Sunteți pe pagina 1din 12

Surface Plasmon Spectra of Silver and Gold

Nanoparticle Assemblies S
Mondona Zangeneh
Roger Terrill
San Jose State University, San Jose, California, U.S.A.

INTRODUCTION Localized Surface Plasmon Resonance in


Noble Metal Nanoparticles
This work is a brief topical review of recent literature
reports of the localized surface plasmon spectra of silver Light of appropriate wavelength can excite collective
and gold nanoparticles (NPs) in various assemblies. The oscillations of the conduction electrons in Au, Ag, and other
desire for such a review arises from the numerous recent metal NPs—the theoretical description of which by Mie
reports of NP assemblies, their optical properties, and the dates back to the turn of the twentieth century.[1,2] This
importance of their potential applications. The optical phenomenon is analogous to the surface plasmon polariton
properties can be viewed from the perspective of isolated that can be excited by evanescent wave irradiation in planar
particles, particles coupled by near-field light interactions metal surfaces. The plasma oscillation in metal NPs of
(roughly when the interparticle separation is less than spherical symmetry is well described by the Mie equations,
particle size), and those coupled by far-field interactions which are solutions to Maxwell’s equations for electro-
(for well separated particles in arrays or gratings). The magnetic (EM) radiation interacting with small particles
NPs reviewed are sized from ca. 20–500 nm in diameter or (d< l/10). The plasma oscillation is variably referred to as a
major axis (except for wires), are of various shapes, e.g., (localized) surface- or particle-plasmon resonance—we
spheres, triangles, cylinders, etc., and are arranged by adopt the term localized surface plasmon (LSPR) coined by
various means including synthetic molecular linking Van Duyne et al. to distinguish the NP phenomenon from
architectures. The preparation of interesting NP systems the propagating surface plasmon polariton of planar metal
builds, in part, on relatively recent NP synthetic strategies surfaces.[3] Because of the very high electronic polariz-
that yield NPs of uniform size and often organized 1-, 2- ability of noble metal NPs, their LSPR oscillations couple
and 3-D NP assemblies. Methods for making NPs fall into very efficiently with light. Accordingly, extinction of
two broadly defined categories: those based on physical transmitted light by NPs is enormous—equivalent to mo-
metal deposition and those based on solution chemistry, lecular absorption with a molar extinction coefficient 1011
the latter including electrodeposition. Physical metal de- M 1 cm 1 in some cases.[4]a Similarly, a 100-nm Ag NP
position methods encompass electron beam lithography scatters light equivalently to the emission of 106 fluorescein
(EBL), nanosphere- and colloidal lithography, metal is- fluorphores.[5] The strong extinction band ranges from the
land films, and cosputtered composite materials. Powerful blue (e.g., 420 nm for 40 nm Ag spheroids in air[6])
EBL methods can produce arbitrary NP shapes and throughout the visible and into the infrared (e.g., 6000 nm
arrangements, and sizes of about 50 nm and larger are in for 2500-nm Ag triangles[4]). In most cases, the peak
the literature. Nanosphere lithography, pioneered by Van wavelength of the LSPR band (lLSPR) will red shift with
Duyne et al. (vide infra), yields arrays of triangular and increasing ambient or substrate dielectric constant (e), in-
related particles in the 90–2500 nm range. Simple metal creasing particle size, or aggregation.[7] The high sensi-
island films, e.g., from 2 to 3 nm mass thickness Au and tivity to dielectric constant (DlLSPR/De), and the highly
Ag evaporated directly onto nonwetting oxide substrates, localized nature of surface electric fields (projecting out
can yield reasonable NP distributions, as can cosputter- from the NP surface by only a small fraction of the light
deposited composites of metal and oxide matrix (e.g., Ag wavelength in some cases) underpins the utility of NPs as
and SiO2). Chemical NP preparations resulting in uniform surface-affinity based chemical and biosensors.[8] The high
size distributions (e.g., <10% variability) have been the intensity of the surface electric fields associated with 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- a
The term extinction refers to the aggregate effect of absorption and
plating methods such as electrodeposition into nanoporous scattering and differentiates LSPR scattering and absorption from mo-
Al2O3 membranes. lecular absorption.

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.


