Citation
Microchip Lasers as Sources of Laser-Induced Breakdown Spectroscopy: Plasma Characteristics and Analytical Performance

Material Information

Title:
Microchip Lasers as Sources of Laser-Induced Breakdown Spectroscopy: Plasma Characteristics and Analytical Performance
Creator:
AMPONSAH-MANAGER, KWABENA ( Author, Primary )
Copyright Date:
2008

Subjects

Subjects / Keywords:
Emission spectra ( jstor )
Impact craters ( jstor )
Integrated circuits ( jstor )
Laser beams ( jstor )
Laser spectroscopy ( jstor )
Lasers ( jstor )
Plasmas ( jstor )
Signals ( jstor )
Spectrometers ( jstor )
Steels ( jstor )

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Source Institution:
University of Florida
Holding Location:
University of Florida
Rights Management:
Copyright Kwabena Amponsah-Manager. Permission granted to University of Florida to digitize and display 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.
Embargo Date:
4/17/2006
Resource Identifier:
76700344 ( OCLC )

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Full Text












MICROCHIP LASERS AS SOURCES FOR LASER-INDUCED BREAKDOWN
SPECTROSCOPY: PLASMA CHARACTERISTICS AND ANALYTICAL
PERFORMANCE















By

KWABENA AMPONSAH-MANAGER


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


2005

































Copyright 2005

by

Kwabena Amponsah-Manager



































This dissertation is dedicated to my mom, Mary, for her belief in me and constant
encouragement.















ACKNOWLEDGMENTS

It has been a wonderful privilege to work under the mentorship of Prof. James D.

Winefordner. I am grateful, and will always be, to him for opening up his laboratory for

me to pursue my graduate studies. It was a risky decision to work with him, because,

pathetically, I knew nothing in this area of science. However, the time spent under his

guidance has been the most fruitful years of my life. I could never show my full gratitude

to him for his friendship and advice.

I thank Dr. Benjamin Smith, who made me enjoy the science of light. In fact, it was

Ben's patience and guidance that have brought me this far. Even when my plan of work

or result did not make any sense, Ben had a uniquely mild way of letting me know how

wrong I am. I do appreciate spectroscopy now, but it is all through my interaction with

Ben Smith.

Dr. Nicol6 Omenetto was a great help to me over the past four years. I always left

his office with his dry-erase board crowded with stuff, sometimes more confused than

before I went there. He made me know that it was not as simple as I think, and he was

always right; I got to know this after our meetings. I am most grateful to him.

I also thank Dr. Igor Gornushkin for many personal discussions and useful

suggestions at group meetings and for the many times that he had to sacrifice his time to

join me at work.

Dr. David Hahn has been of great encouragement to me. I admire his enthusiasm

for research. I got great research ideas from him though our quarterly meeting with him









and Aerodyne Research Inc. I appreciate the times spent with Drs. Andrews Freedman

and Jody Wormhoudt of Aerodyne Research, Inc. Their contributions were always

invaluable.

I would thank all the Winefordner/Harrison research group members for their

friendship and support. Everyone brings some unique quality that makes the laboratory a

great place to work. Some former group members that I cannot leave out include Drs.

Tiffany Correll, Paige Eagan-Oxley, Kevin Turney and Elizabeth Hastings. I miss their

friendship. I would like to acknowledge the help of Dr. Qian Li. At least one chapter in

this thesis would not have been be possible without her assistance. I am really grateful to

her.

I thank Ms. Cristina Moreno-Lopez of the University of Malaga, Spain, who joined

me on this research in the summer of 2004. The time spent with Cristina was remarkably

fruitful and memorable.

I made many sweet friends in Gainesville. I regret that space and time will not

permit me to acknowledge them all by name. Nevertheless, I am thankful for the role

every one of them played in my life and studies. I especially thank Kwame for his many

sacrifices and Adjoa Otubea for her friendship and editorial comments.

Needless to say, I am grateful, as always, to my family for their patience, prayers

and encouragement. I am especially thankful to my mom for the pride and confidence she

has in me.
















TABLE OF CONTENTS

page

A C K N O W L E D G M E N T S ................................................................................................. iv

LIST OF TABLES ....................................................... ............ ....... ....... ix

LIST OF FIGURES ............................... ... ...... ... ................. .x

ABSTRACT ........ .............. ............. ...... ...................... xiv

CHAPTER

1 INTRODUCTION TO LASER-INDUCED BREAKDOWN SPECTROSCOPY
(L IB S ) ..................................................................................... ....... 1

B background ....................................................................................................... ....... 2
LIB S Over the Y ears ............................................. ..................... ....
Instrum ental C challenges ................. .... ........ .................... .. ...... .......... .... ....
A nalytical Perform ance of LIB S ........................................ .......................... 10

2 SOLID STATE PASSIVELY Q-SWITCHED MICROCHIP LASERS AS
SOURCES FOR LASER-INDUCED BREAKDOWN SPECTROSCOPY ..............13

Passive Q-switched M icrochip and Lasers..... .......... ....................................... 14
P massive Q -sw itching ............................................ .. ........ .... ....... ... 14
The M icrochip Laser .............. ................................. .... ...... .............. 15
Design and Fabrication of Microchip lasers............ ..... ..................16
Materials and wavelengths Used in Microchip Lasers .............. ..... ........ 16
E xperim ental A rrangem ent............................................ ....................................... 18
Results and D discussion ........... .. ................................. ..... .... .. ............ 19
C conclusion ............. ................................................................................. 23

3 MICROCHIP LASER ABLATION OF METALS: INVESTIGATION OF THE
ABLATION PROCESS IN VIEW OF ITS APPLICATION TO LASER-
INDUCED BREAKDOWN SPECTROSCOPY ............... ................................. 24

Sum m ary ...................................... ................. ................. .......... 24
Background ..................................... ................................. ........... 25
Experim mental .................................................. ............... ..... ... .... 27
R esu lts an d D iscu ssion ......................................................................................... 2 8









The MCL and PCL as Microprobe Analyzers.........................................28
Target M odification ............................................. ............ ... ... ........ 31
M a ss R e m o v a l ............................................................................................... 3 3
A blation Efficiency .............. .............. .. .. ......... .. ........... ... 36
Effect of Target Temperature on Mass Removal: ...................................42
Effect of Crater Depth and Laser Irradiance on Plasma Intensity and
C o m p o sitio n ............................................................................................... 4 4
C conclusion ...................................................................................................... ....... 47

4 DIAGNOSTICS OF MICROCHIP LASER-INDUCED PLASMAS AS
RELATED TO LASER-INDUCED BREAKDOWN SPECTROSCOPY ................49

S u m m ary ...................................... .................................................. 4 9
T h e o ry ...................................... .................................................... 4 9
Experim mental ..................................... ................................ ........... 52
R result and D discussion ................. .. ...... .... ...................... .... .. ...... .......... 53
Absorption Properties of the microchip Laser-Induced Plasma..........................53
Em mission Tem poral Profile........................ ...... ...... ................ ... 57
PCL Plasma Diagnostics by Means of Electrical Signal Measurements ............58
B reakdow n T hreshold .............................................................. .....................62
The Focusing C challenge ........................................................... ............... 65
Plasma Temperature Measurements............... .........................................69
C o n clu sio n s..................................................... ................ 7 0

5 TRACE METAL ANALYSIS BY MICROCHIP LASER-INDUCED
BREAKDOW N SPECTROSCOPY ....................................... ........................ 72

S u m m a ry ......................................................................................................7 2
Intro du action .................................................................................................... 72
E x p erim mental .................................................................................................73
Results and Discussion ................................................. 75
Quantitative Analysis of Low Alloy Steel ................ ................. ............. ..75
Microchip LIBS with Non-intensified versus Intensified CCD Spectrometers..80
Perform ance in O their M atrices ................................................ .....................83
C o n clu sio n s..................................................... ................ 8 6

6 AIRBORNE PARTICLE DETECTION BY MICROCHIP LASER-INDUCED
BREAKDOWN SPECTROSCOPY...................................... ......................... 89

Introdu action ................. ...... .... ....... ................ .. .... .. .....................89
Review of Laser Spectroscopy Techniques for Aerosol Analysis..............................90
E xperim mental ......................................................................................................92
R results and D discussion ............. ........................................... ............. ... ....... .... 94
Dependence of Signal Intensity and Trigger Rate on Particle Size...................99
Identification of Particles by Emission Signal ............................102
Conclusion ..................................... ................................. ......... 105









7 CONCLUSION AND FUTURE WORK .............................107

C o n c lu sio n ........................................................................................................... 1 0 7
F future W ork ............................................................................................ ......... 109

LIST OF REFEREN CE S ............................................................. ........................ 111

BIOGRAPHICAL SKETCH ............................................................. ..................117















































viii
















LIST OF TABLES


Table page

1-1 M ethods used for modifying the output of a laser ............................. ... ............11

1-2 Some laser systems that have been employed in LIBS ...............................11

3-1 Laser-induced crater depth and diameter for a 500 ps microchip laser compared
to that of 8 ns laser. Data in bold were obtained for the 8 ns laser ........................35

3-2 Ablation efficiency of 7 PJ microchip laser compared to values reported for
conventional N d: Y A G lasers. ............................................................................ 37

4-1 Plasma breakdown threshold measured for different targets. Silicon 251.6 nm
line was monitored for all targets except for steel where Cr 425.43 nm was
u se d ............................................................................. 6 3

5-1 Composition of the steel standards. Concentrations are expressed as % weight. ....75

5-2 Selection of spectral lines and internal standards. In some instances, the
background continuum (Bgd) in the vicinity of the element line was used as
internal standard. ......................................................................77

5-3 Analytical figures of merit of the elements analyzed using both the portable high
resolution spectrometer and the intensified spectrometer as detector. SLR
denotes studied linear range. The data in bold were obtained for the portable,
non-intensified spectrom eter........................................................ ................ 84

6-1 Common airborne particles and their respective size range..................................92

6-2 Elemental concentration as percent by weight in some biological samples. Bg is
Bacillus subtilis var. niger, a common simulant for Bacillus camul/ i%. In the
case of oat, wheat and corn, it was fungal spores on these samples that were
analyzed ..................... ..... ........... ..... ............ ........... .......... 92
















LIST OF FIGURES


Figure page

1-1 LIBS experimental set up. FL-focusing lens; CL- collection lens............................1

1-2 Schematic representation of the processes involved in plasma plume formation......3

1-3 Multimode laser: (a) and (b) A laser oscillating on an inhomogeneous transition
with many modes above threshold; (c) Simultaneous oscillating modes in a laser
cav ity ................................................................................ 7

1-4 Experimental arrangement for a mode-locked laser using an ultrasonic wave.........7

1-5 Optical set up for generating Q-switched pulses.................................. ...................9

2-1 Schematic of a passively Q-switched laser system. The gain medium is usually
Nd: YAG and the saturable absorber is Cr4+: YAG. .........................................15

2-2 M icrochip laser fabrication process .............................................. ............... 17

2-3 LIBS setup with a 7PJ microchip laser. The collection of the plasma emission
was done with or without the collection lens. .................................. ............... 19

2-4 Spectra of metal foils and silicon wafer obtained with the USB 2000 and the
m icrochip laser. Integration tim e w as 1 s..................................... ..................20

2-5 Spectra of metal foils obtained with the USB 2000 and the microchip laser.
Integration tim e w as 1 s. ................................... ............ ........ ............20

2-6 Scanning electron micrographs (SEM) images of crater produced by the
microchip laser. D denotes mean crater diameter. ................................................. 21

2-7 Cadmium spectrum obtained with the broadband spectrometer LIBS 2000+ and
the microchip laser. (Top) Full acquisition window of the spectrometer;
(Bottom) Segments showing identification of some Cd lines. Integration time
w as 1 s. ..............................................................................22

3-1 Powerchip laser micro-ablation of copper substrate showing: (left) the ablation
scheme devised; and (right) single craters obtained at 1 kHz. ................................29

3-2 Depth profiling of a thin film created on steel surface by the 50 0pJ powerchip
laser. (a) Spectra obtained from the coated and polished steel surface.









Integration time was 3 s (b) Time-dependent intensity distribution of the line
from the "coating" and iron matrix. .............................................. ............... 32

3-3 Effect of the laser-induced crater as shown in the inter-crater spaces. ...................33

3-4 Microchip laser-induced crater on cadmium foil showing the crater structure and
droplet redeposition on surface. ........................................ ......................... 34

3-5 Dependence of crater radius and mass removed per laser shot on the melting
point temperature (shown in parenthesis) and heat of fusion of the target. Mass
removed were calculated based on the crater volume and the density of the
m ateria l ......... .................. .................................................................... 3 4

3-6 Comparison of (a) 500 ps passive Q-switched powerchip-induced crater, and (b)
crater induced by an 8 ns active Q-switched laser on a lead target..........................37

3-7 Variation of crater volume with laser energy for: (a) cadmium and (b) copper.
The arrows indicate the points of the curve where different slopes begin ..............38

3-8 Plasma emission intensities of cadmium and copper compared at different laser
pulse energies. Integration time was 400 ms, with 5 spectra averaged (i.e. each
spectrum is an accumlatiuon of 2000 spectra). Each data point represents the
m ean of 20 spectra .............. .............. .. ........................ .. .. ........ .... 41

3-9 Ablation sensitivity (red line) and efficiency (black line) of Cd (top) and Cu
(bottom) as a function of laser pulse energy. ................................ ..................42

3-10 Effect of target temperature on plasma composition and emission intensity. (a) is
the background corrected emission intensity and (b) is the intensity normalized
to Fe 400.52 nm line ....................................... ............... .. ........ .... 43

3-11 Effect of laser-induced crater on plasma emission intensity...............................45

3-12 Effect of crater and laser energy on plasma composition: (a) Temporal
dependence of the Zn-Cu ratio in brass when the plasma is created on the same
spot. Integration time was 300 ms with 5 spectra averaged. (b) Effect of laser
pulse energy on Zn-Cu intensity ratios. Each data point is the average of 30
spectra with an integration time of 300 ms and 5 spectra averaged......................47

4-1 Spatial component of a laser plasma diagnostics. ........................................... 51

4-2 Plasma diagnostic experimental set up. GP-glass plate; M-mirror; PD-
photodiode; T-target; L-collimating lens; PCL-powerchip laser. The collection
lens & fiber coupler take the position of PD2 in emission measurements ..............52

4-3 Fraction of probe beam absorbed by the LIP as a function of delay time. The
inset is the temporal profiles of the 1064 and the 532 nm beams. .........................54









4-4 Radiative temporal behavior of the laser-induced plasma. ............. ...............57

4-5 Characteristic electron pulse collected during microchip laser ablation of copper
substrate at 50 PJ. Probe bias voltages are indicated on the curves......................59

4-6 Variation of probe current with bias voltage (top) and laser irradiance (bottom).
The inset is a curve by a similar experimental set up by Isaac et al.(65) showing
an initial rise of probe current which plateaus at higher irradiance. ........................61

4-6 Effect of focusing on plasma characteristics. Variation of (top) plasma lifetime
and (bottom) signal to background ratio, S/B, with target position from the
focusing objective. ........................ ........................ .. .... ..... .. ............67

4-7 Photographic images of the LIP. The camera was positioned at approximately
(a) 45 and )b)90 to the direction of propagation of the laser pulse. The laser
beam is coming from the left-hand side. ..................................... ............... 68

4-8 Boltzmann plot with selected iron lines. El and E2 are upper energy levels of
line 1 and 2 respectfully. ..................... ................ .............. ......... 70

5-1 Quantitative LIBS experimental setup. .................................... ..................... 74

5-2 (a) Spectrum obtained from microchip laser-induced plasma on steel and (b)
superposition of 8 nm spectral window for a pure Fe standard and that of a steel
sample containing 1.92% Cr. Spectrometer HR 2000 was used with integration
tim e of 1 s. ............................................................................76

5-3 Shot-to-shot fluctuations in LIBS signal intensity: (a) Intensity of Cr normalized
to the background continuum emission; (b) Net intensity of Cr line and (c)
intensity of Cr normalized to an Fe line. ........................................ ............... 78

5-4 Reduction of noise by signal averaging: (a) Fluctuation of the emission intensity
of Mn 403.1 nm and (b) variation of the standard deviation (in intensity units) of
the signal by progressive averaging of the collected data points. ............................78

5-5 Calibration curve for Mo using the compact spectrometer, HR 2000. The lines
used are Mo (I) 386.41 nm normalized to Fe (I) 387.25 nm...............................80

5-6 Spectra obtained on iron foil and steel using (a) an intensified CCD and (b) a
non-intensified CCD spectrom eters. ............................................. ............... 81

5-7 Calibration curves using the intensified CCD spectrometer. (Top) Ni (I) 341.47
nm normalized to Fe (I) 342.71 nm and (bottom) Si (I) 288.16 nm normalized to
F e (I) 2 87 .4 1 n m .................................................................................... .. 82

5-8 Spectrum of silicon dioxide: (a) pure and (b) spiked with iron ore .......................85









5-9 Calibration curves for (a) magnesium and (b) iron ore in sand (silicon dioxide).
In (a), the signal is presented in form of intensity ratio of Mg (1) 285.2 nm to Si
(I) 288.16 nm while in (b) the net intensity is used........................ ...... ......... 87

5-10 Effect of sample homogeneity on data reproducibility: (a) A mixture of iron ore
and silicon dioxide blended for 5 min. and (b) sample blended for 10 min.............88

6-1 Single particle microchip LIBS setup. ........................................ ............... 95

6-2 Intensity distribution of sparks on NaCl particles, 0.024% Na by weight .............96

6-3 Variation of trigger rate (fraction of laser pulses that produce sparks with signal
at least 10 mV as a percentage of the total number of laser pulses fired).
Concentrations are presented as mass % NaC ........................................... ........... 97

6-4 Variation of aerosol spark intensity with concentration. Data were obtained with
a PMT. Concentrations are presented as mass % NaC1. ......................................98

6-5 Variation of trigger rate with concentration: (Black) threshold set at -10 mV and
(Red) threshold set at -40 mV. Concentrations are presented in
m ass % M gC l2. .........................................................................99

6-6 Photographs of sparks on MgCl2 and CaCl2: (Top): Full laser energy in use,
interference filter in front of camera removes 1064 nm light, (Bottom) Laser
energy attenuated below breakdown threshold; scattered laser beam shows
particle flow in the focal volume e................................................ ........ ....... 100

6-7 LIBS spectra of solution containing 0.05% Ca presented as AlC13 .....................103

6-8 LIBS spectra of solution containing 0.15% Ca presented as CaCl2...................103

6-9 LIBS spectra of an ICP grade standard solution containing 0.05% Na, 0.04% Ca
and 0.027% M g ........... ..... .......................... ...... ..... ........ 104

6-10 Spectrum of solution containing 0.3% Cd. ................................. ..................104

6-11 Signal dependence on concentration for Mg aerosol. .........................................105














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


MICROCHIP LASERS AS SOURCES FOR LASER-INDUCED BREAKDOWN
SPECTROSCOPY: PLASMA CHARACTERISTICS AND ANALYTICAL
PERFORMANCE

By

Kwabena Amponsah-Manager

December 2005

Chair: James D. Winefordner
Major Department: Chemistry

Laser-induced breakdown spectroscopy (LIBS) is an analytical technique that has

been given significant attention as a method for fast elemental analysis. Even though

LIBS has many advantages over other analytical methods, size requirements have limited

most applications to laboratory analysis.

This project was set forth to investigate the possibility of employing all-solid-state

diode-pumped miniature (microchip) lasers as sources of light for LIBS and to estimate

the analytical performance of LIBS based on these systems.

The study began with the diagnostics of the microchip laser-induced plasma.

Plasma parameters such as size, temperature, electron number density and temporal

behavior of the emission were studied using both traditional spectroscopy and CCD

photography. The small plasma size (100 |tm above target surface) and short lifetime

(1.5-2 ns) did not allow detailed spatial and temporal study of plasma by conventional









means. However, a pump-probe method based on an optical delay setup provided

information about the absorption properties of the plasma on the sub-nanosecond time

scale. Maximum absorption was measured 1.2 ns after the laser pulse while the plasma

became almost transparent after 4 ns.

The effect of both target properties and laser parameters on the ablation properties

of the microchip laser was studied. Microchip lasers produce well-defined craters, which

allow easy estimation of the mass removed per laser shot. The high spatial and depth

resolution of the microchip laser ablation was employed in applications such as depth

profiling and trace element analysis. Detection limits for Cr, Si, Ni, and Mo in steel

alloys were 100 ppm or lower, but were a hundred times higher in powdered substrates.

The microchip laser was employed in the detection of aerosols by LIBS. Laser-

induced plasma was formed on particles which passed through the focal volume of a

tightly focused laser during the laser pulse. The efficiency of detecting particles of

various particle types and sizes was investigated as well as the use of the plasma emission

for the identification of these particles. The results show the potential usefulness of

microchip laser LIBS for the real-time detection and identification of particles in air.

Potential applications of such a capability include real-time assessment of industrial

atmospheres, clean room monitoring and bio-safety.














CHAPTER 1
INTRODUCTION TO LASER-INDUCED BREAKDOWN SPECTROSCOPY LIBSS)

Laser-induced breakdown spectroscopy (LIBS), also known as laser-induced

plasma spectroscopy (LIPS), is an analytical technique based on the emission by atomic

and ionic species in microplasmas induced during laser ablation at high power densities.

In simple terms, it is the use of optical signals from laser-generated plasma for analytical

purposes. A typical LIBS configuration is shown in Figure 1-1. The output from a pulsed

laser is focused on a target, which can be a solid, liquid, gas, or aerosol particles. The

high laser power creates a microplasma on the target which excites and ionizes a small

amount of the target material. The optical radiation from the atomic and ionic species in

the laser-induced plasma is collected by lenses or optical fibers into spectrometers and

spectrally resolved. The emitting species in the laser-induced plasma can be identified

and quantified by their unique spectral wavelength and line intensities.


Figure 1-1 LIBS experimental set up. FL-focusing lens; CL- collection lens.









Background

When a focused, pulsed laser strikes the surface of a material, an initial heating

causes a rapid rise in the temperature of the surface which results in melting and

vaporization of a small portion of material into ionized gas. The process leading to the

ionization of this gas (i.e. plasma breakdown) can either be electron ionization (equation

1-1) or multiphoton ionization (equation 1-2) (1).

e +M 2e +M+ (1-1)

mhv + M M + e (1-2)

Interaction of the laser pulse with the solid sample results in the laser radiation

being absorbed by an electron whose energy rises above the band gap of the solid. The

high energy electron then collides with the neutral metal to ionize the solid to form a gas.

Because the electron concentration increases exponentially during the time the laser

emission is on, this process results in a cascade breakdown.

Whenever multiple photons are absorbed by an atom or molecule and the energy of

these photons is sufficient to eject an electron from the valence to the conduction band of

the solid, a metal ion and an electron result. Electrons produced by this process undergo

many collisions with themselves and the surrounding atoms causing further ionization.

This process is called multiphoton ionization. The energy of the electrons is passed on to

the target, resulting in a surface temperature rise, melting and vaporization, provided the

energy deposited in the layer of molten metal is greater than the latent heat of

vaporization of the material (2).

Figure 1-2 is a schematic representation of the processes leading to the formation of

a plasma plume. In Figure 1-2c, the removal of particulate matter from the surface leads

to the formation of vapor in front of the sample. When this vapor condenses as









submicrometer size particles, it leads to scattering and absorption of the laser radiation

and results in heating, ionization and plasma formation (Figure 1-2d). Other mechanisms

that follow these include fast expansion of photoablated material (Figure 1-2e), formation

of polyatomic aggregates and clusters (Figure 1-2f), and deposition of the ablated and

molten material around the crater (Figure 1-2h and 1-2g).



Laser
(ia\ ^1 Reflections (eI
(a) ,,] Expansion of
photo-ablated
material
M I Formation of
(b) polyatomic
aggregates
and clusters


Fragmentation { )
fusion, melting
sublimation Shock wave
subli n Re-deposition
atomization (h) of ablated
... material

Emission

Figure 1-2 Schematic representation of the processes involved in plasma plume
formation. Adapted from Vadillo and Laserna (3).

LIBS Over the Years

The LIBS technique was reported shortly after the invention of the laser (4), and

understanding of the principles involved parallel advances in lasers (5). Even in these

preliminary studies, useful analytical curves were obtained for nickel and chromium in

steel samples. In fact, by 1967, the first instrument based on LIBS had been developed

(6). This was followed by a few commercial instruments such as that developed by

Jarrell-Ash Corporation. The method, however, could not compete favorably with respect









to precision and accuracy with competing technologies at the time such as conventional

spark spectroscopy, electrothermal atomization atomic absorption spectrometry (ATA-

AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES).

In the early years, the method was normally used by physicists for fundamental

studies on breakdown in gases, the mechanisms that led to this breakdown as well as the

influence of target properties and laser parameters (pulse width, wavelength, beam

diameter) on breakdown thresholds (1). It was during the 1980s that the method began to

receive widespread attention as a solution to practical problems such on-line elemental

analysis at a distance (2). This late interest was driven by two notable factors. The first

factor was the unique advantages of the LIBS technique such as the need for no sample

preparation, minimum destruction to targets, possibility for remote analysis, (also

referred to as stand-off LIBS) and multi-element capability. The second factor that was

partly responsible for the revival in the 1980s was the emergence of reliable, small and

inexpensive lasers as well as the development of sensitive imaging detectors. In addition

to increased sensitivity, these detectors brought with them the potential to do LIBS

measurements in a suitable time window that provides higher line to background

emission signal.

The 1990s continued the revolution started in the early 1980s and witnessed an

explosion in both analytical and industrial research employing LIBS (7). The technique

began to move out from the basic science laboratory into the real world of applications.

Application areas embraced the monitoring of environmental contamination and quality

control, material processing (8), detection of toxic substances (9), removal of coatings,

and planetary exploration (10). With this in view, LIBS configurations concentrated on









developing rugged, robust and field portable systems (11). This ushered in fiber optics for

both sending the laser beam and collection of the plasma emission, a step towards remote

analysis. By 1988, a portable beryllium monitor based on LIBS had been built at the Los

Alamos National Laboratory (12).

More and more laboratories throughout the world are advancing the technique in

several respects. However, challenges still remain. After over 40 years of laboratory

work, both researchers and their funding agencies have come to realize that the time has

come for LIBS to find more "real-field" application. The challenges that need to be met

for such real-field applications include instrumental ruggedness and the sensitivity that is

required in the most demanding environmental and quality control settings. Each of these

will be briefly addressed in the following sections.

Instrumental Challenges

Laser-induced breakdown spectroscopy is one of the several applications of lasers

that require short (nanosecond and sub-nanosecond) pulses with high peak powers and

pulse energies of several mJ. The traditional method of producing sub-nanosecond pulses

is called mode-locking. Mode locking is a process whereby the phases of several modes

of light in a cavity are locked by pulsing or oscillating the cavity. The pulse duration of a

laser is the inverse of the frequency distribution of the laser output (13) For a laser

with q output modes, the pulse duration is mathematically expressed by equation 1-3,


pulse duration = = 1- L (1-3)
qAV rvq qc

where 1/Av is the pulse separation time and L is the length of the laser cavity. Equation

(1-3) above shows that we can obtain short pulses either by increasing the number of









oscillating modes in phase or by decreasing the length of the cavity. Due to practical

limitations on the size of the cavity, the former technique is mostly used.

This leads to the coherent and constructive addition of the electric fields for a short

period of time and results in a repetitive train of high intensity ultra-short pulses. The

inter-pulse separation in such a system is equal to the round-trip time of flight in the

cavity, that is, length of the laser (14). A schematic of a mode-locked system and output

is shown in Figure 1-3. Figure 1-3a and 1-3b illustrate a laser oscillating on an

inhomogeneous transition with many modes above threshold and lasing. By considering

the numeric, one can readily see that there can be a large number of modes oscillating in

such a system, with simultaneous oscillating modes as shown in Figure 1-3c. The number

of modes that can oscillate simultaneously depends on the Doppler width of the transition

and the length of the cavity (15).

Mode-coupling or mode-locking can be realized by optical modulators inside the

laser resonator. This case is referred to as active mode-locking. It can also be achieved

passively using saturable absorbers or by a combination of both schemes (16, 17). Figure

1-4 is a typical experimental arrangement for generating a train of mode-locked pulses

using a standing ultrasonic wave. Mode-locking is normally used in application areas that

require very short pulses such as x-ray generation, machining, time-resolved studies and

terahertz generation (18).

The intensity of a light wave is proportional to the square of the electric field

amplitude; therefore for two superimposed waves with intensity E, the resultant intensity

is given by (13),
















v0


(b) d2d:4-




-3 -2 -1 0 +1 -2 +3

(c)
I._X,



0 kRT


Figure 1-3 Multimode laser: (a) and (b) A laser oscillating on an inhomogeneous
transition with many modes above threshold; (c) Simultaneous oscillating
modes in a laser cavity.

modulator

Laser
M


Piezo


f/2




Figure 1-4 Experimental arrangement for a mode-locked laser using an ultrasonic wave.
Adapted from from Demtroder (14).

(E + E)2 = 4E2 (1-4)

That is, the resultant intensity is four times the intensity of a single wave. Despite this

amplification, the large number of pulses produced per second results in low pulse









energies. Therefore, only lasers with extremely high average powers can produce enough

pulse energies for some applications. In order to produce energetic pulses, the technique

called Q-switching is employed.

In Q-switching, the ratio of the energy stored in the cavity to that lost (leaked by

the mirrors) is modified by external commands which facilitate population inversion, and

inhibit stimulated emission while keeping spontaneous emission as low as possible. Once

population inversion reaches a critical threshold, stimulated emission starts and a large

pulse of laser light with several 100s of mJ energy is emitted.

Figure 1-5 is an illustration of an optical set up for generating Q-switched pulses.

Until a specific time after the start of the pump pulse at t = 0, the cavity losses of a laser

are kept high by an optical switch inside the resonator. In this way the oscillating

threshold cannot be reached. A large population inversion builds up and the switch is

suddenly opened. This increases the Q-value of the cavity and converts the energy stored

in the cavity into a giant light pulse. The type of Q-switching described above is called

active Q-switching. Active Q-switching can be achieved using electro-optic and acousto-

optic shutters which can be externally opened or closed to create variable pulse duration

and frequencies. Electro-optic Q switches are capable of faster switching than acousto-

optic devices because the speed of light is faster than the speed of sound. However,

electro-optic systems generally require relatively higher voltage electronics than are

required by acousto-optic devices. Q-switching can also be done mechanically using a

rotating mirror placed in the laser cavity that only reflects the light and allow stimulated

emission at certain geometries. Due to their speed, mechanical switches are being

replaced in most systems except in cases where optical damage limits the use of the










alternative technologies. A handful of techniques and various combinations of them are

available for both producing and controlling the output of a laser. These will not be

discussed in detail in this thesis but Table 1-1 is a summary of some of the methods

available and pulse properties. The values listed are typical of those reported in the

literature, although in many cases there is a significant spread in the reported values.


Shutter
Pump
Area A /


m Laser medium


R2 R'





threshold
Optical power


Population
S version

High T=O Low t
loss loss

Figure 1-5 Optical set up for generating Q-switched pulses.

Lasers used in LIBS are conventionally actively Q-switched lasers with

neodymium crystals doped with yttrium-aluminum garnet (Nd3+:Y3A15012) as the lasing

medium. Nd: YAG has been the most widely used gain medium because of its unusual

combination of optical, thermal and mechanical properties. Favorable properties of this

medium include its temperature index variation, thermal expansion coefficient, thermal

conductivity, and melting point (19). Pumped with a Xe-arc flash lamp, the output is at

1064 nm. Various wavelengths down to the 5th harmonic can be obtained from this









fundamental output by the use of non-linear crystals appropriately placed in the laser

path. Other lasers have been used in LIBS; Table 1-2 lists a few of these laser systems

and their typical operating parameters.

Even though, highly energetic pulses can be produced by Q-switching, size

requirements and the mechanisms by which the pulse is produced do not allow the

production of sub-ns pulses. Methods exist for the production of both sub-ns and

energetic pulses (such as amplifying a mode-locked laser or Q-switching a mode-locked

laser). However, these methods result in complex systems with high power consumption

due to the high speed and high voltage electronics that are needed for proper Q-

switching. For LIBS to find real-field applications, alternative light sources that are

compact, robust, easy to operate, and have minimum requirements for maintenance will

play a big role.

Analytical Performance of LIBS

In addition to instrumental requirements, every technique has to satisfy analytical

performance criteria before it can be embraced as a routine method for laboratory

measurements, quality control assessment and field deployment. The performance criteria

are referred to as analytical figures of merit (11). These include the detection power (limit

of detection, LOD) of the technique, linear dynamic range (LDR), capability for absolute

analysis and selectivity. In this regard, LIBS may be considered as lagging behind

competing methods such as inductively coupled plasma optical emission spectrometry

(ICP-OES) spectrometry or ICP-mass spectrometry (ICP-MS). To bring this into

perspective, both LIBS and ICP-OES use plasma excitation and the emitted light from the

plasma as bases of analysis. However, ICP-OES, which is the most used emission based









multi-element technique, provides detection limits in the sub-ppb range while LIBS

provides detection limits in the ppm range.

Table 1-1 Methods used for modifying the output of a laser.
Laser system Peak power Pulse width Period of pulse
repetition
Mode-locked 100 W 100 ps >10 ns

Cavity-dumped 10-100 W >10 ns Variable

Mode-locked & Cavity- >10 W >0.1 ns Variable
dumped

Synchronously pumped >100 W >1 ps >10 ns

Synchronously pumped & >1 kW >10 ps Variable
Mode locked


Taken from Van Hecke (13)

Table 1-2 So ne laser s stems that have


n eeb emplo ed n LIBS ( )


Type Wavelength Pulse Pulse energy Features
(Im) width (J)

Nd:YAG 1.064 7-12 ns 0.3-1.0 Low maintenance, compact,
relatively cheaper

CO2 10.6 1-300 0.5-500 Simple design, special IR lenses
tsec required for laser pulses,


Excimer 0.194-0.351 10-30 ns 0.25 UV wavelength, toxic gases,
quartz optics required



Other performance criteria which are equally important, although not considered as

analytical figures of merit, include sample preparation, sample size requirements,

automation, bulk versus surface analysis, destructive versus non-destructive, instrument

compactness and operating cost (11). The rest of this dissertation will be devoted to






12


addressing some of these performance requirements. Chapter 2 will answer the question

of instrument compactness, size requirements and operation cost, as well as present some

preliminary investigation using a 7 pJ per pulse microchip laser. In Chapter 3, a study of

microchip laser ablation will be presented while Chapter 4 will be devoted to the

diagnostics of the microchip laser-induced plasma. The analytical performance of the

microchip LIP in both quantitative and qualitative analysis and single particle detection

will be presented in Chapter 5 and Chapter 6, respectively.














