Surface Plasmon Spectra of Silver and Gold
Nanoparticle Assemblies
Mondona Zangeneh
Roger Terrill
San Jose State University, San Jose, California, U.S.A.
INTRODUCTION
This work is a brief topical review of recent literature
reports of the localized surface plasmon spectra of silver
and gold nanoparticles (NPs) in various assemblies. The
desire for such a review arises from the numerous recent
reports of NP assemblies, their optical properties, and the
importance of their potential applications. The optical
properties can be viewed from the perspective of isolated
particles, particles coupled by near-field light interactions
(roughly when the interparticle separation is less than
particle size), and those coupled by far-field interactions
(for well separated particles in arrays or gratings). The
NPs reviewed are sized from ca. 20–500 nm in diameter or
major axis (except for wires), are of various shapes, e.g.,
spheres, triangles, cylinders, etc., and are arranged by
various means including synthetic molecular linking
architectures. The preparation of interesting NP systems
builds, in part, on relatively recent NP synthetic strategies
that yield NPs of uniform size and often organized 1-, 2-
and 3-D NP assemblies. Methods for making NPs fall into
two broadly defined categories: those based on physical
metal deposition and those based on solution chemistry,
the latter including electrodeposition. Physical metal de-
position methods encompass electron beam lithography
(EBL), nanosphere- and colloidal lithography, metal is-
land films, and cosputtered composite materials. Powerful
EBL methods can produce arbitrary NP shapes and
arrangements, and sizes of about 50 nm and larger are in
the literature. Nanosphere lithography, pioneered by Van
Duyne et al. (vide infra), yields arrays of triangular and
related particles in the 90–2500 nm range. Simple metal
island films, e.g., from 2 to 3 nm mass thickness Au and
Ag evaporated directly onto nonwetting oxide substrates,
can yield reasonable NP distributions, as can cosputter-
deposited composites of metal and oxide matrix (e.g., Ag
and SiO2). Chemical NP preparations resulting in uniform
size distributions (e.g., <10% variability) have been the
subject of extensive recent development and are pre-
dominantly from two methods: 1) solution phase synthesis
(often with a fractional precipitation step); and 2) tem-
plating methods such as electrodeposition into nanoporous
Al2O3 membranes.
Dekker Encyclopedia of Nanoscience and Nanotechnology
DOI: 10.1081/E-ENN 120021413
Copyright D 2004 by Marcel Dekker, Inc. All rights reserved.
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
S
Localized Surface Plasmon Resonance in
Noble Metal Nanoparticles
Light of appropriate wavelength can excite collective
oscillations of the conduction electrons in Au, Ag, and other
metal NPs—the theoretical description of which by Mie
dates back to the turn of the twentieth century.[1,2] This
phenomenon is analogous to the surface plasmon polariton
that can be excited by evanescent wave irradiation in planar
metal surfaces. The plasma oscillation in metal NPs of
spherical symmetry is well described by the Mie equations,
which are solutions to Maxwell’s equations for electro-
magnetic (EM) radiation interacting with small particles
(d< l/10). The plasma oscillation is variably referred to as a
(localized) surface- or particle-plasmon resonance—we
adopt the term localized surface plasmon (LSPR) coined by
Van Duyne et al. to distinguish the NP phenomenon from
the propagating surface plasmon polariton of planar metal
surfaces.[3] Because of the very high electronic polariz-
ability of noble metal NPs, their LSPR oscillations couple
very efficiently with light. Accordingly, extinction of
transmitted light by NPs is enormous—equivalent to mo-
lecular absorption with a molar extinction coefficient 1011
M 1 cm 1 in some cases.[4]a Similarly, a 100-nm Ag NP
scatters light equivalently to the emission of 106 fluorescein
fluorphores.[5] The strong extinction band ranges from the
blue (e.g., 420 nm for 40 nm Ag spheroids in air[6])
throughout the visible and into the infrared (e.g., 6000 nm
for 2500-nm Ag triangles[4]). In most cases, the peak
wavelength of the LSPR band (lLSPR) will red shift with
increasing ambient or substrate dielectric constant (e), in-
creasing particle size, or aggregation.[7] The high sensi-
tivity to dielectric constant (DlLSPR/De), and the highly
localized nature of surface electric fields (projecting out
from the NP surface by only a small fraction of the light
wavelength in some cases) underpins the utility of NPs as
surface-affinity based chemical and biosensors.[8] The high
intensity of the surface electric fields associated with the
a
The term extinction refers to the aggregate effect of absorption and
scattering and differentiates LSPR scattering and absorption from mo-
lecular absorption.
LSPR of NPs and NP aggregates also underpin spectral
enhancements such as the Raman effect.[9] NPs and NP
films are also interesting for their potential applications in
nonlinear optics.[10,11] The dynamics of NP LSPR pro-
cesses occur on the femtosecond time scale, and have been
explored by Link and El-Sayed.[12]
Theory and Simulation of Nanoparticle
Surface Plasmon Spectra
There are a number of excellent recent papers covering
theoretical aspects of the optical response, i.e., extinction,
scattering, and electric field strengths, of Au and Ag
NPs.[13–17] The following is merely an overview intended
to elucidate points about: 1) the Mie theory;[18] 2) the
calculation of the small-particle dielectric constants from
the bulk-metal values;[13–15] 3) calculations of effective
refractive index (RI) for particle aggregates;[15,19,20] and
4) computational solutions for arbitrary shapes and
arrangements.[16,17] Discrete electronic structure is not
seen in the LSPR spectra of Au and Ag particles larger
than about 2 nm and is not discussed.
Mie theory is a set of exact solutions to Maxwell’s
equations for light interacting with small spherical parti-
cles, and is an excellent model for a wide range of NPs of
spherical or nearly spherical symmetry. Typically, Mie
theory is used to calculate the extinction cross section (s)
of NPs, and for particles of less than about 20 nm, only the
dipolar solution is important:
3=2
9VeM oeðoÞ
s ¼ 0
c ðeðoÞ þ 2eM Þ2 þ eðoÞ2
where s is the scattering cross section, V is the particle
volume, eM is the dielectric constant of the medium, and
the complex dielectric constant of the metal is e =
e(o)’ + ie(o)@. For a real and fairly constant eM, resonance
condition is fulfilled when e(o)’ =
2eM for spheres (or
e(o)’ =
eM for long rods when the electric field is po-
larized perpendicular to the long axis). The wavelength
dependence of lSPR originates from three places—the
wavelength and size dependence of e(o), the appearance
of quadrupole resonances (higher order Mie solutions) for
particles larger than about 20 nm, and damping when,
because the particle is approaching or exceeds the light
wavelength, the electric field is no longer homogeneous
within the particle. Mie theory can also be used to cal-
culate local field strengths.
Accurate application of Mie theory requires good
estimates of the frequency-dependent dielectric [e(o)] of
the NP. But for smaller NPs, adjustments are needed,
especially as the NP radius approaches the bulk metal
electron mean free path, RB. At this point, e(o) appears
to diverge from that of bulk metal. If one considers
the contribution to e(o) from the free electrons to be
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
distinct from other sources, Drude theory can be applied to
the confined conduction electrons, and accurate predic-
tions of LSPR band position and shape can be made.
