mixture. One exception was the
run where glass plates and W on Si chips were placed in the plasma
chamber ~3 cm from the target impact and exposed to the plasma produced
in 100% He at 1330 Pa. After 15,000 laser pulses these plates had a
shiny metallic Au coating similar to those produced in Au evaporation
systems. There was no carryover of Au into the recovery system and the •
substrates displayed stratified films consistent with line of sight
deposition.
The 5 cm long piece of W ribbon placed in the recovery system
glass tubing and irradiated with the Ar ion laser while being exposed
to the reaction products produced in a H2/natural-gas/Au plasma showed
a stratified color change from yellow-brown to purple to black starting
-1 mm away from the laser impact point. The pattern was symmetrical on
both sides and indicative of the expected thermal gradient.
The 1 cm long piece of W ribbon that was irradiated with the same
laser through a quartz window while being exposed to the reaction
products from a H2/CH4/AU plasma was completely free of deposits at the
end of the run. Recall that this ribbon glowed red under vacuum and

113
was a very dull red under the experimental conditions. Thus, it
appeared that the surface temperature of the W was too high to allow
the plasma reaction products, or their resultant thermal decomposition
products, to stick.
The Scotch brand transparent tape, adhesive side, that was exposed
to the H2/CH4 reaction products in the substrate coating chamber had a
shiny metallic gold appearance even though the glass and W substrates
adjacent to it appeared black when coated. This behavior was
consistent throughout the study whenever the tape was used to hold
other substrates in place or exposed by itself. This was a very
interesting phenomenon and the coated tape was selected for further
characterization of the Au film. When the other side of the tape was
coated the film was purple-black in color, similar to the appearance of
the film when coated on glass.
The Scotch brand black electrical tape displayed the reverse
behavior: The plasma reaction products could not be seen on the sticky
side, but the deposits appeared as a dull metallic yellow film on the
back side of the tape. Samples of this surface were also subjected to
further tests.
All of the product coatings were easily wiped off of the
substrates, except for the metallic films on the two tapes, and thus
were not capable of withstanding a profilometry test for thickness
determination. The tape samples were not flat enough to undergo
profilometry. The remaining substrates that were coated were subjected
to annealing and/or further testing.

114
Substrate annealing conditions were described in the last chapter
and listed in Table 4. The Au bearing material behaved consistently in
all experiments. Substrates heated in air to 470 K changed in color
from black to deep purple. This color persisted even when left at 470
K for 12 hours. When the temperature was increased to 500 K the color
changed to pink within a few minutes. At temperatures > -650 K the
color change took place in a few seconds. Similar results were
observed in substrates heated in H2, except the final color had a brown
tint. Samples that were first annealed in air and then Hg, and vice
versa, did not exhibit a change in color after the first anneal.
Early in the study the unfocused pulsed CO2 laser beam was used to
anneal a coated glass chamber window. The first few pulses produced a
visible vapor cloud originating at the coated surface. At the same
time the black coating turned purple. After -20 pulses the coating had
turned pink, and after -40 pulses the coating had turned a bright gold.
Under an optical microscope relatively large flakes of Au (hundreds of
microns) were clearly visible. These flakes formed an overlapping
discontinuous film. The surface was exposed to another 20 pulses of
the laser with no change in appearance. The coating was very tenacious
and was difficult to scratch off the glass surface.
The W on Si substrate that was annealed in the rf coil by bringing
it to red heat appeared to lose most of the product coating in the form
of a vapor cloud. This may have been caused by the rapid heating and
vaporization of the carbonaceous species that caused the small Au
particles to be physically blown off the substrate surface with the
expanding gas plume.

115
The same type of substrate was subjected to pulsed rf heating
under a vacuum (0.013 Pa) and looked similar to convectively heated
samples. A coated glass substrate annealed under the same conditions
did not exhibit a color change. These observations indicated that the
annealing effect on the W coated chip was due to the heating of the W
layer and not the Au plasma product thin film.
The coated W on Si substrates that were heated with the focused
argon ion laser beam in air showed a very light, thin line of
discoloration (dark brown) at all laser power levels and substrate pull
rates. The one sample that was exposed to the beam continuously for 10
seconds in one spot was subjected to SEM analysis and showed only a
slight change in appearance between the annealed and unannealed areas.
This difference appeared as an increase in size of pores between
grains, as would be expected if material had volatilized rapidly. It
was also apparent from the micrographs that the W substrate had
conducted the incoming heat away from the impact point, thus limiting
the local heating effect of the laser beam. These micrographs are
presented in the section on thin film characterization.
The coated glass substrates that were exposed to the focused Ar
ion laser beam displayed radically different behavior. At the higher
power levels the beam path appeared as a strip of bright metallic gold
islands. At the lowest power level the line was a semi-continuous
double ridge of metallic Au with a trough in the middle where the
center of the beam had passed. These observations were indicative of
direct and rapid heating of the product film by the beam on the non-
conductive glass surface. This meant that the thermal conductivity of

116
the product film must have been of the same order of magnitude as W in
order to not exhibit formation of metal islands on the W surface even
after the extremely long exposure times relative to the glass
substrates.
Product Volatility Study Results
This phase of the overall study was divided into three sections,
as described in the last chapter. The results of the first two
sections, described below, indicated that there were no detectable
volatile Au compounds present in the reaction products that were
capable of being isolated by differential condensation or sublimation.
The results of the third section indicated that gold-carbide compounds
could be formed in a pulsed Nd:YAG laser stimulated plasma in 1% CH4 in
He at -100,000 Pa.
Sublimation Experiments
The two sublimation experiments described in the last chapter were
both negative. The Au was associated with the purple-black soot-like
superfine particles in all tests and could not be isolated by thermal
desorption even at reduced pressure. In addition, all attempts to
isolate or separate volatile Au compounds from the product gas stream
by differential condensation using staged cold traps were also
negative. These results lead to the next section of mass spectrometer
tests that attempted to identify Au compounds in the plasma reaction
products.

117
Mass Spectrometer Experiments
Samples subjected to MS analyses and the pertinent conditions are
listed in Table 5 in Chapter II. In the first experiment a sample of
the black tar-like residue found on the Au target after a plasma run
that utilized a 3:1 He/CH4 gas mixture at 1330 Pa was placed in a
solids probe and slowly heated to 670 K while observing the mass
response from 0-494 a.m.u. A total ion count spectra from this test is
presented in Figure 15. The most striking feature is the prominent
peak at mass 155 and the preponderance of compounds between mass 100
and 200. There were also significant amounts of compounds over mass
200, but there were no prominent peaks. These results were considered
encouraging at the time and prompted further MS investigations.
In the second MS analysis a sample from the chamber sidewall that
was recovered after a plasma run that utilized a 93% H2/8% C2H2 gas
mixture at 1330 Pa was dissolved/suspended in acetone and injected into
the GC/MS system described earlier. No mass peaks larger than the
background signal were observed over 59 a.m.u. The most prominent peak
appeared at mass 43. Table 7 lists the mass response and relative
counts of the peaks between 0-60 a.m.u. Note that the measured mass
values listed are off by 1 a.m.u. as evidenced by the N2 and O2 peaks
appearing at listed values of 27 and 31 a.m.u., respectively.
All of the remaining tests in the MS study used plasma reaction
products formed in 75% He/25% CH4/AU plasma experiments. These
compounds are referred to as "P.R.P." throughout the remainder of the
text and figure headings. Any different conditions are noted
explicitly.

100.0n
155
", ' 1 1 1 » T“
100 200 300 400
a.m.u.
Figure 15. Total Ion Count Mass Spectra of Target Residue

119
Table 7. GC/MS Results from an Acetone Extract of
H2/C2H2/AU Plasma Reaction Products
Measured Mass
No. Points
Absolute
Intensity
% Int. Base
60
10
230.
0.02
59
25
3610.
0.32
58
35
101848.
8.89
57
25
3293.
0.29
55
21
1318.
0.12
53
25
1708.
0.15
52
14
524.
0.05
45
25
2935.
0.26
44
43
31945.
2.79
43
10
218.
0.02
43
10
260.
0.02
43
10
294.
0.03
43
100
1145792.
100.00 f
43
14
397.
0.03
43
10
222.
0.02
43
8
243.
0.02
42
51
97096.
8.47
41
51
31701.
2.77
40
71
15236.
1.33
39
35
64466.
5.63
38
29
40396.
3.53
38
25
1340.
0.12
37
29
37884.
3.31
36
43
13643.
1.19
35
14
313.
0.03
32
21
573.
0.05
32
29
12302.
1.07
31
29
16568.
1.45
30
21
1662.
0.15
30
25
3212.
0.28
29
35
53504.
4.67 *
29
35
71524.
6.24 *
28
25
38747.
3.38 *
28
43
121284.
10.59 *
27
71
241396.
21.07
26
51
168440.
14.70
25
35
41736.
3.64
24
29
8783.
0.77
20
35
6703.
0.59
19.5
29
4904.
0.43
19
29
8404.
0.73
18
29
51041.
4.45

120
In the third experiment a cold trap coated with the P.R.P. was
connected to the solids probe inlet and heated to 680 K while observing
the mass response from 0-500 a.m.u. The results of this test were
similar to the first MS test with the most prominent peaks occurring at
44 and 150 a.m.u. (results not shown). No significant peaks appeared
over 150 mass units, while a preponderance of the peaks appeared below
100 a.m.u.
The fourth experiment utilized the Nicolet ICRMS to look at a
sample of the cold trap contents collected after a glass wool plug
during a P.R.P. production experiment. The most prominent peak was at
mass 44 and the remainder of the peaks were below 100 a.m.u. (results
not shown). A sample of triethylphosphinegold chloride (TEPGC) was
placed in the solids probe following this analysis and the resultant
spectra of the volatile Au compound (Figure 16) confirmed the
instrument's response. The parent ion peak (minus one H) appeared at
349 a.m.u. and the parent ion minus Cl appears at 315 a.m.u.
In the fifth MS experiment a glass plate coated with P.R.P. was
placed in the inhouse fabricated ICRMS adjacent to the ICR cell and
observed as it rose to 180°C over one hour. Figure 17 shows the large
amount of low mass peaks that appeared at two minutes. After 10
minutes mass 44 was the most prominent peak (Figure 18) and mass 150
was starting to grow in. By 25 minutes mass 150 had become very
prominent, mass 296 was prevalent, and mass 44 was still the highest
peak (Figure 19). After 55 minutes the mass 44 signal had decreased
substantially and mass 149 was the highest peak while mass 296 had also
increased (Figure 20).