CHAPTER 2
SOLID STATE PASSIVELY Q-SWITCHED MICROCHIP LASERS AS SOURCES
FOR LASER-INDUCED BREAKDOWN SPECTROSCOPY

Miniaturization of instruments is a trend in almost every area of industry. The

reason for this trend is that instrument portability and the speed with which an analysis is

performed can be considerably improved. Also, miniaturized systems can reduce the

required sample size and consumption of costly reagents. Miniaturization of instruments

is usually accompanied by increased functional capabilities.

In the near future, miniaturization will be a key factor if spectroscopy will continue

to play its unique role in defense and biomedicine. Significant progress has already been

achieved in miniaturization of optical detectors. With respect to LIBS, for example, a

commercial broadband spectrometer (LIBS2000+, Ocean Optics, Inc., USA) covers a

wide spectral range (200-1000 nm) with an impressive resolution- under 0.1 nm (20).

When this spectrometer is operated by a notebook computer, the spectrometer is perfectly

portable and self-contained. Lasers, however, remain a bottleneck in the development of

portable LIBS devices.

The conventional laser sources for LIBS, described in Chapter 1, that is, actively

Q-switched Nd: YAG lasers (or Q-switched mode-locked lasers) are characterized by

some limitations which do not made them attractive for use in field-friendly LIBS

systems. For instance, mode-locked Q-switched lasers can be several feet high and

consume kilowatts of electrical power. For "fieldable" systems, the possibility to operate

under battery power is ideal. The absence of bulky water cooling systems and minimum









requirements for periodic maintenance are some of additional desired properties

properties.

It is for this reason that this work was carried out to investigate all-solid-state

passively Q-switched microchip lasers as sources for LIBS.

Passive Q-switched Microchip and Lasers

Passive Q-switching

The principle behind the operation of a passively Q-switched laser is simple.

Unlike actively Q-switched systems which use electro-optic, acousto-optic or mechanical

device to turn off and on the Q of the laser cavity, passively Q-switched lasers employ an

intra-cavity saturable absorber that prevents the beginning of lasing until population

inversion reaches a critical threshold (21). At the beginning of the pumping, this saturable

device absorbs the light emitted at 1064 nm by the laser material and prevents the

amplification of the laser light. When the average inversion density exceeds the

saturation threshold of the saturable absorber, this material becomes transparent and a

giant laser pulse is delivered in a short period of time (a few 100 ps to 2 ns, typically).

After the laser pulse is delivered, the saturable absorber again becomes opaque to the

laser light and begins to absorb the light. The process is analogous to the charge and

discharge of an electrical capacitor. This mechanism of generating a laser pulse is called

passively Q-switching because no external commands are needed to trigger the delivery

of the pulse. A schematic of passive Q-switching is illustrated in Figure 2-1.

In passively Q-switched systems, the pulse repetition frequency (PRF) can simply

be changed by increasing or decreasing the pump power, which causes the saturation

threshold of the saturable absorber to be reached faster or slower. The pulse width, pulse









energy and other characteristics are determined by both the design of the oscillator and

the choice of saturable absorber (22).


Gain medium Saturable
absorber






Pump








Mirrors

Figure 2-1 Schematic of a passively Q-switched laser system. The gain medium is usually
Nd: YAG and the saturable absorber is Cr4+: YAG.

The Microchip Laser

The microchip laser (MCL) is an all-solid-state diode pumped passively Q-

switched laser system. It is perhaps the ultimate in miniaturization of diode-pumped

solid-state lasers. In its simplest form, the MCL is like any other solid state laser: a piece

of laser material placed in an optical cavity between two mirrors. The active ions in the

laser material are excited by externally pumping with a diode laser. Though the concept

of these compact laser systems was conceived in the 1960s, it was not until the 1980s that

attention was given to the idea, especially following the demonstration of a diode-laser

pumped device in Nd:YAG (23). Since then, diode-pumped, neodymium microchip laser









oscillating around 1.06 [tm have been reported in many host materials, including NPP

(23) and YVO4 (24).

Design and Fabrication of Microchip lasers

The design of a laser is dictated by several inter-dependent factors such as the

requirements in the output beam wavelength, spectral purity, tunabiltiy, power stability,

as well the operating environment temperature and humidity. Other practical

considerations such as size, cost, and available power also play a major, decisive role.

Microchip lasers are mass produced beginning with a piece of laser material such as

Nd:YAG. A cylindrical slab of this material is sliced into several wafers of few mm thick

(1-2 mm typically). The wafers are polished on both surfaces and the mirrors are

deposited using sputtering or evaporation. With a dicing saw, these wafers are then cut

into several square microchips and each chip is then coupled to a pump diode laser. This

coupling can be done directly or through the use of a multi-mode optical fiber. The

saturable absorber used in most microchip laser designs is Cr4+:YAG (21) which is grown

on the surfaces of the laser material (diced wafer) using a technique called liquid phase

epitaxy (22). The process is schematically described in Figure 2-2. With this collective

fabrication process, it is reported (22) that up to 2000 microchip lasers per fabrication lot

can be obtained.

Materials and wavelengths Used in Microchip Lasers

The active material used in most microchip lasers is neodymium. The choice of the

doping material, however, depends on the required wavelength. For laser materials doped

with materials such as yttrium aluminum garnet (Y3A15012 or YAG), YLF, or yttrium

orthvanadate (YVO4), the emission wavelength is around 1000-nm. With Nd doped with

Tm, for instance, the output is at 2-am. Microchip lasers based on Nd are pumped with









standard GaA1As or GaInAs diode lasers with outputs around 800-nm; Er and Yb lasers

are pumped around 980-nm while Tm doped materials are pumped around 790-nm (19).

The fabrication process of the microchip laser results in miniaturized systems

which have low power consumption and excellent optical properties. Microchip lasers

produce sub-nanosecond, multi-kilowatt pulses at high repetition rates (23, 24). They

have several unique properties that make them attractive as sources of light for

application areas such as surgery, micromachining, spectroscopy, material processing,

micro-marking, high precision ranging and several non-linear optical systems.


Safer cutting Nd:YAG, 1 inch, 500-2000 pm

Polishing

O R LIQUID PHASE EPITAXY, Ctr:YAG, 100-150 pm


polishing and thickness adjustment, Cr:YAG, 30-50 pm


input and output mirrors deposition

f i dicing of microchip lasers xi mm2

Figure 2-2 Microchip laser fabrication process. (This is followed by the process
illustrated by Figure 2-1).

The attractive features of microchip lasers include the short length of the cavity

which permits single frequency operation (19). Unlike the multi-mode outputs from the

majority of conventional lasers, the output from a microchip laser is devoid of mode

beating.

Mathematically, the spectral range, also known as frequency spacing between

adjacent longitudinal modes of a cavity is given by equation (2-1) (13, 19),










Av .f = (2-1)
trt

where tt is the round trip time of flight in the cavity. It can be seen that single-mode

operation is possible because of the short cavity length which ensures that longitudinal

mode spacing is greater or at least comparable to the gain bandwidth. In many

applications of lasers, example LIBS, mode quality is at least as important as total power.

A significant source of error in LIBS measurements is the pulse-to-pulse variations in the

LIBS emission signal due partly to the anomalous mode beating in conventional lasers

sources.

The goal of the remaining section of this chapter is to demonstrate the feasibility of

using the first commercial microchip laser as part of a miniature LIBS setup which

includes a small non-gated detector. Such a setup may be a prototype for a commercial

portable LIBS spectrometer for field applications. Both the experimental details and

discussion of the results will be scanty but will set the stage for a more detailed study in

the subsequent chapters.

Experimental Arrangement

The experimental set-up is shown in Figure 2-3. The laser used is a diode-pumped

passively Q-switched Nd: YAG laser (model JDS Uniphase, Nanolase, Meylan, France).

It operated at 1064 nm and emitted pulses of 550 ps duration and 7 PJ pulse energy

yielding 13 kW peak power at a repetition rate of 5.45 kHz. The laser beam waist, 200

[tm in diameter, located 25 mm from the laser face, is placed in the focus of a collimating

lens (f = 48 mm). A nearly parallel beam is formed behind the lens which was guided to

a 50X microscope objective. With the microscope objective, the laser was focused to a

spot of 8 [m in diameter with a resulting irradiance of 25 GW/cm2. The laser beam was










focused on several metallic substrates and the plasma emission was collected at 450

degrees with respect to the laser beam using a fiber optic probe. The 600 [tm diameter

optical fiber was connected to a miniature grating spectrometer (USB2000 or

LIBS2000+, Ocean Optics, Inc., USA) to monitor the plasma spectrum on a PC computer

screen.




objective x50 les ft48 mm


W win = trmm 7 COmmi 7pp E
Coo mrochip hir

Fiber coupler

fiber




Computer rperameter USB2000


Figure 2-3 LIBS setup with a 7PJ microchip laser. The collection of the plasma emission
was done with or without the collection lens.

Results and Discussion

A set of metallic foils were used in this study in order to study the spectral

characteristics of the microchip laser plasma. The spectral acquisition window was

limited by the spectral range of the spectrometer used. Representative spectra are shown

in Figures 2-4 and 2-5. Generally, background continuum radiation was tolerable without

any temporal gating but was relatively higher for tin (Sn) and lead (Pb) as shown in

Figure 2-5.






































Wavelength (nm)


Fe


200 20 2 40 260 280 300 320 340 360 380
Wavelength (nm)


TI II TI II


_______ 200 220 240 260 230 300 320 340 360 380
200 220 240 260 280 300 320 340 360 380 Wavelength (nm)
Wavelength (nm)

Figure 2-4 Spectra of metal foils and silicon wafer obtained with the USB 2000 and the

microchip laser. Integration time was 1 s.


200 220 240 260 280 300 3 2 3io 360 3m
Wavelength (nm)


200 20 240 260 280 300 320 340 360 380
Wavelength (nm)


200 220 240 260 280 300 320 340 360 380 20 22 0 24 0 26 20 3;0 32 0 360 30
Wavelength (nm) Wavelength (nm)


Figure 2-5 Spectra of metal foils obtained with the USB 2000 and the microchip laser.

Integration time was 1 s.


4000-

3500-

3000-

2500-

- 2000-

1500-

1000-

500-

0-


3500-

3000-

2500-

S2000-

- 1500-

1000-

500-

0-









It was observed that with the same acquisition parameters and experimental

conditions, line emission intensity with respect to the background continuum was higher

for materials with higher melting point such as Ni, Fe, and Si than substrates such as Sn

and Pb. For the later substances, the spectra tend to be smaller, weaker and less luminous;

however, craters were bigger as shown in Figure 2-6. It was speculated at this time that

much of the material removed by the laser pulse is simply melted and sprayed on the

target surface and did not enter the plasma. In Chapter 3, a parametric study of the

relationship between emission and target thermal properties will be presented. It should

also be noted that the spectra are composed of both atomic and ionic lines. It may

therefore be possible to couple microchip laser LIBS to other analytical methods such as

mass spectrometry.

Ni Cd

D = 10 pm D=22pm
















Pb Si

D = 20Am D = 10im
Figure 2-6 Scanning electron micrographs (SEM) images of crater produced by the
microchip laser. D denotes mean crater diameter.











1000-


800-


3 600-









03
c 400 -


200





200 400 600 800 1000
Wavelength (nm)

Cd
400- 800- C
Cd I, 259 2
Cd I, 228 8 Cd 259 2
Cd II, 231 3 Cd II, 274 85 600-

2a 00 400-
S\Cd I C dl
200-

0-
200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500
Wavelength (nm) Wavelength (nm)



Figure 2-7 Cadmium spectrum obtained with the broadband spectrometer LIBS 2000+
and the microchip laser. (Top) Full acquisition window of the spectrometer;
(Bottom) Segments showing identification of some Cd lines. Integration time
was 1 s.


Spectra were also obtained using a broadband spectrometer, LIBS2000+ (Ocean


Optics, Inc. USA). This spectrometer employs a large fiber bundle consisting of seven


fibers arranged in a circular configuration at one end. Since the total bundle diameter was


larger than the size of the plasma, it was difficult to illuminate the entire bundle


simultaneously. Therefore, a single fiber was used to collect the emission while moving


from channel to channel until the entire spectrum was acquired. A typical spectrum taken


with this spectrometer on a cadmium foil is shown in Figure 2-7. The negative peaks









result from the shift from channel to channel of the spectrometer while the spikes are due

to the fixed pattern noise of the CCD. This is a higher resolution spectrometer but it is

characterized by low light throughput. When used together with the microchip laser, it

can be particularly important in applications aimed at portable systems for on-site

material identification.

There are several other features in typical conventional LIBS spectra that are absent

in microchip laser spectra. For instance, traditional LIBS spectra are generally rich in

nitrogen bands (N2) or lines, and hydrogen lines. These do not appear in microchip LIBS

spectra, implying that the microchip plasma does not appear to interact with the

surrounding gas to the same extent.

Conclusion

A laser-induced breakdown spectroscopy setup with the first commercial microchip

laser was investigated in this chapter. The microchip laser-induced plasma has several

features that distinguished it from plasmas induced by conventional pulsed lasers. The

background continuum emission was low, while nitrogen and hydrogen bands

characteristic of high power lasers were absent. The lower emission intensities did not

provide high expectations for quantitative analysis; however, the microchip laser together

with a spectrometer that offers a wider spectral window would provide a compact and

portable system for online material characterization and sorting














CHAPTER 3
MICROCHIP LASER ABLATION OF METALS: INVESTIGATION OF THE
ABLATION PROCESS IN VIEW OF ITS APPLICATION TO LASER-INDUCED
BREAKDOWN SPECTROSCOPY

Summary

Metal ablation with a short pulse, low energy microchip laser was investigated with

respect to its application to laser-induced breakdown spectroscopy (LIBS). Target surface

modifications and crater parameters as a function of laser pulse properties were studied.

The effect of the laser pulse is limited to the focal spot, but surface modification by the

laser-induced plasma can extend several micrometers beyond the focal spot depending on

the target thermal properties. Mass removal per shot was found to depend upon the heat

of fusion of the target, while appreciable plasma emission was observed only at high

pulse energies. Plasma composition and emission intensity can change significantly with

the surface properties, requiring that a fresh, flat surface to be exposed to each laser

pulse. Increasing the temperature of the target by heating it resulted in a corresponding

increase in plasma emission due to an increased mass removal per laser shot; however,

selective ablation was not observed at temperatures up to 550C. Fractionation was

observed at low laser irradiances and inside deep craters, but it was minimal compared to

the results reported for other laser ablation systems. Characteristics such as precision in

the mass removal process, well-defined crater parameters, and good spatial resolution

make the microchip laser an attractive laser sampling tool.









Background

Laser ablation is a process in which an intense burst of energy, delivered by a

short-pulse laser beam is focused onto a target surface. A finite mass of the target is

removed which can be analyzed for both qualitative and quantitative information. Unlike

conventional dissolution techniques, there is little chance with laser ablation for exposure

to hazardous materials or introduction of contaminants into the sample. Laser ablation is

further applicable to all materials in all states and the absence of complicated sample

preparation procedures reduces analysis time (25). In addition, unlike beam and particle

techniques such as secondary ionization mass spectrometry (SIMS) and electron probe

analysis (EPA), there are minimal requirements for high vacuum, extensive matrix-

related interference corrections, and specialized personnel for operation and data

treatment.

Microchip lasers are becoming increasingly attractive in laser-induced breakdown

spectroscopy (LIBS) (20, 26-28). Advantages of microchip lasers in laser ablation

include minimal modification and destruction of the target which is required in the

analysis of precious ornaments and historical artifacts. Again, the high pulse repetition

frequency (up to several kHz) and good beam quality (29) permit spatial characterization

of sample heterogeneity with micrometer and submicrometer resolution. These and

several other potential advantages of laser ablation techniques cannot be fully exploited

with the use of conventional laser sources, the limitations of which include bulky

instrumentation, low probing frequency, excessive target modification and relatively poor

beam quality. By overcoming the limitations associated with conventional laser ablation

sources, solid state microchip lasers may find wide application because they can be easily

incorporated into small commercial ablation systems.









Traditional detection systems for laser ablation sources have been Inductively

Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Atomic

Emission Spectrometry (ICP-AES) (30, 31). In these cases, inert gases such as argon and

helium are typically used to carry the laser-ablated material to the ICP excitation source.

By analyzing the spectra from the ICP-AES or ICP-MS, the composition of the material

can be established. Chemical analysis with laser-induced breakdown spectroscopy is

gaining world-wide attention in recent years (11, 20).

Studies in the subsequent chapters of this dissertation will be focused on plasma

diagnostics and the use of the microplasma for qualitative and quantitative analysis.

Because plasma formation is preceded by laser ablation, which results in crater formation

on the solid matter surface, characterization of the laser-induced crater is important in

understanding the ablation process and the subsequent plasma formation and propagation.

The ablation process alone has found wide application in areas such as laser surgery (32),

matrix assisted laser desorption/ionization (MALDI) (33) surface micro-fabrication (34)

and pulsed laser deposition of organic thin films, just to cite a few. Nevertheless, the

fundamental mechanisms underlying the laser ablation process have yet to be fully

understood, even for conventional lasers which have been in use for decades.

The aim of this chapter is to evaluate the ablation performance of these miniature

lasers and to compare the characteristics of the craters obtained with those given by

conventional lasers sources having pulse widths of several nanoseconds and pulse

energies of tens of mJ. The effect of target properties on crater development and the

effect of the laser-induced crater and laser irradiance on plasma intensity and composition

will also be presented and discussed.









Experimental

The experimental setup is illustrated in Figure 2-3. Two laser sources were used in

this work, a 7 0pJ per pulse microchip (MCL) laser (model JDS Uniphase Nanolase, NP-

10620-100, Meylan, France) operating at 5 kHz, and a 50 p.J per pulse microchip

(referred to as powerchip, PCL) laser (model JDS Uniphase Powerchip Nanolaser, PNP-

005025-040, Meylan, France) operating at 1 kHz. Both were diode pumped, passively Q-

switched, all solid state lasers with a wavelength of 1064 nm and a pulse width of about

500 ps. The laser beam was focused by a 50X microscope objective (Mitutoyo, M plan

NIR 50). The distance between the objective and the target location was adjusted to

obtain a focal spot diameter of the order of 8-10 |tm. Typical objective-target distance

was approximately 1.8 cm. The targets investigated were metal foils, a silicon wafer and

several steel samples.

In order to precisely quantify the mass removal per laser shot and also to sustain the

plasma formation, the target was placed on a rotating disc which was mounted on an x-y-

z translational stage, thus exposing a fresh target surface to each laser pulse. Different

speeds, predetermined for either the microchip laser at 5 kHz or the powerchip laser at 1

kHz, were selected for the target motion. In all cases, the vertical translation speed was

100 [tm/s but the disc rotation speed was varied depending on the laser repetition rate.

For a higher spatial resolution, an additional chopper was placed between the laser and

the focusing lens to effectively limit the laser repetition rate. Ablation was carried out at

atmospheric pressure in air.

Target surface modification was studied with a scanning electron microscope

(Hitachi S-4000 FE-SEM) while crater profiles were obtained with a profilometer









(WYKO NT 1000, Veeco Instruments) operating in vertical scanning interferometer

(VSI) mode. Plasma emission intensity was measured with a 600 [im diameter fiber optic

coupled to Ocean Optics miniature spectrometers, HR2000 (2400 grooves mm-1 and 0.03

nm FWHM optical resolution) and SD 2000 (0.3 nm FWHM resolution) (Ocean Optics

Inc., USA). All spectrometers used were non-gated and non-intensified. The

spectrometers were calibrated with a tungsten lamp and the emission intensities were

corrected for the different response of the spectrometer-detection apparatus at the

wavelength of interest.

Results and Discussion

The MCL and PCL as Microprobe Analyzers

As pointed out before, the first challenge in working at high pulse repetition

frequencies is to obtain single craters. It is essential to expose a fresh area of target to

each laser pulse for the following reasons: i) In the case of the MCL and PCL(20), as

with other laser sources, the formation of a plasma with each laser pulse and the

parameters of the laser-induced plasma are strongly dependent on focusing conditions; ii)

a deeper crater can completely or partially envelope the microplasma and significantly

affect the emission intensity and spectral composition (20); iii) it is possible that any re-

deposited material will have composition different from the composition of the bulk

sample due to fractionation. Emission spectra taken from plasma breakdown on the

melted sample may therefore lead to erroneous qualitative and quantitative information.

A basic requirement in laser ablation for microchemical analysis is to transform a

finite amount of sample into the vapor phase with a stoichiometric representation of the

sample. One should therefore be able to know how much mass is removed by each laser

pulse and whether the ablated mass has the same composition as the bulk material.









Therefore, in all experiments with the microchip lasers, special efforts were taken to

avoid the problems enumerated above by ensuring that mass ablation from successive

laser shots did not occur from the same focal spot. As mentioned in the experimental

section, this was accomplished with two independent motorized stages. Figure 3-1 shows

the pattern resulting from the ablation scheme devised. The rotating disc, together with

the x-y-z stage, translated in the plane perpendicular to the laser beam gave spiral-shaped

single craters. The distance between each pair of craters was determined by the speed of

the moving stage. Figure 3-1 further shows that, with the PCL and MCL, highly

reproducible and precise craters were obtained. The minimal jitter in the MCL and PCL

laser systems, compared to conventional flash lamp-pumped lasers, contributed to the

better precision and control. For the PCL used in this work, the timing jitter was better

than 0.3 ns and the amplitude RSD was better than 4%.

















Figure 3-1 Powerchip laser micro-ablation of copper substrate showing: (left) the ablation
scheme devised; and (right) single craters obtained at 1 kHz.

The large number of single craters distributed over a small target area (Fig. 3-la and 3-

lb) indicates that the powerchip and microchip lasers should be nearly ideal tools for

elemental surface cartography, particulate sampling, and rapid characterization of









material homogeneity, microanalysis and laser surface microprocessing. Coupled with a

technique such as LIBS, where the elemental composition of material is analyzed by

vaporization of mass from a very small spot, PCL and MCL systems will then be capable

of microprobe analysis (29, 32, 33) with micrometer resolution in terms of lateral and

depth dimensions.

Over the past few years, surface characterization of materials has attracted growing

interest in chemistry and material science. For some materials, scientists not only need to

know the accurate composition of the bulk sample, but also the exact location of

interfaces and characterization of concentration gradients. For example, in the

pharmaceutical industry, some tablets possess a multifunctional coating of which the

thickness needs to be accurately controlled. Some techniques that have been applied

satisfactorily as surface characterization tools include Raman spectroscopy, IR

spectroscopy, and Auger electron spectroscopy. Laser ablation has also been used by

several researchers to provide information about the atomic composition of materials as a

function of depth(35).

A potential application of the PCL in surface depth profiling is illustrated in Figure

3-2, where a steel matrix with a thin coating on the surface (due to target heating -

described later) was analyzed. As can be seen, within the 25 s time duration, the effect of

the crater on the emission intensity was minimal since the intensity of Fe 400.52 line

remains nearly constant. However, a line observed at 393.36 nm suffered a steep decrease

in intensity, reaching the background level after 15 s. This line is most probably due to

Ca, although it was not experimentally proved. Previous studies reported Ca II as a

common contaminant on steel surfaces though not in steel matrix at a relevant









concentration (36). Ideally, we expect the intensity of the iron line to increase as the line

from the coating decreases. It is not clear as to why the intensity of the iron line stays

constant but it is speculated that the increase in intensity as a function of depth is

cancelled by the effect of the laser-induced crater. Assuming that this line originates from

the coating due to target heating, knowing the mean ablation depth per laser pulse and the

number of pulses used, the thickness of this film could be estimated. When LIBS is used

in depth profile analysis with conventional lasers, the main limitations are the poor spatial

and temporal quality of the beam profiles (unless particular care is taken in shaping the

beam), which result in limited depth resolution. The operating features of the microchip

laser, combined with the simplicity of the technique make these sources attractive tool in

depth profile analysis. In situations where the analysis time frame compatible with

industrial requirements are desirable, microchip LIBS for surface characterization may

constitute and alternative to existing methods such as x-ray photoelectron spectroscopy

(XPS), glow discharge spectroscopy (GDS) and Rutherford back-scattering spectroscopy

(RBS).

Target Modification

Pulsed lasers have applications not only in spectroscopy but in other areas such as

pulse laser deposition and micromachining (37). In all these cases, the laser-target

interaction and the plasma-generated thermal damage to the target can be employed

constructively but can also be a major obstruction. The interaction of the laser pulse with

the target depends both on the laser parameters and the target properties (25, 37, 38). In

this study, because the damage caused by the laser pulse interaction with the target and

the damage caused by the plasma melting of the surface could not be separated in time,

the effect of the laser-induced plasma was studied by imaging the target at the inter-crater











spaces. Figure 3-3 shows SEM images taken from the inter-crater spaces of Cd and Cu. It

was observed that the damage to the target by the laser-created plasma was thermal in

nature, characterized by the melting of the target. The extent of melting depends on the

thermal properties of the target such as melting temperature and heat of fusion.


(a) (b)

2 ls Line 39336 nm
Coated 1a3
393.36 nm 400O 52
S ignif ico ..re i ft w* t
= ia F *
s1O a n Und ted *i h l n Fe 140052 nm



;10 15 4] 25
3 394 3I9, I0, I IS CM 2, 5
Wave le ngth rn m Time/s

Figure 3-2 Depth profiling of a thin film created on steel surface by the 50 jtJ powerchip
laser. (a) Spectra obtained from the coated and polished steel surface.
Integration time was 3 s (b) Time-dependent intensity distribution of the line
from the "coating" and iron matrix.

Significant melting and re-deposition of larger droplets were observed for targets

such as Sn, Pb, and Cd which have lower melting points than others such as Ni, Fe and

Cu. The re-deposited material probably consists of both liquid phase expulsion and

plasma particle condensation(39), which can be particularly high at atmospheric pressure

(40). Finally by comparison of the crater and focal spot diameters, it was inferred that

plasma modification of the surface was more predominant than the damage done by the

laser pulse itself. This is possibly due to the short pulse duration and hence less time for

thermal diffusion into the target to occur (40).









Cu


Cd


Figure 3-3 Effect of the laser-induced crater as shown in the inter-crater spaces.

Mass Removal

Single crater diameters were estimated from scanning electron micrographs while

the crater depth was obtained by a profilometer. Because of the almost perfectly

Gaussian laser beam profiles of the MCL and PCL (20, 29), the shapes of the ablation

craters become prominently cone-like (41), especially after several laser pulses have been

directed on the same spot as shown in Figure 3-4. Other laser types, for example, those

with flat top beam profiles or inferior Gaussian profiles may produce straight wall craters

or other crater types with irregular shapes(42, 43). In this work, based on the diameter

and depth profile, a conic or half-filled spherical shape was assumed for single craters

from which the volume was obtained. Figure 3-5 shows the variation of the amount of

material removed per laser shot and the crater radius with the heat of fusion and melting

point. The lower the heat of fusion of the material, the greater the amount of material

removed per laser shot. For example, the material removed varied from 0.5 to 0.8 ng for

silicon and 9 to 11 ng for tin. Considering that the focal spot diameter was just 8 am, it

can be seen that in the case of materials such as Ni and Si, with radii 5 and 4 am,

respectively, the damage to the surface is limited to the focal spot while for materials











such as Pb or Sn, the crater diameter is nearly two times bigger than the focal spot


diameter. This is due to the pronounced effect of the LIP as explained earlier.


Figure 3-4 Microchip laser-induced crater on cadmium foil showing the crater structure
and droplet redeposition on surface.


0 10 20 30 40 50
Heat of fusion IkJmole1


-6

E



I
-4







2


Figure 3-5 Dependence of crater radius and mass removed per laser shot on the melting
point temperature (shown in parenthesis) and heat of fusion of the target.
Mass removed were calculated based on the crater volume and the density of
the material.


Sn
(231.9 "C)


*- Material removed
v- Crater radius


Ni
(1455 "C)


Pb C
(327.5 C)


Si
(1412 C)


'~' '~









From the measured spectra, it was interesting to note that, at 7 PJ/pulse, the higher

mass removal in materials such as tin, lead or cadmium was not reflected in

correspondingly higher emission intensities. The low emission intensities in such

materials can be ascribed to excessive re-deposition of the melted material which has a

higher breakdown threshold. At 50 PJ, there is still redeposition of melted material on

targets such as Cd, but the overall emission intensities are higher than those observed for

targets such as copper, although the increase in emission intensity does not follow

proportionally the increase in the mass removed.

Table 3-1 Laser-induced crater depth and diameter for a 500 ps microchip laser compared
to that of 8 ns laser. Data in bold were obtained for the 8 ns laser.
Height/[m) Diameter/[m

Si 12 11
2.2 125
Al 16 13
Ni 12.4 11.6
3.5 100
Fe 12.7 12.5
2.7 115
Cu 15 13
Pb 16 14
10.5


Table 3-1 collects the depths and diameters of craters for various metal foils and a

silicon wafer created by a 0.5 ns microchip laser and by 8 ns flash lamp-pumped Nd-

YAG laser (1064 nm, beam divergence 7 mrad, beam diameter 2.8 mm, pulse energy 0.7

mJ). No effort was made to optimize the shape of the laser beam profile in the case of the

8 ns laser. Values for the 8 ns laser are presented in bold. The average focal spot diameter

was 8-10 atm for the PCL and 28-35 atm (in the absence of significant plasma melting)









for the 8 ns laser. The data presented were obtained under the best focusing conditions

obtainable. It is especially interesting to note that, in the case of the microchip laser, the

craters are narrower (limited to the focal spot) but deeper, while with the 8 ns laser, the

craters have larger diameters but are shallower. This is further revealed in Figure 3-5

where a crater profile of the 8 ns laser pulse is compared to that from the PCL. The crater

from the 8 ns laser pulse is shallower and mountainous unlike the PCL crater which is

deeper and relatively uniform inside. The difference in the spatial and temporal energy

distributions for the two lasers could play a significant role in this observation. As

mentioned before, the MCL and PCL systems are characterized by Gaussian intensity

profiles, single mode output and low pulse to pulse variation, while conventional flash

lamp-pumped lasers do not compete favorably with MCL/PCL laser with respect to the

above properties. For quantitative ablation, it is clearly easier to quantify the mass

removed by the PCL than by the 8 ns laser source. Generally, the depth-to-diameter ratio

of microchip lasers is greater than that of the 8 ns pulse, which might be partly due to the

lower energy losses through thermal dissipation, which is a function of the laser pulse

duration (29, 38, 44) and increased plasma shielding in the case of the 8 ns pulse.

Ablation Efficiency

Several papers have characterized the laser ablation efficiency (38, 40, 45) which is

simply considered here as the ratio of the yield of target property (mass or volume) to the

laser energy input. A review of literature yielded at least three common definitions

including: the ratio of crater volume to laser energy, ratio of crater depth to laser fluence,

and the ratio of mass removed to laser energy. Based on these definitions, the ablation

efficiency of the microchip laser at 7 PJ was compared to those reported for other laser

sources. The results for this study are shown in Table 3-2 and reveal that the ablation













efficiency of the microchip laser can be up to two orders of magnitude higher compared


to other laser sources. Laser ablation is a complex phenomenon depending on laser


wavelength and pulse duration, focal spot size, and target properties (25, 37, 38, 40, 44).


It was therefore of interest to study both the effect of several experimental parameters and


laser properties on laser ablation.


4-
2-
0-
-2-
-4-
E -6-
. -8-
o -10-
-12-
-14-
-1 -
-18-


[ 10 20
Diameter 1tm


30 40


Diameter.ipm


Figure 3-6 Comparison of (a) 500 ps passive Q-switched powerchip-induced crater, and

(b) crater induced by an 8 ns active Q-switched laser on a lead target.


Table 3-2 Ablation efficiency of 7 PJ microchip laser compared to values reported for

conventional Nd: YAG lasers. Refs. (38, 40)

Ref Pulse Pulse Fluence, Jcm-2 Volume/pulse Depth/fluence,
width energy pJ (Irradiance energy, pm3j-1 m/J cm-2
(ns) GWcm-2)

Salle at al 4 60 120(30) 0.2 x 105
(532 nm)


Samerok 4 65 130 (32) 0.1
et al


Microchip 0.5 7 14(25) 2x 108 1.5
laser




In Figure 3-7, the behavior of the ablation volume of Cu and Cd is shown. It can be


seen that in both cases there is increase in crater volume with an increase in laser energy.


a







................. ................................... ....... .......... ............... ......... ........................ ... ..............................
................. ................................... ......... ......... ............... ....... .......................... ... ..............................
................. .......................... ....... .......... ....... ............... ...... ............................ ... ..............................
................. ................................... ........... ...... ............... .... ............................. ... ..............................
................. ................................... ............. ..... ............... ... .............................. ... ..............................
................. ................................... ................ .. .. .. ................................... ... ..............................










The plots however are characterized by different slopes, which most likely indicate that

different regimes are operative in the ablation process. In the case of Cd, the crater depth

increases steeply with laser energy up to 15 uJ, after which a different ablation regime

with a lower slope begins. A similar process is observed in the case of Cu, except that the

second slope is the steeper one. Similar results in which the crater volume increased with


:D0 200 -





SI


50 I





Figure 3-7 Variation of crater volume with laser energy for: (a) cadmium and (b) copper.
The arrows indicate the points of the curve where different slopes begin.

with laser energy until the occurrence of a threshold were observed by Russo et al (46).

The second regime was explained in terms of explosive boiling of the target. At this

stage, the target material makes a sharp transformation from superheated liquid into a

mixture of liquid droplets and vapor leading to an excessive mass ejection from the

surface (47). In the case of Cd, the slope decreases after the threshold. As mentioned
0 ID 20 30 40 50 I I I I I









earlier, in the mass ablation process, there is significant re-deposition of melt flush on the
target surface. In the case of Cd, characterized by a lower melting point, the effect of the

meltFigure 3-7 Varial is more pronounced than with laser energy for: (a) cadmium and (b) copper or silicon.

Since the breakdown threshold inmate the points higher than that of the urve where different slopes begin.d surface

(20), th laser energsitivity faluntil the ocurrencwn by the of a thresholds steep slope. For Cu, characterized by higher a (46).
The second regime was explained in terms of explosive boiling of the target. At this

stage, the target material makes a sharp transformation from superheated liquid into a

mixture of liquid droplets and vapor leading to an excessive mass ejection from the

surface (47). In the case of Cd, the slope decreases after the threshold. As mentioned

earlier, in the mass ablation process, there is significant re-deposition of melt flush on the

target surface. In the case of Cd, characterized by a lower melting point, the effect of the

melted material is more pronounced than with other targets such as copper or silicon.

Since the breakdown threshold in the melt is higher than that of the undisturbed surface

(20), the sensitivity falls as shown by the less steep slope. For Cu, characterized by higher









melting point, the opposite effect is observed, with the sensitivity increasing during the

second ablation regime.

The above definition of ablation efficiency cannot be directly translated into

corresponding emission intensity, because it is the amount of sample that goes into the

vapor phase and is excited in the plasma that controls the emission intensity. Again, the

increase in volume is not necessarily directly proportional to the increase in energy,

(which would give a single slope). As can be from Figure 3-7, for Cd, the ablation

efficiency is 7 X107 [tm3/J at 15 0pJ and 4 X107 [tm3/J at 30 iJ. This, together with the

results shown in Table 3-2, leads to the conclusion that in order to obtain higher ablation

efficiency, lower pulse energy is recommended. In an attempt to better characterize the

ablation process, the definition of the ablation efficiency will be extended by taking into

consideration:

1. The change in emission intensity with the change in mass removed. Provided that
optically thin lines are chosen, the change in emission intensity should be directly
related to the mass removed that goes into the gas phase.

