Nanopraticle Synthesis

ACS-PRF Summer School on Nanoparticles 2004
Polyelectrolytes and Nanoparticles:

Synthesis and Mediation
Rigoberto C. Advincula
Department of Chemistry
University of Houston
Houston, TX 77204
E-mail: radvincula@uh.edu
www.chem.uh.edu
R.C. Advincula/ University of Houston

Nanoscience or Nanotechnology ?
- self-assembly
- quantum effects
- molecular building blocks
- surface science
- Self-assembly or directed
assembly

Nanostructured Materials
Molecular and Macromolecular

Design and Engineering at the nanoscale
-Design, synthesis, characterization
-application
- Crystal Eng.
- Interfacial - Solid state
Phenomena - High Vacuum
- Ultrathin Films -Fundamental
Science
-Technology
Organic and Polymer Inorganic Materials

Materials - crystals, quantum dots,films,
- Surfactants, polymers, dendrimers, nanotubes, nanoparticles
molecular organic crystals, films, - Functional materials (optical,
micelles, nanoparticles electrical, spectroscopic)
-Functional materials (optical, -Anisotropic or long
electrical, spectroscopic) range order and “hard”
-Isotropic and “soft”
Hybrid materials/
Nanocomposites

Convergence of Materials in Interfacial and

Colloidal Phenomena
500 nm
• Quantum dot nanoparticles

• Colloidal particles
• Organic nanoparticles
100nm • Polyelectrolytes, surfactants
• Hybrid organic-inorganic
R.C. Advincula/ University of Houston • nanocomposites
Innovative Surface Sensitive Analytical Techniques
CCD camera
Electrochemical
instrumentation
Lenses
He-Ne Laser (632.8 nm)
θ0
Polarizer
Au
Electrochemical cell
Electropolymerization
Microcontact Printed SAM (ODT) Polypyrrole
• Scanning probe microscopy

• Time-resolved and frequency resolved
spectroscopy
• Evanescent wave techniques
• Light scattering methods
• Surface sensitive acoustic methods
Patterning Methods and Devices

PDMS Stamp
Ink
ODT
solution
Dried
under niotrogen
ODT
ODT
Stamp
source drain
ODT SAM Gold

BOTTOM CONTACT
molecularly
assembled
Micropatterned ODT SAM oligothiophene
semiconductor
Schematic representation of microcontact printing

Gate Silicon
SiO2 Substrate
• Lithographic and nonlithographic methods TOP CONTACT
• Photolithography and soft-lithography

• Semiconductor devices source drain
• Display and nonlinear optical devices

Nanoparticles
1. Silver: catalysis, photographic

processes
2. CdS: optoelectronics,
photoluminescence
3. Gold: optoelectronics, electronics,
biosensors
4. Silica: insulator, catalyst support,
membrane, filling material
5. Palladium: catalysis
6. TiO2: photoelectrochemistry
7. Metal oxide: Mg, Ca, Mn, Fe, Co, Ni,
Cu: magnetic properties
8. Polymer: conducting composite,
drug delivery
Nanoparticles with
Nanoparticles with
II 1. Size and shape uniformity
1. Size and shape uniformity
Synthesis 2. Stability
Synthesis 2. Stability
(Stable
(Stable andwell-defined
and well-defined 1. Unique properties
nanoreactor) 1. Unique properties
nanoreactor) 2. Ordered deposition
2. Ordered deposition
3.3.Selective
Selectivedecoration
decoration

Synthesis of Nanoparticles: the Concept of Nanoreactors
Nanoparticles as colloidal systems of a solid-state material -

dimensions in between molecules and a bulk solid-state material.
Strategies for the synthesis of nanoparticles: surfactant or
polymeric amphiphiles (block copolymers) micelles as a “nanoreactor” for
nanoparticle synthesis.
Mechanism - Metal ions trapped inside the particles exposed to
precipitating or reducing agents to start nanoparticle growth: the number
of metal ions initially trapped inside the particle determine growth.
Key step: Control over the diffusion of reagents into the micelle.
Design: The possibility of attaching coordinating ligands to the
polymer in order to stabilize both precursors and nanoparticles within.
• Strategies for the gold nanoparticle preparation
Amphiphilic Self-assembled
Cationic
block copolymers Dendrimers monolayers
polyelectrolytes
(PS-b-P2VP) (PAMAM) (n-Alkanethiols)
• “Stable Nanoreactor” for the control of size and shape of nanoparticles
Nanoparticles and nanostructured Films;