RELATIVE INTENSITY
Figure 16
ICRMS of Triethylphosphine Gold Chloride

Figure 17. ICRMS (0-400 a.m.u.) of P.R.P., 2 Minutes

RELATIVE INTENSITY
Figure 18. ICRMS (0-400 a.m.u.) of P.R.P., 10 Minutes

RELATIVE INTENSITY
Figure 19. ICRMS (0-400 a.m.u.) of P.R.P., 25 Minutes

RELATIVE INTENSITY
Figure 20.
ICRMS (0-400 a.m.u.) of P.R.P.,
55 Minutes

126
At this point the pulsed Nd:YAG laser was used to irradiate the
sample and the mass 44 signal increased dramatically (Figure 21). Even
after 20 minutes of continuous pulsing with the laser, the mass 44
signal still dominated the spectrum (Figure 22). Next, the electron
beam was turned off and the spectrum was recorded while the laser was
still pulsing. Figure 23 shows the resultant mass spectra with no
peaks over -20 a.m.u. significantly stronger than the background.
This experiment was repeated in the Nicolet ICRMS and spectra were
recorded at temperatures of ~50°C (Figures 24 and 25), 125°C (Figure
26), and 175°C (Figures 27 and 28). The low mass hydrocarbon pattern
that had been observed in all previous mass spectra of the P.R.P. was
again present along with several prominent high mass peaks at 195, 255,
334, and 349 a.m.u. These peaks had not been observed before and there
was a sharp cutoff at mass 349 as shown in the 0-1000 a.m.u. spectra in
Figure 28. This spectra also shows the mass 44 and 149 peaks that were
noted in previous work.
Since there was some question of possible contamination from other
sources (the instrument was used extensively to analyze a variety of
samples), CID reactions were run on the high mass peaks 195, 255, 334,
and 349. Figures 29 and 30 show the results of CID on mass 334 at -0-
collision time and after 50 msec of collision time, respectively. The
major product appeared at mass 255. The CID on mass 349 under the same
conditions is shown in Figures 31 and 32. Some increase in mass 255
signal, and the appearance of a moderate signal at 178 a.m.u., were the
only changes noted. The CID reactions on the remaining compounds

RELATIVE INTENSITY
Figure 21. ICRMS (0-400 a.m.u.) of P.R.P., 60 Minutes, Laser On

RELATIVE INTENSITY
Figure 22. ICRMS (0-400 a.m.u.) of P.R.P., 80 Minutes, Laser On

Figure 23. ICRMS (0-400 a.m.u.) of P.R.P., Laser On, e-Beam Off
RELATIVE INTENSITY
621

Figure 24. ICRMS (0-400 a.m.u.) of P.R.P. at ^50°C

RELATIVE INTENS:
Figure 25. ICRMS (0-100 a.m.u.) of P.R.P. at *50°C

Figure 26. ICRMS (0-400
Relative Intensity
Zíl

Figure 27. ICRMS (0-400 a.m.u.) of P.R.P. at 175°C

Relative Intensity
Figure 28. ICRMS (0-1000 a.m.u.) of P.R.P. at 175°C

GO
en
Figure 29. ICRMS of CID of Mass 334, No Collission Time

Figure 30. ICRMS of CID of Mass 334, 50 msec Collision Time

Relative Intensity
UO
Figure 31. ICRMS of CID of Mass 349, No Collision Time

Relative Intensity
Figure 32.
ICRMS of CID of Mass 349, 50 msec Collision Time

139
mentioned were all negative with respect to the appearance of Au+ ion.
Mass 44 was identified as CO2 by a charge transfer reaction with water.
Thus, the presence of volatile Au compounds could not be
established by the MS study results. The identification of CO2 and the
ubiquitous presence of a compound with a charge to mass ratio of 149 or
150 was firmly established, as was the presence of many low mass
compounds (<100 a.m.u.) that exhibited a hydrocarbon type pattern.
These results seem reasonable considering the H2/CH4 plasma reactants.
The abundance of CO2, especially under highly energetic conditions,
would seem to indicate its ease of formation within the system. These
points are discussed further in the last section of this chapter.
Time of Flight MS Experiment
In this experiment Au to AU7 positive ion clusters were produced
in the pulsed Nd:YAG stimulated plasma described earlier and observed
with the TOFMS. The purpose of this experiment was to determine if
Au/carbonaceous ion clusters could be produced (and detected) by adding
CH4 to the He gas normally used in the cluster beam apparatus. The
results confirmed that this was possible.
Recall that the horizontal deflector (HD) voltage directly
affected the ion signals as previously discussed. Thus, when a spectra
scanning several hundred a.m.u. was recorded the greatest sensitivity
was for the central mass region. This limitation did not apply to the
narrow range scans (< 100 a.m.u.). All of the comparative spectra of
species formed in He and He/CH4 plasmas were recorded at the same HD
voltages.

140
It should also be noted that there are several possible mechanisms
responsible for the observed changes in the positive ion spectra when
the CH4 gas was added to the plasma. The three major mechanisms
are
1) neutralization
Au(n)+ + R” = Au(n) + R
2) combination/dissociation
Au(n)+ + Au = Au(n+1)+
3) ion product reactions
Au(n)+ + R + He = Au(n)R+ + He*
Au(n) + R+ + He = Au(n)R+ + He*
Au(n)R + He* = Au(n)R+ + He + e'
Au(n-1)R+ + Au + He = Au(n)R+ + He*
where the * denotes a transíationally hot species. No attempt was made
to identify any of these, or any other mechanisms, as the one(s)
responsible for the changes in ion signals observed.
Figure 33 shows the Au to AU5 ion signals, along with respective
first and second oxide peaks, which were formed in the He plasma. (The
oxide peaks were ubiquitous in this apparatus and most likely were
formed from residual moisture in the target and holder.) When -1% CH4
was added to the He gas stream, a dramatic change in the ion spectra
occurred (Figure 34). The Au and Au£ signals decreased by nearly two
orders of magnitude, the AU3 signal decreased by a factor of three, the
AU4 signal decreased by a factor of seven and the AU5 signal increased

Intensity (volts)

50
40
30
20
10
0
! 1 1 1 1 1 1 f—
.1 0.3 0.5 0.7 0.9
Thousands a.m.u.
Figure 34. TOFMS of Au to Au^ Clusters Formed in 1% CH^/He Plasma

143
by one order of magnitude. There was also a plethora of new peaks
which appeared at staggered intervals after each Au cluster peak.
Similar scans of the AU3 to AU7 region (Figures 35 and 36) showed
the same effect of additional peaks appearing when CH4 was added to the
plasma. These spectra also show the large increase in the AU5 signal
(and its oxides) as well as moderate increases in the Aug and AU7
signals. Once again the AU3 signal appeared to be relatively
insensitive to the addition of CH4 to the plasma.
The experiment was repeated with the HD set to optimize the Au
signal. Figures 37 and 38 show the spectra from species produced in
the helium and helium/methane plasmas, respectively. These spectra
indicate the high sensitivity of the Au, AuO, and AuO£ signals to the
plasma conditions. The most prominent new peaks occurred at 38, 44,
54, and 76 mass units above 197 (the Au mass). These peaks were
evidently due to the addition of carbon and hydrogen to the Au and AuO
species. For example, the largest peak at +76 mass units could have
been due to either AUC5H4 or AUOC5, among other possibilities.
The Au2 region was observed in the next experiment and the spectra
are presented in Figures 39 and 40. The pattern of additional peaks
was even more pronounced in this test. They appeared at 12, 13, 25,
37, 49, 61, 73, 85, 97, 109, and 121 mass units above the Au£ signal at
394 a.m.u. This was strongly suggestive of the ordered addition of C,
CH, C2H, C3H, C4H, C5H, CgH, C7H, CgH, CgCH, and Cjoh to the Au2 dimer.
The signals at +37 and +61 dominated the new peaks.
Very similar results were observed in the AU3 spectrum when CH4
was added to the plasma. The before and after spectra, presented in

