Exploitation of Localized Surface Plasmon

Resonance**
By Eliza Hutter and Janos H. Fendler*
1. Introduction
Localized surface plasmons (LSPs) are charge density oscil-
lations confined to metallic nanoparticles (sometimes referred
to as metal clusters) and metallic nanostructures (Fig. 1).
[1]
Excitation of LSPs by an electric field (light) at an incident
wavelength where resonance occurs (Fig. 1) results in strong
light scattering, in the appearance of intense surface plasmon
(SP) absorption bands, and an enhancement of the local elec-
tromagnetic fields. The frequency (i.e., absorption maxima or
color) and intensity of the SP absorption bands are character-
istic of the type of material (typically, gold, silver, or plati-
num), and are highly sensitive to the size, size distribution,
and shape of the nanostructures, as well as to the environ-
ments which surround them.
[2,3]
These are the precise proper-
ties which have prompted the ongoing intense interest in LSPs
and fueled the construction of LSP-based sensors and devices
in ever increasing variety.
The intense red color of aqueous dispersions of colloidal
gold particles is, of course, a manifestation of localized surface
plasmon resonance. Colloidal gold has fascinated people for
centuries. It provided color for medieval cathedral windows
and until the eighteenth century was believed to have life-
prolonging and rejuvenating benefits if taken internally as
aurum potabilis.
[4]
In our times, there has been an exponential
growth in the exploitation of colloidal gold for biological
labels, markers, and stains for various microscopies.
[5]
More
recently, metallic nanoparticles and nanostructures have been
fruitfully employed as molecular-recognition elements and
amplifiers in sensors and biosensors, in addition to serving as
components in nanoscale optical devices.
[6]
It is these more
recent and significant developments which will be detailed in
the present review.
R
E
V
I
E
W
Adv. Mater. 2004, 16, No. 19, October 4 DOI: 10.1002/adma.200400271 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1685
Recent advances inthe exploitationof localizedsurface plasmons (charge
density oscillations confined to metallic nanoparticles and nanostruc-
tures) in nanoscale optics and photonics, as well as in the construction of sensors and biosensors,
are reviewed here. In particular, subsequent to brief surveys of the most-commonly used methods
of preparation and arraying of materials with localized surface plasmon resonance (LSPR), and
of the optical manifestations of LSPR, attention will be focused on the exploitation of metallic
nanostructures as waveguides; as optical transmission, information storage, and nanophotonic
devices; as switches; as resonant light scatterers (employed in the different near-field scanning
optical microscopies); and finally as sensors and biosensors.

[*] Prof. J. H. Fendler, Dr. E. Hutter,

Department of Chemistry and Center for Advanced Materials
Processing
Clarkson University, Potsdam, NY 13699 (USA)
E-mail: fendler@clarkson.edu
[**] We thank the US National Science Foundation (E. H. Grant No.
INT-0206923) and the Department of Energy (JHF) for their finan-
cial support.
Figure 1. Top: Schematics for plasmon oscillation for a sphere, showing
the displacement of the conduction electron charge cloud relative to the
nuclei. Reproduced, with permission, from reference [106]; copyright
2003, the American Chemical Society. Bottom: Field lines of the Poynting
vector (excluding that scattered) around a small aluminum sphere illumi-
nated by light of energy 8.8 eV where resonance occurs (left hand side)
and 5 eV where there is no resonance (right hand side). Reproduced with
permission from [109].
Following brief surveys of the most commonly used current
methods of preparation and arraying materials with localized
surface plasmon resonance (Sec. 2), and of the optical mani-
festations of localized surface plasmon resonance (Sec. 3) we
shall discuss recent advances in the construction of nanoscale
optics and photonics and the exploitation of metallic nano-
structures as waveguides, switches, superlenses, information
storage devices, and as resonant light scatterers in the differ-
ent near-field scanning optical microscopies, NSOMs (Sec. 4).
Finally, we shall summarize the use of metallic nanoparticles
and nanostructures as sensors and biosensors (Sec. 5). We
shall not cover the vast area of propagating surface plasmons,
PSPs, usually referred to as just surface plasmons, SP (i.e., the
longitudinal charge density oscillations at a flat 40200 nm-
thick metal film, typically gold or silver, deposited onto a
dielectric such as glass) and their applications in surface plas-
mon resonance, SPR, spectroscopy. There are several recent
reviews which cover these topics.
[79]
Attention in this review
is focused on LSPs as manifested by isolated, coupled, and
arrayed metallic nanoparticles and nanostructures. We shall,
however, summarize the beneficial amplification of SPR sig-
nals by LSPs.
2. Preparation and Arraying of Materials
with Localized Surface Plasmon Resonance
As the title of this section indicates, we consider in our
review all materials that, upon suitable excitation, demon-
strate localized surface plasmon resonance. Accordingly, we
shall survey the recent advances in the preparation and stabi-
lization of metallic nanoparticles by colloid chemical methods
(Sec. 2.1); fabrication of ultrathin metallic nanoislands by vac-
uum evaporation; lithographically nanopatterned structures,
including the arraying of nanoparticles and the construction
of periodic particle arrays, PPAs (Sec. 2.2); and nanostruc-
tures prepared by laser ablation (Sec. 2.3) and electrodeposi-
tion (Sec. 2.4).
2.1. Recent Advances in the Colloid Chemical Preparations
of Metallic Nanoparticles
Traditionally, metallic nanoparticles are prepared by the
controlled precipitation and concurrent stabilization of the
incipient colloids.
[10,11]
In homogeneous solution this is accom-
plished by the judicious adjustment of the precipitating condi-
tions (type, concentration, order and rate of additions of the
reagents and stabilizers, temperature, and solvent). The ap-
proach is illustrated by the classical synthesis of 12 nm diame-
ter gold nanoparticles by the sodium citrate reduction of gold
chloride in an aqueous solution.
[12]
The nanoparticles formed
are coated by negatively charged electrical double layers
(composed of bulky citrate ions, chloride ions, and the cations
attracted to them) which provide required stabilization.
Recipes for the preparation of colloidal gold nanoparticles in
diameters ranging from 0.82 nm to 64 nm are provided by
Handley.
[13]
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1686 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Eliza Hutter was bornandraisedinHungary. She obtainedanMDdegree at the Medical Institute in
Leningrad (now St. Petersburg) in 1991 and launched her scientific career in the Department of
Virology at the B. Johan National Institute of Public Health in Budapest, Hungary. In 1995 she
obtained a postdoctoral position at SUNYHealth Science Center, Syracuse, NY, in a researchgroup
whose attention was focused on the influence of the enzymes of pentosephosphate pathway on
programmed cell death. Subsequently, she obtained a Ph.D. degree in Chemistry at Clarkson
University (2001). Her thesis work consisted of construction of ordered two-dimensional and three-
dimensional nanostructures and studying the molecular interactions therein. She is currently an
NSF International Research Fellow. Her research interests include DNA films, DNA-derivatized
nanoparticles, and the development of more sensitive surface-plasmon-resonance-based detection
devices.
Janos H. Fendler is the Distinguished CAMP Professor of Chemistry at Clarkson University, New
York, USA. He received his B.Sc. fromthe University of Leicester (England) and his Ph.D. and his
D.Sc. from the University of London. He used surfactant assembliesaqueous and reversed
micelles, Langmuir monolayers, LangmuirBlodgett films, vesicles and polymerized vesicles, and
bilayer lipid membranesfor molecular organization and compartmentalization. His research has
been reported in more than 306 primary publications and summarized in 96 review articles and
three books. He has received several awards, including the Langmuir Distinguished Lecturer award
and the ACS National Award for Colloid and Surface Chemistry.
Advantage has also been taken of ultrasonic power to form
metallic nanoparticles, complex nanoparticles, and metallic
nanoparticles deposited on silica spheres.
[1419]
Recent reports
on controlling sizes and size distributions of gold and silver
nanoparticles are particularly significant.
[20,21]
Stabilization of metallic nanoparticles by covalently at-
tached thiol- and disulfide-functionalized monolayers repre-
sented a significant milestone.
[2224]
These nanoparticles, stabi-
lized by covalent metalsulfur bonds, became known as
monolayer-protected clusters, MPCs.
[25]
The unique feature of
MPCs is that they behave as if they were large individual mac-
romolecules. Indeed, MPCs can be isolated from their disper-
sions as solids and redispersed in a solvent without structural
or chemical alterations. Importantly, highly monodispersed
populations of MPCs can be prepared by fractional crystalli-
zation.
[26]
MPCs can also be functionalized and subjected to
all the synthetic procedures (without breaking the AuS
bonds) known to chemists. The relative ease of preparation of
MPCs in substantial quantities is equally important, since it
greatly facilitates characterizations by such standard methods
as elemental analysis, differential scanning calorimetry, NMR
spectroscopy (both solution and solid-state), absorption, and
Fourier-transform infrared (FTIR) spectroscopy.
[27,28]
A sin-
gle-phase, one-pot approach has been recently reported for
the gram-scale preparation of gold MPCs in controllable sizes
and size distributions.
[29,30]
Thiol-functionalized metallic (Au,
Ag, Pt, Pd) and composite metallic (Au/Ag, Au/Co, Ag/Co,
Au/Pt, Au/Pd, and more complex bi- and tri-metallic core
shell-like) particles have also been reported.
[25,3134]
Slow
evaporation of gold MPC dispersions have been shown to lead
to the spontaneous formation of highly ordered three-dimen-
sional superlattices.
[35,36]
Covalent stabilization of metallic nanoparticles is generally
restricted to the use of metalthiol bond. Alternatively, they
can be stabilized by enclosing them in non-metallic shells
(latex, silica, polystyrene), thus providing a chemically differ-
ent surface for the immobilization of molecules without losing
the spectral features of the metal core.
[37,38]
Metallic nanoparticles are also stabilized if they are in-situ
generated, trapped in (or on) templates, or confined in the
restricted volumes of nanoreactors.
[39]
Such surfactant aggre-
gates as aqueous micelles, reversed micelles, microemulsions
(both oil-in-water, O/W, and water-in-oil, W/O), surfactant
vesicles, and polymerized surfactant vesicles have been fruit-
fully employed as templates (and/or nanoreactors) for the in-
situ generation of nanoparticles.
[39,40]
Alternatively, preformed
nanoparticles have also been incorporated into surfactant
aggregates. Some degree of size and shape control has been
achieved by generating metallic nanoparticles in reversed
micelles.
[4143]
Ultimate stabilization is achieved, of course, by
the prompt covalent capping of the nanoparticles generated
in reversed micelles.
Polymers have also been used as templates for the in-situ
generation or incorporation of metallic nanoparticles. Parti-
cularly significant is the versatile use of dendrimers
[44,45]
and
di- and triblock copolymers.
[4653]
Judicious selection of appro-
priate block copolymers in appropriate concentrations have
resulted in the formation of large variety of self-assembled
structures including those which resemble aqueous micelles,
reversed micelles, microemulsions, and surfactant vesicles. All
of these structures can, in principle, be used as templates for
nanoparticle generation or incorporation. It should be
remembered that partial entrapment of nanoparticles in rigid
compartments obviates the need for surface coverage (i.e.,
modification). Metallic nanoparticles can be, therefore, exam-
ined (and employed) in their pristine states.
Preparation of metallic nanoparticles by soft solution pro-
cessing (i.e., direct fabrication in aqueous solution at moder-
ate temperatures and pressures) has gained increasing accep-
tance. Hydrothermal synthesis (hydrothermal technique) is a
soft solution processing which involves the heterogeneous
reaction between powdered solids and water above ambient
temperature and at pressure greater than 1 atm in a closed
system.
[54]
The relative ease (appropriate powdered reagents
and water are placed in a teflon-lined autoclave and heated
without stirring at moderate to high temperatures and pres-
sures for the desired time) and the possibility of predicting
optimum reaction conditions by electrolyte thermodynamics
(in terms of phase diagrams) are the advantages of the hydro-
thermal synthesis.
[55]
Spherical metallic (mostly gold) nanoparticles have been
converted to nanorods, with controllable aspect ratios, by a
seed-mediated sequential growth process.
[5660]
Citrate-ion-
stabilized nanoparticles were used as seeds in a series of gold
chloride solutions in a hexadecyltrimethylammonium chloride
aqueous micellar solution containing ascorbic acid as a reduc-
ing agent.
[5660]
The technique was also adapted for growing
gold nanorods on mica surfaces (to several hundred nanome-
ters length, with diameters in the range of 1020 nm).
[61]
Gold nanoshells have been synthesized by reacting aqueous
HAuCl
4
solutions with solid templates such as silver nanopar-
ticles. The morphology, void space, and wall thickness of these
hollow nanostructures were all determined by the templates,
which were completely converted into soluble species during
the replacement reaction.
[62]
Replacement reactions between
silver nanocubes and aqueous gold chloride provided a versa-
tile method for generating nanostructures with hollow inte-
riors.
[63]
2.2. Vacuum Deposition and Electron-Beam Lithography
Vacuum deposition or sputtering involves the condensation
of atoms produced by evaporation of a metal shot placed on a
heating element.
[64]
The thickness of the metal film is moni-
tored by an in-situ quartz crystal microbalance. Ultrathin (less
than 10 nm nominal thickness) evaporated gold films have
well-defined island structures and optical properties similar to
those of colloidal gold nanoparticles.
[6567]
Figure 2 shows typ-
ical transmission electron microscopy (TEM) images of gold
nanoislands obtained by the slow (0.00140.0028 nms
1
) evap-
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1687
oration of gold onto Formvar-covered, carbon-coated, 200
mesh copper grids.
[68]
Preparation of arrayed, triangular silver nanoparticles
(referred to as periodic particle arrays, PPAs) is a combined col-
loid chemical and vacuum deposition technique. The approach
involves the drop coating of a substrate by a monolayer of
monodispersed polystyrene particles, which serves as a deposi-
tion mask through which the silver is evaporated (in a vacuum
evaporator) to a desired thickness. Removal of the polystyrene
particles by sonication in ethanol leaves the triangular silver
nanoparticles patterned on the substrate surface.
[6973]
Electron-beam (EB) lithography is physicists' first choice
for fabricating arrays consisting of monodispersed (typically
better than 99 %) metallic nanoparticles in desired sizes,
shapes, patterns, and interparticle distances on glass sub-
strates. Typically, this process involves the following steps:
1) spin-coating of a conducting substrate (either an indium tin
oxide (ITO) glass or a glass slide coated by a ca. 10 nm thick
gold film) with a 70100 nm electron-sensitive resist, usually
poly(methyl methacrylate), PMMA); 2) forming the desired
pattern by EB lithography (which burns off the polymer and
the thin gold film); 3) chemical development of the exposed
PMMA; 4) thermal evaporation (at a rate of 12 nms
1
) of
the gold (or silver) film; 4) removal of the remaining PMMA
film by acetone (and the 10 nm gold film, if present, by etch-
ing using an aqueous solution of KI and I
2
(4.0 g and 1 g
respectively in 15 mL water); 5) imaging the pattern by scan-
ning electron microscopy (SEM) and/or atomic force micros-
copy (AFM).
