ABSTRACT

UNDERSTANDING GOLD NANOISLAND FORMATION USING

TRANSPORT MEASUREMENT
By
Toyanath Joshi
August 2010
Novel metal nano-clusters are always being an interest of scientists and
researchers because of their unique optical and chemical properties. This thesis studies
the formation mechanism of gold nanoisland film by studying transport properties. We
used layer-by-layer self-assembled multilayer gold samples and annealed them at the
temperature ranging from room temperature to 625C. Transport properties, particularly
the resistance and capacitance, were measured in situ during annealing and compared
with the surface morphology and UV-vis studies. Five films of the 8-layer gold and one
film of the 5-layer silver and 5-layer gold nanoparticle sequentially self-assembled
samples were measured. Temperature dependent resistance curves were plotted and
analyzed. From the resistance curves, we were able to identify the actual temperature
for polymer evaporation and nanoisland formation. These data were re-verified by
comparing them with the temperature dependent studies of surface morphology and UV-
vis spectroscopy. The effect of measuring condition, like heating rate and pre-annealing
time factor, was also analyzed. Particularly, the slow heating and long pre-annealing
time effected nanoisland growth mechanism.
UNDERSTANDING GOLD NANOISLAND FORMATION USING
TRANSPORT MEASUREMENT
A THESIS
Presented to the Department of Physics and Astronomy
California State University, Long Beach
In Partial Fulfillment
of the Requirements for the Degree
Master of Science
Committee Members:
Chuhee Kwon, Ph.D. (Chair)
Yahannes Abate, Ph.D.
Young-Seok Shon, Ph.D.
College Designee:
Patric Kenealy, Ph.D.
By Toyanath Joshi
M. Sc, 1997, Tribhuwan University
August 2010
UMI Number: 1490392
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ACKNOWLEDGEMENT
I would like to acknowledge the following people who were integral to the
completion of this project. Dr. Chuhee Kwon's support and guidance was indispensable
and key to the achievement of this thesis. The assistance provided by Dr. Young-Seok
Shon greatly facilitated my understanding for the world of nanoislands. This project
could not have been started without his assist in sample preparation process. Dr.
Yohannes Abate has always been a source of encouragement and motivation. Dr.
Andreas Bill and Dr. Thomas Gredig's words of wisdom and advice provided the
momentum necessary to move forward. Irene Howard and Sandy Dana have always been
helpful despite their busy schedules and many responsibilities. Devid Rave, Mike
Aquino, Michael V. Ramirez, and Mathew Byrne have been a great help in the lab as
well as throughout my graduate career. Finally, the support from Dr. Patrik Kenealy
(department chair) and The Richard and Florence Scalettar Research Scholarship
Program to complete this research project is really appreciated.
Thank you all for your assistance and support. I have greatly enjoyed working with
you and appreciate the time and effort you took in support of this work. This thesis effort
was a positive experience and a project that achieved success because of the contributions
made by everyone involved.
CONTENTS
Page
ACKNOWLEDGEMENT iii
LIST OF TABLES vi
LIST OF FIGURES vii
LIST OF ABBREVIATIONS x
CHAPTER
1. INTRODUCTION 1
2. THEORY 5
Nanoparticle-Polymer Multilayer Thin Films 5
UV-vis Spectroscopy 6
Theory of Electric Transport Measurement 7
Four-Point-Probe Connection Technique 9
Resistance Characteristic of Gold 10
3. EXPERIMENT 15
Sample Preparation For In Situ Transport Measurement 15
Transport Measurement 19
Lab VIEW Remote Control System 21
Measurement Consistency Testing Using LCR Meter 27
IDE Sample Survey 30
Heating Furnace and Temperature Measurement 32
4. RESULT AND DISCUSSION 34
Post Annealing Transport Measurement 34
In-Situ Annealing Study 36
Bare Sample 36
IV
CHAPTER Page
Gold Samples 37
Gold sample Gl 40
Gold sample G2 41
Gold sample G3 43
Gold sample G4 43
Gold/Silver Compounded Sample 45
Variation of Capacitance with Temperature 48
Impedance Variation 48
Sputtering Sample 49
Post Annealing Surface Morphology 51
Post Annealing UV-vis Spectroscopy 53
Hopping Energy 54
5. CONCLUSION 58
APPENDICES 60
A. IDE SAMPLE SURVEY 61
B. SOP 1: NANOPARTICLE DEPOSITION ON IDE 64
C. SOP 2: CONTACT POINT FORMATION 67
D. SOP 3: LCRMETER 70
E. SOP 4: SAMPLE HEATING 72
E. SPUTTERING SAMPLES 75
REFERENCES 78
v
LIST OF TABLES
TABLE Page
1. List of Gold Samples 38
2. 8/KB Ratios of Different Samples 56
3. Equations for Surface Roughness Parameters 62
4. Linear Roughness Parameters for Glass and Gold Surfaces 63
5. Surface Roughness Parameters for Glass and Gold Surfaces 63
VI
LIST OF FIGURES
FIGURE Page
1. Nanoparticle Multilayers 5
2. Schematic diagram for absorption spectra of a gold nanoisland sample... 6
3. Impedance 8
4. Four-point-probe connection 10
5. Theoretical value of resistivity of gold plotted against the thickness of
the layer 11
6. Theoretical curve for resistance versus temperature for nanoislands 13
7. Metal thin layer and nanoislands 14
8. An IDE and connection settings 17
9. Experimental setup 18
10. Four-point-probe measurement system 19
11. Input VI (logarithmic) 21
12. Input VI (linear) 22
13. Write VI 22
14. Time Generator 23
15. Fetch VI 23
16. DAQ Assistance VI 24
vii
Pag
17. Output VI
18. A complete overview 25
19. Lab VIEW Front Panel 26
20. Standard Deviation produced by LCR Meter for Resistance and
capacitance measurement 28
21. Capacitance values measured with different operating frequencies 28
22. Resistance values measured with different operating frequencies 29
23. The frequency dependent variation of resistance 29
24. AFM Picture showing gold and glass surface and the height of the
electrode 31
25. Shift in temperature data recorded by two different thermocouples 32
26. Average resistance and capacitance of bare sample (B), Sample
annealed at 500C (G500) and the sample annealed at 625C (G625) 35
27. Resistance Variation in Bare Sample 37
28. R versus T curves for different samples 38
29. Resistance of different samples at different temperatures 39
30. Resistance variation of Gl 40
31. Resistance variation of Rfor G2 42
32. Time curves 42
33. Resistance variation of G3 44
34. Resistance variation of G4 44
35. Resistance variation of 5Au/5Ag with temperature while annealing 46
Vl l l
Page
36. Temperature dependence of capacitance 48
37. The impedance (Z) variation of sample Gl plotted together with the
resistance of the same sample 49
38. Temperature dependence R of Sputtered samples plotted together with
Gl 50
39. UV-vis Spectroscopy 52
40. The temperature dependence of grain size 52
41. Temperature dependence of R plotted together with grain size and
resonance wavelength variation 54
42. LN (R) versus T"
1
curves for the region B of Figure 28 55
43. Hopping Energy of different sample while cooling down after
annealing 55
44. Hopping energy variation for different samples 56
45. A glass slab as a sample holder 69
46. Sample on the Glass Slab 69
47. Sputtering samples 76
48. AFM picture of sputtering sample Spl 77
IX
LIST OF ABBRIBATIONS
NPs
MUA
UV-Vis
SOP
IDE
LCR
GPIB
LabVIEW
rms
DUT
A/D
DAQ
VI
VISA
AFM:
Ra
Sa
TC
Nanoparticles
Mercaptoundenic Acid
Ultraviolet Visible
Standard Operation Procedure
Interdigited Electrodes
Inductance-capacitance-resistance
General Purpose Interface Bus
Laboratory Virtual Instrumentation Engineering
Workbench
Root Mean Squire
Device Under Test
Analogue/Digital
Data Acquisition
Virtual Instrument
Virtual Instrument Software Architecture
Atomic Force Microscopy
Linear Roughness
Surface Roughness
Thermocouple
CHAPTER 1
INTRODUCTION
Though there were a lot of applications of gold in bulk state, people were
unfamiliar with the nanoparticle state of the gold till Michael Faraday and George
Gabriel Stokes identified it. In 1856, Faraday postulated that the ruby color of aqueous
solution of gold (mixed with either SO3 or phosphorus) is due to the finely divided gold
particles [1-2]. Before this, gold had been used for the gold plating and glass staining
purposes. But actual modern scientific evaluation of colloidal gold began after Faradays
work. Due to the unique optical and electronic properties of gold nanoparticles, they
soon attracted the attention from scientists.
Novel metals like gold are vigorously active toward chemical reaction in
nanoparticle state in contrast to their inertness in bulk state. These nanoparticles are
being used for the catalysts for many of the chemical reactions. Gold catalysts have been
shown to be active for hydrogenation of the unsaturated hydrocarbons like 1,3-butadiene,
acetylene, pent-1-ene, alfa,beta-unsturadedaldehydes, prop-1-yne and others [3]. They
also have been shown to be active for oxidation reactions like oxidation of sulfides and
dithioalkanes [4-5].