This is accomplished by recalculating the electron
damping frequency, oD = vF/R, where vF is the Fermi
velocity, using a reduced mean free path, REFF = (R
1
NP +

1
1
RB ) that reflects electron scattering from the NP sur-
face.[14,15] This adjustment also predicts the rapid broad-
ening of NP LSPR bands into baseline as the radius falls
below about 2 nm. Electronic fine structure is just dis-
cernible in the derivative spectra of Au particles of 1.4 nm
and smaller, but does not substantially impact the overall
band shapes.[14]
Prodan et al. very recently contributed a theoretical
approach to the description of LSPR modes. This model is
described as the electromagnetic analog of molecular or-
bital theory, in that it uses a hybridization approach di-
rectly analogous to that describing atomic and molecular
electronic structures.[21] This approach is supported by
successful calculations of nanoshell LSPR modes by
Nordlander, who treat the electronic structure of the shell
with ab initio electronic structure calculations (time-de-
pendent local density approximation) and within the jel-
lium approximation.[22] In this method, the nanostructure
LSPR is described as the sum of simpler, interacting ones.
Or, in other words, the plasmon modes of the simpler or
elementary structures hybridize to form new modes. For
example, the LSPR of a Au nanoshell (e.g., an Au-coated
SiO2 sphere) is well known to have two prominent LSPR
modes. In the hybridization model, these are clearly seen
to arise from the symmetric and antisymmetric combina-
tions of the dipolar plasmons of two, more elementary
structures: 1) an Au sphere; and 2) a dielectric cavity in an
Au medium. Building on this result, two concentric
nanoshells can then be described by the symmetric and
antisymmetric sums of the inner and outer shell LSPR
modes. Hybridization model spectra of concentric nano-
shells are in excellent agreement with experiment.
For NP assemblies where the NP volume fraction is
significant, there arises the problem of how to accurately
account for NP contributions to the medium dielectric
constant eM. In general, the Maxwell–Garnett (MG) the-
ory seems to be the more successful, established theory,
although the Bruggeman theory is also used.[15,19,20,23]
The MG theory predicts the aggregate (complex) dielec-
tric constant, eC, assuming a composite material made up
of a matrix of eM and a volume fraction, fM, significantly
less than 0.5, of ‘‘infinitesimal’’ particles (i.e., much
smaller than l) of dielectric e0:
 
eC
e0 eM
e0
¼ fM
eC þ ke0 eM þ ke0
The factor k is a shape-dependent factor equal to 2 for
spherical particles, and 1 for infinitely long ‘‘needles’’
 oriented perpendicularly to the incident EM field. For
example, Mulvaney[24] applied the MG theory to spherical
SiO2-coated Au NPs of variable Au volume fraction. In
this case, the MG theory was very well able to predict the
red shift in lSPR for Au volume fractions less than about
0.5, but somewhat underestimated it thereafter. The MG
theory was also adapted by Foss et al.[25] to apply to
nanorods with variable aspect ratios through the incor-
poration of a wavelength-dependent kEFF value. The kEFF
model, also known as dynamic Maxwell–Garnett theory,
successfully predicts shape-dependent trends in lSPR, but
systematically overestimates them. In contrast, naı̈vely
applying Mie theory to the same rods leads to systematic
underestimation of lSPR.
Clearly, a more general approach to the prediction of
optical and electrostatic aspects of NPs and NP assemblies
is desirable. These approaches are generally in the form of
computational solutions to Maxwell’s equations using fi-
nite-difference approaches. An excellent example of this
approach is the work of Schatz et al.[16] on the discrete
dipole approximation (DDA), which divides the object of
interest into a lattice of polarizable cubes whose individ-
ual dipole polarizations are determined self-consistently.
According to Schatz et al., appropriately applied DDA
calculations yield extinction spectra that are consistently
within about 10% of the exact or experimental ones in-
dependent of the particle size or shape. Other approaches
include the multipole–multipole[26] and finite difference
time domain[27–29] variants.
NANOPARTICLES AND THEIR ASSEMBLIES
The variety of NP shapes, sizes, architectures, and strat-
egies for organizing and studying NPs inspires this sec-
tion—hence it moves topically through a cross section of
the literature by the dimensionality of the NP assembly in
question. Other important themes such as LSPR coupling
and multipolar LSPR modes span various dimensionalities
and are noted throughout. Nanoparticles have been studied
individually, in random 2- and 3-D arrangements and in
lithographically organized assemblies or as determined by
molecular architectures. Various studies examine LSPR
spectra as a function of particle size, shape, spacing, di-
electric medium, polarization, and incident angle of light.
Single Particles, Dimers,
Trimers, and Tetramers
Single nanoparticle spectroscopy
Recent spectroscopic reports of single noble metal NPs
characterizing roughly spherical and ‘‘wire’’ geometries
with attention to their potential application as single-par-
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
ticle sensor platforms include reports by Shultz et al.,[6,30]
Raschke et al.,[31] and McFarland and Van Duyne.[32]
These studies are akin to single molecule spectroscopy, S
but are technologically easier because of the extremely
large Rayleigh scattering efficiency (typically equivalent
to 105–106 fluorophors) of the surface plasmon peak in
an NP.[5]
The first of these studies[30] examines silver, gold, and
nickel nanowires (and various segmented variations)
prepared by a combination of electroless and electro-
chemical deposition steps within the pores of commercial
polycarbonate filtration membranes (by Nucleopore) and
subsequently released. The nanoscopic pores are produced
by high-energy alpha-particle perforation of polycarbon-
ate films and are uniquely suited to the templating of
nanoparticles because they are highly uniform in diameter
and aspect ratio, the former controlled by the manufac-
turer by etching the filtration membrane, and the latter by
variation of the electrodeposition time. In this case, the
pores (and hence nanowires) have nominal dimensions of
15  7000 nm. As in the latter studies, the wires were
imaged with conventional light microscopy under dark
field illumination, and detected by virtue of their intense
light scattering cross sections. Spectra were acquired by
imaging scattered light onto a single monochromator with
charge-couple device (CCD) detector.
In wires, the plasma resonance observed is a transverse
(radial), dipolar one. The longitudinal (axial) resonance is
not seen because the wires are very long. In these,[30]
resonances that were evident as peaks in the scattering
spectra at ca. 400 nm for Ag and 540 nm for Au–Ni wires
did not yield a spectral peak. Mie scattering calculations
gave an excellent fit to the observed Au and the feature-
less Ni spectra, but failed to capture the ca. 400 nm res-
onance for Ag.
In a subsequent report by Mock et al.,[6] the response of
the dipole resonance to changes in refractive index for
single, 60-nm quasispherical particles was measured by
using a series of index matching oils. The observed
DlMAX/Dn was 160 nm—in qualitative agreement with
Mie calculations (210 nm) that ignore the SiO2 substrate
half space.
