Beruflich Dokumente
Kultur Dokumente
1. Introduction
Adv. Mater. 2004, 16, No. 19, October 4 DOI: 10.1002/adma.200400271 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1685
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
Following brief surveys of the most commonly used current strate localized surface plasmon resonance. Accordingly, we
methods of preparation and arraying materials with localized shall survey the recent advances in the preparation and stabi-
surface plasmon resonance (Sec. 2), and of the optical mani- lization of metallic nanoparticles by colloid chemical methods
festations of localized surface plasmon resonance (Sec. 3) we (Sec. 2.1); fabrication of ultrathin metallic nanoislands by vac-
shall discuss recent advances in the construction of nanoscale uum evaporation; lithographically nanopatterned structures,
optics and photonics and the exploitation of metallic nano- including the arraying of nanoparticles and the construction
structures as waveguides, switches, superlenses, information of periodic particle arrays, PPAs (Sec. 2.2); and nanostruc-
storage devices, and as resonant light scatterers in the differ- tures prepared by laser ablation (Sec. 2.3) and electrodeposi-
ent near-field scanning optical microscopies, NSOMs (Sec. 4). tion (Sec. 2.4).
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, 2.1. Recent Advances in the Colloid Chemical Preparations
PSPs, usually referred to as just surface plasmons, SP (i.e., the of Metallic Nanoparticles
longitudinal charge density oscillations at a flat 40±200 nm-
thick metal film, typically gold or silver, deposited onto a Traditionally, metallic nanoparticles are prepared by the
dielectric such as glass) and their applications in surface plas- controlled precipitation and concurrent stabilization of the
mon resonance, SPR, spectroscopy. There are several recent incipient colloids.[10,11] In homogeneous solution this is accom-
reviews which cover these topics.[7±9] Attention in this review plished by the judicious adjustment of the precipitating condi-
is focused on LSPs as manifested by isolated, coupled, and tions (type, concentration, order and rate of additions of the
arrayed metallic nanoparticles and nanostructures. We shall, reagents and stabilizers, temperature, and solvent). The ap-
however, summarize the beneficial amplification of SPR sig- proach is illustrated by the classical synthesis of 12 nm diame-
nals by LSPs. 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
2. Preparation and Arraying of Materials (composed of bulky citrate ions, chloride ions, and the cations
with Localized Surface Plasmon Resonance attracted to them) which provide required stabilization.
Recipes for the preparation of colloidal gold nanoparticles in
As the title of this section indicates, we consider in our diameters ranging from 0.82 nm to 64 nm are provided by
review all materials that, upon suitable excitation, demon- Handley.[13]
Eliza Hutter was born and raised in Hungary. She obtained an MD degree 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 SUNY Health Science Center, Syracuse, NY, in a research group
whose attention was focused on the influence of the enzymes of pentose±phosphate 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. from the University of Leicester (England) and his Ph.D. and his
D.Sc. from the University of London. He used surfactant assembliesÐaqueous and reversed
micelles, Langmuir monolayers, Langmuir±Blodgett films, vesicles and polymerized vesicles, and
bilayer lipid membranesÐfor 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.
1686 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
Advantage has also been taken of ultrasonic power to form priate block copolymers in appropriate concentrations have
metallic nanoparticles, complex nanoparticles, and metallic resulted in the formation of large variety of self-assembled
nanoparticles deposited on silica spheres.[14±19] Recent reports structures including those which resemble aqueous micelles,
on controlling sizes and size distributions of gold and silver reversed micelles, microemulsions, and surfactant vesicles. All
nanoparticles are particularly significant.[20,21] of these structures can, in principle, be used as templates for
Stabilization of metallic nanoparticles by covalently at- nanoparticle generation or incorporation. It should be
tached thiol- and disulfide-functionalized monolayers repre- remembered that partial entrapment of nanoparticles in rigid
sented a significant milestone.[22±24] These nanoparticles, stabi- compartments obviates the need for surface coverage (i.e.,
lized by covalent metal±sulfur bonds, became known as modification). Metallic nanoparticles can be, therefore, exam-
monolayer-protected clusters, MPCs.[25] The unique feature of ined (and employed) in their pristine states.
