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Oriented inorganic particles prepared in a Langmuir-Blodgett film

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Title:
Oriented inorganic particles prepared in a Langmuir-Blodgett film
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Pike, John K., 1960-
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English
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ix, 179 leaves : ill., photos ; 29 cm.

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Subjects / Keywords:
Cadmium ( jstor )
Conceptual lattices ( jstor )
Crystals ( jstor )
Halides ( jstor )
Langmuir Blodgett films ( jstor )
Manganese ( jstor )
Molecules ( jstor )
Nickel ( jstor )
Particle diffraction ( jstor )
Photoelectrons ( jstor )
Chemistry thesis Ph.D
Chemistry, Inorganic ( lcsh )
Dissertations, Academic -- Chemistry -- UF
Thin films multilayered ( lcsh )
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bibliography ( marcgt )
non-fiction ( marcgt )

Notes

Thesis:
Thesis (Ph. D.)--University of Florida, 1994.
Bibliography:
Includes bibliographical references (leaves 165-178).
General Note:
Typescript.
General Note:
Vita.
Statement of Responsibility:
by John K. Pike.

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University of Florida
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University of Florida
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Copyright [name of dissertation author]. Permission granted to the University of Florida to digitize, archive and distribute this item for non-profit research and educational purposes. Any reuse of this item in excess of fair use or other copyright exemptions requires permission of the copyright holder.
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002021961 ( ALEPH )
32838537 ( OCLC )
AKK9455 ( NOTIS )

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ORIENTED INORGANIC PARTICLES PREPARED
IN A LANGMUIR-BLODGETT FILM

















By

JOHN K. PIKE


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


1994




ORIENTED INORGANIC PARTICLES PREPARED
IN A LANGMUIR-BLODGETT FILM
By
JOHN K. PIKE
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
1994


To Mom and Dad.


ACKNOWLEDGMENTS
I would like to thank Dan Talham for making a couple of completions to a big,
slow, tight-end (with great hands!) on a field in Gainesville a couple of years ago.
Looking back, I dont know which was the more courageous actputting my graduate
education in the hands of a brand new professor with no lab and little funding or the
same young professor trusting his research to an equally new and very average graduate
student. I made a pretty good choice. Daniel R. Talham is one of the most capable,
level-headed individuals I have ever had the privilege to work with and I am glad to have
had the opportunity. He has given me nothing but good advice, made me more confident
of my ability, and shown me through his example what is required of a good scientist.
I would like to thank my fellow charter group members, Dr. Houston Byrd and
Mrs. Margaret Showalter. Special thanks go to Houston for his hard work and
innovation. He kept the lab "up and running" by providing genuine inspiration (scientific
and spiritual) when it was needed.
I wish to thank my coauthor and expert electron microscopist, Dr. Augusto A.
Morrone, for all the conversations, arguments, and "shots in the dark." Thanks are due
to Mr. Eric Lambers and the Major Analytical Instrumentation Center for trusting me with
the good XPS instrument. Thanks also go to Dr. Greg Erdos, Donna, and Lorraine at the
Core Electron Microscopy Lab for taking a wayward chemist into their darkroom.


IV
I would like to thank my committee members, Dr. James M. Boncella, Dr. Russell
S. Drago, Dr. Mark W. Meisel, and Dr. Willis B. Person, for their encouragement and
support. I would also like to acknowledge the University of Florida for providing a nice
place in which to do chemistry, go to football games, and watch basketball. Go Gators!
I would also like to thank Jeanne Zachary for her help, kind words, and good coffee.
Very special thanks go to Jeri, Joel, Bill, Michael, Gary, Deborah, Gail, Eileen,
Ken, Margaret, Maya, Phyllip, and Alicia for always being right there. I would like to
thank my Grandma Pike and Grandma Lee for their inspiration and unfailing belief. I
would especially like to thank Virgil and Marvel Johnson for their love and
encouragement.
I would like to thank my parents, Bette and Ray Pike, for their unconditional love,
acceptance, and support throughout my entire life. I wish to thank my Mom, for giving
me her laughter and who never gave up on me, and thank my Dad for his gentle nature
and for instilling in me a love of reading. Thanks also for the open door policy at the
Food Palace!
Lastly, I would like to express my sincere gratitude to my wife and best friend
Sherri and profess my love for her with all that I am and all that I have. I am truly
blessed to have her delightful companionship on a voyage which, because of her, gets
better every day. And we are both very much blessed by a little traveler who arrived just
last year. He is bright and adventurous and his name is William Johnson Pike. I am very
thankful to have such a fine son.


TABLE OF CONTENTS
ACKNOWLEDGMENTS iii
ABSTRACT viii
CHAPTERS
1. INTRODUCTION 1
Scope of Dissertation 1
The Organic Template 4
Micelles and Reversed Micelles 4
Vesicles 6
Bilayer Lipid Membranes 7
Tubular Microstructures 8
Cast Multibilayer Films 9
Floating Langmuir Monolayers 10
Crystallization from supersaturated solutions 12
Crystallization by chemical reaction 17
Electrocrystallization 21
Deposition of pre-formed clusters 21
Deposited Langmuir-Blodgett Films 23
Insertion-reduction templating 25
Reaction with gaseous chalcogenides 26
Other Template Systems 28
Requirements for Oriented Crystallization 29
2. FORMATION OF CADMIUIM IODIDE, BROMIDE, AND
CHLORIDE PARTICLES IN A LANGMUIR-BLODGETT
FILM 32
Introduction 32
Objective 32
Cadmium Dihalide Structure 33
Experimental Details 35
Materials 35
v


Substrate Preparation 36
Instrumentation 37
Langmuir-Blodgett trough 37
Transmission electron microscope 37
FT-infrared spectrometer 37
X-ray photoelectron spectrometer 38
Procedure 38
Results 39
Attenuated Total Reflectance FT-Infrared Spectroscopy ... 39
X-Ray Photoelectron Spectroscopy 40
Transmission Electron Microscopy 46
Discussion 69
Organic Template Reaction 69
Particle Orientation 71
Lattice Matching 76
3. FORMATION OF MANGANESE IODIDE, BROMIDE, AND
CHLORIDE PARTICLES IN A LANGMUIR-BLODGETT
FILM 80
Introduction 80
Objective 80
Manganese Dihalide Structure 81
Experimental Details 82
Materials and Procedures 82
Results 83
Attenuated Total Reflectance FT-infrared Spectroscopy ... 83
X-Ray Photoelectron Spectroscopy 89
Transmission Electron Microscopy 92
Discussion 106
Organic Template Reaction 106
Particle Orientation 113
Lattice Matching 114
4. XPS OF TMNIN 116
Introduction 116
Structure of TMNIN 116
The Chemical Shift in the XPS 118
Experimental Details 119
Development of the TMNIN XPS Project 119
Model Compounds for XPS Study 120
Method of Sample Preparation 120
XPS Instrument Conditions 121
vi


Results and Discussion 122
Composition from Survey Spectra 122
Variable Take-Off Angle Experiment 123
Argon Sputtering 131
Sputter Effects on the Ni(2p) Region 133
Curve Fitting of XPS Data 150
Conclusion 156
5. CONCLUSIONS AND FUTURE WORK 158
Oriented Metal Dihalide Particles in Langmuir-Blodgett Films ... 158
Future Work 161
APPENDIX ION SPUTTER OPERATION 163
REFERENCE LIST 165
BIOGRAPHICAL SKETCH 179
vii


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
ORIENTED INORGANIC PARTICLES PREPARED
IN A LANGMUIR-BLODGETT FILM
By
John K. Pike
August, 1994
Chairperson: Dr. Daniel R. Talham
Major Department: Chemistry
For the first time, oriented arrays of inorganic particles have been synthesized in
a Langmuir-Blodgett (LB) film. Particles of MX2, where M = Cd and Mn and X = I, Br,
and Cl, are formed by the reaction of a deposited cadmium or manganese arachidate LB
film with the corresponding gaseous hydrogen halide. The reactions are monitored by
attenuated total reflectance FT-infrared spectroscopy which shows that they go to
completion and that the organic LB film remains crystalline afterward. X-ray
photoelectron spectroscopy and transmission electron diffraction are used to identify the
metal halides and show that in each case only one inorganic species is formed.
Transmission electron diffraction shows that Cdl9 particles are formed exclusively with
their [001] crystal axes perpendicular to the plane of the LB film and for domain sizes
9
up to several pm discrete particles have the same in-plane orientation. CdBr2 and CdCl2


particles are each observed to form with a mixture of two discrete orientations; [001] axis
parallel or [001] axis perpendicular to the LB plane. Mnl2, MnBr2, and MnCl9 particles
are also oriented with their [001] axes either parallel or perpendicular to the plane but to
a lesser degree than the cadmium halides. In all of the samples, domains are observed
where arrays of particles exhibit common in-plane orientations. It is proposed that the
organized organic matrix is responsible for orienting the inorganic particles, and potential
lattice matching between the inorganic particles and the organic matrix is discussed.
In a separate project, an X-ray photoelectron spectroscopic investigation was
performed on the novel one-dimensional magnetic chain compound tetramethylammonium
nickelnitrite. This material was synthesized in our lab and has an interesting crystal
structure in which there are two chemically distinct nickel centers. The results of
experiments aimed at resolving those two nickel centers are discussed.
IX


CHAPTER 1
INTRODUCTION
Scope of Dissertation
This dissertation presents the experimental results from the synthesis and
characterization of metal halide particles in deposited Langmuir-Blodgett films. Chapter
1 will provide a literature review on the subject of template-directed crystallization of
particles. From experiments in our laboratory and from the literature, a list of
requirements for "good" template-directed crystallization will be presented. Chapter 2
will describe the synthesis and characterization of oriented cadmium halides in a
deposited Langmuir-Blodgett film. The work in Chapter 2 is the first observation of
oriented inorganic particle formation in Langmuir-Blodgett fdms. Chapter 3 will describe
the formation of oriented manganese halides in deposited Langmuir-Blodgett fdms.
Chapters 2 and 3 will include a summary at the end of each chapter. Also included in
Chapter 3 will be a comparison of the cadmium and manganese systems with regard to
the observed differences in their orientation as it relates to their structures. Chapter 4 will
present in detail the results of an extensive X-ray photoelectron spectroscopic
investigation of a novel magnetic compound synthesized in our laboratory by Chou Liang-
Kwei.
1


2
The original goal of this work was to use an organized organic template to develop
a magnetic monolayer. The magnetic monolayer would be electronically isolated from
the organic template and ideally be a monolayer analog of a bulk inorganic extended
lattice. In this way, the magnetic properties of the monolayer could be compared to those
of the bulk materal. Organized organic assemblies have frequently been used in schemes
to prepare inorganic particles in which the organic structure serves as either a template
or a reaction vessel of limited size. The general goal is to produce inorganic particles
with limited size, dispersion, or orientation. This approach draws inspiration from
naturally occurring examples of organic-mediated crystallization of inorganic materials.
While we have not yet realized the goal of a monolayer material, the observation of
oriented inorganic particles formed within the organized organic template encourages us
to think that a single layer of inorganic is possible. In the laboratory, there are several
advantages to using organic molecules as templates. From a "design" standpoint, there
is more "architectural freedom" using organic molecules because of the large number of
organic compounds and structures available. The means of modifying existing organic
molecules to achieve a desired structure or property are usually within the grasp of a good
synthetic chemist. In contrast to "dry" surface preparative methods of chemical vapor
deposition or molecular beam epitaxy, the actual templating process onto organic films
usually occurs via "wet" chemistry on the benchtop. More often than not, organic
materials have the advantage of being electronically and magnetically transparent. In
contrast to "inorganic" host materials such as zeolites, aluminosilicates, and clays, organic
template materials are usually more amenable to modification. In addition, organic host


3
systems are seen as being more "flexible" and may accommodate a variety of inorganic
guests without requiring a perfect epitaxial match. Although it is not always the case,
laboratory analysis is often very straightforward for these organic template systems. The
advantage of using organic materials for template reactions then, lies in their overall
flexibility and accessibility.
If only it were as simple as "designing" the perfect organic template, performing
a simple benchtop reaction, analyzing the results, and harvesting the bounty of perfectly
mediated inorganic crystals! As usual, nature continues to achieve the best results and
those in the laboratory must do the best they can. The introductory chapter of this
dissertation will describe the systems in which organics have been used successfully to
control or mediate the growth of inorganic (and organic) crystals. It is worth stating that
the dimensions of the inorganic particles as formed are somewhere between the molecular
and the bulk level, usually on the order of several nanometers, and it is this size effect
which often gives rise to some interesting physical properties. The potential device
applications arising from these "quantum" size effects are the driving force for some of
the research. Some of these so-called "nanophase" particles that have been made by
organic templating include semiconductors, catalysts, magnetic materials and metallic
particles. But there is much to be learned regarding biological organic-inorganic
interfaces as well. The organic systems described herein are surfactants, having a
hydrophobic and a hydrophilic region. They may take on a variety of dimensions and
shapes; from a micelle tens of angstroms across to a vesicle thousands of angstroms in
size to a thin film with good crystalline order extending over several millimeters in two


