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Nanoparticles

Lecture 2

Top-down Approaches

milling or attrition
thermal cycles
10 ~ 1000 nm; broad size distribution
varied particle shape or geometry
impurities
for nanocomposites and nanograined bulk
materials (lower sintering temperature)

Bottom-up Approaches
Two approaches
thermodynamic equilibrium approach
generation of supersaturation
nucleation
subsequent growth

kinetic approach
limiting the amount of precursors for the growth
confining in a limited space

Homogeneous nucleation
Liquid, vapor or solid
supersaturation
temperature reduction
metal quantum dots in glass matrix by
annealing
in situ chemical reactions (converting highly
soluble chemicals into less soluble chemicals)

Homogeneous nucleation
Driving force
Gv
Fig 3.1

Homogeneous nucleation
Energy barrier

16
G
(3Gv ) 2
*

Surface energy

r 2
Gv
*

Gibss free energy change

Nuclei
formation favor:
high initial concentration or supersaturation
low viscosity
low critical energy barrier

uniform nanoparticle size:


same time formation
abruptly high supersaturation -> quickly brought
below the minimum nucleation concentration

Nuclei growth
Steps

growth species generation


diffusion from bulk to the growth surface
adsorption
surface growth

size distribution
A diffusion-limited growth VS. a growth-limited
processes

Diffusion-limited growth
monosized nanoparticles
how?
Low/controlled supply growth species
concentration
increase the solution viscosity
introduction a diffusion barrier

Metallic nanoparticles
Reduction of metal complexes in dilute
solution
Diffusion-limited process maintaining
Example: nano-gold particles
chlorauric acid (2.5 x 10-4 M) 20 ml boiling
solution+ sodium citrate (0.5%) 1 ml
100C till color change + water to maintain volume
uniform and stable 20 nm particles

Table 3.1

Other cases

3
3
RhCl3 CH 3OH Rh HCHO 3HCl
2
2
PdCl2 Na2CO3 2 H 2O Pd (OH ) 2 H 2CO3 2 Na 2Cl

Pd (OH ) 2 H 2 Pd 2 H 2O

PtCl4 H 2O Pt ( H 2O)Cl3 Cl

Pt ( H 2O)Cl3 H 2O Pt ( H 2O) 2 Cl2 Cl

Reduction reagents
Affect the size and size distribution
weak reduction reaction
larger particles
wider or narrower distribution (depends on
diffusion limited)

Affect the morphology


type, concentration, pH value

Fig 3.10

Fig 3.12

Polymer stabilizer
To prevent agglomeration
surface interaction:
surface chemistry of solid, the polymer, solvent and
temperature
Strong adsorbed stabilizers occupy the growth sites
and reduce the growth rate

A. Henglein, Chem. Mater. 10, 444 (1998).


polyethyleneimine, sodium polyphosphate, sodium
polyacrylate and poly(vinylpyrrolidone)

stabilizer concentration

temperature

Semiconductor nanoparticles
Pyrolysis ( ) of organometallic precursor(s)
dissolved in anhydrate solvents at elevated
temperatures in an airless environment in the
presence of polymer stabilizer (i.e., capping
material)
Coordinating solvent
Solvent + capping material
phosphine + phosphine oxide (good candidate)
controlling growth process, stabilizing the colloidal
dispersion, electronically passivating the surface

Process
discrete nucleation by rapid increase in the
reagent concentration -> Ostwald ripening ( )
during aging at increased temperature (large
particle grow)-> size selective precipitation
Ostwald ripening
A dissolution-growth processes
large particles grow at the expense of small particles
produce highly monodispersed colloidal dispersions

Semiconductor nanocrystallites
C.B. Murray (CdE, E=S, Se, Te), 1993
Dimethylcadmium (Me2Cd) + bis(trimethylsilyl)
sulfide ((TMS)2S) or trioctylphosphine selenide
(TOPSe) or Trioctylphosphine telluride (TOPTe) +
solvent (Tri-n-octylphosphine, TOP) + capping
material (tri-n-octylphosphine oxide, TOPO)
before aging (440 ~ 460nm), after aging at 230260C (1.5~11.5 nm)
Size-selective precipitation

Oxide nanoparticles
Several methods
principles: burst of homogeneous nucleation +
diffusion controlled growth
most commonly: sol-gel processing
most studied: silica colloids

Sol-gel process
Synthesis
inorganic and organic-inorganic hybrid materials
colloidal dispersions
powders, fibers, thin film and monolith( )
low temperature and molecular level homogeneity

Ref
Sol-Gel Science by Brinker and Scherer; Introduction
to Sol-Gel Processing by Pierre; Sol-Gel Materials by
Wright and Sommerdijk

Sol-gel process
Hydrolysis
e.g. M (OEt ) 4 xH 2O M (OEt ) 4 x (OH ) x xEtOH

Condensation of precursors
e.g.