MPCs is that they behave as if they were large individual mac- Preparation of metallic nanoparticles by soft solution pro-
romolecules. Indeed, MPCs can be isolated from their disper- cessing (i.e., direct fabrication in aqueous solution at moder-
sions as solids and redispersed in a solvent without structural ate temperatures and pressures) has gained increasing accep-
or chemical alterations. Importantly, highly monodispersed tance. Hydrothermal synthesis (hydrothermal technique) is a
populations of MPCs can be prepared by fractional crystalli- soft solution processing which involves the heterogeneous
zation.[26] MPCs can also be functionalized and subjected to reaction between powdered solids and water above ambient
all the synthetic procedures (without breaking the Au±S temperature and at pressure greater than 1 atm in a closed
bonds) known to chemists. The relative ease of preparation of system.[54] The relative ease (appropriate powdered reagents
MPCs in substantial quantities is equally important, since it and water are placed in a teflon-lined autoclave and heated
greatly facilitates characterizations by such standard methods without stirring at moderate to high temperatures and pres-
as elemental analysis, differential scanning calorimetry, NMR sures for the desired time) and the possibility of predicting
spectroscopy (both solution and solid-state), absorption, and optimum reaction conditions by electrolyte thermodynamics
Fourier-transform infrared (FTIR) spectroscopy.[27,28] A sin- (in terms of phase diagrams) are the advantages of the hydro-
gle-phase, one-pot approach has been recently reported for thermal synthesis.[55]
the gram-scale preparation of gold MPCs in controllable sizes Spherical metallic (mostly gold) nanoparticles have been
and size distributions.[29,30] Thiol-functionalized metallic (Au, converted to nanorods, with controllable aspect ratios, by a
Ag, Pt, Pd) and composite metallic (Au/Ag, Au/Co, Ag/Co, seed-mediated sequential growth process.[56±60] Citrate-ion-
Au/Pt, Au/Pd, and more complex bi- and tri-metallic core± stabilized nanoparticles were used as seeds in a series of gold
shell-like) particles have also been reported.[25,31±34] Slow chloride solutions in a hexadecyltrimethylammonium chloride
evaporation of gold MPC dispersions have been shown to lead aqueous micellar solution containing ascorbic acid as a reduc-
to the spontaneous formation of highly ordered three-dimen- ing agent.[56±60] The technique was also adapted for growing
sional superlattices.[35,36] gold nanorods on mica surfaces (to several hundred nanome-
Covalent stabilization of metallic nanoparticles is generally ters length, with diameters in the range of 10±20 nm).[61]
restricted to the use of metal±thiol bond. Alternatively, they Gold nanoshells have been synthesized by reacting aqueous
can be stabilized by enclosing them in non-metallic shells HAuCl4 solutions with solid templates such as silver nanopar-
(latex, silica, polystyrene), thus providing a chemically differ- ticles. The morphology, void space, and wall thickness of these
ent surface for the immobilization of molecules without losing hollow nanostructures were all determined by the templates,
the spectral features of the metal core.[37,38] which were completely converted into soluble species during
Metallic nanoparticles are also stabilized if they are in-situ the replacement reaction.[62] Replacement reactions between
generated, trapped in (or on) templates, or confined in the silver nanocubes and aqueous gold chloride provided a versa-
restricted volumes of nanoreactors.[39] Such surfactant aggre- tile method for generating nanostructures with hollow inte-
gates as aqueous micelles, reversed micelles, microemulsions riors.[63]
(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 2.2. Vacuum Deposition and Electron-Beam Lithography
nanoparticles have also been incorporated into surfactant
aggregates. Some degree of size and shape control has been Vacuum deposition or sputtering involves the condensation
achieved by generating metallic nanoparticles in reversed of atoms produced by evaporation of a metal shot placed on a
micelles.[41±43] Ultimate stabilization is achieved, of course, by heating element.[64] The thickness of the metal film is moni-
the prompt covalent capping of the nanoparticles generated tored by an in-situ quartz crystal microbalance. Ultrathin (less
in reversed micelles. than 10 nm nominal thickness) evaporated gold films have
Polymers have also been used as templates for the in-situ well-defined island structures and optical properties similar to
generation or incorporation of metallic nanoparticles. Parti- those of colloidal gold nanoparticles.[65±67] Figure 2 shows typ-
cularly significant is the versatile use of dendrimers[44,45] and ical transmission electron microscopy (TEM) images of gold
di- and triblock copolymers.[46±53] Judicious selection of appro- nanoislands obtained by the slow (0.0014±0.0028 nm s±1) evap-
