Synthesis of Nanomaterials

Junior Research Seminar

Spring 2004
4 May 2004

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Approaches to Nanoscale Structures

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Chemical approaches to nanostructures

Zero dimensional structures

One dimensional structures

Three dimensional structures

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Zero Dimensional (0D) Growth

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Nanoparticle Growth within Dendrimers

Polymer macromolecules (poly

(amido amine)) bind limited
numbers of metal ions (Cu, Ag, Au,
Pt, Pd)
Driving force for encapsulation
includes electrostatics, steric
confinement, covalent bonds
Reducing agent causes the metal
ions to coalesce
Nanoparticles as small as 1 nm

Useful composite material

Metal particles not aggregated
Dendrimer branches control
access of other molecules
Terminal groups on dendrimer can
be used to control solubility,
linking to surfaces

R. Crooks, Acc. Chem. Res. 34, 181 (2001)

E.W. Meijer, Chem. Rev. 99, 1665 (1999)

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Reverse Micelles

Spherical water in oil droplets

surfactant is sodium bis(2-ethylhexyl)
sulfosuccinate) Na(AOT)
Size of water content depends on
relative surfactant concentration

Reduction of metal ions or

precipitation forms particles
Semiconductor particles (CdS) from 1
- 4 nm
Metals from 1 - 12 nm

M.P. Pileni, J. Phys. Chem. 97, 6961 (1993)

M.P. Pileni (France) Langmuir, 13, 3266 (1997)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Cluster Growth within a Zeolite

Zeolite-OH + M(CH3)2

Intercalation of M ion into zeolite by ion exchange

Activation of M+ loaded zeolite
Reaction of activated M+ with H2S
Zeolite Y high dielectric, aluminosilicate host

Zeolite-OH + M(CH3)2

Zeolite-O-M(CH3) + CH4
H2S

Zeolite-O-M-SH + CH4
Repeat

Examples: MS nanoclusters CdS, ZnS, SnS, Ag2S

Calzeferri (U. Bern), J. Phys. Chem. B 103, 6397 (1999)

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Arrested Precipitation: General Approach

C.B. Murray (IBM)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Arrested Precipitation

Aqueous reduction of metal

salts (Ag, Au) in the presence of
citrate ions

Strong reducing agent

Chemisorption of organic ligands

for handling
Distribution varies > 10%

II-VI ME nanocrystals (NCs) (M =

Zn, Cd, Hg; X = S, Se, Te)
Metal alkyls + organophosphine
chalcogenides

~200-250 C

Phosphine binding to M
controlled by temperature
Ostwald ripening allows for sizeselective aliquots; growth time for
1-2 nm NCs in minutes

Metal salts and stabilizers

(metal halides + inert solvent
+ R3P + long chain acids)

Schmid G. 1992. Chem. Rev. 92:170927

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Size-Dependent Properties:
Metallic Particles

Ag Nanoprisms Au Spheres Au Spheres

~100 nm
~50 nm
~100 nm
200nm

200 nm

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Ag Spheres Ag Spheres Ag Spheres

~80 nm
~40 nm
~120 nm

Size-Dependent Properties:
Semiconducting Particles

10 m
A. Libchaber (NEC) Science 298, 1759 (2002)
A.P. Alivisatos (U.C. Berkeley), Science 281, 2013 (1998)
Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Chemical approaches to nanostructures

Zero dimensional structures

One dimensional structures

Three dimensional structures

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

One Dimensional (1D) Growth

Adapted after Y. Xia et al., Adv. Mat. 15, 353 (2003)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Electrodeposition within Nanoporous Membranes

Alumina, polycarbonate track

etched, and silica membranes
5-10 m thick with pore sizes
down to 10 nm

M. Natan (Penn State), Science 294, 137 (2001)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Templating against Existing 1D Nanostructures

GaN from ZnO Nanowires

P. Yang, Nature 422, 599 (2003)

TiC nanorods from MWNTs

C.M. Lieber, Chem. Mater., 8, 2041 (1996)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Templating vs. Other Approaches?