Fendler, J. H., Ed.; Wiley-VCH; Weinheim,
R.C. Advincula/ University of Houston 1998.
Synthesis of Nanoparticles in General
a b c
Star block
Schematic representation of the copolymer
(PS-b-P2VP)
concurrent process during reduction
N:Au=10:1
reaction inside block copolymer 0.5
micelles. P4VP (NaBH4)

PAMAM Dendrimer (UV)
0.4
a) Reduction is initiated by the entry of PS-b-P2VP (Hydrazine)
the reducing agent into the core of the Absorbance

0.3
micelles loaded by precursor salt.
b) Destabilized micelles exchange block 0.2
copolymer and may coagulate.

0.1
C) “Empty” micelles are formed besides

block copolymer stabilized gold particles. 0.0
400 450 500 550 600 650 700
H: reduction agent; O: precursor salt; Wavelength (nm)
crystal.
__200 nm

Mechanism:
• Reduction:
- Cl
-
Cl
HAuCl4 Au
reduction Cl
- -
Cl
• Reducing agent
(Organic or inorganic reducing agent, UV irradiation, electrochemistry, etc)
• The relative rate of Nucleation and Growth of Nanoparticles
- Manage the particle size
γ
• Nucleation RC ∝
Ln(C/C o)
Where Rc is radius of initial particle, γ is interfacial tension, and C/Co is the
degree of supersaturation.
• Growth
- Ostwald-ripening process: One particle per domain

PS-b-P2VP Micelles Containing Gold nanoparticles:

Aggregation
M. Moller et al., Macromolecules, 2000, 33, 4791.
PS(300)-b-P[2VP Au0.5(300)]
A dried film
(a) Directly after deduction (b) 30 min after reduction C=0.01mg/ml solution
Organic Ultrathin Film Multilayer Assemblies
• How different is this from spin-

coating?
Langmuir-Blodgett • Nanostructured multilayer

(LB) Film architecture
• control molecular orientation and

organization on the nanoscale
Si O Si
O O Organic
and Polymeric • precisely tunes the macroscopic
Ultrathin properties of the organic and
Si O Si
Multilayer films polymer thin films
O O
Layer-by-Layer
(LbL) Film • Applications in microelectronics,
Chemisorption electro-optics, sensors, and
biotechnology
• To be explored? Organic and

polymer multilayers by vapor
deposition and thermal
evaporation methods

Nanostructured Layer-by-layer Self-assembly

from Solution
Deposition Process
Equilibrium of Deposition
• Electrostatic (coulombic forces)

• Interfacial phenomena
• Solution properties:
concentration,pH +-
salts,temperature +- - +-
+-
-+`+ ++ +-
+-
-+`+ ++
+- - +- -+ + +- -
• Surface sensitive techniques
+- - +- -+ + +- -++ ++
+- - +- -+ + -+
++---
+
+- - ++ - -+ -+ + -
Structure – Fuzzy Nanoassemblies?
1.0
0.8
(A/Bd)n
Relative Composition
substrate
0.6
0.4
0.2
0.0
- Neutron reflectometry
1 2 3 4 5 6 7 8 9 10
Bragg peaks appear (NR-3 ~6) Layer Number
((A/B)m(A/Bd))n, m = 1, 2, 3
- Interpenetration
- Stratification