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1687
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
1688 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
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
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1689
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
1690 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 19, October 4
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
4. Nanoscale Optical and Photonic Devices
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1691
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
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Table 1. Nanoscale optical and photonic devices based on 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
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
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 30±60 nm thick, 1±2.5 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 1±15 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± 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-
15 lm.[128] Surface plasmon propagation has been investigated cal microscope image of a 4.7 lm long Au rod exposed to through-prism
in several additional systems.[130] TIR illumination at 532 nm. Note the strong scattering at the rod input
Significantly, surface plasmons were reconverted to light by and the absence of scattering at distal tip. c) Image of the same Au rod
two arrays of 250 nm diameter holes in a 150 nm thick gold 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
film, placed 30 lm apart.[126] One array contained illuminated at 532 and 820 nm, respectively. Emission is observed from
41 41 holes and the other array 11 11 holes. Surface plas- both tips at both wavelengths in the case of Ag. Note: In panels b±e), the
mons launched by a Ti:sapphire laser at the smaller array (the incident laser is focused to include a distribution of wave vectors, but the
source) propagated to the sink, the larger array, where they 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 b±e).
reconverted to light (Fig. 9).[126] This possibility of reversibly
Dotted outlines of the rods are meant only as visual guides to the reader.
converting light to surface plasmons opens the door to the ex- Reproduced with permission from [128]; copyright 1998, the American
tension of nano-optical devices to the millimeter scale. Chemical Society.
In 1998, Ebbesen and co-workers reported an extraordinary
light transmission through 150 nm diameter holes (with a reg- Clearly, the array is actively involved in light transmission,
ular periodicity between 600 and 1800 nm) formed by a fo- most likely via resonant interactions with surface plasmons,
cused ion beam through 200 nm thick silver films (on quartz localized in and around the holes in the metallic film.
substrates).[131] The extraordinary light transmission mani- Extraordinary light transmission has been modeled by sev-
fested itself in the appearance of much more light (with only a eral approaches.[133±137] Appropriately, it was soon realized
small angular divergence!) than expected from the diffraction that the model employed should represent the experimental
theory of isolated holes.[131] The transmitted light was charac- structure (arrayed nanoholes, gratings on one or both sides of
terized by a narrow silver surface plasmon peak (at 326 nm) the metallic films, with or without slits, etc.). For example,
and a set of well-defined minima and maxima related to the modeling a narrow-grooved zeroth-order (i.e., the pitches are
geometry of the hole array (Fig. 10).[131,132] This behavior is in smaller than k/2) silver grating which had the same periods on
contrast with the classical theory which predicts transmission both sides indicated the resonance tunneling of p-polarized
efficiencies in the order of 10±3 through a 150 nm diameter photons through the metal film via surface plasmons localized
hole and a monotonic decrease (instead of the observed in- in the grooves of the opposite surfaces.[135] Conversely, theory
crease) of the light transmission with increasing wavelength. predicted the complete reflection of s-polarized photons by
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1693
E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
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REVIEW
that judiciously arrayed metallic (silver, gold, or copper) cles, both aligned with their long axis perpendicular to the
nanowires and their composites can be used as LHMs in the propagation of the incident light. In C, in addition to the two
near-infrared and visible part of the spectrum.[141,142] Experi- silver nanoparticles which were aligned as those in B, a third
mentally, negative index of refraction has only been demon- silver nanoparticle was placed parallel to the propagation of
strated in the microwave region to date.[143] A two-dimen- the incident light close to one end of the other two particles.