LSPR of NPs and NP aggregates also underpin spectral distinct from other sources, Drude theory can be applied to
enhancements such as the Raman effect.[9] NPs and NP the confined conduction electrons, and accurate predic-
films are also interesting for their potential applications in tions of LSPR band position and shape can be made.
nonlinear optics.[10,11] The dynamics of NP LSPR pro- This is accomplished by recalculating the electron
cesses occur on the femtosecond time scale, and have been damping frequency, oD = vF/R, where vF is the Fermi
explored by Link and El-Sayed.[12] velocity, using a reduced mean free path, REFF = (R 1
NP +
1 1
RB ) that reflects electron scattering from the NP sur-
Theory and Simulation of Nanoparticle face.[14,15] This adjustment also predicts the rapid broad-
Surface Plasmon Spectra ening of NP LSPR bands into baseline as the radius falls
below about 2 nm. Electronic fine structure is just dis-
There are a number of excellent recent papers covering cernible in the derivative spectra of Au particles of 1.4 nm
theoretical aspects of the optical response, i.e., extinction, and smaller, but does not substantially impact the overall
scattering, and electric field strengths, of Au and Ag band shapes.[14]
NPs.[13–17] The following is merely an overview intended Prodan et al. very recently contributed a theoretical
to elucidate points about: 1) the Mie theory;[18] 2) the approach to the description of LSPR modes. This model is
calculation of the small-particle dielectric constants from described as the electromagnetic analog of molecular or-
the bulk-metal values;[13–15] 3) calculations of effective bital theory, in that it uses a hybridization approach di-
refractive index (RI) for particle aggregates;[15,19,20] and rectly analogous to that describing atomic and molecular
4) computational solutions for arbitrary shapes and electronic structures.[21] This approach is supported by
arrangements.[16,17] Discrete electronic structure is not successful calculations of nanoshell LSPR modes by
seen in the LSPR spectra of Au and Ag particles larger Nordlander, who treat the electronic structure of the shell
than about 2 nm and is not discussed. with ab initio electronic structure calculations (time-de-
Mie theory is a set of exact solutions to Maxwell’s pendent local density approximation) and within the jel-
equations for light interacting with small spherical parti- lium approximation.[22] In this method, the nanostructure
cles, and is an excellent model for a wide range of NPs of LSPR is described as the sum of simpler, interacting ones.
spherical or nearly spherical symmetry. Typically, Mie Or, in other words, the plasmon modes of the simpler or
theory is used to calculate the extinction cross section (s) elementary structures hybridize to form new modes. For
of NPs, and for particles of less than about 20 nm, only the example, the LSPR of a Au nanoshell (e.g., an Au-coated
dipolar solution is important: SiO2 sphere) is well known to have two prominent LSPR
modes. In the hybridization model, these are clearly seen
3=2
9VeM oeðoÞ to arise from the symmetric and antisymmetric combina-
s ¼ 0
c ðeðoÞ þ 2eM Þ2 þ eðoÞ2 tions of the dipolar plasmons of two, more elementary
structures: 1) an Au sphere; and 2) a dielectric cavity in an
where s is the scattering cross section, V is the particle Au medium. Building on this result, two concentric
volume, eM is the dielectric constant of the medium, and nanoshells can then be described by the symmetric and
the complex dielectric constant of the metal is e = antisymmetric sums of the inner and outer shell LSPR
e(o)’ + ie(o)@. For a real and fairly constant eM, resonance modes. Hybridization model spectra of concentric nano-
condition is fulfilled when e(o)’ = 2eM for spheres (or shells are in excellent agreement with experiment.
e(o)’ =  eM for long rods when the electric field is po- For NP assemblies where the NP volume fraction is
larized perpendicular to the long axis). The wavelength significant, there arises the problem of how to accurately
dependence of lSPR originates from three places—the account for NP contributions to the medium dielectric
wavelength and size dependence of e(o), the appearance constant eM. In general, the Maxwell–Garnett (MG) the-
of quadrupole resonances (higher order Mie solutions) for ory seems to be the more successful, established theory,
particles larger than about 20 nm, and damping when, although the Bruggeman theory is also used.[15,19,20,23]
because the particle is approaching or exceeds the light The MG theory predicts the aggregate (complex) dielec-
wavelength, the electric field is no longer homogeneous tric constant, eC, assuming a composite material made up
within the particle. Mie theory can also be used to cal- of a matrix of eM and a volume fraction, fM, significantly
culate local field strengths. less than 0.5, of ‘‘infinitesimal’’ particles (i.e., much
Accurate application of Mie theory requires good smaller than l) of dielectric e0:
estimates of the frequency-dependent dielectric [e(o)] of  
the NP. But for smaller NPs, adjustments are needed, eC  e0 eM  e0
¼ fM
especially as the NP radius approaches the bulk metal eC þ ke0 eM þ ke0
electron mean free path, RB. At this point, e(o) appears
to diverge from that of bulk metal. If one considers The factor k is a shape-dependent factor equal to 2 for
the contribution to e(o) from the free electrons to be spherical particles, and 1 for infinitely long ‘‘needles’’

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


oriented perpendicularly to the incident EM field. For ticle sensor platforms include reports by Shultz et al.,[6,30]
example, Mulvaney[24] applied the MG theory to spherical Raschke et al.,[31] and McFarland and Van Duyne.[32]
SiO2-coated Au NPs of variable Au volume fraction. In These studies are akin to single molecule spectroscopy, S
this case, the MG theory was very well able to predict the but are technologically easier because of the extremely
red shift in lSPR for Au volume fractions less than about large Rayleigh scattering efficiency (typically equivalent
0.5, but somewhat underestimated it thereafter. The MG to 105–106 fluorophors) of the surface plasmon peak in
theory was also adapted by Foss et al.[25] to apply to an NP.[5]
nanorods with variable aspect ratios through the incor- The first of these studies[30] examines silver, gold, and
poration of a wavelength-dependent kEFF value. The kEFF nickel nanowires (and various segmented variations)
model, also known as dynamic Maxwell–Garnett theory, prepared by a combination of electroless and electro-
successfully predicts shape-dependent trends in lSPR, but chemical deposition steps within the pores of commercial
systematically overestimates them. In contrast, naı̈vely polycarbonate filtration membranes (by Nucleopore) and
applying Mie theory to the same rods leads to systematic subsequently released. The nanoscopic pores are produced
underestimation of lSPR. by high-energy alpha-particle perforation of polycarbon-
Clearly, a more general approach to the prediction of ate films and are uniquely suited to the templating of
optical and electrostatic aspects of NPs and NP assemblies nanoparticles because they are highly uniform in diameter
is desirable. These approaches are generally in the form of and aspect ratio, the former controlled by the manufac-
computational solutions to Maxwell’s equations using fi- turer by etching the filtration membrane, and the latter by
nite-difference approaches. An excellent example of this variation of the electrodeposition time. In this case, the
approach is the work of Schatz et al.[16] on the discrete pores (and hence nanowires) have nominal dimensions of
dipole approximation (DDA), which divides the object of 15  7000 nm. As in the latter studies, the wires were
interest into a lattice of polarizable cubes whose individ- imaged with conventional light microscopy under dark
ual dipole polarizations are determined self-consistently. field illumination, and detected by virtue of their intense
According to Schatz et al., appropriately applied DDA light scattering cross sections. Spectra were acquired by
calculations yield extinction spectra that are consistently imaging scattered light onto a single monochromator with
within about 10% of the exact or experimental ones in- charge-couple device (CCD) detector.
dependent of the particle size or shape. Other approaches In wires, the plasma resonance observed is a transverse
include the multipole–multipole[26] and finite difference (radial), dipolar one. The longitudinal (axial) resonance is
time domain[27–29] variants. 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
NANOPARTICLES AND THEIR ASSEMBLIES gave an excellent fit to the observed Au and the feature-
less Ni spectra, but failed to capture the ca. 400 nm res-
The variety of NP shapes, sizes, architectures, and strat- onance for Ag.
egies for organizing and studying NPs inspires this sec- In a subsequent report by Mock et al.,[6] the response of
tion—hence it moves topically through a cross section of the dipole resonance to changes in refractive index for
the literature by the dimensionality of the NP assembly in single, 60-nm quasispherical particles was measured by
question. Other important themes such as LSPR coupling using a series of index matching oils. The observed
and multipolar LSPR modes span various dimensionalities DlMAX/Dn was 160 nm—in qualitative agreement with
and are noted throughout. Nanoparticles have been studied Mie calculations (210 nm) that ignore the SiO2 substrate
individually, in random 2- and 3-D arrangements and in half space.
lithographically organized assemblies or as determined by More recently, Raschke et al.[31] and McFarland and
molecular architectures. Various studies examine LSPR Van Duyne[32] have examined single nanoparticles
spectra as a function of particle size, shape, spacing, di- immobilized on glass in the context of their potential
electric medium, polarization, and incident angle of light. application as chemo- or biosensors with extremely low
mass detection limits. Single NP sensors are a tantalizing
Single Particles, Dimers, prospect because of the extreme mass sensitivity and
Trimers, and Tetramers spatial resolution of single NP LSPR. For example, just
60,000 molecules could be detected in a volume smaller
Single nanoparticle spectroscopy than a cellular organelle by single NP scattering, or con-
versely, a very large number of different assays might be
Recent spectroscopic reports of single noble metal NPs simultaneously conducted in a very small area and volume
characterizing roughly spherical and ‘‘wire’’ geometries with an assay based on many uniquely identifiable
with attention to their potential application as single-par- NPs.[33] In the report by McFarland and Van Duyne,[32]