M (OEt ) 4 x (OH ) x M (OEt ) 4 x (OH ) x


(OEt ) 4 x (OH ) x 1 MOM (OEt ) 4 x (OH ) x 1 H 2O

typical precursors: metal alkoxides or


inorganic and organic salts

Multicomponents materials
Sol-gel route
ensure hetero-condensation reactions between
different constituent precursors
reactivity, electronegativity, coordination number, ionic
radius
precursor modification: attaching different organic
ligands (e.g. reactivity: Si(OC2H5)4 < Si(OCH3)4) )
chemically modify the coordination state of the alkoxides
multiple step sol-gel

Organic-inorganic hybrids
Incorporating organic components into an
oxide system by sol-gel processing
co-polymerization
co-condense
trap the desired organic (or bio) components
inside the network
biocomponents-organic-inorganic hybrids

Sol-gel products
Monodispersed nanoparticles
temporal nucleation followed by diffusioncontrolled growth
complex oxides, organic-inorganic hybrids,
biomaterials
size = f(concentration, aging time)
colloid stabilization: not by polymer steric
barrier, by electrostatic double layer

Sol-gel example: silica


Precursors:
silicone alkoxides with different alkyl ligand
sizes
Vigorous stirring

catalyst:

ammonia

solvent:
various alcohols

water

Vapor phase reactions


Same mechanism as liquid phase reaction
Elevated temperatures + vacuum (low
concentration of growth)
Collection on a down stream non-sticking
substrate @ low temperature
example: 2~3 nm silver particles
may migrate and agglomerate

Vapor phase reactions


Agglomerates:
large size spherical particles
needle-like particle
Au on (100) NaCl and (111) CaF substrate
Ag on (100) NaCl substrate

change in temperature and precursor concentration


did not affect the morphology

size affections
reaction and nucleation temperature

Solid state phase segregation


applications
metals and semiconductor particles in glass matrix

homogeneous nucleation in solids state


metal or semiconductor precursors introduced to and
homogeneously distributed in the liquid glass melt at
high temperature
glass quenching to room temperature
glass anneal above the Tg
solid-state diffusion and nanoparticles formed

Solid state phase segregation


Glass matrix (or via sol-gel, polymerization):
metallic ions

Reheating (or UV, X-ray, gamma-ray):


metallic atoms

Nuclei growth by solid-state diffusion (slow!)

Solid state phase segregation

Heterogeneous nucleation
A new phase forms on a surface of another
material
thermal oxidation, sputtering and thermal oxidation, Ar
plasma and ulterior thermal oxidation
associate with surface defects (or edges)

Heterogeneous nucleation

Kinetically confined synthesis


Spatially confine the growth
limited amount of source materials or available
space is filled up

groups

liquid droplets in gas phase (aerosol & spray)


liquid droplets in liquid (micelle & microemulsion)
template-based
self-terminating

Micelles or microemulsion
micelles
surfactants or block polymers
two parts: one hydrophilic and one hydrophobic
self-assemble at air/aqueous solution or
hydrocarbon/aqueous solution interfaces

microemulsion
dispersion of fine organic liquid droplets in an
aqueous solution

Micelle
CdSe nanoparticles by Steigerwald et al.
surfactant AOT (33.3g) + heptane (1300ml)+ water
(4.3ml)
stirred -> microemulsion
1.0M Cd2+ (1.12 ml) + microemulsion
Se(TMS)2 (210l) + heptane (50ml) + microemulsion
(syringe, )
formation of CdSe crystallites

Polymer nanoparticles
Water-soluble initiator + surfactant + water
+ monomer

monomer (large droplets, 0.5 ~ 10m )


initiator
polymerization
nanoparticles (50 ~ 200nm)

Aerosol synthesis
Characteristics
Regarded as top-down (maybe?)
can be polycrystalline
needs collection and redispersion

process
liquid precursor -> mistify -> liquid aerosol ->
evaporation or reaction -> nanoparticles
polymer particle 1~20 m (from monomer droplets)

Size control by termination


Termination by organic components or alien
ion occupation

Spray pyrolysis
Solution process
metal (Cu, Ni ) and metal oxide powders
converting microsized liquid droplets of precursor
or precursor mixture into solid particles through
heating
droplets -> evaporation -> solute condensation ->
decomposition & reaction -> sintering
e.g. silver particle: Ag2CO3, Ag2O and AgNO3 with
NH4HCO3 @ 400C

Template-based synthesis
Templates
cation exchange resins with micropores
zeolites
silicate glasses

ion exchange
gas deposition on shadow mask (template)

Core-shell nanoparticles
The growth condition control
no homogeneous nucleation occur and only
grow on the surface
concentration control: not high enough for
nucleation but high enough for growth
drop wise addition
temperature control

Semiconductor industry

Semiconductor industry