[7477]
Figure 3 shows a typical pair-wise interact-
ing gold nanoparticles fabricated by EB lithography.
[76]
Difficulty of scale-up, beyond a few microscopic slides at a
time, and the expenses involved are the disadvantages of EB
lithography.
2.3. Laser Ablation
Formation of metallic nanoparticles by the photo- and radi-
olytic reduction of metal ions has been the subject of exten-
sive investigations since the early 1960s.
[39,7880]
In fact, much
of our understanding of how metallic clusters evolve has been
obtained by the pulse-radiolytic investigations of the sequen-
tial transient absorbances formed in the reduction of silver
cations.
[80,81]
Absorbances appearing initially were ascribed to
Ag
0
, Ag
2
+
, and Ag
4
+
; longer irradiation led to formation of
non-metallic clusters and ultimately to the appearance of a
surface plasmon absorption band indicating the transforma-
tion to metallic silver nanoparticles.
[80,81]
Laser ablation (usually using a pulsed laser with controlled
energy and pulse duration) of metal plate targets immersed in
aqueous solution, containing NaCl or surfactants or cyclodex-
trin, resulted in the formation of metallic nanoparticles
[8290]
and composite alloyed nanoparticles (AuAg,
[91]
for example).
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1688 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Figure 2. A typical TEM image of ultrathin gold nanoislands (2.5 nm
nominal thickness), evaporated onto Formvar-covered, carbon-coated,
200-mesh copper grids at a rate of 0.00140.0028 nms
1
. The gold nano-
islands were found to be slightly elongated; therefore the two axes are
separately shown in the inserted histogram. Reproduced with permission
from [68]; copyright 2003, the American Chemical Society.
Figure 3. SEM images of identical 150 nm diameter gold nanoparticles
deposited by EB-lithography to heights of 17 nm at 450 nm (a), 300 nm
(b), and 150 nm (c) center-to-center distance. Reproduced with permis-
sion from [76]; copyright 2003, Elsevier.
Transformation of spherical metallic nanoparticles to nano-
rods,
[92,93]
nanodisks,
[94]
nanoprisms,
[95]
and nanonetworks
[86]
by light (and/or laser beams) at selected wavelength is quite
interesting.
[96]
The shape control has been rationalized by as-
suming the fastest growth of a given shape of nanoparticle
that has the largest absorption coefficient at the rotationally
averaged irradiation wavelength.
[94]
2.4. Electrodeposition
Electrochemical deposition of nanoparticles (or nanostruc-
tured films) is attractive since a high degree of control can be
achieved by the judicious employment of Faraday's laws
(using 96 500n Coulombs of electricity results in the deposi-
tion of 1 g mol
1
of materials, where n is the number of elec-
trons passed in depositing one mole of the deposit). Further-
more, composition, defect chemistry, and shape (along with
thickness) are controllable at a reasonable cost. Anodic
depositions are limited to metallic substrates, since the pro-
cess involves the electrolytic reduction of metal in the pres-
ence of the appropriate anions. Gold and palladium MPCs
were prepared on silicon surfaces, for example, by the galva-
nostatic reduction (using 0.5 mAcm
2
current) of HAuCl
4
and
PdNO
3
in methanol, in the presence of dodecanethiol.
[97,98]
Galvanic replacement reactions have been used for alloying
and dealloying silver and gold nanoparticles as well as for pre-
paring nanoshells.
[99]
Sequential electrodeposition within a porous template was
used to prepare multimetal microrods intrinsically encoded
with submicrometer stripes. Variations in composition along
the length of the wire permit the incorporation of electrical
functionality, optical contrast, and/or desired surface chemis-
try.
[100,101]
3. Optical Manifestations of Localized Surface
Plasmon Resonance
Well-separated metallic nanoparticles and nanostructures,
with dimensions significantly smaller than the wavelength of
the exciting light, are characterized by a broad, intense
absorption band in the visible range of the spectrum. The
bandwidth, the peak height, and the position of the absorption
maximum depend markedly, as stated in the Introduction, on
the size, size distribution, surface state, surface coverage, and
surrounding environment of the given nanoparticles and
nanostructures.
[2,3,102]
The significant difference in the absorp-
tion spectra of the same concentration of ethylenediamine-
tetraacetic acid (EDTA)-stabilized, 22.8 5.8 nm and
37.8 9.0 nm diameter silver nanoparticles illustrates the
point well (Fig. 4).
[103]
Varying the dielectric constant of the
media introduced between and above silver nanoislands,
deposited onto quartz and sapphire substrates, changed the
absorption maximum of the LSPR band from 482 nm to
1310 nm.
[104]
It was Gustav Mie who first rationalized the observed in-
tense color of dispersed colloidal gold particles in 1908.
[105]
Relative simplicity and versatility are the advantages of the
classical Mie theory, which assumes that the particle and the
surrounding medium are homogeneous and can be described
by bulk optical dielectric functions.
[1,106]
Solving Maxwell's
equations lead to a relationship for the extinction cross-sec-
tion, r
ext
(r
ext
=r
abs
+r
sca
=absorption cross-section +scatter-
ing cross-section) for metallic nanoparticles as a summation
over all electric and magnetic oscillations. For nanoparticles
which are significantly smaller than the wavelength of the
exciting light (k >>2R, where R is the nanoparticle radius) the
Mie theory is reduced to:
[1]
r
ext
x 9
x
c
e
3=2
V
O
e
2
x
e
1
x2e
m

2
e
2
x
2
(1)
where V
O
=(4p/3)R
3
, x is the angular frequency of the excit-
ing radiation, e
m
is the dielectric function of the medium sur-
rounding (or embedding) the metallic nanoparticles, and e
1
and e
2
are the real and imaginary part of the dielectric func-
tion of the metallic nanoparticles, respectively. As indicated in
Equation 1, the surface plasmon absorption band appears
when e
1
(x) 2e
m
if e
2
(x) is small or if it is only weakly
dependent on x. The bandwidth and peak height are well ap-
proximated by e
2
(x); however, contrary to the experimental
evidence, no size dependency of the peak position is predicted
by Equation 1. The size dependency of the position of the
surface plasmon absorption band of metallic nanoparticles
and nanostructures can be accommodated by assuming size-
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1689
Figure 4. Absorption spectra of 22.8 5.8 nm and 37.8 9.0 nm silver
nanoparticles showing characteristic surface plasmon bands at 406 and
428 nm, respectively. Reproduced with permission from [103].
dependent dielectric functions.
[26,107]
The observed spectral
changes that accompany the electrochemical charging and dis-
charging of metallic nanoparticles, as well as metal adatom
deposition, and alloying and formation of bimetallic core
shell type nanoparticles, have been rationalized by applying
Drude's theory for describing free-electron behavior in the
Mie equation.
[3,108]
Equation 1 does not adequately describe the optical behav-
ior of larger (2R30 nm) metallic nanoparticles. For such
nanoparticles the extinction cross-section is dominated by
higher-order multipole absorption and scattering, and the full
Mie equation needs to be used to model the absorption spec-
tra.
[109,110]
Surface plasmons are unevenly distributed around non-
spherical metallic nanoparticles and nanostructures and this
manifests in shape-dependent LSPR absorption spectra.
[111]
In
particular, for metallic nanorods the plasmon resonance splits
into low- and high-energy absorption bands. The high-energy,
or transverse, absorption band corresponds to the electron
oscillations perpendicular to the major axis; while the low-en-
ergy, or longitudinal, absorption band results from the oscilla-
tion of the electrons along the major axis. As the aspect ratio
of the nanorods increases, separation between the two plas-
mon bands becomes more pronounced (Fig. 5).
[96,112]
Signifi-
cantly, triangular particles exhibit multiple plasmon reso-
nance, a longitudinal (bulk) plasmon mode and a very large
localized enhancement at their sharp tips.
[113,114]
Mie theory
has been extended to cylindrical and needle-like nanopar-
ticles,
[96]
and using discrete dipole approximations optical
properties (absorption, extinction, and scattering efficiencies)
have been calculated for metallic nanoparticles having arbi-
trary shapes.
[106,115,116]
Examination of the scattering spectrum
of differently shaped (spherical, rod-like, triangular, penta-
gons, tetrahedrons) individual nanoparticles (of silver, gold,
and nickel), by total internal reflection (pseudo-dark-field)
spectroscopy (Fig. 6), has obviated the need for producing
highly monodispersed populations of nanoparticles in desired
shapes, and provided meaningful correlations between shape,
environment, and spectra.
[117]
Mie theory is only applicable to non-interacting nanoparti-
cles that are well separated in their solid state or are present
at low concentrations in dispersions. For interacting particles
the plasmon resonance red-shifts with the concomitant
appearance of a lower energy absorption band (similar to the
longitudinal absorption band observed for nanorods). Two
types of interactions prevail between arrayed metallic nano-
particles: near-field coupling (between particles that nearly
touch each other) and far-field dipolar interactions.
[118120]
Dipolar interactions are electrodynamic in nature; the dipole
fields, resulting from a plasmon oscillation of a single particle,
induce surface plasmon oscillation in the adjacent parti-
cle(s).
[121]
The effect of changing the interparticle distance be-
tween pairs of electron-beam deposited gold nanoparticles
(150 nm diameter, 15 nm height, see Fig. 3) on their s- and
p-polarized extinction spectra is shown in Figure 7.
[76]
The
observed spectra were rationalized in terms of a simple di-
poledipole interaction model.
[76]
Significantly, these far-field
dipolar interactions permit the use of aligned metallic nano-
particles as waveguides (see Sec. 4.2).
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1690 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Figure 5. a) TEM image of gold nanorods synthesized electrochemically
in micellar solutions. b) Size distribution of the nanorods. c) Absorption
spectrum of the nanorods. d) Simulated absorption spectra of the nano-
rods with different aspect ratios. Reproduced with permission from [235];
copyright 2001, the American Chemical Society.
4. Nanoscale Optical and Photonic Devices
Near-field coupling of localized surface plasmon resonance
is increasingly being exploited for the construction of nano-
scale optical and photonic devices.
[122124]
This highly exciting
and potentially rewarding development is based upon the sub-
stantial enhancement of the electric field around and between
the metallic nanoparticles, subwavelength holes, corrugations,
and textures in metallic films. Fabricating these nanostruc-
tures with an unprecedented (nanometer-level precision) con-
trol over their sizes, shapes, and spacings is an essential
requirement for the construction of nanoscale optical and
photonic devices. In essence, advantage is taken in nano-opti-
cal devices of converting photons to electromagnetic modes
of radiation (i.e., to localized surface plasmons, LSPs) that are
not diffraction limited (i.e., they can be focused more tightly
than k/2) and can be employed as optical elements (mirrors,
lenses, switches, or waveguides, for example) within their
propagation lengths (up to 150 lm at 700 nm for Ag
[125]
).
Furthermore, decoupling of surface plasmons to light has
been recently demonstrated.
[126]
Propagation of light is, of
course, not limited by distance. It is fair to state in the intro-
duction to this section that while extensive numerical simula-
tions have been performed in these systems, theoretical un-
derstanding of the complex relationship between the nature
of surface plasmon modes and the surface states of metallic
nanostructures is only in its infancy.
Here we shall survey the propagation of surface plasmons,
the extraordinary optical light transmission, superlenses, and
optical data storage (in Sec. 4.1); plasmon waveguides and
nano-optics (in Sec. 4.2); the different near-field scanning
optical microscopies; the mapping of localized and propagat-
ing surface plasmons (in Sec. 4.3); and nanophotonics (in
Sec. 4.4). Table 1 summarizes the most pertinent publications.
4.1. Surface Plasmon Propagation, Extraordinary Optical
Transmission of Light, Superlenses, and Optical Data Storage
Conversion of photons to surface plasmons allows the sub-
wavelength manipulation of electromagnetic radiation. Opti-
mally this conversion can reach 100 % efficiency. However,
the intensity of surface plasmons, propagating along the me-
tallic surface, gradually decays over the 10200 micrometer
range. This propagation length (the distance after which the
intensity of the surface plasmons decreases to <E1-e>, L
SP,
)
can be theoretically modeled and is given by:
[127]
L
SP

1
2k
SP

c
x
e
0
m
e
d
e
0
m
e
d
!3=2
e
0
m
2
e
m
(2)
where k
SP
is the imaginary part of the complex surface plas-
mon wavevector, e
m
, and e
m
are the real and imaginary parts
of the dielectric function of the metal, c is the speed of the
light and x is the optical excitation frequency. Equation 2
predicts that longer propagation lengths can be realized with
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1691
Figure 6. Schematics of the total internal reflection (pseudo-dark-field)
spectroscope, TIRS. The angle of incident light (tungsten halogen lamp
and a high throughput monochromator and polarizer) is chosen for total
internal reflection (i.e., all the light is reflected). The nanorods placed in
the evanescent field above the substrate surface scatter the light out of
this field. Only the scattered light is collected by a conventional micro-
scope objective and focused onto a spectrophotometer or onto a CCD
camera (for microscopic images, not shown).
Figure 7. Extinction spectra of 150 nm diameter gold nanoparticles de-
posited by EB-lithography to heights of 17 nm at 450 nm (a), 300 nm (b)
and 150 nm (c) center-to-center distance. The orthogonal particle sepa-
ration is kept constant, as can be seen in Figure 3. The polarization direc-
tion of the excitation light is parallel (top) and orthogonal (bottom) to
the long axis of the particle pairs. Reproduced with permission from [76];
copyright 2003, Elsevier.
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1692 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Table 1. Nanoscale optical and photonic devices based on localized surface plasmon resonance.