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


dark field microscopy/spectroscopy was used to detect that put an E-field component along the particle–particle
alkanethiol adsorption to single Ag nanoparticles prepared axis. A subsequent paper by Gluodenis and Foss[36] delves
by citrate reduction. The bulk refractive index (RI) sen- into simulation and theory for side–side and end–end
sitivity of selected particles, DlMAX/Dn =203 nm, agreed interactions of NP rod pairs.
well with Mie theory predictions. The response to Subsequent reports by Rechberger et al.[37] and Su
monolayer alkanethiol adsorption was very large, with a et al.[38] examine ensembles and individual NP pairs (re-
hexadecanethiol self-assembled monolayer (SAM) pro- spectively) fabricated by using electron beam lithography.
ducing an easily detectable 40.7 nm red shift at saturation, Leitner et al. examined 150-nm disks, that were 17 nm
and corresponding to only ca. 60,000 molecules detected. thick and spaced between 150 and 450 nm apart; Zhang et
The similar report by Raschke et al.[31] employed Au NPs al. studied elliptical particles in the 100–150nm range.
derivatized with biotinylated bovine serum albumin and Zhang et al. report a red shift in lSPR as the particles are
binding diffusing streptavidin. They observed a signifi- brought into proximity. By examining polarizations both
cant, but small 1.2 nm shift corresponding to saturation— parallel and perpendicular to the interparticle axis, Leitner
again, just slightly less than that predicted by Mie theory et al. resolved a strong red shift (+ 78 nm) and a weaker
for a 4p stearadian change in RI. These authors suggest blue shift ( 30 nm) as the 150-nm particles were brought
that a rod NP would produce higher sensitivity. into edge contact. The red shift is attributed to favorable
head–tail interparticle electrostatic interactions arising
Nanoparticle dimers, trimers, and tetramers from parallel particle dipoles arranged end to end. The
weaker blue shift is attributable to particle dipoles ar-
A number of recent articles have examined the optical ranged side-by-side. Notably, these interactions did not
response of pairs, dimers, and trimers of NPs. In contrast produce band splitting observed for the smaller, chemi-
to the above studies, these systems were studied as cally synthesized NPs of Novak and Feldheim.[34]
ensembles, but the degree of particle homogeneity is high
and the results are likely to be representative of the 2-, 3-, Nanoparticle Chains with
or 4-particle systems. Novak and Feldheim[34] used rigid Near-Field Coupling
molecular linkers of variable lengths in the 2–30 nm range
to create bridged NP structures. The thioactyl-terminated Au and Ag NPs arranged in chains, i.e., in a row, are of
phenylacetylene bridges were prepared in three varieties; interest in the technological arena as ‘‘plasmonic light
the first, simply a straight rigid rod-like molecule, and the waveguides’’ for guiding light in subdiffraction spaces
second and third having a central branching point with and for the production of electron tunneling electronics
three and four branches, respectively. These were reacted such as single electron transistors. Chains have been
with 30-nm-diameter Ag NPs, and the resulting symmetric reported in two predominant contexts: 1) systems such as
dimers, trimers, and tetramers were confirmed with those fabricated by Atwater et al.[39–41] using electron
transmission electron microscopy. These important solu- beam lithography for plasmonic waveguide experiments;
tion-extinction spectroscopy experiments confirmed that and 2) smaller NPs templated by naturally faceted sur-
as the linker is shortened, the near-field coupling first faces of h1010i Al2O3[42] and h110i NaCl (Ref. [43], no
slightly red-shifts, and then spawns a high-frequency band optical data). Atwater et al. use sophisticated electron
as the separation approaches about 4 nm. beam lithography to make chains of 50-nm diameter Ag
A more recent paper by Sandrock and Foss[35] employs NPs with varying interparticle spacing. For these systems,
a template analogous to the NucleoporeTM ones employed the longitudinal (E-field parallel to NP chain) and trans-
above—transparent and porous Al2O3 membranes to verse SP modes slightly red and blue shift, respectively, as
produce varied pairs of NPs within the individual pores the interparticle spacing approaches 75 nm, but do not
and to study them in place, without releasing them from explore closer spacing. Atwater et al. are also one of the
the Al2O3 template. Au and Ag were alternately deposited few groups to employ finite difference time domain
and Ag later dissolved away to create controlled Au–Au (FDTD) simulations to simulate the optical responses of
spacing. In this way, sphere–sphere, rod–rod, and rod– these systems. One of the qualities of the FDTD simula-
sphere near-field interactions could be probed. An im- tion is that in addition to E(x,y,z), it gives E(t), which is
portant aspect of this motif is that it allows the study of the useful for characterizing the properties of NP chains
linear dichroic properties of the NP pairs. For example, as optical energy waveguides. FDTD simulations of the
because all pores in the Al2O3 support are normal to the E-field intensities in these chains agree well with experi-
surface, it is possible to control the polarization of the ments, and are useful for estimating collective properties
incident light such that it is predominantly axial or radial such as waveguide loss. The Al2O3 templated Ag NPs are
in character. Interparticle interactions were indicated by fabricated by pulsed laser deposition, followed by high-
spectral results that showed splitting under polarization temperature (1400°C, 8 hr) annealing, yielding slightly