4
dimensions but only a few nanometers in the third. The interfacial region between the
organic and the inorganic is not fully understood in most systems, and the defining
interactions are thought to be a combination of electrostatic, geometric, stereochemical,
and kinetic effects. Taken together, this is an exciting area of research and one which is
of interest across scientific disciplines for a variety of reasons.
The Organic Template
Micelles and Reversed Micelles
A surfactant molecule has a polar, hydrophilic part and a nonpolar, hydrophobic
part, and is then said to be amphiphilic. Irving Langmuir first discovered that a single
molecule may have two different "independent surface actions" (Langmuir, 1917). If the
hydrophobic "tails," usually alkyl chains, are short enough the polar "headgroup" will
dominate the solubility and the molecule is water soluble. In water, when the
concentration of surfactant molecules reaches a characteristic concentration, groups of 50-
100 surfactant molecules will spontaneously associate into spherical or rod-like assemblies
known as micelles (Fendler, 1987). In a micelle, the surfactant molecules are arranged
with their hydrophobic tails directed into the center of the micellar body and the
hydrophilic or polar part of the surfactant molecule is directed outward so as to be in
contact with the aqueous solution. It is a cooperative arrangement; opposing forces of
repulsion between the polar headgroups and associative van der Waals forces between the
hydrophobic tails are responsible for micellation (Fendler, 1987). Micelles are stable for
months in aqueous solutions so long as their concentration is kept above the critical level


5
required for micellation (Fendler, 1987). Although they may surround pockets of non
polar solvents, micelles do not solubilize ionic molecules and traditionally are not used
as organic templates. However, a new family of mesoporous silicate-aluminosilicate
structures first reported by Beck (Beck et al., 1992; Kresge et al., 1992) employs
trimethylammonium surfactant molecules which, perhaps through a micellar intermediate,
appear to template and direct the formation of the silicate framework. A lamellar to
micellar phase transition has been observed in cetyltrimethylammonium bromide
mesophases (Auvray et al., 1989). Stucky (Monnier et al., 1993) reports a similar phase
transition in the synthesis of the new silicate mesostructures and outlines a model for their
formation.
Because of their ability to solubilize a large number of water molecules reversed
or inverted micelles are employed frequently to template inorganic particles (Kortan et
al., 1990; Chandler; Coffer, 1993; Petit et al., 1993). A reverse micelle forms when
surfactants having the appropriate hydrophobic lipophilic balance undergo self-association
in a non-polar solvent. In the reverse micelle the surfactant molecules are oriented with
their polar headgroups directed toward the center while the lipophilic tails are directed
outward toward the non-polar solvent. The interior "cavity" formed by the polar head
groups can then immobilize relatively large pools of water. For example, one molecule
of sodium bis(2-ethylhexyl)sulfosuccinate, or "AOT," is able to solubilize up to 60 water
molecules in a hydrocarbon solvent (Fendler, 1987). Spherical silver "nanoparticles" 27-
75 A in diameter were obtained by the reduction of Ag+ ions in AOT reverse micelles
using hydrazine and sodium borohydride in an isooctane solvent (Petit et al., 1993). The


6
silver clusters were extracted after centrifugation into water and it was found that they
had not increased in size, indicating that the clusters retained their surfactant coating.
Inverse micelle solutions provide a good medium for the synthesis of stable, size-selected
semiconductor particles of CdS (Dameron et ah, 1989), and CdSe on ZnS (Kortan et ah,
1990). There remains the tendency for these small clusters to agglomerate, however, and
clever means have been reported of chemical surface capping and passivating by
thiophenol attachment to CdS clusters (Herron et ah, 1990; Chandler; Coffer, 1993) and
by trimethylsilane attachment to CdSe, HgSe, and CdTe clusters (Steigerwald et ah,
1988).
Vesicles
In contrast to the monolayered micelle and reversed micelle, vesicles are
comprised of bilayers of surfactant molecules. The vesicle wall is made up of two
surfactant molecules oriented tail-to-tail; the polar headgroup of the outer surfactant is
directed outward, that of the inner surfactant is pointed toward the interior of the vesicle
body. Vesicles are formed by sonication of surfactants in an aqueous solution and are in
general much larger (> 10,000A in diameter), and more durable than micelles (vesicles
are not destroyed by H20 dilution) (Fendler, 1987). Vesicles may have single
(bimolecular) or unilamellar walls, or multilamellar walls and several compartments with
room for solvent between the walls. Because of their similarity to biological cellular
systems, vesicles have traditionally been the workhorse of the research aimed at biological


7
control of mineralization or "biomineralization" (Mann, 1983; Mann et al., 1984; Mann
et al., 1993).
A classic example of vesicle-mediated inorganic crystal growth is described by
Williams and co-workers (Mann et al., 1986). Using unilamellar phospholipid vesicles
to encapsulate various solutions of Fe(II) and Fe(III), they observed by electron
microscopy that the iron was bound to the inside perimeter of the 300 diameter vesicles.
Upon raising the pH with NaOH, the iron was oxidized and the precipitate was
constrained within the vesicle, in contrast to non-encapsulated bulk iron solutions. The
bulk Fe(II) solution precipitate was a mixture of poorly ordered a- and y-FeOOH crystals
but the intravesicular precipitate produced disk or spherically shaped Fe304 crystals with
an average diameter of 30-50. It was proposed that the rate of infusion of the OH'
ions into the vesicles, and subsequent Fe(II) oxidation, was controlled by the slower
effusion of the intravesicular CF ions which favor the Fe304 product. In addition, it was
proposed that the observed spherical particle shape was due to the initial nucleation of the
oxidized iron occurring at the lipid interfacial binding sites on the vesicle interior. In
another study Fendler (Herve et al., 1984) observed an -87% increase in the alcohol
product of the photoreduction of benzophenone when the reaction was run within a
Fe304-containing vesicle.
Bilayer Lipid Membranes
Bilayer lipid membranes are formed by brushing an organic solution of a
surfactant or lipid (phospholipid) across a pinhole which separates two aqueous phases


8
(Fendler, 1987). The resulting single bimolecular layer spans the pinhole and, like the
wall of a unilamellar vesicle, has the polar headgroups directed outward. Anionic bilayer
lipid membranes of glyceryl monooleate have been observed (Zhao et al., 1989) to bind
cationic Fe304 particles exclusively at the polar headgroup region of the membrane. The
interesting result is that penetration of the particles to the hydrophobic interior of the
membrane was not observed. The authors (Zhao et al., 1989) reported a monolayer film
of magnetite particles bound so strongly to the bilayer lipid membrane by the electrostatic
interaction that the particles could not be pulled off of the film with a magnet. In another
study (Baral; Fendler, 1989), a film of CdS was grown on one side of a bilayer lipid
membrane and was used to mediate photoelectric effects. It was proposed that a vectorial
charge-transfer across the semiconductor-coated membrane was enhanced due to the
asymmetric membrane potential as a result of the adsorbed CdS particles (Baral; Fendler,
1989).
Tubular Microstructures
Phospholipid tubules are hollow, open-ended structures with a high aspect ratio
(0.5pm in diameter and 50-100pm in length) and are formed by the spontaneous self
aggregation of chiral phospholipid molecules (Baral; Schoen, 1993) and more recently
sugar based surfactants (Archibald; Mann, 1993). The walls are similar to those of
unilamellar or multilamellar vesicles and the tubules are stable in aqueous solutions below
a critical melting temperature (Baral; Schoen, 1993). Using a sol-gel synthesis in an
aqueous dispersion of phospholipid tubules, a 50A-thick film of silica was self-assembled


9
onto the tubules (Baral; Schoen, 1993). The resulting silica-coated tubules were hollow
and the silica film had an amorphous structure. The authors observed that the
phospholipid could apparently be baked out of the silica tubules which retained their
shape, and the tubules were subsequently coated with nickel or palladium (Baral; Schoen,
1993). In a more recent communication (Archibald; Mann, 1993), sugar-based tubules
were used to mediate the mineralization of iron oxides. Although the resulting iron
oxidation products were mixed a- and y-FeOOH, it was found that chemical enrichment
of certain phases of the tubules prior to mineralization resulted in different morphologies
of the templated iron oxides. In addition, treatment of the y-FeOOH coated tubules with
Fe(II) under N2 resulted in the formation of Fe304 and retention of the tubular structure.
In each of the above studies (Baral; Schoen, 1993; Archibald; Mann, 1993) templating
of the inorganic product was not limited to the interior of the tubules.
Cast Multibilayer Films
Cast films of N-(co-(Triethylammonio)undecanoyl)dioctadecyl-L-glutamate bromide
have been reported (Kimizuka et ah, 1993) to give several orders of diffraction with
grazing angle X-rays indicating that the films are in the form of multibilayers.
"Dimension-diminished" clusters of anionic PbBr4 molecules have been synthesized in
these films by ion-exchange (Kimizuka et ah, 1993). In this study, cross-sections of these
assemblies observed in a scanning electron microscope confirm that the films retain their
layered nature. Other research by the same group (Okada et ah, 1990) reported the
formation of oriented particles of Fe304 within the cast multibilayer films. Electron


10
diffraction confirmed the magnetite structure, but not a preferred orientation. Scanning
electron microscopy showed the presence of layers in the particle-containing cast film,
however. Magnetic studies of the particle-containing cast film indicated some magnetic
anisotropy (Okada et ah, 1990).
Floating Langmuir Monolayers
Recall that a surfactant molecule is amphiphilic in nature, having a hydrophobic
alkyl chain and a hydrophilic polar headgroup. If the alkyl chain of a surfactant molecule
is long enough (approximately greater than 13 carbons), the surfactant molecule does not
dissolve in aqueous solution but rather forms a fdm of monomolecular thickness on the
surface (Roberts, 1990) with the hydrophobic part of the molecule directed away from the
aqueous phase, and the hydrophilic part in contact with the aqueous phase (Langmuir,
1917). Because part of the surfactant molecule is "dissolved" in the water, the surface
tension of the water is reduced according to the Gibbs adsorption isotherm (Gaines,
1966). Surface tension is the force, due to unbalanced molecular attractions, which tends
to pull molecules into the interior of a liquid phase. All else being equal, the surface
tension is a function of the chemical potential of the solutions components. Using the
Gibbs isotherm, it is possible to evaluate the surface excess of a solute from the observed
variation in surface tension. If the surface tension of a solution decreases as the solute
activity increases, then there must be a positive excess or adsorption of the solute in the
surface region of the solvent (Adamson, 1967). The converse is also true: if the
concentration of surface-confined solute molecules can be varied (by changing their


11
available area) the result will be a change in surface tension. Langmuir observed that
certain materials effected a change in the surface tension of water which could be varied
by manipulating the "water" surface with a mechanical barrier. The surface tension of
water at 25C is 71.97 mN/m (1986). With an adsorbed layer of stearic acid it is
typically reduced to between 20-50 mN/m. Langmuir suggested that it is perhaps more
intuitive to think in terms of the lateral pressure exerted by the surface film and
developed the term "surface pressure" denoted by the symbol, k (Gaines, 1966). The
relation between surface tension, y, and surface pressure, k, is
k = y0- y (i-i)
where y0 is the surface tension of the pristine liquid and y is the surface tension of the
surfactant-coated liquid. Surface pressure, then, is usually a positive number and, in fact,
the surface "pressure" effects of these monolayer films can be pretty amazing to watch
(Pike, Byrd, unpublished results).
Langmuir monolayers are formed by spreading a solution of surfactant molecules
onto the surface of an aqueous subphase. The surfactant solution solvent (usually
chloroform or hexane) evaporates leaving the surfactant molecules on the water surface.
A mechanical barrier is employed to "sweep" the surfactant molecules to one end of the
water surface, until a desired surface pressure is attained. Langmuir monolayers may be
quite durable, lasting for many hours at constant surface pressure in our lab, although
there are reports of floating monolayer fdms lasting for days or weeks (Fendler, 1987).
At various combinations of temperatures, surface pressures and pH, floating Langmuir
monolayers exhibit distinct and stable phases (Durbin et al., 1994). The undersurface of


12
the Langmuir monolayer forms a periodic, and depending upon pH, charged surface.
Recently, researchers have exploited the ability of these floating organic "structural"
surfaces to mimic crystalline habits and ionicities in order to nucleate and template
inorganic and organic materials from solution. This section will describe some of the
elegant means by which floating Langmuir monolayers are used to accomplish this, and
the results will be discussed in terms of the geometric, electrostatic and stereochemical
effects on crystallization.
Crystallization from supersaturated solutions
The objective is to use floating organic monolayers as "surfaces" to nucleate and
effect the crystallization of inorganic salts from supersaturated aqueous solutions.
Langmuir monolayers are prepared at some constant surface pressure over a
supersaturated aqueous solution (hereafter "subphase") and over time the subphase ions
nucleate onto the undersurface of the floating monolayer, eventually growing into small
particles which may remain attached to the surface film. The entire surface monolayer-
nascent-crystal assembly is lifted off of the surface and transferred intact usually to a light
or electron microscope where the crystals are studied. The surface film and particle
assembly have sometimes been observed directly on the trough by low angle X-ray
diffraction. In addition, the remaining subphase can be characterized by chromatographic
or spectroscopic methods.
In a pioneering study, Landau and co-workers (Landau et al., 1985) observed that
floating Langmuir monolayers of chiral a-amino acids induced the formation of oriented
crystals of a-glycine from a racemic subphase. Homochiral monolayers of the R


13
configuration of a-amino acids induced subphase glycine crystals to form with their (010)
or "/?" face attached to the undersurface of the monolayer. Monolayers of the 5
configuration caused the glycine to crystallize with the (010) or "5" face attached to the
monolayer. The oriented crystallization was observed to occur within seconds after the
monolayer was compressed to the limiting surface area per molecule (-25). Monolayers
that were 100% in R or 5 molecules resulted in -90% "R-face" or "5-face" glycine
crystallization, respectively. Fifty-fifty R, S monolayer mixtures gave approximately 50-
50 mixtures of (010) and (00) glycine crystals. These percentages were determined by
HPLC analysis of the attached crystals. When the monolayers were replaced by
amphiphiles having the same amino acid polar headgroups (-(NH-^-CC^) with a
modified hydrocarbon tail having a larger area per molecule (38A vs. 25) glycine
crystallization was observed to be slow and unoriented. The authors (Landau et al., 1985)
proposed that a structural match between the face presented by the chiral monolayer and
the face of the burgeoning glycine crystals is responsible for the observed orientation.
More recent work by the same group (Weissbuch et al., 1988) describes a model in which
kinetic and hydrophobic effects determine the nature and growth of a-amino acids on the
face of glycine substrates. Recently, the same group (Landau et al., 1989) deposited the
floating amino acid monolayers onto solid substrates as Langmuir-Blodgett films and
observed the behavior of glycine crystallization. They report identical behavior in that
the glycine crystallized in an enantioselective manner whenever a favorable nucleating
surface was presented.