Intensity (volts)
, [ r 1 1 1 1 1 r~
0.5 0.7 0.9 1.1 1.3
Thousands a.m.u.
Figure 35. TOFMS of Au^ to Aug Formed in Helium Plasma
aoctowi «nil
1.5

Figure 36. TOFMS of Au^ to Aug Formed in 1% CH^/He Plasma

Intensity (volts)
16
12
4 -
Au
i/yw
AuO
AuO,
V\rJ l/V
CT>
JPO
2/0
230
250
270
a.m.u,
Figure 37. TOFMS, Expanded Au Region (from Helium Plasma)
220

o
3 4
>>
+->
c/)
c
cu
+J
c
Au
AuOH
AuH
AuO
AuOr
+38
l/V, AJ
N J
+44
+54
v W\,
+64
7+76
jvj /-.
t
T
/«O
210 230 230 270
a.m.u.
Figure 38. TOFMS, Expanded Au Region (from 1% CH4/He Plasma)
-P*



150
Figures 41 and 42, show the major additional peaks occurring at 37, 49,
61, 73, 85, 97, and 109 mass units above the AU3 signal at 591 a.m.u.
This was highly suggestive of the ordered addition of C3H, C4H, C5H,
CgH, C7H, CgH, and CgH. The +37 peak was the dominant new peak in this
spectra. The low reactivity of AU3 was again demonstrated by the
comparatively low signals of the additional peaks arising from the
addition of CH4 to the plasma.
This series of experiments showed that the addition of CH4 to the
He/Au plasma formed by the pulsed Nd:YAG laser had a significant impact
on the mass of the positive ion clusters detected by the TOFMS. The
evidence suggested that the ordered addition of carbon atoms, along
with one hydrogen atom, to the Au clusters was the probable cause of
the additional ion peaks observed. The +38 and +76 mass peaks
dominated the Au spectral additions, the +37 and +61 peaks dominated
the Au2 spectrum additions, and the +37 mass peak was the strongest
additional signal in the AU3 positive ion spectrum. Also, the Au3+ ion
appeared to be significantly less sensitive to the addition of CH4 to
the He/Au plasma.
Despite the fact that the cluster beam experiments showed that Au
was very reactive with CH4 in an energetic plasma, the overall results
of the volatility study indicated that significant quantities of
volatile gold compounds could not be isolated from the plasma reaction
products. However, the P.R.P. were very effective in transporting Au
downstream from the plasma reaction chamber and could be collected on
substrates to yield gold films of varying quality, depending on
deposition and annealing conditions. Thus, the P.R.P. films were

Figure 41. TOFMS, Expanded Au^ Region (from He Plasma)

Figure 42. TOFMS, Expanded Au^ Region (from 1% CH^/He Plasma)

153
subjected to further analyses to determine some of their properties.
These analyses were also intended to determine the state of the Au in
the P.R.P.
Gold Thin Film Characterization Results
Visible Absorption Spectroscopy
Figure 43 shows the results of visible absorption spectra (325-800
nm) of acetone extract/suspensions of P.R.P. formed in pure CH4, He/CO,
and He/CH4/air plasmas. The spectra of 10,000 /¿g Au/ml (water) and 10
ng Au/ml (acetone) are also included in this figure. The most
significant feature of these spectra is the presence of the Au metallic
absorption band centered at -560 nm in the He/CO and He/CH4/air P.R.P.
extract/suspensions, denoting the presence of suspended Au particles.
The conspicuous absence of this band in the CH4 P.R.P.
extract/suspension agreed with earlier observations in the screening
study.
Optical Microreflectometry
Reflectance spectra, 400-900 nm, were recorded for the Harris
Standard sputtered Au film (Figure 44), P.R.P. coated W/Si (Figure 45),
P.R.P. coated glass (Figure 47), and P.R.P. coated Scotch brand black
electrical tape and transparent tape (Figure 46). The major
comparative features in these spectra are the sharp increase in
reflection of Au between 500 and 550 nm and the relatively high
reflectivity of Au from 600-900 nm (see Figure 44).

Absorbance
n. 70
Wavelength (nm)
Figure 43. Visible Absorbance Spectra of Acetone Extracts of Reaction Products
from CH^/Au, He/CO/Au, and He/CH^/Air/Au Plasmas

30
20
10
0
mo
500
]1 i
600 700 800
Wavelength (nm)
Figure 44. Visible Reflectance Spectra of Harris Stnd. Sputtered Au Film
155

30
20
10
0
500 600 700 800
Wavelength (nm)
Visible Reflectance Spectra of P.R.P. on W/Si
—*— As Deposited ••••
Annealed in Hg, 400°C, 1 hr - - -
CJ1
CT>
re 45.
Annealed in Air, 320°C, 18 hrs
Etched Spot on Air Anneal Sample

30
20
10
0
en
^4
too
500
-J I
600 700
Wavelength (nm)
re 46. Visible Reflectance Spectra of P.R.P. on Glass
A) 25°C Deposition,
B) After 400°C, 1.5 hr H? Anneal, and
C) 100°C Deposition
-.1..
800

30
20
10
0
en
00
—I
500
J 1
600 700
Wavelength (nm)
fe
re 47. Visible Reflection Spectra of P.R.P. on
A) Adhesive Side, Scotch Brand Transparent Tape
B) Back Side, Scotch Brand Black Electrical Tape

159
In Figure 45 the reflectance spectra for the P.R.P. on W/Si are
compared for four different samples. As-deposited, air-annealed, and
hydrogen-annealed samples all had similar spectra with no sharp
increase in reflectivity, and overall low reflectivity below 800 nm.
This was indicative of highly carbon contaminated films. The sample
that was subjected to argon ion etching displayed the W reflection
spectrum, indicating removal of the annealed P.R.P. film by the etching
process.
The coated glass substrates displayed the most variable spectra.
The as-deposited sample spectrum was similar to the coated W/Si
spectra, while the air-annealed sample on glass displayed the sharp
transition at -500 nm but was not highly reflective until 600 nm. The
glass plate that was coated with P.R.P. at 100°C was the most similar
to the Au standard in its reflectance properties, with the sharp
transition occurring at -550 nm and high reflectivity lasting to -800
nm.
The two tape samples also displayed sharp transitions at -500 nm,
indicating that the P.R.P. film was highly reflective as deposited on
these substrates. The coated adhesive side of the transparent tape was
particularly reflective, as its spectrum shows (Figure 47).
These spectra provided a measure of the P.R.P. reflectance
properties on the different substrates. They also indicated the low
reflectivity of the dark colored films on W/Si substrates, and the
highly reflective, metallic looking film on the transparent tape (25°C
deposition) and the 100°C deposited film on glass.

160
X-Ray Photoelectron Spectroscopy
The XPS studies determined the P.R.P. film compositions and the
binding energy of the Au in the films. Three types of P.R.P. samples
coated on W/Si were analyzed along with the Harris standard Au film:
as deposited, annealed in air at 250°C or 320°C for 18 hours, and
annealed in H2 at 320°C for 18 hours and 300°C for one hour. The
Harris standard, and one each of the air and H2 annealed samples, were
subjected to Ar ion etching, as described earlier. The photoelectron
takeoff angle (Theta) was relatively low (30°) in the first two etch
runs listed. The third etched sample was also subjected to initial
analyses at Theta equal to 10° and 70°. The other samples were
subjected to surface analyses at a high Theta of 75°. The XPS
anaytical conditions and results are listed in Table 8.
The heavy atomic concentration of C on the surface (84.6%) of the
standard Au film was indicative of the handling that the sample
experienced before analysis. The C concentration fell to -1/2 of its
starting concentration after 15 minutes of etching. After one hour of
etching the C mass concentration was stable at -1.5%. The atomic
concentration of the Au in the bulk (i.e., after one hour of etching)
was 80%, or 98.5% mass concentration.
The P.R.P. film sample from experiment #880602 that had been
annealed in air and subjected to profile analysis showed a maximum gold
mass concentration of 91% after 30 minutes of etching. After 50
minutes of etching the Au concentration dropped to 88 mass percent and

Table 8. XPS Analytical Conditions and Results
Instru¬
ment
Sample
Angle
Au
4f 7/2
Au
C
Is
C
Etch
Time
(min)
B.E.
(eV)
Width
(eV)
Atomic
%
Mass
%
B.E.
(eV)
Width
(eV)
Atomic
%
Mass
%
Relative
%
GCA
Harris Stnd.
30°
0
★
1.45
15
75
★
1.92
85
25
100
30
15
★
--
★
1.80
—
- -
53
30
30
★
--
--
★
1.78
- -
37
30
45
★
1.60
76
98
*
1.92
24
1.8
35
30
60
★
1.61
80
98.5
★
1.88
20
1.5
29
GCA
880602
30
0
84
1.49
23
83
284
2.01
77
17
100
Air, 320°C,
30
30
84
1.60
39
91
284
2.03
61
8.7
80
18 hr
30
50
84
1.52
32
88
284
1.74
68
12
89
Kratos
870901
10
0
_ _
2.4
29
..
97
81
100
H2, 300°C,
70
0
--
--
45
93
55
7.0
57
18 hr
70
15
--
--
51
95
49
5.3
51
70
60
61
96
--
--
39
3.7
40
Kratos
Harris Stnd.
75
0
83.9
# 1.10
56
95
283.7
1.73
44
4.6
--
Kratos
880602
75
0
84.1
1.15
37
91
283.6
1.78
63
9.3
H2, 300°C,
1 hr
Kratos
880527
75
0
84.1
1.12
52
95
283.8
1.76
48
5.3
Air, 250°C,
18 hr
Kratos
880527
75
0
84.1
1.19
51
94
283.5
1.78
49
5.6
as deposited
*Sample not grounded properly.
^Used as calibration standard to adjust instrument scale.
-I9I-