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


prolate particles broadly distributed about 25 nm in dia- terestingly, the arrays exhibited a correlated oscillation in
meter and about 31 nm apart. These chains exhibit a far lSPR and luminescence lifetime (2 tSPR 8 fsec), as the
more pronounced dichroism than those of Atwater et al.: particle spacing increased. Specifically, they observed a S
lTRANSVERSE = 455 nm and lLONGITUDINAL =550 nm, strong (60 nm) redshift and broadening of the LSPR band
reflecting both the smaller particle sizes (ca. 25 nm) and for L values corresponding first to lSPR/nSUBSTRATE, and
their closer proximity (ca. 31 nm). Theoretical work by then to lSPR. This effect, called the ‘‘grating’’ effect,
Zhao et al.[44] has also contributed to understanding of evidently reflects the increased radiative fields existing
chains structures. between particles as the particle spacing produces con-
Previous examples have been of 1-D NP chains, but structive interparticle interference first in the substrate
individual NP pairs have also been examined. For exam- (where the effective radiated wavelength is l/n), and then
ple, Sandrock and Foss made gold particle pairs by al- in the airspace above the gradient.
ternately electrodepositing Au and Ag into porous Al2O3. In the latter work, Aussenegg et al. reported studies of
In this setting, the electrodeposition time controls the Au EBL-fabricated Ag nanowires (wire widths 60 w 200
and Ag NP lengths, and the pore their widths. Following nm) and nanowire gratings (spacing 290 d 680 nm)
electrodeposition, Ag sections can be removed with with extinction spectroscopy.[46] Similarly to NP chains,
HNO3, leaving voids of controlled size between Au NPs Ag nanowires exhibit strong LSPR bands under transverse
of controlled length.[35] Accordingly, paired ‘‘spheres’’ magnetic (TM) irradiation—i.e., when the E-field is po-
(i.e., unity aspect ratio rods), paired rods, and rod–sphere larized perpendicularly to the long axis of the wire. For
pairs were studied. For these organized NP pairs, the individual wires, lSPR was found to be linearly dependent
effects of interparticle spacing and the light polarization on wire width, w, between 65 and 90 nm. For wire grat-
and incident angle could be systematically studied. At ings, they similarly find lSPR to be a sensitive function of
higher angle of incidence (yi), the light E-field falls in- spacing, L. lSPR redshifts and broadens when L ap-
creasingly along the interparticle axis. For example, for proaches lSPR/nSUBSTRATE, corresponding to a transition
large interparticle spacing (114 nm) between paired between evanescent and radiative character for the light
spheres, lSPR (= 548 nm) is independent of yi. However, if field in the substrate half space. This type of effect also
a smaller interparticle spacing is employed (52 nm), lSPR appears in recent computations by Zhao et al.,[16] who
redshifts with an increasing in incidence angle reflect- simulated LSPR for arrays of period L equal to and
ing the favorable near-field coupling of LSPR dipoles. greater than the particle size.
Rod–sphere pair structures exhibited a long-wavelength Haynes et al.[47] have also used EBL to produce silver
shoulder with increasing yi, similarly indicating near-field and gold particle arrays. The arrays comprise triangular
interactions. Theoretical models used to evaluate sphere (170 nm) and circular (200 nm) particles (trigonal prisms
pair systems such as simple quasistatic (i.e., total particle and cylinders considering their 35 nm height) in both
pair size
l), modified long wavelength approximation square and hexagonal lattices of variable spacing between
(MLWA), and discrete dipole approximation (DDA) 230 and 500 nm—smaller distances relative to lSPR when
models reflected experimental shifts in lSPR with yi, but compared to the studies by Schider et al.,[45,46] but still
did not accurately reproduce peak position or shape. interacting predominantly in the far field. Van Duyne and
Schatz observe a linear red shift with increasing lattice
Two-Dimensional NP Arrays constant (ca. 40 optical nm per 100 nm) that is supported
qualitatively by coupled dipole simulations. Theoretical
A rich variety of structures, some highly organized, for calculations used by Zhao and coworkers[44] on particle
example, by intermolecular interactions, have been re- pairs also support far-field interparticle coupling effects
ported for NPs on surfaces. Also, some of the more in- seen for large lattice spacing.
triguing spectral behaviors come from 2-D arrays of
optically coupled NPs. Two-dimensional NP arrays made by
nanosphere lithography (NSL)
Two-dimensional NP arrays made by electron
beam lithography (EBL) Van Duyne and coworkers have performed a large body of
work using an NP fabrication method they had developed
Aussenegg et al.[45,46] have contributed important papers and dubbed ‘‘nanosphere lithography’’ (NSL). In NSL, a
on the optical properties of NP arrays in the far-field substrate is coated with hexagonally close-packed mono-
coupling regime. The former report employs square arrays layer of highly monodisperse polymer nanospheres by a
(spacing L = 350–850 nm) of circular (d= 150 nm) gold simple drop casting procedure. The nanosphere coating, in
EBL-fabricated NPs studied by both extinction and fem- turn, serves as a mask for the evaporation of Ag or Au into
tosecond time resolved luminescence measurements. In- the interstitial hollows where substrate surface is exposed.

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


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-
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
Fig. 1 AFM image of a Ag nanoparticle array created by na- well described by a simple oblate spheroid theory,[53] and
nosphere lithography. Reprinted with permission from Ref. [3]. showed the expected red shift in lSPR with increasing
Copyright 2003 American Chemical Society. particle size and ambient dielectric.

Metal evaporation at normal (or other) incidence, followed Spontaneously organized 2-D
by rinsing away the nanosphere mask, thus produces well- nanoparticle assemblies
ordered 2-D arrays of triangular metal nanoprisms (or
variations thereof) (Fig. 1).[3] Nanospheres are commer- The process of 2-D NP self-assembly has been recently
cially available in a wide range of sizes, corresponding to reviewed in the context of microelectronics.[54]
a range of NP sizes that exhibit lSPR spanning the entire In many examples in this category, NPs are modified
visible, near, and mid infrared spectral regions (Fig. 2). with molecular adsorbates that, in turn, guide the NPs into
The NP shape can also be altered by evaporating through organized, closely packed assemblies. For example, Tripp
the nanosphere mask at variable angles—called angle- and Wei employ an alkane-tailed and ‘‘cup-shaped’’
resolved nanosphere lithography (AR-NSL).[48] By se- resorcinarene tetrathiol to decorate 16–170 nm Au NPs.
quentially depositing at different angles, AR-NSL can be The ligand shell and its alkane tails have a very strong
used to fabricate structures such as ‘‘nanooverlaps,’’ organizing effect leading to hexagonally packed NP arrays
‘‘nanogaps,’’ and NP chains. Van Duyne et al. have on the air–water interface that can be transferred to quartz
employed NSL–NP arrays in numerous studies focusing substrates.[55] Kanehara et al.[56] find similar results for
on NP size, dielectric environment,[3] adsorbate binding an amine-terminated disulfide surfactant. In this case, a
(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 Fig. 2 Size dependence of the LSPR spectra of Ag NP’s
fabricated using nanosphere lithography. The dimension ‘‘a’’
Hanarp et al.[52] report a related ‘‘lithographic’’ prepara- refers to the NP diameter (for disk particles) or base–apex length
tion yielding disordered arrays of nearly identical nano- (for triangular ones). Dimension ‘‘b’’ refers to the NP height.
disks. As with NSL, this preparation begins with an Reprinted with permission from Ref. [3]. Copyright 2003
adsorbed layer of monodisperse polymer nanospheres. American Chemical Society.