14
Floating monolayers were found (Landau et al., 1986) to induce oriented
crystallization of solid sodium chloride from a 6M NaCl subphase. The crystal
orientation of the NaCl was dependent upon the type of surfactant used. Cationic,
anionic, and zwitterionic monolayers were employed in the study (Landau et al., 1986).
Monolayers of long-chain carboxylates (R-C02) induced crystallization in which the
(111) face of NaCl was in contact with the monolayer. The (111) NaCl face can be
constructed to present a hexagonal array of sodium ions. The authors state that the Na-Na
packing in such a projection is similar in distance and symmetry to the headgroup packing
in the floating long-chain carboxylate monolayer (Landau et al., 1986). Although the
symmetry of each face (monolayer and crystal) is hexagonally symmetrical, the Na-Na
spacing given in the paper for the (111) projection is somewhat smaller (by about 0.6)
than that of the stearic acid monolayer. However, when the hydrocarbon chains were
replaced by bulkier steroid groups, no nucleation under the monolayer was observed.
Cationic monolayers of octadecylamine were observed to bind NaCl crystals in the (100)
projection. The (100) projection of NaCl is an alternating cubic array of (+) and (-)
charges. It was proposed that the repeat surface area of the NaCl (100) face was very
closely matched to that of the octadecylamine monolayer and it was further suggested that
the chloride ions penetrate between the octadecylammonium molecules to form such a
structure (Landau et al., 1986). Zwitterionic amphiphilic monolayers with (R-(NH3+)-
C02) headgroups induced the formation of the (110) face of NaCl with 70% a selectivity
at a pH of 1-3. The (110) NaCl face consists of rows of alternating (+) and (-) charges.
When the pH was increased to 4-6, the percentage of (110) crystals dropped to about 40-


15
50% and (111) crystals started to appear. The authors (Landau et ah, 1986) mentioned
that the (110) and (111) faces do not occur naturally, rather, bulk NaCl crystallizes
exhibiting the (100) face preferentially. In each case, when the limiting mean molecular
area of the monolayer was increased, either by the addition of bulky side groups or by
decreasing the surface pressure, crystallization was slow and preferred orientation was not
observed. These results suggest that preferential crystallization at floating monolayers is
a combination of structural and electrostatic effects. Oriented crystallization is determined
by the extent to which the symmetry, periodic spacing, and charge distribution of the
"host" template can mimic a face of the nascent "guest" crystal.
Using floating stearic acid monolayers, another group (Mann et ah, 1988) observed
the role of the organic template in determining the orientation, morphology, and the
crystal structure of CaC03 grown from a supersaturated solution. Crystallization in the
absence of the monolayer resulted in the formation of the rhombohedral calcite form of
CaC03 whereas in the presence of the monolayer the vaterite form was observed (Mann
et al., 1988). Calcite and vaterite are polymorphs of calcium carbonate. In the semi-
compressed monolayer, the immature vaterite (monolayer-induced) crystals were very well
oriented with their (001) face parallel to the monolayer and had a narrow particle size
distribution (2.2pm 0.2pm) whereas in the fully compressed monolayer the authors
report that the vaterite crystals are much smaller (1.3pm 0.5pm). The authors suggest
that since the Ca-Ca packing density is smaller in the vaterite than in the fully
compressed stearic acid monolayer by about 0.5 and certainly smaller still than the
semi-compressed stearic acid monolayer, geometric matching is not as important as are


16
stereochemical and electrostatic matching. Apparently the orientation of the carboxylate
group is of importance; the carboxylate groups are perpendicular to the vaterite [110] axes
and parallel to the calcite [110] axes. The authors report that the stearic acid monolayer
carboxylate groups are oriented similar to those in vaterite, and even though there is a
closer lattice match between calcite and the monolayer with respect to packing density,
the crystals grow with the vaterite structure (Mann et al., 1988; Mann et ah, 1990). In
addition, the more liquid-like (semi-compressed) stearic acid monolayer promotes more
uniform vaterite crystallization, indicating that some flexibility is required of the organic
template in this case.
A more complete study was presented by the same authors (Rajam et al., 1991;
Heywood et al., 1991) in which the effect of different surfactant molecules on CaC03
crystallization was observed. Floating Langmuir monolayers of octadecanol,
octadecylamine, cholesterol in addition to stearic acid were employed to induce CaC03
crystals to grow from a supersaturated solution (Rajam et al., 1991; Heywood et ah,
1991). The crystals were observed by transmission electron diffraction. To complement
the above-mentioned study (Mann et al., 1988; Mann et al., 1990) stearic acid was found
to grow oriented calcite or vaterite depending on the subphase calcium concentration
(high [Ca ] gives calcite, low [Ca ] gives vaterite). Octadecylamine monolayers grew
two vaterite orientations independent of calcium concentration. Octadecanol inhibited
crystallization completely, and cholesterol monolayers gave rise to random, non-oriented
calcite crystals (Rajam et al., 1991; Heywood et al., 1991). To account for the
observations, the authors cite geometric and stereochemical matching between the


17
monolayer carboxylate headgroups and the ions in the (l 10) crystal face of calcite. For
vaterite on stearic acid, there is no geometric match, but there is a stereochemical
relationship similar to the 1988 paper (Mann et al., 1988). For octadecylamine, Heywood
and Mann (1991) suggest that bidentate binding of HC03" may be important in
determining the preferential orientation of the vaterite. This report (Rajam et al., 1991;
Heywood et al., 1991) in two parts and a very recent paper by the same group (Heywood;
Mann, 1994) shows how geometric, stereochemical, and electrostatic factors in floating
organic templates may be manipulated extensively to mediate the growth of an inorganic
crystal. Recently, Heywood and Mann have grown BaS04 crystals under floating
Langmuir monolayers of long-chain carboxylates and sulfates (Heywood; Mann, 1992;
Heywood; Mann, 1992). Again, oriented crystals were observed in both systems, but the
authors observed crystals of irregular shape in the carboxylate-grown BaS04 and suggest
that, because no geometric or stereochemical lattice match exists, the kinetic product is
being formed as a result of electrostatic interactions or charge accumulation at the
template-crystal interface. Heywood and Mann publish with an eye on the biological
aspects of organic-template directed crystallization and are leaders in the field of
crystallization from supersaturated solutions onto floating monolayers. The interested
reader is invited to peruse Mann, who has written several good reviews on the subject
(Mann, 1983; Mann, 1988; Mann et al., 1990; Mann, 1993).
Crystallization by chemical reaction
This section will outline the work in which crystallization is induced by proactive
chemical means at the undersurface of a floating Langmuir monolayer. Normally this is


18
accomplished by the slow infusion of a gas (usually an acid chalcogenide) over the
surface of a Langmuir trough while a Langmuir monolayer is maintained at constant
surface pressure. The gas reacts with ions in the aqueous subphase causing crystals to
nucleate and form along the monolayer undersurface. There are reports of particles
generated in situ by wet chemical means, however, and they are included in this section.
More often than not, the purpose of the studies that follow is to produce semiconducting
particulate thin films for potential device applications, rather than elucidate the nature of
bioorganic-mediated crystallization. Size quantization (limitation) of the semiconducting
particles is often observed in these systems, which may be transferred intact to solid
substrates by Langmuir-Blodgett deposition methods. With two exceptions (Zhao et al.,
1992; Yi et ah, 1994) the formation of oriented particles is not observed in these systems,
possibly due to the equilibrium process being "pushed" too rapidly by the addition of the
reacting gas. Perhaps any orienting influence the organic template might have is
overwhelmed here by the rapid growth and large size of the nascent crystal.
Fendler and co-workers have grown particles of semiconducting CdS and ZnS
(Zhao et ah, 1990; Zhao; Fendler, 1991a; Zhao; Fendler, 1991b) at floating Langmuir
monolayers using a variety of surfactants with essentially the same result. They observe
the formation of particles at the film-water interface which may be size mediated by
limiting their exposure to the gas. The particles begin as isolated clusters and, over
several hours, grow laterally along the undersurface of the monolayer until they run into
a neighboring particle. Only then do the particles grow downward into the subphase. By
controlling the rate of gas infusion, it is apparently possible to control the morphology


19
of the particles from a spheroid shape 25-30 in diameter, to a disk shaped 50-100
o # o
across and 25-30A thick. Thicker particles (up to 1800A) are observed to form over
longer time periods, but in each case the whole monolayer-particle arrangement may be
transferred intact onto a solid substrate by Langmuir-Blodgett deposition. The particulate
films as deposited are described as a porous network of disk-shaped particles with the
broad face parallel to the monolayer (Zhao et al., 1990; Zhao; Fendler, 1991a; Zhao;
Fendler, 1991b). The films are well characterized by a variety of techniques and the
absorption spectra (Zhao; Fendler, 1991a) confirm a size-quantization of the particles, a
layer by layer deposition, and a linear increase in intensity as the particles themselves
become thicker. Characterization by scanning probe microscopy (Zhao et al., 1990; Zhao;
Fendler, 1991a) and transmission electron diffraction (Zhao; Fendler, 1991a) indicates that
the particles grow in an unorganized fashion, and no preferential orientation is observed.
In another study, Fendler and co-workers (Zhao et al., 1991) generated CdSe particles in
situ at Langmuir monolayers and observed size-quantized behavior.
H2S exposure of a Pb(II) subphase coated with an arachidic acid Langmuir
monolayer resulted in the formation of oriented PbS crystals at the monolayer solution
interface (Zhao et al., 1992). In the presence of the monolayer, the cubic crystals were
oriented with their [111] direction perpendicular to the surface; in the absence of the
monolayer, there was observed a mixture of (111), (hOO) and (hkO) orientations. The PbS
crystals are observed to be evenly-spaced, well-formed equilateral triangles. In addition,
the fact that coherent electron diffraction was observed over sample areas containing
several particles (selected areas of diffraction or SAD = 2pm in diameter) indicates that


20
discrete crystals are oriented with respect to one another within the plane of the
monolayer (Zhao et al., 1992). Crystals formed equally well in uncompressed (it = 0
mN/m) and compressed (7t s 25mN/m) arachidic acid fdms. However, particles formed
in a circular Langmuir trough exhibited polycrystalline orientation similar to that of
particles formed in the absence of a monolayer; those formed in a rectangular trough
exhibited excellent orientation (Zhao et al., 1992). The authors do not rationalize the
latter observations, but infer that the organization of floating amphiphilic molecules is
dependent upon the shape of each Langmuir trough and the uniformity of compression.
Slow H2S infusion was reported to give better results with regard to particle morphology,
orientation, and size distribution. The results are rationalized in terms of a near perfect
lattice match between the Pb-Pb distance in PbS (4.20) and the dj00 spacing of the
arachidic acid headgroups (4.16).
Very recently, Fendler and co-workers (Yi et al., 1994) formed silver particulate
films beneath monolayers of various surfactants by slow exposure of the Ag+ subphase
to formaldehyde vapor. Silver particle formation was found to be influenced by silver
concentration, pH, the type of monolayer used, and the presence of ammonia or copper(II)
in the subphase. The morphology of the size-quantized silver particles was described as
fractal in nature and the immature particles in some cases were oriented with their (111)
face parallel to the monolayer (Yi et al., 1994). As the particles grew they became non
fractal and orientations other than the (111) were observed. The mature films were
described as similar to those of particulate semiconductors discussed previously (Zhao;
Fendler, 1991b) except that transfer by vertical Langmuir-Blodgett deposition was