2. The change in target mass versus the mass removed per shot. With negligible re-
deposition, the change in the two parameters should be the same.

3. The ratio of the volume of crater up to volume down. Estimates of "volume up"
and "volume down" can be easily obtained using crater profile images taken by the
profilometer used in this work. This definition approximates 'volume up' (the
volume of the material deposited on the crater rim) as the mass removed that does
not go into vapor phase to contribute to the plasma emission and 'volume down' as
the total material removed.

All three definitions above will ensure that the ablation efficiency is presented as

the fraction of mass removed that contributes to plasma emission, which is the fraction

that has spectroscopic relevance. None of these, however, is meant to provide a universal

definition but rather diagnostic information as how LIBS performance based on the

microchip laser could be affected by the physical mechanisms involved in the ablation









process. Also, the term 'ablation sensitivity' will be introduced, which will be defined as

the ratio of the total detector counts obtained per shot to the laser pulse energy. In this

definition, it is the total mass ablated that goes into the plasma and emits that is

considered. It is important to note that at 50 [J, the crater volume for Cu is about 10

times smaller than the crater volume for Cd (200 tmm3 and 2000 trm3 for Cu and Cd,

respectively).

Figure 3-8 shows the behavior of the signal (counts), corrected for the detector

response, versus laser energy for Cd and Cu. All data were integrated over 400 ms, which

was chosen to ensure that the detector would not be saturated at the maximum laser

energy and that there would be measurable intensity at the lower energies. An interesting

point to note is that for Cu, the emission intensity is only about half that of Cd, despite

the crater volume being approximately 10 times less. The lines used for this investigation

were 361.05 nm for Cd and 406.26 nm for Cu. By taking into account the transition

probabilities of these lines, one would expect the intensity of Cd to be approximately

eight times greater than that of Cu. This suggests that there are other phenomena beyond

the spectroscopic parameters of these lines. Similar observations were made whenever

materials such as Cd, Sn, and Pb were compared to others such as Ni, and Fe. This may

suggest that at low energies, in the case of lower melting point materials, a significant

amount of the ablated material is not vaporized but is just re-deposited as droplets on the

target surface, while, even though less mass is removed for substrates such as Cu and Ni,

a relatively larger fraction is vaporized and available for emission.

To further clarify this point, the behavior of ablation sensitivity and ablation

efficiency with pulse energy for both Cu and Cd were compared. The results for this are







41



shown in Figure 3-9. One can see that in both cases, the ablation efficiency is higher at


lower energies. In the case of Cu, there is an initial decrease in ablation efficiency


followed by a steady rise after 20 pJ. An opposite observation is made for Cd in which


there is a fall after an initial rise. This observation is consistent with the two regimes of


ablation discussed earlier in this chapter. With regard to ablation sensitivity, the graphs


show that for Cd, ablation sensitivity increases with pulse energy and levels off at about


65 X 106 counts/J at 25 pJ. The ablation sensitivity of Cu, however, remains nearly


constant at all energy levels except for 5 pJ, where it is about 15 X 106 count/J. Cu will


be considered as nearly the ideal situation, where the emission intensity increases at the


same rate as the laser energy. The result could also have to do with the excess energy


available for atomization, ionization and excitation. There could be significant increase in


mass removal for materials with low thermal properties, but there is just enough energy


left for the latter phenomenon (atomization, ionization and excitation).


1600-
3500 1400

3000- Cd 1400(Cu)
1200-
2500 -
20 1000-
2000 8 800-
0 800
1500- 600-

a 1000- 400-

500 200-
0 0-
0-1
S 10 20 30 40 50
0 10 20 30 40 50 Energy
Energy /Er/
Energy/Jr J


Figure 3-8 Plasma emission intensities of cadmium and copper compared at different
laser pulse energies. Integration time was 400 ms, with 5 spectra averaged (i.e.
each spectrum is an accumlatiuon of 2000 spectra). Each data point represents
the mean of 20 spectra.







42


-65
i 70 Cadmium


o 60 I


3 50- -50





-- 35
S-40 LD








32- 6
-, Copper

CD A


S 24 X
----- --- --- 1--6--- -





20
-42



0 10 20 30 40 50

Pulse energy (pJ)



Figure 3-9 Ablation sensitivity (red line) and efficiency (black line) of Cd (top) and Cu
(bottom) as a function of laser pulse energy.

Effect of Target Temperature on Mass Removal:


Experiments have shown that, during laser target interaction, thermal diffusion into

the target precedes the ablation process (48) In the case of long pulses (of the order of

10 to 100's of nanoseconds), thermal diffusion can be very high (49-51) and can reduce

the actual amount of incident energy that is involved in material removal. Conversely, the
the actual amount of incident energy that is involved in material removal. Conversely, the










same phenomenon does not need to be considered in the case of ablation with short

pulses, in the ps and fs regime (51-54) since diffusion of the laser energy into the target is

minimal.

Investigation of the effect of target temperature on ablation rate and plasma

composition will not only provide knowledge from the fundamental point of view but

may also lead to modifications in instrumental and experimental configurations for real-

time analysis in production sites, such as in the steel industry, where molten material in

high temperature furnace may need to be analyzed in situ for enhanced productivity.

In this work, an attempt was made to increase the sensitivity of the mass ablation

process by increasing the target temperature. The expectation was that with the target

already at a higher temperature, thermal diffusion of the laser pulse energy into the target

would be smaller, thus involving more of the incident energy in solid matter removal,

atomization, ionization and excitation. A steel sample was heated on a hot plate and

quickly transferred to the ablation stage. The emission intensity, plasma composition and

crater profile of the hot and cold targets were obtained after ablation with the PCL.


3 Intensity at 550oC
300. = Intensity at 300C 0 550tC
r 3000C
25-
o
2500 -
20
2000 -
(a) (b)
X 15.
1500-
10'
1000-0

500 05

0 00
Mo Mn Cr Mo/Fe Mn/Fe Cr/Fe
Element Element

Figure 3-10 Effect of target temperature on plasma composition and emission intensity.
(a) is the background corrected emission intensity and (b) is the intensity
normalized to Fe 400.52 nm line.









The signal enhancement of three atomic lines from Mn, Mo, and Cr at 3000 C and

5500 C are shown in Figure 3-10. The results show that an increase in target temperature

results in enhancement of emission lines, especially significant for Cr. This could be due

to either an increase in mass removal or an increase in plasma temperature or both. In

quantitative analysis of trace elements by LIBS, the possibility of a selective

enhancement of some lines of the elements with respect to the matrix is of great interest.

To determine whether there is any such phenomenon, the intensities were expressed as a

ratio of the intensity of the selected lines of Mo, Mn or Cr to the iron atomic line at

400.52; iron was the main matrix element in the sample. The results, shown in 3-10b, do

not reveal any significant change in the intensity ratios whether the sample was hot or

cold. A Boltzmann plot (77) was used to determine whether the increase of the target

temperature would lead to any changes in the plasma electron temperature. A sample plot

is presented in chapter 4 (figure 4-8). Temperatures obtained for heated and room

temperature targets were similar, of the order of 11,300K, + 200 K in either case. It can

be concluded that the increase in the emission line intensity shown in Figure 3-10a is

primarily due to an increase in the mass removed per shot, and not to a change in the

plasma thermal properties. It will be informative to observe the changes in spectral

composition and plasma emission intensities as the target is heated to temperatures near

the melting temperature of some of the elements of interest; however, technical problems

associated with this did not permit such an experiment at this time.

Effect of Crater Depth and Laser Irradiance on Plasma Intensity and Composition

Because thermal properties, such as melting and vaporization temperatures, vary by

orders of magnitude, laser ablation of multi-element materials may result in selective











removal of some species, a process referred to as fractionation. Experiments show that


crater depth and its aspect ratio contribute to this effect (55). Another experiment was


designed to show the changes in the net emission intensity and time dependent ratios of


Cr, Mn, Mo, and Ni to matrix (Fe) as the crater was developing during repetitive laser


pulses along a single circular crater trench. Figure 3-11 shows the time profile of four


elements of interest in a steel target. Slight adjustment of the focusing was done after


every 30 s to ensure that the lens to focal spot distance did not change significantly over


the time duration of the measurement. The spectra were taken from the same circular


crater trench with 1.5 cm diameter. The gradual decrease in emission intensity in all cases


could be due to the fact that plasma is partly buried in the crater, decreasing the solid


angle the collection system makes with the plasma.


a
-- b
-Cr
400 --Mn
1Mo 5-
350- Cr Fe
I I -4- MnFe
S300- Mn / 4-- M Fe NI/Fe
NIFe
8 Fe
250- 3-
250 Mo/Fe
Mo a
200-
r" 2 -r Mn/Fe
150- NI /

100-

-20 0 20 40 60 80 100 120 140 160
Times 0 5 10 15 20 25 30 35
Time (s)



Figure 3-11 Effect of laser-induced crater on plasma emission intensity.

Selective removal of some elements and material can be caused by laser interaction


with the sample, a process resulting elemental fractionation. The microplasma hidden


inside a deep crater may contribute to the sampling process, leading to fractionation (25).









In addition, with increasing crater depth the actual irradiance may decrease due to

changes in effective surface area exposed to the laser beam (42) which might not only

decrease the net emission intensity but can also influence fractionation. To investigate

whether such a situation could occur, the net emission intensities of the lines were

normalized to a line belonging to the matrix. There was no significant change in the

relative intensities with time when the target was rotated as described. The experiment

was repeated with fresh target but at the same focal spot, with periodic adjustment of the

focusing. Figure 3-1 lb shows pronounced changes in the Ni-Fe intensity ratios especially

after the 30th data point. One reason could be that in the case when the target was rotated,

there was enough time for the redeposited material to solidify before the next mass

removal while in the case of Figure 3-1 Ib, there was not enough time for the phase

change. A piece of brass containing 30% Zn and 70% Cu was measured to determine the

effect of the crater on the Zn-Cu ratio. The intensities of the Zn emission line at 481 nm

and Cu at 327.4 nm were monitored. For every data point, the background in the vicinity

of the Zn and Cu lines was measured and subtracted from the signal. Figure 3-12 shows

a steep decrease in the Zn-Cu ratio during the first 15 s. The decrease could be partly

explained in terms of decreasing irradiance as the crater develops. Earlier in this work(20,

56), we observed that at lower irradiances, low melting/vaporization point elements have

lower emission intensities compared to high melting point elements despite higher mass

removal in the former. Other reports have established that the laser-induced cavity aspect

ratio increases elemental fractionation (57).







47




(a) (b)
45-

40 Zn481/Cu3274 32
35-
28-
o 0
30
I 25- 24-
N
20-
2020
15- \ 2
1 0
0 2 4 6 8 10 12 14 16
0 10 20 30 40 50
Successive data point number
Energy (pJ)



Figure 3-12 Effect of crater and laser energy on plasma composition: (a) Temporal
dependence of the Zn-Cu ratio in brass when the plasma is created on the
same spot. Integration time was 300 ms with 5 spectra averaged. (b) Effect of
laser pulse energy on Zn-Cu intensity ratios. Each data point is the average of
30 spectra with an integration time of 300 ms and 5 spectra averaged.

In Figure 3-12b, the effect of laser energy on the Zn-Cu ratio is presented. Again,


the Zn-Cu intensity ratios remained nearly constant at all energies except at 5 PIJ, which


was significantly lower than the values obtained at other laser intensities. Thermal


properties of the Zn and Cu might suggest that at lower laser energies, more Zn will be


removed. However, as has been pointed out earlier, this might not necessarily lead to an


increase Zn-Cu ratio, as a larger fraction of this mass may be re-deposited as droplets.


Because the effect of laser energy on plasma composition is minimal, as has been


observed for ps and fs laser pulses, unlike nanosecond laser pulses, thermal effects do not


play a significant role in fractionation (45). By employing higher laser intensities with


pulses in the ps and fs regime, fractionation can be eliminated or reduced significantly.


Conclusion

The potential of MCL and PCL lasers as ablation sources for analytical systems has


been demonstrated. Compared to conventional laser sources, there is minimal damage to


the target using the MCL/PCL and mass removal can be precisely quantified because the









craters can be easily characterized. The high probing frequency, which can be several

kHz, and good beam properties ensure high spatial and depth resolution. However,

translation is necessary to sustain plasma formation and ensure stoichiometric mass

removal and also to provide a flat surface for plasma formation so that the microplasma

will not be hidden from the emission collection systems.

The parameter ablation sensitivity was introduced and was considered as the

detector count per laser pulse energy during the mass removal process. Unlike the

traditional definition of ablation efficiency, ablation sensitivity considers the fraction of

the mass removed that is vaporized and contributes to plasma emission.

Microchip lasers have not yet been used appreciably in the analytical world.

However, due to their compact size, low maintenance cost, portability and precision in

material removal, they may, someday, find wide application in commercial analytical

systems such as LA-ICP-MS or LA-ICP-AES and LIBS. In addition, applications may

extend beyond metals to areas such as polymers (58) and biomaterials (58, 59).














CHAPTER 4
DIAGNOSTICS OF MICROCHIP LASER-INDUCED PLASMAS AS RELATED TO
LASER-INDUCED BREAKDOWN SPECTROSCOPY

Summary

The ablation properties of the microchip laser were studied in Chapter 3 and the

analytical performance in trace element analysis will be presented in Chapter 5. In order

to bring the findings into perspective, a deeper understanding of the properties of the

micro-plasma created by these lasers is needed. Chapter 4 reports an approach to achieve

such goals and several preliminary results. Spectral analysis, time-resolved pump-probe

absorption measurements, electrical signals from the plasma, and CCD photography were

used to characterize the micro-LIBS plasma and its behavior. The plasma breakdown

threshold on several targets is reported for the powerchip laser as well as the challenge of

tight focusing required to induce breakdown.

Theory

Even though the principle behind the LIBS technique is simple, the physics

involved in the ablation process and the plasma formation and subsequent expansion as

well as the plasma emission are complex. Laser-induced plasmas (LIPs) have very short

temporal existence with a fast evolution of their characteristic parameters. The

parameters of the LIP are heavily dependent on irradiation conditions such as incident

laser intensity, ambient gas pressure and composition, and irradiation spot size. Even

under the same irradiation conditions these parameters can vary with the axial or radial

distance from the target surface.









Different diagnostic techniques exist for studying laser-induced plasmas. These

include spectroscopy (optical emission spectroscopy, OES)(60), laser interferometry,

Langmuir probe methods, and Thompson scattering(61). Among these, emission

spectroscopy seems to be the simplest as far as instrumentation is concerned, even though

it is less direct and more theory dependent than, for instance, Thompson scattering. Also,

absolute intensity measurements are difficult to make with high accuracy, even when the

source is compared to a standard source, due to variations in solid angles, equivalent light

paths and apertures. In addition, because most sources have cylindrical symmetry and

hence a radial temperature gradient, when viewed side-on the radiation comes from an

inhomogeneous medium. Therefore the condition for uniform optical thinness is usually

difficult to achieve. Different instrumental schemes and optical setups can be employed

to alleviate these problems.

Plasma diagnostics consist of both temporal and spatial structures. In Figure 4-1,

the spatial structure involved in the diagnostics of laser-induced plasma is illustrated(]).

The process begins with absorption and scattering of incident laser energy and proceeds

through the transport of this energy to denser regions. The laser light is often absorbed by

inverse Bremsstrahlung for local plasma frequencies less than the laser frequency, i.e. up

to the region where n = no, the critical density. When the plasma frequency equals to

laser frequency, the laser energy is either reflected (or scattered) or absorbed. Optical

diagnostics provide much of the needed information in the region from the critical

surface outward towards the laser. The absorption process and the local plasma

conditions can be studied by measuring the scattered or shifted frequency and harmonic

light resulting from these processes.







51


*Thomson scattering
Optical probing -Faraday rotation
*Interferometry


.......... ............................... .......... ..... ..... --- H x-Hard x-rays
................................................... soft x-rays
........... ................. .................. Harm onics (no,)
................................ Raman scattered light

"-Thermal
Zc onductIor




-Generation of
nj4 suprathermal electrons
Ablation Critical Expanding sheath
surface surface (nr)
Figure 4-1 Spatial component of a laser plasma diagnostics.

In plasma diagnostics, the information that is needed can either be obtained

measuring self-emission from the plasma or by probing with external radiation(60). The

former is simpler and provides more local information. Optical emission, however, may

not be suitable for dense plasmas where emission cannot escape due to large opacity.

Probing overcomes this, and further, provides time-resolved information because the

probing radiation can be introduced in the form of short bursts timed with respect to the

evolution of the plasma.

This chapter focuses on characterization of the microchip laser-induced plasmas by

analyzing the emission spectra from the plasma, and the changes undergone by radiation

introduced into the plasma from a probe beam. The plasma temporal profile and its

relation to the laser pulse and the absorption and electrical properties of the plasma were

addressed. The combination of CCD photography with spectroscopy adds another

dimension to the plasma diagnostic by providing two-dimensional snap-shots of the

three-dimensional plume propagation. The effect of experimental conditions, such as

focusing and pulse energy, on the physical and temporal properties of the laser-induced









plasma will be discussed as well as the challenges and/or the benefits these present when

these types of lasers are used in LIBS.

Experimental

The experimental set is illustrated in Figure 4-2. The laser source used in this study

was a 50 PJ per pulse microchip laser (referred to as powerchip laser, PCL) having a

wavelength of 1064 nm and 0.5 ns pulse width. In plasma transmission studies, a portion

of this beam was split off with a beam splitter. A 532 nm component of this portion,

henceforth called the probe beam, was obtained by second harmonic generation using a

KTP crystal. Using an optical delay set up, the probe beam was sent through the laser-

induced plasma orthogonally at different delay times following the laser pulse in order to

estimate the transmission through the plasma.


Computer Ocan Optics
spectrometers
Figure 4-2 Plasma diagnostic experimental set up. GP-glass plate; M-mirror; PD-
photodiode; T-target; L-collimating lens; PCL-powerchip laser. The collection
lens & fiber coupler take the position of PD2 in emission measurements.









Plasma emission was collected with a 600 |tm diameter optical fiber into a

miniature spectrometer, HR 2000 (2400 grooves/mm grating, 0.03 nm optical resolution)

or various photo-detectors. The laser beam and the plasma pulse temporal characteristics

were measured with a 200 ps MCP/PMT (Hamamatsu R1564U-07) connected to the exit

port of a monochromator (American ISA Inc, H-10V) and a fast photo-detector (Electro-

Optics Inc., ET 3000). The signal was monitored with a 6 GHz digital oscilloscope

(Tektronix, TDS 6604). For estimation of the plasma breakdown threshold, linear

attenuation of the laser beam was achieved with a circular neutral density filter and the

laser energy was monitored with a power meter. Plasma images were obtained with a

CCD camera, Pixera Professional PVC 100C (Pixera Corporation, USA).

Result and Discussion

Absorption Properties of the microchip Laser-Induced Plasma

Laser-induced plasmas (LIP) are transient. Even for high power active Q-switched

lasers with energies of 100s ofmJ per pulse, the LIP has an emission lifetime of 100 [tS

or less. In the case of the microchip lasers, the plasma lifetime is of the order of 100s of

ps to a few ns after the breakdown event. Time-gated measurements of such transient

pulses using conventional gated ICCD detectors are challenging and have not yet been

feasible with the microchip LIP. Time integrated measurements alone do not provide a

complete picture of the physical and chemical processes taking place in the LIP. On the

other hand, time-resolved measurements provide useful information not only from the

fundamental point of view but also with regard to the dynamic processes such as the

evolution of electron number density and plasma continuum emission. Such knowledge is










needed to improve the analytical utility of the LIP for both qualitative and quantitative

work.

These issues were addressed by studying the time-resolved absorption behavior of

the LIP using an optical delay setup based on pump-probe measurements. The plasma

was always formed by the 1064 nm fundamental frequency but the probe beam was either

the 1064 nm beam or the frequency doubled 523 nm light obtained by splitting a portion

of the pump beam as shown in Figure 4-2. The probe beam was focused and passed

through the plasma at different delay times following the laser pulse. The intensity of the

probe beam was measured before and after passing through the plasma in order to obtain

the fraction of light 'absorbed' by the plasma. In Figure 4-3, time-resolved measurements

of the plasma transmission as a function of the optical delay between the laser pulse

initiating the plasma (pump beam) and the split off beam focused through the plasma

(probe beam) are presented.

0.6- 1064 nm probe
532 nm probe
0.5


( 0.4-
0.
0Q 2






0.1 -

0.0
0.1I II




-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Delay (ns)
Figure 4-3 Fraction of probe beam absorbed by the LIP as a function of delay time. The
inset is the temporal profiles of the 1064 and the 532 nm beams.









The temporal profiles of the two probe beams are shown as the insert in Figure 4-3.

Absorbance was calculated from the ratio of the laser pulse energy transmitted through

the LIP to the pulse energy in the absence of LIP.

Approximately 1.2 ns following the laser pulse, about 50% of thel064 nm and 40%

at 532 nm probe beams were absorbed by the plasma. Thus, the plasma has maximum

absorption approximately 1.2 ns following the laser pulse and is nearly transparent 4 to 5

ns later. In a similar study by Hohreiter et al.(62), using a laser pulse with 275 mJ per

pulse and 10 ns pulse width, the percentage of the 1064 nm and 532 nm probe beams

absorbed were 84% and 91% respectively, approximately 40 and 30 ns following the

laser pulse.

The absorption of the probe beam by the LIP in this work is significantly lower

than that obtained by Hohreiter et al. Several reasons could account for the lower

absorption values observed in this work. First, the absorption path-length across the

plasma in this work is at least 10 times less than to that said in Ref (62). And the electron

number density obtained in this study is two orders of magnitude lower than that reported

in Ref. (62). The width of the PCL pulse is 0.5 ns while that used in ref. (62) is 10 ns. A

laser spark is produced through an initial breakdown followed by growth and heating of

the plasma. For longer pulse durations as used in the above reference, the latter part of the

laser pulse can heat the preformed plasma significantly. The heating results in plasma

ionization which increases the absorption of the laser through inverse Bremsstraahlung

processes- a condition where a laser photon is absorbed by an electron in the field of an

ion causing direct plasma heating. For pulse durations in the fs to ps regime, the laser

pulse does not interact with the expanding plume sufficiently (63) and so the plasma is









relatively cold. Therefore, post-breakdown processes such as ionization of species in the

plasma are minimal, and therefore, less absorption of the probe beam is expected.

In Ref (62), a linear correlation was observed between the 532 nm probe beam

absorption and the temporal profile of the electron number density at each similar

temporal delay. Temporal profiles of the electron number density have not yet been

obtained in this work but an integrated estimate based on the Stark broadening of selected

atomic emission lines is of the order of 1016cm-3. In this regime, the plasma frequency Vp,

as calculated from equation [4-1](64)

v =8.9*103n05
e [4-1]

where ne is the electron number density, is of the order of 1012 Hz, which is significantly

lower than the frequencies of the 532 nm (5.656 x 1014 Hz) and 1064 nm (2.828 x 1014

Hz) probe beams. In this case, reflection by free electrons and Thompson scattering

cannot be neglected. However, the plasma frequency is close enough to the probe beam

frequencies to allow significant absorption of the probe beams by the plasma, since in

fact, ne used in the above calculation in this work is both space and time integrated and

could have higher values over the plasma lifetime. Therefore, even though scattering

effects by the free electrons can not be neglected, the temporal behavior of the electron

number density during the plasma lifetime can be inferred from the absorption profile.

The theoretical absorption cross-section of the 532 nm beam in fully ionized plasma can

be employed to obtain numerical values of the time-depended electron number density. In

this sense, the absorption measurements provide a convenient way to make time resolved

measurements of the short-lived microchip laser-induced plasma over time scales not

easily attainable using electronic gated detectors. Because the time interval between the







57


pump and probe beam can be measured using appropriately positioned photodiodes and

an oscilloscope, measurements obtained by this approach might be more precise than

those obtained using electronic gated detectors, especially for ps and sub-ns pulses.

Emission Temporal Profile

In Figure 4-4, the emission profile of the plasma induced on a copper target is

present. It can be seen that plasma initiation begins almost simultaneously with the

excitation laser pulse and has a FWHM of approximately 1.5 ns. Accurate measurement

of the time relationship between the laser pulse and the emission is important in

application areas such as single particle detection (an on-going and future direction in this

laboratory).





PCL pulse
S075- Cu 327-nm
075


050- 1.5ns
E

025

0
0 oo00


-0 25
2 4 6 8
Time (ns)



Figure 4-4 Radiative temporal behavior of the laser-induced plasma.

Different targets were investigated but plasma durations beyond 4 ns (FWHM) have not

been measured. The present work was initiated with a 7 aJ per pulse microchip laser. In

that work, the plasma duration was of the order of 0.8-1.5 ns. It is interesting to note that

with approximately 8 times increase in pulse energy, the emission temporal profile does









not change proportionally. It is expected that these time scales are determined by the

properties of these lasers, such as the pulse duration, which in part controls the processes

of plasma formation and of energy transfer within the plasma, as well as the radiative

properties of the atoms whose emission is observed.

The transient nature of laser plasmas requires that, in analytical applications, the

observation of the emission is delayed with respect to the laser pulse. Even though, this

introduces further instrumentation and complexity, a temporal window is normally used

where the background continuum is minimal with respect to the line emission. A

consequence of the short plasma duration as observed in the case of the microchip lasers

is that, such gated measurements are not as feasible and necessary as with microsecond

plasmas. However, because the continuum emission is low compared to other laser types,

both qualitative and quantitative work with the microchip have been carried out without

any gating and analytical figures of merit comparable to those reported for conventional

laser sources have resulted. For instance, detection of Mo, Si, and Mn in low alloy steel

samples resulted in detection limits of 100 ppm or lower with a non-intensified, non-

gated detector. These studies will be discussed in Chapter 5.

PCL Plasma Diagnostics by Means of Electrical Signal Measurements

As part of the diagnostic measurements, a thin tungsten wire probe (100 [tm by

0.25 cm) was placed as close as possible to the substrate on which the plasma was

formed. The probe was connected to an oscilloscope and a voltage pulse was measured

whenever the plasma was formed. Depending on whether the probe was biased positively

or negatively with respect to the target, a pulse resulted due to collection of plasma

electrons or positive ions. Only the negative (electron) current will be briefly discussed

here.










A typical electron pulse collected during microchip laser ablation of copper is

shown in Figure 4-5. The widths of these current pulses observed are in the 4-6 ns range,

with both widths and peak amplitudes increasing with increasing bias voltage. It is

important to note that the temporal FWHM of the Cu emission is less than the FWHM of

the current pulse, which could extend beyond 20-ns depending on the bias.


0-




-50-


E 2V

-100
3V


-150-

0 10 20 30
Time (ns)

Figure 4-5 Characteristic electron pulse collected during microchip laser ablation of
copper substrate at 50 pJ. Probe bias voltages are indicated on the curves.

The voltage bias was gradually increased until further increase in bias did not result

in an increase in probe signal. At this point, the area under each voltage pulse was used to

estimate the charge on the probe. From Figure 4-6 (top), it is seen that as the probe bias

voltage was increased, the charge on the probe reached a limiting value. However, the

fraction of the total electrons in the LIBS plasma actually collected is not known, and so

charge on the probe does not necessarily represent the total number of charges in the

plasma. A variety of probe configurations are currently being evaluated in an effort to

determine the efficiency of extraction of plasma electrons and the proper correction









factors to the limiting value of number of electrons extracted which can be converted to

electron number density by dividing by the plasma volume (estimated from photographic

images). This value can then be compared with the electron number density obtained

from the width due to Stark broadening of the LIBS emission lines. The line width

measurement, in turn, must be corrected for the finite resolution of the spectrometer. It

can be seen that the systematic errors in the two techniques are expected to be in opposite

directions: incomplete probe collection will give low values of electron number density,

while using observed line widths without correcting for instrumental broadening will

yield values that are too high. It is encouraging that even at the current stage of the work,

the two estimates of electron number density agree within an order of magnitude (1015

cm-3 from electric probes and 2*1016 cm-3 from line broadening).

Probe current observations may also provide another insight into plasma processes.

A study was made of the variation of probe current with laser irradiance (W cm-2).

Studies in the literature have documented the expected dependence for conventional

(high pulse energy) LIBS, in which an initial linear rise in the probe current eventually

reaches a constant limiting value(65). This is explained as saturation due to plasma

screening of the laser pulse. A study of the variation of probe current with irradiance for

the microchip laser showed no sign of such a plateau, but rather, there was a rate of

increase in probe current that became larger with higher irradiance (Figure 4-6).

Therefore plasma shielding might not yet be effective. Of course the minimal absorption

of the probe beam by the LIP, discussed earlier in this work, might also suggest minimal

shielding of the laser pulse by the pre-formed plasma.



































0 2 4 6 8 10 12 14 16 18 20
Voltage bias (V)


545
< g "


0 6 12 1l 24
LASER INTENSIlTY (1O 0 Wemn)


0 2 4 6 8 10 12 14

Irradiance(xl 010 Wcm-2)


16 18 20


Figure 4-6 Variation of probe current with bias voltage (top) and laser irradiance
(bottom). The inset is a curve by a similar experimental set up by Isaac et
al.(65) showing an initial rise of probe current which plateaus at higher
irradiance.


The probe current density, J (A/cm2), showed a power law dependence on the laser


irradiance, I (W/cm2). That is Ja I" (66), where n is an integer representing the number of


5 F-









absorbed photons such that nhv is approximately equal to or larger than the work function

of the material (h is the Planck's constant, and v is the frequency of the light). In this

study the estimated value of n was 1.41 and hence nhv is approximately 1.65 eV which is

less than the work function of copper (4.7 eV), the target used in this work. It is inferred

from this that multi-photon surface photoelectric effects do not contribute significantly to

the charge on the probe and that the signal on the probe can be considered as

predominantly resulting the plasma.

Breakdown Threshold

High density plasmas with extremely sharp density gradients such as those

encountered in LIBS, are currently of great interest particularly from the point of view of

generating ultra-short x-rays pulses(67, 68). Laser-induced plasmas are also employed in

ignition processes(69). In such situations, it is essential that the breakdown laser fluence

is well characterized. Such diagnostics offer a better way to understand fluctuations in the

spark energy and hence the intensity of the emission signal in application involving

LIBS.

The concept of breakdown threshold can be defined in several ways depending on

the method used to study it. One method used is based on a pump-probe set up and is

based on the assumption that, when the plasma threshold is exceeded, a dense plasma is

formed, which causes a distinct change in the optical reflectivity of the plasma(68).

Laser-induced breakdown is a probabilistic process(70). The energy density required to

induce breakdown in a gas, for instance, is strongly depended on gas pressure and can

vary by more than a factor of two(69). Other authors described breakdown threshold as

the number of laser pulses producing plasmas divided by the number of pulses used for

each measurement(69). In another study, Milan and Lasema defined the breakdown









threshold as the minimum laser fluence needed to detect an emission signal from the

ablated material(71). The breakdown threshold reported in this work was estimated as the

minimum irradiance or fluence needed to produce an emission S/N of at least 3. Table 4-

1 shows the threshold values calculated for the materials used -silicon wafer, silicon

dioxide pellets, fused silica and steel. The emission of the Si atomic line at 251.6 nm was

monitored in all the targets except in the steel target where Cr (I) at 425.44 nm was used.

As Table 4-1 shows, plasma breakdown thresholds can vary significantly among

different targets for the same laser parameters and experimental conditions. This has

consequences in the application of the LIBS plasma for chemical analysis since the

relative strength of the emission lines and the background continuum are affected. It is

important to note that significant plasma emission is obtained at low laser energies. Pulse

energies of 70 mJ in colloids(72), 75 mJ in glass(73), 300 0pJ on silicon wafers(71), and

170 mJ on aluminum(74) were required for various focusing conditions by other workers

to overcome the breakdown threshold. In our experiments, we employed tight focusing of

the laser beam which allowed us to reach the breakdown threshold while staying at low

pulse energies.

Table 4-1 Plasma breakdown threshold measured for different targets. Silicon 251.6 nm
line was monitored for all targets except for steel where Cr 425.43 nm was
used.
Material Line used (nm) Threshold Threshold fluence
irradiance (Jcm-2)
(GWcm-2)
Si wafer Si,251.6 11 5.5
Si02 (pressed pellet) Si,251.6 19.8 10
Fused Silica Si,251.6 127.2 64
Steel Cr,425.43 7 3.5









The focal length of the lens used in focusing a laser beam has a considerable effect

on the breakdown probability. For example, for a Q-switched laser operating in a single

longitudinal mode (as used in this study), the photon flux, Fph (in photons/cm2s) is given

by equation 4-2

FPh = P Y h (4-2)

where Pw is the laser power (W), r is the focal spot radius, c is the speed of light and h is

the Planck's constant and
2A f
r = (4-3)
zr d
wherefis the focal length of the lens and dis the beam diameter.

It can be shown from equations (4-2) and (4-3) that a short focal length lens results

in a much smaller focal volume, a high power density, a higher photon flux and a

stronger electric field. The higher values of these parameters ensure the production of

initial electrons leading to the electron cascading process(67, 75). The consequences of

such tight focusing will be discussed later in this work.

Other important factors to consider are the pulse duration and surface properties of

the target. For shorter pulses in the ps to fs range, there is reduction in energy threshold

for breakdown(75). Table 4-1 also shows the effect of target surface properties. The

results show that the breakdown threshold on a pellet of silicon dioxide powder was

nearly twice that observed for the silicon wafer with a smooth surface. In quantitative

work with the microchip laser, the LOD for such powder materials were found to be 10 to

100 times poorer than that obtained for the same species in targets with much more

uniform surface.









The Focusing Challenge

Laser plasmas are known to be highly dependent on the laser fluence (energy/area)

at the surface and measured parameters can vary significantly, even for a single lens. The

low pulse energies of microchip lasers present another demand on the choice of focusing

optics. In this study, a microscope objective with a 1.7 mm working distance was used to

focus the laser beam onto the target. The target was placed such that the focal spot

diameter was of the order of 8 to 10 atm, providing irradiances ranging from -27 to -190

GW/cm2 for the 7 PJ/pulse microchip and the 50 PJ/pulse powerchip laser. Tight focusing

to obtain such high irradiances is important to initiate plasma formation. A consequence

of this is that the plasma behavior and its physical properties are extremely sensitive to

the distance of the target from the focusing lens. In order to show the effect of the

focusing conditions on the plasma, the objective which was mounted on micrometer stage

was moved toward or away from the target in 0.25 mm increments. The results of such an

experiment can be understood in terms of spot size and fluence; however, only a

qualitative treatment will be provided here. Plasma images were taken with a CCD

camera; line emission with a spectrometer and emission lifetime (FWHM) was measured

using a MCP/PMT, photodiodes and an oscilloscope. In Figure 4-6a, the emission

lifetime (FWHM) is presented as a function of the focusing distance. When the laser was

focused behind the target (i.e. d<17 mm), performance of the laser in initiating a

breakdown on the target was poor. The plasma lifetime increases substantially when the

laser was focused above the target (d>17 mm) and then it began to decrease to levels

comparable to the duration of the laser pulse as d increased to 19 mm and longer. In

Figure 4-6b, the integrated emission intensity together with the S/B ratio at these

distances were measured. Both parameters followed the pattern observed for the lifetime









measurements above. Figure 4-7 shows the digital images of the plasma at different

focusing distance. In Figure 4-7a, the camera was positioned approximately 450 to the

direction the laser beam while in Fig. 4-7b, the camera position was perpendicular to the

laser beam. The plasma physical dimensions also showed significant sensitivity to the

focusing conditions, as did the emission time profile and intensity. For the target used in

this work, the maximum plasma height from target surface measured was 100 [tm;

smaller and slightly larger plasmas have been observed on other targets at the same

conditions.