Metal nanoparticles (NPs) have mainly been studied because of their unique
electric and optical properties. These properties, in fact, depend upon the shape and size
of the nanoparticles [5]. These particles are intensively sensitive toward visible light and
can show clear band of absorption spectra, which is absent in bulk metal state as well as
1
in atomic state. Their origin is attributed to the collective oscillation of the free
conduction electrons induced by an interacting electromagnetic field [6-8]. These
resonances are also denoted as surface plasmon resonance.
Because of this characteristic, gold nanoparticles have potential diagnostic and
treatment application. Gold particles with small diameter can be used as the
photothermal converter near infrared region due to their high absorption cross-section.
So, they can be used to detect and destroy the tumor cells, for example, in case of cancer
treatment [9].
Similar to the nanoparticle state, the metal nano-structure deposited on solid
substrate is equally active toward catalytic activity and equally sensitive toward visible
light. They are being used in the plasmonic sensing system, catalytic system, and photo-
thermal converter. This thesis is particularly concentrated toward these types of thin
films instead of colloidal nanoparticles [10].
There are several methods to deposit nanoparticles in a substrate. Direct vacuum
evaporation method by Rubinstein involves the preparation of ultrathin semitransparent
gold island films by vacuum evaporation into inert transparent substrates followed by
thermal annealing [10-11]. Nanosphere lithographic technique is another famous
techniques proposed by Van Duyne in which nanospheres are used as a mask to deposit
novel metals like gold and silver in the solid substrate. After removing nanosphere mask
by sonicating in solvent, it yields arrays of surface-bond triangular nanoislands. Well-
ordered and nearly homogeneous sub-100-nm array structure can be produced using this
method with controlled shapes, sizes, and spacing [12].
2
For this research purpose, we used layer-by-layer self-assembled gold
nanoparticle deposition method proposed by Dr. Young-Seok Shon from Department of
Chemistry and Biochemistry, California State University, Long Beach. In this method,
11-mercaptoundecanoic acid-fiinctionalized gold nanoparticles (MUA Nps) (diameter
about 3.2 nm) are deposited layer-by-layer onto glass substrate. This method is simple
and requires only common laboratory supplies and equipment for the entire preparation
process [11]. The thickness of the multilayer films can be controlled either by using
different numbers of layers or by using the nanoparticles with different core size.
When these nanoparticle layers, deposited on a glass substrate are heated up to the
temperature about 625C, the polymer used to synthesize are evaporated and the
nanoparticles fuse together to form a cluster shape, called nanoislands. These
nanoislands have the size ranging from 10 to 30 nm.
There are a lot of studies concerning gold nanoislands toward optical properties,
surface structure and their application toward science and technology [11] but the self-
assembly, nanoisland formation and a lot of other behavior of nanoclusters are still a
mystery and great interest of research matter for scientist and researchers. During this
research work, we tried to study the nanoisland characteristics from third anglethe
transport study besides surface morphology and UV-vis spectroscopy.
This thesis contains five chapters and six appendices. Chapter 1 is about the
introduction of the gold nanocluster with background of this research work. Chapter 2
provides theoretical aspects of the gold nanoparticle formation, optical properties and
theory of transport measurement. The third chapter presents the idea about the
experiment and equipment arrangement. Chapter 4 is experimental results and analysis
3
of the outcomes. Chapter 5 is a conclusion of the present work and suggestion for the
future study. Finally, the appendix contains some Standard Operation Procedures
(SOPs).
4
CHAPTER 2
THEORY
Nanoparticle-Polymer Multilayer Thin Films
Layer-by-layer self-assembly method was used to prepare gold nanoparticle-
polymer multilayer samples on glass substrate. Detailed sample preparation process can
be found in Appendix B. The mercaptoundecanoic acid-functionalized gold
nanoparticles (MUA NPs) are deposited layer-by-layer onto glass substrate. The
substrate is then placed alternatively in to the aqueous solution, containing poly
(allylamine hydrochloride) and in the nanoparticle solution, to produce multilayer
nanoparticle film. Figure 1(a) is the schematic diagram of the multilayer nanoparticle-
polymer thin films. The thickness of the multilayer film can be controlled either by using
different numbers of layers or by using the nanoparticles with different core sizes.
(a) ^ ^ (b)
A.M. . J., ,'i S^JJL^^JL^^L,
FIGURE 1. Nanoparticle Multilayers, (a) Layer-by-layer assembly of organic polymer
functionalized gold nanoparticle film (b) and (c) nanoislands after annealing [11].
5
Wave Length
FIGURE 2. Schematic diagram for absorption spectra of gold nanoisland sample [13].
When this polymer-nanoparticle multilayer film is heated, the polymers are
evaporated leaving layers of gold nanoparticles. These nanoparticles fuse together to
form island shaped arrays of gold called nanoislands Figure 1(b).
UV-vis Spectroscopy
When we apply the electromagnetic wave of visual wavelength region, it is seen
that gold nanoparticles show the strong absorption spectra for some particular
wavelength. No bulk or atomic state can show this behavior. Free electrons of the metal
absorb the radiation and start to oscillate. If the frequency of the applied electromagnetic
wave is equal to the natural frequency of the electron, all electrons start to oscillate
collectively. This collective motion of the electron is called a "plasma oscillation'.
This behavior can be explained by Classical Mie Theory, which corresponds to
the rigorous analytical solution of Maxwell's equations for the optical properties of a
spherical particle [11-13]; If the size of the nanoparticle is much smaller than the
wavelength of-the UV-light, the Mie analysis for the extinction coefficient E(X), which is
6
the sum of the absorption and scattering cross section of a spheroid metallic nanoparticle,
is given by the following equation [14]:
E(X) oc [ _ i _ _ ] (1)
where,
me
d is the dielectric constant of the surrounding medium, X is the wavelength of
the UV~light, % is the form factor, and Si and s
r
are the real and imaginary parts of the
dielectric function of nanoparticle respectively. When | s
r
| ei
s
for a spherical metal
nanoparticle, E(X) is maximum when s
r
(co) ~ - %e
me
d, which is the Surface Plasmon
Resonance condition.
Theory of Electric Transport Measurement
All circuit components, resistors, capacitors or inductors, have parasitic
components, for example, unwanted resistance in a capacitor, unwanted capacitance and
inductance in a resistor, or unwanted resistance and capacitance in an Inductor [15].
Impedance In an ac circuit is given by
Z = R + iX (2)
where, the real part R Is the resistance and imaginary part X Is the reactance. The
magnitude of the impedance is then,
= V ^ +
X
; 2
and, (3)
| X|
tan^ =
R
where, 0 is the phase angle'of the impedance. For DC current circuit, X = 0 and Z = R.
7
V
(a)
x I
JyiJI
e
R
(b)
FIGURE 3. Impedance, (a) Circuit elements and (b) complex representation [15].
Figure 3 represents the complex representation of impedance in a complex plane.
Thus, the impedance Z can be written as
Z = \Z\e
w
= |Z|Cos<9 + i | Z| Sin# = R + iX (4)
Again, let us consider V
s
and I
s
represent the sinusoidal wave applied with the
phase angels 0) and 6
2
respectively, then,
V
s
( t ) = | z | . | I
s
| e^
9
^
and,
Re(V
s
(t))= | Z| .\l
s
\cos(cot + e + e
2
) (5)
8
This equation provides the current (Input) and voltage (output) phase relation. The
phase of the output voltage Is the sum of the phase of the Impedance plus the phase of the
input current.
The Imaginary part, reactance, depends on capacitance or the Inductance as follows
1
X = OJL = (6)
mC
If X > 0
?
It Is said to be Inductive where the phase of the voltage leads the phase of the
current; if X = 0, it Is purely resistive; and If X < 0, It Is capacltive where phase of the
voltage lags the phase of the current [16].
Four-Point-Probe Connection Technique
Four-point-probe connection method was used during transport measurement to
minimize the effect of contact resistance. Although, silver epoxy is used as a contact
material during entire research process, which has an Infinitesimal resistance, four-point-
probe connection method is necessary for accurate measurement purpose,
Four-point-probe measurement helps to minimize the contact resistance and Its
effect on the voltage response measurement. Using two separate contacts to bias, the
sample forces all the current to pass through those contacts and through the sample. No
current passes through the voltage contacts due to the high input impedance of the digital
voltmeter. In two-point-probe method, some of the applied signal is dropped across the
contact affecting all of the transport parameters of actual sample. Since no current flows
through the voltmeter In four-point-probe measurement, there Is no voltage drops across
Rc
5
and no effect of contact resistance during measurement, as shown in Figure 4.
9
FIGURE 4. Four-point-probe connection [20].
Resistant Characteristic of Gold
Gold Is highly conductive with resistivity of about 2,2xl0~
8
n.m [16]. The
electronic configuration of gold Is 4f
10
5d
10
6s
i
. So
5
a gold atom has one free electron In
conduction band, which can move freely. But the story Is different In the case of thin
film (Figure 7(a)). Thin metal films condensed on non-metallic substrates unusually
manifest an exceptionally high specific resistivity. This Is due to the shortened mean free
path of the conduction electrons by collision with the boundary faces of the conductor,
Lovell and Appleyard have derived the following relation between resistivity p and
thickness t of the thin film [17].