21
accomplished only with difficulty. The results were not rationalized in terms of any
complementarity between the organic monolayer and the particles.
Electrocrystallization
We are aware of only one report (Kotov et al., 1993) describing the formation of
metallic particles on the undersurface of a floating monolayer by electrochemical
reduction. Electrochemical silver reduction occurred at the solution-monolayer interface
resulting in a "two-dimensional" silver particulate film. Size-quantization of silver
particles was observed (500-700) and no silver particles were observed to form under
monolayers of positively charged or bulky headgroups. Transmission electron diffraction
recorded no preferred orientation. Silver reduction at floating monolayer interfaces was
reported to occur at more negative potentials than is required at electrode surfaces in bulk
solution (Kotov et al., 1993) and particulate formation occurred only at the frontier
regions of the advancing two-dimensional silver particulate film beneath the organic
monolayer.
Deposition of pre-formed clusters
An interesting hybrid method in which floating Langmuir monolayers are used to
manipulate inorganic particles is described in this section. Although not strictly a
"templating" technique, it is included here for completeness. Pre-formed inorganic
clusters are incorporated into Langmuir-Blodgett films by two means. First, the pre
formed clusters are put into the subphase solution and are electrostatically bound to either
the floating monolayer or the hydrophilic side of a deposited monolayer. The substrate
is withdrawn and another particle-surfactant layer assembly is deposited resulting in a


22
bilayer "sandwich". These techniques have been demonstrated by Fendler and co-workers
to make Langmuir-Blodgett films of size-quantized hexametaphosphate-stabilized CdS
clusters between bilayers of dioctadecyldimethylammonium chloride (Xu et al., 1990) and
unstabilized "cationic" Fe304 particles within arachidic acid Langmuir-Blodgett films
(Zhao et al., 1990). The second technique is to spread pre-formed, organic stabilized
particles onto the surface of the Langmuir-Blodgett trough. The clusters are then treated
as a monolayer-compressed and deposited directly onto the solid substrate without an
accompanying surfactant molecule. It is presumed that the on-trough behavior of such
materials is "ornery" because there is no clear hydrophobic-hydrophilic aspect to the
stabilized particles, which is generally a requirement for a well-behaved Langmuir
monolayer. Nevertheless, Fendler and co-workers (Kotov et al., 1994) report the
deposition of monoparticulate layers of dodecylbenzenesulfonic acid-stabilized size-
quantized CdS clusters from a Langmuir-Blodgett trough without an accompanying
surfactant. Brewster angle microscopy shows that the Langmuir monolayer consists of
isolated islands that aggregate into a close-packed film upon compression. Absorbance
versus number of layers indicates a linear increase in intensity with increasing number of
layers as well. In addition, the position of the absorption edge, which is often used to
determine the size of the so-called "q-state" clusters, does not shift with the increase in
the number of layers. The results are rationalized by the authors (Kotov et al., 1994) to
mean that the individual CdS particles do not agglomerate into larger clusters upon
deposition and drying of the film. This work was repeated with similar results by a


23
another group (Du et al., 1992) using hexametaphosphate-stabilized CdS colloids in a
mixed behenic acid-octadecylamine LB film.
Deposited Langmuir-Blodgett Films
Katherine Blodgett showed that it is possible to transfer floating Langmuir
monolayers onto solid supports (Blodgett, 1935). The Langmuir-Blodgett (LB) method
is experiencing a revival of sorts due to its potential in device applications. In addition,
the LB method is attractive because it provides a way to have some (slight!) mechanical
control over what molecules do. LB films are good experimental platforms. The
observation of low-dimensional magnetic phenomena (Pomerantz et al., 1978),
measurement of electron mean-free pathlengths (Brundle et al., 1979) and inorganic
extended lattice formation (Byrd et al., 1993) are examples of the experimental variety
possible with Langmuir-Blodgett films. The advent of computer controlled film
deposition equipment (Ulman, 1991; Roberts, 1990) has resulted in better quality films.
The increased accessibility of physical methods such as scanning probe microscopy,
electron microscopy, and FTIR gives us a better understanding of LB films. These
factors will continue to spur interest in LB films and the associated academic and perhaps
industrial applications.
The Langmuir-Blodgett method has been described by this author (Pike, 1992) and
others (Blodgett, 1935; Gaines, 1966; Roberts, 1990; Ulman, 1991). Briefly, if an
appropriate solid support (hereafter substrate) is moved through a floating Langmuir
monolayer that is held at constant surface pressure the floating monolayer can be


24
transferred intact to the substrate. By repeated insertions and withdrawals, multiple layers
can be built up on the substrate. The most common configuration of the deposited film
is the Y-type (Roberts, 1990) layer in which the polar headgroup layers are in contact
with one another and the hydrophobic alkyl tails are in contact with one another as well.
In this way the Y-type LB film is composed of bilayers; the center of which is where the
polar headgroups face one another. For some amphiphilic molecules, it is possible to
incorporate metal ions into the interstitial region between the polar headgroups by
adjusting the pH of the subphase so that it is above the pKa of the amphiphiles
headgroup but below the pKb of the metal hydroxide. Proper pH is usually sufficient for
metal incorporation into LB films of the carboxylic acids, CH3(CH2)nCOOH. For the
alkyl phosphonic acids, CH3(CH2)nP03H2, the situation can be more complex (Byrd,
1994). The deposited LB film will then contain the metal as the salt of the amphiphile.
Typically, the amphiphile of choice is a long chain carboxylic acid such as stearic acid
(CH3(CH2)16COOH) or arachidic acid (CH3(CH2)j8COOH). Metal ions may also be
inserted into the film by leaving the deposited film of the unionized acid in a solution of
metal ions at the appropriate pH for a few minutes (Leloup et al., 1985). An ion
exchange mechanism will give rise to a film of the metal salt. However, given that the
films are often easier to deposit as the metal salt of the fatty acid than as the fatty acid
alone, the latter method of metal insertion into LB films is not often used.
This section will describe the work in which deposited Langmuir-Blodgett films
have been used as organic templates for the synthesis of inorganic particles and clusters.


25
Typically the LB films are deposited as the metal-fatty acid salt then subjected to further
reaction by exposure to gas-phase reactants.
Insertion-reduction templating
Barraud and co-workers (Leloup et al., 1985; Ruaudel-Teixier et al., 1986;
Zylberajch et al., 1988) and Toumarie (Belbeoch et al., 1985) have used the insertion
method discussed previously to ion-exchange Ag+ ions into deposited LB films of behenic
acid (CH3(CH2)2qCOOH). The films were observed by X-ray diffraction to be in the
form of well ordered layers before and after insertion of the Ag+ (Belbeoch et al., 1985).
Infrared spectroscopic analysis shows the films to be in the form of the protonated fatty
acid prior to silver insertion (Leloup et al., 1985). After insertion IR showed the film to
be the fatty acid salt (Leloup et al., 1985). The silver behenate films were then exposed
to hydrazine (N2H4) vapor which reduced the Ag+ to the metal. X-ray diffraction showed
that the film remained as well-ordered layers (Belbeoch et al., 1985) and IR analysis
showed the return of the protonated behenic acid form (Leloup et al., 1985). Electron
diffraction and microscopy showed the presence of small silver particles 300-500 in
diameter in the film. There was not any preferred orientation observed in the silver and
the authors observe that the clusters are not coherent with the matrix of behenic acid
(Belbeoch et al., 1985).
In an interesting communication (Sastry et al., 1992), a Langmuir-Blodgett film
of lead arachidate deposited in the usual way was bombarded by 4.5 keV electrons. The
authors observed in the XPS a shift toward lower binding energy of the Pb(4/)


26
photoelectron peak and speculate that the Pb2+ in the LB film is being reduced to lead
metal. The authors do not speculate on the fate of the organic template.
Reaction with gaseous chalcogenides
A recent report (Leloup et al., 1992) describes the insertion of copper and
subsequent conversion to Cu2S within an LB film of behenic acid. The conversion is
effected by exposure of the deposited copper-containing film to gaseous H2S. No data
is presented regarding the physical structure of the films, however (Leloup et al., 1992).
In a pioneering experiment, researchers at the University of Texas at Austin
(Smotkin et al., 1988) deposited LB films of cadmium arachidate onto solid substrates and
exposed the film to H2S. The resulting CdS particles were determined, by UV-vis
spectroscopy, to be about 50A in size (Smotkin et al., 1988). The CdS-containing films
were observed to have a linear increase in absorbance (at 380 nm) with increasing number
of layers. Ellipsometric measurements showed the films to be thicker by about 3 per
bilayer after conversion to CdS. Electron microscopy of the converted films showed the
presence of small particles, but electron diffraction did not confirm the CdS structure
(Smotkin et al., 1988). We now suspect that the authors were observing spurious particles
of copper sulfide in the electron microscope which came about possibly due to a side
reaction of the H2S with the copper electron microscope grid. We attempted to reproduce
their results using the same type of materials and confirmed the formation of copper
sulfide particles by electron diffraction. Scanning electron micrographs of the copper
microscope grid showed the formation of large particles on the surface of the grid after
exposure to H2S. However, the observation of size-limited or quantized semiconducting


27
particles formed in a Langmuir-Blodgett films is evidence in support of the templating
ability of LB films. A more complete study of CdS particles formed in deposited films
was recently reported by Fendler and co-workers (Geddes et al., 1993). In this paper, the
time-dependent growth of the CdS is monitored by a quartz crystal microbalance, UV-vis,
and surface plasmon resonance. In a 20-layer cadmium arachidate film the reaction with
H2S appears to go to completion in about 20 minutes (Geddes et al., 1993).
Unfortunately, the authors do not report the details of the amount of H2S gas required to
effect complete reaction. The size of the CdS particles and the changes in film thickness
are consistent with the results reported by Smotkin et al. (1988).
Another group (Scoberg et al., 1991) describes the synthesis of semiconducting
CdS, CdSe, CdTe, and CdSxSexl in deposited LB films of polymerizable long-chain
diynoic acids. The cadmium-containing LB films were exposed to H2X (X = S, Se, or
Te) for several minutes in a sealed container. The resulting films were studied by UV-vis
spectroscopy. Size-quantization was observed on the order of 40-50A for all particles and
did not change after the diynoic LB film is polymerized (Scoberg et al., 1991). The
authors reported a reduction in the particle size when dihexadecylphosphate was mixed
into the diynoic acid monolayer prior to deposition.
There are two reports (Zhu et al., 1992; Peng et al., 1992) of size-quantized lead
sulfide particles formed in LB films of stearic acid. The first group (Zhu et al., 1992)
synthesizes the particles in the usual manner and observes the resulting particles by UV-
vis and scanning tunneling microscopy (STM). The STM measurements confirm the 1.5-
2.0 nm PbS particle size derived from UV-vis measurements (Zhu et al., 1992).


28
Interestingly, the authors interpretation of STM measurements conducted on the films
after the organic portion of the LB film had been pyrolyzed at 120C was that the
nanoparticles remained discrete and intact (Zhu et ah, 1992). However, UV-vis analysis
was not performed after pyrolysis to confirm this result. In the second report (Peng et
ah, 1992), the authors report the formation of non-stoichiometric PbS in a stearic acid LB
film. The initial 1 to 1.5 Pb to S ratio was found by XPS to increase over a period of
two months of exposure to air. The authors report that the sulfur is lost as H2S or S02
and the Pb remains in the form of the stearic acid salt (Peng et ah, 1992).
Other Template Systems
To be sure, there are other systems which have been used to template and mediate
the growth of inorganic particles. Size-quantized CdS and PbS clusters have been formed
in zeolites (Herron et ah, 1989; Wang; Herron, 1987; Moller et ah, 1989). Layered metal
phosphonate hosts (Cao et ah, 1991) have templated the formation of oriented, size-
quantized CdSe, CdS, ZnSe, and PbS. In the latter system, particle growth and
orientation occurs cooperatively with the layered host lattice, but the host lattice is
destroyed in the process. In a very interesting letter (Golan et ah, 1992), CdSe
nanocrystals were electrodeposited onto {111} gold surfaces. An epitaxial match between
the gold (111) face and the CdSe (001) face was proposed for the observed exclusive
orientation of the CdSe. Size-quantization has also been observed in the ion-exchange
membrane "Nafion" by cadmium doping then reacting with H2S (Smotkin et ah, 1990).
Finally, there are two groups which report the formation of size-quantized particles of PbS


29
(Mahler, 1988) and CdS (Bianconi et al., 1991; Lin; Bianconi, 1991) in polymeric
matrices. Bianconi (Bianconi et al., 1991; Lin; Bianconi, 1991) observed size-quantized
CdS particles in a dip-coated polyethyleneoxide film after a 7-day immersion in an
organic sulfur solution. Oriented CdS crystals were observed by electron diffraction after
the sulfur solution had been treated with the surfactant sodium bis(2-
ethylhexyl)sulfosuccinate (Bianconi et al., 1991). The authors observed that the size of
the CdS particles could be controlled by adjusting the initial Cd(II) concentration. It was
also observed that the use of different polymer matrices altered the morphology of the
CdS (Bianconi et al., 1991).
Requirements for Oriented Crystallization
In each of the above studies, organized organic assemblies were used in schemes
to prepare inorganic particles. The organic structure serves as either a template or a
reaction vessel of limited size (Heuer et al., 1992). The goal is generally to produce
inorganic particles with limited size, dispersion, or orientation (Stucky; MacDougall,
1990; Henglein, 1989) The approach draws inspiration from naturally occurring examples
of organic-mediated crystallization of inorganic materials (Berman et al., 1988; Dameron
et al., 1989; Addadi; Weiner, 1985).
It is possible, then, to lay out the requirements for templating inorganic particles
by organic structures. First, the organic must provide a surface or a region which
concentrates one of the eventual reactants. This requirement is concomitant with
electrostatic complementarity. In most cases it is the metal ion which is concentrated,