More recently, Raschke et al.[31] and McFarland and
Van Duyne[32] have examined single nanoparticles
immobilized on glass in the context of their potential
application as chemo- or biosensors with extremely low
mass detection limits. Single NP sensors are a tantalizing
prospect because of the extreme mass sensitivity and
spatial resolution of single NP LSPR. For example, just
60,000 molecules could be detected in a volume smaller
than a cellular organelle by single NP scattering, or con-
versely, a very large number of different assays might be
simultaneously conducted in a very small area and volume
with an assay based on many uniquely identifiable
NPs.[33] In the report by McFarland and Van Duyne,[32]
dark field microscopy/spectroscopy was used to detect
alkanethiol adsorption to single Ag nanoparticles prepared
by citrate reduction. The bulk refractive index (RI) sen-
sitivity of selected particles, DlMAX/Dn =203 nm, agreed
well with Mie theory predictions. The response to
monolayer alkanethiol adsorption was very large, with a
hexadecanethiol self-assembled monolayer (SAM) pro-
ducing an easily detectable 40.7 nm red shift at saturation,
and corresponding to only ca. 60,000 molecules detected.
The similar report by Raschke et al.[31] employed Au NPs
derivatized with biotinylated bovine serum albumin and
binding diffusing streptavidin. They observed a signifi-
cant, but small 1.2 nm shift corresponding to saturation—
again, just slightly less than that predicted by Mie theory
for a 4p stearadian change in RI. These authors suggest
that a rod NP would produce higher sensitivity.
Nanoparticle dimers, trimers, and tetramers
A number of recent articles have examined the optical
response of pairs, dimers, and trimers of NPs. In contrast
to the above studies, these systems were studied as
ensembles, but the degree of particle homogeneity is high
and the results are likely to be representative of the 2-, 3-,
or 4-particle systems. Novak and Feldheim[34] used rigid
molecular linkers of variable lengths in the 2–30 nm range
to create bridged NP structures. The thioactyl-terminated
phenylacetylene bridges were prepared in three varieties;
the first, simply a straight rigid rod-like molecule, and the
second and third having a central branching point with
three and four branches, respectively. These were reacted
with 30-nm-diameter Ag NPs, and the resulting symmetric
dimers, trimers, and tetramers were confirmed with
transmission electron microscopy. These important solu-
tion-extinction spectroscopy experiments confirmed that
as the linker is shortened, the near-field coupling first
slightly red-shifts, and then spawns a high-frequency band
as the separation approaches about 4 nm.
A more recent paper by Sandrock and Foss[35] employs
a template analogous to the NucleoporeTM ones employed
above—transparent and porous Al2O3 membranes to
produce varied pairs of NPs within the individual pores
and to study them in place, without releasing them from
the Al2O3 template. Au and Ag were alternately deposited
and Ag later dissolved away to create controlled Au–Au
spacing. In this way, sphere–sphere, rod–rod, and rod–
sphere near-field interactions could be probed. An im-
portant aspect of this motif is that it allows the study of the
linear dichroic properties of the NP pairs. For example,
because all pores in the Al2O3 support are normal to the
surface, it is possible to control the polarization of the
incident light such that it is predominantly axial or radial
in character. Interparticle interactions were indicated by
spectral results that showed splitting under polarization
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
that put an E-field component along the particle–particle
axis. A subsequent paper by Gluodenis and Foss[36] delves
into simulation and theory for side–side and end–end
interactions of NP rod pairs.
Subsequent reports by Rechberger et al.[37] and Su
et al.[38] examine ensembles and individual NP pairs (re-
spectively) fabricated by using electron beam lithography.
Leitner et al. examined 150-nm disks, that were 17 nm
thick and spaced between 150 and 450 nm apart; Zhang et
al. studied elliptical particles in the 100–150nm range.
Zhang et al. report a red shift in lSPR as the particles are
brought into proximity. By examining polarizations both
parallel and perpendicular to the interparticle axis, Leitner
et al. resolved a strong red shift (+ 78 nm) and a weaker
blue shift (
30 nm) as the 150-nm particles were brought
into edge contact. The red shift is attributed to favorable
head–tail interparticle electrostatic interactions arising
from parallel particle dipoles arranged end to end. The
weaker blue shift is attributable to particle dipoles ar-
ranged side-by-side. Notably, these interactions did not
produce band splitting observed for the smaller, chemi-
cally synthesized NPs of Novak and Feldheim.[34]
Nanoparticle Chains with
Near-Field Coupling
Au and Ag NPs arranged in chains, i.e., in a row, are of
interest in the technological arena as ‘‘plasmonic light
waveguides’’ for guiding light in subdiffraction spaces
and for the production of electron tunneling electronics
such as single electron transistors. Chains have been
reported in two predominant contexts: 1) systems such as
those fabricated by Atwater et al.[39–41] using electron
beam lithography for plasmonic waveguide experiments;
and 2) smaller NPs templated by naturally faceted sur-
faces of h1010i Al2O3[42] and h110i NaCl (Ref. [43], no
optical data). Atwater et al. use sophisticated electron
beam lithography to make chains of 50-nm diameter Ag
NPs with varying interparticle spacing. For these systems,
the longitudinal (E-field parallel to NP chain) and trans-
verse SP modes slightly red and blue shift, respectively, as
the interparticle spacing approaches 75 nm, but do not
explore closer spacing. Atwater et al. are also one of the
few groups to employ finite difference time domain
(FDTD) simulations to simulate the optical responses of
these systems. One of the qualities of the FDTD simula-
tion is that in addition to E(x,y,z), it gives E(t), which is
useful for characterizing the properties of NP chains
as optical energy waveguides. FDTD simulations of the
E-field intensities in these chains agree well with experi-
ments, and are useful for estimating collective properties
such as waveguide loss. The Al2O3 templated Ag NPs are
fabricated by pulsed laser deposition, followed by high-
temperature (1400°C, 8 hr) annealing, yielding slightly
 prolate particles broadly distributed about 25 nm in dia-
meter and about 31 nm apart. These chains exhibit a far
more pronounced dichroism than those of Atwater et al.:
lTRANSVERSE = 455 nm and lLONGITUDINAL =550 nm,
reflecting both the smaller particle sizes (ca. 25 nm) and
their closer proximity (ca. 31 nm). Theoretical work by
Zhao et al.[44] has also contributed to understanding of
chains structures.
Previous examples have been of 1-D NP chains, but
individual NP pairs have also been examined. For exam-
ple, Sandrock and Foss made gold particle pairs by al-
ternately electrodepositing Au and Ag into porous Al2O3.
In this setting, the electrodeposition time controls the Au
and Ag NP lengths, and the pore their widths. Following
electrodeposition, Ag sections can be removed with
HNO3, leaving voids of controlled size between Au NPs
of controlled length.[35] Accordingly, paired ‘‘spheres’’
(i.e., unity aspect ratio rods), paired rods, and rod–sphere
pairs were studied. For these organized NP pairs, the
effects of interparticle spacing and the light polarization
and incident angle could be systematically studied. At
higher angle of incidence (yi), the light E-field falls in-
creasingly along the interparticle axis. For example, for
large interparticle spacing (114 nm) between paired
spheres, lSPR (= 548 nm) is independent of yi. However, if
a smaller interparticle spacing is employed (52 nm), lSPR
redshifts with an increasing in incidence angle reflect-
ing the favorable near-field coupling of LSPR dipoles.