In other cases where the lens-to-sample distance have been varied in such a

manner, plasma parameters such as intensity and size attained higher values for both

positive and negative defocusing distances(76). Positive defocusing refers to focusing

above the sample surface and negative defocusing refers to focusing behind the sample.

In this work, positive defocusing produced higher values for all parameters measured.

The target position for maximum plasma intensity also produced the minimum focal spot

diameter (8 to 10 jam in most cases) resulting in higher irradiances. Such strong

dependence of the plasma properties on focusing places a demand on the accurate

positioning of the target in subsequent experiments in order to obtain reproducible data.

Other normal lenses with long focal lengths and working distances are being investigated

in order to find a suitable compromise between a higher irradiance and larger working

volume.

LIBS plasmas are known to be inhomogeneous in temperature, electron number

density and emission intensity(77). Ideally, LIBS spectra are to be observed with a

narrow slit width in order to obtain good spectral resolution. The plasma, however,









1.8-

1.6-

1.4-

1.2-

1.0-

0.8-

0.6-


17.0 17.5 18.0 18.5 19.0 19.5


Distance from objective (mm)


1000





100 -



0)
0


Distance (mm)


Figure 4-6 Effect of focusing on plasma characteristics. Variation of (top) plasma lifetime
and (bottom) signal to background ratio, S/B, with target position from the
focusing objective.












d


a.


400 um


S--


Figure 4-7 Photographic images of the LIP. The camera was positioned at approximately
(a) 45 and )b)90 to the direction of propagation of the laser pulse. The laser
beam is coming from the left-hand side.









expands rapidly immediately following formation and hence only a small amount of light

reaches the detector. Since the distribution of species in the plasma is non-uniform, the

fraction of light that is collected must be constant for spectral lines of all species in order

that the spectral information will be representative of the material on which the plasma

was formed. In the case of microchip laser plasmas, the small size of the plasma

minimizes this spatial inhomogeneity since in most cases, the plasma image size is

smaller than the slit width. The challenge is that spatially resolved data are difficult to

obtain. In the absence of both time- and space-resolved information, concepts such as

local thermodynamic equilibrium lose their significance since these have a temporal and

spatial components.

Plasma Temperature Measurements

Temperature is an important parameter of plasmas that has been studied for

decades, and continues to be studied even for conventional laser systems, because

temperature controls ionization processes in the plasma and the composition of the

emission spectrum. A critical assumption made in the construction of LIBS calibration

curves, where intensity ratios are used, is that the plasma is in a state of local

thermodynamic equilibrium. In order to ascertain this condition, accurate determination

of the plasma temperature and electron number density is vital. In most cases, spatially

and time-resolved measurements provide a better picture of the condition of the plasma.

Even though such measurements have been difficult with the microchip lasers due to the

small size and short lifetime of the plasma, space and time-integrated measurements will

be presented as a preliminary characterization of the plasma. The intensities were

averaged over the entire time history of the entire emitting plume. Boltzmann plots (78)

were used to estimate the plasma temperature and it followed the expected linear









behavior. Figure 4-8 is a sample plot using selected iron lines from plasma formed on

iron foil. Temperatures obtained were similar for a set of metallic targets (Cu, Cd, Pb) ~

10,000 K + 300 K. Iron and silicon yielded a significantly higher temperature, 11,200 K

and 13,700 respectfully, 200 K in either case. These measurements will be useful both

in validating a first principle model and in estimating the performance of the microchip

laser LIBS.


3-


2-
A AIlz2
1 B AI2g4)
Ln A/B
0-


-1-


-2- ,2

-2 -1 0 1 2
E,-E2 (eV)

Figure 4-8 Boltzmann plot with selected iron lines. El and E2 are upper energy levels of
line 1 and 2 respectfully.

Conclusions

The feasibility of a LIBS system based on the microchip laser, the ablation

properties and the analytical performance of the microchip laser in both qualitative and

quantitative application have been demonstrated in other sections of this work. Using a

pump-probe diagnostic scheme, this chapter further characterized the laser-induced

plasma at sub-ns time scale. The plasma showed a maximum absorption approximately

1.2 ns following the laser pulse and became almost transparent at times larger than 4 ns.









In spite of the eight times increase in pulse energy, the temporal profile of the plasma is

similar to that observed for the case of the microchip laser plasma at lower energy. To

fully characterize these lasers, a detailed time-dependent study of the plasma in both

cases is necessary. Lower pulse energies require that the laser beam be focused tightly to

obtain high irradiances in order to overcome the plasma breakdown threshold on most

targets making the plasma properties extremely sensitive to focusing conditions. A study

of the electrical properties of the plasma together with the absorption measurements

indicated that plasma shielding is minimal with these laser types compared to lasers

typically used in LIBS.














CHAPTER 5
TRACE METAL ANALYSIS BY MICROCHIP LASER-INDUCED BREAKDOWN
SPECTROSCOPY

Summary

The development of a compact laser-induced breakdown spectroscopy (LIBS)

system will increase the possibilities of applying the technique in industrial process

monitoring. In this chapter, the quantification of elemental composition of several

matrices using a higher power microchip ("powerchip") laser was undertaken. A

prototype setup for real time, in situ quantification of trace metals in steel alloys by

microchip laser LIBS was investigated as a means of enhancing the applicability of the

LIBS technique to process monitoring in the steelmaking industry. The performance of

the LIBS technique based on a microchip laser and a portable non-intensified, non-gated

detector for elemental quantification was evaluated and compared to that obtained using

an intensified detector. Calibrations were achieved for Cr, Mo, Ni, Mn and Si in steel

with linear regression coefficients between 0.98-0.99 and limits of detection below 100

ppm in most cases, but the performance in non-metallic samples was marginal.

Introduction

Laser-induced breakdown spectroscopy (LIBS) is exhibits certain problems as a

quantitative analytical tool. Difficulties presented by various matrix effects, poor

accuracy and precision limit the performance of LIBS in quantitative analysis. Recently,

the capacity of LIBS for quantitative elemental analysis has been demonstrated in









numerous fields: environment; metallurgy; mining, etc(32). Applications in the

pharmaceutical sector have also appeared recently ((79, 80).

As part of the preliminary investigation described in Chapter 2, an assessment of

the analytical capability of the microchip laser LIBS was carried out. The LIBS system

based on that setup was characterized by a relatively low sensitivity in the detection of

magnesium in a graphite matrix (20). The aim of this chapter is to assess the feasibility of

using a higher power microchip laser (also referred to as 'Powerchip') LIBS for the

quantitative analysis of trace elements. Matrices used include low alloy steel samples,

silicon dioxide (washed sand) and graphite. Steel particularly was chosen because in

recent years, quantitative analysis of steels by LIBS have been performed successfully by

several authors ((36) achieving good figures of merit. Therefore a comparison of the

performance of the microchip laser LIBS to a number of previous studies which used

more conventional experimental arrangements can be made. Elements of interest in the

steel work are Cr, Mn, Mo, Ni, and Si while Mg, Si, and Fe will also be determined in

sand and graphite. Graphite was also chosen as a matrix to study because LIBS of

graphite has several applications: For instance, carbon thin films, due to their diamond-

like properties, have been attracting intense theoretical and experimental investigations

(81). LIBS of graphite is also important for fullerene synthesis (82). The results obtained

using a portable spectrometer as the detector were compared with those obtained using a

conventional intensified CCD array spectrometer.

Experimental

A schematic diagram of the quantitative powerchip LIBS system is shown in

Figure 5-1. It consists of four primary components: A powerchip laser, a focusing









microscope objective, a fiber optic and spectrometers. The laser beam was focused by a

50X microscope objective unto various targets as described in Chapter 3.

Plasma emission was collected with a 600 |tm diameter fiber optic coupled to a

high resolution miniature fiber optic spectrometer (HR 2000, Ocean Optics Inc., USA)

with 0.03nm FWHM spectral resolution and a grating with 2400 grooves mm-1. No

optics were used to collect the plasma emission. The fiber tip was simply placed within a

few mm of the plasma. The data were collected and processed by the OOI Base32

software (Ocean Optics, Inc.) running on a laptop computer. The experiments were

repeated with a gated, intensified CCD spectrometer, SpectroPro -500i (Acton Research

Corp.) with 0.02 nm spectral resolution and a 40 rm entrance slit operating in a free

running (non-gated) mode. For these experiments, spectral segments of 8 nm for the

plasma emission were recorded using a grating with 2400 grooves mm-1. Spectral data

were collected and processed with Winspec 32 software running in a desktop computer.

Pcwer supply







targetholder Pulst gnsrator





Potble L ipto co ut
spectrometer or
Intensified CCD

Figure 5-1 Quantitative LIBS experimental setup.









Samples analyzed were steel alloys (cast iron spectrometric reference materials)

and graphite and silicon dioxide each spiked with varying concentrations of iron,

magnesium, and aluminum. These samples were mixed and presented as pressed pellets.

Results and Discussion

Quantitative Analysis of Low Alloy Steel

In Table 5-1, the composition of the steel samples and their respective

concentrations are shown. Figure 5-2a shows a typical powerchip laser spectrum of steel

which is spectrally rich due to the complexity of the matrix. When a narrow portion of

this spectrum is screened, distinct emission lines belonging to various elements can be

identified. For example, Figure 5-2b is an 8 nm spectral window showing the overlap of a

pure Fe spectrum and that obtained from a steel sample with Cr lines at 425.44 nm and

427.48 nm.

Table 5-1 Composition of the steel standards. Concentrations are expressed as % weight.
Sample C Cr Cu Fe Mn Mo Ni Si
CKD/232 1.930 1.190 0.038 91.859 0.090 0.850 0.026 3.500
CKD/233 2.120 1.920 0.110 92.184 0.260 0.023 0.052 2.590
CKD/234 2.460 0.460 0.275 91.969 1.390 0.210 0.305 2.020
CKD/235 2.730 0.410 0.157 91.772 1.860 0.450 0.195 0.920
CKD/236 2.850 0.050 0.215 91.814 1.080 0.064 1.774 1.650
CKD/237 3.030 0.150 0.545 92.135 0.130 1.340 0.700 1.200
CKD/238 3.360 0.018 0.920 91.897 0.480 0.115 1.110 1.550
CKD/239 4.150 0.052 0.085 91.877 0.760 0.007 2.420 0.270

Data analysis of LIBS spectra is an aspect of significant importance in order to

demonstrate the suitability of the method as compared to other conventional methods.

This requires skill in the selection of optimum wavelength and the establishment of the

most accurate and robust calibration curves. For this reason, the stability of the signal

during laser sampling was characterized first. One of the main noise contributions

influencing the response stability is the fluctuation noise due to random changes in the










plasma intensity from pulse-to-pulse (83). Typically, the shot-to-shot relative standard

deviation during LIBS analysis can be up to 20%. A significant part of this variability is

due to the fact that a single laser shot ablates only a very small fraction of a relatively

heterogeneous sample. One technique used to reduce this variability is normalization of

the emission intensities to that of a carefully selected internal standard. In this work, peak

intensities were normalized to the intensity of the background continuum emission or to a

suitably selected Fe emission line. Table 5-2 shows the emission lines from the elements

of interest and the internal standards employed in the calibration curves. The

normalization lines were carefully selected taking into account the features that

characterize a suitable internal standard while avoiding the interference of emission lines

in such a complex steel matrix, previously studied by other authors (84).


(a) (b)

1800- 1600 Pure Fe (0% Cr)
1600- 1400--Steel (1.92% Cr)
1400- Cr 1, 425 43
1200
1200- Fe 425 01 Fe 1, 426 04 Cr I, 427 48
10001000
a 800- 800-
600- 600
400oo 400
200- 200

360 380 400 420 440 422 424 426 428
422 424 426 428
Wavelength /nm
Wavelength (nm)

Figure 5-2 (a) Spectrum obtained from microchip laser-induced plasma on steel and (b)
superposition of 8 nm spectral window for a pure Fe standard and that of a
steel sample containing 1.92% Cr. Spectrometer HR 2000 was used with
integration time of 1 s.

Figure 5-3 is a plot showing the variation of the net emission intensity and the

intensity normalized to the background or an Fe emission line. It can be seen that the

shot-to-shot reproducibility improves by using both approaches. The means of handling









the spectral data using the background continuum or a line belonging to the matrix is

known as internal standardization and has the potential to significantly improve both

precision and accuracy. With the data in Figure 5-3, the RSD for curves a, b, and c are

respectively 1.6%, 6.3% and 2.5%. With the microchip laser, fluctuation in laser power

stability is minimal (20). Therefore, the variation in the signal in the case of the net

intensity is ascribed to changes in the target surface angle due to rotation and translation

described previously. Again, although the sample was always in continuous rotation, the

microplasma created at such a high repetition rate could be partially hidden in the crater

depth, affecting the emission intensity in a random fashion from shot to shot.

Table 5-2 Selection of spectral lines and internal standards. In some instances, the
background continuum (Bgd) in the vicinity of the element line was used as
internal standard.
X (nm) X (nm) Fe normalization
Emission line
Cr(I) 425.43 nm Fe(I) 425.07
Bgd, 425.68
Mn(I) 403.07 nm Fe(I) 400.52
Mo(I) 386.41 nm Fe(I) 387.25
Ni(I) 341.47 nm Fe(I) 342.71
Si(I) 288.16 nm Fe(I) 287.41

Another way of improving precision in LIBS is shot averaging. The experiments

were carried out at a pulse repetition frequency of 1 kHz, and an acquisition time of 1000

ms, which effectively adds up the emission from 1000 sequential plasmas. 5-4 shows

two curves: a) the fluctuation of the emission intensity of Mn (I) 403.1 nm, where each

point represents the sum of 1000 shots; and b) the standard deviation of this signal

obtained by averaging the collected data points progressively (i.e. moving average of

previous data points).































0.8 -


3 (a)
o- \ -o- -_ oo_ ooo_


S(b) b









(c)
^ -^ --"^ o-^ O'-0-n -13-13 -0-0'-


0 5 10 15 20 25
Data number


Figure 5-3 Shot-to-shot fluctuations in LIBS signal intensity: (a) Intensity of Cr
normalized to the background continuum emission; (b) Net intensity of Cr line
and (c) intensity of Cr normalized to an Fe line.


-22

-20

-18

-16

-14
SD
-12

-10

-8

-6


4 6 8 10 12 14 16 18 20 22 24 26 28
Data number



Figure 5-4 Reduction of noise by signal averaging: (a) Fluctuation of the emission
intensity of Mn 403.1 nm and (b) variation of the standard deviation (in
intensity units) of the signal by progressive averaging of the collected data
points.


r-
-250


-225


-200


S13-13 (a)



b- 0


(b)



..-
''----*









It was observed among most of the targets studied that the fluctuations in the initial

collected data points were generally higher than the latter points, unless special care was

taken to clean the samples before analysis. After exposure of the target surface to several

laser pulses, the variation in the emission intensities was low and more uniform. The

initial fluctuations can be partly due to target surface impurities. As mentioned in

previous papers (85), the samples need to be exposed to a certain number of preparatory

laser shots before performing the measurements in order to eliminate any surface

impurities and also to ensure that the surface of the target is representative of the bulk

composition. In the steel analysis described in the following section, 10 surface cleaning

data points and 15 data points for data acquisition (all integrated over 1000 ms) were fixed

as the best acquisition conditions to minimize signal fluctuations. This capability of LIBS

where the focused laser pulse cleans the target surface offers a great advantage over other

analytical techniques. For example, both LIBS and spark emission spectrometry are

based on the same technique. However, spark emission technique requires samples with

well ground and polished surfaces; LIBS does not because the ablation pulse is capable of

the surface treatment prior to data collection. The high spatial resolution and repetition

frequency of microchip lasers even makes surface cleaning faster and more effective.

Figure 5-5shows the calibration curve for Mo using the compact spectrometer.

Similar curves were obtained for Cr, Mn and Mo were correlation coefficient of 0.98 or

better and relative standard deviation of 3.6, 6.3, and 5.5 % respectively. The RSD values

were obtained with the samples with the lowest concentration of the analyzed element

(see Table 5-1).










0.30


0.25
E

0.20
00
LL
E 0.15

CO
S0.10
0

0.05


0.00-

0.000 0.004 0.008 0.012 0.016
Conc. of Mo/ conc. of Fe
Figure 5-5 Calibration curve for Mo using the compact spectrometer, HR 2000. The lines
used are Mo (I) 386.41 nm normalized to Fe (I) 387.25 nm

Microchip LIBS with Non-intensified versus Intensified CCD Spectrometers

Quantitative analysis of the same steel samples was performed using a conventional

spectrometer fitted with an intensified CCD as detector. Figure 5-6shows an 8 nm

spectral region of 15 averaged data points using a), SpectraPro 500 Intensified

spectrometer which allows 8 nm acquisition window and b), HR 2000 portable non-

intensified spectrometer which allows 90 nm acquisition window. The acquisition data

parameters for both experiments were the same: a free running mode for both detectors

and each data point is an average of 1000 laser shots. Resolution is slightly better for the

ICCD than the portable spectrometer except that a few spectral details appear in the

spectra obtained with the portable spectrometer for the same sample. For instance, the

line 426.42 nm, appearing at the shoulder of the Fe 426.04 nm does not appear in the







81


spectrum with the ICCD. In the data acquisition mode employed in this work, the most

significant difference between the two detection systems is the detector. As expected, the

signal and background in the intensified spectrometer were much higher than when the

non-intensified CCD was used. The intensified CCD spectrometer was capable of

detecting more elements in the steel samples than the portable one because of the

flexibility in the selection of wavelength windows. On the other hand, the narrow

spectral window provided by this spectrometer presents a problem in performing a real-

time multielemental analysis. Figure 5-7 shows the calibration curves for Ni and Si with

the intensified CCD system. These elements could not be detected with the portable CCD

spectrometer due to strong interference from other transitions at the wavelengths of

interest.

Copper (Cu I, 360.2 nm) and carbon (227.7 nm) were also identified in the steel

samples using the portable spectrometer and the iCCD system, respectively; even though

these elements were not quantified.



2600000
Steel (1 92% Cr) 1600- Pure Fe (0% Cr) Fe 142718
2400000-- Pure Fe (0% Cr) S teel (1 92% Cr)
1400
Fe I 1462 04
S2200000- 1200-
2 'Cr 142543
2000000- 1000 Fe 142501 C42748
C 800-
1800000-
600-
1600000- 400
400
1400000 200 -_
422 424 426 428 422 424 426 428
Wavelength (nm) Wavelength (nm)

Figure 5-6 Spectra obtained on iron foil and steel using (a) an intensified CCD and (b) a
non-intensified CCD spectrometers.


























0.000 0.005 0.010 0.015
Conc. Si / Conc.Fe


0.020 0.025


0.12


0.04-



0.00- /


0.000 0.005 0.010 0.015 0.020 0.025 0.030

Con. Ni / onc.Fe
Figure 5-7 Calibration curves using the intensified CCD spectrometer. (Top) Ni (I)
341.47 nm normalized to Fe (I) 342.71 nm and (bottom) Si (I) 288.16 nm
normalized to Fe (I) 287.41 nm.

Table 5-3 summarizes the limits of detection (LOD) for the species studied using

the two spectrometers. The LOD was estimated as three times the standard deviation of

the background signal divided by the slope of the calibration curve (86). The highlighted

values are those obtained using the non-intensified portable spectrometer. For Cr, the









LOD obtained with the portable, non-intensified spectrometer is lower than that obtained

with the ICCD but the data obtained for Mo and Mn are comparable for the two

spectrometers. Relative standard deviation (RSD) of the two detection systems was

comparable except that it was several times better in the case of Mn with the ICCD than

the non-intensified CCD detector. Earlier work(87, 88) showed that the signals obtained

with the ICCD were usually at least an order of magnitude higher, the SNR is typically

three times better and the LOD an order of magnitude lower than values for the non-

intensified system. It is not clear at the moment the reason for the comparable sensitivity

for the two detectors with the microchip laser systems. It should be noted that the

intensified CCD used in this work was operated in a non-triggered, non gated mode. In

the earlier work referred to above, the detector was operated with gate delay with respect

to the plasma-initiating laser pulse. Generally, LIBS data conventionally collected this

way have higher signal to background and sensitivity than those obtained in the mode

used in this work. The conclusion from the above discussion is that, with regards to

overall cost, field deployability, speed of data acquisition and processing, microchip laser

LIBS with portable non-intensified non-gated detectors offers advantages over traditional

systems.

Performance in Other Matrices

The performance of the microchip laser LIBS to detect and quantify elemental

composition in pellet samples was also investigated. Figure 5-8 is a spectrum showing

iron emission lines in silicon dioxide. Figure 5-9 shows the variation of signal with

element concentration for iron and magnesium. The samples were in a powder form and

presented as pressed pellets after blending in a mixer. Samples of this nature are more









Table 5-3 Analytical figures of merit of the elements analyzed using both the portable
high resolution spectrometer and the intensified spectrometer as detector. SLR
denotes studied linear range. The data in bold were obtained for the portable,
non-intensified spectrometer
Emission Line SLR RSD LOD
(%) (%) (%)
Cr(I) 425.43 nm 0.018-1.92 4.6 0.01
3.6 0.003
Mn(I) 403.1 nm 0.09-1.86 1.2 0.003
6.3 0.004
Mo(I) 384.4 nm 0.007-1.34 5.2 0.008
5.5 0.009
Ni(I) 341.42 nm 0.052-2.42 1.3 0.009
Si (I) 288.16 nm 0.27-2.02 4.6 0.02

heterogeneous than the steel samples studied in this chapter, which have been

commercially blended to achieve acceptable homogeneity. Because the microchip laser

removes just ng to pg samples for analysis, it will be expected that poorer reproducibility

and lower correlation between element concentration and signal intensity will be obtained

from such samples. The bending of the calibration curves at higher concentrations,

especially in the case of Mg, might rather be due to matrix effects as well as self-reversal.

Ideally, transitions that are not coupled to ground state (i.e. non-resonance lines) should

be used to avoid this effect. However in this study, no suitable emission lines free of

interference from the matrix were available within the spectral window provided by the

spectrometer.

Even though for all the elements studied, the most sensitive lines within the

wavelength window provided by the spectrometer were used, detection limits (LODs)

were between 0.1 and 0.2%. These values are at least 100 times higher than what was

observed in the steel analysis described above. Several reasons could account for the

poorer LODs in these matrices. The most significant, perhaps, is the higher breakdown
















1500-
.6
Si 1, 243.52 Fe I
1000
(a)
500


230 240 250 260 270 280 290 300
Wavelength (nm)


Figure 5-8 Spectrum of silicon dioxide: (a) pure and (b) spiked with iron ore.

thresholds in these pellets compared to the steel targets. The higher breakdown thresholds

can be ascribed to the material morphology as well as the surface quality as these

determine the mechanisms of dissipation of laser energy in bulk solids (see Table 4-1).

Generally, the laser-induced spark on pure metals and alloys was larger in size and more

luminous than observed on pellets. In metals, the conduction band electrons absorb laser

energy and then dissipate it through the thermal conductivity via electron-phonon

collisions (20). As the metal character of the material decreases, the laser-matter

interaction becomes more complicated including multiphoton absorption, absorption on

structural defects, etc. Electron-lattice coupling also changes, affecting the efficiency of

energy transfer from laser-heated electrons to the material bulk. Equally important is the

surface quality of the target. The surface of the pellets is more grainy and loose than that

of metal samples. It is therefore easy for an aerosol to form above the sample surface

which blocks the emission from the collection lens. Again it is expected that more

material will be removed per laser shot in the pellets than in pure metallic samples. Much

less material is expected to contribute to plasma emission as discussed in Chapter 3,




Full Text

PAGE 1

MICROCHIP LASERS AS SOURCES FOR LASER-INDUCED BREAKDOWN SPECTROSCOPY: PLASMA CHARACTERISTICS AND ANALYTICAL PERFORMANCE By KWABENA AMPONSAH-MANAGER A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL OF THE UNIVERSITY OF FLOR IDA IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY UNIVERSITY OF FLORIDA 2005

PAGE 2

Copyright 2005 by Kwabena Amponsah-Manager

PAGE 3

This dissertation is dedicated to my mom, Mary, for her belief in me and constant encouragement.

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ACKNOWLEDGMENTS It has been a wonderful privilege to work under the mentorship of Prof. James D. Winefordner. I am grateful, and will always be, to him for opening up his laboratory for me to pursue my graduate studies. It was a risky decision to work with him, because, pathetically, I knew nothing in this area of science. However, the time spent under his guidance has been the most fruitful years of my life. I could never show my full gratitude to him for his friendship and advice. I thank Dr. Benjamin Smith, who made me enjoy the science of light. In fact, it was Bens patience and guidance that have brought me this far. Even when my plan of work or result did not make any sense, Ben had a uniquely mild way of letting me know how wrong I am. I do appreciate spectroscopy now, but it is all through my interaction with Ben Smith. Dr. Nicol Omenetto was a great help to me over the past four years. I always left his office with his dry-erase board crowded with stuff, sometimes more confused than before I went there. He made me know that it was not as simple as I think, and he was always right; I got to know this after our meetings. I am most grateful to him. I also thank Dr. Igor Gornushkin for many personal discussions and useful suggestions at group meetings and for the many times that he had to sacrifice his time to join me at work. Dr. David Hahn has been of great encouragement to me. I admire his enthusiasm for research. I got great research ideas from him though our quarterly meeting with him iv

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and Aerodyne Research Inc. I appreciate the times spent with Drs. Andrews Freedman and Jody Wormhoudt of Aerodyne Research, Inc. Their contributions were always invaluable. I would thank all the Winefordner/Harrison research group members for their friendship and support. Everyone brings some unique quality that makes the laboratory a great place to work. Some former group members that I cannot leave out include Drs. Tiffany Correll, Paige Eagan-Oxley, Kevin Turney and Elizabeth Hastings. I miss their friendship. I would like to acknowledge the help of Dr. Qian Li. At least one chapter in this thesis would not have been be possible without her assistance. I am really grateful to her. I thank Ms. Cristina Moreno-Lopez of the University of Malaga, Spain, who joined me on this research in the summer of 2004. The time spent with Cristina was remarkably fruitful and memorable. I made many sweet friends in Gainesville. I regret that space and time will not permit me to acknowledge them all by name. Nevertheless, I am thankful for the role every one of them played in my life and studies. I especially thank Kwame for his many sacrifices and Adjoa Otubea for her friendship and editorial comments. Needless to say, I am grateful, as always, to my family for their patience, prayers and encouragement. I am especially thankful to my mom for the pride and confidence she has in me. v

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TABLE OF CONTENTS page ACKNOWLEDGMENTS .................................................................................................iv LIST OF TABLES .............................................................................................................ix LIST OF FIGURES .............................................................................................................x ABSTRACT .....................................................................................................................xiv CHAPTER 1 INTRODUCTION TO LASER-INDUCED BREAKDOWN SPECTROSCOPY (LIBS)...........................................................................................................................1 Background...................................................................................................................2 LIBS Over the Years....................................................................................................3 Instrumental Challenges...............................................................................................5 Analytical Performance of LIBS................................................................................10 2 SOLID STATE PASSIVELY Q-SWITCHED MICROCHIP LASERS AS SOURCES FOR LASER-INDUCED BREAKDOWN SPECTROSCOPY..............13 Passive Q-switched Microchip and Lasers.................................................................14 Passive Q-switching............................................................................................14 The Microchip Laser...........................................................................................15 Design and Fabrication of Microchip lasers........................................................16 Materials and wavelengths Used in Microchip Lasers........................................16 Experimental Arrangement.........................................................................................18 Results and Discussion...............................................................................................19 Conclusion..................................................................................................................23 3 MICROCHIP LASER ABLATION OF METALS: INVESTIGATION OF THE ABLATION PROCESS IN VIEW OF ITS APPLICATION TO LASER-INDUCED BREAKDOWN SPECTROSCOPY........................................................24 Summary.....................................................................................................................24 Background.................................................................................................................25 Experimental...............................................................................................................27 Results and Discussion...............................................................................................28 vi

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The MCL and PCL as Microprobe Analyzers.....................................................28 Target Modification.............................................................................................31 Mass Removal.....................................................................................................33 Ablation Efficiency.............................................................................................36 Effect of Target Temperature on Mass Removal:...............................................42 Effect of Crater Depth and Laser Irradiance on Plasma Intensity and Composition.....................................................................................................44 Conclusion..................................................................................................................47 4 DIAGNOSTICS OF MICROCHIP LASER-INDUCED PLASMAS AS RELATED TO LASER-INDUCED BREAKDOWN SPECTROSCOPY................49 Summary.....................................................................................................................49 Theory.........................................................................................................................49 Experimental...............................................................................................................52 Result and Discussion.................................................................................................53 Absorption Properties of the microchip Laser-Induced Plasma..........................53 Emission Temporal Profile..................................................................................57 PCL Plasma Diagnostics by Means of Electrical Signal Measurements............58 Breakdown Threshold.........................................................................................62 The Focusing Challenge......................................................................................65 Plasma Temperature Measurements....................................................................69 Conclusions.................................................................................................................70 5 TRACE METAL ANALYSIS BY MICROCHIP LASER-INDUCED BREAKDOWN SPECTROSCOPY...........................................................................72 Summary.....................................................................................................................72 Introduction.................................................................................................................72 Experimental...............................................................................................................73 Results and Discussion...............................................................................................75 Quantitative Analysis of Low Alloy Steel...........................................................75 Microchip LIBS with Non-intensified versus Intensified CCD Spectrometers..80 Performance in Other Matrices...........................................................................83 Conclusions.................................................................................................................86 6 AIRBORNE PARTICLE DETECTION BY MICROCHIP LASER-INDUCED BREAKDOWN SPECTROSCOPY...........................................................................89 Introduction.................................................................................................................89 Review of Laser Spectroscopy Techniques for Aerosol Analysis..............................90 Experimental...............................................................................................................92 Results and Discussion...............................................................................................94 Dependence of Signal Intensity and Trigger Rate on Particle Size.....................99 Identification of Particles by Emission Signal..................................................102 Conclusion................................................................................................................105 vii

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7 CONCLUSION AND FUTURE WORK.................................................................107 Conclusion................................................................................................................107 Future Work..............................................................................................................109 LIST OF REFERENCES.................................................................................................111 BIOGRAPHICAL SKETCH...........................................................................................117 viii

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LIST OF TABLES Table page 1-1 Methods used for modifying the output of a laser...................................................11 1-2 Some laser systems that have been employed in LIBS ...........................................11 3-1 Laser-induced crater depth and diameter for a 500 ps microchip laser compared to that of 8 ns laser. Data in bold were obtained for the 8 ns laser..........................35 3-2 Ablation efficiency of 7 J microchip laser compared to values reported for conventional Nd: YAG lasers..................................................................................37 4-1 Plasma breakdown threshold measured for different targets. Silicon 251.6 nm line was monitored for all targets except for steel where Cr 425.43 nm was used...........................................................................................................................63 5-1 Composition of the steel standards. Concentrations are expressed as % weight.....75 5-2 Selection of spectral lines and internal standards. In some instances, the background continuum (Bgd) in the vicinity of the element line was used as internal standard.......................................................................................................77 5-3 Analytical figures of merit of the elements analyzed using both the portable high resolution spectrometer and the intensified spectrometer as detector. SLR denotes studied linear range. The data in bold were obtained for the portable, non-intensified spectrometer....................................................................................84 6-1 Common airborne particles and their respective size range.....................................92 6-2 Elemental concentration as percent by weight in some biological samples. Bg is Bacillus subtilis var. niger, a common simulant for Bacillus anthracis. In the case of oat, wheat and corn, it was fungal spores on these samples that were analyzed....................................................................................................................92 ix

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LIST OF FIGURES Figure page 1-1 LIBS experimental set up. FL-focusing lens; CLcollection lens.............................1 1-2 Schematic representation of the processes involved in plasma plume formation......3 1-3 Multimode laser: (a) and (b) A laser oscillating on an inhomogeneous transition with many modes above threshold; (c) Simultaneous oscillating modes in a laser cavity..........................................................................................................................7 1-4 Experimental arrangement for a mode-locked laser using an ultrasonic wave.........7 1-5 Optical set up for generating Q-switched pulses........................................................9 2-1 Schematic of a passively Q-switched laser system. The gain medium is usually Nd: YAG and the saturable absorber is Cr 4+ : YAG.................................................15 2-2 Microchip laser fabrication process.........................................................................17 2-3 LIBS setup with a 7J microchip laser. The collection of the plasma emission was done with or without the collection lens...........................................................19 2-4 Spectra of metal foils and silicon wafer obtained with the USB 2000 and the microchip laser. Integration time was 1 s.................................................................20 2-5 Spectra of metal foils obtained with the USB 2000 and the microchip laser. Integration time was 1 s...........................................................................................20 2-6 Scanning electron micrographs (SEM) images of crater produced by the microchip laser. D denotes mean crater diameter....................................................21 2-7 Cadmium spectrum obtained with the broadband spectrometer LIBS 2000+ and the microchip laser. (Top) Full acquisition window of the spectrometer; (Bottom) Segments showing identification of some Cd lines. Integration time was 1 s......................................................................................................................22 3-1 Powerchip laser micro-ablation of copper substrate showing: (left) the ablation scheme devised; and (right) single craters obtained at 1 kHz..................................29 3-2 Depth profiling of a thin film created on steel surface by the 50 J powerchip laser. (a) Spectra obtained from the coated and polished steel surface. x