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-
Fig. 3 LSPR spectrum of a closely spaced 100-nm Ag ticle spacing simply by stretching the substrate. Fig. 3
nanoparticle array on a silicone elastomer support. The shows the resulting normal incidence transmission spec-
collective nature of the sharp band at 420 nm is evident in its trum and the strong dependence of the sharp, high-fre-
hypersensitivity to interparticle spacing. The band at 420 nm quency band on interparticle separation. The mode
disappears as the elastomer is stretched and interparticle spacing
disappears as the elastomer is stretched, presumably be-
decreases (as indicated by the arrow). Reprinted with permission
from Ref. [64]. Copyright 2003 American Chemical Society.
cause this spoils the near-field coupling. In contrast to
(View this art in color at www.dekker.com.) 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
carboxylic acid adjuvant helps to organize solvent cast
plasmon mode illustrated in Fig. 4. Chumanov argues that,
NP films.
for strong coherent interparticle coupling, the quadrupole
Stabilized (if not necessarily highly organized) NP as-
mode has a more favorable symmetry because all inter-
semblies on surfaces have also been made using bidentate
particle forces are equivalent. In other words, neighboring
ligands—one end of which has affinity for the NP and the
particles experience either repulsive (as in Fig. 4b), or
other end for the surface of the support. For example, an
attractive (as in Fig. 4c) forces. In contrast, the dipolar
amino-terminated alkylsilane monolayer on glass will bind
excitation of Fig. 4a leads to some attractive interactions
mercaptopropionic acid coated NPs by forming covalent
(head–tail) and some repulsive ones (side-by-side).
(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.
Fig. 4 Proposed in-plane dipolar and quadrupolar LSPR
modes. Interparticle dipolar interactions in a are inequivalent
Coupled LSPR in 2-D nanoparticle assemblies (some dipoles are arranged head–tail and others are side-by-
side), but interparticle forces for quadrupolar modes in b and c
Near-field LSPR coupling is evident in some spontane- are all equivalent. Reprinted with permission from Ref. [64].
ously organized NP assemblies. This coupling manifests Copyright 2003 American Chemical Society. (View this art in
in a band splitting that is sensitive to polarization, angle, color at www.dekker.com.)

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


Three-Dimensional Assemblies has been exploited for colorimetric sensing of specific
of Nanoparticles oligonucleotides in solution.[67] In this motif, a given
target ssDNA strand is detected by a pair of ssDNA
A comprehensive discussion of the variety and properties derivatized Au NPs, each NP complimentary to the op-
of three-dimensional (3-D) NP assemblies is far beyond posite half of the target ssDNA. When the target strand is
the scope of this review. Instead, we present a brief cross hybridized by both NPs, a large red shift and broadening
section of studies that touch on some important aspects of in the NP LSPR band occurs as a result of near-field
3-D NP assemblies. However, one fairly general obser- coupling. This changes the NP solution from an intense
vation is that LSPR bands tend to broaden and red shift red to a faint purple. Because of the enormous extinction
when the component NPs aggregate, or are assembled into coefficient of the NPs, a target as small as 50 pm could be
a lattice.[65] detected with this simple colorimetric test. Other studies
of DNA-linked assemblies are cited in Refs. [68,69].
DNA linked 3-D assemblies
Dithiol 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- Brust et a.[70] have used dithiol linkers to assemble NP
semblies of NPs. For example, Taton et al.[66] use a films in a controlled layer-by-layer fashion. The oxide
strategy for controlled NP film growth wherein a substrate substrate was first derivatized with 3-mercaptotriethoxy-
surface and NP’s ‘‘a’’ and ‘‘b’’ are derivatized with dif- silane, so that it would present the –SH moiety to solution
ferent, noncomplementary ssDNA oligomers, illustrated and bind bare Au, ca. 6 nm NPs from solution. Then, this
in Fig. 5. Adding ssDNA oligomers that are the comple- NP-coated surface was rinsed and treated with an a-o
mentary, on opposite ends, to the surface and to NP-a will dithiol that, in turn, leaves the NP-coated surface pre-
make a monolayer of NP-a. Further aggregation will not senting the –SH moiety as a basis for further assembly.
take place because the linker ssDNA does not connect Assembly induced considerable broadening and red
‘‘a’’ to ‘‘a’’ or ‘‘a’’ to ‘‘b.’’ Rinsing and subsequent shifting in the NP LSPR, but this did not increase after the
treatment with an ‘‘a’’–‘‘b’’ linker will add a layer of NP- first few layers.
b, etc. In addition to 3-D NP architectures, this strategy
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
Fig. 5 Controlled NP aggregate (A) and film (B) growth using film.[10] Similarly, sol–gel methods can be used to prepare
‘‘bidentate’’ single stranded DNA linkers. Linkers are specific Au/BaTiO3 and other thin film nanocomposites.[72] In
to either (SiO2)–a, or a–b. From Ref. [66]. D American Chem- particular, nanocomposite films appear to be of interest
ical Society, 2003. for nonlinear optical applications due in part to the large