2 my 1
P =
(7)
Ne
2
2(1+log (^))
where e
5
m and v are electronic charge, mass and velocity respectively. LT is the mean-
free-path of the electron in the bulk metal at temperature T, N Is the electron density and t
Is the thickness of the layer.
10
400 i
*
3 5
"I
G 300
S 250
| 200 "|
% 1 50 i|
1 1 00 "I
m I
* 50 1
0
0 200 400 600
Thickness (nn)
800
FIGURE 5. Theoretical value of resistivity of gold plotted against the thickness of the
layer [16].
Wilkinson simplified above equation as
P f = Pb 1 +
t)
(8)
where A = 4L/p%
?
pf and pb are the resistivity of the film and bulk metal respectively and t
is the thickness of the film [18]. For gold, using mean free path value LT = 970 A, or A =
1230
?
pb = 5.5 x 10" O.m, the theoretical pf versus t curve takes the form as shown In
Figure 5.
The resistivity of metal thin film decreases suddenly as thickness Increases to 200
nm. Thickness above 300 nm almost shows the characteristic of bulk gold (Figure 5).
The resistivity of the metal arises from the collision among freely moving electrons,
which depends on the mean free path of the motion. The resistivity of the metal, p
3
Is
given by [19]:
p =
m
2
(9)
11
and,
1
T = (10)
V
F
where, m is the electron mass, e is* the electronic charge, n is the number of electron per
unit volume, % is collision time, I is the mean free path and vp is Fermi velocity of the
electron,
Equations (9) and (10) suggest that the resistivity of the metal depends inversely
on collision time. The mean free path and the collision time decrease with increasing
temperature. So, the resistivity increases with increasing temperature.
However, the temperature dependence is different in case of nanoislands, If we
consider nanoislands are isolated to each other, then electron can jump from one island to
another only if it has enough energy to do so (Figure 7(b)), The overall conductivity of
the sample, therefore, depends on the barrier energy and the hopping rate of the electrons.
As the temperature increases, the hopping rate of the electrons increases increasing the
conductivity of the island film. The relation between the resistant and temperature can be
expressed as
-e
R = RQCKBT (11)
or,
(~e\ 1
ln(R) = - + ln(Ro) (12)
v KB / T
where, s is the hopping energy of the conduction electron, KB is the Boltzmann constant
and Ro is a constant. Considering e for the gold is constant, resistant decreases
exponentially with temperature as shown in Figure 6.
12
Temperature
FIGURE 6. Theoretical curve for resistance versus temperature for nanoislands.
In a gold nanolsland film, R versus T curve should vary in the similar way to the
theoretical curve as shown in Figure 6 unless something else happens within the system.
For the nano-islandformation study, we plot R versus T and see.the abnormal change In
R-value during heating or cooling. This abnormal change in R Indicates that the other
phenomena, for example the rearrangement or redistribution of gold atoms deposited on
the sample, dominates the usual trend of R variation. Hence, in situ monitoring of R can
be utilized to study the nanoisland formation process while annealing the sample.
Figure 7 is the schematic diagram of glass surface and a thin gold layer deposited
on it. In Figure 7(a), the gold layer is uniform and the resistivity follows equation (8) for
varying thickness. In this particular case, the resistivity exhibits metallic characteristics.
Resistivity of the layer Increases with increasing temperature since the length of the mean
free path of the colliding electron decreases.
13
Figure 7(b) is an ideal case when nanolslands form from a nanolayer after annealing.
When nanoparticles aggregate together to take the shape of the islands, certain gap is
produced among them. Thus, the transport is dominated by hopping of the electron
across the islands. When the temperature of the sample is Increased, hopping rate of the
electron increases, decreasing the resistivity as shown In Figure 6.
The hopping energy of the electron can be determined using equation (11) from
the temperature dependent variation In R. If we plot logarithmic value of R against
Inverse temperature in Kelvin, the slope of the curve gives the ratio S/KB as shown In
equation (13).
d(ln(R)) e
=
_
( 1 3 )
d(l / T) K
B
(a)
Nano-islands
(b)
FIGURE 7, Metal thin layer and nanoislands. (a) A thin layer of gold deposited onto the
surface of the gold, (b) Ideal Islands after annealing. In later case, resistance Increases
abruptly due to the gap between nanolslands.
14
CHAPTER 3
EXPERIMENT
Sample Preparation for In Situ Transport Measurement
Eight-layer gold nanoparticle-polymer deposited samples provided by Dr. Y.S.
Shon were used for this thesis project, Instead of plane glass substrate, gold Inter-
digiteted electrodes (IDE) were used (Figure 8(a)). An IDE has dimension of 5 mm x 5
mm, It. has 10 pairs of electrodes, separated by 400 \im. Detailed sample preparation can
be found in the section 2-1 and Appendix A. Gold nanoparticle-polymer multilayers
were deposited on IDE and the connection points were settled at the big patches shown In
Figure 8(b). Industrially manufactured IDEs supplied by Essential Research, Inc. were
used to provide the uniformity to each measurement.
Nanoparticles were deposited onto the gold IDE by layer-by-layer self-assembly
method as described earlier. Either gold or the gold and silver compounded sample can
be used. For this thesis, we selected gold and gold-silver compounded samples. A bare
sample and two sputtered samples were measured to compare with the previous samples.
The first step was to prepare the sample and to make the connection setting for the
measurement. Since the IDE has a dimension of 5 mm, It was risky and tricky to make
four separate connection points. A lot of attention was paid and four-point connection
setting was established at the wider patch of IDE. In general, Indium can be used as a
soldering material. But It does not work at high temperature measurement, particularly
15
during in situ measurement, because It has melting point less than 250C. Also
3
indium
has a few- more drawbacks, for example,, low adhesiveness and high contact resistance.
To remove these difficulties, we used new contact material named silver epoxy
(Item no H20E-175) produced by Epoxy Technology, Inc. This silver epoxy Is an
adhesive with high electric conductivity, highly stable even at high temperature, and easy
to use. The only drawback Is that the sample has to be heated to 170C to make the
setting stable. This may be problematic for some cases. Since evaporation temperature
of polymer Is about 500C
9
this heating has no effect on the sample.
Next step was to select connecting wires. Copper and tin wires showed the
burning effect at the surface of wire at the temperature above 600C, which caused the
increase In contact resistance. So
?
we selected the gold and platinum wires. Both type of
wires are highly stable at high temperature and do not brittle even if they were heated
numerously. The gold wire is more flexible than the platinum and easier to operate.
Four pieces of gold or platinum wires with thickness less than 0.5mm were used
to make the connection setting. A glass slab was used as a sample holder for IDE. Silver
epoxy was prepared by mixing two types of epoxies, part A (epoxy resin and silver
power) and part B (harder and silver powder) In the similar proportion. Four-point
connection setting was built using gold or platinum wires and silver epoxy as shown in
Figure 8(b) and as described In Appendix B.
We used four-point connection method to measure transport properties (Figure 4,
10). Four-point-probe measurement helps to minimize the contact resistance and the
effect on the voltage' response measurement. Using two separate contacts to blas
5
all
16
FIGURE 8, An IDE and connection settings, (a) Interdigited Electrode Sample (b) Four-
point connection settings.
current is forced to passes through the sample. No current passes through the voltage
contacts due to the high input impedance of the digital voltmeter and there is no voltage
drop due to the contact resistant Though we measured the resistant in the mega-ohms
range and the contact resistance of few ohms could be neglected, we used four-point
contact method for more precise measurement. Among four contact wires
5
two were
used to bias the current terminal and other two were used to measure the voltage response
of the sample.
The optimized standard operating procedure (SOP) for the sample preparation is
summarized in Appendix C.
17
FIGURE 9. Experimental set up. (a) LCR Meter, (b) Heating furnace, (c) DAQ Box, (d)
Lab VIEW front panel, and (e) Heating furnace inside connection view (a).
18
* * \ ,y?.jn:
output H
C
' - : '- I ^
w
< * ^- - * ~ ^ ~ OUT; * ^ ^ " i/ * ^
Oasn *!!$& r
Hp ''* Lp
-*- *
\,
i
V **- * -^ -^
S y * t * n <, ss _ _ j U
. <8TOU* I 0 * ^
FIGURE 10. Four-point-probe measurement system [20].
Transport Measurement
Agilent 4284A Precision LCR Meter, which has four-terminal pair measurement
configuration, was used to measure the transport properties of the sample (Figure 10).
The unknown terminals consist of four coaxial connectors: High Current (H'CUR)
9
High
Potential (H
PO
T)
?
LOW Potential (L
PO
T) and Low Current (LCUR). LCR Meter has
powerful correction functions, cable length correction, and OPEN, SHORT, and LOAD
corrections. These correction functions are used to correct additional error due to the test
fixture and the test leads [19],
Prior to this, some measurement set up for LCR meter were performed. The
OPEN/SHORT correction was carried out to correct the residual errors. First, the
correction was done without any connection to the measurement terminals and then, It
was repeated shortening all of the terminals.