Decher, G. Science 1997, 277, 1232.
A Variety of Materials for the LbL Technique
Polyelectrolytes
Typical polyelectrolytes conjugated polymer; poly(phenylene vinylene)
precursor, poly(p-phenylene), polyaniline,
sulfonated polyaniline, polythiophenes
dendrimers, liquid crystalline polyelectrolytes,
n n diazo-resins, azo-polymers
N Cl Bio-organic materials
proteins, virus, lipids, albumin, DNA, polypeptides,
Poly(diallyldimethylammonium chloride) (PDADMAC)
SO3Na enzymes, avidin, bacteriorhodopsin
Polysaccharides; chitosan, dextan sulfate,
Poly(styrene sulfonated) (PSS)
n cellulose sulfate
CH2
Inorganic materials
NH3 Cl
Poly(allyamine hydrochloride) (PAH) n Charged nanoobjects; Silica, metal oxides,
C O
CH2CH2NH2
semiconductor nanoparticles (CdS, TiO2, CdSe,
OH CdTe), metal colloids (Au, Pt), charged latex
N
N co Poly(acrylic acid) (PAA) spheres, microcrystallites, metallo-supramolecular
n
n complexes
H
Poly(ethyleneimine) (PEI)
clay platelets; Montmorillonte, hectorite, saponite
a-zirconium phosphate, graphite oxide, MoS2
Small organic materials
bolaamphiphiles, phthalocyanine, Azobenzene
dyes, cyanine dyes

New Applications and Devices from LBL films
http://www.chem.fsu.edu/multilayers/multilayerpatents.htm
Ultrathin Film Electrochromic Devices
Anti-reflective Coatings
Electrochemical Photovoltaic Devices
Corrosion Resistance Films
Modification of PLED and OLED Devices

Nanoporous and Ion-permselective Membranes
Field Effect Transistor Devices
Solid-State Polyelectrolyte materials
Electro-resistive and Piezoelectric Thin Films

Nonlinear Optical Thin Film Materials
Chemical and Gas-sensor Devices
POLYELECTROLYTES and NANOPARTICLES
• Mediate synthesis of nanoparticles: precursor approach

• Adsorption of nanoparticles to polyelectrolytes and vice
versa: fundamental studies in adsorption kinetics,
flocculation, electrical double layer, etc.
• Active and passive media: separation of nanoparticles,
synthesis of nanoparticles, interaction of nanoparticles
(stabilization)
• Preparation of thin films containing nanoparticles: flat
substrates and colloidal particles with nanoparticles
• Coating of Colloidal Particles with Polyelectrolyetes and
Nanoparticles: subject of a future review
• Tethering of polyelectrolytes to nanoparticles: DNA and
proteins.
• Nanocomposite preparation

Nanoparticles and colloidal stability
• Particles in colloid (A) uncharged

particles are free to collide and
agglomerate and (B) charged
particles repel each other
• Steric stabilization of particles by

(A) entropic effects and (B)
osmotic effects
• Droplet of a colloid suspension

dried slowly, the particles
aggregate at the rim of the
droplet because of attractive
capillary forces.

Interfacial Behavior of Polyelectrolyte Nanoparticle Systems
• The stability of a colloidal system is primarily determined by the electrostatic and

van der Waals interaction present in the system.
• The co-adsorption of nanoparticles to polyelectrolytes causes extensive swelling of
polyelectrolyte surface layers
• Surface force measurements: The electrostatic repulsive forces are reinforced by
the presence of particles while attractive binding forces are decreased
(separation)
• Nanoparticle adsorption is slow due to complex formation, retarded diffusion, and
barrier effects.
• Ionic strength, concentration, and adsorption history dependent.
• Importance in flocculation and multilayer thin films.