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


third-order nonlinear susceptibility lent to these materials 3. Haynes, C.L.; Van Duyne, R.P. Nanosphere lithog-
by the LSPR active NPs.[73] Similarly, nanocomposites raphy: A versatile nanofabrication tool for studies of
are of interest for their potential applications to electronics size-dependent nanoparticle optics. J. Phys. Chem., S
and as sensors.[74,75] Al-Rawashdeh et al.[23,76] have pre- B 2001, 105, 5599 – 5611, (review).
pared ordered polyethylene–Au nanorod composites. The 4. Jensen, T.R.; Malinsky, M.D.; Haynes, C.L.; Van
plastic polyethylene matrix provided a means for shear Duyne, R.P. Nanosphere lithography: Tunable local-
orientation of the nanorods, which, in turn, lend dichroic ized surface plasmon resonance spectra of silver
optical properties to the material. nanoparticles. J. Phys. Chem., B 2000, 104, 10549 –
10556.
5. Yguerabide, J.; Yguerabide, E.E. Light-scattering
submicroscopic particles as highly fluorescent
CONCLUSION
analogs and their use as tracer labels in clinical
and biological applications: II. Experimental char-
The localized surface plasmon spectra of silver and gold
acterization. Anal. Biochem. 1998, 262, 157– 176.
nanoparticles are interesting in a number of contexts.
6. Mock, J.R.; Smith, D.R.; Shultz, S. Local refractive
Spherical NP LSPR spectra are often in good agreement
index dependence of plasmon resonance spectra
with theory-given adjustments to the metal dielectric
from individual nanoparticles. Nano Lett. 2003, 3
function for NPs comparable to, or smaller than, the
(4), 485 – 491.
electron mean free path. However, calculation of the
7. Kreibig, U.; Vollmer, M. Optical Properties of Metal
LSPR spectra of nonspherical shapes are still quite chal-
Clusters; Springer-Verlag: New York, 1995; Vol. 25.
lenging because exact electrodynamic solutions such as
8. Riboh, J.C.; Haes, A.J.; McFarland, A.D.; Yonzon,
the Mie theory do not exist, and finite difference simu-
C.R.; Van Duyne, R.P. A nanoscale optical biosen-
lations, while sometimes quite successful, are far from
sor: Real-time immunoassay in physiological buffer
routine calculations. However, a recently reported ap-
enabled by improved nanoparticle adhesion. J. Phys.
proach based on hybridization of the LSPR modes of more
Chem., B 2003, 107, 1772 – 1780.
elementary shapes that, in combination, describe others is
9. Haynes, C.L.; Van Duyne, R.P. Plasmon-sampled
quite promising.
surface-enhanced Raman excitation spectroscopy. J.
Basic LSPR spectroscopic phenomena have been the
Phys. Chem., B 2003, 107, 7426– 7433.
subject of many recent articles. Examples include the
10. Yang, G.; Wang, W.; Zhou, Y.; Lu, H.; Yang, G.;
observation of multiple LSPR bands for a given NP based
Chen, Z. Linear and nonlinear optical properties of
on electronic polarization along the different principle
Ag nanocluster/BaTiO3 composite films. Appl.
axes of the NP, or sometimes for higher-order polariza-
Phys. Lett. 2002, 81 (21), 3969 – 3971.
tions in particles with sizes comparable to or greater than
11. Liao, H.B.; Wen, W.; Wong, G.K.L. Preparation and
l. Films of NPs often exhibit optical dichroism because of
optical characterization of Au/SiO2 composite films
electromagnetic interactions between particles, or, in the
with multilayer structure. J. Appl. Phys. 2003, 93
case of oriented NPs, because of the optical anisotropy of
(8), 4485 –4488.
the particles themselves.
12. Link, S.; El-Sayed, M.A. Spectral properties and
NP LSPR spectroscopy has potential application in
relaxation dynamics of surface plasmon electronic
numerous technological areas such as subdiffraction light
oscillations in gold and silver nanodots and
guiding, nonlinear optical applications, Raman enhance-
nanorods. J. Phys. Chem., B 1999, 103, 8410 –8426.
ment, and chemical sensing. Sensing applications are
13. Hovel, H.; Fritz, S.; Hilger, A.; Kreibig, U.;
quite promising given the popularity of the related metal
Vollmer, M. Width of cluster plasmon resonances:
film reflection based surface plasmon sensors. NP sensing
Bulk dielectric functions and chemical interface
can, in theory, detect as few as 60,000 molecules in a
damping. Phys. Rev., B 1993, 48, 18178– 18188.
volume far smaller than a typical cell.
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.
REFERENCES Phys. Chem., B 1997, 101, 3706 – 3712.
15. Ung, T.; Liz-Marzan, L.M.; Mulvaney, P. Gold
1. Mie, G. Contributions to the optics of turbid media, nanoparticle thin films. Colloids Surf., A 2002, 202,
especially colloidal metal solutions. Ann. Phys. 119 – 126.
1908, 25, 377– 445. 16. Zhao, L.L.; Kelly, K.L.; Schatz, G.C. The extinction
2. Ostwald, W. Theoretical and Applied Colloid spectra of silver nanoparticle arrays: Influence of
Chemistry; Wiley: New York, 1992; 200. array structure on plasmon resonance wavelength