Localized Surface Plasmon
Resonance Material
Principle (Potential) Function,
Application
Ligand coated silver nanoparticles arrayed
on water (metal-liquid-like films, MELLFS)
High reflectivity versatile and inexpensive surfaces are
formed which can be readily manipulated
by magnetic and electromagnetic fields
High quality parabolic mirrors [219]
20 nm diameter, 1 15 lm long Au, Ag, and Au/Ag nanowires
(prepared by template directed electrosynthesis)
exposed through prism total internal reflection illumination
Metal- and wavelength dependent unidirectional
plasmon propagation over distances > 10 lm are
demonstrated
Nanoscale optical coupling, plasmon
waveguides [130]
Periodic arrays of 600 1800 nm diameter holes in 200 nm
silver film on quartz substrate
Coupled LSPR enhanced optical transmission Extraordinary optical transmission through
subwavelength holes [131]
A single 40 nm-diameter 10 lm long slit, surrounded by
a finite array of grooves, made on a 350 nm-thick silver film
Coupled LSPR enhanced optical transmission by:
(i) groove cavity mode excitation (controlled by the depths
of the grooves); (ii) in-phase groove re-emission (controlled
by the period in the groove array); (iii) slit waveguide mode
(controlled by the thickness of the film)
40-fold light transmission enhancement has
been experimentally observed [138]
A single subwavelength aperture surrounded by an equally
spaced finite array of grooves, made on a metallic film
Lensing controlled by the output grooves (transmission
controlled by the input grooves, see above)
Theoretical analysis demonstrates the display
of a lensing effect [139]
Periodic arrays of 150 nm diameter holes
in 200 500 nm thick silver films
Resonant interaction of the coupled
LSPR with the incident radiation
Wavelength selected transmission with 1000
times increased efficiencies [132]
Periodic arrays of 250 400 nm diameter holes
in 200 300 nm thick silver and nickel films
Resonant interaction of the coupled
LSPR with the incident radiation
Transmission enhancement depend on the
dielectric properties of the metal [220]
Nickel microarrays of subwavelength apertures Resonant interaction of the coupled
LSPR with the incident radiation
Microarray transmit about 3 times the
intensity of light incident upon the holes [221]
1-dodecanethiol monolayer self-assembled onto
nickel microarrays of subwavelength apertures
Resonant interaction of the coupled
LSPR with the incident radiation
Intensity of the absorption of the methyl CH2
band (in the 2800 3000 cm-1 region) is
enhanced by 100-fold with respect to
traditional IRRAS [221]
A bigger (4141 holes) and a smaller (1111 holes) periodic
arrays of 250 nm diameter holes in 150 nm thick gold films
placed 30 lm apart
Focusing a Ti-sapphire laser onto smaller array
(the source) lit up the bigger array (the probe)
Surface plasmons launched at the source
array appears as a streak between the two
arrays and then decouple to light[126]
Electron beam deposited 35 nm thick, 30 nm diameter,
and 150 nm long elongated silver nanoparticles are organized
into different configurations
Scattering spectra of the LSPR band for a given polarization
direction have maxima at 680 nm and 480 nm for vertically
and horizontally oriented particles, respectively
Optical data storage[145]
(i) 50 nm diameter silver or gold nanoparticles are patterned
(with 75 nm center-to-center distance) on
ITO substrates by EB lithography (ii) 30 nm diameter
gold nanoparticles are manipulated by the AFM-tip to desired
pattern on ITO substrates
Dipole fields, resulting from LSPS of a single
nanoparticle, induce plasmon oscillations in
neighboring particles leading to coherent modes
with a wavevector k along the nanoparticle arrays
Waveguides below the diffraction limit of
light [122]
EB-lithographic generation of eighty 50 nm diameter
gold nanoparticles with 75, 100, and 125 nm
center-to-center spacing
Optical properties, determined by far-field polarization
spectroscopy, indicate the presence of longitudinal
and transverse plasmon modes
Optical information transfer below the
diffraction limit [119]
40 nm thick silver film (deposited onto a glass substrate)
textured with a hexagonal array of 100 nm diameter dots
(composed of a photoresist) with a 300 nm periodicity
Reflectivity from TM polarized (scanned between 400 nm
and 800 nm), coupled to the surface plasmon was collected
at the full range of propagation directions
Light propagation is prohibited in all direc-
tions between 1.9 eV and 2.0 eV [166]
A two-dimensional array of repeated unit cells of
copper strips and split ring resonators on interlocking strips
of standard circuit-board material
The negative refractivity material (above 20 Ghz)
enhanced transmissivity of the evanescent field
Construction of diffraction-free collecting and
focusing superlenses [143,229]
50 nm thick silver film, deposited onto the flat side
of a semi-spherical glass prism
Negative permittivity broadened the surface plasmon band
and enhances the transmissivity of the evanescent field
Construction of diffraction-free collecting and
focusing superlenses [144]
40 nm high, 100 nm diameter oblate spheroidal
gold arrays, with 65020 nm periods, prepared
by EB-lithography on a glass prism (substrate)
Appropriate coupling of the localized surface plasmon fields
gave rise to subwavelength spots between the gold
structures (measured by an apertureless near field scanning
optical microscope)
Subwavelength patterning [230]
A bull's eye structure surrounding a cylindrical hole in a
suspended silver film (groove periodicity, 500 nm; groove
depth, 60 nm; hole diameter, 250 nm; film thickness,
300 nm)
Light is transmitted with low divergence, directionality and
high efficiency
Miniature phase-array antennas in the optical
regime which can transmit or receive light for
a given wavelength [231]
A vertical-cavity surface-emitting laser array, VCSEL, is
fabricated. It consists of 12 pairs of p-type distributed
Bragg reflectors, DBRs, and 34.5 pairs of n-type DBRs
with a 2.8 lm oxide aperture which is covered by a layer
(Y2N thick) of SiO
2
and a 100 nm thick gold film (with
a single aperture of 200 nm) diameter
Optical near field is strongly enhanced by the excitation
of localized surface plasmon around the metal aperture.
The far-field power radiated from the apertures is enhanced
by sixteen-fold (with respect to a single aperture VCSEL). Peak
power density = 2.5 mW/lm
2
with a 260 nm spot size.
High density optical data storage[232]
40 nm-high and 480 nm-wide silver wire gratings,
with a 577 nm period fabricated on a glass slide by
soft-lithography
Dispersion of surface plasmons show a clear energy gap
when the two plasmons (at the air/silver and glass/silver
interface) interfere
Metallo-dielectric gratings with
subwavelength gaps in the thin metal limit
[233]
silver than with gold, and that the propagation length in-
creases with increasing wavelength. Indeed propagation
lengths of up to 150 lm were observed for silver at 700 nm,
while gold under the same conditions only propagated surface
plasmons for up to 30 lm.
[123,128]
Experimental probing of the
surface plasmon propagation length involved optical and
photonic scanning microscopies in the near field; and dark-
field or total internal reflection microscopy and/or spectro-
scopy in the far field.
[122,125,128,129]
For example, gold and silver
waveguides (typically 3060 nm thick, 12.5 lm wide metallic
stripes deposited onto an optically transparent glass) were
excited by light generated by total internal reflection via a
prism, and the scattered light was visualized by photon scan-
ning microscopy.
[125]
Plasmon propagation has also been
examined in electrochemically generated 115 lm long,
20 nm diameter gold, silver, and bimetallic (with distinct gold
and silver segments, i.e., gold and silver heterojunctions)
nanorods.
[128]
Arrangements were made in this work to selec-
tively launch the surface plasmons only at one end of the
nanorods. Scattered light from gold nanorods was observed
upon 820 nm irradiation, but not on using a 532 nm light as
the excitation source. Conversely, silver nanorods propagated
both the 532 nm and the 820 nm irradiation (Fig. 8).
[128]
Bimetallic nanorods were found to be directionally selective.
Surface plasmons were found to propagate the 532 nm light
from the silver end of the rod, whereas the 820 nm light could
be propagated from both the silver and the gold ends of the
bimetallic nanorods. These observations pave the way to
nano-optical devices in which optically encoded information
is transmitted with nanoscale accuracy over distances of 10
15 lm.
[128]
Surface plasmon propagation has been investigated
in several additional systems.
[130]
Significantly, surface plasmons were reconverted to light by
two arrays of 250 nm diameter holes in a 150 nm thick gold
film, placed 30 lm apart.
[126]
One array contained
41 41 holes and the other array 11 11 holes. Surface plas-
mons launched by a Ti:sapphire laser at the smaller array (the
source) propagated to the sink, the larger array, where they
reconverted to light (Fig. 9).
[126]
This possibility of reversibly
converting light to surface plasmons opens the door to the ex-
tension of nano-optical devices to the millimeter scale.
In 1998, Ebbesen and co-workers reported an extraordinary
light transmission through 150 nm diameter holes (with a reg-
ular periodicity between 600 and 1800 nm) formed by a fo-
cused ion beam through 200 nm thick silver films (on quartz
substrates).
[131]
The extraordinary light transmission mani-
fested itself in the appearance of much more light (with only a
small angular divergence!) than expected from the diffraction
theory of isolated holes.
[131]
The transmitted light was charac-
terized by a narrow silver surface plasmon peak (at 326 nm)
and a set of well-defined minima and maxima related to the
geometry of the hole array (Fig. 10).
[131,132]
This behavior is in
contrast with the classical theory which predicts transmission
efficiencies in the order of 10
3
through a 150 nm diameter
hole and a monotonic decrease (instead of the observed in-
crease) of the light transmission with increasing wavelength.
Clearly, the array is actively involved in light transmission,
most likely via resonant interactions with surface plasmons,
localized in and around the holes in the metallic film.
Extraordinary light transmission has been modeled by sev-
eral approaches.
[133137]
Appropriately, it was soon realized
that the model employed should represent the experimental
structure (arrayed nanoholes, gratings on one or both sides of
the metallic films, with or without slits, etc.). For example,
modeling a narrow-grooved zeroth-order (i.e., the pitches are
smaller than k/2) silver grating which had the same periods on
both sides indicated the resonance tunneling of p-polarized
photons through the metal film via surface plasmons localized
in the grooves of the opposite surfaces.
[135]
Conversely, theory
predicted the complete reflection of s-polarized photons by
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1693
Figure 8. a) Photograph of 20 nm diameter Au and Ag rods. The two
labeled rods are typical of the ones used for these experiments. b) Opti-
cal microscope image of a 4.7 lm long Au rod exposed to through-prism
TIR illumination at 532 nm. Note the strong scattering at the rod input
and the absence of scattering at distal tip. c) Image of the same Au rod
under TIR illumination at 820 nm. Under these conditions, both ends of
the rod exhibit strong emission/scattering. d,e) A 4.7 lm long Ag rod
illuminated at 532 and 820 nm, respectively. Emission is observed from
both tips at both wavelengths in the case of Ag. Note: In panels be), the
incident laser is focused to include a distribution of wave vectors, but the
primary direction of propagation points vertically on the page. The scale
bar in panel (b) is equivalent to 1 lm and is valid for images be).
Dotted outlines of the rods are meant only as visual guides to the reader.
Reproduced with permission from [128]; copyright 1998, the American
Chemical Society.
these gratings. This polarization selectivity could lead to the
construction of nanoscale polarizers. Two different mecha-
nisms were proposed for the extraordinary light transmission
through thin metal films with narrow grooves of different
periodicities on both sides.
[137]
Both propagating and localized
surface plasmon modes were found to be responsible for the
efficient transmission of the p-polarized light through the film
and the complete reflection of the s-polarized light. Interest-
ingly, the different plasmon resonance modes were calculated
to have different features. Thus the propagating surface plas-
mons had a narrow resonance peak corresponding to a large
phase lag and long time delay. In contrast, the localized sur-
face plasmon modes had a broad resonance peak and their
electric field highly concentrated in the grooves at both sides
of the film.
[137]
Experimental verification of these models are
awaiting the interested scientists.
Substantial transmission enhancements have also been ob-
served on using a single subwavelength aperture surrounded
by an equally spaced finite array of grooves.
[138,139]
Images of metallic nanostructures, taken in the near field by
photon scanning tunneling microscopy (see Fig. 11), contain
all the optical information about the scatterer. Moving to the
far field, however, the evanescent field decays exponentially,
and information on subwavelength features are lost. Pendry
recently proposed an ingenious way to overcome this problem
by passing the light through a material with a negative refrac-
tive index, which enhances the evanescent field and hence
permits subwavelength resolution.
[140]
Negative refractive in-
dex materials are also referred to as left-handed materials,
LHMs, (since the electric and magnetic vectors lie along the
direction of k for propagating plane waves and thus form a
left-handed system, as opposed to the right-handed system
which prevails for ordinary materials) or more generally as
metamaterials (implying properties and functionalities which
are unattainable in naturally occurring materials, but which
can be tailor made). Numerical simulations have indicated
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1694 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Figure 9. Top: SEM image of coupled arrays of subwavelength holes. The
arrays have a period of 760 nm and are separated by 30 lm. The hole di-
ameter is 250 nm. The small array on the right (11 11 holes) is the
source array whereas the big array on the left (41 41 holes) is not illu-
minated by the laser light and acts as a probe array. Inset: zoom in on
the holes of one array. Bottom: Transmission spectrum recorded in the
far field when the sample is illuminated by a collimated source of white
light. Reproduced with permission from [126]; copyright 1998, the Ameri-
can Institute of Physics.
Figure 10. Zero-order transmission spectrum of an Ag array (a
o
=0.9 lm,
d = 150 nm, f =200 nm). Reproduced with permission from[131]; copy-
right 1998, Nature Publishing Group.
Figure 11. Schematic of the optics used in photon scanning tunneling
microscopy of gold and silver nanoparticles [157]. The incident light is
coupled to the surface plasmon modes of the gold nanoparticles in the
total internal reflection mode (Kretschmann configuration). Near-field
images are probed by a sensitive photomultiplier (not shown) placed at
the end of a sharply elongated uncoated optical fiber (the tip) which is
used to scan the sample. Using the same fiber to deliver laser pulses
through the optical fiber onto the sample (a thin metal film, rather than
metallic nanoparticles) provides a means for lithographically introducing
surface defects which can, of course be imaged in the scanning tunneling
microscopic mode (i.e., replacing the photomultiplier at the end of the
optical fiber) [155]. The light reflected from the prism is monitored by a
photodiode (PD).
that judiciously arrayed metallic (silver, gold, or copper)
nanowires and their composites can be used as LHMs in the
near-infrared and visible part of the spectrum.
[141,142]
Experi-
mentally, negative index of refraction has only been demon-
strated in the microwave region to date.
[143]
A two-dimen-
sional (2D) array of repeated unit cells of copper strips and
split ring resonators on interlocking strips of standard circuit
board material was shown to have negative index of refraction
above 10.2 GHz.
[141]
Enhanced transmissivity of the evanes-
cent field was demonstrated by taking advantage of the natur-
al roughness of a 50 nm thick silver film deposited onto the
flat surface of a hemispherical glass prism in a reversed atten-
uated total reflection system (i.e., the collimated Ar-ion laser
beam is incident normal to the center of the silver-coated flat
side of the prism, and the angle distribution of the relative
light intensity is determined by a charge-coupled detector,
CCD, camera placed 5 cm from the center of the hemispheric
side of the prism).
[144]
The negative permittivity of the silver
film (approaching 1) was considered to be responsible for
the observed broadened surface-plasmon bandwidth and en-
hanced transmissivity of evanescent waves.