30
although in the studies by Mann (Rajam et al., 1991) it was suggested that the initial
binding of HC03' was a key step in orienting the calcium carbonate. Second, this initial
"binding region" should have ion-affinities high enough to hold the initial participants in
place for reaction, but low enough to allow the particle-forming reaction to occur. In the
deposited Langmuir-Blodgett films this is accomplished by a mechanism in which the
stronger acid, HnXn, is able to protonate the metal-carboxylate, (R-COO)mMm+ forming
the inorganic M^+X^' and the carboxylic acid, RCOOH. Third, for size-quantization to
occur, there should be some means of limiting a) the initial total number of potential
reactants in a given region, or b) the spatial area in which the nascent particles have to
grow. The latter limitation is probably less important than the former, as we have seen
how the growing guest can outgrow and destroy the host structure (Cao et al., 1991), even
if the host structure is a covalent compound. However, there is supporting evidence for
(b) in that size-quantization was observed in deposited Langmuir-Blodgett films, which
are probably not the most durable structures. Fourth, for dispersion limitation to occur,
there should be some means of limiting the rate, pathlength, or direction of the diffusing
species within the host template. This requirement is most easily seen in the chemical
capping and passivating of the nanoparticle surfaces which, if left to themselves, would
otherwise agglomerate into bulk structures (Herron et al., 1990). Also, from the literature,
it is conducive to "good" crystallization if the rate of the particle-forming can be slowed
so as not to overwhelm the provisional initial ordering forces of the template; witness the
rate limiting properties of the vesicle walls in the formation of the magnetite particles
(Mann et al., 1986). Fifth, for orientation to occur, the requirement of geometric and


31
stereochemical lattice matching between the host and the guest should be met, but it is
perhaps more clear in some cases (Pike et ah, 1993) than in others (Bianconi et ah, 1991)
exactly how, and to what degree, this requirement is satisfied.


CHAPTER 2
FORMATION OF ORIENTED CADMIUM IODIDE, BROMIDE, AND CHLORIDE
PARTICLES IN A LANGMUIR-BLODGETT FILM
Introduction
Objective
An objective of this work is to develop methods for preparing single layers of
inorganic extended lattice solids (Byrd et al., 1994a; Byrd, Pike et ah, 1993; Byrd, Pike
et ah, 1994a; Byrd, Pike et ah, 1994b; Byrd et al., 1994b; Pike, Byrd et ah, 1993; Pike,
Byrd et ah, 1994). Such systems should allow for investigation of materials properties
such as magnetism, conductivity, semiconductivity or even superconductivity in the two-
dimensional limit of a monolayer. The approach uses layered organic assemblies, such
as LB films or self-assembled monolayers, as templates for forming inorganic monolayers
in analogy to how the organic assemblies described Chapter 1 have been used to form
inorganic particles. For example, in a preparation that uses an LB film as a component
of a mixed organic-inorganic layered solid (Day, 1985), we have reported monolayer and
multilayer film analogues of the layered transition-metal phosphonates (Byrd, Pike et ah,
1994a; Byrd, Pike et ah, 1994b; Byrd, Pike et ah, 1994c; Byrd, Pike et ah, 1993; Byrd
et ah, 1994a; Byrd et al., 1994b). A different approach is to use the organic assembly to
prearrange the metal ions into a layered array for further reaction that produces an
32


33
extended inorganic lattice inside the organic matrix (Pike, Byrd et al., 1993; Pike, Byrd
et ah, 1994). The idea is that the layered organic template should limit diffusion of the
metal ions to individual planes of the organic matrix. If the inorganic solid has a layered
structure, then the lattice energy may favor formation of single layers of the inorganic
lattice.
Cadmium Dihalide Structure
The initial attempt (Figure 2-1) at this approach targets the cadmium dihalides,
CdX2 (Pike, Byrd et ah, 1993). The "Cdl2" structure (Wells, 1984) is described by a
hexagonal-close-packing of the anions in which every other layer of octahedral holes is
occupied by a metal ion. The CdCl7 and CdBr7 structures are analogous to that of Cdl2
except for a cubic-close-packing of the chloride and bromide ions (Wells, 1984). The
structure of a single layer, however, is the same in both structure types. In these layered
structures, the bonding within the anion-metal-anion layer is ionic-covalent, while the
anion-anion interaction between layers is van der Waals in nature and easily cleaved
(Wells, 1984).
Although single layers have not yet been identified, this chapter will present
electron diffraction studies that show the template-formed-CdI2 is oriented exclusively
with the Cdl2 layers parallel to the LB layers (Cdl2 [001] axis normal to the LB layer).
9
In addition, for domain sizes up to several pm arrays of discrete particles are aligned
with respect to one another about the [001] axis. The results suggest that the organic
matrix is responsible for both orienting the Cdl2 particles and favoring crystal growth


34
Figure 2-1:
Cartoon representation depicting reaction of Langmuir-Blodgett fdm
with gaseous HX.


35
parallel to the LB planes. In this chapter we will present data on the LB-formed CdBr?
and CdCl2 particles formed by the same method. As it happens, the situation is a little
more complex with these two systems. As with the formation of Cdl2 particles, CdBr0
and CdCl2 particles are produced with preferred orientations in the organic template,
although two orientations of both the bromide and chloride are observed. The systems
are characterized by attenuated total reflectance FT-infrared spectroscopy (ATR-FTIR),
X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and
transmission electron diffraction (TED).
Experimental Details
Materials
Octadecyltrichlorosilane (OTS, Cjgf^-ySiC^, 95%) was obtained from Aldrich
Chemical Co. (Milwaukee, WI) and stored under N2 until use. Octadecanoic acid (stearic
acid, C17H35COOH, 99.5%) was used as received from EM Science (Cherry Hill, NJ).
Eicosanoic acid (arachidic acid, C19H39COOH, 99%) and cadmium chloride
hemipentahydrate (CdCl9 2 Vi H20, 98%) were purchased from Aldrich and used
without further purification. Hydrogen bromide, 99.8%, technical hydrogen chloride,
99.0% and hydrogen iodide, 98.% were obtained from Matheson Gas Products (Atlanta,
GA). Spectrograde chloroform, hexadecane and hexane were used as received. 300-mesh
titanium electron microscope grids were purchased from the Ted Pella Company
(Redding, CA). Formvar resin was purchased from Ted Pella and dissolved in
spectrograde 1, 2-dichloroethane before use. Silicon monoxide (325 mesh powder) was


36
purchased from Aldrich. The water used as subphase in the LB experiment was purified
via a Sybron/Bamstead Nanopure (Boston, MA) system immediately before use and had
an average resistivity of 18 Mf-cm.
Substrate Preparation
For all XPS measurements, single crystal (100) 20 x 15 x 1 mm3 n- and p-type
silicon wafers were purchased from Semiconductor Processing Company (Boston, MA).
For the infrared experiments, silicon ATR crystals, 45 50 x 10x3 mm3, were purchased
from Wilmad Glass Company (Buena, NJ). The silicon XPS and IR substrates were
cleaned using the RCA procedure (Kern, 1990) and dried under N2. OTS was self-
assembled (Netzer; Sagiv, 1983; Maoz; Sagiv, 1984) onto the silicon substrates by placing
the clean substrates in a 2% solution of OTS in hexadecane for 30 minutes. Substrates
were then rinsed in a chloroform Soxhlett extractor for 30 minutes. Upon removal from
the Soxhlett, the substrates were hydrophobic. TEM substrates were electron microscope
grids sandwiched between a 600 thickness of Formvar film and a 75 x 25 x 1 mm3
glass microscope slide. A home-built electron-beam evaporator system was used to
deposit 300 A of SiO onto the Formvar layer at a rate of 1-2 A/s as monitored by a
quartz crystal microbalance. Pressure within the evaporator chamber was maintained at
o
4 x 10 atm. The basic TEM substrate preparation procedure is described in the
literature (Fischer; Sackmann, 1986). The entire slide was then made hydrophobic with
OTS as described above except that hexane was substituted for chloroform in the rinsing
step.


37
Instrumentation
Langmuir-Blodgett trough
The LB films were deposited using a KSV Instruments (Stratford, CT) Model
5000 LB system with a PTFE trough and hydrophobic barriers (Pike, 1992). The surface
pressure was measured with a platinum Wilhelmy plate suspended from a KSV
microbalance.
Transmission electron microscope
TEM and TED analyses were performed on a JEOL (Peabody, MA) JEM 200CX
electron microscope. In all cases, the electron beam was normal to the sample LB basal
plane. Beam exposure was purposefully kept to a minimum to avoid sample degradation.
Exposure times were typically less than 5 s for images and less than 11 s for diffraction
patterns. The instrument was operated at 80, 100 and 200 kV as necessary and the
electron beam was collimated with a 200-pm-diameter (hereafter pm-d.) condenser
aperture. In some cases, focussing and other conditions were set in areas immediately
adjacent to the region of interest, which was then shifted to the center of the image plane
for photographic recording.
FT-infrared spectrometer
Infrared spectra were recorded with a Mattson Instruments (Madison, WI)
Research Series-1 FTIR spectrometer using a narrow-band mercury cadmium telluride
detector. A Harrick (Ossining, NY) TMP stage was used for the ATR experiments. All
spectra consisted of 1000 scans at 2.0 cm'1 resolution and were referenced to the clean
OTS-coated Si ATR crystal.


38
X-ray photoelectron spectrometer
X-ray photoelectron spectra were obtained using a Perkin-Elmer (Eden Prairie,
MN) PHI 5000 Series spectrometer. All spectra were taken using the Mg Ka line source
at 1253.6 eV. The spectrometer has a typical resolution of about 1.7 eV, with anode
voltage and power settings of 15 kV and 300 W, respectively. Typical operating pressure
was less than 5 x 109 atm. Survey scans were performed at a 70 take-off angle with
respect to the sample surface parallel using a pass energy of 89.45 eV. Multiplex scans,
20 scans over each peak, were run over a 45-50 eV range with a pass energy of 17.90 eV.
Sample exposure to the X-ray beam and detector dead time were minimized to avoid
unnecessary sample degradation.
Procedure
Langmuir-Blodgett films were prepared by spreading 100 pL of a 4.5 mM solution
of stearic or arachidic acid in chloroform onto the subphase and allowing 15 minutes for
the solvent to evaporate prior to compression. The subphase temperature was maintained
at 16 1 C. For stearic acid and arachidic acid films, a pure water subphase was used
(pH = 5.2). Stearic acid and arachidic acid Langmuir monolayers were linearly
compressed at a rate of 10 mN/(m min) to a surface pressure of 24 mN/m and deposited
at rates of 25-50 mm/min. Transfer ratios were unity. Cadmium arachidate LB films
n i
were deposited from a 4 mM Cd subphase that was pH-adjusted upward with KOH to
pH 6.2 0.1. The subphase was allowed to equilibrate for several hours prior to
spreading while the pH was constant. The cadmium arachidate Langmuir monolayer was


39
compressed linearly at a rate of 10 mN/(m min) to a surface pressure of 30 mN/m and
deposited at rates of 25-50 mm/min with 10 min between successive dips for drying.
Transfer ratios were unity.
Metal-halide-containing films were produced by exposing the LB films to the
gaseous hydrohalic acids. The sample was placed within a glass test tube fitted with a
sidearm stopcock valve and sealed with a rubber septum. The 80 mL tube containing the
sample was evacuated and backfilled with dry Ar several times before 5 mL of gaseous
HX was introduced through the rubber septum via gastight syringe. After a period of
time the tube was purged with a positive pressure of dry Ar. Typical reaction conditions
were 6.4 x 10 atm partial pressure of HX in argon for 5-15 minutes. Great care was
taken throughout the procedure to avoid sample contamination.
Results
Attenuated Total Reflectance FT-Infrared Spectroscopy
Reactions of the cadmium arachidate (CdArac) LB films with hydrogen halide
(HX) gas were monitored by ATR-FTIR. Figure 2-2 shows the ATR-FTIR spectra from
1500-3500 cm'1 of 10-bilayer CdArac LB films before and after exposure to HC1, HBr,
and HI. Peaks at 2953 cm'1, 2917 cm'1 and 2849 cm'1 in the CdArac spectrum (Figure
2-2a) are the asymmetric methyl va(CH3), asymmetric methylene va(CH2) and symmetric
methylene vs(CH9) stretches, respectively, of the close-packed, all-trans hydrocarbon
chains in the LB film (Wood et al., 1989; Porter et al., 1987). The band at 1545 cm'1
is the asymmetric carboxylate stretch, va(COO'), characteristic of the metal carboxylate


40
salt. The small peak at 1681 cm'1 is a carbonyl stretching band, v(C=0), and appears
as a result of incomplete salt formation in the LB film. At a pH of 6.2, used to deposit
the CdArac films, we estimate 90-95% salt formation (Ahn; Franses, 1991; Peltonen et
al., 1994; Schwartz et al., 1993). Upon exposure to HX (Figure 2-2b-d) the va(COO')
band completely disappears, and in all three cases a new band at 1701 cm'1 (v(C=0)) is
observed resulting from protonation of the amphiphile and formation of the carboxylic
acid. There is no change in position, intensity, or fwhm of the methyl and methylene
stretching bands indicating that the organic layers do not undergo any gross changes in
structure during the reaction, and that there is no loss of organic material under the
reaction conditions used. In a series of control experiments, 10-bilayer films of metal-free
arachidic acid were exposed to each of the hydrogen halides and no changes in the ATR-
FTIR spectra were observed. In the arachidic acid and HX-exposed CdArac LB films,
a broad absorbance between 3300 and 2500 cm'1 is observed which can be attributed to
the acid O-H stretch. We do not observe any lattice or metal-coordinated water in the
HX-exposed CdArac LB films (Nakamoto, 1963).
X-Ray Photoelectron Spectroscopy
Control experiments were run on stearic acid LB films to determine whether the
gaseous HX is incorporated into either the non-metal-containing LB film, the OTS layer,
or the silicon substrate. Stearic acid LB films were exposed to each of the HX gases then
placed in the XPS for study. XPS multiplex spectra over the appropriate halogen regions
show that no halides are present in the non metal-containing LB films.