sional (2D) array of repeated unit cells of copper strips and B and A had a single absorption maximum at 680 nm and
split ring resonators on interlocking strips of standard circuit 480 nm, respectively, while the absorption spectra of C was
board material was shown to have negative index of refraction characterized by two maxima. Organizing a large number of
above 10.2 GHz.[141] Enhanced transmissivity of the evanes- A, B, and C structures in a given area, 500 nm apart, provided
cent field was demonstrated by taking advantage of the natur- a data storage system in which the information could be read
al roughness of a 50 nm thick silver film deposited onto the by irradiation with blue (488 nm) and red (633 nm)
flat surface of a hemispherical glass prism in a reversed atten- lasers.[145,146] Using this approach the information density is
uated total reflection system (i.e., the collimated Ar-ion laser limited by a) the area observable by the objective of the total
beam is incident normal to the center of the silver-coated flat internal reflection spectroscope, TIRS, b) the number of
side of the prism, and the angle distribution of the relative nanorods which manifest different scattering spectra in that
light intensity is determined by a charge-coupled detector, observable area, and c) the number of distinctly resolvable
CCD, camera placed 5 cm from the center of the hemispheric resonance lines originating in the scattering spectra in the
side of the prism).[144] The negative permittivity of the silver observable area. The far-field resolution of a microscope is
film (approaching ±1) was considered to be responsible for roughly a 500 nm diameter circular area. This is, in fact, the
the observed broadened surface-plasmon bandwidth and en- area typically occupied by a single pit in a conventional com-
hanced transmissivity of evanescent waves.[144] These results pact disk. Smaller areas can be observed by photon scanning
open the door to the construction of diffraction-free image tunneling microscopy (by using a sharply elongated optical
collecting and focusing of subwavelength superlenses. fiber, instead of the scanning tunneling microscope tip, and
Optical data storage has been demonstrated by the spectral placing a sensitive photomultiplier at the end of this fiber to
coding of differently organized 35 nm thick, 30 nm diameter, observe the surface plasmons generated on the platform of
and 150 nm long silver nanorods (Fig. 12).[145] Three different the TIRSÐFig. 6). Limiting the spectral range to the visible
arrangements of the nanorods, A, B, and C, constitute the range a sixfold enhancement of information content of a com-
building blocks of the data storage system. In A, a single silver pact disk pit is achievable.[145]
nanorod was aligned with its long axis parallel to the propaga-
tion of the incident light. B consisted of two silver nanoparti-
4.2. Plasmon Waveguides and Nano-optics
Adv. Mater. 2004, 16, No. 19, October 4 http://www.advmat.de 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1695
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vices incorporating reflectors, mirrors, beam splitters, face plasmons near the surface. Photon scanning tunneling
switches, and other components.[124] 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
4.3. Apertureless Near-Field Scanning Optical Microscopy, hypotenuse face of a right angle prism).[156] The same fiber was
Scanning Plasmon Near-Field Microscopy, Photon Scanning then used to obtain near-field images of the defects created.[156]
Tunneling Microscopy, and Mapping Localized, Coupled, Additionally, the probe±sample interactions can be observed
and Propagating Surface Plasmons at far field (for example an angle of 75 from the probe axis in
the backscattering direction with respect to the incident wave
Propagating and localized surface plasmons have signifi- vector[157]) by a photomultiplier via a microscope objective,
cantly aided the development of high-resolution near-field band-pass filter, polarizer, and lens (see Fig. 11).