Polyelectrolyte Nanoparticle Composites: LBL assembly

Topic 1: Collective and Individual Plasmon Resonance in

Nanoparticle LBL films by Spin-assisted assembly
• Nanoscale films with Au nanoparticles (NPs) and

polyelectrolyte LBL were prepared by spin-
assembly.
• Plasmon resonance peaks from isolated NPs and
interparticle interactions were analyzed from the
UV-vis spectra.
• Collective plasmon resonance observed on films
with sufficient density: intralayer coupling (620
nm), and interlayer, interparticle resonance
observed at 800 nm
• Environment of NP’s in polyelectrolyte critical for
sensing.
• Au/PAH-PSS structure deposited on PEI surface
• Topographic AFM image and height histogram
• UV-vis of solutions for small and large nanoparticle
• Tsukruk et. al. Langmuir 2004, 20, 882
Interlayer and intralyer interaction in Au nanoparticles
• UV-visible extinction
spectrum of the Au (PAH-
PSS) film with 22% Au NP
surface density with three
major absorption bands
• UV-vis absorption with
different NP densities.
• Variation of plasmon
resonance peak positions
and their intensity ratio
• Tsukruk et. al. Langmuir 2004, 20, 882

Topic 2: Enhanced Luminescence of Quantum Dots on Gold

colloids in Polyelectrolyte LbL Media
• Enhancement of PL of the CdSe core-shell QD on gold colloids as

a function of distance between metal and QD. LBL polyelectrolyte
was uses as spacer layer with distance dependent enhancement
and quenching.
• PL intensity versus the number of polyelectrolyte layers between
the QD and the gold colloids. Excitation at 550 nm.
• SPR enhancement of the PL
• Absorption spectra of Au colloidal film on glass.
• Differential AFM image of AU colloidal film on glass.
• Artemyev et. al. Nanoletters 20002, 12, 1449

Topic 3: DC Transport in Nanocrystal assemblies
• Follow the film conductivity:function of the number of layers

• Linear increase in conductance with increasing layers
• Probe both in-layer and cross-layer charge transport
• Conductor to insulator transition

Effect of the linker on the conductivity of the assemblies

Topic 4: Electrostatically assembled Fluorescent Thin Films of

Rare-earth doped Lanthanum Phosphate Nanoparticles
• LbL films of rare earth (QDs) base on (Ce, Tb, Eu, Dy, etc.) on
flat substrates and PS microspheres.
• PL spectra of PS sphere coated with one layer of a mixture of
Ce/Tb doped and Ce/Dy doped nanoparticles. 273 nm
excitation.
• Plot of PL intensity vs. composition of the mixture of green and
yellow NP.
• TEM image of the LaPO4 NPs (green) dried from an aqueous
solution illustrating high monodispersity. The close packing is
due to the high concentration of NP.
• Caruso et. al. Chem. of Mater. 2002, 14, 4509

Topic 5: Ultrathin Cross-linked Nanoparticle Membranes
• Chemical cross-linking of the ligands attached to

the nanoparticles as an effective route to
“freeze” interfaces. Vinylbenzene ligand and
AIBN initiator from solution
• Nm thick membranes prevent convection but
allow diffusion of small molecules across the
interface- liquid/liquid interface.
• Fluorescence confocal microscopy on a
nanoparticle assembly where an air bubble was
introduced by a micropipet showing (a)
preferential segregation of the CdSe at the
interface at oil/water and water/oil.
• Nanoparticle sheets (free standing)
• Organic dye (red solution) becoming entrapped
and then diffusing across a membrane of cross-
linked nanoparticles.
• Emrick et. al. JACS 2003, 125, 12690

Topic 6: Grafted Block Copolymer Brushes: Synthesis of

Nanoparticles
• Polyelectrolyte brushes of PS and PAA tethered

to a Si/SiOx surface using the grafting from
strategy. Silver or Pd ions were complexed.
NPs were formed after addition of reducing
agent and high temperature treatment.
• Analyzed by AFM, FT-IR and XPS.
• Boyes et. al. Macromolecules 2003, 36, 9539

Topic 7: Complexation Approach to Hybrid Nanocomposite

Materials
• In-situ synthesis of nanoparticle on the

surface of microspheres by employing ion
exchange of counterions in the electrical
double layer of latex beads
• The use of a three layer hybrid core shell
particle as structural units of the
nanocomposite material.
• TEM micrographs of PMMA-PMASS beads
covered with CdS and Ag NP’s obtained
under different magnification. (A) periodic
array, (B) fragment (C) high resolution image
of CdS particle.
• Kumacheva, J. Am. Chem. Soc. 2002, 124, 14512