19
Required measurement function was chosen and the appropriate values for test
frequency, oscillator level, DC bias and integration time were selected. Several trial
measurements were done using a test sample for different values of test frequency,
oscillator level, DC bias and Integration time and the best value was selected for each
parameter for future applications. These parameters can be controlled either by manually
using Measurement Display page of LCR Meter under Measurement Setup or by remote
operation using remote commands through GPIB via Lab VIEW front panel,
: Test frequency has the range 20Hz to 1MHz while oscillator level has the range 0
to 2 V. Oscillator level can be set as the effective value (rms value) of a sine wave of the
test frequency and can be set either the oscillator voltage level or the oscillator current
level It also has a DC bias option, which can be used to bias the Device Under Test
(DUT). The range of bias bolt Is 0 to 2V but when the option 001 Installed in 4284A, the
bias volt can be extended to 40V, or the DC bias current can be set from 0 to 100mA.
Integrating time can be selected as Long, Medium, or Short. The integrating time is the
time required to perform an analogue to digital (A/D) conversion. In general, longer
conversion time will result In more stable and accurate measurement results.
The LCR Meter was controlled by GPIB (General Purpose Interface Bus). A
GPIB Device can be a Talker, a Listener, and/or a Controller. Controller Is a GPIB
device that manages the flow of information on the GPIB by sending commands to all
devices, A computer usually handles the controller function. Listener receives data
messages from the talker. On the other hand, the Controller manages the flow of
information on the GPIB by sending commands to all devices,
20
Lab VIEW Remote Control System
A program was constructed using Lab VIEW virtual instrumentation to control the
LCR Meter, to command it, and to receive and record the data obtained from Device
Under Test (DUT). The Lab VIEW block diagram has five parts: Input VI, Read VI,
Fetch VI, DAQ Assistant VI, and Output VI The Input part particularly controls
measurement parameters of the LCR Meter (Figure 11, 12). Using these Vis, the
measurement parameters, the range of variable, the number of data to be taken and the
data interval can be chosen. Either a fixed value, or a logarithmically or linearly varying
value can be applied as needed.
The second part has the VISA (Virtual Instrument Software Architecture) Write
VI (Figure 13). This VISA Write VI writes the Input data to the LCR Meter.
Appropriate syntax Is applied to the LCR Meter through VISA Write VI. The third part
Is the Fetch VI (Figure 15). It reads the data values from LCR Meter. Particularly
FIGURE 11. Input VI (logarithmic).
21
i f Ut *
^^cEsls^zff
Lxj>-
FIGURE 12. Input VI (linear).
MMMMMMMmMMmMMEmMMMMMMMMMmm^ 0[0..3j ^ ^ ^ ^ ^ S ^ ^ ^ ^ ^ ^ M ^ ^ ^ ^ ^ ^ M ^
FUNGIHP
FIGURE 13. Write VI.
22
FIGURE 14. Time Generator.
FIGURE 15. Fetch VI.
23
FIGURE 16. DAQ Assistant VI.
FIGURE 17. Output VI.
24
25
' linear
| Clear Chmt
| First ryn j
VISA Source
| GPI B0; ; I 7; ^
Changing Value*-***
mm
Ft eguency Value
C when s^raphirK) versus Time)
:
' l000
Figure 19, Lab VIEW Front Pannel.
26
Fetch VI contains VISA Read VI. The fourth part Is the DAQ (Data Acquisition)
Assistant VI (Figure 16). It contains the DAQ-Assistant VI and used to capture heating
furnace temperature data derived by Thermocouple. The final part is the output part
(Figure 17). Output part records the data In the form of Graph and/or Arrays or It can
stores the data In the form of Excel Spreadsheet.
Figure 19 shows the Lab VIEW Front Panel used to control the system.
Frequency range, number of steps, delay time, GPIB address, and file location can be
selected using this front panel. Instead, it can display data as a graph or arrays.
Measurement Consistency Testing Using LCR Meter
The consistency measurement was done for LCR Meter to check the
reproducibility of the measurements for the meter and to find out the measurement
parameters for which the measured values are consistent. Oscillating frequency,
oscillator level, DC bias and Integration time were tested for this purpose. Four of the
samples were used: a bare IDE (B), a gold sample annealed at 500C (G500) and a gold
sample annealed at 625C (G625),
This consistency test shows the LCR Meter can produce very consistent data for
transport measurement. The resistance and capacitance of the samples B, G500 and
G625 were measured several times. Each time, the data produced were identical with a
great consistency. The standard deviations, produced by LCR Meter for resistance and
capacitance, are shown in Figure 20, The resistance deviates from Its main value by less
than 3% and the capacitance deviates by less than 0.6%.
27
0? \
CZ ! ^
.2 i
15 2 -
"5
ci i
xi 1 ~
d
CO
m
o ~~

niii
y.^y.my^^


O500
# K
V *"

si l l
1
_ ^ _ _ _ _ _ _ ^
FIGURE 20. Standard deviation produced by LCR Meter for resistance and capacitance
measurement. The samples used are Bare IDE (B), Gold annealed at 500C (G500)
?
Gold
annealed at 625C (G625).
o
o
1.10
105 H
1.00
0.95
0.90
500Hz
1000Hz
100KHz
-500KHz
7 9 11 13
Time (sec)
15 17 19
FIGURE 21. Capacitance values measured with different operating frequencies. This
figure shows there is less than 5% fluctuation in values what ever be the applied
operating frequency. The waiting time was 4 seconds in each time.
28
o
a:
1.15
1.1
1.06
1 H
0.95
0.9
-100Hz
"500Hz
-1000Hz
*100Khz
SOOKhz
1MHz
\* <P <$>
<>
Time (sec)
# <<? <> ^
FIGURE 22. Resistance values measured with different operating frequencies. This
figure shows there is less than 5% fluctuation in values except in the case of very lower
frequency (100Hz). The waiting time was 4 seconds.
FIGURE 23. The frequency dependent variation of resistance. Resistance values are
highly fluctuation for the frequency lower than 200Hz,
29
Similarly,, a number data were taken with same samples to figure out the suitable
value of test frequency., oscillator level, DC bias, and integration time for further
application. Ten-sets of resistance versus frequency data were recorded with different
values of waiting time. The resistance and capacitance values fluctuated a lot for waiting
time 1 and 2 seconds. All other values are close with each other with a great consistency.
So, at least 4 second of waiting time is needed for better operation of the
measurement system. In most of the preliminary data, 4 second of waiting time is used.
Same amount of waiting time is used in case of post annealing measurements, but the
heating and cooling during in situ measurement takes a lot of time and produces
thousands of data points, which in fact creates complexity in analysis. So, 10 to 30
seconds waiting time was used depending on the number of data-points needed.
In the similar fashion, the best operating values of oscillator level and integrating
time was selected. 0.5, L0, 1.5 and 2V of oscillator level were used and frequency
depended resistance curve were found and IV oscillator level was selected. Again,
medium-integrating time was selected from the plot of frequency versus resistance curve
for different integrating timeshort, long and medium.
The best operating values for LCR Meters selected for future purpose are (a)
oscillating frequency-1 KHz, (b) the oscillator level voltage- IV, (c) waiting time-
>4sec. (d) bias voltage--0 to 2V, and (e) integrating timemedium.
IDE Sample Survey
We chose an IDE (Interdigiteted Electrode) on grass as a substrate instead plain
glass. An IDE has 10 pairs of electrode alternate of each are connected to the opposite
30
patches. The dimension of an IDE is 5 mm x 5 mm. We used Industrially manufactured
IDE by Essential Research, Inc. to provide uniformity In measurement.
General survey of IDE sample was done using an Easy Scan AFM. Figure 24
shows a 49 jim x 49 \un AFM Image of gold and glass boundary from an IDE. The
roughness of the glass surface and gold surface Is estimated using Nanosurf software.
For gold, the average linear roughness (Ra) was. 1.882 nm and average surface roughness
(Sa) was found 4.244 nm. Similarly, for glass surface, the average linear roughness was
found 1.841 nm and average surface roughness was 2.027 nm. The image processing
was not performed because it could modify' the surface roughness. So, the actual
roughness parameter given above might be less than given values due to the external
disturbance, especially caused by environmental radiations, light, sound and other
vibrations while capturing the Image.
FIGURE 24. AFM Picture showing gold and glass surface and the height of the electrode.
31
The height of the gold electrode from the glass surface was measured as 382.17 (
16.27) nm: (Figure 24). If the average size of the nanoparticles is about 3.2 ran in
diameter, eight layers of nanoparticles cover less, than one-eighth part of total height.
Detailed survey of IDE is presented in Appendix A.
Heating Furnace and Temperature Measurement
Thermolyne 1300 closed heating furnace from Thermo Scientific is used to heat
the sample. It has a few openings in backside of the furnace so that we can get the
connection wires and thermocouple wire inside the furnace. Thermolyne Heating
Furnace has the heating range from room temperature to 1050C. It has a temperature
display, which displays the temperature recorded by a built-in thermocouple. Instead, we
used standard thermocouple manufactured by Omega Incorporation as an external
temperature data source.