scanning optical microscopies (NSOMs). These microscopies, More recently, silver and gold nanoparticles have been inves-
in turn, have provided an experimental means for imaging tigated by photon scanning tunneling microscopy (Fig. 11).[157]
and mapping localized, coupled and propagating surface plas- The normal component of the scattered electric field was
mons. examined as functions of incident light polarization and tip-to-
Near-field scanning optical microscopy is not diffraction sample distance. Resonant excitation (at 415.4 nm), using
limited; optical resolution is primarily determined by the inte- transverse magnetic (TM) illumination, indicated spatial con-
rior diameter of the tip of a sharply elongated metal-coated finement and local enhancement of the electric field around
optical fiber through which illumination is introduced. The the silver nanoparticles. Under the same conditions, off-reso-
tip-to-sample distance is a few nanometers (i.e., it is a near nance excitation of gold nanoparticles indicated a substantial
field optical measurement).[147,148] The tip (or the sample) is contribution of the propagating components of the scattered
raster-scanned by a piezoelectric drive, typically employing a field. Transverse electric (TE) illumination resulted in a much
commercially available scanning force microscope, to obtain larger scattering cross-section for silver than for gold nanopar-
nanoscale optical images (either in the transmission or reflec- ticles.[157] These results significantly impact our understanding
tion mode). In addition, topographic images can be recorded of surface plasmon propagation.
using the tip as an atomic force microscopy (AFM) probe. Single photon tunneling (analogous to single electron tun-
Problems of preparing uniformly pulled and metal-coated neling) has also been demonstrated recently by measuring the
fibers with a nanoscale interior diameters at their tips, through intensity of the light traveling through individual subwave-
which laser light of appropriate energy (just sufficient to illu- length pinholes in a gold film (deposited on a glass prism in
minate the sample, but not too much to photo-damage it) can an optical arrangement similar to that shown in Fig. 11) cov-
be introduced, and intensity decays in the tunneling region ered by a layer of polydiacetylene.[158]
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 4.4. Nanophotonics
nanometers with apertureless NSOM is a consequence of
the enhanced optical field at and near the tip±sample Photonic bandgap materials, wavelength scale insulators,
region.[149±151] and semiconductors which are periodically structured affect
An alternative approach is to take advantage of propagating the properties of photons in much the same way as a semicon-
surface plasmons, generated from a thin gold or silver film, de- ductor affects the properties of an electron.[159±162] That is to
posited on a prism.[152] The incident light is coupled to the sur- say, photons can have band structures, bandgaps (i.e., frequen-
face plasmon modes of the metallic film in the total internal cies between which light propagation is prohibited), localized
reflection mode by a prism (Kretschmann configuration) and defect states, and surface states. Consequently, photonic band-
the reflected light is detected by a photodiode. As the sharp gap materials can mold and guide light. Photonic bandgap
scanning tunneling microscopy (STM) tip scans the substrate materials can be prepared by chemical approaches. Synthesis
close to the surface it slightly increases intensity of the of barium titanate inverted opals illustrates one of the most
reflected light (by reducing the destructive interference) and common methods. The procedure involves: i) the introduction
thus produces topography-dependent signals. This approach, of barium titanate into the interstices of the polystyrene opal
termed scanning plasmon near-field microscopy, permits up to template; ii) polycondensation; and iii) removal of the poly-
3 nm resolution.[153] Using a sharply elongated uncoated opti- styrene opal by solvent extraction or calcination.[163] The
cal fiber, instead of the STM tip to scan the sample (at a con- three-dimensional network of ferroelectric barium titanate
stant tip-to-surface distance), and placing a sensitive photomul- surrounding the spherical air packets (whose dimensions can
tiplier at the end of this fiber allow the near-field optical be controlled by selecting the size of polystyrene particles
imaging of the sample. This configuration is referred to as which form the three dimensional opal template) were dem-
photon scanning tunneling microscopy.[154,155] Photon scanning onstrated to function as a photonic crystal.[163] Alternatively,
tunneling microscopy directly measures the propagating sur- three-dimensional semiconductor photonic crystals can be di-
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rectly self-assembled.[164] Chemical approaches provide a vi- 5. Sensors and Biosensors
able economic alternative to EB lithography.