[144]
These results
open the door to the construction of diffraction-free image
collecting and focusing of subwavelength superlenses.
Optical data storage has been demonstrated by the spectral
coding of differently organized 35 nm thick, 30 nm diameter,
and 150 nm long silver nanorods (Fig. 12).
[145]
Three different
arrangements of the nanorods, A, B, and C, constitute the
building blocks of the data storage system. In A, a single silver
nanorod was aligned with its long axis parallel to the propaga-
tion of the incident light. B consisted of two silver nanoparti-
cles, both aligned with their long axis perpendicular to the
propagation of the incident light. In C, in addition to the two
silver nanoparticles which were aligned as those in B, a third
silver nanoparticle was placed parallel to the propagation of
the incident light close to one end of the other two particles.
B and A had a single absorption maximum at 680 nm and
480 nm, respectively, while the absorption spectra of C was
characterized by two maxima. Organizing a large number of
A, B, and C structures in a given area, 500 nm apart, provided
a data storage system in which the information could be read
by irradiation with blue (488 nm) and red (633 nm)
lasers.
[145,146]
Using this approach the information density is
limited by a) the area observable by the objective of the total
internal reflection spectroscope, TIRS, b) the number of
nanorods which manifest different scattering spectra in that
observable area, and c) the number of distinctly resolvable
resonance lines originating in the scattering spectra in the
observable area. The far-field resolution of a microscope is
roughly a 500 nm diameter circular area. This is, in fact, the
area typically occupied by a single pit in a conventional com-
pact disk. Smaller areas can be observed by photon scanning
tunneling microscopy (by using a sharply elongated optical
fiber, instead of the scanning tunneling microscope tip, and
placing a sensitive photomultiplier at the end of this fiber to
observe the surface plasmons generated on the platform of
the TIRSFig. 6). Limiting the spectral range to the visible
range a sixfold enhancement of information content of a com-
pact disk pit is achievable.
[145]
4.2. Plasmon Waveguides and Nano-optics
Construction of optical devices at the nanoscale requires
the efficient guiding of light well below the diffraction limit,
even around 90 bends, without radiation losses. Traditional
metallic pipe waveguides only transmit microwaves without
losses and the dielectric guides, operating in the infrared and
visible range of the spectra, are restricted to moderate curva-
ture bends by radiation losses. In contrast, aligned gold and
silver nanoparticles, by virtue of their coupled surface plas-
mon resonance modes, have been shown to propagate electro-
magnetic energy well below the diffraction limit in a coherent
fashion, with negligible radiation losses, at velocities approxi-
mating 10 % of the speed of the light.
[122]
Furthermore, trans-
mission losses for nanoparticle chain arrays, 90 corners, and
T-structures were negligible.
[122]
Far-field polarization spec-
troscopy of 50 nm gold nanoparticles, aligned with 75 nm,
100 nm, and 150 nm center-to-center spacing, indicated the
presence of longitudinal and transverse plasmon modes.
[119]
Polarization dependence of the extinction spectrum of aligned
metallic particles is in accord with the point dipole model of
these structures and permits the exploration of the bandwidth
dispersion relationship, which in turn, will aid the design of
improved plasmon waveguides.
Plasmon waveguides and metallic nanostructures can there-
fore lead to the construction of integrated nano-optical de-
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1695
Figure 12. Top: SEM images of the nano-optical letters. The double arrow
indicates the polarization direction of the incident light. Bottom: Scatter-
ing spectra corresponding to the nano-optical letters. Reproduced with
permission from [145]; copyright 2000, Optical Society of America.
vices incorporating reflectors, mirrors, beam splitters,
switches, and other components.
[124]
4.3. Apertureless Near-Field Scanning Optical Microscopy,
Scanning Plasmon Near-Field Microscopy, Photon Scanning
Tunneling Microscopy, and Mapping Localized, Coupled,
and Propagating Surface Plasmons
Propagating and localized surface plasmons have signifi-
cantly aided the development of high-resolution near-field
scanning optical microscopies (NSOMs). These microscopies,
in turn, have provided an experimental means for imaging
and mapping localized, coupled and propagating surface plas-
mons.
Near-field scanning optical microscopy is not diffraction
limited; optical resolution is primarily determined by the inte-
rior diameter of the tip of a sharply elongated metal-coated
optical fiber through which illumination is introduced. The
tip-to-sample distance is a few nanometers (i.e., it is a near
field optical measurement).
[147,148]
The tip (or the sample) is
raster-scanned by a piezoelectric drive, typically employing a
commercially available scanning force microscope, to obtain
nanoscale optical images (either in the transmission or reflec-
tion mode). In addition, topographic images can be recorded
using the tip as an atomic force microscopy (AFM) probe.
Problems of preparing uniformly pulled and metal-coated
fibers with a nanoscale interior diameters at their tips, through
which laser light of appropriate energy (just sufficient to illu-
minate the sample, but not too much to photo-damage it) can
be introduced, and intensity decays in the tunneling region
impose fundamental sensitivity limits to NSOM. These prob-
lems have been overcome by the development of apertureless
NSOM, in which a sharp metallic probe is illuminated and the
scattered light is detected at far field. Resolution of a few
nanometers with apertureless NSOM is a consequence of
the enhanced optical field at and near the tipsample
region.
[149151]
An alternative approach is to take advantage of propagating
surface plasmons, generated from a thin gold or silver film, de-
posited on a prism.
[152]
The incident light is coupled to the sur-
face plasmon modes of the metallic film in the total internal
reflection mode by a prism (Kretschmann configuration) and
the reflected light is detected by a photodiode. As the sharp
scanning tunneling microscopy (STM) tip scans the substrate
close to the surface it slightly increases intensity of the
reflected light (by reducing the destructive interference) and
thus produces topography-dependent signals. This approach,
termed scanning plasmon near-field microscopy, permits up to
3 nm resolution.
[153]
Using a sharply elongated uncoated opti-
cal fiber, instead of the STM tip to scan the sample (at a con-
stant tip-to-surface distance), and placing a sensitive photomul-
tiplier at the end of this fiber allow the near-field optical
imaging of the sample. This configuration is referred to as
photon scanning tunneling microscopy.
[154,155]
Photon scanning
tunneling microscopy directly measures the propagating sur-
face plasmons near the surface. Photon scanning tunneling
microscopy has also been employed to create surface defects
lithographically (by focusing an excimer laser through the
uncoated optical fiber onto the silver film, evaporated onto the
hypotenuse face of a right angle prism).
[156]
The same fiber was
then used to obtain near-field images of the defects created.
[156]
Additionally, the probesample interactions can be observed
at far field (for example an angle of 75 from the probe axis in
the backscattering direction with respect to the incident wave
vector
[157]
) by a photomultiplier via a microscope objective,
band-pass filter, polarizer, and lens (see Fig. 11).
More recently, silver and gold nanoparticles have been inves-
tigated by photon scanning tunneling microscopy (Fig. 11).
[157]
The normal component of the scattered electric field was
examined as functions of incident light polarization and tip-to-
sample distance. Resonant excitation (at 415.4 nm), using
transverse magnetic (TM) illumination, indicated spatial con-
finement and local enhancement of the electric field around
the silver nanoparticles. Under the same conditions, off-reso-
nance excitation of gold nanoparticles indicated a substantial
contribution of the propagating components of the scattered
field. Transverse electric (TE) illumination resulted in a much
larger scattering cross-section for silver than for gold nanopar-
ticles.
[157]
These results significantly impact our understanding
of surface plasmon propagation.
Single photon tunneling (analogous to single electron tun-
neling) has also been demonstrated recently by measuring the
intensity of the light traveling through individual subwave-
length pinholes in a gold film (deposited on a glass prism in
an optical arrangement similar to that shown in Fig. 11) cov-
ered by a layer of polydiacetylene.
[158]
4.4. Nanophotonics
Photonic bandgap materials, wavelength scale insulators,
and semiconductors which are periodically structured affect
the properties of photons in much the same way as a semicon-
ductor affects the properties of an electron.
[159162]
That is to
say, photons can have band structures, bandgaps (i.e., frequen-
cies between which light propagation is prohibited), localized
defect states, and surface states. Consequently, photonic band-
gap materials can mold and guide light. Photonic bandgap
materials can be prepared by chemical approaches. Synthesis
of barium titanate inverted opals illustrates one of the most
common methods. The procedure involves: i) the introduction
of barium titanate into the interstices of the polystyrene opal
template; ii) polycondensation; and iii) removal of the poly-
styrene opal by solvent extraction or calcination.
[163]
The
three-dimensional network of ferroelectric barium titanate
surrounding the spherical air packets (whose dimensions can
be controlled by selecting the size of polystyrene particles
which form the three dimensional opal template) were dem-
onstrated to function as a photonic crystal.
[163]
Alternatively,
three-dimensional semiconductor photonic crystals can be di-
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1696 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
rectly self-assembled.
[164]
Chemical approaches provide a vi-
able economic alternative to EB lithography.
Photonic bandgap material has also been prepared by sur-
face (instead of bulk) modulation of thin metallic films.
[124,165
168]
Characterization of a full photonic bandgap, between 1.91
and 2.00 eV, was first reported on a 40 nm thick silver film
(deposited onto a glass substrate) which was textured with a
hexagonal array of 100 nm diameter dots (composed of a
photoresist) with a 300 nm periodicity (Fig. 13).
[166]
The inci-
dent TM polarized light (scanned between 400 nm and
800 nm) was coupled to the surface plasmon modes of the sil-
ver film in the total internal reflection mode by a prism (in
the Kretschmann arrangement, similar to that shown in
Fig. 12) and the reflectivity data were collected as a function
of photon energy and photon wave vector in the plane of the
silverair interface at the full range of propagation direction.
Dispersion curves for each propagation direction exhibited a
clear energy gap between 1.91 eV and 2.0 eV (Fig. 13), indi-
cating that there is no propagation of energy in this range in
any direction at the silver/air interface.
[166]
Emission from a
laser dye 4-dicyanomethylene-2-methyl-6-(p-(dimethylamino)-
styryl-4H-pyran (DMC), spin-coated on a textured silver film,
was also found to be inhibited in the bandgap region.
[165]
5. Sensors and Biosensors
Localized surface plasmon resonance has been exploited in
several ways for sensing applications (see Tables 25 for a
summary).
[169]
First, the sensitivity of surface plasmon band to
its immediate environment offers, in itself, an opportunity to
detect attached molecules and environmental changes (assays
based on changes of the localized surface plasmon resonance
absorbance, Sec. 5.1). Second, the reversible aggregation of
plasmon resonant particles through specific linkers (oligonu-
cleotides, for example) provides an excellent means for colori-
metric assays (assays based on the aggregation of metallic
nanoparticles, Sec. 5.2). Third, the ultrabright light scattering
from each plasmon resonant particle makes the optical detec-
tion of a single molecular target possible (labeling by metallic
nanoparticles manifesting localized surface plasmon reso-
nance, Sec. 5.3). Fourth, localized surface plasmon resonance
amplifies the signal of several optical techniques to give rise
to surface-enhanced Raman scattering, SERS, surface-en-
hanced resonance Raman scattering, SERRS, surface-en-
hanced infrared reflection absorption spectroscopy, SEIR-
RAS, localized surface plasmon (LSP)-enhanced surface
plasmon resonance spectroscopy (SPR), and enhanced fluo-
rescence spectroscopy. Since there are many recent reviews
on SERS and SERRS,
[170,171]
as well as on SEIRRAS,
[172]
and
surface-plasmon enhanced fluorescence spectroscopy
[96,173175]
we shall focus our discussion only to the LSP-enhanced SPR
(in Sec. 5.4).
5.1. Assays Based on Changes of the Localized Surface
Plasmon Resonance Absorbance
The fact that the color of metallic nanoparticles and nanois-
lands depends markedly on the refractive index of the sur-
rounding medium has been exploited for sensing applications.
Significant amounts of work have been published on the sens-
ing, detection, and quantification of molecules attached to
metallic nanoparticles and nanostructures by the shift they in-
flict upon the surface plasmon resonance absorption band.
These type of assays were conducted in dispersions,
[62,176179]
on metallic nanoparticles immobilized on substrates,
[180182]
on
metallic nanoislands,
[6568,183,184]
and periodic particle arrays
(PPAs) deposited onto substrates.
[70,72,73,185,186]
(see Table 2).
Functionalization of colloidal gold nanoparticles by mono-
clonal antibodies, specific for single or multiple epitopes (sites
on antigens which are recognized by the antibody) and moni-
toring the shift of their SPR absorbance peak upon interacting
with their ligand illustrate the approach in dispersions.
[176,177]
The shift of the surface plasmon absorption band was found
to be proportional to the concentration of the ligand and
related to the kinetics of the interaction.
[177]
Several similar
approaches in dispersions have been reported (see Table 2).
Most assays have been carried out, however, on surface-
immobilized sensing elements. Confinement of the metallic
nanoislands or PPAs onto substrates has manifold advantages.
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1697
Figure 13. a) A scanning electron micrograph of the hexagonal array of
dots. The dots are composed of photoresist on a glass substrate. The
surface has been coated with a thin film of silver to support the propaga-
tion of SPPs. b) The energies of the upper and lower branches of the SPP
energy gap plotted as a function of the propagation direction w. The an-
gles are accurate to 0.2and the energies to 0.01 eV. There is a full gap
between 1.91 and 2.00 eV. Reproduced with permission from [166]; copy-
right 1996, the American Physical Society.
First, their interparticle distances and positions can be con-
trolled, since they are immobilized on the substrate. Second,
they need not contain any capping agents or stabilizers and
can, therefore, be readily functionalized or indeed used for
sensitive measurements in their pristine state. Third, adsorbed
substances can be desorbed and bound molecules can be
released with the concomitant recovery of the original local-
ized surface plasmon absorption band; thus sensing can be
repeatedly and continuously performed.
Development of transmission localized surface plasmon
resonance, T-LSPR, spectroscopy merits a special emphasis.
Two different approaches for the exploitation of T-LSPR
spectroscopy have been reported to date. The first method,
developed by the Rubinstein group,
[6567,187]
is based on the
vacuum deposition of 210 nm thick gold nanoislands onto
freshly cleaved mica sheets or quartz slides. Depending on
individual preparations, the T-LSPR maximum of the gold
surface plasmon absorption band was observed between 570
and 630 nm. Self-assembly of cyclic disulfide monolayers onto
the gold nanoislands could be monitored quite readily by the
position and intensity change of the T-LSPR band (ca. 0.02
absorbance units, Fig. 14).