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Integration time was 3 s (b) Time-dependent intensity distribution of the line from the coating and iron matrix..........................................................................32 3-3 Effect of the laser-induced crater as shown in the inter-crater spaces.....................33 3-4 Microchip laser-induced crater on cadmium foil showing the crater structure and droplet redeposition on surface................................................................................34 3-5 Dependence of crater radius and mass removed per laser shot on the melting point temperature (shown in parenthesis) and heat of fusion of the target. Mass removed were calculated based on the crater volume and the density of the material.....................................................................................................................34 3-6 Comparison of (a) 500 ps passive Q-switched powerchip-induced crater, and (b) crater induced by an 8 ns active Q-switched laser on a lead target..........................37 3-7 Variation of crater volume with laser energy for: (a) cadmium and (b) copper. The arrows indicate the points of the curve where different slopes begin...............38 3-8 Plasma emission intensities of cadmium and copper compared at different laser pulse energies. Integration time was 400 ms, with 5 spectra averaged (i.e. each spectrum is an accumlatiuon of 2000 spectra). Each data point represents the mean of 20 spectra....................................................................................................41 3-9 Ablation sensitivity (red line) and efficiency (black line) of Cd (top) and Cu (bottom) as a function of laser pulse energy............................................................42 3-10 Effect of target temperature on plasma composition and emission intensity. (a) is the background corrected emission intensity and (b) is the intensity normalized to Fe 400.52 nm line.................................................................................................43 3-11 Effect of laser-induced crater on plasma emission intensity....................................45 3-12 Effect of crater and laser energy on plasma composition: (a) Temporal dependence of the Zn-Cu ratio in brass when the plasma is created on the same spot. Integration time was 300 ms with 5 spectra averaged. (b) Effect of laser pulse energy on Zn-Cu intensity ratios. Each data point is the average of 30 spectra with an integration time of 300 ms and 5 spectra averaged.........................47 4-1 Spatial component of a laser plasma diagnostics.....................................................51 4-2 Plasma diagnostic experimental set up. GP-glass plate; M-mirror; PD-photodiode; T-target; L-collimating lens; PCL-powerchip laser. The collection lens & fiber coupler take the position of PD2 in emission measurements...............52 4-3 Fraction of probe beam absorbed by the LIP as a function of delay time. The inset is the temporal profiles of the 1064 and the 532 nm beams............................54 xi

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4-4 Radiative temporal behavior of the laser-induced plasma.......................................57 4-5 Characteristic electron pulse collected during microchip laser ablation of copper substrate at 50 J. Probe bias voltages are indicated on the curves........................59 4-6 Variation of probe current with bias voltage (top) and laser irradiance (bottom). The inset is a curve by a similar experimental set up by Isaac et al.(65) showing an initial rise of probe current which plateaus at higher irradiance.........................61 4-6 Effect of focusing on plasma characteristics. Variation of (top) plasma lifetime and (bottom) signal to background ratio, S/B, with target position from the focusing objective....................................................................................................67 4-7 Photographic images of the LIP. The camera was positioned at approximately (a) 45 o and )b)90 o to the direction of propagation of the laser pulse. The laser beam is coming from the left-hand side...................................................................68 4-8 Boltzmann plot with selected iron lines. E 1 and E 2 are upper energy levels of line 1 and 2 respectifully..........................................................................................70 5-1 Quantitative LIBS experimental setup.....................................................................74 5-2 (a) Spectrum obtained from microchip laser-induced plasma on steel and (b) superposition of 8 nm spectral window for a pure Fe standard and that of a steel sample containing 1.92% Cr. Spectrometer HR 2000 was used with integration time of 1 s.................................................................................................................76 5-3 Shot-to-shot fluctuations in LIBS signal intensity: (a) Intensity of Cr normalized to the background continuum emission; (b) Net intensity of Cr line and (c) intensity of Cr normalized to an Fe line...................................................................78 5-4 Reduction of noise by signal averaging: (a) Fluctuation of the emission intensity of Mn 403.1 nm and (b) variation of the standard deviation (in intensity units) of the signal by progressive averaging of the collected data points.............................78 5-5 Calibration curve for Mo using the compact spectrometer, HR 2000. The lines used are Mo (I) 386.41 nm normalized to Fe (I) 387.25 nm....................................80 5-6 Spectra obtained on iron foil and steel using (a) an intensified CCD and (b) a non-intensified CCD spectrometers.........................................................................81 5-7 Calibration curves using the intensified CCD spectrometer. (Top) Ni (I) 341.47 nm normalized to Fe (I) 342.71 nm and (bottom) Si (I) 288.16 nm normalized to Fe (I) 287.41 nm.......................................................................................................82 5-8 Spectrum of silicon dioxide: (a) pure and (b) spiked with iron ore.........................85 xii

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5-9 Calibration curves for (a) magnesium and (b) iron ore in sand (silicon dioxide). In (a), the signal is presented in form of intensity ratio of Mg (1) 285.2 nm to Si (I) 288.16 nm while in (b) the net intensity is used..................................................87 5-10 Effect of sample homogeneity on data reproducibility: (a) A mixture of iron ore and silicon dioxide blended for 5 min. and (b) sample blended for 10 min.............88 6-1 Single particle microchip LIBS setup......................................................................95 6-2 Intensity distribution of sparks on NaCl particles, 0.024% Na by weight..............96 6-3 Variation of trigger rate (fraction of laser pulses that produce sparks with signal at least 10 mV as a percentage of the total number of laser pulses fired). Concentrations are presented as mass % NaCl........................................................97 6-4 Variation of aerosol spark intensity with concentration. Data were obtained with a PMT. Concentrations are presented as mass % NaCl...........................................98 6-5 Variation of trigger rate with concentration: (Black) threshold set at -10 mV and (Red) threshold set at -40 mV. Concentrations are presented in mass % MgCl 2 ..........................................................................................................99 6-6 Photographs of sparks on MgCl 2 and CaCl 2 : (Top): Full laser energy in use, interference filter in front of camera removes 1064 nm light, (Bottom) Laser energy attenuated below breakdown threshold; scattered laser beam shows particle flow in the focal volume............................................................................100 6-7 LIBS spectra of solution containing 0.05% Ca presented as AlCl 3 .......................103 6-8 LIBS spectra of solution containing 0.15% Ca presented as CaCl 2 .......................103 6-9 LIBS spectra of an ICP grade standard solution containing 0.05% Na, 0.04% Ca and 0.027% Mg......................................................................................................104 6-10 Spectrum of solution containing 0.3% Cd.............................................................104 6-11 Signal dependence on concentration for Mg aerosol.............................................105 xiii

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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 MICROCHIP LASERS AS SOURCES FOR LASER-INDUCED BREAKDOWN SPECTROSCOPY: PLASMA CHARACTERISTICS AND ANALYTICAL PERFORMANCE By Kwabena Amponsah-Manager December 2005 Chair: James D. Winefordner Major Department: Chemistry Laser-induced breakdown spectroscopy (LIBS) is an analytical technique that has been given significant attention as a method for fast elemental analysis. Even though LIBS has many advantages over other analytical methods, size requirements have limited most applications to laboratory analysis. This project was set forth to investigate the possibility of employing all-solid-state diode-pumped miniature (microchip) lasers as sources of light for LIBS and to estimate the analytical performance of LIBS based on these systems. The study began with the diagnostics of the microchip laser-induced plasma. Plasma parameters such as size, temperature, electron number density and temporal behavior of the emission were studied using both traditional spectroscopy and CCD photography. The small plasma size (100 m above target surface) and short lifetime (1.5-2 ns) did not allow detailed spatial and temporal study of plasma by conventional xiv

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means. However, a pump-probe method based on an optical delay setup provided information about the absorption properties of the plasma on the sub-nanosecond time scale. Maximum absorption was measured 1.2 ns after the laser pulse while the plasma became almost transparent after 4 ns. The effect of both target properties and laser parameters on the ablation properties of the microchip laser was studied. Microchip lasers produce well-defined craters, which allow easy estimation of the mass removed per laser shot. The high spatial and depth resolution of the microchip laser ablation was employed in applications such as depth profiling and trace element analysis. Detection limits for Cr, Si, Ni, and Mo in steel alloys were 100 ppm or lower, but were a hundred times higher in powdered substrates. The microchip laser was employed in the detection of aerosols by LIBS. Laser-induced plasma was formed on particles which passed through the focal volume of a tightly focused laser during the laser pulse. The efficiency of detecting particles of various particle types and sizes was investigated as well as the use of the plasma emission for the identification of these particles. The results show the potential usefulness of microchip laser LIBS for the real-time detection and identification of particles in air. Potential applications of such a capability include real-time assessment of industrial atmospheres, clean room monitoring and bio-safety. xv

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CHAPTER 1 INTRODUCTION TO LASER-INDUCED BREAKDOWN SPECTROSCOPY (LIBS) Laser-induced breakdown spectroscopy (LIBS), also known as laser-induced plasma spectroscopy (LIPS), is an analytical technique based on the emission by atomic and ionic species in microplasmas induced during laser ablation at high power densities. In simple terms, it is the use of optical signals from laser-generated plasma for analytical purposes. A typical LIBS configuration is shown in Figure 1-1. The output from a pulsed laser is focused on a target, which can be a solid, liquid, gas, or aerosol particles. The high laser power creates a microplasma on the target which excites and ionizes a small amount of the target material. The optical radiation from the atomic and ionic species in the laser-induced plasma is collected by lenses or optical fibers into spectrometers and spectrally resolved. The emitting species in the laser-induced plasma can be identified and quantified by their unique spectral wavelength and line intensities. Figure 1-1 LIBS experimental set up. FL-focusing lens; CLcollection lens. 1

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2 Background When a focused, pulsed laser strikes the surface of a material, an initial heating causes a rapid rise in the temperature of the surface which results in melting and vaporization of a small portion of material into ionized gas. The process leading to the ionization of this gas (i.e. plasma breakdown) can either be electron ionization (equation 1-1) or multiphoton ionization (equation 1-2) (1). e + M 2e + M + (1-1) mh + M M + + e (1-2) Interaction of the laser pulse with the solid sample results in the laser radiation being absorbed by an electron whose energy rises above the band gap of the solid. The high energy electron then collides with the neutral metal to ionize the solid to form a gas. Because the electron concentration increases exponentially during the time the laser emission is on, this process results in a cascade breakdown. Whenever multiple photons are absorbed by an atom or molecule and the energy of these photons is sufficient to eject an electron from the valence to the conduction band of the solid, a metal ion and an electron result. Electrons produced by this process undergo many collisions with themselves and the surrounding atoms causing further ionization. This process is called multiphoton ionization. The energy of the electrons is passed on to the target, resulting in a surface temperature rise, melting and vaporization, provided the energy deposited in the layer of molten metal is greater than the latent heat of vaporization of the material (2). Figure 1-2 is a schematic representation of the processes leading to the formation of a plasma plume. In Figure 1-2c, the removal of particulate matter from the surface leads to the formation of vapor in front of the sample. When this vapor condenses as

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3 submicrometer size particles, it leads to scattering and absorption of the laser radiation and results in heating, ionization and plasma formation (Figure 1-2d). Other mechanisms that follow these include fast expansion of photoablated material (Figure 1-2e), formation of polyatomic aggregates and clusters (Figure 1-2f), and deposition of the ablated and molten material around the crater (Figure 1-2h and 1-2g). Figure 1-2 Schematic representation of the processes involved in plasma plume formation. Adapted from Vadillo and Laserna (3). LIBS Over the Years The LIBS technique was reported shortly after the invention of the laser (4), and understanding of the principles involved parallel advances in lasers (5). Even in these preliminary studies, useful analytical curves were obtained for nickel and chromium in steel samples. In fact, by 1967, the first instrument based on LIBS had been developed (6). This was followed by a few commercial instruments such as that developed by Jarrell-Ash Corporation. The method, however, could not compete favorably with respect

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4 to precision and accuracy with competing technologies at the time such as conventional spark spectroscopy, electrothermal atomization atomic absorption spectrometry (ATA-AAS) and inductively coupled plasma-atomic emission spectrometry (ICP-AES). In the early years, the method was normally used by physicists for fundamental studies on breakdown in gases, the mechanisms that led to this breakdown as well as the influence of target properties and laser parameters (pulse width, wavelength, beam diameter) on breakdown thresholds (1). It was during the 1980s that the method began to receive widespread attention as a solution to practical problems such on-line elemental analysis at a distance (2). This late interest was driven by two notable factors. The first factor was the unique advantages of the LIBS technique such as the need for no sample preparation, minimum destruction to targets, possibility for remote analysis, (also referred to as stand-off LIBS) and multi-element capability. The second factor that was partly responsible for the revival in the 1980s was the emergence of reliable, small and inexpensive lasers as well as the development of sensitive imaging detectors. In addition to increased sensitivity, these detectors brought with them the potential to do LIBS measurements in a suitable time window that provides higher line to background emission signal. The 1990s continued the revolution started in the early 1980s and witnessed an explosion in both analytical and industrial research employing LIBS (7). The technique began to move out from the basic science laboratory into the real world of applications. Application areas embraced the monitoring of environmental contamination and quality control, material processing (8), detection of toxic substances (9), removal of coatings, and planetary exploration (10). With this in view, LIBS configurations concentrated on

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5 developing rugged, robust and field portable systems (11). This ushered in fiber optics for both sending the laser beam and collection of the plasma emission, a step towards remote analysis. By 1988, a portable beryllium monitor based on LIBS had been built at the Los Alamos National Laboratory (12). More and more laboratories throughout the world are advancing the technique in several respects. However, challenges still remain. After over 40 years of laboratory work, both researchers and their funding agencies have come to realize that the time has come for LIBS to find more real-field application. The challenges that need to be met for such real-field applications include instrumental ruggedness and the sensitivity that is required in the most demanding environmental and quality control settings. Each of these will be briefly addressed in the following sections. Instrumental Challenges Laser-induced breakdown spectroscopy is one of the several applications of lasers that require short (nanosecond and sub-nanosecond) pulses with high peak powers and pulse energies of several mJ. The traditional method of producing sub-nanosecond pulses is called mode-locking. Mode locking is a process whereby the phases of several modes of light in a cavity are locked by pulsing or oscillating the cavity. The pulse duration of a laser is the inverse of the frequency distribution of the laser output (13) For a laser with q output modes, the pulse duration is mathematically expressed by equation 1-3, qcLLCqq11duration pulse (1-3) where 1/v is the pulse separation time and L is the length of the laser cavity. Equation (1-3) above shows that we can obtain short pulses either by increasing the number of

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6 oscillating modes in phase or by decreasing the length of the cavity. Due to practical limitations on the size of the cavity, the former technique is mostly used. This leads to the coherent and constructive addition of the electric fields for a short period of time and results in a repetitive train of high intensity ultra-short pulses. The inter-pulse separation in such a system is equal to the round-trip time of flight in the cavity, that is, length of the laser (14). A schematic of a mode-locked system and output is shown in Figure 1-3. Figure 1-3a and 1-3b illustrate a laser oscillating on an inhomogeneous transition with many modes above threshold and lasing. By considering the numeric, one can readily see that there can be a large number of modes oscillating in such a system, with simultaneous oscillating modes as shown in Figure 1-3c. The number of modes that can oscillate simultaneously depends on the Doppler width of the transition and the length of the cavity (15). Mode-coupling or mode-locking can be realized by optical modulators inside the laser resonator. This case is referred to as active mode-locking. It can also be achieved passively using saturable absorbers or by a combination of both schemes (16, 17). Figure 1-4 is a typical experimental arrangement for generating a train of mode-locked pulses using a standing ultrasonic wave. Mode-locking is normally used in application areas that require very short pulses such as x-ray generation, machining, time-resolved studies and terahertz generation (18). The intensity of a light wave is proportional to the square of the electric field amplitude; therefore for two superimposed waves with intensity E, the resultant intensity is given by (13),

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7 Figure 1-3 Multimode laser: (a) and (b) A laser oscillating on an inhomogeneous transition with many modes above threshold; (c) Simultaneous oscillating modes in a laser cavity. Figure 1-4 Experimental arrangement for a mode-locked laser using an ultrasonic wave. Adapted from from Demtroder (14). 224)(EEE (1-4) That is, the resultant intensity is four times the intensity of a single wave. Despite this amplification, the large number of pulses produced per second results in low pulse

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8 energies. Therefore, only lasers with extremely high average powers can produce enough pulse energies for some applications. In order to produce energetic pulses, the technique called Q-switching is employed. In Q-switching, the ratio of the energy stored in the cavity to that lost (leaked by the mirrors) is modified by external commands which facilitate population inversion, and inhibit stimulated emission while keeping spontaneous emission as low as possible. Once population inversion reaches a critical threshold, stimulated emission starts and a large pulse of laser light with several 100s of mJ energy is emitted. Figure 1-5 is an illustration of an optical set up for generating Q-switched pulses. Until a specific time after the start of the pump pulse at t = 0, the cavity losses of a laser are kept high by an optical switch inside the resonator. In this way the oscillating threshold cannot be reached. A large population inversion builds up and the switch is suddenly opened. This increases the Q-value of the cavity and converts the energy stored in the cavity into a giant light pulse. The type of Q-switching described above is called active Q-switching. Active Q-switching can be achieved using electro-optic and acousto-optic shutters which can be externally opened or closed to create variable pulse duration and frequencies. Electro-optic Q switches are capable of faster switching than acoustooptic devices because the speed of light is faster than the speed of sound. However, electro-optic systems generally require relatively higher voltage electronics than are required by acousto-optic devices. Q-switching can also be done mechanically using a rotating mirror placed in the laser cavity that only reflects the light and allow stimulated emission at certain geometries. Due to their speed, mechanical switches are being replaced in most systems except in cases where optical damage limits the use of the

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9 alternative technologies. A handful of techniques and various combinations of them are available for both producing and controlling the output of a laser. These will not be discussed in detail in this thesis but Table 1-1 is a summary of some of the methods available and pulse properties. The values listed are typical of those reported in the literature, although in many cases there is a significant spread in the reported values. Figure 1-5 Optical set up for generating Q-switched pulses. Lasers used in LIBS are conventionally actively Q-switched lasers with neodymium crystals doped with yttrium-aluminum garnet (Nd 3+ :Y 3 Al 5 O 12 ) as the lasing medium. Nd: YAG has been the most widely used gain medium because of its unusual combination of optical, thermal and mechanical properties. Favorable properties of this medium include its temperature index variation, thermal expansion coefficient, thermal conductivity, and melting point (19). Pumped with a Xe-arc flash lamp, the output is at 1064 nm. Various wavelengths down to the 5 th harmonic can be obtained from this

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10 fundamental output by the use of non-linear crystals appropriately placed in the laser path. Other lasers have been used in LIBS; Table 1-2 lists a few of these laser systems and their typical operating parameters. Even though, highly energetic pulses can be produced by Q-switching, size requirements and the mechanisms by which the pulse is produced do not allow the production of sub-ns pulses. Methods exist for the production of both sub-ns and energetic pulses (such as amplifying a mode-locked laser or Q-switching a mode-locked laser). However, these methods result in complex systems with high power consumption due to the high speed and high voltage electronics that are needed for proper Q-switching. For LIBS to find real-field applications, alternative light sources that are compact, robust, easy to operate, and have minimum requirements for maintenance will play a big role. Analytical Performance of LIBS In addition to instrumental requirements, every technique has to satisfy analytical performance criteria before it can be embraced as a routine method for laboratory measurements, quality control assessment and field deployment. The performance criteria are referred to as analytical figures of merit (11). These include the detection power (limit of detection, LOD) of the technique, linear dynamic range (LDR), capability for absolute analysis and selectivity. In this regard, LIBS may be considered as lagging behind competing methods such as inductively coupled plasma optical emission spectrometry (ICP-OES) spectrometry or ICP-mass spectrometry (ICP-MS). To bring this into perspective, both LIBS and ICP-OES use plasma excitation and the emitted light from the plasma as bases of analysis. However, ICP-OES, which is the most used emission based

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11 multi-element technique, provides detection limits in the sub-ppb range while LIBS provides detection limits in the ppm range. Table 1-1 Methods used for modifying the output of a laser. Laser system Peak power Pulse width Period of pulse repetition Mode-locked 100 W 100 ps >10 ns Cavity-dumped 10-100 W >10 ns Variable Mode-locked & Cavity-dumped >10 W >0.1 ns Variable Synchronously pumped >100 W >1 ps >10 ns Synchronously pumped & Mode locked >1 kW >10 ps Variable Taken from Van Hecke (13) Table 1-2 Some laser systems that have been employed in LIBS (1) Type Wavelength (m) Pulse width Pulse energy (J) Features Nd:YAG 1.064 7-12 ns 0.3-1.0 Low maintenance, compact, relatively cheaper CO 2 10.6 1-300 sec 0.5-500 Simple design, special IR lenses required for laser pulses, Excimer 0.194-0.351 10-30 ns 0.25 UV wavelength, toxic gases, quartz optics required Other performance criteria which are equally important, although not considered as analytical figures of merit, include sample preparation, sample size requirements, automation, bulk versus surface analysis, destructive versus non-destructive, instrument compactness and operating cost (11). The rest of this dissertation will be devoted to

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12 addressing some of these performance requirements. Chapter 2 will answer the question of instrument compactness, size requirements and operation cost, as well as present some preliminary investigation using a 7 J per pulse microchip laser. In Chapter 3, a study of microchip laser ablation will be presented while Chapter 4 will be devoted to the diagnostics of the microchip laser-induced plasma. The analytical performance of the microchip LIP in both quantitative and qualitative analysis and single particle detection will be presented in Chapter 5 and Chapter 6, respectively.

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CHAPTER 2 SOLID STATE PASSIVELY Q-SWITCHED MICROCHIP LASERS AS SOURCES FOR LASER-INDUCED BREAKDOWN SPECTROSCOPY Miniaturization of instruments is a trend in almost every area of industry. The reason for this trend is that instrument portability and the speed with which an analysis is performed can be considerably improved. Also, miniaturized systems can reduce the required sample size and consumption of costly reagents. Miniaturization of instruments is usually accompanied by increased functional capabilities. In the near future, miniaturization will be a key factor if spectroscopy will continue to play its unique role in defense and biomedicine. Significant progress has already been achieved in miniaturization of optical detectors. With respect to LIBS, for example, a commercial broadband spectrometer (LIBS2000+, Ocean Optics, Inc., USA) covers a wide spectral range (200-1000 nm) with an impressive resolutionunder 0.1 nm (20). When this spectrometer is operated by a notebook computer, the spectrometer is perfectly portable and self-contained. Lasers, however, remain a bottleneck in the development of portable LIBS devices. The conventional laser sources for LIBS, described in Chapter 1, that is, actively Q-switched Nd: YAG lasers (or Q-switched mode-locked lasers) are characterized by some limitations which do not made them attractive for use in field-friendly LIBS systems. For instance, mode-locked Q-switched lasers can be several feet high and consume kilowatts of electrical power. For fieldable systems, the possibility to operate under battery power is ideal. The absence of bulky water cooling systems and minimum 13

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14 requirements for periodic maintenance are some of additional desired properties properties. It is for this reason that this work was carried out to investigate all-solid-state passively Q-switched microchip lasers as sources for LIBS. Passive Q-switched Microchip and Lasers Passive Q-switching The principle behind the operation of a passively Q-switched laser is simple. Unlike actively Q-switched systems which use electro-optic, acousto-optic or mechanical device to turn off and on the Q of the laser cavity, passively Q-switched lasers employ an intra-cavity saturable absorber that prevents the beginning of lasing until population inversion reaches a critical threshold (21). At the beginning of the pumping, this saturable device absorbs the light emitted at 1064 nm by the laser material and prevents the amplification of the laser light. When the average inversion density exceeds the saturation threshold of the saturable absorber, this material becomes transparent and a giant laser pulse is delivered in a short period of time (a few 100 ps to 2 ns, typically). After the laser pulse is delivered, the saturable absorber again becomes opaque to the laser light and begins to absorb the light. The process is analogous to the charge and discharge of an electrical capacitor. This mechanism of generating a laser pulse is called passively Q-switching because no external commands are needed to trigger the delivery of the pulse. A schematic of passive Q-switching is illustrated in Figure 2-1. In passively Q-switched systems, the pulse repetition frequency (PRF) can simply be changed by increasing or decreasing the pump power, which causes the saturation threshold of the saturable absorber to be reached faster or slower. The pulse width, pulse

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15 energy and other characteristics are determined by both the design of the oscillator and the choice of saturable absorber (22). Figure 2-1 Schematic of a passively Q-switched laser system. The gain medium is usually Nd: YAG and the saturable absorber is Cr 4+ : YAG. The Microchip Laser The microchip laser (MCL) is an all-solid-state diode pumped passively Q-switched laser system. It is perhaps the ultimate in miniaturization of diode-pumped solid-state lasers. In its simplest form, the MCL is like any other solid state laser: a piece of laser material placed in an optical cavity between two mirrors. The active ions in the laser material are excited by externally pumping with a diode laser. Though the concept of these compact laser systems was conceived in the 1960s, it was not until the 1980s that attention was given to the idea, especially following the demonstration of a diode-laser pumped device in Nd:YAG (23). Since then, diode-pumped, neodymium microchip laser

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16 oscillating around 1.06 m have been reported in many host materials, including NPP (23) and YVO 4 (24). Design and Fabrication of Microchip lasers The design of a laser is dictated by several inter-dependent factors such as the requirements in the output beam wavelength, spectral purity, tunabiltiy, power stability, as well the operating environment temperature and humidity. Other practical considerations such as size, cost, and available power also play a major, decisive role. Microchip lasers are mass produced beginning with a piece of laser material such as Nd:YAG. A cylindrical slab of this material is sliced into several wafers of few mm thick (1-2 mm typically). The wafers are polished on both surfaces and the mirrors are deposited using sputtering or evaporation. With a dicing saw, these wafers are then cut into several square microchips and each chip is then coupled to a pump diode laser. This coupling can be done directly or through the use of a multi-mode optical fiber. The saturable absorber used in most microchip laser designs is Cr 4+ :YAG (21) which is grown on the surfaces of the laser material (diced wafer) using a technique called liquid phase epitaxy (22). The process is schematically described in Figure 2-2. With this collective fabrication process, it is reported (22) that up to 2000 microchip lasers per fabrication lot can be obtained. Materials and wavelengths Used in Microchip Lasers The active material used in most microchip lasers is neodymium. The choice of the doping material, however, depends on the required wavelength. For laser materials doped with materials such as yttrium aluminum garnet (Y 3 Al 5 O 12 or YAG), YLF, or yttrium orthvanadate (YVO 4 ), the emission wavelength is around 1000-nm. With Nd doped with Tm, for instance, the output is at 2-m. Microchip lasers based on Nd are pumped with

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17 standard GaAlAs or GaInAs diode lasers with outputs around 800-nm; Er and Yb lasers are pumped around 980-nm while Tm doped materials are pumped around 790-nm (19). The fabrication process of the microchip laser results in miniaturized systems which have low power consumption and excellent optical properties. Microchip lasers produce sub-nanosecond, multi-kilowatt pulses at high repetition rates (23, 24). They have several unique properties that make them attractive as sources of light for application areas such as surgery, micromachining, spectroscopy, material processing, micro-marking, high precision ranging and several non-linear optical systems. Figure 2-2 Microchip laser fabrication process. (This is followed by the process illustrated by Figure 2-1). The attractive features of microchip lasers include the short length of the cavity which permits single frequency operation (19). Unlike the multi-mode outputs from the majority of conventional lasers, the output from a microchip laser is devoid of mode beating. Mathematically, the spectral range, also known as frequency spacing between adjacent longitudinal modes of a cavity is given by equation (2-1) (13, 19),

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18 rtfsrt1 (2-1) where t rt is the round trip time of flight in the cavity. It can be seen that single-mode operation is possible because of the short cavity length which ensures that longitudinal mode spacing is greater or at least comparable to the gain bandwidth. In many applications of lasers, example LIBS, mode quality is at least as important as total power. A significant source of error in LIBS measurements is the pulse-to-pulse variations in the LIBS emission signal due partly to the anomalous mode beating in conventional lasers sources. The goal of the remaining section of this chapter is to demonstrate the feasibility of using the first commercial microchip laser as part of a miniature LIBS setup which includes a small non-gated detector. Such a setup may be a prototype for a commercial portable LIBS spectrometer for field applications. Both the experimental details and discussion of the results will be scanty but will set the stage for a more detailed study in the subsequent chapters. Experimental Arrangement The experimental set-up is shown in Figure 2-3. The laser used is a diode-pumped passively Q-switched Nd: YAG laser (model JDS Uniphase, Nanolase, Meylan, France). It operated at 1064 nm and emitted pulses of 550 ps duration and 7 J pulse energy yielding 13 kW peak power at a repetition rate of 5.45 kHz. The laser beam waist, 200 m in diameter, located 25 mm from the laser face, is placed in the focus of a collimating lens (f = 48 mm). A nearly parallel beam is formed behind the lens which was guided to a 50X microscope objective. With the microscope objective, the laser was focused to a spot of ~8 m in diameter with a resulting irradiance of 25 GW/cm 2 The laser beam was

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19 focused on several metallic substrates and the plasma emission was collected at 45 o degrees with respect to the laser beam using a fiber optic probe. The 600 m diameter optical fiber was connected to a miniature grating spectrometer (USB2000 or LIBS2000+, Ocean Optics, Inc., USA) to monitor the plasma spectrum on a PC computer screen. Figure 2-3 LIBS setup with a 7J microchip laser. The collection of the plasma emission was done with or without the collection lens. Results and Discussion A set of metallic foils were used in this study in order to study the spectral characteristics of the microchip laser plasma. The spectral acquisition window was limited by the spectral range of the spectrometer used. Representative spectra are shown in Figures 2-4 and 2-5. Generally, background continuum radiation was tolerable without any temporal gating but was relatively higher for tin (Sn) and lead (Pb) as shown in Figure 2-5.

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20 20022024026028030032034036038005001000150020002500 Ti II Ti ITi II Ti IIIIntensity (a.u)Wavelength (nm) Ti2002202402602803003203403603800200400600800 Si I288.16Si I251.61Intensity (a.u)Wavelength (nm) Si200220240260280300320340360380-50005001000150020002500300035004000 Intensity (a,u)Wavelength (nm) Fe2002202402602803003203403603800200400600800 Cd I348.37Cd I Cd II274.85Cd I Cd II226.5 Cd II219.46Intensity (a.u)Wavelength (nm) Cd Figure 2-4 Spectra of metal foils and silicon wafer obtained with the USB 2000 and the microchip laser. Integration time was 1 s. 2002202402602803003203403603800500100015002000250030003500 Zn IZn II255.8Intensity (a.u)Wavelength (nm) Zn20022024026028030032034036038005001000150020002500 Pb I Pb IIntensity (a.u)Wavelength (nm) Pb2002202402602803003203403603805001000150020002500 Sn I317.51Sn I 303.41Sn I284Sn I240.82Intensity (a.u)Wavelength (nm) Sn20022024026028030032034036038001000200030004000 Intensity (a.u)Wavelength (nm) Ni Figure 2-5 Spectra of metal foils obtained with the USB 2000 and the microchip laser. Integration time was 1 s.

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21 It was observed that with the same acquisition parameters and experimental conditions, line emission intensity with respect to the background continuum was higher for materials with higher melting point such as Ni, Fe, and Si than substrates such as Sn and Pb. For the later substances, the spectra tend to be smaller, weaker and less luminous; however, craters were bigger as shown in Figure 2-6. It was speculated at this time that much of the material removed by the laser pulse is simply melted and sprayed on the target surface and did not enter the plasma. In Chapter 3, a parametric study of the relationship between emission and target thermal properties will be presented. It should also be noted that the spectra are composed of both atomic and ionic lines. It may therefore be possible to couple microchip laser LIBS to other analytical methods such as mass spectrometry. Figure 2-6 Scanning electron micrographs (SEM) images of crater produced by the microchip laser. D denotes mean crater diameter.

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22 2002202402602803000200400 Cd II, 274.85 Cd I, 259.2 Cd II, 231.3 Cd I, 228.8 Cd I, 226.5Intensity (a.u)Wavelength (nm) Cd3203403603804004204404604805000200400600800 Cd ICd ICd ICd IIntensity (a.u)Wavelength (nm) 200400600800100002004006008001000 Intensity (a.u)Wavelength (nm)2002202402602803000200400 Cd II, 274.85 Cd I, 259.2 Cd II, 231.3 Cd I, 228.8 Cd I, 226.5Intensity (a.u)Wavelength (nm) Cd3203403603804004204404604805000200400600800 Cd ICd ICd ICd IIntensity (a.u)Wavelength (nm) 200400600800100002004006008001000 Intensity (a.u)Wavelength (nm) Figure 2-7 Cadmium spectrum obtained with the broadband spectrometer LIBS 2000+ and the microchip laser. (Top) Full acquisition window of the spectrometer; (Bottom) Segments showing identification of some Cd lines. Integration time was 1 s. Spectra were also obtained using a broadband spectrometer, LIBS2000+ (Ocean Optics, Inc. USA). This spectrometer employs a large fiber bundle consisting of seven fibers arranged in a circular configuration at one end. Since the total bundle diameter was larger than the size of the plasma, it was difficult to illuminate the entire bundle simultaneously. Therefore, a single fiber was used to collect the emission while moving from channel to channel until the entire spectrum was acquired. A typical spectrum taken with this spectrometer on a cadmium foil is shown in Figure 2-7. The negative peaks

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23 result from the shift from channel to channel of the spectrometer while the spikes are due to the fixed pattern noise of the CCD. This is a higher resolution spectrometer but it is characterized by low light throughput. When used together with the microchip laser, it can be particularly important in applications aimed at portable systems for on-site material identification. There are several other features in typical conventional LIBS spectra that are absent in microchip laser spectra. For instance, traditional LIBS spectra are generally rich in nitrogen bands (N 2 ) or lines, and hydrogen lines. These do not appear in microchip LIBS spectra, implying that the microchip plasma does not appear to interact with the surrounding gas to the same extent. Conclusion A laser-induced breakdown spectroscopy setup with the first commercial microchip laser was investigated in this chapter. The microchip laser-induced plasma has several features that distinguished it from plasmas induced by conventional pulsed lasers. The background continuum emission was low, while nitrogen and hydrogen bands characteristic of high power lasers were absent. The lower emission intensities did not provide high expectations for quantitative analysis; however, the microchip laser together with a spectrometer that offers a wider spectral window would provide a compact and portable system for online material characterization and sorting

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CHAPTER 3 MICROCHIP LASER ABLATION OF METALS: INVESTIGATION OF THE ABLATION PROCESS IN VIEW OF ITS APPLICATION TO LASER-INDUCED BREAKDOWN SPECTROSCOPY Summary Metal ablation with a short pulse, low energy microchip laser was investigated with respect to its application to laser-induced breakdown spectroscopy (LIBS). Target surface modifications and crater parameters as a function of laser pulse properties were studied. The effect of the laser pulse is limited to the focal spot, but surface modification by the laser-induced plasma can extend several micrometers beyond the focal spot depending on the target thermal properties. Mass removal per shot was found to depend upon the heat of fusion of the target, while appreciable plasma emission was observed only at high pulse energies. Plasma composition and emission intensity can change significantly with the surface properties, requiring that a fresh, flat surface to be exposed to each laser pulse. Increasing the temperature of the target by heating it resulted in a corresponding increase in plasma emission due to an increased mass removal per laser shot; however, selective ablation was not observed at temperatures up to 550 o C. Fractionation was observed at low laser irradiances and inside deep craters, but it was minimal compared to the results reported for other laser ablation systems. Characteristics such as precision in the mass removal process, well-defined crater parameters, and good spatial resolution make the microchip laser an attractive laser sampling tool. 24

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25 Background Laser ablation is a process in which an intense burst of energy, delivered by a short-pulse laser beam is focused onto a target surface. A finite mass of the target is removed which can be analyzed for both qualitative and quantitative information. Unlike conventional dissolution techniques, there is little chance with laser ablation for exposure to hazardous materials or introduction of contaminants into the sample. Laser ablation is further applicable to all materials in all states and the absence of complicated sample preparation procedures reduces analysis time (25). In addition, unlike beam and particle techniques such as secondary ionization mass spectrometry (SIMS) and electron probe analysis (EPA), there are minimal requirements for high vacuum, extensive matrix-related interference corrections, and specialized personnel for operation and data treatment. Microchip lasers are becoming increasingly attractive in laser-induced breakdown spectroscopy (LIBS) (20, 26-28). Advantages of microchip lasers in laser ablation include minimal modification and destruction of the target which is required in the analysis of precious ornaments and historical artifacts. Again, the high pulse repetition frequency (up to several kHz) and good beam quality (29) permit spatial characterization of sample heterogeneity with micrometer and submicrometer resolution. These and several other potential advantages of laser ablation techniques cannot be fully exploited with the use of conventional laser sources, the limitations of which include bulky instrumentation, low probing frequency, excessive target modification and relatively poor beam quality. By overcoming the limitations associated with conventional laser ablation sources, solid state microchip lasers may find wide application because they can be easily incorporated into small commercial ablation systems.