Photonic bandgap material has also been prepared by sur- Localized surface plasmon resonance has been exploited in
face (instead of bulk) modulation of thin metallic films.[124,165± several ways for sensing applications (see Tables 2±5 for a
168]
Characterization of a full photonic bandgap, between 1.91 summary).[169] First, the sensitivity of surface plasmon band to
and 2.00 eV, was first reported on a 40 nm thick silver film its immediate environment offers, in itself, an opportunity to
(deposited onto a glass substrate) which was textured with a detect attached molecules and environmental changes (assays
hexagonal array of 100 nm diameter dots (composed of a based on changes of the localized surface plasmon resonance
photoresist) with a 300 nm periodicity (Fig. 13).[166] The inci- absorbance, Sec. 5.1). Second, the reversible aggregation of
dent TM polarized light (scanned between 400 nm and plasmon resonant particles through specific linkers (oligonu-
800 nm) was coupled to the surface plasmon modes of the sil- 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[96,173±175]
we shall focus our discussion only to the LSP-enhanced SPR
(in Sec. 5.4).
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Table 2. Assays based on changes of the localized surface plasmon resonance absorbance.
First, their interparticle distances and positions can be con- of i) the advancing contact angle of water deposited onto the
trolled, since they are immobilized on the substrate. Second, self-assembled monolayer (SAM: formed at different times of
they need not contain any capping agents or stabilizers and immersion of the gold nanoislands into a CHCl3 solution of
can, therefore, be readily functionalized or indeed used for the cyclic disulfide), and ii) the absorbance due to the cyclic
sensitive measurements in their pristine state. Third, adsorbed disulfide.[65±67] The absorption of other molecules (metallo-
substances can be desorbed and bound molecules can be porphyrin and metallophthalocyanine monolayers,[67] 4-ami-
released with the concomitant recovery of the original local- nothiophenol, 4-mercaptopyridine, aminoethanethiol, long-
ized surface plasmon absorption band; thus sensing can be chain thiols,[65] and a submonolayer of thiolated oligonuc-
repeatedly and continuously performed. leotides[62]) onto gold nanoislands was also readily detected
Development of transmission localized surface plasmon by T-LSPR (Table 2).
resonance, T-LSPR, spectroscopy merits a special emphasis. Advantage has been taken in the second approach of the
Two different approaches for the exploitation of T-LSPR sensitivity of the localized surface plasmon absorption band
spectroscopy have been reported to date. The first method, of 50 nm high and ca. 100 nm wide triangular silver nanoparti-
developed by the Rubinstein group,[65±67,187] is based on the cles (PPAs).[70,185±188] Exposed to different solvents the PPAs
vacuum deposition of 2±10 nm thick gold nanoislands onto underwent structural changes which manifested themselves in
freshly cleaved mica sheets or quartz slides. Depending on dramatic shifts of the T-LSPR absorption maximum. Self-as-
individual preparations, the T-LSPR maximum of the gold sembly of hexadecanethiol monolayer shifted the absorption
surface plasmon absorption band was observed between 570 maximum of the triangular silver nanoparticles from 564 nm
and 630 nm. Self-assembly of cyclic disulfide monolayers onto to 604 nm; this corresponded to a red-shift of 3 nm for every
the gold nanoislands could be monitored quite readily by the carbon atom in the alkanethiol chain caused by only 60 000
position and intensity change of the T-LSPR band (ca. 0.02 molecules per nanoparticle.[66] SAM-functionalized triangular
absorbance units, Fig. 14).[65] The validity of the technique has silver nanoparticles have been shown to function as a biosen-
been demonstrated by the observed parallel linear increases sor. Electrostatic binding of a cationic polypeptide to mercap-
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Table 3. Assays based on the aggregation of metallic nanoparticles.