[65]
The validity of the technique has
been demonstrated by the observed parallel linear increases
of i) the advancing contact angle of water deposited onto the
self-assembled monolayer (SAM: formed at different times of
immersion of the gold nanoislands into a CHCl
3
solution of
the cyclic disulfide), and ii) the absorbance due to the cyclic
disulfide.
[6567]
The absorption of other molecules (metallo-
porphyrin and metallophthalocyanine monolayers,
[67]
4-ami-
nothiophenol, 4-mercaptopyridine, aminoethanethiol, long-
chain thiols,
[65]
and a submonolayer of thiolated oligonuc-
leotides
[62]
) onto gold nanoislands was also readily detected
by T-LSPR (Table 2).
Advantage has been taken in the second approach of the
sensitivity of the localized surface plasmon absorption band
of 50 nm high and ca. 100 nm wide triangular silver nanoparti-
cles (PPAs).
[70,185188]
Exposed to different solvents the PPAs
underwent structural changes which manifested themselves in
dramatic shifts of the T-LSPR absorption maximum. Self-as-
sembly of hexadecanethiol monolayer shifted the absorption
maximum of the triangular silver nanoparticles from 564 nm
to 604 nm; this corresponded to a red-shift of 3 nm for every
carbon atom in the alkanethiol chain caused by only 60 000
molecules per nanoparticle.
[66]
SAM-functionalized triangular
silver nanoparticles have been shown to function as a biosen-
sor. Electrostatic binding of a cationic polypeptide to mercap-
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1698 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Table 2. Assays based on changes of the localized surface plasmon resonance absorbance.
Sensing Element Principle Analyte Detected
Gold nanoparticles, functionalized by
monoclonal antibody, in dispersions
Absorption maximum of the LSPR in the sensing element is
redshifted by the molecularly recognized ligand
Ligand recognized by the monoclonal antibody
[176,177]
Mannose-functionalized gold
nanoparticles in dispersions
The LSPR spectrum of gold nanoparticles changes when the mannose
interacts with lectin
Lectin [179]
Amide-functionalized gold
nanoparticles in dispersions
The LSPR spectrum of gold nanoparticles changes in the presence
of anions
Anions [178]
Gold nanoshell dispersions The LSPR wavelength of gold nanoshells changes when functionalized
by alkanethiols
Alkanethiols [62]
Gold and silver nanoparticles
attached to quartz substrates
and functionalized by anti-HSA
(Human Serum Albumin)
The LSPR spectrum of immobilized gold and silver nanoparticles
changes when the anti-HSA interacts with HSA
Human Serum Albumin (HSA) [180]
Surface attached single gold
nanoparticle functionalized by biotin
The LSPR spectrum of single gold nanoparticle shifts upon the
interaction between biotin and streptavidin molecules
Streptavidin [181]
Gold nanoislands on a fiber
(fiber optic sensor)
The LSPR spectrum of gold nanoislands shifts upon immersion
of the fiber into a medium other that air
Any change in the surrounding medium [183,184]
Gold nanoislands, prepared by
vacuum evaporation onto
transparent substrates (T-LSPR)
The LSPR spectrum of gold nanoislands shifts upon attaching
the analyte to them
Metalloporphyrin and metallophtalocyanine monolayers
[67], 4-aminothiophenol, 4-mercaptopyridine, cyclic
disulfides, long-chain thiols [65]. Oligonucleotides
and their hybridization [68]
Gold nanoislands, vacuum
evaporated onto transparent
substrates, modified by cystamine,
and then reacted with biotin
The LSPR spectrum of gold nanoislands shifts upon the interaction
between biotin and avidin molecules
Avidin molecules [188]
Silver PPAs (T-LSPR) The LSPR spectrum of silver PPAs shifts upon attaching the analyte to
them
Alkanethiols [70,72], Streptavidin [185]
Biotin functionalized silver PPAs
(T-LSPR)
The LSPR spectrum of silver PPAs shifts upon the interaction between
biotin and anti-biotin molecules
Anti-biotin [73]
Cap-shaped gold nanostructures
evaporated onto a dense monolayer
of polystyrene spheres
The LSPR spectrum of the sensing element shifts upon the binding
of analyte molecules
Octadecanethiol, biotin, avidin [186]
Thin film of dodecylamine-capped
Au nanocrystals
The LSPR spectrum of the Au nanocrystals shifts upon the binding
of analyte molecules
Propanethiol [182]
toundecanoic acid, self-assembled to triangular silver nano-
particles, caused the absorption maximum to shift from
744.6 nm to 749.8 nm and upon the release of the polypeptide
the absorption maximum returned to 744.6 nm.
[70]
5.2. Assays Based on the Aggregation of Metallic
Nanoparticles
The aggregation of metallic nanoparticles results in substan-
tially altered surface plasmon absorption spectra, i.e., in a visi-
ble change of color. Based on this principle, a colorimetric
DNA hybridization assay was developed, detecting the spec-
tral change of thiolated oligonucleotide-covered gold nano-
particles when they aggregated in the presence of a comple-
mentary target oligonucleotide.
[189193]
The spectral changes
were found to be completely reversible by heating: the DNA
strands dehybridized and the particles separated from each
other. The melting transition of DNA-linked nanoparticle
aggregates was extremely sharp (compared to the melting
transition of unattached, free DNA), the melting tempera-
ture was relatively high, and very sensitive to base mis-
matches.
[190]
The detection limit of these assays was in the
femtomolar range.
[189]
Silver nanoparticles have also been functionalized by thio-
lated oligonucleotides and the spectral changes upon their
hybridization proved to be different from those of gold nano-
particles, exhibiting a marked decrease in intensity of the SPR
peak, as opposed to a shift of its maximum.
[194]
This specific
behavior is sufficiently different to that of the gold nanoparti-
cles to warrant the use of silver nanoparticles as a second mar-
ker in DNA hybridization experiments.
[194]
An interesting and exceptionally simple variant of this col-
orimetric DNA hybridization assay has been based on the
aggregation of oligonucleotide-functionalized large (3.1 lm)
white latex and small (13 nm) red gold particles in the pres-
ence of a target DNA strand (Fig. 15). After the hybridiza-
tion, the dispersion was filtered through a 0.45 lm membrane,
which allowed the unhybridized small gold particles to pass,
but not the large latex or the joined latexgold complexes. If
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1699
Table 3. Assays based on the aggregation of metallic nanoparticles.
Sensing Element Principle Analyte Detected
Oligonucleotide-functionalized gold nanoparticles
in aqueous dispersions
Hybridization of oligonucleotides links the gold nanoparticles
and their proximity changes the LSPR spectrum
Oligonucleotides complementary to
those in the sensing element [189193]
Surface immobilized, oligonucleotide-functionalized
gold nanoparticles
Hybridization of oligonucleotides links the gold nanoparticles
and their proximity changes the LSPR spectrum
Oligonucleotides complementary to
those in the sensing element
[211,222,223]
Oligonucleotide-functionalized gold and latex nanoparticles in
aqueous dispersions
Hybridization of oligonucleotides attach the gold nanoparticles
to the latex particles and their complex appears red
Oligonucleotides complementary to
those in the sensing elements (latex and
gold) [195]
Oligonucleotide-functionalized gold nanoparticles
and oligonucleotide-functionalized streptavidin
in aqueous dispersions
Hybridization of oligonucleotides links the gold nanoparticles
and streptavidin molecules to each other which changes
the LSPR spectrum
Oligonucleotides complementary to
those in the sensing element [224]
A protein recognition element attached to an oligonucleotide is
hybridized to gold nanoparticles,
that are functionalized by the complementary oligonucleotide
The antibodies (with two recognition sites) attach
to the proteins and link the gold nanoparticles,
changing thus their LSPR spectrum; Dehybridization
properties are specific for the DNA sequence, allowing
to identify a series of analyte (bio-barcodes)
IgG1 and IgE [196]
Gold nanoparticles modified by a-lactosyl-x-mercapto-
poly(ethylene glycol)
Reversible aggregation of gold nanoparticles in the presence
of analyte
Lectin [200]
Protein A coated gold nanoparticles, in aqueous dispersions Aggregation of gold nanoparticles in the presence of analyte Anti-protein A [197]
Gold MPCs capped by 11-mercaptoundecanoic acid,
in aqueous dispersions
Reversible aggregation of gold nanoparticles in the presence
of analyte (enhanced hyper-Rayleigh scattering!)
Heavy-metal ions(Pb
2+
, Hg
2+
, Cd
2+
)
[201]
Gold nanoparticles modified by 15-crown-5,
in aqueous dispersions
The K
+
ions link the gold nanoparticles together
and the LSPR spectrum changes;
K
+
ion [202]
Gold nanoparticles with pyrenyl units on the surface,
in aqueous dispersions
The dinitrophenyl units link the pyrenyl conjugated
gold nanoparticles together and the LSPR spectrum changes;
temperature dependent reversible
aggregation
Dinitrophenyl units [203]
Gold nanocrystals modified by disulfide biotin
analogue, in aqueous dispersions
Binding of streptavidin to the disulfide biotin
analogue induces the aggregation of gold nanocrystals and
changes in the LSPR spectra
Streptavidin [198]
A mixture of Au nanoparticles with surface attached
IgE molecules (against dinitrophenyl (DNP)) and Ag
nanoparticles with surface conjugated anti-biotin IgG
antibodies
The analyte links the Au and Ag nanoparticles which
results in their aggregation and changes in the LSPR spectra
Hetero-Janus DNP-biotin antigen [199]
Molecularly imprinted polymer with embedded
gold nanoparticles
The polymer swells upon binding of the analyte,
altering the proximity of the immobilized Au
nanoparticles and causing to shift their LSPR spectrum
Adrenalin [234]
hybridization has not occurred (in the absence of target oligo-
nucleotide), the membrane held the white latex particles only;
in case of hybridization (positive result), the goldlatex com-
plexes were trapped, and the membrane appeared red (see
Fig. 15).
[195]
Aggregation assays for the detection of proteins (based on
antibodyantigen, biotinstreptavidin interaction), lectin,
dinitrophenyl, K
+
, and several heavy-metal ions were also
demonstrated (Table 3).
[197203]
An interesting approach for
constructing sensors is the immobilization of the gold nano-
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1700 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Table 4. Labeling by metallic nanoparticles manifesting localized surface plasmon resonance.
Sensing Element Principle [a] Analyte Detected
DNA microarray Molecular recognition between the sensing element and analyte and labeling
of analyte by gold nanoparticles
Oligonucleotides complementary to those
in the sensing element
[208,211,224]
DNA microarray Molecular recognition between the sensing element and analyte and labeling
of analyte by anti-biotin conjugated gold nanoparticles
Biotinylated oligonucleotide, complementary
to those in the sensing element
[209,225]
DNA microarray Attachment of biotinylated detection oligonucleotides to the template DNA
with the subsequent labeling of them by anti-biotin conjugated silver
nanoparticles; single particle counting!
DNA polymorphism in template
oligonucleotides
[206]
Substrate bound antibodies
against Toxin A, in a commercial
ELISA sandwich assay
Toxin A was sandwiched between the sensing element and a biotinylated
(detection) antibody against Toxin A; The detection antibody was labeled
by anti-biotin conjugated gold nanoparticles
Toxin A
[209]
Gold nanoparticle conjugated
antibodies
against CD4, in aqueous dispersions
The antibodies (and their gold nanoparticle label with them) attach to the
lymphocytes surface
CD4 lymphocyte
[209]
Mouse antibody against HER-2/neu
tyrosine kinase
Breast carcinoma tissue was sequentially reacted with the sensing element,
biotinylated antimouse antibody and anti-biotin conjugated gold nanoparticles
(label)
HER-2/neu tyrosine kinase (transmembrane
glycoprotein) in breast carcinoma tissue
[209]
Human Papilloma Virus specific
DNA probe, labeled with FITC
(fluorescein isothiocyanate)
Fixed interface nuclei from HPV infected cells were hybridized with the sensing
element and reacted sequentially with mouse antifluorescein antibody,
biotinylated antimouse antibody and gold anti-biotin IgG (label)
Human Papilloma Virus in infected cells
[209]
Biotinylated DNA probe In situ hybridization of sensing element to analyte and labeling of the complex
by anti-biotin conjugated silver nanoparticles
Targeted DNA site
[205]
Mouse anti-ryanodine antibody Chicken skeletal muscle tissue was sequentially reacted with the sensing
element and anti-mouse antibody conjugated silver nanoparticles (label)
Ryanodine receptors in chicken skeletal
muscle
[205]
Multisegmented metallic
(Au, Ag, Ni) rods (barcodes)
derivatized with
oligonucleotides or antibodies
for human and rabbit IgG
Identification of analyte by the barcode patterns Oligonucleotides, antibodies for human
and rabbit IgG
[100,101]
[a] The labels are detected optically (under microscope, by CCD cameras).
Table 5. Signal amplification by localized surface plasmon resonance.
Sensing Element Method of Detection Analyte Detected
Antibody (anti human IgG (c)) immobilized
on gold film
Colloidal gold enhanced SPR Spectroscopy Antigen (human IgG (c)[214]
Oligonucleotides immobilized
on gold film
Colloidal gold enhanced SPR Spectroscopy Oligonucleotides, complementary to those in the
sensing element and labeled by gold nanoparticles
[218,225]
Oligonucleotides immobilized
on gold nanoislands
Colloidal gold enhanced T-SPR Spectroscopy Oligonucleotides, complementary to those in the
sensing element and labeled by gold nanoparticles [73]
Oligonucleotides immobilized on micropatterned
chemoresponsive diffraction grating
Colloidal gold enhanced diffraction
measurements
Oligonucleotides, complementary to those in the
sensing element and labeled by gold nanoparticles [223]
Gold colloidal film, covered by
layer-by-layer self-assembled polyelectrolyte film
Colloidal gold enhanced luminescence CdSe quantum dots (on the top of the multilayered
structure) [226]
Oligonucleotides immobilized
on silver nanoparticle coated
substrates
Colloidal silver enhanced emission Oligonucleotides, complementary to those in the
sensing element and labeled with fluorescein [227]
Antibody conjugated silver and
gold nanoislands on aminodextrane-coated
polystyrene beads
Colloidal gold and silver enhanced flow
cytometry
CD4+ and CD8+ lymphocytes [228
]
particles in molecularly imprinted polymers.
[204]
The polymer
swells upon selective binding of the analyte, the distance be-
tween immobilized gold nanoparticles increases, and hence
their T-LSPR spectrum changes.
5.3. Labeling by Metallic Nanoparticles Manifesting Localized
Surface Plasmon Resonance
Advantage has been taken of the extremely high scattering
flux (an 80 nm diameter metallic nanoparticle is estimated to
have a scattering flux which corresponds to those of 10
6
fluo-
rescein molecules
[205]
) and stable metallic nanoparticles to
replace (or complement) established radioactive, fluorescent,
chemiluminescent, or colorimetric labels, used in biochemis-
try, cell biology, and medical diagnostic applications.
