Metal Nanoparticles of Various Shapes

Jie Gao, Min Xu Apr. 1, 2007

Outline


Advantages of metal nanoparticles. Why we need nanorods? Synthesis of metal nanoparticles. Synthesis of gold nanorods. Growth mechanism of gold nanorods. Synthesis of gold nanoparticles of different shapes. Advantage of seed-mediated method Other issues to consider

Advantages of Metal Nanoparticle

Strong plasma absorption Enhance Rayleigh scattering Surface enhanced Raman scattering

Advantage of Metal Nanoparticles

Biological detector Biological system imaging Determine chemical information on
metallic nanoscale substrate

Why we need nanorods?

Limitations of nanospheres

S. Eustis, M. A. El-Sayed, Chem. Soc. Rev. 2006, 35, 209-217

Synthesis of metal nanoparticles

Bottom up method--assemble atoms to
nanostructures 1. Nanosphere lithography. 2. Templating, chemical, electrochemical, sonochemical, thermal and photochemical reduction techniques. Top down method--cut into pieces in nanoscale 1. Photolithography 2. Electron beam lithography

Synthesis of metal nanoparticles

Nanosphere lithography

W. Huang, W. Qian, M. A. El-Sayed, Proc. SPIT Int. Soc. Opt. Eng. 2005, 5927, 592701

Synthesis of metal nanoparticles

Citrate Reduction Method
Turkevitch in 1951 sodium citrate + HAuCl4

Synthesis of metal nanoparticles

Two Phase Reactions Inverse Micelles

General idea of chemical method: reduction + capping

Synthesis of gold nanorods

Seed-mediated method Two steps: produce seed particles + seed
grow into rod

C. J. Murphy, T. K. Sau, A. M. Gole, C. J. Orendorff. J. L. Gou, S. E. Hunyadi, T. Li, J. Phys. Chem. B 2005, 109, 13857-13870

Synthesis of gold nanorods

Synthesis of gold nanorods

Factors related to the growth
1. Seed size 2. Length of tails of CTAB (cetyltrimethylammonium bromide )

Synthesis of gold nanorods

dependence of nanorod aspect ratio on seed size

Synthesis of gold nanorods

Dependence of aspect ratio on length of tails of CTAB

Growth mechanism of gold nanorods

Zipping fashion formation of gold nanorods
:C16TAB

Growth mechanism of gold nanorods

Planar density of atoms of FCC structure {111}: 0.907

{100}: 0.785
{110}: 0.555

crystallography picture of gold nanorods: pentatetradedral

Growth mechanism of gold nanorods

tail contribution to the free energy

formation of a bilayer on gold

G(10)= -29.6 kJ/mol, (12)= -35.8 kJ/mol, (14)= -41.9 kJ/mol,(16)= -48.1 kJ/mol

Growth mechanism of gold nanorods

Growth mechanism of gold nanorods

Synthesis of gold nanoparticles of different shapes

General idea is the same as the growth of

gold nanorods (seed-mediated method) Slightly change the conditions when growing nanorods (concentration of different reactants) Cubes, hexagon, triangle, tetropods, branched
T. K. Sau, C. J. Murphy, J. Am. Chem. Soc. 2004, 126, 8648-8649

Synthesis of gold nanoparticles of different shapes

[AA] increases from A to C and seed concentration increases from C to D. Scale bar = 100 nm

Synthesis of gold nanoparticles of different shapes

TEM images showing cubic to rod-shaped gold particles produced with low AA concentration in the presence of small quantity of silver nitrate. [CTAB] is increased (A) to (B, C, D). [Au3+] decreases from B to C, and seed concentration increased form C to D. Scale bar = 100 nm

Synthesis of gold nanoparticles of different shapes

TEM images of brached Au nanoparticles, varying in the dimension and number of branches

Synthesis of gold nanoparticles of different shapes

Summary of experimental procedure

1. The concentrations are interdependent

2. Growth mechanism is similar to that of rod

Advantage of water seed-mediated method

High yield Monodisperse Cheap, easy

Other issue to consider

The nucleation process in growth of seed
is still mysterious Limitation in length and aspect ratio maximum length: ~600nm maximum aspect ratio: ~25

Summary

Advantages of metal nanoparticles. Why we need nanorods? Synthesis of metal nanoparticles. Synthesis of gold nanorods. Growth mechanism of gold nanorods. Synthesis of gold nanoparticles of different shapes. Advantage of seed-mediated method Other issues to consider