Rod–sphere pair structures exhibited a long-wavelength
shoulder with increasing yi, similarly indicating near-field
interactions. Theoretical models used to evaluate sphere
pair systems such as simple quasistatic (i.e., total particle
pair size
l), modified long wavelength approximation square and hexagonal lattices of variable spacing between
(MLWA), and discrete dipole approximation (DDA)
models reflected experimental shifts in lSPR with yi, but
did not accurately reproduce peak position or shape.
Two-Dimensional NP Arrays
A rich variety of structures, some highly organized, for
example, by intermolecular interactions, have been re-
ported for NPs on surfaces. Also, some of the more in-
triguing spectral behaviors come from 2-D arrays of
optically coupled NPs.
Two-dimensional NP arrays made by electron
beam lithography (EBL)
Aussenegg et al.[45,46] have contributed important papers
on the optical properties of NP arrays in the far-field
coupling regime. The former report employs square arrays
(spacing L = 350–850 nm) of circular (d= 150 nm) gold
EBL-fabricated NPs studied by both extinction and fem-
tosecond time resolved luminescence measurements. In-
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
terestingly, the arrays exhibited a correlated oscillation in
lSPR and luminescence lifetime (2  tSPR  8 fsec), as the
particle spacing increased. Specifically, they observed a S
strong (60 nm) redshift and broadening of the LSPR band
for L values corresponding first to lSPR/nSUBSTRATE, and
then to lSPR. This effect, called the ‘‘grating’’ effect,
evidently reflects the increased radiative fields existing
between particles as the particle spacing produces con-
structive interparticle interference first in the substrate
(where the effective radiated wavelength is l/n), and then
in the airspace above the gradient.
In the latter work, Aussenegg et al. reported studies of
EBL-fabricated Ag nanowires (wire widths 60  w  200
nm) and nanowire gratings (spacing 290 d  680 nm)
with extinction spectroscopy.[46] Similarly to NP chains,
Ag nanowires exhibit strong LSPR bands under transverse
magnetic (TM) irradiation—i.e., when the E-field is po-
larized perpendicularly to the long axis of the wire. For
individual wires, lSPR was found to be linearly dependent
on wire width, w, between 65 and 90 nm. For wire grat-
ings, they similarly find lSPR to be a sensitive function of
spacing, L. lSPR redshifts and broadens when L ap-
proaches lSPR/nSUBSTRATE, corresponding to a transition
between evanescent and radiative character for the light
field in the substrate half space. This type of effect also
appears in recent computations by Zhao et al.,[16] who
simulated LSPR for arrays of period L equal to and
greater than the particle size.
Haynes et al.[47] have also used EBL to produce silver
and gold particle arrays. The arrays comprise triangular
(170 nm) and circular (200 nm) particles (trigonal prisms
and cylinders considering their 35 nm height) in both
230 and 500 nm—smaller distances relative to lSPR when
compared to the studies by Schider et al.,[45,46] but still
interacting predominantly in the far field. Van Duyne and
Schatz observe a linear red shift with increasing lattice
constant (ca. 40 optical nm per 100 nm) that is supported
qualitatively by coupled dipole simulations. Theoretical
calculations used by Zhao and coworkers[44] on particle
pairs also support far-field interparticle coupling effects
seen for large lattice spacing.
Two-dimensional NP arrays made by
nanosphere lithography (NSL)
Van Duyne and coworkers have performed a large body of
work using an NP fabrication method they had developed
and dubbed ‘‘nanosphere lithography’’ (NSL). In NSL, a
substrate is coated with hexagonally close-packed mono-
layer of highly monodisperse polymer nanospheres by a
simple drop casting procedure. The nanosphere coating, in
turn, serves as a mask for the evaporation of Ag or Au into
the interstitial hollows where substrate surface is exposed.
 However, in this case, the spheres are intentionally de-
posited such that they are separated on the surface, and the
surface is precoated with Au or Ag. Melting of the spheres
creates a removable mask that withstands an ion etch re-
moval of the unmasked metal film, and later, solvent re-
moval of the polymer leaves circular metal NPs. Unlike
the observations of Lamprecht et al.,[45] Schider et al.,[46]
and Haynes et al.[47] for regular periodic arrays, the av-
Fig. 1 AFM image of a Ag nanoparticle array created by na-
nosphere lithography. Reprinted with permission from Ref. [3].
Copyright 2003 American Chemical Society.
Metal evaporation at normal (or other) incidence, followed
by rinsing away the nanosphere mask, thus produces well-
ordered 2-D arrays of triangular metal nanoprisms (or
variations thereof) (Fig. 1).[3] Nanospheres are commer-
cially available in a wide range of sizes, corresponding to
a range of NP sizes that exhibit lSPR spanning the entire
visible, near, and mid infrared spectral regions (Fig. 2).
The NP shape can also be altered by evaporating through
the nanosphere mask at variable angles—called angle-
resolved nanosphere lithography (AR-NSL).[48] By se-
quentially depositing at different angles, AR-NSL can be
used to fabricate structures such as ‘‘nanooverlaps,’’
‘‘nanogaps,’’ and NP chains. Van Duyne et al. have
employed NSL–NP arrays in numerous studies focusing
on NP size, dielectric environment,[3] adsorbate binding
(sensor),[14] and surface-enhanced Raman activity.[9]
The dielectric response of NSL–NP arrays is of con-
siderable interest given the potential utility of these
structures in a sensor platform. As is generally observed,
lSPR increases with ambient dielectric;[49,50] however, in
the case of a surface (i.e., alkanethiol adsorbate)-induced
De, this red shift is larger (3 nm/CH2) than predicted for
spherical particles of comparable size. This observation
is supported (but somewhat overestimated) by discrete
dipole approximation (DDA).[51] This is a promising
property for a surface sensor because, for the most
challenging SPR sensing applications, bulk De contributes
to noise, whereas surface De reflects the binding of mo-
lecular analyte.
Two-dimensional NP arrays made by
colloidal lithography
Hanarp et al.[52] report a related ‘‘lithographic’’ prepara-
tion yielding disordered arrays of nearly identical nano-
disks. As with NSL, this preparation begins with an
adsorbed layer of monodisperse polymer nanospheres.
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
erage interparticle spacing (d) in the d  dP regime does
not change the lSPR of particles produced via nanosphere
lithography, presumably because of the lack of long-range
order. Otherwise, the particles’ LSPR spectra were fairly
well described by a simple oblate spheroid theory,[53] and
showed the expected red shift in lSPR with increasing
particle size and ambient dielectric.
Spontaneously organized 2-D
nanoparticle assemblies
The process of 2-D NP self-assembly has been recently
reviewed in the context of microelectronics.[54]
In many examples in this category, NPs are modified
with molecular adsorbates that, in turn, guide the NPs into
organized, closely packed assemblies. For example, Tripp
and Wei employ an alkane-tailed and ‘‘cup-shaped’’
resorcinarene tetrathiol to decorate 16–170 nm Au NPs.