162
it was obvious from visual inspection after the run that the film was
nearly etched away.
The second sample P.R.P. film that was subjected to depth profile
analysis was an air annealed film from experiment #870901. This film
had a near surface C atomic concentration of 97%, determined by a Theta
= 10° initial scan. A Theta = 70° initial scan showed a C atomic
concentration of 55%, indicating the near surface nature of the carbon.
The Au concentration was 45 atomic percent (93% mass) under the same
conditions. After 15 minutes of etching the Au concentration was 51
atomic percent (95% mass). After one hour of etching the bulk Au
atomic concentration in this film was determined to be 61%, or 96% mass
concentration. Figure 48 shows the XPS survey scan spectra of the film
before and after etching. The appearance of strong W bands indicated
that the underlying substrate had been exposed by the process, probably
be removal of the hydrocarbon layer that coated the entire film. The
P.R.P. formed a discontinuous film and areas of the substrate were
visible after the sample was removed. Figures 49 and 50 show the XPS
spectra associated with the high and low Theta analyses for the C Is
peak and the Au 4f5/2 and 4f7/2 peaks, respectively, and indicates the
near surface nature of the carbon.
The remaining samples that were subjected to high Theta (75%)
surface analyses in order to observe binding energy (B.E.) shifts had
Au atomic concentrations of 56% (Harris std.), 37% (880602 H2 anneal),
52% (880527 air anneal), and 51% (880527 as deposited). These
concentrations were consistent with the other analyses and showed that
the Au/C ratios were more dependent on the sample source than on the

Intensity (Counts)

Intensity (Counts)
Figure 49. XPS Scan of Au 4f5/2 7/2 Peaks at High and Low Photoelectron Takeoff Angles

Intensity (Counts)
Figure 50. XPS Scan of C15 Peak at High and Low Photoelectron Takeoff Angles

166
annealing conditions. Both the H2 and air annealed samples from 880602
had the same bulk Au mass concentration of 91%. Even the unannealed
sample from 880527 had the same bulk Au mass concentration as its air
annealed counterpart (-94%). These results were also consistent with
the results of the gravimetric/AA study which indicated a range of 82-
99% Au mass concentration in the as deposited films, with an average
value of 91%.
The B.E.s and widths of the Au 4f peaks in all of the samples were
not significantly different from the B.E.s and widths of the standard
Au film. This was a critical factor in determining the probable
formation mechanism of the P.R.P. superfine particles. The Au existed
in the metallic state in the as deposited, air annealed and H2 annealed
sample films. The 0.2 eV difference in B.E. was not considered
significant in the Kratos instrument and in fact similar shifts were
observed in spectra of the Au standard taken several hours apart.
Shifts due to Au-C bonding were expected to be 0.4 eV or greater.76*78
Scanning Electron Spectroscopy with Energy Dispersive Spectroscopy
The SEM/EDS analyses were performed on the standard Au film and
P.R.P. coated sc W/Si, glass and polymeric tape substrates in order to
determine grain size and film morphology. The Harris standard sputter
deposited Au film was photographed as received and after undergoing one
hour of Ar ion etching in the XPS study (Figures 51 and 52). The
pebble-like film had a surface grain size of -1000 nm and was fairly
uniform in appearance. This is a typical structure for a sputter
deposited Au film and is indicative of three dimensional hillock growth

Figure 51. SEM Photograph of Harris Stnd. Sputtered Au Film

ICG

Figure 52. SEM Photograph of Harris Stnd. Sputtered Au Film
After 1 Hour of Argon Ion Etching

170

171
on islands. This was verified by the SEM of the same film after
etching, which revealed the underlying Au island structure. The early
stages of the hillock formation are visible on the larger island
structures (Figure 52). These photographs also serve to illustrate
some of the limitations of the sputter deposition process mentioned in
Chapter I.
The EDS spectrum of the as etched film is presented in Figure 53.
The large Au signal is the most prevalent peak, but the significant Si
signal from the underlying substrate illustrates the sampling depth of
several hundred Angstroms typical of EDS systems at 15 KV.
Figure 54 shows the EDS spectrum at 15 KV of the P.R.P. as formed
and placed in a pile on the SEM mount. The strong Au signal is
apparent. (Note that the intensity scales of the EDS spectra are given
at the bottom right of each figure.) The SEM view of this sample was
not revealing due to the mounting technique.
However, the as deposited P.R.P. film on sc W/Si clearly showed a
uniform grain of -4000 Angstroms (Figure 55). The 15 KV EDS spectrum
of this surface (Figure 56) indicated that the Au/C film was very thin.
A lower energy spectrum was not recorded for this sample.
The SEM photograph of the air annealed P.R.P. film on sc W/Si
(Figure 57) shows a similar uniform grain size, but the structure is
altered significantly. The Au particules appear to have joined to form
a chain-mail type of structure with the carbonaceous material located
in the interstitial areas. The 5 and 15 KV EDS spectra of this surface
are presented in Figures 58 and 59. The strong Au signal in the former
spectrum versus the higher energy spectrum again illustrates the

Intensity (counts)
0 000 *VFS = 2048 10.240
K e.V.
no
Figure 53. EDS of Harris Stnd. Sputtered Au Film on Si; 15 KV
*Vertical Full-Scale, Counts

Intensity (counts)
4096
If
I
H
J
i
j
n i
LI
1 R
; U
ñ
U
"â– vâ„¢
j-
*>=
'
i lr,
: : :
•T’rrrrrvv
j
1 1,^.
0.000 *VFS = 4096 10.240
K e.V.
Figure 54. EDS of H^/CH^/Au Plasma Reaction Product (P.R.P.); 15 KV
*Vertical Full-Scale, Counts

Figure 55. SEM Photograph of P.R.P. on W/Si

175

Intensity (counts)
0.000 K e.V. *VFS = 4036 10.240
Figure 56. EDS of P.R.P. on W/Si; 15 KV
*Vertical Full-Scale, Counts

Figure 57. SEM Photograph of P.R.P. on W/Si After 250°C,
18 Hour Anneal in Air


Intensity (counts)
0.000 *VFS = 256 10.240
K e.V.
Figure 58. EDS of P.R.P. on W/Si After 250°C, 18 Hour Anneal in Air;
5 KV
*Vertical Full-Scale, Counts

Intensity (counts)
Figure 59. EDS of P.R.P. on W/Si After 250°C, 18 Hour Anneal in Air;
15 KV
CO
o
♦Vertical Full-Scale, Counts

181
thinness of the film and verifies that the photographed surface is
composed of the Au/C system.
The SEM/EDS analysis of a hydrogen annealed P.R.P. film yielded
results similar to the air annealed sample. The SEM photograph shows
the same chain-mail structure but has less contrast between the Au and
C areas (Figure 60). This may be due to the presence of a surface
hydrocarbon film, as was indicated by the XPS results. Only the high
energy EDS spectrum was recorded for this sample (Figure 61), and it
verifies the presence of a thin Au surface film.
The SEM photograph of a P.R.P. film on sc W/Si that was deposited
at 100°C is presented in Figure 62. The three dimensional crystal
structure of the Au film is very apparent, indicating advanced stages
of growth. This can be explained by considering the high substrate
temperature in the deposition process that formed the film. The
increased motion of Au atoms and clusters on this surface allowed the
small Au particles to agglomerate in the lowest energy structure
accessible, i.e., the face centered cubic crystal structure. The
overlapping crystals formed a very thin film, similar to the other
P.R.P. samples, as indicated by the low and high energy EDS spectra
pictured in Figures 63 and 64, respectively.
The P.R.P. coated on glass and annealed in air showed no
discernible grain structure under SEM analysis. The 5000X image is
shown in Figure 65, but images up to 50,OOOX were observed during the
course of the analysis with the same results. The low and high energy
spectra (Figures 66 and 67) were similar to the other samples with

Figure 60. SEM Photograph of P.R.P. on W/Si After 320°C,
18 Hour Anneal in Hydrogen

133

Intensity (counts)
2048
i
w
•
E !
is
w
=L
/? Ji j
-'â– n lili
_A_
W
—.rvt'CTV
0.000 * VFS = 2043 10.240
K e.V.
Figure 61. EDS of P.R.P. on W/Si After 320°C, 18 Hour Anneal in Hydrogen:
15 KV
*Vertical Full-Scale, Counts

Figure 62. SEM Photograph of P.R.P. on W/Si, 100°C
Deposition


Intensity (counts)
2048
i i
i i 1
Figure 63. EDS of P.R.P. on W/S1, 100°C Deposition; 5 KV
â– ^Vertical Full-Scale, Counts