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


and width. J. Phys. Chem., B. 2003, 107, 7343 – particle chain waveguides of different lengths:
7350. Estimation of waveguide loss. Appl. Phys. Lett.
17. Kelly, K.L.; Coronado, E.; Zhao, L.L.; Schatz, G.C. 2002, 81 (9), 1714 – 1716.
The optical properties of metal nanoparticles: The 30. Mock, J.J.; Oldenburg, J.S.; Smith, D.R.; Schultz,
influence of size, shape, and dielectric environment. D.A.; Shultz, S. Composite plasmon resonant
J. Phys. Chem., B 2003, 107, 668 –677. nanowires. Nano Lett. 2002, 2 (5), 465 –469.
18. Bohren, C.F.; Huffman, D.R. Absorption and 31. Raschke, G.; Kowarik, S.; Franzl, T.; Sonnichsen,
Scattering of Light by Small Particles; Wiley: C.; Klar, T.A.; Feldmann, J. Biomolecular recogni-
New York, 1983. tion based on single gold nanoparticle light scat-
19. Al-Rawashdeh, N.A.F.; Sandrock, M.L.; Seugling, tering. Nano Lett. 2003, 3 (7), 935 –938.
C.J.; Foss, C.A. Visible region polarization spectro- 32. McFarland, A.D.; Van Duyne, R.P. Single silver
scopic studies of template-synthesized gold nano- nanoparticles as real-time optical sensors with
particles oriented in polyethylene. J. Phys. Chem., B zeptomole sensitivity. Nano Lett. 2003, 3 (8),
1998, 102, 361 – 371. 1057– 1062.
20. Hornyak, G.L.; Patrissi, C.J.; Martin, C.R. Fabrica- 33. Nicewarner-Pena, S.R.; Freeman, G.R.; Reiss, B.D.;
tion, characterization, and optical properties of gold He, L.; Pena, D.J.; Walton, I.D.; Cromer, R.;
nanoparticle/porous alumina composites: The non- Keating, C.D.; Natan, M.J. Submicrometer metallic
scattering Maxwell–Garnett limit. J. Phys. Chem., B barcodes. Science 2001, 294, 137 –141.
1997, 101, 1548– 1555. 34. Novak, J.P.; Feldheim, D.L. Assembly of phenyl-
21. Prodan, E.; Radloff, C.; Halas, N.J.; Nordlander, P. acetylene-bridged silver and gold nanoparticle
A hybridization model for the plasmon response of arrays. J. Am. Chem. Soc. 2000, 122, 3979 –3980.
complex nanostructures. Science 2003, 302, 419 – 35. Sandrock, M.L.; Foss, C.A., Jr. Synthesis and linear
422. optical properties of nanoscopic gold particle pair
22. Prodan, E.; Nordlander, P. Structural tunability of structures. J. Phys. Chem., B 1999, 103, 11398 –
the plasmon resonances in metallic nanoshells. Nano 11406.
Lett. 2003, 3, 543 –547. 36. Gluodenis, M.; Foss, C.A. The effect of mutual
23. Al-Rawashdeh, N.A.F.; Sandrock, M.L.; Seugling, orientation on the spectra of metal nanoparticle rod–
C.J.; Foss, C.A., Jr. Visible region polarization rod and rod–sphere pairs. J. Phys. Chem., B 2002,
spectroscopic studies of template-synthesized gold 106, 9484 –9489.
nanoparticles oriented in polyethylene. J. Phys. 37. Rechberger, W.; Hohenau, A.; Leitner, A.; Krenn,
Chem., B 1998, 102, 361– 371. J.R.; Lamprecht, B.; Aussenegg, F.R. Optical
24. Mulvaney, P. Surface plasmon spectroscopy of properties of two interacting gold nanoparticles.
nanosized metal particles. Langmuir 1996, 12, Opt. Commun. 2003, 220, 137 –141.
788 – 800. 38. Su, H.-H.; Wei, Q.-H.; Zhang, X.; Mock, J.J.;
25. Foss, C.A.; Hornyak, G.L.; Stockert, J.A.; Martin, Xmith, D.R.; Sjultz, S. Interparticle coupling effects
C.R. Template synthesized nanoscopic gold parti- on plasmon resonances of nanogold particles. Nano.
cles: Optical spectra and the effects of particle size Lett. 2003, 3 (8), 1087 –1090.
and shape. J. Phys. Chem. 1994, 98, 2963. 39. Maier, S.A.; Brongersma, M.L.; Kik, P.G.; Atwater,
26. Moreno, E.; Ermi, D.; Hafner, C.; Vahldieck, R. H.A. Observation of near-field coupling in metal
Multiple multipole method with automatic multipole nanoparticle chains using far-field polarization
setting applied to the simulation of surface plasmons spectroscopy. Phys. Rev., B 2002, 65, 193408-1-4.
in metallic nanostructures. J. Opt. Coc., A. 2002, 19, 40. Maier, S.A.; Brongersma, M.L.; Kik, P.G.; Meltzer,
101– 111. S.; Requicha, A.A.G.; Atwater, H.A. Plasmonics—
27. Krenn, J.R.; Schider, G.; Rechberger, W.; Lam- A route to nanoscale optical devices. Adv. Mater.
precht, B.; Leitner, A.; Aussenegg, F.R.; Weeber, 2001, 13 (19), 1501 – 1505.
J.C. Design of multipolar plasmon excitations in 41. Maier, S.A.; Kik, P.G.; Atwater, H.A. Observation
silver nanoparticles. Appl. Phys. Lett. 2000, 77 (21), of coupled plasmon-polariton modes in Au nano-
3379 – 3381. particle chain waveguides of different lengths:
28. Taflove, A. Computational Electrodynamics: The Estimation of waveguide loss. Appl. Phys. Lett.
Finite-Difference Time-Domain Method; Artech 2002, 81 (9), 1714 – 1716.
House: Boston, 1995; 599. 42. Fort, E.; Ricolleau, C.; Sau-Pueyo, J. Dichroic thin
29. Maier, S.A.; Kik, P.G.; Atwater, H.A. Observation films of silver nanoparticle chain arrays on facetted
of coupled plasmon-polariton modes in Au nano- alumina templates. Nano Lett. 2003, 3, 65 –67.