Absorbance
41
3600 3200 2800 2400 2000 1600
Wavenumbers (cm-1)
ATR-FTIR spectra of 10-bilayer LB films of cadmium arachidate: (a)
before reaction; and after 5-min exposure to (b) HI; (c) HBr; (d) HC1. In
spectra b-d, the disappearance of the vaCOO' band indicates that the
reaction goes to completion.
Figure 2-2:


42
Figure 2-3 presents XPS multiplex spectral data for 10-bilayer CdArac LB films
after reaction with HC1, HBr and HI. In each case, XPS reveals that the halogen is
incorporated into the metal-containing film. The binding-energy peak areas are then
integrated and corrected with an atomic sensitivity factor (5000 Series ESCA Systems
Version 2.0 Instruction Manual, 1989; Wagner et al., 1981) to yield the observed relative
concentrations for each element of interest (Table 2-1). The observed relative
concentrations presented in Table 2-1 do not change over a wide range of HX-exposure
conditions.
When using XPS to quantify elemental percentages in heterogenous samples, the
effects of photoelectron attenuation by an overlayer must be considered (Seah; Dench,
1979). The inelastic mean free path, A.m, of a photoelectron depends upon the
photoelectrons kinetic energy and upon the material through which the escaping
photoelectron travels. The XPS signal intensity, I, for any given element in the sample
is reduced to the extent that that elements photoelectrons are attenuated by an overlayer.
The relation is given by the attenuation equation (Briggs; Seah, 1990):
I = (r)exp(-dm/(Xmsin0)) (2-1)
where I is the peak area normalization or sensitivity factor (Wagner et al., 1981), dm
is the overlayer thickness of material m, A.m is the inelastic mean free path of the
photoelectron through material m, and 0 is the take-off angle with respect to the surface
parallel.


43
415 405 395 75 65 55
Binding Energy (eV)
Figure 2-3: XPS spectra of 10-bilayer LB films of cadmium arachidate after 5 min
exposure to: (a) HI; (b) HC1; and (c) HBr. The observed relative M:X
concentrations calculated in the text are (a) 32:68; (b) 45:55; and (c) 40:60.


44
The relative concentration for element A, CA, is then given by:
EexP(~
m^4
ct =
Ka s10'
d) exp(-^A) +
(2-2)
E exP(~
Ka sine
sin0
where the denominator is summed over all the elements of interest (Holloway; Bussing,
1992). To model the cadmium halide-LB assembly, we assume a Y-type (Roberts, 1990)
matrix of tail-to-tail arachidic acid bilayers separated by CdX9 monolayers where the
topmost layer is an arachidic acid monolayer. For organic overlayers, values of are
generally longer than those of inorganic overlayers (Seah; Dench, 1979) and estimates in
the literature vary by about an order of magnitude (Seah; Dench, 1979; Akhter et al.,
1989; Laibinis et al., 1991; Sastry et al., 1991; Ohnishi et al., 1978). For Xm > dm
however, the predicted relative concentrations for the Cd3d, Cl9p, Br3d, and I3d
photoelectron peaks are nearly insensitive to changes in number of bilayers and changes
in A.m and vary by only about 1% over the range of Xm values in the literature (Seah;
Dench, 1979; Akhter et al., 1989; Laibinis et al., 1991; Sastry et al., 1991; Ohnishi et al.,
1978). Using the model described above and dm = 27.6 for the thickness of a CdArac
monolayer (Brundle et al., 1979; Tippmann-Krayer et al., 1992; Jark et al., 1989), relative
concentrations of 35.0% for Cd and 65.0% for I are predicted for a 1:2 Cd:I system in


45
Table 2-1: Summary of XPS multiplex data for 10 bilayer films of cadmium
arachidate after exposure to HX.
LB Film/HX
Peak
KEa (eV)
Observed
Relative
Concentration
(%)
Predicted*3
Relative
Concentration
(%)
CdArac/HI
Cd3d
840
32 3C
35
!3d
624
68
65
CdArac/HBr
Cd3d
839
40 2d
32
Br3d
1049
60
68
CdArac/HCl
Cd3d
839
45 4e
31
ci2d
1179
55
69
aKinetic energies are not corrected for peak-shifting due to sample charging effects.
Calculated for MX2 stoichiometry from Equation 2-2 in text using 7.Cd = 319 A; ^=275
A; A.Br= 356 ; Xq = 378 . c95% confidence limits N=5. d95% confidence limits N=9.
e95% confidence limits N=5.


46
the LB matrix. For Cd-I, the predicted relative concentrations compare well with the
observed relative concentrations of 32% Cd to 68% I for the Fll-treated samples. For the
CdArac-HBr system the observed relative concentrations, 40% Cd and 60% Br, are
exactly centered between the models predictions for 1:2 and 1:1 Cd:Br stoichiometries.
For the Cd:Cl systems, the observed relative concentrations are 45:55, while the model
predicts relative concentration values of 32:68 and 49:51 for the 1:2 and 1:1 ratios,
respectively. The XPS data are tabulated in Table 2-1 and are compared to the predicted
relative concentrations calculated using the layered model with a CdX2 stoichiometry.
Transmission Electron Microscopy
Control experiments were performed on LB films of arachidic acid to verify that
the hydrogen halides do not react with either the un-ionized carboxylic acid, SiO,
Formvar or the Ti support grid. TEM images of multilayer arachidic acid LB films after
HX exposure were featureless, and we have been able to record only diffuse scattering
in electron diffraction measurements from the non metal-containing LB films. Titanium
support grids were used because copper grids react with the hydrogen halides. In another
control experiment, a film of bulk CdArac was cast from hexane onto an electron
microscope grid and then exposed to HI. Prior to reaction, the cast film appears in Figure
2-4 as a random assortment of needles in the TEM, and only diffuse scattering is
observed in diffraction (Figure 2-5). After exposure of the cast CdArac film to HI,
distinct particles are formed and appear in the micrograph (Figure 2-6) as darker regions


Figure 2-4: TEM image of a cast cadmium arachidate film prior to reaction with HI
(30K magnification, 200kV).
Figure 2-5: TED pattern of 2.6 pm-d. area in Figure 2-4.


48


Figure 2-6:
Figure 2-7:
TEM image of a cast cadmium arachidate Film after exposure to HI (30K
magnification, 200 kV).
TED pattern of 2.6 pm-d. area in Figure 2-6. Diffraction originates from
a polycrystalline array of Cdl9.


os


51
against the lighter organic material. The particles have an average size of about 0.1 pm.
Electron diffraction from a 2.6-pm-d. area of the Hi-exposed cast film is shown in Figure
2-7. The diffraction pattern can be assigned to the Cdl2 structure, arising from a sample
of randomly oriented particles.
As seen in Figures 2-8 and 2-9, CdArac LB films are featureless in the TEM, but
yield crystalline diffraction in TED with the expected in-plane hexagonal symmetry and
an observed spacing of 4.26 0.06 A consistent with the literature values (Reigler,
1989; Inoue et al., 1989; Garoff et al., 1986). After exposing the CdArac LB film to HI,
bright field TEM (Figure 2-10, 2-12) shows the appearance of particles. The observed
particles range in size from 100 nm up to several pm across with an average size of about
0.4 pm. Some of the smaller particles have a hexagonal shape, while the larger
crystallites lack well defined edges. TED from the Hi-exposed CdArac LB film is shown
in Figures 2-11 and 2-13. During the diffraction experiment, Bragg spots from both the
organic lattice and inorganic lattice are seen. The organic lattice diffraction pattern fades
away within several seconds, while that of the inorganic lattice does not change position
or orientation upon extended exposure to the electron beam (Pike, Byrd et al., 1993).
TED from the large, continuous particle (> 0.7pm) in Figure 2-10 is shown in Figure 2-11
and yields a single-crystal diffraction pattern corresponding to the Cdl2 [001] zone axis.
Bragg spots corresponding to J-spacings of 3.63 0.02 , 2.12 0.02 , and 1.38
0.02 can be assigned to the [100], {110}, and {120} reflections of Cdl2, and several
orders of each reflection are seen (Pinsker, 1941; Wyckoff, 1982; Finch; Wilman, 1937).
Table 2-2 indexes the diffraction spots for the template-formed particles by comparing


Figure 2-8:
TEM image of a 10-bilayer LB film of cadmium arachidate (10K
magnification, 200kV).
Figure 2-9: TED pattern in Figure 2-8 reveals the expected in-plane hexagonal
symmetry of cadmium arachidate. Diffraction spots correspond to (a)
{100}; (b) {110} reflections and a yield a J10q spacing of 4.26 0.06 A.


53


Figure 2-10: TEM image of a single Cdl2 particle > 0.7 pm in size formed in a 10-
bilayer cadmium arachidate LB fdm after reaction with HI (30K
magnification, 200kV).
Figure 2-11: 200 kV TED pattern from Figure 2-10. The pattern corresponds to the
[001] zone axis of Cdl2. Diffracted spots can be assigned to the (a) {100};
(b) {110}; (c) {120}; and (d) {140} reflections of Cdl2.


55


56
them with the bulk Cdl2 -spacings (Pinsker, 1941; Wyckoff, 1982; Finch; Wilman,
1937). The TED pattern in Figure 2-13 arises from a 2.6-pm d. area in Figure 2-12, and
dark field TEM of the same region shows that several discrete crystals contribute to this
diffraction pattern. Like the single particle in Figure 2-10, the observed diffraction from
a group of several particles corresponds to the Cdl2 [001] zone axis. The diffraction
spots have an angular variance of 4 indicating that each particle has nearly the same
in-plane orientation about the [001] zone axis.
Figures 2-14 through 2-17 present typical TEM images and a TED pattern from
particles resulting from the reaction of a 10-bilayer CdArac LB film and HBr. The
particles can be grouped into two size categories: (1) large particles several hundred
nanometers to one micrometer across, and (2) small particles tens of nanometers in size.
Figure 2-14 is an electron micrograph of several large particles which have been
identified as CdBr2 from electron diffraction (Table 2-2). Like the Cdl2 particles,
diffraction from the large CdBr2 particles, shown in Figure 2-15, gives rise to several
orders of {hkO} reflections in a hexagonal pattern which originates from the [001] zone
axis. At higher magnification, areas are observed where two types of smaller particles
are grouped together in a relatively homogenous distribution (Figure 2-16). In these areas
there are "needles", generally 10-50 nm long with an aspect ratio of about 10, and
"round" particles 10-50 nm in diameter. Throughout the area shown in Figure 2-16, the
needle-like particles are oriented at about 120 relative to one another. The corresponding
TED pattern is shown in Figure 2-17 and presents evidence for two different orientations
of the same crystallographic phase.


57
Table 2-2: Summary of transmission electron diffraction data for 10-bilayer cadmium
arachidate Langmuir-Blodgett films after exposure to HX.
hkl
CdI2
rf(Obs)
(A)
CdI2
i/(Lit.)a
0
(A)
CdBr2
if(Obs)
(A)
CdBr2
(Lit.r
0
(A)
CdCl2
if(Obs)
o
(A)
CdCl2
<7(Lit.)c
o
(A)
100
3.63
3.69
3.4
3.42
3.31
3.33
110
2.12
2.12
1.99
1.98
1.93
1.93
120
1.38
1.38
1.29
1.29
1.26
1.26
200
1.8
1.83
1.67
1.71
1.66
1.67
220
1.05
1.06
0.99
0.99
0.96
0.96
130
1.01
1.02
0.94
0.95
300
1.23
1.22
1.16
1.14
1.11
1.11
003
6.3
6.22
5.84
5.82
006
3.1
3.11
2.92
2.91
009
1.95
1.94
0012
1.59
1.56
1.46
1.45
aPinsker, 1941; Finch; Wilman, 1937 (C3m) bPinsker, 1942 (Rim) cPinsker; Tatarinova,
1941 (R3m).