Topic 8: Catalysis: Selective Hydrogenation by Pd Nanoparticles

Embedded in Polyelectrolyte Multilayers
• Catalytic properties of nanoparticles

embedded in polyelectrolyte films. High
surface area by limiting aggregation of
NPs (stabilization) and also impart
catalytic selectivity (decreases
unwanted isomerization) by restricting
access to active sites.
• TEM image of 3.5 bilayers in copper
grid
• Bruening et. al. JACS 2004, 126, 2658

Topic 9: Nanorainbows: Graded Semiconductor Films from

Quantum Dots
• LBL deposition of 1-D graded

semiconducting films. Possibilities for
photodetectors, bipolar transistors,
waveguides, etc.
• CdTe dispersion of different sizes allow
for the preparation of graded films.
• AFM image of the PDDA/CdTe films
with polymer and NPs as last layers
• PL spectra of different sizes
• Cross-sectional confocal microscopy
image of the graded LBL film of CdTe
NPs made of 10 bilayers of green,
yellow, orange, and red NPs. 220 nm
thickness.
• Kotov et. al. JACS 2001, 123, 7738

Topic 10: Lateral Patterning of CdTe Nanocrystal Films by the

Electric Field Directed LBL Assembly Method
• Electric field directed LBL assembly

(AFDLA) was used to patter 2 different
types of CdTe nanocrystals on ITO.
Pixel array of CdTe with different colors
for EL device.
• Use of bias voltage to control amount
of deposition of NP and polyelectrolyte
(PDDA): monitored by QCM
• Large contrast was observed.
• Gao et. al. Langmuir 2002, 18, 4098

Patterning and EL Device Behavior
• PL and EL spectra of PDDA/CdTe with

different sizes. EL spectra at 5V bias.
• Lateral structures of the CdTe (green)
and CdTe (red).
• Large contrast was observed.
• Gao et. al. Langmuir 2002, 18, 4098

ADVINCULA GROUP
• Project 1. Synthesis of Nanoparticles using Star Block copolymers

• Project 2. REDOX Formation of Au Nanoparticles in LBL Films

The Concept of Block Copolymers as Nanoreactors
Nanoparticles as colloidal systems of a solid-state material -

dimensions in between molecules and a bulk solid-state material.
Strategies for the synthesis of nanoparticles: surfactant or
polymeric amphiphiles (block copolymers) micelles as a “nanoreactor” for
nanoparticle synthesis.
Mechanism - Metal ions trapped inside the particles exposed to
precipitating or reducing agents to start nanoparticle growth: the number
of metal ions initially trapped inside the particle determine growth.
Key step: Control over the diffusion of reagents into the micelle.
Design: The possibility of attaching coordinating ligands to the
polymer in order to stabilize both precursors and nanoparticles within.
• Strategies for the gold nanoparticle preparation
Amphiphilic Self-assembled
Cationic
block copolymers Dendrimers monolayers
polyelectrolytes
(PS-b-P2VP) (PAMAM) (n-Alkanethiols)
• “Stable Nanoreactor” for the control of size and shape of nanoparticles

Synthesis of Nanoparticles in General
a b c
Star block
Schematic representation of the copolymer
(PS-b-P2VP)
concurrent process during reduction
N:Au=10:1
reaction inside block copolymer 0.5
micelles. P4VP (NaBH4)

PAMAM Dendrimer (UV)
0.4
a) Reduction is initiated by the entry of PS-b-P2VP (Hydrazine)
the reducing agent into the core of the Absorbance

0.3
micelles loaded by precursor salt.
b) Destabilized micelles exchange block 0.2
copolymer and may coagulate.