Intensity (counts)
8192
w
"i
j
i
in
W j
!
•:'U
L.
w
0.000 *VFS = 3192 10.240
K e.V.
Figure 64. EDS of P.R.P. on W/Si, 100°C Deposition; 15 KV
*Vertical Full-Scale, Counts

Figure 65. SEM Photograph of P.R.P. on Glass After
400°C, 1.5 Hour Anneal in Air

150

Intensity (counts)
4096
I
t
JM R
R
Ü
r.
iü L jl
r^yr/l
i
L
"K R"
A
t -—•
0.000 *VFS = 4096 10.240
K e.V.
Figure 66. EDS of P.R.P. on Glass After 400°C, 1.5 Hour Anneal in Air;
15 KV
*Vertical Full-Scale, Counts

Intensity (counts)
512
i
Fj
IJ
t
f
=IG R
i
«1 :
1 .
1
VA.J
j
1
0.000
K e.V.
* VFS = 512
10.240
Figure 67. EDS of P.R.P. on Glass After 400°C, 1.5 Hour Anneal in Air;
5 KV
^Vertical Full-Scale, Counts

193
respect to the strong substrate signal (from Si in this case)
indicating the thinness of the Au film.
The SEM photograph of a P.R.P. sample deposited on glass at 100°C
showed an even more uniform, grainless structure (Figure 68). Again,
the film was viewed under much higher magnification than pictured
without obtaining additional structural information. The low and high
energy EDS spectra for this surface (Figures 69 and 70) indicated that
this was also a very thin film.
The P.R.P. deposited on the adhesive side of Scotch brand
transparent tape and subjected to SEM analysis is pictured in Figure
71. A uniform dispersion of -1000 Angstrom size grains is visible on
the even finer grained background. The EDS spectrum (Figure 72)
verified the presence of Au on this surface.
The last three SEM photographs included in this section (Figures
73, 74, and 75) show the laser annealed P.R.P. coated sc W/Si surface
described earlier. Figure 73 clearly shows the dissipation front of
the heat wave generated by the laser beam. The target spot is near the
center of the photograph. Figures 74 and 75 show the effect of the
heat described earlier. The increased openness of the grain structure
is clearly evident in these shots taken at a 30° angle.
Electrical Resistance Measurements
The electrical feedthroughs that were subjected to air and
hydrogen anneals while observing the resistance across a P.R.P. coated
surface experienced problems with the electrode contacts. The
electrodes were coated with a low melting alloy that was apparently

Figure 68. SEM Photograph of P.R.P. on Glass,
100°C Deposition

t
Wák
0001 10KU
ss
»
000
lHm ND1

Intensity (counts)
4096
0.000 *VFS = 4096 1S.240
K e.V.
Figure 69. EDS of P.R.P. on Glass, 100°C Deposition; 5 KV
♦Vertical Full-Scale, Counts

Intensity (counts)
K e.V.
Figure 70. EDS of P.R.P. on Glass, 100°C Deposition; 15 KV
*Vertical Full-Scale, Counts

Figure 71. SEM Photograph of P.R.P. on Adhesive Side
of Scotch Brand Transparent Tape


512
ñ
y
Í
CT
I |
i
ill
i C
; L
1 \ ,
K
¡rtfS{
11 f'ilh.
‘t: K'V^Vv
‘|^T>V»i4ry.
t'.
rTT-,V-v*v* - >
Vr^.n-i-.k-A
'•i'iv;v.yr'rn'-
0.000 *VFS = 512 10.240
K e.V.
Figure 72. EDS of P.R.P. on Adhesive Side of Scotch Brand Transparent Tape;
14 KV
r\D
o
o
*Vertical Full-Scale, Counts

Figure 73. SEM Photograph of Laser Annealed Area of
P.R.P. on W/Si


Figure 74. SEM Photograph of Unannealed P.R.P. on W/Si


Figure 75. SEM Photograph of Laser Annealed Spot of
P.R.P. on W/Si


207
meant to facilitate soldering. This film melted and broke the contact
in the first test (air annealed sample). The feedthrough used in the
second test (H2 anneal) was etched in con. HC1 and baked at 600°C for
18 hours before being coated with the P.R.P. The results of this test
are presented in Figure 76.
Figure 76 illustrates the electrical properties of a forming Au
film. The early conductance (low resistance) of the film indicated
that the closely packed particles had enough contact to complete the
circuit. As the temperature was increased the particles coalesced into
separated islands and lost contact with one another. As the
temperature rose to over 300°C the Au islands began merging and
eventually completed the circuit again. This island formation and
coalescence has been observed by other investigators and is typical of
Au film growth.79>80
Four point probe resistance measurements showed a sheet resistance
value (Rs) of 0.09 Ohms per square mm for the Harris standard Au film.
The two coated glass plates that were analyzed by SEM/EDS showed
infinite resistance at all input settings, indicating the discontinuity
of the films. The same results were observed with the coated black
electrical tape, the coated transparent tape, and an air annealed
coated GFF sample.
The glass plate coated with Au from He plasma (by line of sight
deposition) had a Rs value of 2.3 Ohms/mm2 and a quartz window thickly
coated with P.R.P. had a Rs value of 5600 Ohms/mm2. These two samples
indicated the effectiveness of the He plasma for producing conductive

15
ro
o
oo
0 1 1 1 1 L
100 200 300 400 500
Temperature (°C)
Figure 76. Electrical Resistance vs. Temperature for a P.R.P. Coated Feedthrough

209
Au films in close proximity to the plasma zone, and the conductivity
possible with a thick layer of the P.R.P., presumably due to the close
proximity of the Au particles to each other and the limited
conductivity of the carbonaceous material.

CHAPTER IV
SUMMARY AND CONCLUSIONS
Discussion of Plasma Reaction Product Formation
The extensive experimental evidence gathered in the production and
characterization of the P.R.P. can be appropriately summarized in a
discussion of its formation. Only a general description of the
gold/carbon ultrafine particle formation can be deduced from this
evidence. A definitive formation mechanism could not be deduced
without substantial additional analytical information, such as
transmission electron microscopy of isolated particles, in situ
diagnostic spectroscopy of the plasma, and in situ mass spectrometry of
plasma generated ions. While these efforts were beyond the scope of
this study, the general mechanism presented below is strongly supported
by the experimental evidence. There are necessarily some missing
details in the proposed mechanism. Each step is presented sequentially
below along with a brief discussion.
1) The first photons in the 250 nanosecond pulse to reach the
gold surface were partially reflected and partially absorbed by
conduction band electrons via an internal photoelectric effect.
Electron-phonon collisions, which occur on a time scale of 10~12 to
10-13 sec -jn g00d conductors, changed the energy input into heat and
caused rapid vaporization of some of the metal.Because of the speed
210

211
of this process, the vapor front was initially the same density as the
solid phase and was highly ionized due to its high temperature.^
2) As the dense, ionized vapor front expanded into the reactive
gas mixture, the shock wave generated by the explosive heating process
traveled in the opposite direction, through the molten surface material
and into the solid bulk. This shock wave caused large chunks of molten
material to be blown off the target. The smallest of these particles
appeared as spheroids greater than 10 microns in diameter. Larger
particles had irregular globular surfaces. Since these particles ended
up in the bottom of the reaction chamber, it is assumed that their role
in the formation of the ultrafine gold/carbon particles collected
downstream from the reaction zone was minimal. However, their presence
complicated the mass-balance determination of the amount of material
that was actually vaporized during each laser pulse. Instead, a
reverse calculation based on the amount of material collected in four
filter catch experiments showed that an average of 8.7 x 1014 atoms of
Au per pulse were vaporized and subsequently reacted to form the
captured product. (The range of averages for the four experiments was
6.6-10.5 x 10*4 atoms/pulse.)
3) The advance of the ionized plume was preceded by hot electrons
which excited the ambient gas before the gold arrived. This resulted
from the production of high energy electrons during step 1) that had a
most probable thermal velocity, Vp = (2kT/m)l/2? and expanded from the
surface in all directions, but with a distribution that favored coaxial
dispersion of the highest energy electrons.81 These electrons caused a
rapid increase in the optical density of the ambient gas (via inverse

212
bremsstrahlung) which led to further excitation of the species present
in a manner analogous to the gas breakdown phenomena described earlier.
This effect also limited the amount of incoming laser energy that
reached the surface of the target. Since electron temperatures are
typically an order of magnitude higher than ion temperatures in this
regime,80*82 and the electron mass is five orders of magnitude smaller
than the Au ion mass, the velocity of the hot electron front was three
orders of magnitude faster than the ion plume front.
Tan et al.82 determined an empirical relationship between the
fastest ion velocities in cm/sec, Vi, and the peak laser fluxes from Nd
glass lasers and CO2 lasers in W/cm2, Ip. They found that Vi was
independent of atomic number and the laser wavelength and was
proportional to the peak irradiation, Ip:
Vi = 5.7 x 106 Ip1/6
Using this relation and the peak irradiation value of 3 x 10° W/cm2
yields a Vi of 2.2 x 108 cm/sec. The experimental evidence presented
by Tan et al. showed that over 80% of the ions have velocities in
excess of 1/2 Vi. This calculated value is in reasonably close
agreement with the experimentally determined value of 3 x 10^ cm/sec
for aluminum ion velocities in similar plasmas with Ip = 2 x 108 W/cm2
reported by Dyer et al. (Note that Tan et al.'s empirical relationship
predicts a Vi of 14 x 10^ cm/sec for this case.) Thus, an upper limit
for the total distance traveled by the ionized plasma front during the
250 ns laser pulse is given by