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26 Traditional detection systems for laser ablation sources have been Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) and Inductively Coupled Plasma-Atomic Emission Spectrometry (ICP-AES) (30, 31). In these cases, inert gases such as argon and helium are typically used to carry the laser-ablated material to the ICP excitation source. By analyzing the spectra from the ICP-AES or ICP-MS, the composition of the material can be established. Chemical analysis with laser-induced breakdown spectroscopy is gaining world-wide attention in recent years (11, 20). Studies in the subsequent chapters of this dissertation will be focused on plasma diagnostics and the use of the microplasma for qualitative and quantitative analysis. Because plasma formation is preceded by laser ablation, which results in crater formation on the solid matter surface, characterization of the laser-induced crater is important in understanding the ablation process and the subsequent plasma formation and propagation. The ablation process alone has found wide application in areas such as laser surgery (32), matrix assisted laser desorption/ionization (MALDI) (33) surface micro-fabrication (34) and pulsed laser deposition of organic thin films, just to cite a few. Nevertheless, the fundamental mechanisms underlying the laser ablation process have yet to be fully understood, even for conventional lasers which have been in use for decades. The aim of this chapter is to evaluate the ablation performance of these miniature lasers and to compare the characteristics of the craters obtained with those given by conventional lasers sources having pulse widths of several nanoseconds and pulse energies of tens of mJ. The effect of target properties on crater development and the effect of the laser-induced crater and laser irradiance on plasma intensity and composition will also be presented and discussed.

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27 Experimental The experimental setup is illustrated in Figure 2-3. Two laser sources were used in this work, a 7 J per pulse microchip (MCL) laser (model JDS Uniphase Nanolase, NP-10620-100, Meylan, France) operating at 5 kHz, and a 50 J per pulse microchip (referred to as powerchip, PCL) laser (model JDS Uniphase Powerchip Nanolaser, PNP-005025-040, Meylan, France) operating at 1 kHz. Both were diode pumped, passively Q-switched, all solid state lasers with a wavelength of 1064 nm and a pulse width of about 500 ps. The laser beam was focused by a 50X microscope objective (Mitutoyo, M plan NIR 50). The distance between the objective and the target location was adjusted to obtain a focal spot diameter of the order of 8-10 m. Typical objective-target distance was approximately 1.8 cm. The targets investigated were metal foils, a silicon wafer and several steel samples. In order to precisely quantify the mass removal per laser shot and also to sustain the plasma formation, the target was placed on a rotating disc which was mounted on an x-y-z translational stage, thus exposing a fresh target surface to each laser pulse. Different speeds, predetermined for either the microchip laser at 5 kHz or the powerchip laser at 1 kHz, were selected for the target motion. In all cases, the vertical translation speed was 100 m/s but the disc rotation speed was varied depending on the laser repetition rate. For a higher spatial resolution, an additional chopper was placed between the laser and the focusing lens to effectively limit the laser repetition rate. Ablation was carried out at atmospheric pressure in air. Target surface modification was studied with a scanning electron microscope (Hitachi S-4000 FE-SEM) while crater profiles were obtained with a profilometer

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28 (WYKO NT 1000, Veeco Instruments) operating in vertical scanning interferometer (VSI) mode. Plasma emission intensity was measured with a 600 m diameter fiber optic coupled to Ocean Optics miniature spectrometers, HR2000 (2400 grooves mm -1 and 0.03 nm FWHM optical resolution) and SD 2000 (0.3 nm FWHM resolution) (Ocean Optics Inc., USA). All spectrometers used were non-gated and non-intensified. The spectrometers were calibrated with a tungsten lamp and the emission intensities were corrected for the different response of the spectrometer-detection apparatus at the wavelength of interest. Results and Discussion The MCL and PCL as Microprobe Analyzers As pointed out before, the first challenge in working at high pulse repetition frequencies is to obtain single craters. It is essential to expose a fresh area of target to each laser pulse for the following reasons: i) In the case of the MCL and PCL(20), as with other laser sources, the formation of a plasma with each laser pulse and the parameters of the laser-induced plasma are strongly dependent on focusing conditions; ii) a deeper crater can completely or partially envelope the microplasma and significantly affect the emission intensity and spectral composition (20); iii) it is possible that any re-deposited material will have composition different from the composition of the bulk sample due to fractionation. Emission spectra taken from plasma breakdown on the melted sample may therefore lead to erroneous qualitative and quantitative information. A basic requirement in laser ablation for microchemical analysis is to transform a finite amount of sample into the vapor phase with a stoichiometric representation of the sample. One should therefore be able to know how much mass is removed by each laser pulse and whether the ablated mass has the same composition as the bulk material.

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29 Therefore, in all experiments with the microchip lasers, special efforts were taken to avoid the problems enumerated above by ensuring that mass ablation from successive laser shots did not occur from the same focal spot. As mentioned in the experimental section, this was accomplished with two independent motorized stages. Figure 3-1 shows the pattern resulting from the ablation scheme devised. The rotating disc, together with the x-y-z stage, translated in the plane perpendicular to the laser beam gave spiral-shaped single craters. The distance between each pair of craters was determined by the speed of the moving stage. Figure 3-1 further shows that, with the PCL and MCL, highly reproducible and precise craters were obtained. The minimal jitter in the MCL and PCL laser systems, compared to conventional flash lamp-pumped lasers, contributed to the better precision and control. For the PCL used in this work, the timing jitter was better than 0.3 ns and the amplitude RSD was better than 4%. Figure 3-1 Powerchip laser micro-ablation of copper substrate showing: (left) the ablation scheme devised; and (right) single craters obtained at 1 kHz. The large number of single craters distributed over a small target area (Fig. 3-1a and 3-1b) indicates that the powerchip and microchip lasers should be nearly ideal tools for elemental surface cartography, particulate sampling, and rapid characterization of

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30 material homogeneity, microanalysis and laser surface microprocessing. Coupled with a technique such as LIBS, where the elemental composition of material is analyzed by vaporization of mass from a very small spot, PCL and MCL systems will then be capable of microprobe analysis (29, 32, 33) with micrometer resolution in terms of lateral and depth dimensions. Over the past few years, surface characterization of materials has attracted growing interest in chemistry and material science. For some materials, scientists not only need to know the accurate composition of the bulk sample, but also the exact location of interfaces and characterization of concentration gradients. For example, in the pharmaceutical industry, some tablets possess a multifunctional coating of which the thickness needs to be accurately controlled. Some techniques that have been applied satisfactorily as surface characterization tools include Raman spectroscopy, IR spectroscopy, and Auger electron spectroscopy. Laser ablation has also been used by several researchers to provide information about the atomic composition of materials as a function of depth(35). A potential application of the PCL in surface depth profiling is illustrated in Figure 3-2, where a steel matrix with a thin coating on the surface (due to target heating described later) was analyzed. As can be seen, within the 25 s time duration, the effect of the crater on the emission intensity was minimal since the intensity of Fe 400.52 line remains nearly constant. However, a line observed at 393.36 nm suffered a steep decrease in intensity, reaching the background level after 15 s. This line is most probably due to Ca, although it was not experimentally proved. Previous studies reported Ca II as a common contaminant on steel surfaces though not in steel matrix at a relevant

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31 concentration (36). Ideally, we expect the intensity of the iron line to increase as the line from the coating decreases. It is not clear as to why the intensity of the iron line stays constant but it is speculated that the increase in intensity as a function of depth is cancelled by the effect of the laser-induced crater. Assuming that this line originates from the coating due to target heating, knowing the mean ablation depth per laser pulse and the number of pulses used, the thickness of this film could be estimated. When LIBS is used in depth profile analysis with conventional lasers, the main limitations are the poor spatial and temporal quality of the beam profiles (unless particular care is taken in shaping the beam), which result in limited depth resolution. The operating features of the microchip laser, combined with the simplicity of the technique make these sources attractive tool in depth profile analysis. In situations where the analysis time frame compatible with industrial requirements are desirable, microchip LIBS for surface characterization may constitute and alternative to existing methods such as x-ray photoelectron spectroscopy (XPS), glow discharge spectroscopy (GDS) and Rutherford back-scattering spectroscopy (RBS). Target Modification Pulsed lasers have applications not only in spectroscopy but in other areas such as pulse laser deposition and micromachining (37). In all these cases, the laser-target interaction and the plasma-generated thermal damage to the target can be employed constructively but can also be a major obstruction. The interaction of the laser pulse with the target depends both on the laser parameters and the target properties (25, 37, 38). In this study, because the damage caused by the laser pulse interaction with the target and the damage caused by the plasma melting of the surface could not be separated in time, the effect of the laser-induced plasma was studied by imaging the target at the inter-crater

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32 spaces. Figure 3-3 shows SEM images taken from the inter-crater spaces of Cd and Cu. It was observed that the damage to the target by the laser-created plasma was thermal in nature, characterized by the melting of the target. The extent of melting depends on the thermal properties of the target such as melting temperature and heat of fusion. Figure 3-2 Depth profiling of a thin film created on steel surface by the 50 J powerchip laser. (a) Spectra obtained from the coated and polished steel surface. Integration time was 3 s (b) Time-dependent intensity distribution of the line from the coating and iron matrix. Significant melting and re-deposition of larger droplets were observed for targets such as Sn, Pb, and Cd which have lower melting points than others such as Ni, Fe and Cu. The re-deposited material probably consists of both liquid phase expulsion and plasma particle condensation(39), which can be particularly high at atmospheric pressure (40). Finally by comparison of the crater and focal spot diameters, it was inferred that plasma modification of the surface was more predominant than the damage done by the laser pulse itself. This is possibly due to the short pulse duration and hence less time for thermal diffusion into the target to occur (40).

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33 Figure 3-3 Effect of the laser-induced crater as shown in the inter-crater spaces. Mass Removal Single crater diameters were estimated from scanning electron micrographs while the crater depth was obtained by a profilometer. Because of the almost perfectly Gaussian laser beam profiles of the MCL and PCL (20, 29), the shapes of the ablation craters become prominently cone-like (41), especially after several laser pulses have been directed on the same spot as shown in Figure 3-4. Other laser types, for example, those with flat top beam profiles or inferior Gaussian profiles may produce straight wall craters or other crater types with irregular shapes(42, 43). In this work, based on the diameter and depth profile, a conic or half-filled spherical shape was assumed for single craters from which the volume was obtained. Figure 3-5 shows the variation of the amount of material removed per laser shot and the crater radius with the heat of fusion and melting point. The lower the heat of fusion of the material, the greater the amount of material removed per laser shot. For example, the material removed varied from 0.5 to 0.8 ng for silicon and 9 to 11 ng for tin. Considering that the focal spot diameter was just 8 m, it can be seen that in the case of materials such as Ni and Si, with radii 5 and 4 m, respectively, the damage to the surface is limited to the focal spot while for materials

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34 such as Pb or Sn, the crater diameter is nearly two times bigger than the focal spot diameter. This is due to the pronounced effect of the LIP as explained earlier. Figure 3-4 Microchip laser-induced crater on cadmium foil showing the crater structure and droplet redeposition on surface. Figure 3-5 Dependence of crater radius and mass removed per laser shot on the melting point temperature (shown in parenthesis) and heat of fusion of the target. Mass removed were calculated based on the crater volume and the density of the material.

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35 From the measured spectra, it was interesting to note that, at 7 J/pulse, the higher mass removal in materials such as tin, lead or cadmium was not reflected in correspondingly higher emission intensities. The low emission intensities in such materials can be ascribed to excessive re-deposition of the melted material which has a higher breakdown threshold. At 50 J, there is still redeposition of melted material on targets such as Cd, but the overall emission intensities are higher than those observed for targets such as copper, although the increase in emission intensity does not follow proportionally the increase in the mass removed. Table 3-1 Laser-induced crater depth and diameter for a 500 ps microchip laser compared to that of 8 ns laser. Data in bold were obtained for the 8 ns laser. Height/m) Diameter/m Si 12 2.2 11 125 Al 16 13 Ni 12.4 3.5 11.6 100 Fe 12.7 2.7 12.5 115 Cu 15 13 Pb 16 10.5 14 Table 3-1 collects the depths and diameters of craters for various metal foils and a silicon wafer created by a 0.5 ns microchip laser and by 8 ns flash lamp-pumped Nd-YAG laser (1064 nm, beam divergence 7 mrad, beam diameter 2.8 mm, pulse energy 0.7 mJ). No effort was made to optimize the shape of the laser beam profile in the case of the 8 ns laser. Values for the 8 ns laser are presented in bold. The average focal spot diameter was 8-10 m for the PCL and 28-35 m (in the absence of significant plasma melting)

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36 for the 8 ns laser. The data presented were obtained under the best focusing conditions obtainable. It is especially interesting to note that, in the case of the microchip laser, the craters are narrower (limited to the focal spot) but deeper, while with the 8 ns laser, the craters have larger diameters but are shallower. This is further revealed in Figure 3-5 where a crater profile of the 8 ns laser pulse is compared to that from the PCL. The crater from the 8 ns laser pulse is shallower and mountainous unlike the PCL crater which is deeper and relatively uniform inside. The difference in the spatial and temporal energy distributions for the two lasers could play a significant role in this observation. As mentioned before, the MCL and PCL systems are characterized by Gaussian intensity profiles, single mode output and low pulse to pulse variation, while conventional flash lamp-pumped lasers do not compete favorably with MCL/PCL laser with respect to the above properties. For quantitative ablation, it is clearly easier to quantify the mass removed by the PCL than by the 8 ns laser source. Generally, the depth-to-diameter ratio of microchip lasers is greater than that of the 8 ns pulse, which might be partly due to the lower energy losses through thermal dissipation, which is a function of the laser pulse duration (29, 38, 44) and increased plasma shielding in the case of the 8 ns pulse. Ablation Efficiency Several papers have characterized the laser ablation efficiency (38, 40, 45) which is simply considered here as the ratio of the yield of target property (mass or volume) to the laser energy input. A review of literature yielded at least three common definitions including: the ratio of crater volume to laser energy, ratio of crater depth to laser fluence, and the ratio of mass removed to laser energy. Based on these definitions, the ablation efficiency of the microchip laser at 7 J was compared to those reported for other laser sources. The results for this study are shown in Table 3-2 and reveal that the ablation

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37 efficiency of the microchip laser can be up to two orders of magnitude higher compared to other laser sources. Laser ablation is a complex phenomenon depending on laser wavelength and pulse duration, focal spot size, and target properties (25, 37, 38, 40, 44). It was therefore of interest to study both the effect of several experimental parameters and laser properties on laser ablation. Figure 3-6 Comparison of (a) 500 ps passive Q-switched powerchip-induced crater, and (b) crater induced by an 8 ns active Q-switched laser on a lead target. Table 3-2 Ablation efficiency of 7 J microchip laser compared to values reported for conventional Nd: YAG lasers. Refs. (38, 40) 1.52 x 10814 (25)70.5Microchip laser0.1130 (32)654Sameroket al0.2 x 105120 (30)604Salle at al(532 nm)Depth/fluence, m/J cm-2Volume/pulse energy, m3J-1Fluence, Jcm-2(Irradiance GWcm-2)Pulse energy JPulse width (ns)Ref 1.52 x 10814 (25)70.5Microchip laser0.1130 (32)654Sameroket al0.2 x 105120 (30)604Salle at al(532 nm)Depth/fluence, m/J cm-2Volume/pulse energy, m3J-1Fluence, Jcm-2(Irradiance GWcm-2)Pulse energy JPulse width (ns)Ref In Figure 3-7, the behavior of the ablation volume of Cu and Cd is shown. It can be seen that in both cases there is increase in crater volume with an increase in laser energy.

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38 The plots however are characterized by different slopes, which most likely indicate that different regimes are operative in the ablation process. In the case of Cd, the crater depth increases steeply with laser energy up to 15 uJ, after which a different ablation regime with a lower slope begins. A similar process is observed in the case of Cu, except that the second slope is the steeper one. Similar results in which the crater volume increased with Figure 3-7 Variation of crater volume with laser energy for: (a) cadmium and (b) copper. The arrows indicate the points of the curve where different slopes begin. with laser energy until the occurrence of a threshold were observed by Russo et al (46). The second regime was explained in terms of explosive boiling of the target. At this stage, the target material makes a sharp transformation from superheated liquid into a mixture of liquid droplets and vapor leading to an excessive mass ejection from the surface (47). In the case of Cd, the slope decreases after the threshold. As mentioned earlier, in the mass ablation process, there is significant re-deposition of melt flush on the target surface. In the case of Cd, characterized by a lower melting point, the effect of the melted material is more pronounced than with other targets such as copper or silicon. Since the breakdown threshold in the melt is higher than that of the undisturbed surface (20), the sensitivity falls as shown by the less steep slope. For Cu, characterized by higher

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39 melting point, the opposite effect is observed, with the sensitivity increasing during the second ablation regime. The above definition of ablation efficiency cannot be directly translated into corresponding emission intensity, because it is the amount of sample that goes into the vapor phase and is excited in the plasma that controls the emission intensity. Again, the increase in volume is not necessarily directly proportional to the increase in energy, (which would give a single slope). As can be from Figure 3-7, for Cd, the ablation efficiency is 7 X10 7 m 3 /J at 15 J and 4 X10 7 m 3 /J at 30 J. This, together with the results shown in Table 3-2, leads to the conclusion that in order to obtain higher ablation efficiency, lower pulse energy is recommended. In an attempt to better characterize the ablation process, the definition of the ablation efficiency will be extended by taking into consideration: 1. The change in emission intensity with the change in mass removed. Provided that optically thin lines are chosen, the change in emission intensity should be directly related to the mass removed that goes into the gas phase. 2. The change in target mass versus the mass removed per shot. With negligible re-deposition, the change in the two parameters should be the same. 3. The ratio of the volume of crater up to volume down. Estimates of volume up and volume down can be easily obtained using crater profile images taken by the profilometer used in this work. This definition approximates volume up (the volume of the material deposited on the crater rim) as the mass removed that does not go into vapor phase to contribute to the plasma emission and volume down as the total material removed. All three definitions above will ensure that the ablation efficiency is presented as the fraction of mass removed that contributes to plasma emission, which is the fraction that has spectroscopic relevance. None of these, however, is meant to provide a universal definition but rather diagnostic information as how LIBS performance based on the microchip laser could be affected by the physical mechanisms involved in the ablation

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40 process. Also, the term ablation sensitivity will be introduced, which will be defined as the ratio of the total detector counts obtained per shot to the laser pulse energy. In this definition, it is the total mass ablated that goes into the plasma and emits that is considered. It is important to note that at 50 J, the crater volume for Cu is about 10 times smaller than the crater volume for Cd (200 m 3 and 2000 m 3 for Cu and Cd, respectively). Figure 3-8 shows the behavior of the signal (counts), corrected for the detector response, versus laser energy for Cd and Cu. All data were integrated over 400 ms, which was chosen to ensure that the detector would not be saturated at the maximum laser energy and that there would be measurable intensity at the lower energies. An interesting point to note is that for Cu, the emission intensity is only about half that of Cd, despite the crater volume being approximately 10 times less. The lines used for this investigation were 361.05 nm for Cd and 406.26 nm for Cu. By taking into account the transition probabilities of these lines, one would expect the intensity of Cd to be approximately eight times greater than that of Cu. This suggests that there are other phenomena beyond the spectroscopic parameters of these lines. Similar observations were made whenever materials such as Cd, Sn, and Pb were compared to others such as Ni, and Fe. This may suggest that at low energies, in the case of lower melting point materials, a significant amount of the ablated material is not vaporized but is just re-deposited as droplets on the target surface, while, even though less mass is removed for substrates such as Cu and Ni, a relatively larger fraction is vaporized and available for emission. To further clarify this point, the behavior of ablation sensitivity and ablation efficiency with pulse energy for both Cu and Cd were compared. The results for this are

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41 shown in Figure 3-9. One can see that in both cases, the ablation efficiency is higher at lower energies. In the case of Cu, there is an initial decrease in ablation efficiency followed by a steady rise after 20 J. An opposite observation is made for Cd in which there is a fall after an initial rise. This observation is consistent with the two regimes of ablation discussed earlier in this chapter. With regard to ablation sensitivity, the graphs show that for Cd, ablation sensitivity increases with pulse energy and levels off at about 65 X 10 6 counts/J at 25 J. The ablation sensitivity of Cu, however, remains nearly constant at all energy levels except for 5 J, where it is about 15 X 10 6 count/J. Cu will be considered as nearly the ideal situation, where the emission intensity increases at the same rate as the laser energy. The result could also have to do with the excess energy available for atomization, ionization and excitation. There could be significant increase in mass removal for materials with low thermal properties, but there is just enough energy left for the latter phenomenon (atomization, ionization and excitation). 010203040502004006008001000120014001600 0 (Cu)JIntensity/countsEnergy /010203040500500100015002000250030003500 CdJIntensity/countsEnergy / Figure 3-8 Plasma emission intensities of cadmium and copper compared at different laser pulse energies. Integration time was 400 ms, with 5 spectra averaged (i.e. each spectrum is an accumlatiuon of 2000 spectra). Each data point represents the mean of 20 spectra.

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42 Figure 3-9 Ablation sensitivity (red line) and efficiency (black line) of Cd (top) and Cu (bottom) as a function of laser pulse energy. Effect of Target Temperature on Mass Removal: Experiments have shown that, during laser target interaction, thermal diffusion into the target precedes the ablation process (48) In the case of long pulses (of the order of 10 to 100s of nanoseconds), thermal diffusion can be very high (49-51) and can reduce the actual amount of incident energy that is involved in material removal. Conversely, the

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43 same phenomenon does not need to be considered in the case of ablation with short pulses, in the ps and fs regime (51-54) since diffusion of the laser energy into the target is minimal. Investigation of the effect of target temperature on ablation rate and plasma composition will not only provide knowledge from the fundamental point of view but may also lead to modifications in instrumental and experimental configurations for real-time analysis in production sites, such as in the steel industry, where molten material in high temperature furnace may need to be analyzed in situ for enhanced productivity. In this work, an attempt was made to increase the sensitivity of the mass ablation process by increasing the target temperature. The expectation was that with the target already at a higher temperature, thermal diffusion of the laser pulse energy into the target would be smaller, thus involving more of the incident energy in solid matter removal, atomization, ionization and excitation. A steel sample was heated on a hot plate and quickly transferred to the ablation stage. The emission intensity, plasma composition and crater profile of the hot and cold targets were obtained after ablation with the PCL. 0500100015002000250030003500 CrMnMoElementIntensity (a.u) Intensity at 550oC Intensity at 300oC 0.00.51.01.52.02.53.0 Cr/FeMn/FeMo/FeIntenstiy ratioElement 550oC 300oC 0500100015002000250030003500 CrMnMoElementIntensity (a.u) Intensity at 550oC Intensity at 300oC 0.00.51.01.52.02.53.0 Cr/FeMn/FeMo/FeIntenstiy ratioElement 550oC 300oC (a) (b) Figure 3-10 Effect of target temperature on plasma composition and emission intensity. (a) is the background corrected emission intensity and (b) is the intensity normalized to Fe 400.52 nm line.

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44 The signal enhancement of three atomic lines from Mn, Mo, and Cr at 300 o C and 550 o C are shown in Figure 3-10. The results show that an increase in target temperature results in enhancement of emission lines, especially significant for Cr. This could be due to either an increase in mass removal or an increase in plasma temperature or both. In quantitative analysis of trace elements by LIBS, the possibility of a selective enhancement of some lines of the elements with respect to the matrix is of great interest. To determine whether there is any such phenomenon, the intensities were expressed as a ratio of the intensity of the selected lines of Mo, Mn or Cr to the iron atomic line at 400.52; iron was the main matrix element in the sample. The results, shown in 3-10b, do not reveal any significant change in the intensity ratios whether the sample was hot or cold. A Boltzmann plot (77) was used to determine whether the increase of the target temperature would lead to any changes in the plasma electron temperature. A sample plot is presented in chapter 4 (figure 4-8). Temperatures obtained for heated and room temperature targets were similar, of the order of 11,300K, 200 K in either case. It can be concluded that the increase in the emission line intensity shown in Figure 3-10a is primarily due to an increase in the mass removed per shot, and not to a change in the plasma thermal properties. It will be informative to observe the changes in spectral composition and plasma emission intensities as the target is heated to temperatures near the melting temperature of some of the elements of interest; however, technical problems associated with this did not permit such an experiment at this time. Effect of Crater Depth and Laser Irradiance on Plasma Intensity and Composition Because thermal properties, such as melting and vaporization temperatures, vary by orders of magnitude, laser ablation of multi-element materials may result in selective

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45 removal of some species, a process referred to as fractionation. Experiments show that crater depth and its aspect ratio contribute to this effect (55). Another experiment was designed to show the changes in the net emission intensity and time dependent ratios of Cr, Mn, Mo, and Ni to matrix (Fe) as the crater was developing during repetitive laser pulses along a single circular crater trench. Figure 3-11 shows the time profile of four elements of interest in a steel target. Slight adjustment of the focusing was done after every 30 s to ensure that the lens to focal spot distance did not change significantly over the time duration of the measurement. The spectra were taken from the same circular crater trench with 1.5 cm diameter. The gradual decrease in emission intensity in all cases could be due to the fact that plasma is partly buried in the crater, decreasing the solid angle the collection system makes with the plasma. a -20020406080100120140160100150200250300350400 CrMnFeMoNiIntensity/countsTime/s Cr Mn Mo Fe Ni05101520253035012345 Mn/FeMo/FeNi/FeRel intensityTime (s) MnFe MoFe NiFe b Figure 3-11 Effect of laser-induced crater on plasma emission intensity. Selective removal of some elements and material can be caused by laser interaction with the sample, a process resulting elemental fractionation. The microplasma hidden inside a deep crater may contribute to the sampling process, leading to fractionation (25).

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46 In addition, with increasing crater depth the actual irradiance may decrease due to changes in effective surface area exposed to the laser beam (42) which might not only decrease the net emission intensity but can also influence fractionation. To investigate whether such a situation could occur, the net emission intensities of the lines were normalized to a line belonging to the matrix. There was no significant change in the relative intensities with time when the target was rotated as described. The experiment was repeated with fresh target but at the same focal spot, with periodic adjustment of the focusing. Figure 3-11b shows pronounced changes in the Ni-Fe intensity ratios especially after the 30th data point. One reason could be that in the case when the target was rotated, there was enough time for the redeposited material to solidify before the next mass removal while in the case of Figure 3-11b, there was not enough time for the phase change. A piece of brass containing 30% Zn and 70% Cu was measured to determine the effect of the crater on the Zn-Cu ratio. The intensities of the Zn emission line at 481 nm and Cu at 327.4 nm were monitored. For every data point, the background in the vicinity of the Zn and Cu lines was measured and subtracted from the signal. Figure 3-12 shows a steep decrease in the Zn-Cu ratio during the first 15 s. The decrease could be partly explained in terms of decreasing irradiance as the crater develops. Earlier in this work(20, 56), we observed that at lower irradiances, low melting/vaporization point elements have lower emission intensities compared to high melting point elements despite higher mass removal in the former. Other reports have established that the laser-induced cavity aspect ratio increases elemental fractionation (57).

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47 024681012141.01.52.02.53.03.54.04.5 Zn 481/Cu 327.4Zn-Cu ratioSuccessive data point number010203040501.62.02.42.83.2 Zn-Cu Int. RatioEnergy (a) (b) (J) Figure 3-12 Effect of crater and laser energy on plasma composition: (a) Temporal dependence of the Zn-Cu ratio in brass when the plasma is created on the same spot. Integration time was 300 ms with 5 spectra averaged. (b) Effect of laser pulse energy on Zn-Cu intensity ratios. Each data point is the average of 30 spectra with an integration time of 300 ms and 5 spectra averaged. In Figure 3-12b, the effect of laser energy on the Zn-Cu ratio is presented. Again, the Zn-Cu intensity ratios remained nearly constant at all energies except at 5 J, which was significantly lower than the values obtained at other laser intensities. Thermal properties of the Zn and Cu might suggest that at lower laser energies, more Zn will be removed. However, as has been pointed out earlier, this might not necessarily lead to an increase Zn-Cu ratio, as a larger fraction of this mass may be re-deposited as droplets. Because the effect of laser energy on plasma composition is minimal, as has been observed for ps and fs laser pulses, unlike nanosecond laser pulses, thermal effects do not play a significant role in fractionation (45). By employing higher laser intensities with pulses in the ps and fs regime, fractionation can be eliminated or reduced significantly. Conclusion The potential of MCL and PCL lasers as ablation sources for analytical systems has been demonstrated. Compared to conventional laser sources, there is minimal damage to the target using the MCL/PCL and mass removal can be precisely quantified because the

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48 craters can be easily characterized. The high probing frequency, which can be several kHz, and good beam properties ensure high spatial and depth resolution. However, translation is necessary to sustain plasma formation and ensure stoichiometric mass removal and also to provide a flat surface for plasma formation so that the microplasma will not be hidden from the emission collection systems. The parameter ablation sensitivity was introduced and was considered as the detector count per laser pulse energy during the mass removal process. Unlike the traditional definition of ablation efficiency, ablation sensitivity considers the fraction of the mass removed that is vaporized and contributes to plasma emission. Microchip lasers have not yet been used appreciably in the analytical world. However, due to their compact size, low maintenance cost, portability and precision in material removal, they may, someday, find wide application in commercial analytical systems such as LA-ICP-MS or LA-ICP-AES and LIBS. In addition, applications may extend beyond metals to areas such as polymers (58) and biomaterials (58, 59).

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CHAPTER 4 DIAGNOSTICS OF MICROCHIP LASER-INDUCED PLASMAS AS RELATED TO LASER-INDUCED BREAKDOWN SPECTROSCOPY Summary The ablation properties of the microchip laser were studied in Chapter 3 and the analytical performance in trace element analysis will be presented in Chapter 5. In order to bring the findings into perspective, a deeper understanding of the properties of the micro-plasma created by these lasers is needed. Chapter 4 reports an approach to achieve such goals and several preliminary results. Spectral analysis, time-resolved pump-probe absorption measurements, electrical signals from the plasma, and CCD photography were used to characterize the micro-LIBS plasma and its behavior. The plasma breakdown threshold on several targets is reported for the powerchip laser as well as the challenge of tight focusing required to induce breakdown. Theory Even though the principle behind the LIBS technique is simple, the physics involved in the ablation process and the plasma formation and subsequent expansion as well as the plasma emission are complex. Laser-induced plasmas (LIPs) have very short temporal existence with a fast evolution of their characteristic parameters. The parameters of the LIP are heavily dependent on irradiation conditions such as incident laser intensity, ambient gas pressure and composition, and irradiation spot size. Even under the same irradiation conditions these parameters can vary with the axial or radial distance from the target surface. 49

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50 Different diagnostic techniques exist for studying laser-induced plasmas. These include spectroscopy (optical emission spectroscopy, OES)(60), laser interferometry, Langmuir probe methods, and Thompson scattering(61). Among these, emission spectroscopy seems to be the simplest as far as instrumentation is concerned, even though it is less direct and more theory dependent than, for instance, Thompson scattering. Also, absolute intensity measurements are difficult to make with high accuracy, even when the source is compared to a standard source, due to variations in solid angles, equivalent light paths and apertures. In addition, because most sources have cylindrical symmetry and hence a radial temperature gradient, when viewed side-on the radiation comes from an inhomogeneous medium. Therefore the condition for uniform optical thinness is usually difficult to achieve. Different instrumental schemes and optical setups can be employed to alleviate these problems. Plasma diagnostics consist of both temporal and spatial structures. In Figure 4-1, the spatial structure involved in the diagnostics of laser-induced plasma is illustrated(1). The process begins with absorption and scattering of incident laser energy and proceeds through the transport of this energy to denser regions. The laser light is often absorbed by inverse Bremsstrahlung for local plasma frequencies less than the laser frequency, i.e. up to the region where n = n c the critical density. When the plasma frequency equals to laser frequency, the laser energy is either reflected (or scattered) or absorbed. Optical diagnostics provide much of the needed information in the region from the critical surface outward towards the laser. The absorption process and the local plasma conditions can be studied by measuring the scattered or shifted frequency and harmonic light resulting from these processes.

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51 Figure 4-1 Spatial component of a laser plasma diagnostics. In plasma diagnostics, the information that is needed can either be obtained measuring self-emission from the plasma or by probing with external radiation(60). The former is simpler and provides more local information. Optical emission, however, may not be suitable for dense plasmas where emission cannot escape due to large opacity. Probing overcomes this, and further, provides time-resolved information because the probing radiation can be introduced in the form of short bursts timed with respect to the evolution of the plasma. This chapter focuses on characterization of the microchip laser-induced plasmas by analyzing the emission spectra from the plasma, and the changes undergone by radiation introduced into the plasma from a probe beam. The plasma temporal profile and its relation to the laser pulse and the absorption and electrical properties of the plasma were addressed. The combination of CCD photography with spectroscopy adds another dimension to the plasma diagnostic by providing two-dimensional snap-shots of the three-dimensional plume propagation. The effect of experimental conditions, such as focusing and pulse energy, on the physical and temporal properties of the laser-induced

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52 plasma will be discussed as well as the challenges and/or the benefits these present when these types of lasers are used in LIBS. Experimental The experimental set is illustrated in Figure 4-2. The laser source used in this study was a 50 J per pulse microchip laser (referred to as powerchip laser, PCL) having a wavelength of 1064 nm and 0.5 ns pulse width. In plasma transmission studies, a portion of this beam was split off with a beam splitter. A 532 nm component of this portion, henceforth called the probe beam, was obtained by second harmonic generation using a KTP crystal. Using an optical delay set up, the probe beam was sent through the laser-induced plasma orthogonally at different delay times following the laser pulse in order to estimate the transmission through the plasma. Figure 4-2 Plasma diagnostic experimental set up. GP-glass plate; M-mirror; PD-photodiode; T-target; L-collimating lens; PCL-powerchip laser. The collection lens & fiber coupler take the position of PD2 in emission measurements.