0.1
C) “Empty” micelles are formed besides

block copolymer stabilized gold particles. 0.0
400 450 500 550 600 650 700
H: reduction agent; O: precursor salt; Wavelength (nm)
crystal.
__200 nm

Project 1: Reduction of Au in Star Copolymers
1. Synthesis of PS-b-P2VP
- Synthesis by anionic polymerization,
complete characterization necessary
m
n
-Stability in solution compared to
N micelles
PS P2VP
- Control of diffusion of salts and
reducing agent in organic solvents
2. Synthesis of Star Block Copolymer
PS-b-P2VP + Coupling Agent

(EGDMA)
(Ethylene glycol dimethacrylate)

H2C=C(CH3)CO-OCH2CH2O-COC(CH3)=CH2
1. Polyionic block 2. Reduction with Hydrazine
4HAuCl4 + 3N2H4 --> 4Au + 3N2 +

-
N NH + AuC l4 16 HCl
+ HAuCl4
Youk, J. H.; Park, M.-K.; Locklin, J.; Advincula, R.;

Yang, J.; Mays, J.; “Preparation of Aggregation
Stable Gold Nanoparticles Using Star-Block
Copolymers”, Langmuir 2002; 18(7); 2455-2458.
Youk, J, H.; Yang, J.; Locklin, J.; Park, M.K.;

Mays, J.; Advincula, R.” Controlled Preparation of
Gold Nanoparticles using Well-defined Star Block
Copolymers” ACS-Polymer Preprints, 2001 42, 2,
358. Polyionic star block copolymer Reduction, Nucleation and Growth

Characterization of Star Block Copolymer: GPC
PS
Polymer Mn Mw PDI
PS 25,100 35,300 1.25

PS-b-P2VP
PS-b-P2VP 33.800 41.200 1.22
Star block copolymer

Star Block 106,200 155,100 1.46
Copolymer
20 25 30 35
Retention time (min)
Star block copolymer: After fractionation with THF
PS: 65.1 wt%, P2VP:34.9wt%

UV-vis spectroscopy
2.5
Au:N = 1:10 • Absorption band at 525 nm for all

samples: Surface plasmon
Au:N = 3:10
2.0
Au:N = 5:10
resonance of Au nanocrystals)
1.5
Absorbance
1.0
• Increase of absorbance intensity
with increasing the size of gold
nanoparticles
0.5
0.0
400 450 500 550 600 650 700
Wavelength (nm)
Langmuir. R. Advincula, M.K. Park, J.Youk; J. Locklin, J. Yang;

J. Mays “The Preparation of Aggregation Stable Gold
Nanoparticles using Star Block Copolymers”- ASAP article-web
TEM
N:Au=10:1
Avg. Size: d=4.1 nm

TEM
N:Au=10:3
Avg. Size: d=5.5 nm

TEM
N:Au=10:5
Avg. Size: d=6.7 nm

UV-vis Spectroscopy (After several Months)
2.5
• Peak position shifted from 525 nm
to 530 nm for N:Au=10:3 and 10:5
N:Au=10:1 after 1 month
N:Au=10:3
2.0 N:Au=10:5
• Shift to longer wavelength
:Increase of the average size of gold
nanoparticles
Absorbance
1.5
• Increase of absorbance intensity for

1.0
N:Au=10:3 and 10:5 with time due to
the additional reduction process
0.5
0.0
400 450 500 550 600 650 700
Wavelength (nm)