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


43. Teranishi, T.; Sugawara, A.; Shimizu, T.; Miyake, 55. Kim, B.; Tripp, S.L.; Wei, A. Self-organization of
M. Planar array of 1D gold nanoparticles on ridge- large gold nanoparticle arrays. J. Am. Chem. Soc.
and-valley structured carbon. J. Am. Chem. Soc. 2001, 123, 7955 –7956. S
2002, 124, 4210 – 4211. 56. Kanehara, M.; Oumi, Y.; Sano, T.; Teranishi, T.
44. Zhao, L.K.; Kelly, L.; Schatz, G.C. The extinction Formation of low symmetric 2D superlattices of
spectra of silver nanoparticle arrays: Influence of gold nanoparticles through surface modification by
array structure on plasmon resonance wavelength acid–base interaction. J. Am. Chem. Soc. 2003, 125,
and width. J. Phys. Chem., B 2003, 107, 7343 –7350. 8708 – 8709.
45. Lamprecht, B.; Schider, G.; Lechner, R.T.; Ditlba- 57. Nath, N.; Chilkoti, A. A colorimetric gold nanopar-
cher, H.; Krenn, J.R.; Leitner, A.; Aussenegg, F.R. ticle sensor to interrogate biomolecular interactions in
Metal nanoparticle gratings: Influence of dipolar real time. Anal. Chem. 2002, 74, 504– 509.
particle interaction on the plamon resonance. Phys. 58. Hutter, E.H.; Fendler, J.H.; Roy, D. Surface plasmon
Rev. Lett. 2000, 84, 4721 –4724. resonance studies of gold and silver nanoparticles
46. Schider, G.; Krenn, J.R.; Gotschy, W.; Lamprecht, linked to gold and silver substrates by 2-aminoeth-
B.; Ditlbacher, H.; Leitner, A.; Aussenegg, F.R. anethiol and 1,6-hexanedithiol. J. Phys. Chem., B
Optical properties of Ag and Au nanowire gratings. 2001, 105, 11159 –11168.
J. Appl. Phys. 2001, 90, 3825 –3830. 59. He, L.; Musick, M.D.; Nicewarner, S.R.; Salinas,
47. Haynes, C.L.; McFarland, A.D.; Zhao, L.; Van F.G.; Benkovic, S.J.; Natan, M.J.; Keating, C.D.
Duyne, R.P.; Schatz, G.C.; Gunnarsson, L.; Prikulis, Colloidal Au-enhanced surface plasmon resonance
J.; Kasemo, B.; Kall, M. Nanoparticle optics: The for ultrasensitive detection of DNA hybridization.
importance of radiative dipole coupling in two- J. Am. Chem. Soc. 2000, 122, 9071 – 9077.
dimensional nanoparticle arrays. J. Phys. Chem., B 60. Hutter, E.; Pileni, M.-P. Detection of DNA hybrid-
2003, 107, 7337 – 7342. ization by gold nanoparticle enhanced transmission
48. Haynes, C.L.; Van Duyne, R.P. Dichroic optical surface plasmon resonance spectroscopy. J. Phys.
properties of extended nanostructures fabricated Chem., B 2003, 107, 6497 – 6499.
using angle-resolved nanosphere lithography. Nano 61. Royer, P.; Goudonnet, J.P.; Warmack, R.J.; Ferrell,
Lett. 2003, 3, 939 –943. T.L. Substrate effects on surface-plasmon spectra in
49. Malinsky, M.D.; Kelly, K.L.; Schatz, G.C.; Van metal-island films. Phys. Rev., B 1987, 35, 3753.
Duyne, R.P. Nanosphere lithography: Effect of 62. Kennerly, S.W.; Little, J.W.; Warmack, R.J.;
substrate on the localized surface plasmon reso- Ferrell, T.L. Optical properties of heated Ag films.
nance spectrum of silver nanoparticles. J. Phys. Phys. Rev., B 1984, 29, 2926.
Chem., B 2001, 105, 2343 – 2350. 63. Taleb, A.; Russier, V.; Courty, A.; Pileni, M.P.
50. Jensen, T.R.; Duval, M.L.; Kelly, K.L.; Lazarides, Collective optical properties of silver nanoparticles
A.A.; Schatz, G.C.; Van Duyne, R.P. Nanosphere organized in two-dimensional superlattices. Phys.
lithography: Effect of the external dielectric medi- Rev., B 1999, 59, 13350 –13358.
um on the surface plasmon resonance spectrum of a 64. Malynych, S.; Chumanov, G. Light-induced coher-
periodic array of silver nanoparticles. J. Phys. ent interactions between silver nanoparticles in two-
Chem., B 1999, 103, 9846 – 9853. dimensional arrays. J. Am. Chem. Soc. 2003, 125,
51. Malinsky, M.D.; Kelly, K.L.; Schatz, G.C.; Van 2896 – 2898.
Duyne, R.P. Chain length dependence and sensing 65. Taleb, A.; Petit, C.; Pileni, M.P. Optical properties
capabilities of the localized surface plasmon reso- of self-assembled 2D and 3D superlattices of silver
nance of silver nanoparticles chemically modified nanoparticles. J. Phys. Chem., B 1998, 102, 2214 –
with alkanethiol self-assembled monolayers. J. Am. 2220.
Chem. Soc. 2001, 123, 1471– 1482. 66. Taton, T.A.; Mucic, R.C.; Mirkin, C.A.; Letsinger,
52. Hanarp, P.; Kall, M.; Sutherland, D.S. Optical R.L. The DNA-mediated formation of supra-
properties of short range ordered arrays of nanome- molecular mono- and multilayered nanoparticle
ter gold disks prepared by colloidal lithography. J. structures. J. Am. Chem. Soc. 2000, 122, 6305 –
Phys. Chem., B 2003, 107, 5768 – 5772. 6306.
53. Bohren, C.F.; Huffman, D.R. Absorption and 67. Reynolds, R.A., III; Mirkin, C.A.; Letsinger, R.L.
Scattering of Light by Small Particles; John Wiley Homogeneous, nanoparticle-based quantitative col-
& Sons: New York, 1983. orimetric detection of oligonucleotides. J. Am.
54. Fendler, J.H. Chemical self-assembly for electronic Chem. Soc. 2000, 122, 3795 – 3796.
applications. Chem. Mater. 2001, 13, 3196 – 3210. 68. Lazarides, A.A.; Schatz, G.C. DNA-linked metal

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.


nanosphere materials: Structural basis for the thin films dispersed with Au nanoparticles. Mater.
optical properties. J. Phys. Chem., B 2000, 104, Lett. 2002, 56, 1048 –1052.
460– 467. 73. Hache, F.; Flytzanis, R.C. Optical nonlinearities of
69. Storhoff, J.J.; Lazarides, A.A.; Mucic, R.C.; Mirkin, small metal particles: Surface-mediated resonance
C.A.; Letsinger, R.L.; Schatz, G.C. What controls and quantum size effects. J. Opt. Soc. Am., B 1986,
the optical properties of DNA-linked gold nanopar- 3 (12), 1647 –1655.
ticle assemblies? J. Am. Chem. Soc. 2000, 122, 74. Feldheim, D.L.; Keating, C.D. Self-assembly of
4640 – 4650. single electron transistors and related devices.
70. Brust, M.; Bethell, D.; Kiely, C.J.; Schiffrin, D.J. Chem. Soc. Rev. 1998, 27, 1 –12.
Self-assembled gold nanoparticle thin films with 75. Shipway, A.N.; Willner, I. Nanoparticles as struc-
nonmetallic optical and electronic properties. Lang- tural and functional units in surface-confined
muir 1998, 14, 5425 – 5429. architectures. Chem. Commun. 2001, 20, 2035 –
71. Mulvaney, P.; Liz-Marzan, L.M.; Giersig, M.; Ung, 2045.
T. Silica encapsulation of quantum dots and metal 76. Al-Rawashdeh, N.; Foss, C.A., Jr. UV/visible and in-
clusters. J. Mater. Chem. 2000, 10, 1259– 1270. frared spectra of polyethylene/nanoscopic gold rod
72. Yang, Y.; Shi, J.; Huang, W.; Dai, S.; Wang, L. composite films: Effects of gold particle size, shape
Preparation and optical properties of barium titanate and orientation. Nanostruct. Mater. 1997, 9, 383 –386.

Copyright © 2004 by Marcel Dekker, Inc. All rights reserved.