The ligand shell and its alkane tails have a very strong
organizing effect leading to hexagonally packed NP arrays
on the air–water interface that can be transferred to quartz
substrates.[55] Kanehara et al.[56] find similar results for
an amine-terminated disulfide surfactant. In this case, a
Fig. 2 Size dependence of the LSPR spectra of Ag NP’s
fabricated using nanosphere lithography. The dimension ‘‘a’’
refers to the NP diameter (for disk particles) or base–apex length
(for triangular ones). Dimension ‘‘b’’ refers to the NP height.
Reprinted with permission from Ref. [3]. Copyright 2003
American Chemical Society.

Fig. 3 LSPR spectrum of a closely spaced 100-nm Ag
nanoparticle array on a silicone elastomer support. The
collective nature of the sharp band at 420 nm is evident in its
hypersensitivity to interparticle spacing. The band at 420 nm
disappears as the elastomer is stretched and interparticle spacing
decreases (as indicated by the arrow). Reprinted with permission
from Ref. [64]. Copyright 2003 American Chemical Society.
(View this art in color at www.dekker.com.)
carboxylic acid adjuvant helps to organize solvent cast
NP films.
Stabilized (if not necessarily highly organized) NP as-
semblies on surfaces have also been made using bidentate
ligands—one end of which has affinity for the NP and the
other end for the surface of the support. For example, an
amino-terminated alkylsilane monolayer on glass will bind
mercaptopropionic acid coated NPs by forming covalent
(amide) bonds to the surface amino group.[57] Similarly,
alkanedithiols have been used to tether Au NPs to Au
surfaces.[58] Single-stranded DNA (ssDNA)-derivatized
Au NPs have also been (selectively) bound to Au surfaces
by the complementary, surface-bound, DNA oligo-
mers.[59,60] This is an important theme, because Au NPs
interact strongly with Au film surface plasmon polaritons,
and thus amplify the surface sensitivity of analytical sur-
face plasmon polariton spectroscopy.
Coupled LSPR in 2-D nanoparticle assemblies
Near-field LSPR coupling is evident in some spontane-
ously organized NP assemblies. This coupling manifests
in a band splitting that is sensitive to polarization, angle,
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
and, as recently shown, interparticle spacing. Observa-
tions of this type of mode date back to the work by Ferrell
et al. in 1987.[61,62] For example, Taleb et al.[63] examined S
arrays of Ag NPs cast from solution and stabilized by
dodecanethiol. In these studies, an electrostatic model of
coupled dipoles in a 2-D hexagonal array was compared to
its experimental counterpart. Both model and experiment
yield a high-frequency side band that grows with in-
creasing out-of-plane electric field. In other words, the
high-frequency band appeared for higher incident angle
and under p-polarization only. Pileni et al. further ob-
served that this mode is more pronounced for more or-
ganized assemblies, and appeared for both 4- and 5-nm
Ag NPs.
Pileni’s observation can be compared to a more recent
one by Malynych and Chumanov,[64] who found a sharp,
high-frequency band that appeared only for smaller
interparticle separation of 100 nm Ag NP films. One
fascinating aspect of this experiment was that the NP film
could be transferred to an elastomer (poly(dimethyl-
siloxane)) that allowed continuous variation in interpar-
ticle spacing simply by stretching the substrate. Fig. 3
shows the resulting normal incidence transmission spec-
trum and the strong dependence of the sharp, high-fre-
quency band on interparticle separation. The mode
disappears as the elastomer is stretched, presumably be-
cause this spoils the near-field coupling. In contrast to
Pileni’s observations, this band actually depends on in-
plane optical fields and diminishes under higher incident
angles for both p- and s-polarization. Chumanov hypo-
thesizes that this is a result of an in-plane quadrupolar
plasmon mode illustrated in Fig. 4. Chumanov argues that,
for strong coherent interparticle coupling, the quadrupole
mode has a more favorable symmetry because all inter-
particle forces are equivalent. In other words, neighboring
particles experience either repulsive (as in Fig. 4b), or
attractive (as in Fig. 4c) forces. In contrast, the dipolar
excitation of Fig. 4a leads to some attractive interactions
(head–tail) and some repulsive ones (side-by-side).
Fig. 4 Proposed in-plane dipolar and quadrupolar LSPR
modes. Interparticle dipolar interactions in a are inequivalent
(some dipoles are arranged head–tail and others are side-by-
side), but interparticle forces for quadrupolar modes in b and c
are all equivalent. Reprinted with permission from Ref. [64].
Copyright 2003 American Chemical Society. (View this art in
color at www.dekker.com.)
Three-Dimensional Assemblies
of Nanoparticles
A comprehensive discussion of the variety and properties
of three-dimensional (3-D) NP assemblies is far beyond
the scope of this review. Instead, we present a brief cross
section of studies that touch on some important aspects of
3-D NP assemblies. However, one fairly general obser-
vation is that LSPR bands tend to broaden and red shift
when the component NPs aggregate, or are assembled into
a lattice.[65]
DNA linked 3-D assemblies
Similar to the case for 2-D assemblies, single-stranded
(ssDNA) oligomers can be used as a linker in 3-D as-
semblies of NPs. For example, Taton et al.[66] use a
strategy for controlled NP film growth wherein a substrate
surface and NP’s ‘‘a’’ and ‘‘b’’ are derivatized with dif-
ferent, noncomplementary ssDNA oligomers, illustrated
in Fig. 5. Adding ssDNA oligomers that are the comple-
mentary, on opposite ends, to the surface and to NP-a will
make a monolayer of NP-a. Further aggregation will not
take place because the linker ssDNA does not connect
‘‘a’’ to ‘‘a’’ or ‘‘a’’ to ‘‘b.’’ Rinsing and subsequent
treatment with an ‘‘a’’–‘‘b’’ linker will add a layer of NP-
b, etc. In addition to 3-D NP architectures, this strategy
Fig. 5 Controlled NP aggregate (A) and film (B) growth using
‘‘bidentate’’ single stranded DNA linkers. Linkers are specific
to either (SiO2)–a, or a–b. From Ref. [66]. D American Chem-
ical Society, 2003.
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
has been exploited for colorimetric sensing of specific
oligonucleotides in solution.[67] In this motif, a given
target ssDNA strand is detected by a pair of ssDNA
derivatized Au NPs, each NP complimentary to the op-
posite half of the target ssDNA. When the target strand is
hybridized by both NPs, a large red shift and broadening
in the NP LSPR band occurs as a result of near-field
coupling. This changes the NP solution from an intense
red to a faint purple. Because of the enormous extinction
coefficient of the NPs, a target as small as 50 pm could be
detected with this simple colorimetric test. Other studies
of DNA-linked assemblies are cited in Refs. [68,69].
Dithiol linked 3-D assemblies
Brust et a.[70] have used dithiol linkers to assemble NP
films in a controlled layer-by-layer fashion. The oxide
substrate was first derivatized with 3-mercaptotriethoxy-
silane, so that it would present the –SH moiety to solution
and bind bare Au, ca. 6 nm NPs from solution. Then, this
NP-coated surface was rinsed and treated with an a-o
dithiol that, in turn, leaves the NP-coated surface pre-
senting the –SH moiety as a basis for further assembly.
Assembly induced considerable broadening and red
shifting in the NP LSPR, but this did not increase after the
first few layers.