TEM (After several months)
N:Au=10:1 N:Au=10:3 N:Au=10:5

Avg. Size: d=4.1 nm Avg. Size: d=6.0 nm Avg. Size: d=8.0 nm

Project 2a. Nanoparticle formation from Poleylectrolyte

Complexes of Sexithiophenes
0.5
0.19/1
0.4 0.38/1
HAuCl4
Slow 0.3
0.95/1
0.2
2 0.1
Absorbance
0.0
250 350 450 550 650
Fast
TT/HAuCl4
0.19/1
0.38/1
1 0.95/1
1.91/1
3.82/1
5.73/1
TT+PSS
Solution
PSS+ATT
Complex 0
250 350 450 550 650
Wavelength (nm)
CH - CH2 S
+
m
S S N+ • Suggestion of Mayer and Mark
(Eur. Polym. J., 1998, 34, 103)
Poly(sodium styrene Amidated
sulfonate) (PSS)
-
SO3 Na+ terthiophene 1. Polymer containing sulfur would
(ATT) have the high affinity to gold
CH - CH2 surfaces
m
2. Polymer possessing reducing
S
groups could be very suitable
-
S S N+ SO3
Polyelectrolyte
Complex (PEC) • PSS increased the solubility of
terthiophene amphiphile
Youk, J, H.; Locklin, J.; Xia, C.; Park, M.K. and Advincula, R.”Langmuir 2001 17(15); 4681-4683.

Coupling of Terthiophenes to form Sexithiophenes simultaneous

with nanoparticle formation
CH - CH 2
l
CH - CH 2
m
• Sexithiophene bolaform amphiphile formation
• Mechanism (electrochemical or oxidative) needs to be

SO 3
- SO 3
N+
-
- determined
- -
+
N
(CH 2 )6 (CH 2 )6
S +
. S
- • Stabilization of gold particles is very important
S S
• Characterization of complexes is very important
•
S S
New materials combining metallic, semi-conductor and organic
S materials: interesting electrical and optical properties.
S
- -- S
- -
(CH 2 ) 6
1.5
N+
-
-
SO 3 PSS + ATT + HAuCl4
PSS+ ATT + FeCl3
CH - CH 2
- 1.0
PSS + AST
AST
Absorbance
N S S 0.5
S + S N
S S
0.0
250 300 350 400 450 500 550 600 650
Wavelength (nm)
S S S N
N S S S

TEM Characterization
0.38/1 0.95/1 5.73/1
300 nm
- As the terthiophene concentration increases, the size of nanoparticles increases

- Nanoparticle partially stabilized: inhomogeneous growth and aggregation
- Increase in size, loss of spectroscopic properties associated with nanoparticle
Youk, J, H.; Locklin, J.; Xia, C.; Park, M.K. and Advincula, R.” Preparation
of Gold Nanoparticles from a Polyelectrolyte Complex Solution of
Terthiophene Amphiphiles” Langmuir 2001 17(15); 4681-4683.

Project 2b. LBL Films as Nanoreactor Hosts for Nanoparticle

Synthesis
• REDOX reaction occurs between

the terthiophene
moeity and the Au precursor with
formation of Au
Nanoparticles and sexithiophene
• Au nanoparticle partially stabilized
by the PE complex
resulting in irregular growth and
aggregation
Preparation of Gold Nanoparticles with PSS:

Water-soluble Terthiophene Complex
(Youk et al. Langmuir 2001, 17, 4681.)
Growth of PVP-3T and PAA films

Gold Nanoparticle Formation in LBL Multilayer Films
Before After
• Red-shift in absorbance of the 3T moiety from 368

to 396 nm attributed to coupling of the terthiophene
units to form sexithiophene with simultaneous
formation of Au nanoparticles (surface plasmon peak
= 580 nm)
• Position of the Au SP band and presence of broad

absorption tail around 700 nm indicate aggregation
and/or particles that deviate from a spherical
geometry J. Phys. Chem. B 1999, 103, 7441.
R.C. Advincula/ University of Houston Adv. Mater. 1998, 10, 133.
TEM Imaging
TEM image of a 3 bilayer PVP3T/PAA film

containing Au nanoparticles after ~ 50 hrs at
60 ˚C/95% humidity. Scale bar = 200 nm.
TEM image depicting dendritic nanostructures

formed with the PVP3T/PAA thin film.