[205210]
The ultrabright, non-bleaching nanoparticles can be observed
individually and can be prepared with a scattering peak at any
color of the visible spectrum, thus enabling the detection of
single molecules and/or multiple targets. Indeed, the detection
of chicken ryanodine receptor and a targeted DNA site on
Drosophila polytene chromosomes was demonstrated by in-
situ hybridization, cytological assay, and immunoassay, using
antibody-coated silver nanoparticles as optical labels (see
Table 4).
[205]
The same type of metallic nanoparticles were ap-
plied in a microarray-based DNA hybridization assay to label
the biotinylated oligonucleotides, and a sensitivity 60 times
greater than that of fluorescent labels was achieved.
[206]
Metallic-nanoparticle-labeled oligonucleotides had a sharp-
er melting (dehybridization) profile than those labeled by
fluorophores. The relatively sudden change of optical signa-
ture due to the separation of DNA-linked nanoparticles at a
sequence- and length-specific melting temperature allows
the discrimination of single-base-pair mismatches with a
selectivity three times greater than that observed with fluoro-
phore labeled targets (Fig. 16).
[211]
This observation, com-
bined with a signal amplification method based on the nano-
particle-promoted reduction of silver(I) and the use of a
conventional flatbed scanner as a reader is the basic principle
of the new scanometric chip-based detection system for
DNA, which has single mismatch selectivity and a sensitivity
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1701
Figure 14. a) TLSPR spectra of gold nanoislands (2.5 nm nominal thick-
ness, evaporated on quartz) before (bottom curve) and after (top curve)
the self-assembly of cyclic disulfide molecules. b) Difference spectrum,
obtained by subtraction of the bottom spectrum from the top one in (a);
the dashed line is a spectrum of a thick layer of the molecules, obtained
by evaporation of a drop on quartz (original spectrum divided by 6).
Reproduced with permission [65].
Figure 15. Schematic representation of gold nano-
particle/latex microsphere-based colorimetric DNA
detection method. Reproduced with permission
from [195].
exceeding that of the analogous fluorophore system by two
orders of magnitude.
[211]
Other examples for nanoparticle labeling are summarized
in Table 4. The commercial availability of gold nanoparticles
and gold-nanoparticle-labeled molecular-recognition ele-
ments merits mentioning in passing.
[212]
5.4. Signal Amplification by Localized Surface Plasmon
Resonance
Metallic nanoparticles have been employed to enhance the
signals in several optical techniques. Significant amplification
of the propagating surface plasmon resonance (SPR) spectro-
scopic signal by gold (or silver) nanoparticles will be discussed
here. An SPR-based sensor device contains four to six strati-
fied layers of different materials (Fig. 17).
[6,7]
In the Kretsch-
mann configuration, layer 1 is a right-angled or hemispherical
prism (which is sometimes optically coupled with a glass slide
made of the prism material), layer 2 is a thin film (~1.0
1.5 nm) of a binding material (like Cr, Ti, or W), usually vacu-
um deposited onto the surface of the prism base (or the opti-
cally coupled glass slide), layer 3 is the 3560 nm thick gold or
silver film which generates the propagating surface plasmons,
layer 4 is a SAM which incorporates the molecular recognition
element. Layer 5 contains the analyte, in the absence or in the
presence of attached (covalently or electrostatically) 1530 nm
diameter gold or silver nanoparticles (Fig. 17). Sensing
involves: i) the experimental determination of the surface plas-
mon resonance spectra of layers 35 (typically by scanning the
relative intensity of the reflected light as a function of the inci-
dent angle =angle-resolved SPR); ii) construction of an appro-
priate model that describes the behavior of the experimen-
tally probed sample well; iii) generation of expected
theoretical data plots (i.e., reflected light versus incident angle
plots) from the model; and iv) comparison of the experimen-
tally and theoretically obtained data plots to obtain the
needed parameters from the best fit for each layer.
[213]
Gold
nanoparticles attached to the analyte (layer 5 in the above
example) caused 25 signal amplification.
[214]
The signal am-
plification was explained by the interaction of localized and
propagating surface plasmon resonances
[213,215217]
and have
been shown to depend on the type of substrate and nanoparti-
cles (gold or silver) as well as on their sizes, shapes, and dis-
tance from the layer generating the propagating surface plas-
mons (layer 5, in the above example).
[213217]
A typical example of metallic-nanoparticle-enhanced SPR
is the derivatization of Au films by an antibody (a-human-
IgG), followed by either direct binding of an antigenAu con-
jugate or by binding of a free antigen and then a secondary
antibodyAu conjugate. In both cases, the signal enhancement
was large enough to allow the detection of solution protein
concentration in picomolar range.
[214]
Based on a similar prin-
ciple, DNA hybridization was measured.
[218]
In this work,
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1702 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
Figure 16. Dissociation of fluorescein-labeled (A) and nanoparticle
labeled (B) targets from the surfaces of oligonucleotide-functionalized
glass beads, monitored by quantifying the dissociated labels at
k = 520 nm (in the solution above the beads) as a function of tempera-
ture. The curves on the right in A,B describe the dissociation of target
and probe from a perfectly complementary capture strand and the curves
on the left describe the analogous process for a capture strand with a sin-
gle mismatch. The experiment clearly shows the advantages of nanopar-
ticle labeling. i) The temperature range of dehybridization of nanoparti-
cle complexes is much narrower than that for the fluorophore probes.
The sharp melting curve translates into high selectivity, because a tem-
perature can be selected so that a high proportion of labeled probe
remains hybridized to perfectly matched capture strands while most of
the probe is dehybridized from mismatched capture strands. (See and
compare the vertical dotted lines in A,B.) ii) The midpoint temperature
in the melting curves (T
m
) for the complexes with nanoparticle probes
also is significantly higher compared to that with fluorophore probes,
and thus the critical concentration below which the complex sponta-
neously melts is lower. This feature increases the sensitivity in the assay.
Reproduced with permission from [211]; copyright 2000, the American
Association for the Advancement of Science.
Figure 17. Schematics showing the five stratified layers of different mate-
rials in a gold-nanoparticle-enhanced SPR based sensor device. Layer 1
is a right-angled (or hemispherical) prism optically coupled (by a refrac-
tive index matching fluid) with a glass slide made of the prism material,
layer 2 is a thin film (~ 1.01.5 nm) of a binding material (like Cr, Ti, or
W), layer 3 is the 3560 nm thick gold or silver film which generates the
propagating surface plasmons, layer 4 is a SAM which incorporates the
molecular recognition element. Layer 5 contains the analyte, attached
(covalently or electrostatically) to 1530 nm diameter gold or silver nano-
particles.
oligonucleotide probes were linked covalently to the gold sur-
face, then hybridized to one half of the target DNA molecule.
In the next step another oligonucleotide, with a sequence
complementary to the other half of the target, was added,
either untagged or conjugated with Au nanoparticles. In addi-
tion to the plotted SPR curves, 2D SPR images of the mea-
sured spots provided an easy way to visualize the results. The
detection limit in these experiments was ~ 10 pM (8 10
8
-
molecules cm
1
).
[218]
The attachment of gold nanoparticles to the materials
adsorbed onto SAMs has enhanced the sensitivity of the
T-LSPR,
[68]
in a manner quite analogous to that observed for
SPR spectroscopy.
[214]
Recently, this approach has been uti-
lized for the detection of DNA hybridization (Fig. 18).
[68]
The
self-assembly of oligoA (12 bases of homogeneous sequence
containing only adenine, thiolated at the 5 end) and mercap-
tohexanol spacer onto gold nanoislands evaporated onto a
glass slide (Fig. 18), as well as the DNA hybridization (by
oligoT=12 bases of homogeneous sequence containing only
thymine, thiolated at the 5 end) could be readily sensed by
T-LSPR (Fig. 18). The sensitivity of T-LSPR was found to
dramatically increase with the functionalization of the com-
plementary DNA by 11.7 1.9 nm diameter gold nano-
particles (Fig. 18). Proximity of the gold nanoparticles to the
gold nanoislands could be readily seen by transmission elec-
tron microscopy (TEM).
[68]
Further examples of LSPR-amplified techniques are col-
lected in Table 5.
6. Conclusion
Exploitation of localized surface plasmons as nanoscale
optical devices and sensors has reached a significant level of
recognition, even though most of the references cited in this
review have been published in this millennium. Reports on
the development of innovative concepts, unprecedented appli-
cations, and fabrication of sensors with previously unimagined
selectivity and sensitivity are seeing daylight at an exponen-
tially increasing rate. Nevertheless, there is much more to be
done, much more to be hoped for. Full realization of the
potential of surface plasmons requires a much better under-
standing of the underlying fundamentals and a greater cooper-
ation between physicists, chemists, and material scientists. It is
sincerely hoped that this review will inspire researchers to
make their own contributions to this exciting and highly rele-
vant fi
Received: February 26, 2004
Final version: June 15, 2004

[1] U. Kreibig, M. Vollmer, Optical Properties of Metal Clusters, Sprin-

ger-Verlag, Berlin, Germany 1995.
[2] S. Underwood, P. Mulvaney, Langmuir 1994, 10, 3427.
[3] P. Mulvaney, Langmuir 1996, 12, 788.
[4] D. G. Richards, D. L. McMillin, E. A. Mein, C. D. Nelson, Int. J.
Neurosci. 2002, 112, 31.
[5] M. Matsumoto, H. Yoshimura, V. S. Kulkarni, K. Nagayama, Colloid
Polym. Sci. 1990, 268, 1174.
[6] M.-C. Daniel, D. Astruc, Chem. Rev. 2004, 104, 293.
[7] J. M. Brockman, B. P. Nelson, R. M. Corn, Annu. Rev. Phys. Chem.
2000, 51, 41.
[8] S. Wang, S. Boussaad, N. J. Tao, in Biomolecular Films: Design,
Function and Applications, Vol. 111 (Ed: J. F. Rusling), Marcel
Dekker, New York 2003, p. 213.
[9] J. Homola, S. S. Yee, G. Gauglitz, Sens. Actuators, B 1999, 54, 3.
[10] D. F. Evans, H. Wennerstrom, The Colloidal Domain: Where Phys-
ics, Chemistry, and Technology Meet, VCH, New York 1999.
[11] D. Goia, J. Mater. Chem. 2004, 14, 451.
[12] J. Turkevich, P. C. Stevenson, J. Hillier, Discuss. Faraday Soc. 1951,
55.
[13] D. A. Handley, in Colloidal Gold: Principles, Methods, and Applica-
tions, Vol. 1 (Ed: M. A. Hayat), Academic Press, Inc., San Diego,
CA 1989, p. 13.
[14] D. Peters, J. Mater. Chem. 1996, 6, 1605.
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1703
Figure 18. Top: Schematic representation of the gold nanoparticle en-
hanced T-LSPR, utilized for DNA detection. Single-stranded DNA was
self-assembled onto gold nanoislands on a glass slide with the subse-
quent introduction of mercaptohexanol spacer molecules (short thiols in
the Fig.) and then hybridized by the complementary DNA, which itself
was functionalized by 11.7 1.9 nm diameter gold nanoparticles. The
diameter of the gold nanoislands and the gold nanoparticles are drawn
to scale, but the length of DNA was increased for clarity. Bottom: T-LSPR
spectra of gold nanoislands in TE (Tris-EDTA) buffer prior (1) and subse-
quent to the self-assembly of single-stranded DNA and mercaptohexanol
and hybridization by the complementary DNA, unlabeled (2) or labeled
(3) by gold nanoparticles. Reproduced with permission from [68]; copy-
right 2003, the American Chemical Society.
[15] T. Fujimoto, S. Terauchi, H. Umehara, I. Kojima, W. Henderson,
Chem. Mater. 2001, 13, 1057.
[16] K. Okitsu, A. Yue, S. Tanabe, H. Matsumoto, Y. Yobiko, Langmuir
2001, 17, 7717.
[17] V. G. Pol, D. N. Srivastava, O. Palchik, V. Palchik, M. A. Slifkin,
A. M. Weiss, A. Gedanken, Langmuir 2002, 18, 3352.
[18] A. Kulak, S. A. Davis, E. Dujardin, S. Mann, Chem. Mater. 2003, 15,
528.
[19] V. G. Pol, A. Gedanken, J. Calderon-Moreno, Chem. Mater. 2003,
15, 1111.
[20] G. H. Fu, W. P. Cai, C. X. Kan, C. C. Li, L. Zhang, Appl. Phys. Lett.
2003, 83, 36.
[21] W. Chen, J. Y. Zhang, Y. Di, Z. M. Wang, Q. Fang, W. P. Cai, Appl.
Surf. Sci. 2003, 211, 280.
[22] M. Giersig, P. Mulvaney, Langmuir 1993, 9, 3408.
[23] M. Brust, M. Walker, D. Bethell, D. J. Schiffrin, R. Whyman,
J. Chem. Soc. Chem. Commun. 1994, 801.
[24] M. J. Hostetler, S. J. Green, J. J. Stokes, R. W. Murray, J. Am. Chem.
Soc. 1996, 118, 4212.
[25] A. C. Templeton, M. P. Wuelfing, R. W. Murray, Acc. Chem. Res.
2000, 33, 27.
[26] M. M. Alvarez, J. T. Khoury, T. G. Schaaff, M. N. Shafigullin, I. Vez-
mar, R. L. Whetten, J. Phys. Chem. B 1997, 101, 3706.
[27] Z. L. Wang, Characterization of Nanophase Materials, Vol. 1, Wiley-
VCH, Weinheim, Germany 2000, p. 406.
[28] L. Q. Wang, G. J. Exarhos, J. Liu, in Characterization of Nanophase
Materials, Vol. 1 (Ed: Z. L. Wang), Wiley-VCH, Weinheim, Ger-
many 2000, p. 243.
[29] N. R. Jana, X. G. Peng, J. Am. Chem. Soc. 2003, 125, 14 280.
[30] S. Stoeva, K. J. Klabunde, C. M. Sorensen, I. Dragieva, J. Am. Chem.
Soc. 2002, 124, 2305.
[31] H. Choo, E. Cutler, Y. S. Shon, Langmuir 2003, 19, 8555.
[32] P. Pengo, S. Polizzi, M. Battagliarin, L. Pasquato, P. Scrimin, J. Mater.
Chem. 2003, 13, 2471.
[33] C. A. Waters, A. J. Mills, K. A. Johnson, D. J. Schiffrin, Chem. Com-
mun. 2003, 540.
[34] E. Hutter, J. H. Fendler, Chem. Commun. 2002, 378.