Figure 2-12: TEM image of a several Cdl2 particles formed in a 10-bilayer cadmium
arachidate LB film after reaction with HI (10K magnification, 200kV).
Figure 2-13: 200 kV TED pattern from Figure 2-12. The pattern corresponds to a 2.6
pm-d. area in Figure 2-12. Diffracted spots can be assigned to the (a)
{100}; (b) {110}; and (c) {120} reflections of Cdl2.




Figure 2-14: TEM image of a typical "large" CdBr2 particle formed in a 10-bilayer
cadmium arachidate LB film after reaction with HBr (30K magnification,
200 kV).
Figure 2-15: TED pattern corresponding to a 0.7 pm-d. area in figure 2-14. Diffracted
spots can be assigned to the (a) {100}; (b) {110}; (c) {120}; (d) {130};
and (e) {140} reflections of CdBr2.


19


Figure 2-16: TEM image of "smaller" CdBr2 particles (50K magnification, 200 kV).
Note the 120 relative rotation of the needles.
Figure 2-17: 200 kV TED pattern of a 0.7 pm-d. area in Figure 2-16. Diffracted spots
can be assigned to the (a) {003}; (b) {100}; (c) {006}; (d) {110}; (e)
{200}; (f) {0012}; and (g) {120} reflections of CdBr2.


£9


64
Diffraction spots correspond to either {MO} or {00/} CdBr2 reflections, and several orders
of each type of reflection are visible. The {MO} reflections have an angular variance of
10 and originate from crystals that have the [001] axis perpendicular to the LB plane.
The limited angular variance indicates that the crystals giving rise to the {hkO} reflections
are oriented relative to one another within the ab plane. The {00/} reflections are
produced by the CdBr2 particles that are oriented with the [001] zone axis parallel to the
LB plane.
TEM and TED results of HCl-exposed CdArac LB films are shown in Figures 2-
18 through 2-21. Large particles (Figure 2-18) ranging from 100 to 600 nm in size are
mixed with regions of homogeneously distributed smaller particles (Figure 2-20) that
range from 10 to 50 nm in size. Some of the larger particles are textured and appear to
be aggregates of small particles. TED patterns can be indexed to the CdCl2 structure and,
like the CdBr2 samples, two discrete sets of reflections are observed. Electron diffraction
from some of the isolated larger particles gives rise to only {M0} reflections and is
shown in Figure 2-19, while others give rise to a mixture of {M0} or {00/} reflections.
Electron diffraction patterns from large areas (> 2.6-pm d.) of evenly distributed smaller
particles (Figure 2-21) gives rise to strong {100} and {110} reflections as well as
reflections from the {00/} planes. The {110} Bragg spots have an angular rotation of
12. The complete indexing for the CdCl2 TED data is listed in Table 2-2 (Pinsker;
Tatarinova, 1941; Wyckoff, 1982).


Figure 2-18: TEM image of typical "large" CdCl9 particle formed in a 10-bilayer
cadmium arachidate LB film after exposure to HC1 (30K magnification,
100 kV).
Figure 2-19: TED pattern of Figure 2-18 can be assigned to the CdCl9 structure.
Diffraction spots correspond to the (a) {100}; (b) {110}; (c) {120}; and
(e) {130} reflections of CdCl2.


66


Figure 2-20: TEM image of "smaller" CdCl2 particles formed in a 10-bilayer Langmuir-
Blodgett film after exposure to HC1 (30K magnification, 100 kV).
Figure 2-21: TED pattern of a 2.6 pm-d. area in Figure 2-20. Diffracted spots can be
assigned to the (a) {003}; (b) {100}; (c) {006}; and (d) {110} reflections
of CdCl2.


* r
Ul Til --7
i 4 *

1 # e
. #
t o *
' I
f
o \ ^
* *
%
r
c
.? % 0
^
:- A > .
.* S'
j, t
*-.
*
' rtf *
> 0 (
. T? / ? *
*ti
%
% '

89


69
Discussion
Organic Template Reaction
ATR-FTIR and XPS results confirm that the reaction of CdArac LB films with
hydrogen halide gases goes to completion. The carboxylate is re-protonated in the
reaction and the halide is incorporated into the film forming the cadmium dihalide. The
C-H stretching bands are unchanged after reaction suggesting that the organic lattice is
intact with the hydrocarbon chains remaining crystalline and in an all-trans conformation.
The reaction does not require high pressures of hydrogen halide and appears to be
complete within a few seconds. All of the inorganic particles that are formed can be
identified by electron diffraction as the corresponding cadmium dihalide, CdX2. No other
inorganic products are observed in the films by XPS and TED measurements. In addition,
the XPS data coupled with the TED results indicate that all of the halogen in the films
is in the form of the metal halide. When an un-ionized film of arachidic acid is reacted
with HX, no halogen is observed in the film by XPS measurements. Halogens are only
seen when the metal ion is present, and in each system, the cadmium to halogen ratio is
independent of sample history (Table 2-1). For the Cdl2 system, the observed Cd:I ratio,
determined by XPS, is exactly the ratio expected for the Cdl2 stoichiometry. In the
CdBr2 and CdCl2 systems, the observed Cd:halogen ratios are greater than that predicted
by the layered model (Equation 2-2). A possible reason for the difference is oxide
formation at the surface of the particles (Peng et al., 1992) which would increase the ratio
of metal to halide observed in the XPS. Literature values of the Cd(35/2) photoelectron


70
binding energies in Cdl9 and CdCl2 show a 0.7 eV difference (Handbook of X-Ray
Photoelectron Spectroscopy, 1989). Relative to the average CdX2 Cd(3<75/2) binding
energy, there is a 0.6 eV difference for the CdO and a 0.8 eV difference for Cd(OH)-,
(Handbook of X-Ray Photoelectron Spectroscopy, 1989). If oxide formation is a factor
in reducing the observed metal to halide ratio it is possible that the shift would not be
resolved by our instrument. Oxidation is more likely to occur at crystal edges, and as the
average crystal size is reduced in the CdBr2 and CdCl2 samples, edge effects at crystal
boundaries will have a greater effect on the observed relative elemental concentrations in
these systems than in the Cdl2 samples. The LB films may also suffer damage due to
photoelectrons generated in the XPS experiment (Graham et al., 1993). We have
observed higher rates of carbon loss for films containing the protonated fatty acid than
for films containing the metal-carboxylate salt (Pike, 1992). Evidence for the desorption
of whole molecules from protonated fatty acid LB films in the XPS has been reported by
Kobayashi et al. (Kobayashi et al., 1988). Loss of organic molecules in the LB film
would tend to invalidate the layered model used to account for the effects of the
photoelectron escape depth. Similarly, TEM images show that discrete particles of the
cadmium dihalides are formed, indicating that the film geometry deviates further from the
alternating layered matrix used to predict the relative elemental concentrations. The most
important observation from the XPS data is that the cadmium-to-halogen ratios do not
vary from experiment to experiment (Figure 2-3, Table 2-1), and are independent of
reaction times and conditions. The fixed metal-to-halogen ratio for each system is


71
consistent with the formation of only one inorganic species and with all of the halogen
existing as the corresponding metal halide identified by TED.
Particle Orientation
It is well known that CdArac LB films give rise to electron diffraction from
domains of crystalline order up to several pm in area (Reigler, 1989; Garoff et al., 1986;
Inoue et al., 1989). In contrast to the solvent-cast films, exposure of CdArac LB films
to HI, HBr or HC1 results in cadmium halide particles that exhibit preferential orientations
relative to the substrate plane and to other particles. In the case of the Cdl2 system we
find that, throughout the film, the particles are oriented exclusively with the [001] axis
normal to the LB film basal plane. In other words, the metal halide layers are always
parallel to the LB layers. By selecting an area of diffraction that includes many particles
(Figure 2-13), we observe single-crystal-like diffraction rather than polycrystalline-type
rings. Not only do the particle basal planes share a common orientation, but domains
exist as large as 2.6 pm-d. where the corresponding in-plane crystal axes have a common
direction.
To account for the observed orientation in this experiment, we can consider two
mechanisms. First, the CdArac precursor film organizes the cadmium ions into an
arrangement similar to that found in the cadmium halides, and thereby directs the growth
of the inorganic lattice by facilitating diffusion parallel to the LB basal plane and limiting
diffusion between planes. Such a mechanism could account for the cadmium halide
particles growing preferentially with the metal halide planes parallel to the LB plane.


72
However, the observation of domains in which discrete cadmium halide particles have the
same in-plane orientation suggests that some degree of lattice matching exists between
the LB template and the cadmium halide, and that this lattice match is responsible for
directing the growth of particles. This mechanism is analogous to how oriented particles
are thought to grow at solution-monolayer interfaces (Mann et ah, 1988; Heywood; Mann,
1992a; Heywood; Mann, 1992b; Rajam et ah, 1991; Landau et ah, 1985; Weissbuch et
ah, 1988; Landau et ah, 1989; Landau et ah, 1986; Popovitz-Biro et ah, 1991; Zhao et
ah, 1992; Mann et ah, 1990). As discussed in Chapter 1, directionally-mediated
crystallization is thought to occur when there is geometric (Heywood; Mann, 1992a;
Heywood; Mann, 1992b; Zhao et ah, 1992), stereochemical (Mann et ah, 1988; Landau
et ah, 1985; Weissbuch et ah, 1988; Landau et ah, 1989; Mann et ah, 1990), or
electrostatic (Rajam et ah, 1991; Landau et ah, 1986; Mann et ah, 1988) complementarity
between the floating monolayer and the crystalline solid. At this point, we can only
speculate about a potential lattice match between the Cdl9 particles and the LB film.
Using a shorthand based on the Wood (Wood, 1964) notation, a (V3 /2 x V3 /2)30
relation is found for the (001) surfaces of Cdl2 and the CdArac precursor, where 2<3^dI2
= ^3-aCdArac (a is the unit cell of the parent lattice; aCdI2 = 4.24 and tfQjArac := 4.92
) (Wyckoff, 1982; Reigler, 1989; Garoff et ah, 1986; Inoue et ah, 1989; Pinsker, 1941).
The superposition of these two surface nets is shown in Figure 2-22 and is very nearly
commensurate, having only a 0.5% lattice mismatch where the lattice mismatch is defined
as (^3-aCdArac 2aCdI2 / ^3-aCdArac) x 100. Of course, after reaction with HI, the
organic layer is no longer present as the cadmium salt and there may be some


73
reorganization of the organic assembly to conform to the Cdl2 (001) surface. This
reorganization would have to be cooperative and over a fairly long-range to result in the
observed orientation of discrete particles over a range of several pm. Calculating the
same (V3 /2 x V3 /2)30 lattice match between an organized arachidic acid layer and the
(001) face of Cdl2 results in a 0.9-2% mismatch, depending on the values of ^arachidic acid
used (Zhao et al., 1992).
In the CdBr2-containing films a larger range of particle shapes and sizes is
observed. The large CdBr2 particles shown in Figure 2-14 give rise to many orders of
{M0} reflections indicating that these particles are oriented with their [001] axis
perpendicular to the LB plane. Electron diffraction from a collection of many discrete
particles confirms that, within the LB plane, they are oriented with respect to each other
as well. As in the Cdl2 case, there may be a lattice match between CdBr2 and the
organic lattice that accounts for the preferential orientation of the CdBr2 particles. The
same (V3 12 x V3 /2)30 relationship suggested for the Cdl2 system results in a > 7%
mismatch in the case of CdBr2. A potentially closer match is a (4/5 x 4/5)0 relationship
between the (001) face of CdBr2 and the basal plane of the precursor CdArac which
would result in only a 0.4% mismatch, where 5aCdBr2 = 4aCdArac (cdBr2 = 3-95 ^ an<^
CdArac = 4-92 A) (Reigler, 1989; Garoff et al., 1986; Inoue et al., 1989; Wyckoff, 1982;
Pinsker, 1942). Electron diffraction from regions containing the smaller "needle-like" and
"round" particles (Figure 2-17) gives rise to two sets of reflections that can be indexed
as the {MO} set and the {00/} set of CdBr2 reflections.


ujuegeo
74
Figure 2-22: Line representation of the proposed (a/3 /2 x V3 /2)30 relation of the
(001) surfaces of Cdl2 and cadmium arachidate, drawn to scale. The d-
spacings correspond to the distances between (100) planes and there is a
30 angle between the two lattice nets.