toundecanoic acid, self-assembled to triangular silver nano- transition of unattached, ªfreeº DNA), the melting tempera-
particles, caused the absorption maximum to shift from ture was relatively high, and very sensitive to base mis-
744.6 nm to 749.8 nm and upon the release of the polypeptide matches.[190] The detection limit of these assays was in the
the absorption maximum returned to 744.6 nm.[70] femtomolar range.[189]
Silver nanoparticles have also been functionalized by thio-
lated oligonucleotides and the spectral changes upon their
5.2. Assays Based on the Aggregation of Metallic hybridization proved to be different from those of gold nano-
Nanoparticles particles, exhibiting a marked decrease in intensity of the SPR
peak, as opposed to a shift of its maximum.[194]This specific
The aggregation of metallic nanoparticles results in substan- behavior is sufficiently different to that of the gold nanoparti-
tially altered surface plasmon absorption spectra, i.e., in a visi- cles to warrant the use of silver nanoparticles as a second mar-
ble change of color. Based on this principle, a colorimetric ker in DNA hybridization experiments.[194]
DNA hybridization assay was developed, detecting the spec- An interesting and exceptionally simple variant of this col-
tral change of thiolated oligonucleotide-covered gold nano- orimetric DNA hybridization assay has been based on the
particles when they aggregated in the presence of a comple- aggregation of oligonucleotide-functionalized large (3.1 lm)
mentary target oligonucleotide.[189±193] The spectral changes white latex and small (13 nm) red gold particles in the pres-
were found to be completely reversible by heating: the DNA ence of a target DNA strand (Fig. 15). After the hybridiza-
strands dehybridized and the particles separated from each tion, the dispersion was filtered through a 0.45 lm membrane,
other. The melting transition of DNA-linked nanoparticle which allowed the unhybridized small gold particles to pass,
aggregates was extremely sharp (compared to the melting but not the large latex or the joined latex±gold complexes. If
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[a] The labels are detected optically (under microscope, by CCD cameras).
hybridization has not occurred (in the absence of target oligo- Aggregation assays for the detection of proteins (based on
nucleotide), the membrane held the white latex particles only; antibody±antigen, biotin±streptavidin interaction), lectin,
in case of hybridization (positive result), the gold±latex com- dinitrophenyl, K+, and several heavy-metal ions were also
plexes were trapped, and the membrane appeared red (see demonstrated (Table 3).[197±203] An interesting approach for
Fig. 15).[195] constructing sensors is the immobilization of the gold nano-
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E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
particles in molecularly imprinted polymers.[204] The polymer 5.3. Labeling by Metallic Nanoparticles Manifesting Localized
swells upon selective binding of the analyte, the distance be- Surface Plasmon Resonance
tween immobilized gold nanoparticles increases, and hence
their T-LSPR spectrum changes. 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 106 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.[205±210]
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 ªmeltingº temperature allows
the discrimination of single-base-pair mismatches with a
selectivity three times greater than that observed with fluoro-
Figure 14. a) TLSPR spectra of gold nanoislands (2.5 nm nominal thick- phore labeled targets (Fig. 16).[211] This observation, com-
ness, evaporated on quartz) before (bottom curve) and after (top curve) bined with a signal amplification method based on the nano-
the self-assembly of cyclic disulfide molecules. b) Difference spectrum, particle-promoted reduction of silver(I) and the use of a
obtained by subtraction of the bottom spectrum from the top one in (a);
conventional flatbed scanner as a reader is the basic principle
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). of the new ªscanometricº chip-based detection system for
Reproduced with permission [65]. DNA, which has single mismatch selectivity and a sensitivity
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REVIEW
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 (~ 1.0±1.5 nm) of a binding material (like Cr, Ti, or
W), layer 3 is the 35±60 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 15±30 nm diameter gold or silver nano-
Figure 16. Dissociation of fluorescein-labeled (A) and nanoparticle particles.
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-
made of the prism material), layer 2 is a thin film (~ 1.0±
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 1.5 nm) of a binding material (like Cr, Ti, or W), usually vacu-
on the left describe the analogous process for a capture strand with a sin- um deposited onto the surface of the prism base (or the opti-
gle mismatch. The experiment clearly shows the advantages of nanopar- cally coupled glass slide), layer 3 is the 35±60 nm thick gold or
ticle labeling. i) The temperature range of dehybridization of nanoparti-
silver film which generates the propagating surface plasmons,
cle complexes is much narrower than that for the fluorophore probes.
