Optical Properties of

Nanomaterials
David G. Stroud,

Department of Physics,
Ohio State University Columbus OH 43210
Work supported by NSF Grant DMR01-04987, the
Ohio Supercomputer Center, and BSF
OUTLINE
Linear Optical Properties of Nanocomposites
Nonlinear Optical Properties of Nanocomposites
Surface Plasmons in Nanoparticle Chains
Gold/DNA Nanocomposites
Conclusions

Labors of the Months (Norwich, England, ca.

1480).
(The ruby color is probably due to embedded
gold nanoparticles.)

What is the origin of the color?

Answer: ``surface plasmons

An SP is a natural oscillation of the electron gas

inside a gold nanosphere.
If the sphere is small compared to a wavelength
of light, and the light has a frequency close to
that of the SP, then the SP will absorb energy.
The frequency of the SP depends on the
dielectric function of the gold, and the shape of
the nanoparticle. For a spherical particle, the
frequency is about 0.58 of the bulk plasma
frequency. Thus, although the bulk plasma
frequency is in the UV, the SP frequency is in
the visible (in fact, close to 520 nm)

Sphere in an applied electric

field
Metallic sphere

Incident electric field

is E_0exp(-i w t)

EM wave

Surface plasmon is excited when a longwavelength electromagnetic wave is

incident on a metallic sphere

Calculation of SP Frequency

Effective conductivity of
a random metal-insulator composite in the
effective-medium approximation

Note the broad ``surface plasmon peak and the

narrow Drude peak above the percolation
threshold. [D. Stroud, Phys. Rev. B19, 1783
(1979)]

Effective conductivity of a composite of Drude metal

and insulator: dots, numerical; full curves, effectivemedium approximation. [From X. Zhang and Stroud,
PRB49, 944 (1994).]

Theory and experiment for transmission

through Ag/SiO2 films

Theory: Maxwell-Garnett approximation (MGA) and effectivemedium approximation (EMA) [D. Stroud,Phys. Rev. B19,
1783 (1979)] ;
Experiment [Priestley et al, Phys. Rev. B12, 2121 (1975)]. (f
is the volume fraction of Ag.)

Nonlinear optical properties of

nanomaterials

Suppose we have a suspension of nanoparticles

in a host (or some other composite which is
structured on the nanoscale).
If an EM wave is applied, the local electric field
may be hugely enhanced near an SP
resonance.
Ifso,one expects various nonlinear
susceptibilities, which depend on higher powers
of the electric field, to be enhanced even more.

The Kerr Susceptibility is

defined by

where D is the electric displacement, E is the

electric field, and epsilon and chi are the linear
and nonlinear electric susceptibilities.
If the electric field is locally large, as near an SP
resonance, then its cube is correspondingly
larger. Thus, near an SP resonance, one expects
a huge enhancement of the cubic nonlinear (Kerr)

Kerr susceptibility for a dilute

suspension of coated spheres

Cubic nonlinear (Kerr) susceptibility for a dilute suspension

of coated metal particles in a glass host, calculated in
Maxwell-Garnett approximation [X. Zhang, D. Stroud, Phys.
Rev. B49, 944 (1994)]. Inset: linear dielectric function of
same composite. Left and right are for two coating
dielectric constants.

Kerr enhancement factor for

metal-insulator composite

Kerr enhancement factor for a random metalinsulator composite, assuming (left) metal and
(right) insulator is nonlinear. Calculation is
carried out numerically, at the metal-insulator
percolation threshold.

Real and imaginary parts of the SHG susceptibility for a

dilute suspension of of metal spheres coated with a
nonlinear dielectric
[Hui, Xu, and Stroud, Phys. Rev. B69, 014203 (2004)]

Left and right panels show susceptibility

enhancement per unit volume of nonlinear material
for two different ratios of coating thickness to metal
particle radius.

Real and imaginary parts of the THG

susceptibility for a dilute suspension of coated
metal spheres in a dielectric host

Susceptility enhancement per unit volume for thirdharmonic generation (THG) for coated metal sphere
suspension [from Hui, Xu, and Stroud, PRB69, 014202
(2004)]

Faraday Rotation in
Composites:
enhanced near SP resonance
Real and
imaginary parts of
the Faraday
rotation angle in a
composite of
Drude metal and
insulator in a
magnetic field
(Xia, Hui, Stroud,
J. Appl. Phys. 67,
2736 (1990)

Faraday rotation in granular

ferromagnets

Frequency-dependence of the real and imaginary parts of

the Faraday rotation angle for a dilute suspension of
ferromagnet in an insulator at two different temperatures
below the Curie temperature [Xia, Hui, and Stroud, J. Appl.
Phys. 67, 2736 (1990)].