[35] R. L. Whetten, J. T. Khoury, M. M. Alvarez, S. Murthy, I. Vezmar,
Z. L. Wang, P. W. Stephens, C. L. Cleveland, W. D. Luedtke,
U. Landman, Adv. Mater. 1996, 8, 428.
[36] R. L. Whetten, M. N. Shafigullin, J. T. Khoury, T. G. Schaaff, I. Vez-
mar, M. M. Alvarez, A. Wilkinson, Acc. Chem. Res. 1999, 32, 397.
[37] C. Radloff, N. J. Halas, Appl. Phys. Lett. 2001, 79, 674.
[38] F. Caruso, Adv. Mater. 2001, 13, 11.
[39] J. H. Fendler, Membrane Mimetic Approach to Advanced Materials,
Vol. 113, Springer-Verlag, Berlin, Germany 1992.
[40] J. H. Fendler, Membrane Mimetic Chemistry, Characterizations and
Applications of Micelles, Microemulsions, Monolayers, Bilayers, Vesi-
cles, Host-Guest Systems and Polyions, John Wiley, New York 1982.
[41] J. Tanori, M. P. Pileni, Langmuir 1997, 13, 639.
[42] M. P. Pileni, Ber. Bunsen-Ges. 1997, 101, 1578.
[43] A. Filankembo, M. P. Pileni, J. Phys. Chem. B 2000, 104, 5865.
[44] D. A. Tomalia, A. M. Naylor, W. A. Goddard III, Angew. Chem. Int.
Ed. Engl. 1990, 29, 138.
[45] J. M. J. Frechet, C. J. Hawker, I. Gitsov, J. W. Leon, J. Macromol.
Sci. Pure Appl. Chem. 1996, a33, 1399.
[46] F. S. Bates, G. H. Fredrickson, Phys. Today 1999, 52, 32.
[47] J. W. Zhai, W. S. Shi, L. Y. Zhang, X. Yao, Ferroelectrics 1999, 230,
541.
[48] V. M. Rudoy, I. V. Yaminskii, O. V. Dement'eva, V. A. Ogarev, Col-
loid J. 1999, 61, 800.
[49] H. Colfen, H. Schnablegger, M. Antonietti, J. Colloid Interface Sci.
1999, 212, 197.
[50] S. T. Selvan, T. Hayakawa, M. Nogami, M. Moller, J. Phys. Chem. B
1999, 103, 7441.
[51] C. Nardin, S. Thoeni, J. Widmer, M. Winterhalter, W. Meier, Chem.
Commun. 2000, 1433.
[52] C. Sonnichsen, T. Franzl, T. Wilk, G. von Plessen, J. Feldmann, Phys.
Rev. Lett. 2002, 88, 077 402.
[53] G. Gorodyska, A. Kiriy, S. Minko, C. Tsitsilianis, M. Stamm, Nano
Lett. 2003, 3, 365.
[54] S. H. Feng, R. R. Xu, Acc. Chem. Res. 2001, 34, 239.
[55] M. M. Lencka, M. Oledzka, R. E. Riman, Chem. Mater. 2000, 12,
1323.
[56] N. R. Jana, L. Gearheart, C. J. Murphy, Adv. Mater. 2001, 13, 1389.
[57] C. J. Johnson, E. Dujardin, S. A. Davis, C. J. Murphy, S. Mann,
J. Mater. Chem. 2002, 12, 1765.
[58] N. R. Jana, L. A. Gearheart, S. O. Obare, C. J. Johnson, K. J. Edler,
S. Mann, C. J. Murphy, J. Mater. Chem. 2002, 12, 2909.
[59] J. X. Gao, C. M. Bender, C. J. Murphy, Langmuir 2003, 19, 9065.
[60] B. Nikoobakht, M. A. El-Sayed, Chem. Mater. 2003, 15, 1957.
[61] N. Taub, O. Krichevski, G. Markovich, J. Phys. Chem. B 2003, 107,
11 579.
[62] Y. G. Sun, Y. N. Xia, Anal. Chem. 2002, 74, 5297.
[63] Y. Sun, Y. Xia, J. Am. Chem. Soc. 2004, 126, 3892.
[64] J. E. Mahan, Physical Vapor Deposition of Thin Films, John Wiley &
Sons, New York 1999.
[65] G. Kalyuzhny, A. Vaskevich, M. A. Schneeweiss, I. Rubinstein,
Chem. Eur. J. 2002, 8, 3850.
[66] G. Kalyuzhny, M. A. Schneeweiss, A. Shanzer, A. Vaskevich, I. Ru-
binstein, J. Am. Chem. Soc. 2001, 123, 3177.
[67] G. Kalyuzhny, A. Vaskevich, G. Ashkenasy, A. Shanzer, I. Rubin-
stein, J. Phys. Chem. B 2000, 104, 8238.
[68] E. Hutter, M.-P. Pileni, J. Phys. Chem. B 2003, 107, 6497.
[69] A. J. Haes, R. P. Van Duyne, A Highly Sensitive and Selective Sur-
face-enhanced Nanobiosensor, in Materials Research Society Symp.
Proc. 2002, 123, pp. O3.1.1.
[70] M. D. Malinsky, K. L. Kelly, G. C. Schatz, R. P. Van Duyne, J. Am.
Chem. Soc. 2001, 123, 1471.
[71] M. D. Malinsky, K. L. Kelly, G. C. Schatz, R. P. Van Duyne, J. Phys.
Chem. B 2001, 105, 2343.
[72] A. D. McFarland, R. P. Van Duyne, Nano Lett. 2003, 3, 1057.
[73] J. C. Riboh, A. J. Haes, A. D. McFarland, C. R. Yonzon, R. P. Van
Duyne, J. Phys. Chem. B 2003, 107, 1772.
[74] W. Gotschy, K. Vonmetz, A. Leitner, F. R. Aussenegg, Appl. Phys. B
1996, 63, 381.
[75] N. Felidj, J. Aubard, G. Levi, J. R. Krenn, M. Salerno, G. Schider,
B. Lamprecht, A. Leitner, F. R. Aussenegg, Phys. Rev. B 2002, 65,
075 419.
[76] W. Rechberger, A. Hohenau, A. Leitner, J. R. Krenn, B. Lamprecht,
F. R. Aussenegg, Opt. Commun. 2003, 220, 137.
[77] C. L. Haynes, A. D. McFarland, L. Zhao, R. P. Van Duyne, G. C.
Schatz, L. Gunnarsson, J. Prikulis, B. Kasemo, M. Kall, J. Phys.
Chem. B 2003, 107, 7337.
[78] M. Akahashi, Y. Miyahara, Chem. Lett. 1998, 917.
[79] M. S. Yeh, Y. S. Yang, Y. P. Lee, H. F. Lee, Y. H. Yeh, C. S. Yeh,
J. Phys. Chem. B 1999, 103, 6851.
[80] A. Henglein, J. Phys. Chem. 1993, 97, 5457.
[81] B. G. Ershov, E. Janata, A. Henglein, A. Fojtik, J. Phys. Chem. B
1993, 97, 4589.
[82] C. H. Bae, S. H. Nam, S. M. Park, Appl. Surf. Sci. 2002, 197, 628.
[83] Y. H. Chen, C. S. Yeh, Colloids Surf., A 2002, 197, 133.
[84] A. V. Kabashin, M. Meunier, C. Kingston, J. H. T. Luong, J. Phys.
Chem. B 2003, 107, 4527.
[85] F. Mafune, J. Kohno, Y. Takeda, T. Kondow, J. Phys. Chem. B 2001,
105, 9050.
[86] F. Mafune, J. Kohno, Y. Takeda, T. Kondow, J. Phys. Chem. B 2003,
107, 12 589.
[87] F. Mafune, J. Kohno, Y. Takeda, T. Kondow, H. Sawabe, J. Phys.
Chem. B 2000, 104, 9111.
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1704 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
[88] F. Mafune, J. Y. Kohno, Y. Takeda, T. Kondow, H. Sawabe, J. Phys.
Chem. B 2000, 104, 8333.
[89] F. Mafune, J. Y. Kohno, Y. Takeda, T. Kondow, J. Phys. Chem. B
2002, 106, 7575.
[90] F. Mafune, J. Y. Kohno, Y. Takeda, T. Kondow, H. Sawabe, J. Phys.
Chem. B 2001, 105, 5114.
[91] I. Lee, S. W. Han, K. Kim, Chem. Commun. 2001, 1782.
[92] C. Y. Wang, H. Y. Fang, J. B. He, W. L. Zhou, K. L. Stokes, J. Col-
loid Interface Sci. 2003, 260, 440.
[93] Y. Niidome, K. Nishioka, H. Kawasaki, S. Yamada, Chem. Commun.
2003, 18, 2376.
[94] M. Maillard, P. Huang, L. Brus, Nano Lett. 2003, 3, 1611.
[95] R. C. Jin, Y. C. Cao, E. C. Hao, G. S. Metraux, G. C. Schatz, C. A.
Mirkin, Nature 2003, 425, 487.
[96] S. Link, M. A. El-Sayed, Annu. Rev. Phys. Chem. 2003, 54, 331.
[97] X. Y. Jiang, R. Ferrigno, M. Mrksich, G. M. Whitesides, J. Am.
Chem. Soc. 2003, 125, 2366.
[98] P. Zhang, T. K. Sham, Appl. Phys. Lett. 2003, 82, 1778.
[99] Y. Sun, Y. Xia, Nano Lett. 2003, 3, 1569.
[100] C. D. Keating, M. J. Natan, Adv. Mater. 2003, 15, 451.
[101] S. R. Nicewarner-Pea, R. G. Freeman, B. D. Reiss, L. He, D. J.
Pea, I. D. Walton, R. Cromer, C. D. Keating, M. J. Natan, Science
2001, 294, 137.
[102] X. Qu, Z. Peng, X. Jiang, S. Dong, Langmuir 2004, 20, 2519.
[103] E. Hutter, Ph.D. Thesis, Clarkson University, Potsdam, NY, 2001.
[104] G. Xu, M. Tazawa, P. Jin, S. Nakao, K. Yoshimura, Appl. Phys. Lett.
2003, 82, 3811.
[105] G. Mie, Ann. Phys. 1908, 25, 377
[106] K. L. Kelly, E. Coronado, L. L. Zhao, G. C. Schatz, J. Phys. Chem. B
2003, 107, 668.
[107] S. Link, M. A. El-Sayed, J. Phys. Chem. B 1999, 103, 4212.
[108] A. C. Templeton, J. J. Pietron, R. W. Murray, P. Mulvaney, J. Phys.
Chem. B 2000, 104, 564.
[109] C. F. Bohren, D. R. Huffman, Absorption and Scattering of Light by
Small Particles, Vol. 1, John Wiley & Sons, Inc., New York 1998.
[110] S. Link, M. A. El-Sayed, Int. Rev. Phys. Chem. 2000, 19, 409.
[111] Y. G. Sun, Y. N. Xia, Proc. SPIEInt. Soc. Opt. Eng. 2003, 5221, 164.
[112] B. M. I. Vanderzande, M. R. Bohmer, L. G. J. Fokkink, C. Schonen-
berger, J. Phys. Chem. B 1997, 101, 852.
[113] J. P. Kottmann, O. J. F. Martin, Opt. Express 2000, 6, 213.
[114] E. Hao, R. C. Bailey, G. C. Schatz, J. T. Hupp, S. Li, Nano Lett.
2004, 4, 327.
[115] I. O. Sosa, C. Noguez, R. G. Barrera, J. Phys. Chem. B 2003, 107,
6269.
[116] E. Hao, S. Li, R. C. Bailey, S. Zou, G. C. Schatz, J. T. Hupp, J. Phys.
Chem. B 2004, 108, 1224.
[117] J. J. Mock, D. R. Smith, M. Barbic, S. J. Oldenburg, D. A. Schultz,
S. Schultz, Proc. SPIEInt. Soc. Opt. Eng. 2003, 5221, 66.
[118] B. Lamprecht, G. Schjider, R. T. Lechner, H. Ditlbacher, J. R.
Krenn, A. Leitner, F. R. Aussenegg, Phys. Rev. Lett. 2000, 84, 4721.
[119] S. A. Maier, M. L. Brongersma, P. G. Kik, H. A. Atwater, Phys. Rev.
B 2002, 65, 193 408.
[120] K. H. Su, Q. H. Wei, X. Zhang, J. J. Mock, D. R. Smith, S. Schultz,
Proc. SPIEInt. Soc. Opt. Eng. 2003, 5221, 108.
[121] J. R. Krenn, A. Dereux, J. C. Weeber, E. Bourillot, Y. Lacroute, J. P.
Goudonnet, G. Schider, W. Gotschy, A. Leitner, F. R. Aussenegg,
C. Girard, Phys. Rev. Lett. 1999, 82, 2590.
[122] S. A. Maier, M. L. Brongersma, P. G. Kik, S. Meltzer, A. A. G.
Requicha, H. A. Atwater, Adv. Mater. 2001, 13, 1501.
[123] P. C. Andersen, K. L. Rowlen, Appl. Spectrosc. 2002, 56, 124A.
[124] W. L. Barnes, A. Dereux, T. W. Ebbesen, Nature 2003, 424, 824.
[125] B. Lamprecht, J. R. Krenn, G. Schider, H. Ditlbacher, M. Salerno,
N. Felidj, A. Leitner, F. R. Aussenegg, Appl. Phys. Lett. 2001, 79, 51.
[126] E. Devaux, T. W. Ebbesen, J. C. Weeber, A. Dereux, Appl. Phys.
Lett. 2003, 83, 4936.
[127] H. Raether, Surface Plasmons on Smooth and Rough Surfaces and
on Gratings, Springer-Verlag, Berlin, Germany 1988.
[128] R. M. Dickson, L. A. Lyon, J. Phys. Chem. B 2000, 104, 6095.
[129] S. A. Maier, P. G. Kik, H. A. Atwater, S. Melyzer, E. Harel, B. Koel,
A. A. G. Requicha, Nat. Mater. 2003, 2, 229.
[130] P. Dawson, A. F. Puygranier, J. P. Goudonnet, Phys. Rev. B 2001, 63,
205 410.
[131] T. W. Ebbesen, H. J. Lezec, H. F. Ghaemi, T. Thio, P. A. Wolff, Na-
ture 1998, 391, 667.
[132] H. F. Ghaemi, T. Thio, D. E. Grupp, T. W. Ebbesen, H. J. Lezec,
Phys. Rev. B 1998, 58, 6779.
[133] U. Schroter, D. Heitmann, Phys. Rev. B 1998, 58, 15 419.