The temperature data obtained from external thermocouples were compared with
the oven temperature. The thermocouple temperature varies slower than the oven
Overs vs, The rmocouple Te mpr
_ 600
E 500
1 400
I 300
I 200
m
H
1 0 Q
2
100 200 300 400 500 600
Oven Temperature f C)
FIGURE 25, Shift in temperature data recorded by two different thermocouples. The
topmost curve is for oven temperature.
32
temperature. Figure 25 shows the thermocouple temperature for two different
temperature plotted against oven temperature. The topmost curve Is the oven temperature
curve along which all of the curves were supposed to vary. In most of the cases.. It Is seen
that the thermocouple temperature Is lagged by up to 100C. We used the oven
temperature or thermocouple (TC) temperature during the in situ measurements that
created a problem in comparing the data between samples. We realized that the better
adjustment for the temperature measurement near the sample Is necessary for future
works.
The sample with four-point pin set up was placed inside the heater and connected
to the four-probe terminals derived from LCR Meter. After appropriate adjustment, the
heating furnace was turned on and the Resistance and Capacitance values were recorded
within the certain period of waiting time. The heating furnace does not have any
programming facility to adjust the heating rate. The temperature can be Increased
gradually to reduce the heating rate. Detailed Standard Operation Procedure is In
Appendix E. It Is always better to use this furnace to measure the transport properties
even if In the case of constant temperature measurement because the furnace can provide
a good shield to the sample from the outer disturbance produced by electromagnetic
radiations, sound, and light.
The-recorded data were analyzed using Excel or OriglnLab Spreadsheet.
Particularly, the logarithmic R versus Temperature and logarithmic C versus Temperature
graphs were plotted. Finally, these data were compared with the AFM results and UV-vis
spectroscopy measurement.
33
CHAPTER 4
RESULT AND DISCUSSION
Post Annealing Transport Measurement
FIrst
9
we tried to pursue transport parameters of previously annealed samples to
figure out the configuration of nanolslands annealed at different temperature. We
measured three sets of eight-layer self-assembled nanopartlcle gold samples, annealed at
two different temperatures 500C (G500) and
:
625C (G625)
?
and one bare sample with
no gold deposited on it (Bare). Average values of resistance and capacitance were
measured for all samples and compared as shown In Figure 26.
Four-point connection method was used to minimize the effect of contact
resistance on measurement. Silver epoxy was used as a contact material and a lot of
attention was paid to create a best electric connection. Particularly, electric short
between LCR terminals or among the electrodes of IDE can provide direct path to electric
flow effecting measurements of transport parameters of actual sample.
The resistance of the bare sample was measured (6.2571.636) xlO
8
O while the
resistance for samples G500 and G625 were (1.0210.592) xlO
8
and (0.8910.551) xlO
8
O respectively. Similarly, the capacitance measured for Bare, G500, and G625 samples
were (4.350.509) xlO"
12
, (4.300.593) xlO"
12
' and (2.9640.546) xlO"
12
F respectively
(Figure 26),
34
a
CO
o
IK
Samples
FIGURE 26. Average resistance and capacitance of bare sample (B), Sample annealed at
500C (G500) and the sample annealed at 625C (G625).
These values indicate that resistance decreases from Bare to gold deposited
sample. In case of gold deposited sample, there is a slight decrease in resistance value
from G500 to G625 but both of them are in the same order of magnitude. In contrast, in
case of capacitance, there is a slight decrease in capacitance value from sample G500 to
G625, but Bare and G500 samples has almost similar capacitance values,
This analysis provides basic idea about the capacitive and resistive behavior of
gold nanoislands annealed at different temperature. Obviously, the gold deposited
sample is more conductive than the bare one because the gold islands on IDE provides
better conducting paths to flow the current. But, among the gold deposited samples, why
it further decreases for the sample annealed at higher temperature is not yet clear. On the
other hand, the capacitive variation of the samples is different than our expectation. The
35
capacitance values were supposed to be increased when any medium is applied between
the capacitor plates. An IDE. has the geometry of a capacitor and have the capacitive
value in the order of 10"
12
F. This capacitance decreases after gold deposition: slightly
from Bare to G500 sample and significantly from G500 to G625 sample (Figure 26).
The post annealing study did not provide enough idea about the nanoisland
growth mechanism. So
9
we decided to study the in situ transport properties of
nanoparticles sample while annealing.
In-Situ Annealing Study
Bare Sample
A bare IDE (Interdigiteted Electrodes) was used to measure the transport
parameter to see the nature of variation in resistance and capacitance with temperature in
absence of nanoparticles on it. Low heating rate (~ 8C/min) was applied and
temperature was recorded by aid of external thermocouple.
Figure 27(b) shows the temperature and resistance versus time curves. Slow
heating was applied, so that, it took 65 minutes to reach 625 C
5
starting from room
temperature. The sample was kept at 625C for an hour and cooled down to room
temperature again turning off the oven. The resistance decreases approximately
exponentially with increasing temperature from a few Giga-ohms to 2126 O and
increases almost similar way while cooling down the sample. A small difference in R-
value at same temperature is observed, and we believe it is caused by the temperature
drag in the sample. The maximum value of this drag temperature is 11.3 C about
15.3KIX The drag temperature is higher when the temperature ranges from 490 to
570C.
36
10000
Time (sec)
(a)
(b)
FIGURE 27. Resistance variation of Bare sample, (a) Temperature dependent variation of
R for Bare sample, (b) Variation-of resistance with time. The dotted curve Is for the
temperature variation with time,
Gold Samples
Four eight-layer gold nanoparticle samples, Gl, G2, G3, and G4 were annealed,
and transport parameters were measured, in situ, at different measuring conditions (Table
1), To examine the effect of heating rate, heating rate ranging from 12C/min (sample
G2) to 23C/min (sample Gl) was applied. Similarly, the samples were kept for different
durations, one to five weeks, before annealing to examine the effect of pre-annealing time
factor,
Resistances for all samples are plotted against temperature in Figure 28,
Resistance values are In the same order of magnitude for all samples around 200C
(Region A, Figure 28), At 100C, the sample Gl has the minimum value, about 32 MO
and the sample G4 has the maximum value, about 8=6 Mfi. All of the curves move
almost similar way till 300C.
37
200 300 400 500 600 700
T(" C)
FIGURE 28, R versus T curves for different samples. These values were measured in situ
while annealing using different measuring conditions.
TABLE 1. List of Gold Samples
Sample
Code
Gl
G2
G3
G4
Received
Date
10/07/2009
10/07/2009
10/07/2009
10/07/2009
Annealing
Date
10/09/2009
10/23/2009
10/30/2009
11/05/2009
Measuring
Conditions
f= l KHz
WT = 30 sec
H = 23.23
f= l KHz
WT= 10sec
H= 12.61
f= IKHz
WT=10sec
H = 21.95
f= l KHz
WT=10sec
H = 21
Temperature
Data Source
Oven
Thermocouple
Thermocouple
Oven
Thermocouple
Rat200C(xl06
O)
Heating
2.769
3.817
4.896
6.353
Cooling
31.627
0.081
51.370
32323
Comments
Sudden decrease
in R at 570C
observed.
A small drop in R
around 5O0C.
No distinct drops
around 570C.
Curve follows Gl
No distinct drops
around 570C.
Curve follows G2
Note: f is the frequency, WT is the waiting time, and H is the heating rate in C/min.
38
a,
a:
10
9
J
10' 4
w
10
6
'
10
5
^J
10
-100C(Heatirig)
-#-200C(Heating)
- ^ - 200C(Cooling)
Bare G1 G2 G3 G4
Samples
FIGURE 29. Resistance of different samples at different temperatures.
There is a slight decrease in R about 250C and slight increase in R between the
temperature ranges 300 to 400C except the sample G4.
After 300C
9
R decrease as marked by B in Figure 28. However, the details in R
are different depending on the samples. All of the samples have a kink
?
smaller or
bigger
?
showing a sudden change in R-value between temperature raging from 500 to
600C. Finally, all of the samples have similar resistance at 625C ranging from 1.6 Kfl
(sample G4) to 1.9 KO (sample Gl). While cooling, resistances vary the similar to the
Bare sample for all samples except for sample G2,
Figure 29 is a plot for the resistance for all samples at particular temperature
while heating and cooling. The curve with circular legend indicates the resistance for
different samples at 200C while heating and the curve with triangular legend indicates
39
the resistance of different samples at the same temperature while cooling. The resistance
of the bare sample fluctuates at low temperature region, but the resistances for other
samples are bigger while cooling than while heating except In the ease of G2.
Measurements of individual samples are discussed In detail '
Gold sample Gl: This sample was annealed within a week of preparation. The
temperature variation was from 70 to 635C with a heating rate of 23.23C/min. This
sample yielded a unique RT curve with a lot of Interesting feature with different segments
and variations (Figure 30(a)). Figure 30(b) is a variation of resistance and temperature
with time. The recorded temperature is the oven temperature. With the help of these
variations in R-value
?
different stages of nanoparticle formation process can be
demonstrated.
10
9
-
10
9
-!
10
T
-
10
4
-
1

J
]
10" -
7^ ^ ^ -^ ^
' / \ /
\ 1
I
j
i
/ 1
/ \
1
I
1
1
\ /
\ / L
/ ^
/
3000 8000 9000 12000
Time (sec.)