Nanoparticle chain
d

Surface plasmons can propagate along a periodic

chain of metallic nanoparticles (above)

Photon STM Image of a Chain

of Au nanoparticles [from
Krenn et al, PRL 82, 2590
(1999)]

Individual particles: 100x100x40 nm, separated

by 100 nm and deposited on an ITO substrate

Calculation of SP modes in
nanoparticle chain

In the dipole approximation, there are three SP

modes on each sphere, two polarized
perpendicular to chain, and one polarized parallel.
The propagating waves are linear combinations of
these modes on different spheres.
In our calculation, we include all multipoles, not
just dipoles. Then there are a infinite number of
branches, but only lowest three travel with
substantial group velocity.
Can be compared to nanoplasmonic experiments,
as discussed by Brongersma et al [Phys. Rev. B62,
16356 (2000) and S. A. Maier et al [Nature
Materials 2, 229 (2003)]

Surface plasmon dispersion

relations, nanoparticle chain

Calculated surface plasmon dispersion relations (left) and

group velocity of energy for the lowest two bands in a metal
nanoparticle chain. Solid curves: L modes; dotted curves: T
modes. Light curves; dipole approximation; dark curves,
including all multipoles. a/d=0.45 [from S. Y. Park and D.
Stroud , Phys. Rev. B (in press); a= particle radius; d=
particle separation]

Composites of Au
nanoparticles and DNA strands

Suppose we put Au nanoparticles and DNA

strands in an acqueous suspension.
Certain DNA strands (capped with thiol
groups) can attach to Au.
At high T, Au particles float in suspension,
with DNA strands attached.
At low T, strands on different grains react to
form links. Particles agglomerate to form a
gel-like structure.
This behavior is easily detected optically.

Methodology

To determine structure, we calculate the probability

that any two bonds on different Au particles form a
link, using an equilibrium condition from simple
chemical reaction theory.
Structure determined by two different models: (i)
Percolation model; (ii) More elaborate model
involving reaction-limited cluster-cluster
aggregation (RLCA)
To treat optical properties (for any given structure)
use the ``Discrete Dipole Approximation (multiple
scattering approach).
References: S. Y. Park and D. Stroud, Phys. Rev.
B67, 212202 (2003); B68, 224201 (2003).

Au/DNA suspension in liquid

state

At high T, Au particles float around in aqueous suspension.

Single strands of DNA capped with thiol groups are attached.

Melting of Au/DNA cluster,

two different models

(a), (b) and (c) are a percolation model: all particles on a

cubic lattice. (a): all bonds present; (b) 50% of bonds
present; (c) 20% of bonds present. (d) Low temperature
cluster formed by reaction-limited cluster-cluster

Extinction coefficient, dilute

suspension

Calculated (full curves) and measured (dashed curves)

extinction coefficient for a dilute Au suspension, plotted
versus wavelength

Extinction coefficient for

compact Au/DNA clusters

Extinction coefficient per unit volume, plotted versus wavelength

(in nm) for LxLxL compact clusters, as calculated using the Discrete
Dipole Approximation (DDA) (from Park and Stroud, 2003)

Calculated extinction
coefficient, RLCA clusters

Calculated extinction coefficient versus wavelength

for RLCA clusters with number of monomers varying
from 1 to 343.

Extinction coefficient versus

wavelength, percolation
model

Extinction coefficient versus wavelength for different

fractions p of Au nanoparticles on a 10 x 10 x 10 simple
cubic lattice. ``p=0 represents an isolated Au particle.
Inset: C, B, and A are isolated particles, compact clusters,
and RLCA clusters. Melting more closely resembles a

Observed absorptance:
comparison of unlinked and
aggregated Au nanoparticles

Absorptance of unlinked and aggregated Au nanoparticles,

as measured by Storhoff et al
[J. Am. Chem. Soc. 120, 1959 (1998)]

Calculated extinction
coefficients versus
temperature at 520 nm

Normalized extinction coefficient at wavelength 520 nm, calculated

for two different models, plotted vs. temperature in C. Full curves:
percolation model (3 diff. Monomer numbers). Open circles: RLCA
model.

Extinction coefficient vs. T at

520 nm for different particle
sizes

Calculated extinction coefficient versus T at wavelength

520 nm for particle radius 5, 10, and 20 nm. Inset:
comparison of extinction for percolation model (open
circles) and RLCA model (squares). Full line in inset is

Measured extinction at fixed

wavelength vs. temperature

(left) extinction of an aggregate (full curve) and isolated

particles (dashed) at 260nm.
[Storhoff et al, JACS 122, 4640 (2000)]. (right) extinction of
an aggregate at 260 nm made from Au particles of three
different diameters [C. H. Kiang, Physica A321, 164 (2003)]

DNA/Au nanocomposite
system Linker
DNA

1. Expected phase diagram

Gel-sol
transitio
n

0
gel

R. Elghanian, et. al.,

Science 277, 1078 (1997).

2. Morpologies from a structural

model

melting
transitio
n

sol

Ind. particles

3. DDA calculation (left) of extinction

cross section (S. Y. Park and D.
Stroud, Phys. Rev. B68 (224201 (2003)

Experiment

gel

sol

melting
transition
Gel-sol
transition

near melting
transition

R. Jin, et. al, J. Am. Chem. Soc

Work in Progress

More realistic model for gold/DNA

nanocomposites
Selective detection of organic molecules,
using gold nanoparticles
SP dispersion relations in other nanoparticle
geometries
Diffuse and coherent SHG and THG
generation
Control of SP resonances using liquid crystals.

Current Collaborators

Dr. Sung Yong Park, Prof. Pak-Ming Hui,

Kwangmoo Kim, Ivan Tornes, Dr. Ha Youn Lee,
Prof. Brad Trees, Prof. David J. Bergman, Prof.
Y. M. Strelniker, Dr. W. A. Al-Saidi, D. ValdezBalderas, Ivan Tornes, K. Kobayashi
Work Supported by the U. S. National Science
Foundation, U. S.-Israel Binational Science
Foundation, and Ohio Supercomputer Center.