213
(2.5 x 10"7 sec) x (2.2 x 108 cm/sec) = 55 cm
Of course the plasma front never extended out to this distance due to
collisional energy losses within the expanding plume itself, and
between the plume front and the ambient gas. The point to be made here
is that the expanding Au plasma was continuously irradiated with the
incoming laser photons during its reactive expansion, and thus ample
energy was available not only from the hot plasma but also from the
incident laser radiation to stimulate high energy reactions in the core
of the plume. Tonon and Rabeau88 measured a mean ion temperature of 30
eV in a hydrocarbon plasma produced by a 100 ns CO2 laser pulse
incident on a solid polyethylene target with a peak intensity of 6 x
108 W/cm8. Assuming an analogous situation occurred in the plasmas
generated in this study, the Au ions were hot enough to be in the plus
2 state (2nd ionization potential of Au = 20.5 eV).
The high temperature (light emitting portion) plasma generated in
this study extended approximately 5 cm from the target surface and was
roughly spherical initially. The plasma shape became more prolate as
target cratering progressed and took on the classic shape of a candle
flame after several minutes of pulsing on the same spot (Figure 77).
The coaxial core of the plasma was white, indicating high temperature
broadband emission, and extended from the target surface to about 2/3
of the distance to the edge of the light emitting zone. This hot core
was only a few millimeters in diameter and it was apparent from
photographs that the plasma was radially symmetric and the brightest
emission was from a hemispherical plume 2-3 mm in diameter that
originated at the garget impact point.

214
(Actual Size Pictured)
Figure 77. Typical Plasma Produced by the Pulsed COp Laser
Incident on a Solid Gold Target in 1350 Pa of
3:1 H2/CH4

215
4) Thus, the ionized gold plume expanded into an excited state
methane/hydrogen atmosphere and approximately 1015 ions/atoms of Au
ultimately reacted with the carbonaceous species present and were
collected downstream from the reaction zone. This step contains the
greatest amount of uncertainty. It was not apparent from the
experimental evidence if the Au and C were intermixed at all levels in
the particles, or if the C was associated primarily with the exterior
of the particles. It was shown conclusively by XPS studies that the Au
exists in the metallic state in particles, or equivalent connected
network structures, no smaller than 50 Angstroms in diameter. This
lower size limit can be assigned since pure Au particles smaller than
this, or Au/C in a bonded state, produce significant shifts in the Au
4f binding energies.®^-86 No such shifts were observed in the spectra.
High angle XPS studies of unannealed and air annealed particle
films formed during the same plasma experiment showed only a small
decrease in the C/Au ratio, from 0.96 to 0.92. Profile XPS studies of
an air annealed and a hydrogen annealed sample (from different plasma
experiments) showed C/Au ratios in the film bulk of 1.56 and 0.64,
respectively. (This compares to a C/Au ratio of 0.25 in the Harris
standard Au film bulk.) However, the conductivity tests, the
reflectance spectra, the MS studies, and the observation of visible
clouds rising from the surface of films during laser anneals, all
indicated that carbon compounds were associated with the exterior
surfaces of the particles.
Thus, there is evidence that the carbon is present on the exterior
of the particles, and that is may also be present in the interior of

216
the particles. It is not clear whether the C is incorporated in the
interior of the particles or is trapped in grain boundaries between
particles in the annealed films. Therefore, it is not possible to
define a mechanism that would accound for the incorporation of C in the
Au particles. It is possible, however, to speculate on the particle
nucleation and growth mechanism by considering the above discussion and
the experimental results.
The total volume of the luminescent plasmas represented by Figure
77 was approximately 40 cm^. At a CH4 partial pressure of 1350 Pa,
there were 3.2 x 10^ molecules of CH4 present in the plasma sweep
volume under static conditions. This was more than three orders of
magnitude greater than the number of Au atoms that reacted to form the
P.R.P. during each pulse. When the plume expanded at -10^ cm/sec this
gas was compressed and partially swept away. The high order of P.R.P.
formation dependency on the CH4 pressure under static conditions
indicated that the density of carbonaceous species at the plume front
(where most of the collisions between Au and C species took place) was
a critical parameter. The formation of P.R.P. using CO and CO2 in
place of CH4 indicated that carbon, rather than some unique
hydrocarbon, was the dominant (along with gold) species involved in the
P.R.P. formation. A more exhaustive study of the pressure dependency
on these three gases would yield further insight into the mechanism of
C inclusion.
5) It seems probable that the Au underwent homogeneous nucleation
in the expanding, cooling, plasma front and formed Au particles larger
than 50 A which then contacted the carbonaceous species and became

217
coated with the C material. At this point more Au may have been
incorporated in the growing pargicle, or the C coating may have
prevented further Au addition. A detailed TEM study of individual
particle cross sections would show which scenario is correct.
Of the four CH4/H2 P.R.P. filter experiments, two had C/Au ratios
of 3.5, one had a ratio of 0.16, and one had a ratio of 28. The CO and
CO2 filter experiments had ratios of 0.85 and 0.69, respectively. This
larger range of ratios supports the exterior growth mechanism for C
addition. Figure 78 shows a plot of the relation of particle size to
the ratio of C/Au required to form a monolayer coating of C on the
exterior of a solid Au particle. (This plot was constructed using a
hard-sphere model with the diameters of Au = 2.9 A and C = 1.4 A.) For
particles in the size range of 100 to 1000 A, ratios of C/Au in the
range of 1.0 to 0.1 would be required. This is consistent with the XPS
data and the experimentally determined C/Au ratios for most of the
tests. The higher ratios, 3.5 and 28, were probably due to additional
C buildup on the exterior of the particle. This point was evident in
the highest ratio sample which lost the bulk of its C weight during an
air anneal. (A precise measurement of the loss was not possible due to
nonreproducible binder losses from the glass fiber filters during the
annealing process.)
So, while a limited amount of C may be incorporated along with Au
on top of a pure Au core in the growing particle, it seems likely that
the majority of the C is added to the exterior of the Au core.
Agglomeration of these C coated particles in the gas phase may account
for their entrainment in the gas phase, or the growth mechanism of the

Particle Diameter (Angstroms)
218
Figure 78. Particle Diameter Versus Ratio of Carbon Atoms, Required
to Form a Monolayer on the Surface, to Gold Atoms in
the Particle

219
individual particles in the presence of the carbon compounds may be
responsible for producing a particle of sufficient size and density to
be entrained in the gas stream. Both of these scenarios depict a
heterogeneous formation mechanism for the P.R.P. The lack of Au
transported to the filter in plasma experiments that utilized inert
gases and hydrogen under similar gas flow regimes, and the lack of soot
collected on the filter in a CH4/H2/graphite plasma experiment, both
support the assumption of a heterogeneous mechanism.
Conclusions
The results of this study showed that superfine particles, or
particle agglomerates, of gold/carbon in the 100-400 nm size range
could be produced in a pulsed CO2 laser stimulated carbonaceous gas
plasma and transported in a gas stream at several hundred Pascals
pressure. The study also showed that the production of these plasma
reaction products was highly dependent on the carbonaceous gas
pressure, even when diluted in helium or hydrogen, and on the incident
laser power density. This suggested a heterogeneous nucleation
mechanism. The best conditions determined for production of the
superfine gold/carbon particles were a partial pressure of 350 Pascals
of methane in hydrogen and a laser power density of 3 x 10^ watts/cm^.
(Higher power densities were not investigated.) The XPS analyses
showed that the Au was present in the metallic state in the reaction
product. The nucleation and growth of thin Au films from the products
resembled other Au film growth scenarios from evaporation and sputter

220
sources, with the exception of the inclusion of substantial amounts of
carbon (-50 atom %).
Although the plasma products gave no indications of being suitable
for use in microelectronic interconnect formation, the optical
properties of the thin Au cluster films were not thoroughly
investigated. Preliminary infrared reflection and transmission
measurements (not reported in the text due to the cursory nature of the
analyses) indicated very high broadband absorption. These properties
may be of interest to the electronic industry for use in bolometers or
other devices requiring infrared absorbers of low thermal mass. Gold
blacks have historically been used for this purpose,87'90 but there is
an operational upper temperature limit of 100-150°C. Above these
temperatures the gold black films, which are composed of agglomerates
of 0.1 to 4 nm diameter Au particles loosely packed in a high porosity
matrix collapse and lose their high absorption characteristics. These
films also are subject to contamination from the crucible and/or
heating element materials that are used in the formation process
(evaporation of Au in the presence of 14 to 2800 Pa of N2, H2, or air).
The P.R.P. reported on in this text has the advantages of being free
from metallic oxide impurities and being resistant to collapse (as
indicated by a sharp color change in the film) at temperatures in
excess of 200°C, presumably due to the thin carbonaceous coating on the
Au particles.
In addition to the infrared characteristics of the P.R.P. films,
the visible properties could also be of great interest to the
electronic industry. There were three distinct colors that could be

221
produced in the P.R.P. films, depending on annealing conditions (and
thus on the amount and location of carbon inclusion): black, purple,
and red/yellow. Since it was shown that an Ar ion laser could cause
local annealing, this material could be utilized as a multi-level,
micro optical encoding medium.
These properties warrant a further investigation of the P.R.P.
formation mechanism and further characterization of its optical
properties.