(a) (b)
FIGURE 30. Resistance variation of Gl. (a) R versus T curve. The middle thin curve is
for bare sample. (b)Resistance and temperature variation with time while annealing.
40
For this sample, Initial resistance at 200C Is about 2.80 MO before annealing.
The resistance slightly decreases while heating and gets the value 2.16 MO at 239C.
The value again Increases to get the maximum of 2.62 MO at 412C After 412C,
resistance decreases exponentially till It reaches to 57.1 KO at 560C, At 560C,
resistance suddenly drops with a sharp kink and attains Its minimum value of 55 O at
604C, After this, resistance remains almost constant till 626C, At 626C, resistance
increases suddenly to 4 KO, During of annealing time of 1 hour at 625 C, the resistance
decreases by 2 KO and after than increases approximately exponentially, parallel to bare
sample, while cooling.
Gold sample G2: The .second sample we measured was G2. This sample was
annealed two weeks after it was prepared. The heating rate was 12,61C/mln about of
half of the heating rate of sample Gl. The temperature data source was thermocouple,
As shown in Figure 31, temperature dependence of R is very different from the other
sample. Especially, during cooling, the resistance of this sample flattens below 400C
and remains stationary except a small fluctuation while all other samples show
exponential increase In R with deceasing T.
Compared with the other samples, we used significantly slow heating rate for
sample G2= It took 9 minutes to raise the temperature from 100 to 200C for the sample
G2, while it took about 3 minutes for other samples to cover the same range of
temperature variation. Sample G2 reached the annealing temperature (625C) after 45
minutes while the same temperature was reached a lot sooner for other samples (~ 24
minutes) (Figure 32).
41
3000 6000 9000 1 2000 1 5000 1 8000
Time (sec.)
(a)
(b)
FIGURE 31. Resistance variation of R for G2. (a)Temperature dependence R plotted
together with GL (b) Resistance and temperature variation with time.
5000 7500
Time (sec)
5000 7500
Time (sec)
(a) (b)
FIGURE 32. Time curves, (a) The resistance variation, (b) The temperature variation for
different samples while annealing,
42
While heating, G2 follows similar R trend In temperature Including a slight
decrease In R at 487C (compared with 550C for Gl, Figure 31). The slow heating and
the different temperature data source (the external thermocouple) are main causes for the
slight differences in the heating curve for G2. The cooling curve for this sample is
distinctly different due to the flattening below 400
G
C. We believe this Is caused either by
the hardening of polymer instead of evaporation or by the amalgamation with the
nanopartlcles due to the slow heating. This also provides the support that the almost
temperature independent of R below 300C Is the characteristics of the polymer.
Gold, sample G3: The sample G3 was measured 3 weeks after it prepared. It was
annealed with the heating rate at about 21 C/min. The measured temperature was done
by oven temperature. This curve does not have a sharp drop In R as In the sample GL
The maximum temperature, in this case, was raised to 650C. While cooling, the
resistance Increases similar to Gl (Figure 33).
Gold sample G4: This sample was measured 4 weeks after It prepared. The
sample was heated by the rate of 22C/min (fast heating). Thermocouple was used as the
temperature data source. The additional condition applied for this sample was the DC
bias voltage of 2 V'to study the effect of the DC bias In the formation of nanoislands.
The heating curve shows the temperature dependent R Is similar to G2 (slow
heating curve) than Gl and G3 No sharp drop In R was observed at 560C (Figure 34).
We believe the change of polymer with time (4 weeks) Is the cause for the resistance
characteristics.
43
10%
1
10
9
^
10' -
10
7
i

s
"
10
s
|
ioS
;
\
F
3
^
bd
| \ yS
\ \ /
1 \ /
rt y^
x
\
1 \ / ""-'-.
i \ /
ioS
2
10 , 1 , 1 , j , J
TCC)
(a)
9000 12000 15000
Time (sec.)
CO-
FIGURE 33. Resistance variation of G3. (a) R versus T curve plotted together with Gl.
(b) Variation of resistance and temperature while annealing.
TCC)
(a)
(b)
FIGURE 3 4 Resistance variation of G4 (a) R versus T curve plotted together with Gl
and G2 (b) Resistance and temperature variation with time*
44
Gold/Silver Compounded Sample
A 5-layer gold and 5-layer silver (total 10 layers) compounded multilayer sample
was measured during annealing. The sample was measured after one week from the date
of preparation and heated with the rate of 22C/min. Figure 35 shows the temperature
dependence of in situ R for the Bare IDE, Gl, and 5Au/5Ag samples.
Over all, the 5Au/5Ag sample,shows'following similar characteristics as Gl:
I. Flat temperature dependence In heating up to 345C.
II. A slight Increase in resistance between 345C and 400C,
HI. The exponential R decreases between 400 and 500C.
Iv. A sharp drop in R around 520C followed by a sharp Increase in R at 558.
v. The cooling curve for the multilayer sample is similar to the Bare IDE and
GL
However, there are differences between Gl and Au/Ag samples:
i While heating, resistance for Au/Ag is relatively bigger than the sample Gl.
At 100C, the resistance for sample Au/Ag Is 72 MO, which Is almost double of the
sample Gl at this temperature. After heating, the resistance of Au/Ag Is lower than the
sample Gl by -10 MO at 200C.
ii. The drop In resistance at 550C is smaller for-5Au/5Ag sample than Gl. For
5Au/5Ag, the resistance drops to 13,4 KO, while it drops to 55 ohms In case of Gl
around 550C.
Hi This difference can be due to the overall thickness differences of the
nanoparticle.layers on the sample. Sample 5Au/5Ag has 2-more polymer-metal
nanoparticle
45
- t " r~ ~" 1 <r~ T r - T -
200 300 400 500 800
T ( C )
FIGURE 35. Resistance variation of 5Au/5Ag with temperature while annealing. R
versus T curves for Bare and Gl are plotted together.
layers making it about 25% thicker than the sample Gl (8-layers). At the same time, the
surface structure of the nanoparticle for this compounded sample can be another reason.
We have observed the different surface morphology due to the different metal elements
and the ordering of the layers [30].
The following Is the summary of our observation from in situ resistance
measurement:
i. In heating, the resistance does not vary up to ~300C. The resistance seems to
be dominated by the polymer layers, so It Is believed to be the temperature characteristic
of the polymer.
ii. Between 350 and 530C In heatings the resistance decreases exponentially
with Increasing temperature. This Is due to the evaporation of polymer from the sample,
iii. A sharp resistance drop In Gl around 530C Is caused by the sublimation the
polymer. Thermo-Gravity Test shows that the sublimation temperature to be about
46
500C. Even though It is not as much R decrease was observed In other samples around
500C
?
we believe that this drop was due to the evaporation of polymers.
iv. The sharp increase in R at 625 C Is due to the aggregation of the nanoparitcles
to nanolslands. Further evidence will be presented later,
v. During 1 hour annealing at 625C
9
the resistance does not change much as
observed.
vi The heating curves for samples G2 and G4 are similar but It seems like they
are shifted toward left by 100C. This Is due to the different temperature data source
used to record the data. The temperature data were recorded by thermocouple, which was
found to be lower than the oven temperature up to 100C as discussed earlier,
vii The cooling curves are very similar in all samples including the Bare IDE
except G2. The detailed analysis of the cooling curves will be presented later. As we
discussed earlier, for G2
?
the slow heating was believed to cause the polymer to harden or
amalgamate Instead of evaporation, Hence
5
the cooling curve shows the characteristic of
the polymer below 300C.
viii. We also found the time delay between the sample preparation and the
annealing caused undesirable effect of polymer hardening. It Is evidenced by the
Increased resistance at 200C
3
decreased resistance between 300 and 500C
?
no distinct R
drop at 550C
?
and no clear R Increase at 625C for the sample other than Gl.
ix. The DC bias voltage of 2V during the annealing does not cause much change
in R dependence.
47
T
^ ( a) " T(ic-) ( b)
FIGURE 36. Temperature dependence of capacitance, (a) Sample GL (b) Sample G2.
Variation of Capacitance with Temperature
The capacitance of the samples was recorded at the same time with the resistance
using LCR Meter, Figure 36(a) shows the temperature dependence of the capacitance for
the sample GL There is a sharp increase in C about 550C where R has a sharp decrease
and there is a sharp decrease about 625 C in C where R-has a sharp increase. Figure
36(b) shows the temperature dependence of the capacitance for the sample 5Au/5Ag
?
which also has the similar trend of capacitance variation with sample GL
We haven't done much analysis of capacitance data. However, there seems to be
correlation between C and R.
Impedance Variation
The impedance of the sample varies with temperature exactly similar to the
resistance of the sample. Figure 37 shows the temperature dependent variation of
impedance of the sample Gl with varying temperature. The thick solid curve is the
48
1 r ,
600 700
TfC)
FIGURE 37. The impedance (Z) variation of sample Gl plotted together with the
resistance of the same sample,
impedance for Gl and the thin curve is for Bare sample. The dotted curve is the
resistance for GL The impedance curve overlaps the resistance curve while heating and
while cooling till 200C. Below 200C, the impedance stops to increase and flattens.