The sharp melting curve translates into high selectivity, because a tem- layer 4 is a SAM which incorporates the molecular recognition
perature can be selected so that a high proportion of labeled probe element. Layer 5 contains the analyte, in the absence or in the
remains hybridized to perfectly matched capture strands while most of presence of attached (covalently or electrostatically) 15±30 nm
the probe is dehybridized from mismatched capture strands. (See and diameter gold or silver nanoparticles (Fig. 17). Sensing
compare the vertical dotted lines in A,B.) ii) The midpoint temperature
in the melting curves (Tm) for the complexes with nanoparticle probes involves: i) the experimental determination of the surface plas-
also is significantly higher compared to that with fluorophore probes, mon resonance spectra of layers 3±5 (typically by scanning the
and thus the critical concentration below which the complex sponta- relative intensity of the reflected light as a function of the inci-
neously melts is lower. This feature increases the sensitivity in the assay. dent angle = angle-resolved SPR); ii) construction of an appro-
Reproduced with permission from [211]; copyright 2000, the American
Association for the Advancement of Science. 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
exceeding that of the analogous fluorophore system by two plots) from the model; and iv) comparison of the experimen-
orders of magnitude.[211] tally and theoretically obtained data plots to obtain the
Other examples for nanoparticle labeling are summarized needed parameters from the best fit for each layer.[213] Gold
in Table 4. The commercial availability of gold nanoparticles nanoparticles attached to the analyte (layer 5 in the above
and gold-nanoparticle-labeled molecular-recognition ele- example) caused 25 signal amplification.[214] The signal am-
ments merits mentioning in passing.[212] plification was explained by the interaction of localized and
propagating surface plasmon resonances[213,215±217]and have
been shown to depend on the type of substrate and nanoparti-
5.4. Signal Amplification by Localized Surface Plasmon cles (gold or silver) as well as on their sizes, shapes, and dis-
Resonance tance from the layer generating the propagating surface plas-
mons (layer 5, in the above example).[213±217]
Metallic nanoparticles have been employed to enhance the A typical example of metallic-nanoparticle-enhanced SPR
signals in several optical techniques. Significant amplification is the derivatization of Au films by an antibody (a-human-
of the propagating surface plasmon resonance (SPR) spectro- IgG), followed by either direct binding of an antigen±Au con-
scopic signal by gold (or silver) nanoparticles will be discussed jugate or by binding of a free antigen and then a secondary
here. An SPR-based sensor device contains four to six strati- antibody±Au conjugate. In both cases, the signal enhancement
fied layers of different materials (Fig. 17).[6,7] In the Kretsch- was large enough to allow the detection of solution protein
mann configuration, layer 1 is a right-angled or hemispherical concentration in picomolar range.[214] Based on a similar prin-
prism (which is sometimes optically coupled with a glass slide ciple, DNA hybridization was measured.[218] In this work,
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E. Hutter, J. H. Fendler/Exploitation of Localized Surface Plasmon Resonance
REVIEW
oligonucleotide probes were linked covalently to the gold sur- self-assembly of oligoA (12 bases of homogeneous sequence
face, then hybridized to one half of the target DNA molecule. containing only adenine, thiolated at the 5¢ end) and mercap-
In the next step another oligonucleotide, with a sequence tohexanol spacer onto gold nanoislands evaporated onto a
complementary to the other half of the target, was added, glass slide (Fig. 18), as well as the DNA hybridization (by
either untagged or conjugated with Au nanoparticles. In addi- oligoT = 12 bases of homogeneous sequence containing only
tion to the plotted SPR curves, 2D SPR images of the mea- thymine, thiolated at the 5¢ end) could be readily sensed by
sured spots provided an easy way to visualize the results. The T-LSPR (Fig. 18). The sensitivity of T-LSPR was found to
detection limit in these experiments was ~ 10 pM (8 108- dramatically increase with the functionalization of the com-
molecules cm±1).[218] plementary DNA by 11.7 ± 1.9 nm diameter gold nano-
The attachment of gold nanoparticles to the materials particles (Fig. 18). Proximity of the gold nanoparticles to the
adsorbed onto SAMs has enhanced the sensitivity of the gold nanoislands could be readily seen by transmission elec-
T-LSPR,[68] in a manner quite analogous to that observed for tron microscopy (TEM).[68]
SPR spectroscopy.[214] Recently, this approach has been uti- Further examples of LSPR-amplified techniques are col-
lized for the detection of DNA hybridization (Fig. 18).[68] The lected in Table 5.
6. Conclusion
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