[134] J. A. Porto, F. J. Garcia-Vidal, J. B. Pendry, Phys. Rev. Lett. 1999, 83,
2845.
[135] W.-C. Tan, T. W. Preist, R. J. Sambles, Phys. Rev. B 2000, 62, 11 134.
[136] E. Popov, M. Neviere, S. Enoch, R. Reinisch, Phys. Rev. B 2000, 62,
16 100.
[137] W.-C. Liu, D. P. Tsai, Phys. Rev. B 2002, 65, 155 423.
[138] F. J. Garciavidal, H. J. Lezec, T. W. Ebbesen, L. Martinmoreno,
Phys. Rev. Lett. 2003, 90, 213 901.
[139] F. J. Garciavidal, L. Martinmoreno, H. J. Lezec, T. W. Ebbesen,
Appl. Phys. Lett. 2003, 83, 4500.
[140] J. B. Pendry, Phys. Rev. Lett. 2000, 85, 3966.
[141] L. V. Panina, A. N. Grigorenko, D. P. Makhnovskiy, Phys. Rev. B
2002, 66, 155 411.
[142] V. A. Podolskiy, Opt. Express 2003, 11, 735.
[143] D. R. Smith, W. J. Padilla, D. C. VGier, S. C. Nemat-Nasser,
S. Shultz, Phys. Rev. Lett. 2000, 84, 4184.
[144] N. Fang, Z. Liu, T.-J. Yen, X. Zhang, Opt. Express 2003, 11, 682.
[145] H. Ditlbacher, J. R. Krenn, B. Lamprecht, A. Leitner, F. R. Ausse-
negg, Opt. Lett. 2000, 25, 563.
[146] C. A. Constantine, K. M. Gattas-Asfura, S. V. Mello, G. Crespo,
V. Rastogi, T. C. Cheng, J. J. De Frank, R. M. Leblanc, J. Phys.
Chem. B 2003, 107, 13 762.
[147] B. Hecht, B. Sick, U. P. Wild, V. Deckert, R. Zenobi, O. J. F. Martin,
D. W. Pohl, J. Chem. Phys. 2000, 112, 7761.
[148] R. C. Dunn, Chem. Rev. 1999, 99, 2891.
[149] F. Zenhausern, M. P. Oboyle, H. K. Wickramasinghe, Appl. Phys.
Lett. 1994, 65, 1623.
[150] Y. Martin, F. Zenhausern, H. K. Wickramasinghe, Appl. Phys. Lett.
1996, 68, 2475.
[151] R. E. Larsen, H. Metiu, J. Chem. Phys. 2001, 114, 6851.
[152] M. Specht, J. D. Pedarnig, W. M. Heckl, T. W. Hansch, Phys. Rev.
Lett. 1992, 68, 476.
[153] J. R. Krenn, M. Salerno, N. Felidj, B. Lamprecht, G. Schider, A. Leit-
ner, F. R. Aussenegg, J. C. Weeber, A. Dereux, J. P. Goudonnet,
J. Microsc. 2001, 202, 122.
[154] S. I. Bozhevolnyi, I. I. Smolyaninov, A. V. Zayats, Phys. Rev. B 1995,
51, 17 916.
[155] I. I. Smolyaninov, D. L. Mazzoni, J. Mait, C. C. Davis, Phys. Rev. B
1997, 56, 1601.
[156] I. I. Smolyaninov, D. L. Mazzoni, C. C. Davis, Phys. Rev. Lett. 1996,
77, 3877.
[157] G. A. Wurtz, J. Hranisavljevic, G. P. Wiederrecht, Nano Lett. 2003,
3, 1511.
[158] I. I. Smolyaninov, A. V. Zayats, A. Gungor, C. C. Davis, Phys. Rev.
Lett. 2002, 88, 187 402.
[159] E. Yablonovitch, J. Phys. Condens. Matter 1993, 5, 2443.
[160] H. Benisty, C. Weisbuch, D. Labilloy, M. Rattier, Appl. Surf. Sci.
2000, 164, 205.
[161] Y. Z. Shen, C. S. Friend, Y. Jiang, D. Jakubczyk, J. Swiatkiewicz,
P. N. Prasad, J. Phys. Chem. B 2000, 104, 7577.
[162] C. Lopez, Adv. Mater. 2003, 15, 1679.
[163] I. Soten, H. Miguez, S. M. Yang, S. Petrov, N. Coombs, N. Tetreault,
N. Matsuura, H. E. Ruda, G. A. Ozin, Adv. Funct. Mater. 2002, 12, 71.
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1705
[164] D. J. Norris, Y. A. Vlasov, Adv. Mater. 2001, 13, 371.
[165] S. C. Kitson, W. L. Barnes, J. R. Sambles, Phys. Rev. B 1995, 52,
11 441.
[166] W. L. Barnes, S. C. Kitson, J. R. Sambles, Phys. Rev. Lett. 1996, 77,
2670.
[167] W. L. Barnes, T. W. Preist, S. J. Kitson, J. R. Sambles, Phys. Rev. B
1996, 54, 6227.
[168] W. L. Barnes, S. C. Kitson, T. W. Preist, J. R. Sambles, J. Opt. Soc.
Am. A 1997, 14, 1654.
[169] S. G. Penn, L. He, M. J. Natan, Curr. Opin. Chem. Biol. 2003, 7, 609.
[170] A. Campion, P. Kambhampati, Chem. Soc. Rev. 1998, 27, 241.
[171] Z. Q. Tian, B. Ren, D. Y. Wu, J. Phys. Chem. B 2002, 106, 9463.
[172] M. Osawa, Bull. Chem. Soc. Jpn. 1997, 70, 2861.
[173] S. A. Levi, A. Mourran, J. P. Spatz, F. C. J. M. van Veggel, D. N. Re-
inhoudt, M. Moller, Chem. Eur. J. 2002, 8, 3808.
[174] N. Calander, Anal. Chem. 2004, 76, 2168.
[175] S. Ekgasit, C. Thammacharoen, F. Yu, W. Knoll, Anal. Chem. 2004,
76, 2210.
[176] P. Englebienne, Analyst 1998, 123, 1599.
[177] P. Englebienne, A. Van Hoonacker, M. Verhas, Analyst 2001, 126,
1645.
[178] S. Watanabe, M. Sonobe, M. Arai, Y. Tazume, T. Matsuo, T. Naka-
mura, K. Yoshida, Chem. Commun. 2002, 2866.
[179] M. Schwarzott, H. Engelhardt, T. Kluhspies, D. Baurecht, D. Nau-
mann, U. P. Fringeli, Langmuir 2003, 19, 7451.
[180] F. Frederix, J.-M. Friedt, K.-H. Choi, W. Laureyn, A. Campitelli,
D. Mondelaers, G. Maes, G. Borghs, Anal. Chem. 2003, 75, 6894.
[181] G. Raschke, S. Kowarik, T. Franzl, S. Sonnichsen, T. A. Klar, J. Feld-
mann, Nano Lett. 2003, 3, 935.
[182] S. M. Briglin, T. Gao, N. S. Lewis, Langmuir 2004, 20, 299.
[183] F. Meriaudeau, T. Downey, A. Wig, A. Passian, M. Buncick, T. L.
Ferrell, Sens. Actuators, B 1999, 54, 106.
[184] F. Meriaudeau, A. Wig, A. Passian, T. Downey, M. Buncick, T. L.
Ferrell, Sens. Actuators, B 2000, 69, 51.
[185] A. J. Haes, R. P. Van Duyne, J. Am. Chem. Soc. 2002, 124, 10 596.
[186] M. Himmelhaus, H. Takei, Sens. Actuators, B 2000, 63, 24.
[187] M. Lahav, A. Vaskevich, I. Rubinstein, Langmuir 2004, 20, 7365.
[188] C. L. Haynes, R. P. Van Duyne, J. Phys. Chem. B 2001, 105, 5599.
[189] R. A. Reynolds III, C. A. Mirkin, R. L. Letsinger, J. Am. Chem.
Soc. 2000, 122, 3795.
[190] J. J. Storhoff, R. Elghanian, R. C. Mucic, C. A. Mirkin, R. L. Let-
singer, J. Am. Chem. Soc. 1998, 120, 1959.
[191] A. C. Mirkin, L. R. Letsinger, C. R. Mucic, J. J. Storhoff, Nature
1996, 382, 607.
[192] J. J. Storhoff, A. A. Lazarides, R. C. Mucic, C. A. Mirkin, R. L. Let-
singer, G. C. Schatz, J. Am. Chem. Soc. 2000, 122, 4640.
[193] R. C. Mucic, J. J. Storhoff, C. A. Mirkin, R. L. Letsinger, J. Am.
Chem. Soc. 1998, 120, 12 674.
[194] I. Tokareva, E. Hutter, J. Am. Chem. Soc., in press.
[195] R. A. Reynolds III, C. A. Mirkin, R. L. Letsinger, Pure Appl. Chem.
2000, 72, 229.
[196] J.-M. Nam, S.-J. Park, C. A. Mirkin, J. Am. Chem. Soc. 2002, 124,
3820.
[197] N. T. K. Thanh, Z. Rosenzweig, Anal. Chem. 2002, 74, 1624.
[198] S. Connolly, D. Fitzmaurice, Adv. Mater. 1999, 11, 1202.
[199] W. Shenton, S. A. Davis, S. Mann, Adv. Mater. 1999, 11, 449.
[200] H. Otsuka, Y. Akiyama, Y. Nagasaki, K. Kataoka, J. Am. Chem. Soc.
2001, 123, 8226.
[201] Y. Kim, R. C. Johnson, J. T. Hupp, Nano Lett. 2001, 1, 165.
[202] S. Y. Lin, S. W. Liu, C. M. Lin, C. H. Chen, Anal. Chem. 2002, 74,
330.
[203] K. Naka, H. Roh, Y. Chujo, Langmuir 2003, 19, 5496.
[204] K. Glinel, A. M. Jonas, A. Laschwesky, P. Y. Vuillaume, in Multi-
layer Thin Films, Sequential Assembly of Nanocomposite Materials,
Vol. 1 (Eds: G. Decher, J. B. Schlenoff), Wiley-VCH, Weinheim,
Germany 2003, p. 177.
[205] S. Schultz, D. R. Smith, J. J. Mock, D. A. Schultz, Proc. Natl. Acad.
Sci. USA 2000, 97, 996.
[206] S. J. Oldenburg, C. C. Genick, K. A. Clark, D. A. Schultz, Anal. Bio-
chem. 2002, 309, 109.
[207] D. A. Schultz, Curr. Opin. Biotechnol. 2003, 14, 13.
[208] J. M. Kohler, A. Csaki, J. Reichert, R. Moller, W. Straube,
W. Fritzsche, Sens. Actuators, B 2001, 76, 166.
[209] J. Yguerabide, E. E. Yguerabide, J. Cell. Biochem. 2001, 37, 71.
[210] P. Englebienne, A. Van Hoonacker, M. Verhas, N. G. Khlebtsov,
Comb. Chem. High Throughput Screening 2003, 6, 777.
[211] T. A. Taton, C. A. Mirkin, R. L. Letsinger, Science 2000, 289, 1757.
[212] http://www.aurion.nl; http://www.nanoprobes.com; http://www.2spi.-
com/catalog/chem/gold.html.
[213] D. Roy, J. H. Fendler, Adv. Mater. 2004, 16, 479.
[214] L. A. Lyon, M. D. Musick, M. J. Natan, Anal. Chem. 1998, 70, 5177.
[215] E. Hutter, J. H. Fendler, D. Roy, J. Phys. Chem. B 2001, 105, 11 159.
[216] E. Hutter, S. Cha, J. F. Liu, J. Park, J. Yi, J. H. Fendler, D. Roy,
J. Phys. Chem. B 2001, 105, 8.
[217] S. Chah, E. Hutter, D. Roy, J. H. Fendler, J. Yi, Chem. Phys. 2001,
272, 127.
[218] L. He, M. D. Musick, S. R. Nicewarner, F. G. Salinas, S. J. Benkovic,
M. J. Natan, C. D. Keating, J. Am. Chem. Soc. 2000, 122, 9071.
[219] H. Yockelllelievre, E. F. Borra, A. M. Ritcey, L. V. Dasilva, Appl.
Opt. 2003, 42, 1882.
[220] D. E. Grupp, H. J. Lezec, T. W. Ebbesen, K. M. Pellerin, T. Thio,
Appl. Phys. Lett. 2000, 77, 1569.
[221] S. M. Williams, A. D. Stafford, K. R. Rodriguez, T. M. Rogers, J. V.
Coe, J. Phys. Chem. B 2003, 107, 11 871.
[222] T. A. Taton, R. C. Mucic, C. A. Mirkin, R. L. Letsinger, J. Am.
Chem. Soc. 2000, 122, 6305.
[223] R. C. Bailey, J. M. Nam, C. A. Mirkin, J. T. Hupp, J. Am. Chem. Soc.
2003, 125, 13 541.
[224] S. J. Park, A. A. Lazarides, C. A. Mirkin, R. L. Letsinger, Angew.
Chem. Int. Ed. 2001, 40, 2909.
[225] A. Yamaguchi, S. Juodkazis, S. Matsuo, H. Misawa, Chem. Lett.
2002, 190.
[226] O. Kulakovich, N. Strekal, A. Yaroshevich, S. Maskevich, S. Gapo-
nenko, I. Nabiev, U. Woggon, M. Artemyev, Nano Lett. 2002, 2,
1449.
[227] J. Malicka, I. Gryczynski, J. R. Lakowicz, Anal. Chem. 2003, 75,
4408.
[228] O. Siiman, A. Burshteyn, J. Phys. Chem. B 2000, 104, 9795.
[229] R. A. Shelby, D. R. Smith, S. Schultz, Science 2001, 292, 77.
[230] R. Quidant, G. Badenes, S. Cheylan, R. Alcubilla, J.-C. Weeber,
C. Girard, Opt. Express 2004, 12, 282.
[231] J. J. Lezec, A. Degiron, E. Devaux, R. A. Linke, L. Martin-Moreno,
F. J. Garcia-Vidal, T. W. Ebbesen, Science 2002, 297, 820.
[232] J. Hashizume, F. Koyama, Appl. Phys. Lett. 2004, 84, 3226.
[233] J. M. Steele, C. E. Moran, A. Lee, N. J. Halas, Proc. SPIEInt. Soc.
Opt. Eng. 2003, 5221, 144.
[234] J. Matsui, K. Akamatsu, S. Nishiguchi, D. Miyoshi, H. Nawafune,
K. Tamaki, N. Sugimoto, Anal. Chem. 2004, 76, 1310.
[235] M. A. El-Sayed, Acc. Chem. Res. 2001, 34, 257.
R
E
V
I
E
W
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
1706 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4