75
In a single-crystal pattern, these reflections cannot be produced simultaneously because
their respective zone axes are normal to one another (Edington, 1976). The observed
diffraction pattern then, is produced from two sets of CdBr2 crystals with distinct
orientations. One set is oriented with the [001] direction perpendicular to the LB plane,
producing the {MO} reflections, while the other set of crystals is oriented with the [001]
direction parallel to the LB plane, producing the [00/] reflections. Attempts to isolate
each set of crystals using dark field imaging were unsuccessful due to the low intensity
of the scattered beams. Figure 2-17 shows that the [00/] reflections are aligned with the
directions and also produce a hexagonal pattern. Since the sets of planes that give
rise to the [00/] reflections have only twofold symmetry, a hexagonal pattern can only
be produced if there are multiple orientations of the crystals related by threefold
symmetry. In Figure 2-16, the needle-like particles are clearly pictured with three
preferred orientations rotated by 120 with respect to one another. This threefold
orientation of the needle-like particles may be a consequence of the in-plane hexagonal-
close-packing of the alkyl chains in the LB film. If indeed the needle-like particles give
rise to the {00/} reflections then the small "round" particles must give rise to the {MO}
reflections and are oriented, like the large CdBr2 particles, with their [001] axis
perpendicular to the LB basal plane. The round particles are also oriented with respect
to one another within the LB plane, although the angular variance is greater than that
observed in the Cdl2 system.
CdCl2, like CdBr2, is also formed in oriented arrays. The CdCl2 particles grow
with their [001] axis either parallel or perpendicular to the LB plane. Unlike the CdBr2,


76
the observation of the two types of CdCl2 particles is not as dramatic in the electron
micrograph. For each set of crystal diffraction, however, the absence of polycrystalline
rings requires that large groups of discrete particles share a common orientation within
the LB plane. Also, like the CdBr2, the CdCl2 {00/} reflections have threefold symmetry
in the diffraction pattern indicating that the crystals giving rise to these reflections must
have three orientations.
Lattice Matching
Comparing the three systems, we observe larger, more contiguous Cdl2 particles
than either of the other metal halides. In some cases, single Cdl2 particles up to 5 pm
across are observed. When selecting arrays of several particles, electron diffraction from
the Cdl2 sample is sharper and more single-crystal-like than from similar arrays of CdBr2
and CdCl9. The Cdl2 particles sampled in Figure 2-12 are oriented by 4 about the
[001] zone axis while those particles giving rise to the same reflections in the CdBr2 and
CdCl2 systems, although still oriented, show a wider variance of in-plane alignment, up
to 12 in the CdCl9 sample. If lattice matching with the organic template is responsible
for the observed particle orientation, perhaps the lattice match is closer for Cdl2 than for
either CdBr9 or CdCl2. Comparing the (V3 /2 x V3 /2)30 relationship between the (001)
faces of the metal halide and the hexagonal close packing seen in CdArac, it is clear that
the match is closest for Cdl2. Of course, the potential lattice match does not need to be
the same in all three cases. With all three systems, however, the organic template is
expected to conform somewhat to the inorganic extended lattice. There is a limit to the


77
extent the LB film can deform before strain develops resulting in defects and domain
boundaries. If the LB layer does play a role in mediating particle growth, such strains
could limit particle size as well as the extent of particle alignment and may account for
the smaller particles and lower degree of orientational order observed for the bromide and
chloride samples. Defect sites or domain boundaries in the LB film could also be
effective nucleation sites for crystals to grow with alternative orientations such as those
observed in the CdBr2 and CdCl2 systems.


78
Figure 2-23: Cartoon representation of the observed orientation of Cdl2 within an LB
film of cadmium arachidate. Flat, hexagonal "plates" represent the layered
planes of the metal dihalide (parallel to the LB basal plane) and do not
imply particle shape or geometry. The particles are portrayed with their
"unit cell" axes aligned with respect to one another.


79
Figure 2-24: Cartoon representation of the observed orientations of CdBr2 and CdCl2
within an LB fdm of cadmium arachidate. Flat, hexagonal
"plates"represent the layered planes of the metal dihalide (parallel and
perpendicular to the LB basal plane) and do not imply particle shape or
geometry. The particles are portrayed with their "unit cell" axes aligned
with respect to one another.


CHAPTER 3
FORMATION OF ORIENTED MANGANESE IODIDE, BROMIDE, AND
CHLORIDE PARTICLES IN A LANGMUIR-BLODGETT FILM
Introduction
Objective
The idea of using the Langmuir-Blodgett method to build an organic template
which in turn limits the growth of an inorganic crystal was discussed in Chapter 1 and
further validated in Chapter 2. With the proper choice of organic and inorganic materials
oriented growth may be attained, and the cadmium halide study was very effective as a
proof of this concept. The next step is to apply the methods learned in that system to
more interesting materials, namely those with potentially interesting magnetic properties
such as the manganese halides. The manganese halides have structures and reactivities
similar to the cadmium halides. In addition, the manganese halides have the added
advantage of being paramagnetic. One of our long-term goals is the realization of a
monolayer analog of a bulk ferromagnetic material. The synthesis and characterization
of organic templated manganese halides is then one means to that end. As it happened,
the choice of the cadmium halides as model systems for the manganese halides was a
fortuitous one. The cadmium systems were occasionally difficult to deposit as Langmuir-
Blodgett films but were very well behaved in every other respect. In contrast, manganese
80


81
arachidate is very easy to manipulate and deposit as a Langmuir-Blodgett film. In terms
of their structure and amenability towards characterization, the manganese-containing LB
films and the manganese halides were a bit more difficult than the cadmium systems. In
this chapter we will describe the synthesis and characterization of the manganese halides
within a deposited Langmuir-Blodgett film.
Manganese Dihalide Structure
The manganese dihalides, MnX2 have structures similar to the cadmium dihalides
(Wells, 1984). They have either the Cdl2-type or the CdCl2-type layer structures where
the anions are hexagonally close packed or cubic close packed, respectively. The metal
ions occupy the octahedral holes in every other layer of anions. In the layered manganese
halide structures, the bonding within the anion-metal-anion layer is ionic-covalent, while
the anion-anion interaction between layers is van der Waals in nature and easily cleaved
(Wells, 1984). Manganese chloride adopts the c.c.p. structure while the iodide adopts the
h.c.p. structure (Wells, 1984; Wyckoff, 1982). The dibromide of manganese, however,
may adopt either structure (Wells, 1984; Wyckoff, 1982; Ferrari; Giorgi, 1929). The
h.c.p. form of manganese bromide has been reported to be metastable at room temperature
and may undergo a c.c.p.- to h.c.p.-type phase transition at about 623 K (Schneider et al.,
1992). The authors (Schneider et ah, 1992) mention that the phase transition in MnBr2
is the only one occurring for these types of layered structure. The electron diffraction
patterns of the two structures are similar, however.


82
Experimental Details
Materials and Procedures
Manganese(II) chloride tetrahydrate, MnC^' 4H20, 99.6% was obtained from
Fisher Chemical and used without further purification. All other chemicals were
described in Chapter 2. The respective substrates for XPS, IR, and TEM were the same
as those described in Chapter 2.
Langmuir-Blodgett depositions of the manganese arachidate were made using
slightly different conditions than for the cadmium systems. The manganese(II)
'J
concentration was made to 1 x 10 M and then the subphase pH was adjusted to 6.4 with
the addition of dilute KOH. We did not observe any precipitate in the subphase at this
pH due to manganese oxide or hydroxide formation. The Langmuir monolayers were
compressed to a surface pressure, n, of 30 mN/m at a linear compression rate of 5
mN/m/min. At this pressure, the floating monolayers were very stable and easy to
deposit. Dipping speeds of 20 mm/min up and down resulted in very steady and uniform
deposition as judged by transfer ratio which was 1.02 0.02 in all cases. The films
deposited on all substrates (OTS coated) were very dry upon withdrawal from the
subphase, indicating that the films were of good quality. A good (and rare) study of
conditions for depositing manganese carboxylates is found in the article by Peltonen et
al. (1994).
The deposited films were exposed to the gaseous hydrogen halides, HC1, HBr, and
HI in various concentrations and for various periods of time. The exposure times ranged


83
from five to fifteen minutes. Partial pressures of HX in argon were typically 6.2 x 10~2
atm. Thicker films (60 layers) required longer HX-exposure times and higher HX
concentrations to effect complete reaction-closer to 15 minutes and 2.5 x 10' atm. In
all of the experiments that are reported, the higher exposure times have been used such
that the reaction has gone to completion.
Results
Attenuated Total Reflectance FT-Infrared Spectroscopy
Reactions of the manganese arachidate (MnArac) LB films with hydrogen halide
(HX) gas were monitored by ATR-FTIR. Figure 3-1 shows the ATR-FTIR spectrum from
1500-4000 cm'1 of a 10-bilayer MnArac LB film. Peaks at 2955 cm'1, 2915 cm'1 and
2850 cm'1 in the MnArac spectrum are the asymmetric methyl va(CH3), asymmetric
methylene va(CH2) and symmetric methylene vs(CH2) stretches, respectively, of the
close-packed, all-trans hydrocarbon chains in the LB film (Wood et al., 1989; Porter et
ah, 1987). The band at 1562 cm'1 is the asymmetric carboxylate stretch, va(COO'),
characteristic of the metal carboxylate salt. The small peak at 1686 cm"1 is a carbonyl
stretching band, v(C=0), and appears as a result of incomplete salt formation in the LB
film. From XPS measurements, Peltonen (1994) estimates a pKa of a manganese stearate
LB film to be 6.2. Using Peltonens estimates (1994), our film (deposited at pH = 6.4)
should be about 60% manganese arachidate, the remainder being the protonated arachidic
acid. Judging from the IR spectrum Figure 3-1 we observe that the v(C=0) at 1686 cm'1
is not very intense while the va(COO') peak at 1562 cm"1 is higher in intensity. Unless


Absorbance (au)
84
Wavenumber (cm-1)
Figure 3-1
ATR-FTIR spectrum of a 10-bilayer MnArac LB film.


85
there are orientational or structural effects leading to a reduction of the observed v(C=0)
band intensity, Peltonens pKa value of 6.2 may be a little high. The film in Figure 3-1
was deposited at a pH of 6.4 and we estimate that the film is predominately in the form
of the metal-carboxylate salt.
Upon exposure to HI (Figure 3-2) the va(COO') band disappears from the IR
spectrum, and several new bands appear. The intense band around 1697 cm'1 (v(C=0))
results from formation of the carboxylic acid. This band is actually a doublet with
maxima at 1701 cm'1 and 1692 cm'1. It is possible that this split is due to a cis-trans
isomerization of the alkyl chains about the hydrogen-bonded dimeric carboxylic acid
headgroups (Rabolt et al., 1983) or otherwise two different crystal forms in the LB film
(Bellamy, 1975). There is no change in position, intensity, or fwhm of the methyl and
methylene stretching bands indicating that the organic layers do not undergo any gross
changes in structure during the reaction, and that there is no loss of organic material
under the reaction conditions used. In Figure 3-2, a broad absorbance between 3300 and
2500 cm'1 is observed which can be attributed to the acid O-H stretch. In contrast to the
HX-exposed cadmium arachidate films, we do observe two sharp peaks at 3502 cm*1 and
3418 cm'1 indicative of some water in the lattice. These peaks, and a small peak at 1581
cm'1, are also seen in the HC1- and HBr-exposed films and will be treated in the
discussion section. Figure 3-3 shows the IR spectrum of an HBr-exposed 10-bilayer
manganese arachidate LB film. Visible are the bands due to the alkyl chains near 2900
cm'1 unchanged from their positions in the unexposed film (Figure 3-1) and the v(C=0)
band at 1699 cm'1. Figure 3-4 presents the spectrum of an HC1-exposed 10-bilayer manganese


Absorbance (au)
86
Wavenumber (cm-1)
Figure 3-2:
ATR-FTIR spectrum of a 10-bilayer MnArac LB film after exposure to HI.


Absorbance (au)
87
Wavenumber (cm-1)
Figure 3-3:
ATR-FTIR spectrum of a 10-bilayer MnArac LB film after exposure to
HBr.


Absorbance (au)
88
Wavenumber (cm-1)
Figure 3-4:
ATR-FTIR spectrum of a 10-bilayer MnArac LB film after exposure to
HC1.


89
arachidate LB film. The skeletal peaks near 2900 cm'1 are unchanged and the v(C=0)
peak at 1702 cm'1 shows that the conversion to the carboxylic acid is complete. The
smaller peak at 1605 cm'1 and the two peaks at 3518 cm"1 and 3453 cm'1 are most
probably due to water in the crystal lattice and are shifted from their values in the HI-
and HBr-exposed films. In addition, the intensity of these peaks has increased relative
to those in Figures 3-2 and 3-3.
X-Ray Photoelectron Spectroscopy
Figure 3-5 presents XPS multiplex spectral data for 10-bilayer MnArac LB films
after reaction with HC1 and HBr. Unfortunately, the Mn(2/?) photoelectron binding energy
region overlaps the I(30 region making interpretation of the Hi-exposed manganese
arachidate spectrum difficult even after repeated attempts at curve fitting and
deconvolution. In each case, XPS reveals that the halogen is incorporated into the metal-
containing film. As before with the cadmium dihalides, the binding-energy peak areas
are then integrated and corrected with an atomic sensitivity factor (5000 Series ESCA
Systems Version 2.0 Instruction Manual, 1989; Wagner et ah, 1981) to yield the observed
relative concentrations which are presented, along with the predicted values derived from
the attenuation equation (Equations 2-1 and 2-2), in Table 3-1. In the case of the HC1-
and HBr-exposed MnArac films, the observed values are in line with the predicted values
of the relative concentrations for MX2 stoichiometries.


N(E)/E
90
Binding Energy (eV)
Figure 3-5: XPS spectra of 10-bilayer MnArac LB films after exposure to HC1 and
HBr. Spectrum of Hi-exposed film is not included as the Mn(2/?) region
overlaps the I(30 region (see text).


Full Text
UNIVERSITY OF FLORIDA
3 1262 08556 9456



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