APPENDIX A
GLASS FIBER FILTER BLANKS
Three borosilicate glass fiber filters of the type used in the
study (Micro Filtrations Systems GB100R47 mm) were chosen randomly from
the box and subjected to blank gravimetric analyses using the Mettler
analytical balance. The filters were placed in glass petri dishes and
dried overnight in a 375 K oven. They were then removed from the oven
and allowed to come to room temperature in a desiccator before being
weighed. Each filter was weighed separately in the bottom half of the
glass petri dish and then transferred to the filter holder and
installed in the plasma reaction system. The petri dish was then
weighed and returned to the desiccator. The initial filter weights
were determined by difference using this method.
The filters were subjected to blank runs by evacuating the plasma
reaction system and then pulling a mixture of 75% H2/25% CH4 gas
through the system at a nominal (atmospheric) flow rate of 200 ml/min
and a nominal pressure of 1,330 Pascals (10 torr) for 30 minutes. The
system was then filled to atmospheric pressure with the gas mixture and
the filter holder was removed. The filter was then removed from the
holder and placed into a pre-weighed petri dish that was already on the
balance. Final filter weights were determined by difference using this
technique.
222

223
All weights were recorded to the nearest 0.01 mg. Great care was
taken to assure that no particles or flakes were produced during the
handling of the delicate filters, as was the practice during production
runs. The initial and final filter weights and the differences (D) are
listed in Table 9. The standard deivation (S) of the blank filter
weights was calculated using the following equation:
S = {[E(D)2]/3}1/2
The value of S for the three filters was determined to be 0.434 mg.
Table 9. Glass Fiber'Filter Blank Weights
Filter
Initial Weight
(mg)
Final Weight
(mg)
Difference
(mg)
1
187.80
187.13
-0.67
2
167.79
168.00
+0.21
3
192.73
193.00
+0.21
In order to determine the contribution of the normal standard
deviation of the balance to the standard deviation of the filter blank
weights, five copper penny weights were each weighed three times (see
Table 10). The sample standard deviation (s) for each penny weight was
calculated using the following equation:
s = ([E(m - x)2]/2}1\2

224
where m is the average of the three weights and x is the individual
weight value. The mean value for s for all five weights was determined
to be 0.220 mg.
Table 10. Repetitive Weighings on the Mettler Analytical Balance
Penny
#
Weight (mg)
Average
Standard
Deviation
(1)
(2)
(3)
1
3088.02
3087.80
3087.55
3087.79
0.235
2
2515.84
2516.00
2516.07
2515.97
0.118
3
2537.43
2536.78
2537.00
2537.07
0.331
4
2554.08
2554.00
2554.40
2554.16
0.212
5
2487.14
2487.32
2486.91
2487.12
0.206

APPENDIX B
ATOMIC ABSORPTION SPECTROMETER CALIBRATION
The Perkin Elmer Model 303 AA spectrometer was fitted with a
Fisher Scientific Au hollow cathode tube and tuned to the 242.8 nm
line. The lamp was operated at 9.0 mamp. A stock solution of
concentrated Au standard was prepared by dissolving 1.0068 grams of
0.999% pure Au wire in 20 ml of aqua regia. This solution was then
diluted to 100.0 ml in a volumetric flask and sealed. Serial dilution
in either deionized water or spectral grade acetone was used to prepare
1-100 ppm (grams per million ml) working standards at the beginning of
each day that analyses were performed.
The instrument's burner flame (acetylene/air) was adjusted to give
the greatest linear response range for each type of solvent. In
practice, this consisted of leaning the gas mixture substantially when
running samples and standards dissolved (or suspended) in acetone
compared to those dissolved in water. The instrument response was
recorded as percent absorption, to the nearest 0.5%, on a stripchart
recorder (see Figure 77). Straight line calibration plots of
absorbance (A) versus concentration were prepared from the transmission
data using the Lambert-Beer relationship, where T = (100 - %
absorption)/100:
-log T = A
225

226
Figure 79 shows a typical calibration plot for the instrument. No
significant differences in instrument performance were noted, once the
flame conditions were optimized, when using acetone solvent versus
water solvent.

Figure 79. Typical AA Calibration Plot of Absorbance
vs. Au Concentration

yg Au/ml
aDsorDance
o o o
• * •
228

APPENDIX C
STANDARD REFLECTANCE VALUES FOR SILICON CARBIDE
R(stnd) for single crystal SiC used to calculate reflectance
curves for microreflectometry analyses are listed below.
Table 11. R(stnd) Values for SiC
Wavelength
(nm)
R(stnd)
(%)
Wavelength
(nm)
R(stnd)
(%)
400
22.2
660
20.0
410
22.1
670
20.0
420
21.9
680
19.9
430
21.8
690
19.9
440
21.6
700
19.9
450
21.5
710
19.9
460
21.3
720
19.8
470
21.2
730
19.8
480
21.1
740
19.8
490
21.0
750
19.8
500
20.9
760
19.7
510
20.8
770
19.7
520
20.7
780
19.7
530
20.6
790
19.7
540
20.6
800
19.7
550
20.5
810
19.7
560
20.5
820
19.7
570
20.4
830
19.7
580
20.3
840
19.7
590
20.3
850
19.7
600
20.2
860
19.6
610
20.2
870
19.6
620
20.1
880
19.6
630
20.1
890
19.6
640
20.0
900
19.6
650
20.0
229

REFERENCES
1. Simon S. Cohen, VLSI Electronics Microstructure Science, Vol. 15:
VLSI Metallization, N.G. Einspruch, S.S. Cohen, and G.S.
Gildenblat, eds. (Academic Press, Inc., Orlando, FL, 1987), Chap.
1.
2. B.M. Welch, D.A. Nelson, Y.D. Shen, and R. Venkataraman, VLSI
Electronics Microstructure Science, Vol. 15: VLSI Metallization,
N.G. Einspruch, S.S. Cohen, and G.S. Gildenblat, eds. (Academic
Press, Inc., Orlando, FL, 1987), Chap. 9.
3. I. Blech, H. Sello, and L.V. Gregor, Handbook of Thin Film
Technology. L.I. Maissel and R. Glang, eds. (McGraw-Hill Book
Company, Inc., New York, 1970), Chap. 23.
4. H.B. Huntington and A.R. Grone, J. Phys. Chem. Solids 25, 335
(1971).
5. F.M. d'Heurle and P.S. Ho, in Thin Films--Interdiffusion and
Reactions. J.M. Poate, K.N. Tu, and J.W. Mayer, eds. (J. Wiley and
Sons, New York, 1978), 243-303.
6. R.C. West, CRC Handbook of Chemistry and Physics. 67th Edition,
R.C. West, M.J. Astle, and W.H. Beyer, eds. (CRC Press, Inc., Boca
Raton, FL, 1986).
7. B.E. Douglas, D.H. McDaniel, and J.J. Alexander, Concepts and
Models of Inorganic Chemistry, 2nd Edition (J. Wiley and Sons, New
York, 1983), Chap. 1.
8. James A. Schwartz, VLSI Electronics Microstructure Science, Vol.
15: VLSI Metallization, N.G. Einspruch, S.S. Cohen, and G.S.
Gildenblat, eds. (Academic Press, Inc., Orlando, FL, 1987), Chap.
8.
9. J.C. Blair, C.R. Fuller, P.B. Ghate, and C.T. Haywood, J. Appl.
Phys. 43(2), 307 (1972).
10.S.O. Colgate, G.J. Palenik, D.W. Schoenfeld, Florida High
Technology and Industry Council Project Report, No. 85092726
(1986).
230

231
11. S. Wolf and R.N. Tauber, Silicon Processing for the VLSI Era, Vol.
1: Process Technology (Lattice Press, Sunset Beach, CA, 1987).
12. E.K. Broadbent, U.S. Patent 4.517.225 (1985).
13. J.L. Beauchamp and P.M. George, U.S. Patent 4,324,854 (1982).
14. S.C. Baber and V.R. Porter, U.S. Patent 4.465.716 (1984).
15. M.F. Rubner and P. Cukor, U.S. Patent 4.486.463 (1984).
16. P.B. Ghate, Thin Solid Films, 93, 359 (1982).
17. D.S. Cambell, Handbook of Thin Film Technology. L.I. Maissel and
R. Glang, eds. (McGraw-Hill Book Company, Inc., New York, 1970),
Chap. 5.
18. Y.P. Butylin, Ukr. Khim. Zh., 53(10), 1021 (1987).
19. C. Patton, Electronics Design 46 (1986).
20. F. Jansen, Plasma Deposited Thin Films. J. Mort and F. Jansen,
eds. (CRC Press, Inc., Boca Raton, FL, 1986), Chap. 1.
21. R.A. Dugdale, Nature, 249, 440 (1974).
22. M.L. Green and R.A. Levy, J. Metals, June, 63 (1985).
23. F.O. Sequeda, J. Metals, May, 43 (1985).
24. T. Tagaki, J. Vac. Sci. Technol. A 2, 382 (1984).
25. W. Knauer and R.L. Poeschel, J. Vac. Sci. Technol. B 6 (1), 456
(1988).
26. D.B. Fraser, U.S. Patent 4.072.768 (1978).
27. Matsushito Electric Industrial Co., Ltd., Jpn. Patent 57/65324
(1982).
28. T. Araya, A. Matsunawa, S. Katayama, S. Kioki, Y. Ibaraki, and Y.
Endo, U.S. Patent 4.619.691 (1986).
29. F.G. Mann, A.F. Wells, and D. Purdie, J. Chem. Soc., Pt. 2, 1828
(1937).
30. V.E. House and S.0. Colgate, 39th Annual Meeting of the Florida
Section of the American Chemical Society, Tampa, FL (1988).
31. R.J. Puddephat and I. Treurnicht, J. Organometallic Chem. 3T9, 129
(1987).