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53 Plasma emission was collected with a 600 m diameter optical fiber into a miniature spectrometer, HR 2000 (2400 grooves/mm grating, 0.03 nm optical resolution) or various photo-detectors. The laser beam and the plasma pulse temporal characteristics were measured with a 200 ps MCP/PMT (Hamamatsu R1564U-07) connected to the exit port of a monochromator (American ISA Inc, H-10V) and a fast photo-detector (Electro-Optics Inc., ET 3000). The signal was monitored with a 6 GHz digital oscilloscope (Tektronix, TDS 6604). For estimation of the plasma breakdown threshold, linear attenuation of the laser beam was achieved with a circular neutral density filter and the laser energy was monitored with a power meter. Plasma images were obtained with a CCD camera, Pixera Professional PVC 100C (Pixera Corporation, USA). Result and Discussion Absorption Properties of the microchip Laser-Induced Plasma Laser-induced plasmas (LIP) are transient. Even for high power active Q-switched lasers with energies of 100s of mJ per pulse, the LIP has an emission lifetime of 100 S or less. In the case of the microchip lasers, the plasma lifetime is of the order of 100s of ps to a few ns after the breakdown event. Time-gated measurements of such transient pulses using conventional gated ICCD detectors are challenging and have not yet been feasible with the microchip LIP. Time integrated measurements alone do not provide a complete picture of the physical and chemical processes taking place in the LIP. On the other hand, time-resolved measurements provide useful information not only from the fundamental point of view but also with regard to the dynamic processes such as the evolution of electron number density and plasma continuum emission. Such knowledge is

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54 needed to improve the analytical utility of the LIP for both qualitative and quantitative work. These issues were addressed by studying the time-resolved absorption behavior of the LIP using an optical delay setup based on pump-probe measurements. The plasma was always formed by the 1064 nm fundamental frequency but the probe beam was either the 1064 nm beam or the frequency doubled 523 nm light obtained by splitting a portion of the pump beam as shown in Figure 4-2. The probe beam was focused and passed through the plasma at different delay times following the laser pulse. The intensity of the probe beam was measured before and after passing through the plasma in order to obtain the fraction of light absorbed by the plasma. In Figure 4-3, time-resolved measurements of the plasma transmission as a function of the optical delay between the laser pulse initiating the plasma (pump beam) and the split off beam focused through the plasma (probe beam) are presented. -0.50.00.51.01.52.02.53.03.54.00.00.10.20.30.40.50.6 6.57.07.58.08.59.09.5-0.10.00.10.20.30.4 Time (ns)Amplitude (mV)Fraction absorbed Delay (ns) 1064 nm probe 532 nm probe Figure 4-3 Fraction of probe beam absorbed by the LIP as a function of delay time. The inset is the temporal profiles of the 1064 and the 532 nm beams.

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55 The temporal profiles of the two probe beams are shown as the insert in Figure 4-3. Absorbance was calculated from the ratio of the laser pulse energy transmitted through the LIP to the pulse energy in the absence of LIP. Approximately 1.2 ns following the laser pulse, about 50% of the1064 nm and 40% at 532 nm probe beams were absorbed by the plasma. Thus, the plasma has maximum absorption approximately 1.2 ns following the laser pulse and is nearly transparent 4 to 5 ns later. In a similar study by Hohreiter et al.(62), using a laser pulse with 275 mJ per pulse and 10 ns pulse width, the percentage of the 1064 nm and 532 nm probe beams absorbed were 84% and 91% respectively, approximately 40 and 30 ns following the laser pulse. The absorption of the probe beam by the LIP in this work is significantly lower than that obtained by Hohreiter et al. Several reasons could account for the lower absorption values observed in this work. First, the absorption path-length across the plasma in this work is at least 10 times less than to that said in Ref. (62). And the electron number density obtained in this study is two orders of magnitude lower than that reported in Ref. (62). The width of the PCL pulse is 0.5 ns while that used in ref. (62) is 10 ns. A laser spark is produced through an initial breakdown followed by growth and heating of the plasma. For longer pulse durations as used in the above reference, the latter part of the laser pulse can heat the preformed plasma significantly. The heating results in plasma ionization which increases the absorption of the laser through inverse Bremsstraahlung processesa condition where a laser photon is absorbed by an electron in the field of an ion causing direct plasma heating. For pulse durations in the fs to ps regime, the laser pulse does not interact with the expanding plume sufficiently (63) and so the plasma is

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56 relatively cold. Therefore, post-breakdown processes such as ionization of species in the plasma are minimal, and therefore, less absorption of the probe beam is expected. In Ref (62), a linear correlation was observed between the 532 nm probe beam absorption and the temporal profile of the electron number density at each similar temporal delay. Temporal profiles of the electron number density have not yet been obtained in this work but an integrated estimate based on the Stark broadening of selected atomic emission lines is of the order of 10 16 cm -3 In this regime, the plasma frequency p as calculated from equation [4-1](64) 5.0310*9.8epn [4-1] where n e is the electron number density, is of the order of 10 12 Hz, which is significantly lower than the frequencies of the 532 nm (5.656 x 10 14 Hz) and 1064 nm (2.828 x 10 14 Hz) probe beams. In this case, reflection by free electrons and Thompson scattering cannot be neglected. However, the plasma frequency is close enough to the probe beam frequencies to allow significant absorption of the probe beams by the plasma, since in fact, n e used in the above calculation in this work is both space and time integrated and could have higher values over the plasma lifetime. Therefore, even though scattering effects by the free electrons can not be neglected, the temporal behavior of the electron number density during the plasma lifetime can be inferred from the absorption profile. The theoretical absorption cross-section of the 532 nm beam in fully ionized plasma can be employed to obtain numerical values of the time-depended electron number density. In this sense, the absorption measurements provide a convenient way to make time resolved measurements of the short-lived microchip laser-induced plasma over time scales not easily attainable using electronic gated detectors. Because the time interval between the

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57 pump and probe beam can be measured using appropriately positioned photodiodes and an oscilloscope, measurements obtained by this approach might be more precise than those obtained using electronic gated detectors, especially for ps and sub-ns pulses. Emission Temporal Profile In Figure 4-4, the emission profile of the plasma induced on a copper target is present. It can be seen that plasma initiation begins almost simultaneously with the excitation laser pulse and has a FWHM of approximately 1.5 ns. Accurate measurement of the time relationship between the laser pulse and the emission is important in application areas such as single particle detection (an on-going and future direction in this laboratory). 1.5 ns 2468-0.250.000.250.500.751.00 Normalized amplitude (a.u)Time (ns) PCL pulse Cu 327-nm Figure 4-4 Radiative temporal behavior of the laser-induced plasma. Different targets were investigated but plasma durations beyond 4 ns (FWHM) have not been measured. The present work was initiated with a 7 J per pulse microchip laser. In that work, the plasma duration was of the order of 0.8-1.5 ns. It is interesting to note that with approximately 8 times increase in pulse energy, the emission temporal profile does

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58 not change proportionally. It is expected that these time scales are determined by the properties of these lasers, such as the pulse duration, which in part controls the processes of plasma formation and of energy transfer within the plasma, as well as the radiative properties of the atoms whose emission is observed. The transient nature of laser plasmas requires that, in analytical applications, the observation of the emission is delayed with respect to the laser pulse. Even though, this introduces further instrumentation and complexity, a temporal window is normally used where the background continuum is minimal with respect to the line emission. A consequence of the short plasma duration as observed in the case of the microchip lasers is that, such gated measurements are not as feasible and necessary as with microsecond plasmas. However, because the continuum emission is low compared to other laser types, both qualitative and quantitative work with the microchip have been carried out without any gating and analytical figures of merit comparable to those reported for conventional laser sources have resulted. For instance, detection of Mo, Si, and Mn in low alloy steel samples resulted in detection limits of 100 ppm or lower with a non-intensified, non-gated detector. These studies will be discussed in Chapter 5. PCL Plasma Diagnostics by Means of Electrical Signal Measurements As part of the diagnostic measurements, a thin tungsten wire probe (100 m by 0.25 cm) was placed as close as possible to the substrate on which the plasma was formed. The probe was connected to an oscilloscope and a voltage pulse was measured whenever the plasma was formed. Depending on whether the probe was biased positively or negatively with respect to the target, a pulse resulted due to collection of plasma electrons or positive ions. Only the negative (electron) current will be briefly discussed here.

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59 A typical electron pulse collected during microchip laser ablation of copper is shown in Figure 4-5. The widths of these current pulses observed are in the 4-6 ns range, with both widths and peak amplitudes increasing with increasing bias voltage. It is important to note that the temporal FWHM of the Cu emission is less than the FWHM of the current pulse, which could extend beyond 20-ns depending on the bias. 01020-150-100-500 30 3 V 2 VmVTime (ns) Figure 4-5 Characteristic electron pulse collected during microchip laser ablation of copper substrate at 50 J. Probe bias voltages are indicated on the curves. The voltage bias was gradually increased until further increase in bias did not result in an increase in probe signal. At this point, the area under each voltage pulse was used to estimate the charge on the probe. From Figure 4-6 (top), it is seen that as the probe bias voltage was increased, the charge on the probe reached a limiting value. However, the fraction of the total electrons in the LIBS plasma actually collected is not known, and so charge on the probe does not necessarily represent the total number of charges in the plasma. A variety of probe configurations are currently being evaluated in an effort to determine the efficiency of extraction of plasma electrons and the proper correction

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60 factors to the limiting value of number of electrons extracted which can be converted to electron number density by dividing by the plasma volume (estimated from photographic images). This value can then be compared with the electron number density obtained from the width due to Stark broadening of the LIBS emission lines. The line width measurement, in turn, must be corrected for the finite resolution of the spectrometer. It can be seen that the systematic errors in the two techniques are expected to be in opposite directions: incomplete probe collection will give low values of electron number density, while using observed line widths without correcting for instrumental broadening will yield values that are too high. It is encouraging that even at the current stage of the work, the two estimates of electron number density agree within an order of magnitude (10 15 cm -3 from electric probes and 2*10 16 cm3 from line broadening). Probe current observations may also provide another insight into plasma processes. A study was made of the variation of probe current with laser irradiance (W cm -2 ). Studies in the literature have documented the expected dependence for conventional (high pulse energy) LIBS, in which an initial linear rise in the probe current eventually reaches a constant limiting value(65). This is explained as saturation due to plasma screening of the laser pulse. A study of the variation of probe current with irradiance for the microchip laser showed no sign of such a plateau, but rather, there was a rate of increase in probe current that became larger with higher irradiance (Figure 4-6). Therefore plasma shielding might not yet be effective. Of course the minimal absorption of the probe beam by the LIP, discussed earlier in this work, might also suggest minimal shielding of the laser pulse by the pre-formed plasma.

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61 024681012141618200.20.40.60.81.01.21.41.61.8 Charge (X10-10)(C)Voltage bias (V)024681012141618200.00.20.40.60.81.01.21.41.6 Probe Current(mA)Irradiance(x1010 Wcm-2) Figure 4-6 Variation of probe current with bias voltage (top) and laser irradiance (bottom). The inset is a curve by a similar experimental set up by Isaac et al.(65) showing an initial rise of probe current which plateaus at higher irradiance. The probe current density, J (A/cm 2 ), showed a power law dependence on the laser irradiance, I (W/cm 2 ). That is J I n (66), where n is an integer representing the number of

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62 absorbed photons such that nh is approximately equal to or larger than the work function of the material (h is the Plancks constant, and is the frequency of the light). In this study the estimated value of n was 1.41 and hence nh is approximately 1.65 eV which is less than the work function of copper (4.7 eV), the target used in this work. It is inferred from this that multi-photon surface photoelectric effects do not contribute significantly to the charge on the probe and that the signal on the probe can be considered as predominantly resulting the plasma. Breakdown Threshold High density plasmas with extremely sharp density gradients such as those encountered in LIBS, are currently of great interest particularly from the point of view of generating ultra-short x-rays pulses(67, 68). Laser-induced plasmas are also employed in ignition processes(69). In such situations, it is essential that the breakdown laser fluence is well characterized. Such diagnostics offer a better way to understand fluctuations in the spark energy and hence the intensity of the emission signal in application involving LIBS. The concept of breakdown threshold can be defined in several ways depending on the method used to study it. One method used is based on a pump-probe set up and is based on the assumption that, when the plasma threshold is exceeded, a dense plasma is formed, which causes a distinct change in the optical reflectivity of the plasma(68). Laser-induced breakdown is a probabilistic process(70). The energy density required to induce breakdown in a gas, for instance, is strongly depended on gas pressure and can vary by more than a factor of two(69). Other authors described breakdown threshold as the number of laser pulses producing plasmas divided by the number of pulses used for each measurement(69). In another study, Miln and Laserna defined the breakdown

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63 threshold as the minimum laser fluence needed to detect an emission signal from the ablated material(71). The breakdown threshold reported in this work was estimated as the minimum irradiance or fluence needed to produce an emission S/N of at least 3. Table 4-1 shows the threshold values calculated for the materials used -silicon wafer, silicon dioxide pellets, fused silica and steel. The emission of the Si atomic line at 251.6 nm was monitored in all the targets except in the steel target where Cr (I) at 425.44 nm was used. As Table 4-1 shows, plasma breakdown thresholds can vary significantly among different targets for the same laser parameters and experimental conditions. This has consequences in the application of the LIBS plasma for chemical analysis since the relative strength of the emission lines and the background continuum are affected. It is important to note that significant plasma emission is obtained at low laser energies. Pulse energies of 70 mJ in colloids(72), 75 mJ in glass(73), 300 J on silicon wafers(71), and 170 mJ on aluminum(74) were required for various focusing conditions by other workers to overcome the breakdown threshold. In our experiments, we employed tight focusing of the laser beam which allowed us to reach the breakdown threshold while staying at low pulse energies. Table 4-1 Plasma breakdown threshold measured for different targets. Silicon 251.6 nm line was monitored for all targets except for steel where Cr 425.43 nm was used. Material Line used (nm) Threshold irradiance (GWcm-2) Threshold fluence (Jcm-2) Si wafer Si,251.6 11 5.5 SiO2 (pressed pellet) Si,251.6 19.8 10 Fused Silica Si,251.6 127.2 64 Steel Cr,425.43 7 3.5

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64 The focal length of the lens used in focusing a laser beam has a considerable effect on the breakdown probability. For example, for a Q-switched laser operating in a single longitudinal mode (as used in this study), the photon flux, Fph (in photons/cm2s) is given by equation 4-2 (4-2) hc r PF wph2 where P w is the laser power (W), r is the focal spot radius, c is the speed of light and h is the Plancks constant and (4-3) df r. 2 where f is the focal length of the lens and d is the beam diameter. It can be shown from equations (4-2) and (4-3) that a short focal length lens results in a much smaller focal volume, a high power density, a higher photon flux and a stronger electric field. The higher values of these parameters ensure the production of initial electrons leading to the electron cascading process(67, 75). The consequences of such tight focusing will be discussed later in this work. Other important factors to consider are the pulse duration and surface properties of the target. For shorter pulses in the ps to fs range, there is reduction in energy threshold for breakdown(75). Table 4-1 also shows the effect of target surface properties. The results show that the breakdown threshold on a pellet of silicon dioxide powder was nearly twice that observed for the silicon wafer with a smooth surface. In quantitative work with the microchip laser, the LOD for such powder materials were found to be 10 to 100 times poorer than that obtained for the same species in targets with much more uniform surface.

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65 The Focusing Challenge Laser plasmas are known to be highly dependent on the laser fluence (energy/area) at the surface and measured parameters can vary significantly, even for a single lens. The low pulse energies of microchip lasers present another demand on the choice of focusing optics. In this study, a microscope objective with a 1.7 mm working distance was used to focus the laser beam onto the target. The target was placed such that the focal spot diameter was of the order of 8 to 10 m, providing irradiances ranging from ~27 to ~190 GW/cm 2 for the 7 J/pulse microchip and the 50 J/pulse powerchip laser. Tight focusing to obtain such high irradiances is important to initiate plasma formation. A consequence of this is that the plasma behavior and its physical properties are extremely sensitive to the distance of the target from the focusing lens. In order to show the effect of the focusing conditions on the plasma, the objective which was mounted on micrometer stage was moved toward or away from the target in 0.25 mm increments. The results of such an experiment can be understood in terms of spot size and fluence; however, only a qualitative treatment will be provided here. Plasma images were taken with a CCD camera; line emission with a spectrometer and emission lifetime (FWHM) was measured using a MCP/PMT, photodiodes and an oscilloscope. In Figure 4-6a, the emission lifetime (FWHM) is presented as a function of the focusing distance. When the laser was focused behind the target (i.e. d<17 mm), performance of the laser in initiating a breakdown on the target was poor. The plasma lifetime increases substantially when the laser was focused above the target (d>17 mm) and then it began to decrease to levels comparable to the duration of the laser pulse as d increased to 19 mm and longer. In Figure 4-6b, the integrated emission intensity together with the S/B ratio at these distances were measured. Both parameters followed the pattern observed for the lifetime

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66 measurements above. Figure 4-7 shows the digital images of the plasma at different focusing distance. In Figure 4-7a, the camera was positioned approximately 45 o to the direction the laser beam while in Fig. 4-7b, the camera position was perpendicular to the laser beam. The plasma physical dimensions also showed significant sensitivity to the focusing conditions, as did the emission time profile and intensity. For the target used in this work, the maximum plasma height from target surface measured was 100 m; smaller and slightly larger plasmas have been observed on other targets at the same conditions. In other cases where the lens-to-sample distance have been varied in such a manner, plasma parameters such as intensity and size attained higher values for both positive and negative defocusing distances(76). Positive defocusing refers to focusing above the sample surface and negative defocusing refers to focusing behind the sample. In this work, positive defocusing produced higher values for all parameters measured. The target position for maximum plasma intensity also produced the minimum focal spot diameter (8 to 10 m in most cases) resulting in higher irradiances. Such strong dependence of the plasma properties on focusing places a demand on the accurate positioning of the target in subsequent experiments in order to obtain reproducible data. Other normal lenses with long focal lengths and working distances are being investigated in order to find a suitable compromise between a higher irradiance and larger working volume. LIBS plasmas are known to be inhomogeneous in temperature, electron number density and emission intensity(77). Ideally, LIBS spectra are to be observed with a narrow slit width in order to obtain good spectral resolution. The plasma, however,

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67 17.017.518.018.519.019.50.40.60.81.01.21.41.61.8 Emission lifetime (FWHM, ns)Distance from objective (mm) 1617181920024681012 Distance (mm)S/B101001000 log (intensity) /a.u Figure 4-6 Effect of focusing on plasma characteristics. Variation of (top) plasma lifetime and (bottom) signal to background ratio, S/B, with target position from the focusing objective.

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68 Figure 4-7 Photographic images of the LIP. The camera was positioned at approximately (a) 45 o and )b)90 o to the direction of propagation of the laser pulse. The laser beam is coming from the left-hand side.

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69 expands rapidly immediately following formation and hence only a small amount of light reaches the detector. Since the distribution of species in the plasma is non-uniform, the fraction of light that is collected must be constant for spectral lines of all species in order that the spectral information will be representative of the material on which the plasma was formed. In the case of microchip laser plasmas, the small size of the plasma minimizes this spatial inhomogeneity since in most cases, the plasma image size is smaller than the slit width. The challenge is that spatially resolved data are difficult to obtain. In the absence of both timeand space-resolved information, concepts such as local thermodynamic equilibrium lose their significance since these have a temporal and spatial components. Plasma Temperature Measurements Temperature is an important parameter of plasmas that has been studied for decades, and continues to be studied even for conventional laser systems, because temperature controls ionization processes in the plasma and the composition of the emission spectrum. A critical assumption made in the construction of LIBS calibration curves, where intensity ratios are used, is that the plasma is in a state of local thermodynamic equilibrium. In order to ascertain this condition, accurate determination of the plasma temperature and electron number density is vital. In most cases, spatially and time-resolved measurements provide a better picture of the condition of the plasma. Even though such measurements have been difficult with the microchip lasers due to the small size and short lifetime of the plasma, space and time-integrated measurements will be presented as a preliminary characterization of the plasma. The intensities were averaged over the entire time history of the entire emitting plume. Boltzmann plots (78) were used to estimate the plasma temperature and it followed the expected linear

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70 behavior. Figure 4-8 is a sample plot using selected iron lines from plasma formed on iron foil. Temperatures obtained were similar for a set of metallic targets (Cu, Cd, Pb) ~ 10,000 K 300 K. Iron and silicon yielded a significantly higher temperature, 11,200 K and 13,700 respectfully, 200 K in either case. These measurements will be useful both in validating a first principle model and in estimating the performance of the microchip laser LIBS. -2-1012-2-10123 11222211ln BALn AgIAgILn A/B E1-E2 (eV) Figure 4-8 Boltzmann plot with selected iron lines. E 1 and E 2 are upper energy levels of line 1 and 2 respectifully. Conclusions The feasibility of a LIBS system based on the microchip laser, the ablation properties and the analytical performance of the microchip laser in both qualitative and quantitative application have been demonstrated in other sections of this work. Using a pump-probe diagnostic scheme, this chapter further characterized the laser-induced plasma at sub-ns time scale. The plasma showed a maximum absorption approximately 1.2 ns following the laser pulse and became almost transparent at times larger than 4 ns.

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71 In spite of the eight times increase in pulse energy, the temporal profile of the plasma is similar to that observed for the case of the microchip laser plasma at lower energy. To fully characterize these lasers, a detailed time-dependent study of the plasma in both cases is necessary. Lower pulse energies require that the laser beam be focused tightly to obtain high irradiances in order to overcome the plasma breakdown threshold on most targets making the plasma properties extremely sensitive to focusing conditions. A study of the electrical properties of the plasma together with the absorption measurements indicated that plasma shielding is minimal with these laser types compared to lasers typically used in LIBS.

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CHAPTER 5 TRACE METAL ANALYSIS BY MICROCHIP LASER-INDUCED BREAKDOWN SPECTROSCOPY Summary The development of a compact laser-induced breakdown spectroscopy (LIBS) system will increase the possibilities of applying the technique in industrial process monitoring. In this chapter, the quantification of elemental composition of several matrices using a higher power microchip (powerchip) laser was undertaken. A prototype setup for real time, in situ quantification of trace metals in steel alloys by microchip laser LIBS was investigated as a means of enhancing the applicability of the LIBS technique to process monitoring in the steelmaking industry. The performance of the LIBS technique based on a microchip laser and a portable non-intensified, non-gated detector for elemental quantification was evaluated and compared to that obtained using an intensified detector. Calibrations were achieved for Cr, Mo, Ni, Mn and Si in steel with linear regression coefficients between 0.98-0.99 and limits of detection below 100 ppm in most cases, but the performance in non-metallic samples was marginal. Introduction Laser-induced breakdown spectroscopy (LIBS) is exhibits certain problems as a quantitative analytical tool. Difficulties presented by various matrix effects, poor accuracy and precision limit the performance of LIBS in quantitative analysis. Recently, the capacity of LIBS for quantitative elemental analysis has been demonstrated in 72

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73 numerous fields: environment; metallurgy; mining, etc(32). Applications in the pharmaceutical sector have also appeared recently ((79, 80). As part of the preliminary investigation described in Chapter 2, an assessment of the analytical capability of the microchip laser LIBS was carried out. The LIBS system based on that setup was characterized by a relatively low sensitivity in the detection of magnesium in a graphite matrix (20). The aim of this chapter is to assess the feasibility of using a higher power microchip laser (also referred to as Powerchip) LIBS for the quantitative analysis of trace elements. Matrices used include low alloy steel samples, silicon dioxide (washed sand) and graphite. Steel particularly was chosen because in recent years, quantitative analysis of steels by LIBS have been performed successfully by several authors ((36) achieving good figures of merit. Therefore a comparison of the performance of the microchip laser LIBS to a number of previous studies which used more conventional experimental arrangements can be made. Elements of interest in the steel work are Cr, Mn, Mo, Ni, and Si while Mg, Si, and Fe will also be determined in sand and graphite. Graphite was also chosen as a matrix to study because LIBS of graphite has several applications: For instance, carbon thin films, due to their diamond-like properties, have been attracting intense theoretical and experimental investigations (81). LIBS of graphite is also important for fullerene synthesis (82). The results obtained using a portable spectrometer as the detector were compared with those obtained using a conventional intensified CCD array spectrometer. Experimental A schematic diagram of the quantitative powerchip LIBS system is shown in Figure 5-1. It consists of four primary components: A powerchip laser, a focusing

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74 microscope objective, a fiber optic and spectrometers. The laser beam was focused by a 50X microscope objective unto various targets as described in Chapter 3. Plasma emission was collected with a 600 m diameter fiber optic coupled to a high resolution miniature fiber optic spectrometer (HR 2000, Ocean Optics Inc., USA) with 0.03nm FWHM spectral resolution and a grating with 2400 grooves mm -1 No optics were used to collect the plasma emission. The fiber tip was simply placed within a few mm of the plasma. The data were collected and processed by the OOI Base32 software (Ocean Optics, Inc.) running on a laptop computer. The experiments were repeated with a gated, intensified CCD spectrometer, SpectroPro -500i (Acton Research Corp.) with 0.02 nm spectral resolution and a 40 m entrance slit operating in a free running (non-gated) mode. For these experiments, spectral segments of 8 nm for the plasma emission were recorded using a grating with 2400 grooves mm -1 Spectral data were collected and processed with Winspec 32 software running in a desktop computer. Figure 5-1 Quantitative LIBS experimental setup.

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75 Samples analyzed were steel alloys (cast iron spectrometric reference materials) and graphite and silicon dioxide each spiked with varying concentrations of iron, magnesium, and aluminum. These samples were mixed and presented as pressed pellets. Results and Discussion Quantitative Analysis of Low Alloy Steel In Table 5-1, the composition of the steel samples and their respective concentrations are shown. Figure 5-2a shows a typical powerchip laser spectrum of steel which is spectrally rich due to the complexity of the matrix. When a narrow portion of this spectrum is screened, distinct emission lines belonging to various elements can be identified. For example, Figure 5-2b is an 8 nm spectral window showing the overlap of a pure Fe spectrum and that obtained from a steel sample with Cr lines at 425.44 nm and 427.48 nm. Table 5-1 Composition of the steel standards. Concentrations are expressed as % weight. Sample C Cr Cu Fe Mn Mo Ni Si CKD/232 1.930 1.190 0.038 91.859 0.090 0.850 0.026 3.500 CKD/233 2.120 1.920 0.110 92.184 0.260 0.023 0.052 2.590 CKD/234 2.460 0.460 0.275 91.969 1.390 0.210 0.305 2.020 CKD/235 2.730 0.410 0.157 91.772 1.860 0.450 0.195 0.920 CKD/236 2.850 0.050 0.215 91.814 1.080 0.064 1.774 1.650 CKD/237 3.030 0.150 0.545 92.135 0.130 1.340 0.700 1.200 CKD/238 3.360 0.018 0.920 91.897 0.480 0.115 1.110 1.550 CKD/239 4.150 0.052 0.085 91.877 0.760 0.007 2.420 0.270 Data analysis of LIBS spectra is an aspect of significant importance in order to demonstrate the suitability of the method as compared to other conventional methods. This requires skill in the selection of optimum wavelength and the establishment of the most accurate and robust calibration curves. For this reason, the stability of the signal during laser sampling was characterized first. One of the main noise contributions influencing the response stability is the fluctuation noise due to random changes in the

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76 plasma intensity from pulse-to-pulse (83). Typically, the shot-to-shot relative standard deviation during LIBS analysis can be up to 20%. A significant part of this variability is due to the fact that a single laser shot ablates only a very small fraction of a relatively heterogeneous sample. One technique used to reduce this variability is normalization of the emission intensities to that of a carefully selected internal standard. In this work, peak intensities were normalized to the intensity of the background continuum emission or to a suitably selected Fe emission line. Table 5-2 shows the emission lines from the elements of interest and the internal standards employed in the calibration curves. The normalization lines were carefully selected taking into account the features that characterize a suitable internal standard while avoiding the interference of emission lines in such a complex steel matrix, previously studied by other authors (84). (b) 360380400420440020040060080010001200140016001800 Intensity (a.u)Wavelength /nm4224244264282004006008001000120014001600 Cr I, 427.48 Fe I, 426.04Cr I, 425.43 Fe I, 425.01 Pure Fe (0% Cr)Intensity (a.u.)Wavelength (nm) Steel (1.92% Cr) (a) Figure 5-2 (a) Spectrum obtained from microchip laser-induced plasma on steel and (b) superposition of 8 nm spectral window for a pure Fe standard and that of a steel sample containing 1.92% Cr. Spectrometer HR 2000 was used with integration time of 1 s. Figure 5-3 is a plot showing the variation of the net emission intensity and the intensity normalized to the background or an Fe emission line. It can be seen that the shot-to-shot reproducibility improves by using both approaches. The means of handling

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77 the spectral data using the background continuum or a line belonging to the matrix is known as internal standardization and has the potential to significantly improve both precision and accuracy. With the data in Figure 5-3, the RSD for curves a, b, and c are respectively 1.6%, 6.3% and 2.5%. With the microchip laser, fluctuation in laser power stability is minimal (20). Therefore, the variation in the signal in the case of the net intensity is ascribed to changes in the target surface angle due to rotation and translation described previously. Again, although the sample was always in continuous rotation, the microplasma created at such a high repetition rate could be partially hidden in the crater depth, affecting the emission intensity in a random fashion from shot to shot. Table 5-2 Selection of spectral lines and internal standards. In some instances, the background continuum (Bgd) in the vicinity of the element line was used as internal standard. (nm) Emission line (nm) Fe normalization Cr(I) 425.43 nm Fe(I) 425.07 Bgd, 425.68 Mn(I) 403.07 nm Fe(I) 400.52 Mo(I) 386.41 nm Fe(I) 387.25 Ni(I) 341.47 nm Fe(I) 342.71 Si(I) 288.16 nm Fe(I) 287.41 Another way of improving precision in LIBS is shot averaging. The experiments were carried out at a pulse repetition frequency of 1 kHz, and an acquisition time of 1000 ms, which effectively adds up the emission from 1000 sequential plasmas. 5-4 shows two curves: a) the fluctuation of the emission intensity of Mn (I) 403.1 nm, where each point represents the sum of 1000 shots; and b) the standard deviation of this signal obtained by averaging the collected data points progressively (i.e. moving average of previous data points).

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78 Figure 5-3 Shot-to-shot fluctuations in LIBS signal intensity: (a) Intensity of Cr normalized to the background continuum emission; (b) Net intensity of Cr line and (c) intensity of Cr normalized to an Fe line. Figure 5-4 Reduction of noise by signal averaging: (a) Fluctuation of the emission intensity of Mn 403.1 nm and (b) variation of the standard deviation (in intensity units) of the signal by progressive averaging of the collected data points.

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79 It was observed among most of the targets studied that the fluctuations in the initial collected data points were generally higher than the latter points, unless special care was taken to clean the samples before analysis. After exposure of the target surface to several laser pulses, the variation in the emission intensities was low and more uniform. The initial fluctuations can be partly due to target surface impurities. As mentioned in previous papers (85), the samples need to be exposed to a certain number of preparatory laser shots before performing the measurements in order to eliminate any surface impurities and also to ensure that the surface of the target is representative of the bulk composition. In the steel analysis described in the following section, 10 surface cleaning data oints and 15 data oints for data acquisition (all integrated over 1000 ms) were fixed as the best acquisition conditions to minimize signal fluctuations. This capability of LIBS where the focused laser pulse cleans the target surface offers a great advantage over other analytical techniques. For example, both LIBS and spark emission spectrometry are based on the same technique. However, spark emission technique requires samples with well ground and polished surfaces; LIBS does not because the ablation pulse is capable of the surface treatment prior to data collection. The high spatial resolution and repetition frequency of microchip lasers even makes surface cleaning faster and more effective. Figure 5-5shows the calibration curve for Mo using the compact spectrometer. Similar curves were obtained for Cr, Mn and Mo were correlation coefficient of 0.98 or better and relative standard deviation of 3.6, 6.3, and 5.5 % respectively. The RSD values were obtained with the samples with the lowest concentration of the analyzed element (see Table 5-1).

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80 0.0000.0040.0080.0120.0160.000.050.100.150.200.250.30 IMo 386.41 nm /I Fe 387.25 nmConc. of Mo/ conc. of Fe Figure 5-5 Calibration curve for Mo using the compact spectrometer, HR 2000. The lines used are Mo (I) 386.41 nm normalized to Fe (I) 387.25 nm Microchip LIBS with Non-intensified versus Intensified CCD Spectrometers Quantitative analysis of the same steel samples was performed using a conventional spectrometer fitted with an intensified CCD as detector. Figure 5-6shows an 8 nm spectral region of 15 averaged data points using a), SpectraPro 500 Intensified spectrometer which allows 8 nm acquisition window and b), HR 2000 portable non-intensified spectrometer which allows 90 nm acquisition window. The acquisition data parameters for both experiments were the same: a free running mode for both detectors and each data point is an average of 1000 laser shots. Resolution is slightly better for the ICCD than the portable spectrometer except that a few spectral details appear in the spectra obtained with the portable spectrometer for the same sample. For instance, the line 426.42 nm, appearing at the shoulder of the Fe 426.04 nm does not appear in the

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81 spectrum with the ICCD. In the data acquisition mode employed in this work, the most significant difference between the two detection systems is the detector. As expected, the signal and background in the intensified spectrometer were much higher than when the non-intensified CCD was used. The intensified CCD spectrometer was capable of detecting more elements in the steel samples than the portable one because of the flexibility in the selection of wavelength windows. On the other hand, the narrow spectral window provided by this spectrometer presents a problem in performing a real-time multielemental analysis. Figure 5-7 shows the calibration curves for Ni and Si with the intensified CCD system. These elements could not be detected with the portable CCD spectrometer due to strong interference from other transitions at the wavelengths of interest. Copper (Cu I, 360.2 nm) and carbon (227.7 nm) were also identified in the steel samples using the portable spectrometer and the iCCD system, respectively; even though these elements were not quantified. 4224244264281400000160000018000002000000220000024000002600000 Intensity (a.u.)Wavelength (nm) Steel (1.92% Cr) Pure Fe (0% Cr)4224244264282004006008001000120014001600 Fe I 427.18 Pure Fe (0% Cr)Intensity (a.u.)Wavelength (nm) Fe I 425.01 Cr I 425.43 Fe I 462.04 Cr 427.48 Steel (1.92% Cr) Figure 5-6 Spectra obtained on iron foil and steel using (a) an intensified CCD and (b) a non-intensified CCD spectrometers.