Nanoscale structures generated by templating methods are

typically not crystalline
Number of defects is larger
Critical dimension (confined dimension) is larger; quantum size effects
usually not observed
Monodispersity is limited by the structure of template
Free-standing, 1D structures are difficult to obtain

What are the requirements for a general, synthetic approach

to nanowires?
Anisotropic growth
Equilibrium constraints
Control of catalyst size

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Laser-assisted Catalytic Growth

(1) Pulsed laser; (2) Focusing lens; (3) Composite target; (4) Furnace; (5) Cold finger; (6) Pump system

C.M. Lieber (Harvard), Science 279, 208 (1998)

Examples: InP, GaAs, InAs (Au colloids); GaN (Fe colloids)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Chemical Vapor Deposition (CVD)

1 m

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Solution-based growth

Dissolution of anisotropic crystal

structures
Dissolve inorganic
metallopolymers in polar
solvents such as dimethyl
sulfoxide (DMSO) to form
hexagonally close packed,
linear chains ~2 nm in diameter
Example: Mo6Se6 wires
Other methods to obtain
anisotropy?
Reduction of an acid or salt in
elevated temperatures and
exploit Ostwald ripening
Decomposition of precursors in
the presence of capping ligands
(followed by fractionation for
size distribution)
Example: BaTiO3 and SrTiO3
(perovskite) nanostructures

F. diSalvo (Cornell), Science 273, 792 (1996)

P. Yang, Adv. Mat. 12, 1526 (2000)

H. Park (Harvard), J. Am. Chem. Soc. 124, 1186 (2002)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Assembly of 0D nanoparticles

Organization of CdTe
nanoparticles into wires
Removal of stabilizer
Assembly over a week in the dark

Recrystallization
Ostwald ripening with Cd2+ and
Te2- ions
Diffusion of CdTe particles

N.A. Koltov (Okla. State), Science 297, 237 (2002)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Chemical approaches to nanostructures

Zero dimensional structures

One dimensional structures

Three dimensional structures

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Three dimensional (3D) nanostructures

Polymer emulsification
Reducing agent is also the solvent
In the presence of a capping reagent
and different ratios of seed source,
different types of structures
Example: reduction of silver nitrate by
ethylene glycol in the presence of
poly(vinyl pyrrolidone)

Replacement reactions
Conversion of one metal to one with a
higher reduction potential
Example: Replacement of Ag with Au
occurred along the crystal facets in
an order commensurate with their free
energies: {110} > {100} > {111}

Y. Xia (U. Wash.), Science 298, 2176 (2002); Nano. Lett., 2, 481 (2002)
Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

3Ag(s) + HAuCl4(aq)

Au(s) + 3AgCl(aq) + HCl(aq)

3D nanostructures: DNA-based assembly

Au nanostructures assembled by DNA

hybridization

Functionalize large and small Au particles with

different DNA strands

Introduce a linker strand that contains

complementary sequence to those on large
and small Au particles

C.A. Mirkin, Inorg. Chem. 39, 2258 (2000)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

3D nanostructures: NC superlattices

CdSe colloidal crystals

Introduce non-solvent to cause
aggregation and precipitation
Slow destabilization by
evaporation from a mixture of
solvents can result in ordered
superlattices

C.B. Murray, Annu. Rev. Mater. 30, 545 (2000)

Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Lab 7: Synthesis of Nanomaterials

Gold colloids
CdSe nanocrystals

Junior Research Seminar: Nanoscale Patterning and Systems

Teri W. Odom

Synthesis of CdSe Nanoparticles

CdO + oleic acid + octadecene
Heat to 250 C to dissolve the CdO
Selenium + octadecene + tributylphosphine
Heat to 150 C to dissolve the selenium
Transfer Se solution to the Cd solution
Take aliquots

http://www.mrsec.wisc.edu/EDETC/cineplex/CdSe/index.html
Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Synthesis of Colloidal Gold

Make HAuCl4 solution in water and pour into a
beaker.
Weigh the HAuCl4 using a teflon-wrapped spatula
Heat the solution to boiling on a hot plate.

Add Na3C6H5O7 to the Au solution in the beaker.

Let the solution boil.

http://www.mrsec.wisc.edu/EDETC/cineplex/gold/index.html
Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom

Gold Particles as a Chemical Sensor

Take a UV-Vis absorbance
spectrum of the Au colloid
solution.
Place 3 mL of the Au
colloid solution in each of
three glass vials. Add 3 mL
of water to dilute the colloid
solution.
Add 5-10 drops 1M NaCl to
the first vial dropwise.
Record what happens as
the salt solution is added.
Add 5-10 drops 1M
sucrose to the second vial
dropwise.
Junior Research Seminar: Nanoscale Patterning and Systems
Teri W. Odom