Silica encapsulated NPs
Mulvaney et al.[71] reviewed the field of silica encapsu-
lation of NPs and noted that these can be assembled into
densely packed films. Silica encapsulation is attractive for
various technological reasons, i.e., transparency, stability,
etc. but also because of the control with which the silica
shell can be deposited by using siloxane hydrolysis
chemistry, initiated on the NP surface by the S-terminus of
3-mercaptoproyltrialkoxysilane. Particles synthesized in
this manner are stabilized by SiO2, and the interparticle
distance in films made from encapsulated NPs are set by
the SiO2 thickness. Color-tuning in films prepared from
SiO2 encapsulated Au is accurately predicted with the
Maxwell–Garnet effective medium theory.[15]
Nanocomposite films
The designation ‘‘nanocomposite’’ is typically applied to
materials made from disordered mixtures of Au or Ag NPs
at substantial volume fraction in an inert host material. For
example, composite films can be prepared by cosputter
coating SiO2/Ag and thermally annealing the resulting
film.[10] Similarly, sol–gel methods can be used to prepare
Au/BaTiO3 and other thin film nanocomposites.[72] In
particular, nanocomposite films appear to be of interest
for nonlinear optical applications due in part to the large
 third-order nonlinear susceptibility lent to these materials
by the LSPR active NPs.[73] Similarly, nanocomposites
are of interest for their potential applications to electronics
and as sensors.[74,75] Al-Rawashdeh et al.[23,76] have pre-
pared ordered polyethylene–Au nanorod composites. The
plastic polyethylene matrix provided a means for shear
orientation of the nanorods, which, in turn, lend dichroic
optical properties to the material.
CONCLUSION
The localized surface plasmon spectra of silver and gold
nanoparticles are interesting in a number of contexts.
Spherical NP LSPR spectra are often in good agreement
with theory-given adjustments to the metal dielectric
function for NPs comparable to, or smaller than, the
electron mean free path. However, calculation of the
LSPR spectra of nonspherical shapes are still quite chal-
lenging because exact electrodynamic solutions such as
the Mie theory do not exist, and finite difference simu-
lations, while sometimes quite successful, are far from
routine calculations. However, a recently reported ap-
proach based on hybridization of the LSPR modes of more
elementary shapes that, in combination, describe others is
quite promising.
Basic LSPR spectroscopic phenomena have been the
subject of many recent articles. Examples include the
observation of multiple LSPR bands for a given NP based
on electronic polarization along the different principle
axes of the NP, or sometimes for higher-order polariza-
tions in particles with sizes comparable to or greater than
l. Films of NPs often exhibit optical dichroism because of
electromagnetic interactions between particles, or, in the
case of oriented NPs, because of the optical anisotropy of
the particles themselves.
NP LSPR spectroscopy has potential application in
numerous technological areas such as subdiffraction light
guiding, nonlinear optical applications, Raman enhance-
ment, and chemical sensing. Sensing applications are
quite promising given the popularity of the related metal
film reflection based surface plasmon sensors. NP sensing
can, in theory, detect as few as 60,000 molecules in a
volume far smaller than a typical cell.
REFERENCES
1. Mie, G. Contributions to the optics of turbid media,
especially colloidal metal solutions. Ann. Phys.
1908, 25, 377– 445.
2. Ostwald, W. Theoretical and Applied Colloid
Chemistry; Wiley: New York, 1992; 200.
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
3. Haynes, C.L.; Van Duyne, R.P. Nanosphere lithog-
raphy: A versatile nanofabrication tool for studies of
size-dependent nanoparticle optics. J. Phys. Chem., S
B 2001, 105, 5599 – 5611, (review).
4. Jensen, T.R.; Malinsky, M.D.; Haynes, C.L.; Van
Duyne, R.P. Nanosphere lithography: Tunable local-
ized surface plasmon resonance spectra of silver
nanoparticles. J. Phys. Chem., B 2000, 104, 10549 –
10556.
5. Yguerabide, J.; Yguerabide, E.E. Light-scattering
submicroscopic particles as highly fluorescent
analogs and their use as tracer labels in clinical
and biological applications: II. Experimental char-
acterization. Anal. Biochem. 1998, 262, 157– 176.
6. Mock, J.R.; Smith, D.R.; Shultz, S. Local refractive
index dependence of plasmon resonance spectra
from individual nanoparticles. Nano Lett. 2003, 3
(4), 485 – 491.
7. Kreibig, U.; Vollmer, M. Optical Properties of Metal
Clusters; Springer-Verlag: New York, 1995; Vol. 25.
8. Riboh, J.C.; Haes, A.J.; McFarland, A.D.; Yonzon,
C.R.; Van Duyne, R.P. A nanoscale optical biosen-
sor: Real-time immunoassay in physiological buffer
enabled by improved nanoparticle adhesion. J. Phys.
Chem., B 2003, 107, 1772 – 1780.
9. Haynes, C.L.; Van Duyne, R.P. Plasmon-sampled
surface-enhanced Raman excitation spectroscopy. J.
Phys. Chem., B 2003, 107, 7426– 7433.
10. Yang, G.; Wang, W.; Zhou, Y.; Lu, H.; Yang, G.;
Chen, Z. Linear and nonlinear optical properties of
Ag nanocluster/BaTiO3 composite films. Appl.
Phys. Lett. 2002, 81 (21), 3969 – 3971.
11. Liao, H.B.; Wen, W.; Wong, G.K.L. Preparation and
optical characterization of Au/SiO2 composite films
with multilayer structure. J. Appl. Phys. 2003, 93
(8), 4485 –4488.
12. Link, S.; El-Sayed, M.A. Spectral properties and
relaxation dynamics of surface plasmon electronic
oscillations in gold and silver nanodots and
nanorods. J. Phys. Chem., B 1999, 103, 8410 –8426.
13. Hovel, H.; Fritz, S.; Hilger, A.; Kreibig, U.;
Vollmer, M. Width of cluster plasmon resonances:
Bulk dielectric functions and chemical interface
damping. Phys. Rev., B 1993, 48, 18178– 18188.
14. Alvarez, M.M.; Khoury, J.T.; Schaff, G.T.; Shafi-
gullin, M.N.; Vezmar, I.; Whetten, R.L. Optical
absorption spectra of nanocrystal gold molecules. J.
Phys. Chem., B 1997, 101, 3706 – 3712.
15. Ung, T.; Liz-Marzan, L.M.; Mulvaney, P. Gold
nanoparticle thin films. Colloids Surf., A 2002, 202,
119 – 126.
16. Zhao, L.L.; Kelly, K.L.; Schatz, G.C. The extinction
spectra of silver nanoparticle arrays: Influence of
array structure on plasmon resonance wavelength
 and width. J. Phys. Chem., B. 2003, 107, 7343 –
7350.
17. Kelly, K.L.; Coronado, E.; Zhao, L.L.; Schatz, G.C.
The optical properties of metal nanoparticles: The
influence of size, shape, and dielectric environment.
J. Phys. Chem., B 2003, 107, 668 –677.
18. Bohren, C.F.; Huffman, D.R. Absorption and
Scattering of Light by Small Particles; Wiley:
New York, 1983.