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82 0.0000.0050.0100.0150.0200.02 5 0.000.040.080.120.16 I Si 288.16nm /I Fe 287.41 nmConc. Si / Conc. Fe0.0000.0050.0100.0150.0200.0250.0300.000.040.080.12 I Ni /I FeConc. Ni / conc. Fe Figure 5-7 Calibration curves using the intensified CCD spectrometer. (Top) Ni (I) 341.47 nm normalized to Fe (I) 342.71 nm and (bottom) Si (I) 288.16 nm normalized to Fe (I) 287.41 nm. Table 5-3 summarizes the limits of detection (LOD) for the species studied using the two spectrometers. The LOD was estimated as three times the standard deviation of the background signal divided by the slope of the calibration curve (86). The highlighted values are those obtained using the non-intensified portable spectrometer. For Cr, the

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83 LOD obtained with the portable, non-intensified spectrometer is lower than that obtained with the ICCD but the data obtained for Mo and Mn are comparable for the two spectrometers. Relative standard deviation (RSD) of the two detection systems was comparable except that it was several times better in the case of Mn with the ICCD than the non-intensified CCD detector. Earlier work(87, 88) showed that the signals obtained with the ICCD were usually at least an order of magnitude higher, the SNR is typically three times better and the LOD an order of magnitude lower than values for the non-intensified system. It is not clear at the moment the reason for the comparable sensitivity for the two detectors with the microchip laser systems. It should be noted that the intensified CCD used in this work was operated in a non-triggered, non gated mode. In the earlier work referred to above, the detector was operated with gate delay with respect to the plasma-initiating laser pulse. Generally, LIBS data conventionally collected this way have higher signal to background and sensitivity than those obtained in the mode used in this work. The conclusion from the above discussion is that, with regards to overall cost, field deployability, speed of data acquisition and processing, microchip laser LIBS with portable non-intensified non-gated detectors offers advantages over traditional systems. Performance in Other Matrices The performance of the microchip laser LIBS to detect and quantify elemental composition in pellet samples was also investigated. Figure 5-8 is a spectrum showing iron emission lines in silicon dioxide. Figure 5-9 shows the variation of signal with element concentration for iron and magnesium. The samples were in a powder form and presented as pressed pellets after blending in a mixer. Samples of this nature are more

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84 Table 5-3 Analytical figures of merit of the elements analyzed using both the portable high resolution spectrometer and the intensified spectrometer as detector. SLR denotes studied linear range. The data in bold were obtained for the portable, non-intensified spectrometer Emission Line SLR (%) RSD (%) LOD (%) Cr(I) 425.43 nm 0.018-1.92 4.6 3.6 0.01 0.003 Mn(I) 403.1 nm 0.09-1.86 1.2 6.3 0.003 0.004 Mo(I) 384.4 nm 0.007-1.34 5.2 5.5 0.008 0.009 Ni(I) 341.42 nm 0.052-2.42 1.3 0.009 Si (I) 288.16 nm 0.27-2.02 4.6 0.02 heterogeneous than the steel samples studied in this chapter, which have been commercially blended to achieve acceptable homogeneity. Because the microchip laser removes just ng to pg samples for analysis, it will be expected that poorer reproducibility and lower correlation between element concentration and signal intensity will be obtained from such samples. The bending of the calibration curves at higher concentrations, especially in the case of Mg, might rather be due to matrix effects as well as self-reversal. Ideally, transitions that are not coupled to ground state (i.e. non-resonance lines) should be used to avoid this effect. However in this study, no suitable emission lines free of interference from the matrix were available within the spectral window provided by the spectrometer. Even though for all the elements studied, the most sensitive lines within the wavelength window provided by the spectrometer were used, detection limits (LODs) were between 0.1 and 0.2%. These values are at least 100 times higher than what was observed in the steel analysis described above. Several reasons could account for the poorer LODs in these matrices. The most significant, perhaps, is the higher breakdown

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85 23024025026027028029030005001000150020002500 Fe I Fe IISi I, 288.16 Si I, 250.69, 251.43, 251.61Wavelength (nm)Intensity (a.u)Si I, 243.52(a)(b) Figure 5-8 Spectrum of silicon dioxide: (a) pure and (b) spiked with iron ore. thresholds in these pellets compared to the steel targets. The higher breakdown thresholds can be ascribed to the material morphology as well as the surface quality as these determine the mechanisms of dissipation of laser energy in bulk solids (see Table 4-1). Generally, the laser-induced spark on pure metals and alloys was larger in size and more luminous than observed on pellets. In metals, the conduction band electrons absorb laser energy and then dissipate it through the thermal conductivity via electron-phonon collisions (20). As the metal character of the material decreases, the laser-matter interaction becomes more complicated including multiphoton absorption, absorption on structural defects, etc. Electron-lattice coupling also changes, affecting the efficiency of energy transfer from laser-heated electrons to the material bulk. Equally important is the surface quality of the target. The surface of the pellets is more grainy and loose than that of metal samples. It is therefore easy for an aerosol to form above the sample surface which blocks the emission from the collection lens. Again it is expected that more material will be removed per laser shot in the pellets than in pure metallic samples. Much less material is expected to contribute to plasma emission as discussed in Chapter 3,

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86 while these bigger craters erodes the surface integrity which deteriorates the focusing condition as the focus depth of the microscope objective is shallow. It should be pointed out that the detection limit of 0.1-0.2% reported for the 50 J microchip laser is 100 times better than what was observed for the microchip laser at 7 J in the preliminary feasibility study (20) in a similar matrix. As mentioned earlier, unlike high power lasers which ablate 100s of ng material for analysis, in the case of the microchip laser, only pg to ng of material is removed and only a fraction of this is expected to be vaporized into the plasma. The situation makes the homogeneity of the material a critical requirement in chemical analysis based on the microchip laser LIBS. The effect of the sample homogeneity was studied using silicon dioxide with varying concentration of iron. The samples were blended with a mixer for different times and the variation of emission intensity with time was assessed. Figure 5-10 was obtained for a 3% Fe sample in silicon dioxide blended for 5 and 10 minutes. The RSDs for data (a) and (b) are respectively 17% and 6.8%, showing a significant improvement in reproducibility with higher mixing time. The values at both times are however higher than the mean RSD obtained for the relatively homogeneous steel samples analyzed earlier. Conclusions The results in this study demonstrate the feasibility of quantitative analysis based on microchip laser LIBS. The robustness of the laser, miniaturization of the detector, and the simplicity of the experimental configuration and data acquisition confer to the technique the advantage of field portability and real-time applications. Analysis of the composition of a low alloy steel has been performed and characterized by remarkably

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87 0123450.00.20.40.60.81.0 Mg 285.2 nm / Si 288.2Mg concentration in SiO2 (% w/w) 0123456050100150200250300350400450 Intensity / CountsConc Fe (%) Figure 5-9 Calibration curves for (a) magnesium and (b) iron ore in sand (silicon dioxide). In (a), the signal is presented in form of intensity ratio of Mg (1) 285.2 nm to Si (I) 288.16 nm while in (b) the net intensity is used.

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88 0246810121416180.250.300.350.400.450.500.55 (a)Relative intensityData number0246810121416180.200.250.300.35 (b)Relative intensity (a.u)Data number Figure 5-10 Effect of sample homogeneity on data reproducibility: (a) A mixture of iron ore and silicon dioxide blended for 5 min. and (b) sample blended for 10 min. good figures of merits. Detection limits in pellet samples was about two orders of magnitude higher than in steel samples possibly due to the higher sample heterogeneity, surface irregularities and different mechanisms involved in the laser interaction with the different matrices. Practically, in the field, the sample possibly cannot be held static at a fixed distance to the focusing and collection optics as used in this work. Field setup will then be more susceptible to fluctuation in the LIBS signal. Again in an industrial setting, for instance, in scrap sorting in steel production, samples with different roughness, thickness and composition of surface layers will be presented to every laser pulse. Detection limits and precision may therefore be poorer than reported in this work. Nevertheless, from the point of view of both economics and response time, there are situations where the capability for real-time, in-situ, non-destructive measurements is more compelling than detection limits and precision.

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CHAPTER 6 AIRBORNE PARTICLE DETECTION BY MICROCHIP LASER-INDUCED BREAKDOWN SPECTROSCOPY Introduction Determination of the source and nature of atmospheric metal and biological particles has been the subject of increasing interest in recent years, especially with regard to their environmental and health implications. There is evidence that submicrometer sized airborne particles are more reactive and more dangerous than larger particles due to large surface-to-volume ratio and higher permeability into respiratory systems (89). Aerosols have been implicated in global warming and heterogeneous chemistry in both the troposphere and stratosphere(90). Airborne particles can vary widely in composition, size, and biological effects and their sources can be traced to wind, sea spray, fires, meteoric and anthropogenic (combustion, industrial and cultivation). In Table 6-1, the approximate size range of some common airborne particles is presented. The very low concentration of some of these particles tends preclude the development of direct or near real-time methods for detection. Conventionally, filters are used to trap particles in the atmosphere for subsequent off-line chemical analysis using techniques such as scanning electron microscopy (SEM), electron probe X-ray microanalysis (EPXMA), and particle-induced X-ray emission (PIXE)(90, 91). The technique of collecting particles on filters for later analysis is characterized by a number of disadvantages. In the first place, it is a time consuming process since the sample collection site is usually distant from the analysis site. Also, a considerable amount of time is normally required to collect a 89

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90 measurable amount of a particular atmospheric agent. The procedure also normally requires high-purity filters (for example, polytetrafluoroethylene, PTFE membrane) with high loading capacity which are difficult to come by. In addition, a high level, short duration, incident exposure may be dangerous but when averaged over an extended period, may not be considered as dangerous. Today, there is a greater awareness that low levels of metal particles may be dangerous due to their accumulation in the body(92). A collection of physical methods for the analysis of airborne particles includes X-ray fluorescence, mass spectrometry, X-ray diffraction and neutron activation analysis(93). Some of these methods are limited to a particular group of compounds (such as volatility), are costly, difficult to automate and may require extensive preliminary sample preparation. Again, many of these techniques are not easily translatable into field instruments. The recent knowledge of the effects of particulate matter together with the shortcomings associated with traditional systems has stimulated growing interest in the development of a direct, continuous or near real-time systems for the determination of particles in the atmosphere. Review of Laser Spectroscopy Techniques for Aerosol Analysis Due their multi-element capability, sensitivity and selectivity, several atomic spectroscopy methods have been employed for the determination, sizing and semi-quantitative analysis of trace metals in complex matrices. These include flame atomic absorption spectrometry (flame AAS), ETAAS (electrothermal~), inductively coupled plasma spectrometry (ICP-MS) and laser-induced breakdown spectroscopy (LIBS), just to mention a few. In reference (93), a survey of atomic spectroscopy methods used in airborne particle analysis and the sensitivity achievable for some elements are provided.

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91 Atomic absorption based on flames is the most commonly used technique for determining atmospheric trace metals, despite the difficulty of directly analyzing solids. ETAAS can be used for direct analysis of metal compounds with greater sensitivity although the capability for multi-element analysis is low. ICP-MS has several attractive features regarding its use in the analysis of airborne particulate matter. Compared with other techniques, ICP-MS has low detection limits for most elements, multi-element analysis capability and simple and easily interpreted spectra. The limitation of ICP-MS in this area of application is that it is seldom field portable. Moreover, sample digestion is usually required which may lead to the loss of trace elements, sample contamination, and spectrometric interference owing to acid-derived background ions. Atomic emission employing arcs, flames, sparks and plasmas is available for both multi-element and single-element analysis. Currently plasma emission spectroscopy appears to present the keenest competition to ETAAS. Higher temperatures attainable in plasmas ensure a higher extent of atomization and ionization resulting in more spectra lines than normally obtained in flames. A further advantage of plasmas is that both metals and non-metals such as sulfur, carbon and the halogens can be detected. In this chapter, microchip laser-induced breakdown spectroscopy (LIBS), which shows great promise for direct and near-real-time determination of metal particles in the atmosphere, will be discussed. LIBS appears to be the most practical means for bringing elemental analysis to the field. Another factor that makes LIBS an attractive technique for particulate analysis is the ability to detect single biological samples. In Table 6-2, typical elemental concentrations (as percent by weight) in some biological particles are presented. It was demonstrated recently by Hahn et al. (94) that Na, Ca, and Mg can be

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92 detected by LIBS in ambient aerosols with absolute mass detection limits of 3.3, 0.5, and 1.2 fg respectively. Given the concentrations of these elements in bioaerosols, and the detection limits reported above and elsewhere, it should be possible to detect these metals in single bioaerosols. In addition to chemical composition, LIBS offers a real-time simultaneous measurement of size distribution and number densities(95). Even though the miniature lasers employed in this work are limited by their output energy, this will be compensated for by other attractive features such as high pulse repetition frequency and low pulse-to-pulse amplitude variation. The potential of microchip LIBS to detect single particles will have applications in areas such as real-time assessment of industrial atmospheres and clean room monitoring. Table 6-1 Common airborne particles and their respective size range Substance Minimum Diameter (m) Maximum Diameter (m) Human hair 35 200 Cement dust 3 100 Metallurgical dust 0.5 100 Insecticide dust 0.3 35 Sulfur dioxide mist 0.3 3 Paint pigments 0.1 5 Metallurgical fume 0.011 Tobacco smoke 0.01 1 Magnesium fume 0.01 0.4 Viruses and proteins 0.003 0.005 Gas molecules 0.0001 0.0006 Experimental A picture of the experimental microchip LIBS setup is shown in Figure 6-1. The excitation source for all experiments in this section was a 50 J per pulse microchip laser, described in detail in Chapter 3. Dry aerosols of sodium chloride (NaCl), magnesium

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93 Table 6-2 Elemental concentration as percent by weight in some biological samples. Bg is Bacillus subtilis var. niger, a common simulant for Bacillus anthracis. In the case of oat, wheat and corn, it was fungal spores on these samples that were analyzed. Element Bg Oat Wheat Corn Ca 1.08 0.16 0.0147 0.12 Mg 0.37 0.20 0.0937 0.19 Na 0.38 0.0132 0.0110 0.0171 K 0.49 1.60 2.24 1.63 Fe 0.57 0.0253 0.0032 0.0081 P 2.32 0.44 0.41 0.58 Mn 0.0122 0.006 0.0024 0.0037 chloride (MgCl 2 ), calcium chloride (CaCl 2 ), aluminum chloride (AlCl 3 ), and silicon dioxide (SiO 2 ) were produced using a commercial ultrasonic nebulizer and a membrane desolvator (CETAC U-6000 AT) designed for an ICP system. Using a peristaltic pump, dilute salt solutions were delivered at 2.5 mL/min into the nebulizer. Carrier gas and sweep gas flow rates were set at 0.6 L/min and 2.0 L/min, respectively. Argon gas was used throughout. Heater and coolant temperatures of the nebulizer were 140 o C and 3 o C, respectively, while the desolvator temperature was 150 o C. Wet aerosol from the nebulizer was introduced into the desolvator where they were dried and resulted in fine dispersion of metallic salts. Dry particles coming out of the desolvator were collected with a polyethylene tube (1.5 m length, 0.5 cm internal diameter) and introduced into the focal point of the microscope objective using a Pasteur pipette (1 mm internal diameter at the exit). Particle flow was perpendicular to the direction of the laser beam. Laser-induced sparks were observed whenever particles happen to be in the working volume during the time of the laser pulse. A CCD camera with a filter to remove any interference from the 1064 nm laser beam was used to collect images of the sparks. Also, a fiber

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94 optics cable coupled to a miniature spectrometer, SD 2000 (Ocean Optics, Inc.), was used to collect and store emission signals from the aerosol plasma. Alternatively, emission signals were collected using a single lens setup and PMT connected to the exit port of a monochromator (HV-10). The monochromator was set to one of the most sensitive lines of the elements of interest. This arrangement, together with a newly acquired digital oscilloscope, (Tektronix TDS 6604), allowed shot-to-shot statistics of spark production in real-time. Results and Discussion Within any measurement time, a volume of gas containing aerosol particles flows past the laser beam. Particles that happen to be in the focal volume during the duration of the pulse have a probability of interaction with the laser beam. The extent of this interaction will depend of the particle velocity, size, shape, and duty cycle of the laser and will determine whether a spark will be formed or not. It has been shown that the traditional averaging of LIBS spectra may lead to lower signal-to-noise ratios of the analyte of interest if the overall sampling rate of the analyte containing particles is low(96, 97). With regard to airborne particulate analysis, ensemble statistics may even make experimental data not useful. This is because the discrete nature of the particles and the laser sampling mechanism make the process an all-or-nothing phenomenon. In other words, either a particle is present in the working volume during the laser pulse or not present. Again different size particles and instantaneous flow rates may occur during every laser pulse. Averaging signals with such heterogeneous distributions may conceal vital information. In view of this background, the first part of the data acquisition in this work was setup to examine individual signals from single laser sparks on particles.

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95 Figure 6-1 Single particle microchip LIBS setup. Signals from individual breakdowns were examined using a PMT and a digital oscilloscope operating in waveform-data-base/histogram mode. This provided both a count rate and an intensity distribution of signals from individual trigger events. In order to avoid false triggers, the experiment was first done with the laser turned off and/or particle flow stream stopped. In this case, no visible sparks were observed in the focus of the microscope objective. Figure 6-2 (top) is a histogram of false triggers obtained resulting from the PMT dark current. Similar plots prior to every experiment were done in order to set the trigger thresholds to reject triggers that may not have resulted from spark formation on particles. The mean of the PMT false signals plus 3 was 0.01 V. Signals with amplitude smaller than this value were excluded from the count rate. Introduction of sample increased both the maximum signal and the frequency of triggers. Figure 6-2 shows the intensity distribution of 0.024% Na with trigger threshold at -20

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96 mV. With the trigger threshold set at 10 mV, NaCl solutions with concentrations ranging from 300 to 5000 ppm were nebulized, dried and introduced into the working region (mass percent of Na in the solutions ranged from 0.012% to 0.2%). For each sample, the percent trigger, (that is, number of trigger events with signal at least 10 mV as a percentage of the total number of laser pulses fired), was calculated. Figure 6-3 shows one of such plots. As the concentration increased, the percentage trigger increased initially but plateau and then decrease. In fact, at 0.5% NaCl concentration, trigger rate was 1.6% (not shown in plot), significantly lower than the value at 0.25% salt solution which was about 2.25%. -0.10-0.09-0.08-0.07-0.06-0.05-0.04-0.03-0.02012345678 Percent Signal (V) Figure 6-2 Intensity distribution of sparks on NaCl particles, 0.024% Na by weight. An alternative calibration was based on the signal intensity versus concentration. Because of the intensity distribution and different frequency of occurrence, as shown in Figure 6-2, the weighted mean signal was used. The signal value in every bin was multiplied by the number of times it occurred and the mean of these values obtained. Even though Figure 6-2 shows substantial variation in the signal intensities, this means of

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97 handling the data reduced the mean errors significantly. Figure 6-4 is the plot of signal intensity versus concentration. Similar to the trigger rate, signals at higher concentrations (not shown in figure) did not increase proportionally with concentration. 0.000.050.100.150.200.250.00.51.01.52.02.5 Triger rate (%)NaCl concentration (%) Figure 6-3 Variation of trigger rate (fraction of laser pulses that produce sparks with signal at least 10 mV as a percentage of the total number of laser pulses fired). Concentrations are presented as mass % NaCl. Magnesium chloride solutions containing up to 0.102% Mg by mass were also measured. Two methods were considered in determining the trigger rate. A study of the PMT false triggers at 285 nm required that for Mg, the trigger threshold should be set not lower than 30 mV. One method implemented was to set the trigger threshold as low as possible in order to avoid rejecting true trigger events. PMT triggers at this low threshold would then be included in calibration and subtracted from the sample triggers;

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98 0.000.050.100.150.200.250.00.20.40.60.81.0 Intensity (V)NaCl concentration (%) Figure 6-4 Variation of aerosol spark intensity with concentration. Data were obtained with a PMT. Concentrations are presented as mass % NaCl. analogous to the treatment applied to blank signals. The next approach was the one discussed earlier that sets a higher enough threshold in order to reject most false triggers. Data from both schemes for MgCl 2 is shown in Figure 6-5. With a more relaxed threshold, there was a significant increase in trigger rate even after correcting for false triggers. For example, for 0.4% MgCl 2 at -10 mV trigger level, the trigger rate after correcting for false triggers was 1.40% while it was 0.7% at -40 mV trigger level. This shows that when the trigger threshold is set too high, there may be loss of data due to actual sparks that fall below the threshold. The latter approach extends the sensitivity to small particle size range. In Figure 6-6, photographs of plasma plumes obtained for breakdowns on MgCl 2 and CaCl 2 particles are shown. The images at the bottom were taken with the laser beam attenuated below the breakdown threshold using a neutral density filter. This was verified by the absence of spark formation when the sample was introduced. This arrangement

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99 allowed the observation of sample flow past the focal volume. When the filter was removed, spark formation was observed as shown by the images at the top. In terms of size, the aerosol plasmas were comparable to plasmas formed on metallic foils. The significant differences were that the aerosol plasmas were less luminous, more spherical and more heterogeneous in size distribution. 0.00.10.20.30.40.20.40.60.81.01.21.41.6 -40 mV trigger threshold Trigger rate (%)MgCl2 concentration (weight %) -10 mV threshold Figure 6-5 Variation of trigger rate with concentration: (Black) threshold set at -10 mV and (Red) threshold set at -40 mV. Concentrations are presented in mass % MgCl 2 Dependence of Signal Intensity and Trigger Rate on Particle Size. With the ultrasonic nebulizer used in this work, increasing concentration is expected to affect the particle size more than the number of particles produced. As bigger particles are more sluggish and also present larger volumes to the laser pulse, it is expected that increasing concentration will lead to higher probability of hitting a particle. It is interesting to note that the dependence of trigger rate on concentration is linear only

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100 Figure 6-6 Photographs of sparks on MgCl 2 and CaCl 2 : (Top): Full laser energy in use, interference filter in front of camera removes 1064 nm light, (Bottom) Laser energy attenuated below breakdown threshold; scattered laser beam shows particle flow in the focal volume. at lower concentrations and bends at higher concentrations (Figures 6-3, 6-4, and 65). Several reasons can be suggested to explain these observations: 1. Transport efficiency may account for particle losses in the sampling line between the aerosol chamber and the laser focus. These losses will be determined by both the length of the tube as well as the particle size. Experiments and calculations have shown that depending on flow rate, pressure and other factors, different size particles may be transported with varying efficiency(94, 98). 2. Inlet transmission between the point where the sample exits the nozzle and the laser working volume. Due to inertial deposition, bigger particles have more likelihood of falling out and not interacting with the laser beam. 3. Efficiency of mass ablation and particle vaporization, even for particles that enter the working volume, may differ from particle to particle, partly depending on particle size. Bigger particles can act as heat sink absorbing the laser energy.

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101 In a related study using a 320 mJ laser source and silica particles, Carranza et al. established 2.1 m as the upper particle size for complete vaporization of aerosol particles(97). This limit may vary for different pulse energies, focusing optics and particle types. An attempt was made to obtain size distribution with a particle sizing instrument based in light scattering. The output data indicated that more than 98% of particles under consideration are below 200 nm. Since minimum display on the instrument is 100 nm, the size distribution could not be obtained. Using the densities of the materials, and assuming the nebulizer produces wet aerosols of 1 m spherical diameter, the estimated mean dry particle sizes are of the order of 50 nm to 200 nm depending on the concentration. The masse of the analytes in these particles are of the order of fg to ag levels. In order to understand the effects of increasing concentration (and hence particle size) on signal intensity and trigger rate, it will be important to consider the processes that lead to mass ablation and particle vaporization in the plasma. In reference(97), it was inferred through experiments and theoretical models that plasma-particle interaction controls the vaporization and dissociation of particles. Specifically, it was concluded that laser-particle interaction contributes to less than 1% of the processes leading to vaporization and dissociation. With the short pulse of the microchip laser (20 times shorter than that used in referenced work), it is expected that much less interaction between the laser pulse and aerosol particles occurs. It has to be pointed out that in the reference(97) a spark or plasma was created with every laser pulse and aerosols particles were introduced into the plasma for vaporization. In the work with the microchip laser, the plasma is only formed if a particle happens to be in the laser focus during the lifetime

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102 of the pulse. A complete understanding of the laser-particle and plasma-particle interaction will therefore require different assumptions and models and will not be treated in this dissertation. Identification of Particles by Emission Signal Detection of particles is only part of the story: An analytical chemist is further interested in identifying the particle or its composition if it is heterogeneous or in a complex matrix. Plasma emission was collected by an optical fiber into a spectrometer. The optical fiber was pointed directly at the plasma without any other optics. The integration time for all samples was 10 s, which required that the experiments be done in complete dark in order to avoid interference from room light. The fixed pattern noise of the spectrometer was subtracted from all spectra. Figure 6-7 to 6-10 are representative spectra for various samples. All samples were introduced as their chloride salts. Several emission lines from Ar were observed in the higher wavelength region in all samples. When the argon gas alone was introduced, no visible sparks were observed. From the hit rate discussed earlier, each of these spectra is expected to be the result of 40 to 60 or fewer single sparks depending on both the inlet and fiber geometry. Since no optics were used to collect the emission into the optical fiber, the fraction of the plasma imaged will depend on the particle location in the focal volume.

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103 2003004005006007008000200400600 Emissions from Ar Al I (g),Al I (g), Intensity (a.u)Wavelen g th ( nm ) Figure 6-7 LIBS spectra of solution containing 0.05% Ca presented as AlCl 3 Figure 6-8 LIBS spectra of solution containing 0.15% Ca presented as CaCl 2

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104 10020030040050060070080090002004006008001000 MgNa I Ca ICa IIIntensity (a.u)Wavelength (nm) Figure 6-9 LIBS spectra of an ICP grade standard solution containing 0.05% Na, 0.04% Ca and 0.027% Mg 3003253503754004254500100200300400500600 Cd II, 441.6Cd I, 361 (3 lines) Intensity (a.u)Wavelength (nm) Figure 6-10 Spectrum of solution containing 0.3% Cd.

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105 Figure 6-11 shows the effect of increasing concentration on the emission signal from Mg. Since the spectrometer could not resolve the Mg II 279.55 nm and Mg II 280.27 nm, the data used to obtain the calibration curve are the net emission intensities of both lines. The large error bars are due partly to the effect of particle size distribution, particle location in the focal volume, as well different hit rates. The results emphasize one of the unique advantages of plasma spectroscopy: the capability to detect both metals and non-metals. In this work, emission from Ar, N 2 (when N 2 was used as carrier gas) and Cl 2 were observed in most samples. 0.000.020.040.060.0802004006008001000 Intensity (a.u)Mg concentration (%) Figure 6-11 Signal dependence on concentration for Mg aerosol. Conclusion Individual nanometer sized airborne particles have been detected by microchip laser-induced breakdown spectroscopy. An attractive feature of the counting statistic employed in this work is that, distinguishing spectral properties or other features of the

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106 particles of interest can be easily retrieved because they are not hidden in averages associated with bulk spectral measurements. Both spark intensity and hit frequency showed a strong dependence on sample concentration and particle size, with this dependence being fairly linear at lower concentrations. Detection of airborne particles by MCL LIBS using their spectral fingerprint has also been demonstrated. The low emission signal required relatively long integration times. The capability to detect submicron particles in real time with microchip laser LIBS will have wide applications. Certain manufacturing industries require that airborne particles are controlled to specified limits. In the preparation of Si wafers or chips in the semi-conductor industry, for instance, particles in the size range used in this work can modify a host of chemical properties and result in product defects. A cheaper, simpler system, as described in this work, could provide the first warning signal should airborne particle density exceed a defined limit.

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CHAPTER 7 CONCLUSION AND FUTURE WORK Conclusion Microchip laser ablation of metals and its application to laser-induced breakdown spectroscopy (LIBS) was studied. The ablation performance of these solid state miniature lasers is superior compared to lasers used in traditional laser ablation systems due to high spatial and depth resolution. The mass removed per laser shot during microchip laser ablation can be easily characterized due to well defined crater parameters resulting from low pulse-to-pulse amplitude fluctuations and good beam quality. At lower energies the ablation efficiency of the microchip laser is higher than that reported for other lasers, but this property does not translate into emission intensity and hence sensitivity of microchip laser LIBS. This lower emission intensity at lower energies was ascribed to the fact that a significant fraction of the ablated material is not vaporized and therefore does not contribute to plasma emission. At relatively higher energies, much less of the ablated target is re-deposited. The parameter ablation sensitivity was introduced to characterize the ablation process and was defined as the detector count per laser pulse energy. Unlike ablation efficiency, values of ablation sensitivity could be easily reconciled with LIBS signal and other observation during the ablation process. Diagnostics of the microchip laser-induced plasma was important in establishing steps that could improve the analytical performance of LIBS based on these lasers. Unlike plasmas induced by long pulse high energy lasers, microchip lasers are short-lived; the plasma lasts for few nanoseconds. This did not allow time-resolved study of the 107

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108 plasma using conventional electronic systems available in the laboratory. Time-depended information on the microchip laser plasma was obtained using the absorption of a probe beam introduced into the plasma at different times after the laser pulse. Maximum attenuation of the probe beam was observed about 1.2 ns after the laser pulse. Other studies in the literature suggest that the evolution of electron number density and temperature can be ascertained from this observation. CCD photography provided snap-shots of the plasma plume propagation. Plasma height above target surface was approximately 100-200 m, depending on focusing conditions and target properties. The low output energy from the microchip laser required tight focusing in order to overcome the breakdown threshold. Using this tight focusing, the breakdown threshold was measured for several targets. This, however, makes plasma parameters heavily dependent on experimental conditions and may represent the most serious limitation of the microchip laser, especially when used as a source for LIBS. Using electrical signal measurements and the absorption studies, a significant observation in microchip laser ablation is that, the plasma interacts to a lesser extent with the laser pulse, compared to conventional laser sources. There is less shielding of the laser pulse and therefore more of the incident energy is deposited onto the target surface and results in material removal. The partly explains the higher ablation efficiency of the microchip lasers discussed above. Microchip laser LIBS was used to determine and quantify trace elements in various matrixes. The high pulse repetition frequency was employed in the cleaning of the target surface which resulted in significant improvement of precision. The elements Cr, Si, Mo and Mn were quantified in steel alloys with detection limits of the order 100 ppm and

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109 accuracy of 6% or better. In powdered samples, sensitivity and accuracy was low due to spurious interference from laser generated aerosol, sample heterogeneity, and surface quality. Due to the small amount of material analyzed, microchip laser LIBS showed strong dependence on sample homogeneity and shot averaging. Detection limits obtained using the microchip LIBS setup and non-intensified CCD (CCD) spectrometer were comparable to those obtained with an intensified CCD detector (iCCD). However, more species could be detected with the iCCD than with the CCD. The compactness of the laser together with the portability of the spectrometer used in this work offer a prototype for field-friendly LIBS setups. Airborne particulate matter ranging in size from 50 to 150 nm was characterized by microchip laser LIBS. Sampling statistics employed here were based on single laser hits and not on bulk averaging normally employed in LIBS. Signal was considered as resulting from plasma breakdown on an aerosol particle if the intensity was above a preset threshold. Two main calibration schemes implemented were the variation of hit versus concentration and variation of the weighted signal intensity versus concentration. Both relationships were fairly linear at lower concentration but deviated from linearity at higher concentrations. Since increasing concentration is normally associated with increasing particle size, it was inferred that the bending of the curve at higher concentrations was partly due to changes in transport efficiency and inlet efficiency. Future Work This dissertation presents the first feasibility of the use of microchip lasers in laser-induced breakdown spectroscopy. Several areas of both fundamental importance and application were studied. Some of the areas investigated need complete studies devoted

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110 to them in order to provide both a deeper understanding as well as to establish figures of merit. An attempt to estimate coating thickness based on time-dependent emission profiles was performed, but the accuracy of the method has not yet been established. If the MCL-based depth profile analysis is compared to a standard technique such as glow discharge, the performance of the system discussed in this dissertation can be quantified. Again, commercially coated samples with known thickness can be analyzed in order to estimate the accuracy obtainable by the MCL technique. It is then that the use of MCLs for depth analysis could be considered as a cheaper alternative to some of the more expensive standard methods. A number of studies have been done to provide clues as to the mechanisms that lead to the vaporization of airborne particles in plasmas. Whether these mechanisms are controlled by the laser-particle interaction or plasma-particle interaction depend on a host of factors including pulse energy, pulse duration, beam focusing as well as particle size and flow conditions. Since these parameters vary for different experimental setups, some of the conclusions from the earlier studies could not be extrapolated to the case with the MCL. It is hoped that a collection of models, mathematical analysis and different experimental configurations will help to answer some of the questions that remain unanswered.

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LIST OF REFERENCES 1. D. A. Cremers, and L. J. Radziemski,, Ed., Laser-Induced Plasmas and Applications (Marcel Dekker, Inc., New York, 1989). 2. J. T. Sneldon, and T.L. Lee, Lasers in Analytical Atomic Spectroscopy (VCH Publishers, Inc., New York, 1997). 3. J. M. Vadillo, J.J. Laserna, Spectrochim. Acta Part B 59, 147 (2004). 4. F. Brench, and L. Cross, Appl. Spectrosc. 16, 5 (1962). 5. L. J. Radziemski, Spectrochim. Acta Part B 57, 1109 (2002). 6. H. Moenke, and L. Moenke-Blankenburg, Laser Micro-Spectrochemical Analysis (Crane, Russak & Co,, New York, 1973). 7. E. Tognoni, V. Palleschi, M. Corsi and G. Cristoforetti, Spectrochim. Acta Part B 57, 1115 (2002). 8. S. Palanco, M. Klassen, J. Skupin, K. Hansen, E. Schubert, G. Sepold and J. J. Laserna, Spectrochim. Acta Part B 56, 651 (2001). 9. D. Bulajic, G. Cristoforetti, M. Corsi, M. Hidalgo, S. Legnaioli, V. Palleschi, A. Salvetti, E. Tognoni, S. Green, D. Bates, A. Steiger, J. Fonseca, J. Martins, J. McKay, B. Tozer, D. Wells, R. Wells, and M. A. Harith, Spectrochim. Acta Part B 57, 1181 (2002). 10. K. Knight, N. L. Scherbarth, D. A. Cremers and J. M. Ferris, Appl. Spectrosc. 54, 331 (2000). 11. J. D. Winefordner, I.B. Gornushkin, T. Correll, E. Gibb, B.W. Smith, and N. Omenetto, J. Anal. At. Spetrom 19, 1061 (2004). 12. D. A. Cremers, Mobile beryllium detector (MOBEDEC), Operating manual. (Los Alamos, NM. 1988). 13. G. R. Van Hecke, A Guide to Lasers in Chemistry (Jones and Bartlett Pubishers, Sudbury, MA, 1997). 111

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BIOGRAPHICAL SKETCH Kwabena Amponsah-Manager was born in Accra, Ghana. He attended the University of Ghana from 1993 to 1997 and graduated with a Bachelor of Science (Honors) in biochemistry. He enrolled for the Master of Philosophy of Science (biochemistry) program in August 1998. In June 2000, Kwabena was awarded a Planetary Biology Internship at the NASA Kennedy Space Center, FL. It was while at KSC that he got interested in the graduate chemistry program at the University of Florida. In August 2001, Kwabena began his doctoral studies in analytical chemistry. Under the mentorship of Professor J. D. Winefordner, he completed his doctoral research in August 2005 and accepted a principal scientist position with GlaxoSmithKline at the Research Triangle Park, NC. 117