232
32. A. Shiotani and H. Schmidbaur, J. Amer. Chem. Soc. 92, 7003
(1970).
33. C.E. Larson, T.H. Baum, and R.L. Jackson, J. Electrochem. Soc.
134(1)i 266 (1987).
34. H. Schmidbaur, Gmelin Handbuch der Anorqanische Chemie: Gold-
Organic Compounds (Springer-Verlag, Berlin, 1980).
35. Cyanopure Corporation, Product Bulletin 159 (1986).
36. R.Y. Jan and S.D. Allen, SPIE 459, 71 (1984).
37. T.H. Baum and C.R. Jones, Appl. Phys. Lett. 47(5), 538 (1985).
38. T.H. Baum and C.R. Jones, J. Vac. Sci. Tech. B 4(5), 1187 (1986).
39. T.H. Baum, E.E. Marinero, and C.R. Jones, Appl. Phys. Lett.
49(18), 1213 (1986).
40. T.T. Kodas, T.H. Baum, and P.B. Comita, J. Appl. Phys. 2(1), 281
(1987).
41. T.H. Baum, J. Electrochem. Soc. 134(10), 2616 (1987).
42. G.M. Shedd, H. Lezec, A.D. Dubner, and J. Melngailis, Appl. Phys.
Lett. 49(23), 1584 (1986).
43. K. Gamo, N. Takakura, N. Samoto, R. Shimuzu, and S. Namba, Jap. J.
Appl. Phys. 23(5), 293 (1984).
44. H.W.P. Koops, R. Weid, D.P. Kern, and T.H. Baum, J. Vac. Sci.
Tech. B 6(1), 477 (1988). . .
45. E.D. Wolley, U.S. Patent 3.440.113 (1969).
46. W.L. Grady and M.M. Bursey, Int. J. Mass. Spectrom. Ion Phys. 55,
111 (1983).
47. W.L. Grady and M.M. Bursey, Int. J. Mass. Spectrom. Ion Phys. 55,
247 (1983).
48. A.K. Chowdhury and C.L. Wilkins, J. Am. Chem. Soc. 109(18), 5336
(1987).
49. D.A. Weil and C.L. Wilkins, J. Am. Chem. Soc. 107, 7316 (1985).
50. E. Kay, A. Dilks, and U. Hetzler, J. Macromol. Sci.-Chem. A 12(9),
1393 (1978). • • :
51. E. Kay and A. Dilks, Thin Solid Films 78, 309 (1981).

233
52. H. Biederman and L. Holland, Nucl. Instrum. Methods 212, 497
(1983).
53. R.A. Roy, R. Meissier, and S.V. Krishnaswamy, Thin Solid Films
109. 27 (1983).
54. E. Kay and M. Hecq, J. Appl. Phys. 55(2), 370 (1983).
55. H. Biederman, Vacuum 34(3-4), 405 (1984).
56. L. Martinu, Thin Solid Films 140, 307 (1986).
57. L. Martinu, Solar Energy Mater. 15, 21 (1987).
58. S.A.Y. Al-Ismail and C.A. Hogarth, J. Phys. E: Sci. Instrum. 20,
344 (1987).
59. D. McIntosh and G.A. Ozin, Inorg. Chem. 16(1), 51 (1977).
60. P.H. Kasai and P.M. Jones, J. Am. Chem. Soc. 107(22), 6385 (1985)
61. P.H. Kasai, J. Am. Chem. Soc. 105(22), 6704 (1983).
62. P.H. Kasai, J. Am. Chem. Soc. 106(H), 3069 (1984).
63. G.M. Schragg, Doctoral Dissertation, University of Florida (1987)
64. H. Khalifa, G. Suehla, and L. Erdey, Talanta 12, 703 (1965).
65. J.R. Eyler, TRAC 5(2), 44 (1986).
66. D. Lesson and P.J. Brucat, J.C.P., submitted December 1988.
67. M. Klasson, J. Hedman, A. Berndtsson, R. Nilsson, and C. Nordling
Physica Scripta 5, 93 (1972).
68. B.L. Henke, Phys. Rev. A 6(1), 94 (1972).
69. Kratos, Inc., XSAM800 Operators Handbook (1984).
70. J.H. Scofield, J. Electron. Spectros. 8, 129 (1976).
71. L.B. Valdes, Proc. IRE 42, 420 (1954).
72. T.P. Hughest, Plasmas and Laser Light (J. Wiley and Sons, New
York, 1975), Chaps. 5 and 6.
73. J.F. Ready, J. Appl. Phys. 35(2), 462 (1965).

234
74. N.F. Mott and H. Jones, The Theory of the Properties of Metals and
Alloys (Dover Publications, Inc., New York, 1958), Chap. III.
75. O.F. Hagena and W. Obert, J. Chem. Phys. 56(5), 1793 (1971).
76. A. Fritsch and P. Legare, Surface Sci. 162, 742 (1985).
77. C.J. Sofield, C.J. Woods, C. Wild, J.C. Riviere, and L.S. Welch,
Mat. Res. Soc. Symp. Proc. 28, 197 (1984).
78. M. Fuggle and R. Martensen, J. Elect. Spect. 24, 275 (1980).
79. I.H. Khan, Handbook of Thin Film Technology. L.I. Maissel and R.
Glang, eds. (McGraw-Hill Book Company, Inc., New York, 1970),
Chap. 10.
80. P.E. Dyer, D.J. James, G.J. Pert, S.A. Ramsden, and M.A. Skipper,
Laser Interaction and Related Phenomena--Interaction of High Power
CO2 Lasers With Solid Targets, Volume 3A, H.J. Schwarz and H.
Hora, eds. (Plenum Press, New York, 1973).
81. N.A. Ebrahim and C. Joshi, Phys. Fluids 24(1), 138 (1981).
82. T.H. Tan, G.H. McCall, and A.H. Williams, Phys. Fluids 27(1), 296
(1984).
83. G. Tonon and M. Rabeau, Phys. Lett. 40A, 215 (1972).
84. C.G. Granquist and 0. Hunderi, Phys. Rev. B 16(8), 3513 (1976).
85. S.B. Dicenzo and G.K. Wertheim, Comments Solid State Phys. 11(5),
203 (1985).
86. L. Oberli, R. Monot, H.J. Mathieu, D. Landolt, and J. Buttet,
Surface Sci. 106, 301 (1981).
87. L. Harris, R.T. McGinnies, and B.M. Siegel, J. Opt. Soc. Am.
38(7), 582 (1948).
88. L. Harris, and J.K. Beasley, J. Opt. Soc. Am. 42, 134 (1951).
89. V.N. Sintsov, Zhurnal Prikladnoi Spektroskoppi 4(6), 503 (1966).
90. D.R. McKenzie, J. Opt. Soc. Am. 66(3), 249 (1975).

BIOGRAPHICAL SKETCH
Charles George Simon was born in West Palm Beach, Florida, on
August 18, 1954. He received the Bachelor of Science degree in
chemistry, under the guidance of Prof. D. Neal Boehnke, from
Jacksonville University in Jacksonville, Florida, in 1976. He then
entered the Graduate School at the University of South Carolina
(U.S.C.) where he worked under the direction of Prof. Terry Bidleman in
the Analytical Chemistry Division. He received the Master of Science
degree from U.S.C. in 1979. From 1979-1985 he worked in the specialty
chemicals and forest products industries as an environmental/analytical
chemist and industrial hygienist. In 1985 he entered the University of
Florida graduate school and worked under the direction of Prof. Sam
Colgate in the Physical Chemistry Division. Subsequent to his pending
completion of the requirements for the Doctor of Philosophy degree, he
has accepted a position with the Extraterrestrial Materials Group,
McDonnell Center for the Space Sciences, Washington University, St.
Louis, Missouri.
235

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Samuel 0. Colgate, Ch
Associate Professor o
rman
Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Martin Vala
Professor of Chemistry
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
// / Iv
Willis B.
Professor
Person
of Chemistry

I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
I certify that I have read this study and that in my opinion it
conforms to acceptable standards of scholarly presentation and is fully
adequate, in scope and quality, as a dissertation for the degree of
Doctor of Philosophy.
Associate Profess^ of Biochemistry and
Molecular Biology
This dissertation was submitted to the Graduate Faculty of the
Department of Chemistry in the College of Liberal Arts and Sciences and
to the Graduate School and was accepted as partial fulfillment of the
requirements for the degree of Doctor of Philosophy.
December, 1988
Dean, Graduate School

«RSITY of florida
3 4 ««A nil lili I
1262 08556 7781