19. Al-Rawashdeh, N.A.F.; Sandrock, M.L.; Seugling,
C.J.; Foss, C.A. Visible region polarization spectro-
scopic studies of template-synthesized gold nano-
particles oriented in polyethylene. J. Phys. Chem., B
1998, 102, 361 – 371.
20. Hornyak, G.L.; Patrissi, C.J.; Martin, C.R. Fabrica-
tion, characterization, and optical properties of gold
nanoparticle/porous alumina composites: The non-
scattering Maxwell–Garnett limit. J. Phys. Chem., B
1997, 101, 1548– 1555.
21. Prodan, E.; Radloff, C.; Halas, N.J.; Nordlander, P.
A hybridization model for the plasmon response of
complex nanostructures. Science 2003, 302, 419 –
422.
22. Prodan, E.; Nordlander, P. Structural tunability of
the plasmon resonances in metallic nanoshells. Nano
Lett. 2003, 3, 543 –547.
23. Al-Rawashdeh, N.A.F.; Sandrock, M.L.; Seugling,
C.J.; Foss, C.A., Jr. Visible region polarization
spectroscopic studies of template-synthesized gold
nanoparticles oriented in polyethylene. J. Phys.
Chem., B 1998, 102, 361– 371.
24. Mulvaney, P. Surface plasmon spectroscopy of
nanosized metal particles. Langmuir 1996, 12,
788 – 800.
25. Foss, C.A.; Hornyak, G.L.; Stockert, J.A.; Martin,
C.R. Template synthesized nanoscopic gold parti-
cles: Optical spectra and the effects of particle size
and shape. J. Phys. Chem. 1994, 98, 2963.
26. Moreno, E.; Ermi, D.; Hafner, C.; Vahldieck, R.
Multiple multipole method with automatic multipole
setting applied to the simulation of surface plasmons
in metallic nanostructures. J. Opt. Coc., A. 2002, 19,
101– 111.
27. Krenn, J.R.; Schider, G.; Rechberger, W.; Lam-
precht, B.; Leitner, A.; Aussenegg, F.R.; Weeber,
J.C. Design of multipolar plasmon excitations in
silver nanoparticles. Appl. Phys. Lett. 2000, 77 (21),
3379 – 3381.
28. Taflove, A. Computational Electrodynamics: The
Finite-Difference Time-Domain Method; Artech
House: Boston, 1995; 599.
29. Maier, S.A.; Kik, P.G.; Atwater, H.A. Observation
of coupled plasmon-polariton modes in Au nano-
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
particle chain waveguides of different lengths:
Estimation of waveguide loss. Appl. Phys. Lett.
2002, 81 (9), 1714 – 1716.
30. Mock, J.J.; Oldenburg, J.S.; Smith, D.R.; Schultz,
D.A.; Shultz, S. Composite plasmon resonant
nanowires. Nano Lett. 2002, 2 (5), 465 –469.
31. Raschke, G.; Kowarik, S.; Franzl, T.; Sonnichsen,
C.; Klar, T.A.; Feldmann, J. Biomolecular recogni-
tion based on single gold nanoparticle light scat-
tering. Nano Lett. 2003, 3 (7), 935 –938.
32. McFarland, A.D.; Van Duyne, R.P. Single silver
nanoparticles as real-time optical sensors with
zeptomole sensitivity. Nano Lett. 2003, 3 (8),
1057– 1062.
33. Nicewarner-Pena, S.R.; Freeman, G.R.; Reiss, B.D.;
He, L.; Pena, D.J.; Walton, I.D.; Cromer, R.;
Keating, C.D.; Natan, M.J. Submicrometer metallic
barcodes. Science 2001, 294, 137 –141.
34. Novak, J.P.; Feldheim, D.L. Assembly of phenyl-
acetylene-bridged silver and gold nanoparticle
arrays. J. Am. Chem. Soc. 2000, 122, 3979 –3980.
35. Sandrock, M.L.; Foss, C.A., Jr. Synthesis and linear
optical properties of nanoscopic gold particle pair
structures. J. Phys. Chem., B 1999, 103, 11398 –
11406.
36. Gluodenis, M.; Foss, C.A. The effect of mutual
orientation on the spectra of metal nanoparticle rod–
rod and rod–sphere pairs. J. Phys. Chem., B 2002,
106, 9484 –9489.
37. Rechberger, W.; Hohenau, A.; Leitner, A.; Krenn,
J.R.; Lamprecht, B.; Aussenegg, F.R. Optical
properties of two interacting gold nanoparticles.
Opt. Commun. 2003, 220, 137 –141.
38. Su, H.-H.; Wei, Q.-H.; Zhang, X.; Mock, J.J.;
Xmith, D.R.; Sjultz, S. Interparticle coupling effects
on plasmon resonances of nanogold particles. Nano.
Lett. 2003, 3 (8), 1087 –1090.
39. Maier, S.A.; Brongersma, M.L.; Kik, P.G.; Atwater,
H.A. Observation of near-field coupling in metal
nanoparticle chains using far-field polarization
spectroscopy. Phys. Rev., B 2002, 65, 193408-1-4.
40. Maier, S.A.; Brongersma, M.L.; Kik, P.G.; Meltzer,
S.; Requicha, A.A.G.; Atwater, H.A. Plasmonics—
A route to nanoscale optical devices. Adv. Mater.
2001, 13 (19), 1501 – 1505.
41. Maier, S.A.; Kik, P.G.; Atwater, H.A. Observation
of coupled plasmon-polariton modes in Au nano-
particle chain waveguides of different lengths:
Estimation of waveguide loss. Appl. Phys. Lett.
2002, 81 (9), 1714 – 1716.
42. Fort, E.; Ricolleau, C.; Sau-Pueyo, J. Dichroic thin
films of silver nanoparticle chain arrays on facetted
alumina templates. Nano Lett. 2003, 3, 65 –67.
 43. Teranishi, T.; Sugawara, A.; Shimizu, T.; Miyake,
M. Planar array of 1D gold nanoparticles on ridge-
and-valley structured carbon. J. Am. Chem. Soc.
2002, 124, 4210 – 4211.
44. Zhao, L.K.; Kelly, L.; Schatz, G.C. The extinction
spectra of silver nanoparticle arrays: Influence of
array structure on plasmon resonance wavelength
and width. J. Phys. Chem., B 2003, 107, 7343 –7350.
45. Lamprecht, B.; Schider, G.; Lechner, R.T.; Ditlba-
cher, H.; Krenn, J.R.; Leitner, A.; Aussenegg, F.R.
Metal nanoparticle gratings: Influence of dipolar
particle interaction on the plamon resonance. Phys.
Rev. Lett. 2000, 84, 4721 –4724.
46. Schider, G.; Krenn, J.R.; Gotschy, W.; Lamprecht,
B.; Ditlbacher, H.; Leitner, A.; Aussenegg, F.R.
Optical properties of Ag and Au nanowire gratings.
J. Appl. Phys. 2001, 90, 3825 –3830.
47. Haynes, C.L.; McFarland, A.D.; Zhao, L.; Van
Duyne, R.P.; Schatz, G.C.; Gunnarsson, L.; Prikulis,
J.; Kasemo, B.; Kall, M. Nanoparticle optics: The
importance of radiative dipole coupling in two-
dimensional nanoparticle arrays. J. Phys. Chem., B
2003, 107, 7337 – 7342.