Sputtering Sample
Self-assembly/annealing method, the initial motivation for this research purpose,
is one method to produce a metal nanoisland film with controlled shape and size. But, we
studied some sputtering samples, in fact, to see what happens to the R-T curve in absence
of organic polymer,
The SPI-Module sputtered coater was used to sputter the gold on glass substrate
for 40 seconds'for the sample Spl and for 10 seconds for sample Sp2 (Appendix F).
These samples were heated from room temperature to 650C and resistance values were
49
10
s
10
8
10
6
J
10
!
G
* 10
4
10
3
J
10
2
J
10
1
i
10
(
ioo 200 300 400
T(C)
-----G1
^ Sp1
- * - S p 2
500 600

1
700
FIGURE 38. Temperature dependence R of Sputtering samplesplotted together with GL
measured while heating. Temperature was recorded from oven display. Figure 38 Is the
plot for resistances against temperature for samples Spl and Sp2 together with the sample
GL
The sputtered gold creates relatively smooth and well-connected thin film, so the
resistance is quite small (about 35 O), Initial resistance is very low for Spl sample and
decreases slightly up to the temperature till 600C. At -600C
5
there Is a sudden Increase
in R similar to sample Gl followed by exponential increase In R in cooling. In case of
Sp2
3
the Initial R-value Is relatively higher than the sample Spl and it decreases
continuously till the temperature reaches to 600C while heating. While cooling, It
follows Spl as well as GL
50
A comparison of the curves for samples Spl and Sp2 with sample Gl indicates
that the aggregation of gold and nanoislands formation takes place around 600C in case
of sputtering samples as well but there is no any sudden decrease in R in case of Spl and
Sp2 samples as it is in case of sample GL This shows that the drop is due to the collapse
of polymer structure. A slightly decrease in R between 550 and 600C indicates that the
gold layer itself is wetting the surface.
Post Annealing Surface Morphology
The temperature dependent surface morphology study using AFM was performed
by David Rave [29]. The purpose was to see the effect of annealing temperature on
nanoisland growth process. Six five-layered gold nanoparticle-polymer samples were
annealed at six different temperatures and surface morphology, particularly the grain size,
was studied using AFM images of each. Figure 40 shows the different values of grain
size for different samples annealed at different temperature. The central solid curve with
triangular legends represents the average values for each sample.
The graph shows the grain sizes for the sample annealed at 500
?
525
5
550 and
575C are similar except a small variation. But the samples annealed above 575C have
the grains smaller than those annealed at lower temperature. So it looks like the samples
are categorized in. two series: first
5
the samples annealed at the temperature lower than
575C which have grain size around 400 nm
2
and second
9
the samples annealed at the
temperature above 575C which have grain size around 200 nm
2
. There is a clear gap
between these two types of series.
51
4 0 0 5 0 0 SO TOO
%fm via teng t h
8 0 0 OO
FIGURE 39. UV-vis Spectroscopy. The data adopted from Dr. Yong-Seok Shon shows
that the peak value of resonance wavelength shifts for the samples annealed above 575C.
600 i
500
?
4 0 0
300
200
100
grain area
- average area
475 500 525 550 575 600
Te mp.(C)
625 650
FIGURE 40, The temperature dependence of grain size. The data adopted from David
Rave shows that there is a sudden drop In grain size about the temperature 575C.
52
Post Annealing U~vis Spectroscopy
The temperature dependent study of UV-vis spectroscopy of gold nanopartlcle
sample was performed by Dr. Y. S. Shon's research group from Department of Chemistry
and Biochemistry, California State University, Long Beach. They studied the
temperature dependent UV-vls absorbance of six five-layered self-assembled
nanopartlcle samples. Figure 39 is the plot of absorbance of UV light versus wavelength
for all six samples. The peak value Indicates the surface plasmon resonance frequency.
Bottom three curves: B, C and A are the curves for the samples annealed at the
temperatures 525, 550 and 500C respectively (bottom to top). The middle one curve, D,
is for the sample annealed at 575C and the top two curves, F and E, are the curves for
the samples annealed at 625 and 600C respectively.
This study shows that resonance absorbance wavelength for three of the samples
annealed at temperature 500 to 550C falls In the region 533 to 535 nn and that of those
annealed at 575 to 625C falls in the region 540 to 541 nm. So, there Is a shift In.
resonance wavelength between the samples annealed at the temperature below 575C and
above of 575C.
Figure 41 shows the in situ resistance variation of Gl during heating, plotted
together with the grain size and UV-vIs spectroscopy. These curves suggest that the shift
In resistance, peak absorbance wavelength and grain size occurs in the same temperature
range. Resistance starts to decrease about 560C while grain size starts to decrease about
575C. The peak value of absorbance frequency starts to Increase about 525C but the
major change occurs about 575C. Speaking overall, there is a sudden shift in values for
all three of the curves between 550 and 600C.
53
500 550 600 650
T( C)
FIGURE 41. Temperature dependence of R plotted together with grain size and
resonance wavelength variation.
The comparison of transport properties with surface morphology gives some
important idea about the nanoislands formation process. If we consider, the shift in R
caused by complete evaporation of organic polymer, then, obviously the decrease in grain
size also caused by complete evaporation of polymer, So
9
the nanoislands annealed
below 570C temperature are not the true nanoislands.
Hopping energy of the samples can be measured using equation 12, Here, two
regions of particular interest in R versus T curves are selected for hopping energy
analysis purpose (Figure 28), Region B: where R~ values start to decrease exponentially
about 400C, and the region D: a part of the cooling curves.
54
J
ID
1 4 -
1 3 -
1 2 -
11 ..
1 0 -
9 -
/ /
/
. [
.
/ ^
/ / /
f '
A
r _ , 1 , - , _
Bare
- G 1
- G 2
- G3
- G 4
- i
0.0015 0.0020 0.0025 0.0030
1/T
Figure 42. LN (R) versus T
1
curves for the region B of Figure 28. Here the slope of these
curves gives the ratio -E/KB-
cr
13
12.
11
10-|
94
0.0021 0.0028
1/T
FIGURE 43. Hopping Energy of different sample while cooling down after annealing,
Almost all of the curve have the same slope and very close to each other.
55
6000- J
P 4000 4
2000 4
y
\
V
/
-* Heat i ng
y Co o l i n g
Bare G1 G2
j
G3
G4
Samples
FIGURE 44. Hopping energy variation for different samples,
TABLE 2. S/KB Ratios of Different Samples
Samples
Bare
Gl
G2
G3
G4
-e/K
B
Heating
4302.6
5899.5
3675.2
5823.8
5035.3
(K
4
)
Cooling
4512.2
4526.6
2058.9
4029.2
1455.6
56
Figure 42 is the LN(R) versus Inverse temperature, in Kelvin scale, for region B
(Figure 26) of all curves while heating, Similarly
?
Figure 43 shows the LN(R) versus
inverse temperature curves for approximately for same temperature region while cooling.
Figure 44 Is the plot s/K
B
values for all of the samples' while heating and cooling. These
values are listed In table 2.
The hopping energy of all samples Is bigger than Bare IDE expect for G2 while
heating but It Is nearly equal or slightly smaller than that for Bare IDE while cooling.
This Indicates that hopping energy arises from polymer and nanopartlcles while heating
but while cooling, It's just the hooping energy of glass. Sample G2
?
for which slow
heating was applied, has comparatively lower hopping energy.
57
CHAPTER 5
CONCLUSION
Formation mechanism of gold nanolsland was studied using in situ measurement
of its transport properties, Nanoparticle multilayer samples deposited on grass substrate
by layer-by-layer self-assembly deposition technique were annealed at different
measuring conditions. Resistance of the samples was measured in situ to observe the
temperature dependence variation in R. Resistance versus temperature curves were
plotted and analyzed.
Five eight-layer gold and one five-layer gold/five-layer silver compounded
samples were used. All samples showed similar type of R trend below 300C
?
but nature
of variation was different for different samples after 300C depending on different
annealing conditions applied to the sample. Sample Gl had a sharp decrease In R about
570C and a sharp Increase at 625C. Other samples barely showed this type of trend.
The gold/silver compounded sample (5Au/5Ag) almost followed Gl except the drop
about 570C was comparatively smaller. While cooling, the resistance varied similar
way to each other and almost followed the Bare sample except G2. For G2
9
R stopped to
Increase about 400C and remained almost flat.
The study of temperature dependent curves Indicates that below 4G0C
?
polymers
dominate resistance characteristics. From 400 to 570C
?
resistance declines Indicating
polymer starts evaporate and particles get closer. A sudden decrease In R about 570C
indicates the complete evaporation of polymers. Finally, a sudden increase In R above
58
60OC mainly causes by nanoparticles aggregation and a slight Immersion of nanoislands
into the glass due to the melting of glass surface at high temperature.
The measuring conditions had a great effect on nanoisland formation. '
+
Particularly, the slow heating caused the hardening or amalgamation of polymer Instead
of evaporation. Similarly, the length of the duration for which sample kept without
annealing also have shown similar effect on nanoisland growth mechanism.