Conclusions
• Nanoparticle (NP) synthesis and colloidal dispersions are essential

nanomaterials: high surface area and qunatum size effects ( PL and
plasmons)
• Polyelectrolytes can be used to mediate synthesis of NPs from
precursors or as media for film assembly of nanoparticles
• Interaction of NPs and nanoparticles follows classical colloidal
phenomena
• Advantages in stability and processing
• Synthesis and assembly of nanoparticles in films and colloids: active
and passive role of polyelectrolytes
• Film preparation results in a variety of functions and phenomena
observed: sensor, devices, optical materials, etc.

Acknowledgment
Students: Chuanjun Xia, Mi-kyoung Park, Xiaowu Fan, Jason Locklin, Derek Patton, Tim Fulghum, Suxiang Deng,
Prasad Taranekar, Post-Docs: Dr. Seiji Inaoka, Dr. Ji Ho Youk, Dr. Shuangxi Wang, Dr. Qing-Ye Zhou, Dr. Ken Onishi,
Dr. Akira Baba, Dr. Mitchell Millan.
Collaborations: Wolfgang Knoll (MPI-P), Futao Kaneko ( Niigata University), Hiroaki Usui (TUAT)
Zhenan Bao
R.C. Advincula/ (Stanford
University University), Jimmy Mays (UT/ORNL)
of Houston

Nanopraticle Synthesis

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ACS-PRF Summer School on Nanoparticles 2004

Polyelectrolytes and Nanoparticles:

R.C. Advincula/ University of Houston

R.C. Advincula/ University of Houston

Molecular and Macromolecular

Organic and Polymer Inorganic Materials

R.C. Advincula/ University of Houston

Convergence of Materials in Interfacial and

• Quantum dot nanoparticles

Innovative Surface Sensitive Analytical Techniques

Microcontact Printed SAM (ODT) Polypyrrole

• Scanning probe microscopy

Patterning Methods and Devices

ODT SAM Gold

Schematic representation of microcontact printing

• Lithographic and nonlithographic methods TOP CONTACT

• Photolithography and soft-lithography

• Display and nonlinear optical devices

1. Silver: catalysis, photographic

R.C. Advincula/ University of Houston

Synthesis of Nanoparticles: the Concept of Nanoreactors

Nanoparticles as colloidal systems of a solid-state material -

• Strategies for the gold nanoparticle preparation

• “Stable Nanoreactor” for the control of size and shape of nanoparticles

Nanoparticles and nanostructured Films;

Synthesis of Nanoparticles in General

micelles. P4VP (NaBH4)

the reducing agent into the core of the Absorbance

copolymer and may coagulate.

C) “Empty” micelles are formed besides

H: reduction agent; O: precursor salt; Wavelength (nm)

R.C. Advincula/ University of Houston

R.C. Advincula/ University of Houston

PS-b-P2VP Micelles Containing Gold nanoparticles:

M. Moller et al., Macromolecules, 2000, 33, 4791.

Organic Ultrathin Film Multilayer Assemblies

• How different is this from spin-

Langmuir-Blodgett • Nanostructured multilayer

• control molecular orientation and

• To be explored? Organic and

R.C. Advincula/ University of Houston

Nanostructured Layer-by-layer Self-assembly

• Electrostatic (coulombic forces)

Structure – Fuzzy Nanoassemblies?

R.C. Advincula/ University of Houston

A Variety of Materials for the LbL Technique

R.C. Advincula/ University of Houston

New Applications and Devices from LBL films

Ultrathin Film Electrochromic Devices

Electrochemical Photovoltaic Devices

Corrosion Resistance Films

Modification of PLED and OLED Devices

Solid-State Polyelectrolyte materials

Electro-resistive and Piezoelectric Thin Films

POLYELECTROLYTES and NANOPARTICLES

• Mediate synthesis of nanoparticles: precursor approach

R.C. Advincula/ University of Houston

Nanoparticles and colloidal stability

• Particles in colloid (A) uncharged

• Steric stabilization of particles by

• Droplet of a colloid suspension

R.C. Advincula/ University of Houston

Interfacial Behavior of Polyelectrolyte Nanoparticle Systems

• The stability of a colloidal system is primarily determined by the electrostatic and