48. Haynes, C.L.; Van Duyne, R.P. Dichroic optical
properties of extended nanostructures fabricated
using angle-resolved nanosphere lithography. Nano
Lett. 2003, 3, 939 –943.
49. Malinsky, M.D.; Kelly, K.L.; Schatz, G.C.; Van
Duyne, R.P. Nanosphere lithography: Effect of
substrate on the localized surface plasmon reso-
nance spectrum of silver nanoparticles. J. Phys.
Chem., B 2001, 105, 2343 – 2350.
50. Jensen, T.R.; Duval, M.L.; Kelly, K.L.; Lazarides,
A.A.; Schatz, G.C.; Van Duyne, R.P. Nanosphere
lithography: Effect of the external dielectric medi-
um on the surface plasmon resonance spectrum of a
periodic array of silver nanoparticles. J. Phys.
Chem., B 1999, 103, 9846 – 9853.
51. Malinsky, M.D.; Kelly, K.L.; Schatz, G.C.; Van
Duyne, R.P. Chain length dependence and sensing
capabilities of the localized surface plasmon reso-
nance of silver nanoparticles chemically modified
with alkanethiol self-assembled monolayers. J. Am.
Chem. Soc. 2001, 123, 1471– 1482.
52. Hanarp, P.; Kall, M.; Sutherland, D.S. Optical
properties of short range ordered arrays of nanome-
ter gold disks prepared by colloidal lithography. J.
Phys. Chem., B 2003, 107, 5768 – 5772.
53. Bohren, C.F.; Huffman, D.R. Absorption and
Scattering of Light by Small Particles; John Wiley
& Sons: New York, 1983.
54. Fendler, J.H. Chemical self-assembly for electronic
applications. Chem. Mater. 2001, 13, 3196 – 3210.
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
55. Kim, B.; Tripp, S.L.; Wei, A. Self-organization of
large gold nanoparticle arrays. J. Am. Chem. Soc.
2001, 123, 7955 –7956. S
56. Kanehara, M.; Oumi, Y.; Sano, T.; Teranishi, T.
Formation of low symmetric 2D superlattices of
gold nanoparticles through surface modification by
acid–base interaction. J. Am. Chem. Soc. 2003, 125,
8708 – 8709.
57. Nath, N.; Chilkoti, A. A colorimetric gold nanopar-
ticle sensor to interrogate biomolecular interactions in
real time. Anal. Chem. 2002, 74, 504– 509.
58. Hutter, E.H.; Fendler, J.H.; Roy, D. Surface plasmon
resonance studies of gold and silver nanoparticles
linked to gold and silver substrates by 2-aminoeth-
anethiol and 1,6-hexanedithiol. J. Phys. Chem., B
2001, 105, 11159 –11168.
59. He, L.; Musick, M.D.; Nicewarner, S.R.; Salinas,
F.G.; Benkovic, S.J.; Natan, M.J.; Keating, C.D.
Colloidal Au-enhanced surface plasmon resonance
for ultrasensitive detection of DNA hybridization.
J. Am. Chem. Soc. 2000, 122, 9071 – 9077.
60. Hutter, E.; Pileni, M.-P. Detection of DNA hybrid-
ization by gold nanoparticle enhanced transmission
surface plasmon resonance spectroscopy. J. Phys.
Chem., B 2003, 107, 6497 – 6499.
61. Royer, P.; Goudonnet, J.P.; Warmack, R.J.; Ferrell,
T.L. Substrate effects on surface-plasmon spectra in
metal-island films. Phys. Rev., B 1987, 35, 3753.
62. Kennerly, S.W.; Little, J.W.; Warmack, R.J.;
Ferrell, T.L. Optical properties of heated Ag films.
Phys. Rev., B 1984, 29, 2926.
63. Taleb, A.; Russier, V.; Courty, A.; Pileni, M.P.
Collective optical properties of silver nanoparticles
organized in two-dimensional superlattices. Phys.
Rev., B 1999, 59, 13350 –13358.
64. Malynych, S.; Chumanov, G. Light-induced coher-
ent interactions between silver nanoparticles in two-
dimensional arrays. J. Am. Chem. Soc. 2003, 125,
2896 – 2898.
65. Taleb, A.; Petit, C.; Pileni, M.P. Optical properties
of self-assembled 2D and 3D superlattices of silver
nanoparticles. J. Phys. Chem., B 1998, 102, 2214 –
2220.
66. Taton, T.A.; Mucic, R.C.; Mirkin, C.A.; Letsinger,
R.L. The DNA-mediated formation of supra-
molecular mono- and multilayered nanoparticle
structures. J. Am. Chem. Soc. 2000, 122, 6305 –
6306.
67. Reynolds, R.A., III; Mirkin, C.A.; Letsinger, R.L.
Homogeneous, nanoparticle-based quantitative col-
orimetric detection of oligonucleotides. J. Am.
Chem. Soc. 2000, 122, 3795 – 3796.
68. Lazarides, A.A.; Schatz, G.C. DNA-linked metal
 nanosphere materials: Structural basis for the
optical properties. J. Phys. Chem., B 2000, 104,
460– 467.
69. Storhoff, J.J.; Lazarides, A.A.; Mucic, R.C.; Mirkin,
C.A.; Letsinger, R.L.; Schatz, G.C. What controls
the optical properties of DNA-linked gold nanopar-
ticle assemblies? J. Am. Chem. Soc. 2000, 122,
4640 – 4650.
70. Brust, M.; Bethell, D.; Kiely, C.J.; Schiffrin, D.J.
Self-assembled gold nanoparticle thin films with
nonmetallic optical and electronic properties. Lang-
muir 1998, 14, 5425 – 5429.
71. Mulvaney, P.; Liz-Marzan, L.M.; Giersig, M.; Ung,
T. Silica encapsulation of quantum dots and metal
clusters. J. Mater. Chem. 2000, 10, 1259– 1270.
72. Yang, Y.; Shi, J.; Huang, W.; Dai, S.; Wang, L.
Preparation and optical properties of barium titanate
Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.
thin films dispersed with Au nanoparticles. Mater.
Lett. 2002, 56, 1048 –1052.
73. Hache, F.; Flytzanis, R.C. Optical nonlinearities of
small metal particles: Surface-mediated resonance
and quantum size effects. J. Opt. Soc. Am., B 1986,
3 (12), 1647 –1655.
74. Feldheim, D.L.; Keating, C.D. Self-assembly of
single electron transistors and related devices.
Chem. Soc. Rev. 1998, 27, 1 –12.
75. Shipway, A.N.; Willner, I. Nanoparticles as struc-
tural and functional units in surface-confined
architectures. Chem. Commun. 2001, 20, 2035 –
2045.
76. Al-Rawashdeh, N.; Foss, C.A., Jr. UV/visible and in-
frared spectra of polyethylene/nanoscopic gold rod
composite films: Effects of gold particle size, shape
and orientation. Nanostruct. Mater. 1997, 9, 383 –386.