Finally, we compared the temperature dependence in R for the sample Gl with
the temperature dependent study of surface morphology by David as well as the UV-vis
Spectroscopy study by Dr. Shon's research Group, All of the studied demonstrated that
there Is a sudden shift In respective values about same temperature range. This provided
a concrete idea about nanoisland growth mechanism. The polymers we used to
synthesize nanoparticles evaporate completely after 570C and annealing temperature
should be more than this temperature for a complete growth of nanoislands.
Though, these analyses demonstrated enough Idea about nanoisland growth
mechanism, we still need few more analysis in future. Particularly, in situ transport
measurement for the samples with different end temperatures, starting from 500C, is
extremely necessary. At the same time, It Is necessary to find more reliable temperature
reading during annealing.
59
APPENDICES
60
APPENDIX A
IDE SAMPLE SURVEY
. IDE SAMPLE SURVEY
Surface Roughness and uniformity measurement of Interdigiteted Electrode was
done using AFM Pictures. Roughness of the surface is the measure of the texture of the
surface, which is quantified by the vertical deviation of the real surface from its ideal
form. Following is the table for the equations used to calculate the linear and surface
roughness [15].
16 of the AFM pictures were taken for the different places of the IDE and
analyzed. The average height of the electrode was found (382 16) nn (See Figure
24, page 31).
TABLE 3. Equations for Surface Roughness Parameters,
Parameters
Roughness Average
The Mean Value
Root-Mean-Square
Roughness
Peak-Valley Height
Linear Roughness
1 M- l
1 1
k=0
| M- l
M
i 1
k=0
R
^
1 M- l
R
p
= R
p
- R
v
Surface Roughness
1 M- 1N- 1
i 1 1
^ K=0 1=0
| M- l N- l
Sm =
HE
2
***'**)
^
| M- l N- l
dp = 5p 5 V
Note: R
p
: Highest Value, R
s
: Lowest Value.
62
TABLE 4. Linear Roughness Parameters for Glass and Gold Surfaces.
Picture
^fe^^^^^^^^W
;
f: ,11 pfi
" 6? lift
x l i put
Parameters
Ra
Rq
R
y
R
P
R
v
R
m
Glass
1.882
2.494
18.812
12.064
-6.748
0.002
Gold
1.841
1.768
7.768
4.547
-3.199
0.211
Tables 4 and 5 show the linear and surface parameter respectively calculated.
using equation listed on the table 3, [28]
TABLE 5. Surface Roughness Parameters for Glass and Gold Surfaces,
Picture
mm.-
-SJPWv -
^ 1 1 % m$
MB
Parameters
S
a
s
q
Sy
s
P
by
5 m
Glass
4.244
11.752
453.93
294.47
-159.46
0.116
Gold
2.027
2.666
'45.149
35.743
-9.406
0.166
63
APPENDIX B
SOP 1: NANOPARTICLE DEPOSITION ON IDE
SOP 1: NANOPARTICLE DEPOSITION ON IDE
Silanized Glass Substrate
1. Place the IDEs In piranha solution (3:1 sulfuric acid: 30% hydrogen peroxide)
for 1 hour,
2. Sonicate In nanopure water for 10 minutes.
3. Rinse IDE alternatively with nanopure water and methanol using a
microplpettor with a plastic tip to prevent scratching the surface of the electrodes.
4. Prepare a solution of 1ml of trlethyl 3~mercaptopropylsllane, 1ml nanopure
water, and 10 ml methanol, and place IDE in the sllanizatlon solution for 24 hours.
5. After 24 hours, sonicate IDE three times in methanol, wash with ethanol, and
gently dry under a stream of nitrogen gas.
Layer-bv-Layer Assembly of Nanoparticle. Multilayer Films
1. After drying, place IDE individually in 5 ml glass vials, Immersed In an
ethanol solution containing mercaptoundecanolc acid-functionalized gold nanoparticles
'(MUA) for 24 hours.
2 Following the overnight immersion in MUA solution, rinse IDEs first with
ethanol, then nanopure water, using a Pasteur pipette to remove the previous solution and '
add the next, closing the vial, and inverting it several times.
3. Add an aqueous solution of poly(allylamine hydrochloride) (PAH) to each
vial and let stand for 5 minutes.
65
4. Upon removing the PAH solution from the vlals
9
rinse IDEs with nanopure
water then ethanol using the same method as described earlier by a Pasteur pipette. Then
add MUA solution again, but for duration of 5 minutes. The process of rinsing and
addition of alternate solutions was repeated 6 more times, to create 8 layers of
nanoparticle films.
66
APPENDIX C
SOP 2: CONTACT POINT FORMATION
SOP 2: CONTACT POINT FORMATION
1. Put on gloves and lab goggles,
2. Take a piece of Aluminum foil, a glass, slide, and four pieces of gold or
platinum wires about half of the length of the slide.
3. Clean the slide with Isopropyl Alcohol and Methanol, and dry It under the
stream of nitrogen gas.
4. Take equal proportion of silver epoxles A and B, and mix It uniformly on the
aluminum foil
5. Place four pieces of gold or platinum wires on glass slide nearly mid-way,
approximately parallel and about V
2
mm apart.
6. Place silver epoxy about the half of the length of each wire such a way that It
fully covers the wires. Heat the slide about 2 minutes at 170C
1. Now, all of the wires are affixed to the glass slide. Cut the tips of the wires to.
make them equal Bend tips downward by
l
A mm as shown In Figure 46.
8, Slightly lift up all of the tips altogether and place the sample such a way that
all of the tips touch the wider patches of IDE, two of them in each side (Figure 47).
AVOID ANY SCRATCH ON THE SAMPLE.
9, Place small amount of silver epoxy at the contact point of each wire by aid of
a thin wire. Do not let any of the four contacts to touch each other and do not put any
silver epoxy between two electrodes.
68
10, Heat the slide again for 2 minutes at 170C.
11. Use a multimeter to check to connection setting. There should be low-
resistance between first two and last two wires and high resistance otherwise. If It Is not
9
check the connection setting again,
Glass Slab
FIGURE 45. A glass slab as a sample holder.
| Glass Slab
FIGURE 46, Sample placed on the glass slab,
69
APPENDIX D
SOP 3: 4284A PRECISION LCR METER
SOPS: 4284A PRECISION LCR METER
1. Turn the power switch on.
2. Press the DISPLAY FORMATE key and go to the MEAS DISPLAY page.
Select the Measurement Functions (Cp~Rp, Cp~D, Cs-Rs, or others),
Measurement Range, Test Frequency, Oscillator Level, DC Bias, and Integrating
Time as desired. For detail, see 4248A Precision LCR Meter, Operational
Manual (pate 3-1).
3. Perform the OPEN, SHOPT, and LOAD correction from the CORRECTION page
under MEAS SET UP to correct the stray admittance, the residual Impedance, and
the other errors. For detail, see 4248A Precision LCR Meter, Operational Manual
(pate 448).
4. Connect LCR Meter to CPU through GPIB, Construct the Lab VIEW software to
control It, Details about control commands can be found in 4248A Precision LCR
Meter, Operational Manual; Chapter 8.
5. Start to collect the data. Provide at least 4 sec. of waiting time between two
iterations. If LCR meter shows abnormally higher or lower than the expected
value, recheck the circuit connections.
6. After measurement is done, simply turn off the power switch,
71
APPENDIX E
SOP 4: SAMPLE HEATING
SOP 4: SAMPLE HEATING
1. Put the heating furnace close to LCR Meter.
2. Find the opening in the backside of the heating chamber. Unscrew the not if is
has.
3. Take four pieces of gold or platinum wires about 10 cm in length. Insert them
halfway inside. Take the help of four-pore insulating tube so that they do not touch each
other,
4. Find another opening and insert Thermocouple wire inside using a two-pore
insulating tube. If there is no any extra openings, use six-pore instead of four-pore in 3
and insert together with gold/platinum wires. Be sure: none of the wires are touching
each other.
5. Put the sample inside the chamber and connect each of the four pins to four of
the wires inserted into the chamber. Put some silver epoxy at connections. Take the
thermocouple tip as closer as possible to the sample.
6. Among the wires from the backside of the oven, separate two pairs connected
to the different patches of the sample (Note: easy way is to measure the resistant, find the
pairs between which the resistance is lower), and connect one of each to the H
PO
T and
HCURR terminals of LCR meter. Similarly, connect other two to the L
P0T
and LCURR
terminal respectively*
7. Connect thermocouple to the DAQ-Board.
73
8* Turn the heater on. Set the annealing temperature or change the temperature
range gradually to maintain the desired heating rate.
,9, If annealing Is done, just tuna off the heater or set the temperature to zero,
74
APPENDIX F
SPUTTIRING SAMPLE
SPETTERING SAMPLE
Sputtering sample was prepared by sputtering gold on glass substrate using SPI-
MODULE Sputter Coater, Digital pictures of two of the samples, sputtered for 10 sec
(Spl) and 40 sec. (Sp2), are shown below before and after annealing with an AFM image.
Figure 47. Sputtering samples. Top: Spl before (a) and after (b) annealing. Below, Sp2
before (c) and after (d) annealing.
16
Figure 48. AFM picture of the sputtering sample Spl.
77
REFERENCES
78
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