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REVIEW
Properties and Applications of Colloidal Nonspherical
Noble Metal Nanoparticles
By Tapan K. Sau,* Andrey L. Rogach,* Frank Jäckel, Thomas A. Klar, and
Jochen Feldmann

synthesis of a large variety of nanomaterials.


Nanoparticles of noble metals belong to the most extensively studied colloidal Many properties of nanoparticles arise from
their large surface-area-to-volume ratio and
systems in the field of nanoscience and nanotechnology. Due to continuing
the spatial confinement of electrons, pho-
progress in the synthesis of nanoparticles with controlled morphologies, the nons, and electric fields in and around these
exploration of unique morphology-dependent properties has gained particles. The large surface-area-to-volume
momentum. Anisotropic features in nonspherical nanoparticles make them ratio in nanoparticles may cause deviations
ideal candidates for enhanced chemical, catalytic, and local field related from the usual bulk atomic arrangements.
applications. Nonspherical plasmon resonant nanoparticles offer favorable The surface of a nanoparticle may be
unstable due to the high surface energy
properties for their use as analytical tools, or as diagnostic and therapeutic
and large surface curvature. A unique
agents. This Review highlights morphology-dependent properties of non- characteristic of nanoparticle surfaces is
spherical noble metal nanoparticles with a focus on localized surface plasmon that they bear a high fraction of edgelike and
resonance and local field enhancement, as well as their applications in various cornerlike curved regions.[1] Edges and
fields including Raman spectroscopy, fluorescence enhancement, analytics corners have more coordinatively unsatu-
rated atoms, i.e., dangling bonds, than flat
and sensing, photothermal therapy, (bio-)diagnostics, and imaging.
surfaces. Large fractions of under-
coordinated surface-, corner- and
edge-atoms in a nanoparticle can affect its chemical reactivity
1. Introduction and surface bonding properties. The electron confinement effect
in a nanoparticle modifies its spectral properties via shifting of
Metal nanoparticles have a long history in terms of preparation, quantum levels and change in transition probabilities.[2] Some
characterization, and applications. Understanding the properties properties, such as particle–particle or particle–environment
of noble metal nanoparticles (NMNPs) and exploring their interactions, are affected by the large surface area:volume ratio as
application potential are two major driving forces behind the well as confinement phenomena. Researchers have started to
develop an understanding of how the shape of a nanoparticle
[*] Prof. T. K. Sau,[+] Prof. A. L. Rogach,[++] Dr. F. Jäckel, Prof. T. A. Klar, influences its properties. Nonspherical nanoparticles with
Prof. J. Feldmann metastable structures are essentially in kinetically frozen states,[3]
Center for NanoScience (CeNS) and the geometric confinement via morphology control results in
Ludwig-Maximilians-Universität München further modifications of the internal structures, surface char-
Schellingstr. 4, 80799 Munich (Germany)
E-mail: tapan.sau@iiit.ac.in
acteristics, and orientational confinement.
andrey.rogach@cityu.edu.hk Due to continued progress in the synthesis of nanoparticles
Prof. T. K. Sau,[+] Prof. A. L. Rogach,[++] Dr. F. Jäckel, Prof. J. Feldmann with controlled morphologies over the last decades, exploration of
Photonics and Optoelectronics Group, Department of Physics unique morphology-dependent properties and their applications
Ludwig-Maximilians-Universität München have gained momentum. In this review, we discuss various
Amalienstr. 54, 80799 Munich (Germany) morphology-dependent physical and chemical properties of
Prof. T. A. Klar colloidal nonspherical NMNPs and summarize some of their
Institute of Physics, Technische Universität Ilmenau
Unterpörlitzer Str. 38, 98693 Ilmenau (Germany)
most important applications. The review is organized as follows:
after a brief discussion of the self-assembly of nonspherical
Prof. T. A. Klar
Institute of Micro- and Nanotechnologies, Technische Universität NMNPs in Section 2, we review their chemical and catalytic
Ilmenau properties in Sections 3 and 4. In Section 5, localized surface
Unterpörlitzer Str. 38, 98693 Ilmenau (Germany) plasmon resonance (LSPR) properties of rod- and prism-shaped,
[+] Present address: International Institute of Information Technology, polyhedral, and branched Ag and Au nanoparticles, including
Hyderabad 500 032, India investigations of single-particle LSPR and local refractive index
[++] Present address: Department of Physics and Materials Science, City sensitivity of the LSPR, are summarized. Effects of particle
University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong
morphology on local field enhancement, surface-enhanced
DOI: 10.1002/adma.200902557 Raman scattering (SERS), and fluorescence of fluorophores in

Adv. Mater. 2010, 22, 1805–1825 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1805
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the close vicinity of NMNPs are reviewed in Sections 6, 7, and 8,


REVIEW

Tapan K. Sau received his


respectively. We discuss several examples of applications of
Ph.D. (1998) in chemistry from
nonspherical NMNPs in Section 9 and present conclusions and
the Indian Institute of
an outlook in Section 10.
Technology-Kharagpur. He
worked as a postdoctoral
fellow at the University of
2. Self-Assembly South Caroline-Columbia and
Clarkson University, NY, and as
The term self-assembly is used to describe the spontaneous
an assistant professor at
formation of highly ordered assemblies or patterns from
Panjab University, Chandigarh,
disordered components by noncovalent interactions. During
India. He was an Alexander-von-
the self-assembly, the system minimizes its free energy thereby
Humboldt Research Fellow
evolving towards equilibrium. It balances attractive and repulsive
(2007–2009) at the Ludwig-Maximilians-Universität
colloidal and intermolecular forces that include van der Waals
München. Presently, he is appointed as an associate
interactions, electrostatic interactions, hydrophobic/hydrophilic
professor at the International Institute of Information
interactions, surface tension, capillary forces, steric forces, and
Technology, Hyderabad, India.
hydrogen bonds such as the hybridization of DNA.[4–14]
Self-assembly of nanoparticles into long-range ordered super-
lattices requires narrow size distribution and uniform shape of
the particles.[15–17] Therefore, particle morphology is an impor- Andrey L. Rogach received his
tant factor in governing the geometrical packing in organized Ph.D. (1995) in chemistry from
structures.[5,6,12,13,16,18] For example, Demortiere et al. observed the Belarusian State University,
different nucleation and growth kinetics for superlattices of and completed his Habilitation
truncated and perfect (i.e., sharp corners and edges) Pt in experimental physics (2009)
nanocubes.[16] Self-assembly of perfect nanocubes generated a at the Ludwig-Maximilians-
primitive cubic lattice via homogeneous nucleation, whereas Universität München. After
truncated nanocubes formed a face-centered cubic (fcc) lattice via several research positions at
a heterogeneous nucleation process (Fig. 1). This was attributed the University of Hamburg
to small differences in the interparticle attraction forces between (1995–2002), he was a lead
two different types of nanocubes during the solvent evaporation. staff scientist at the Photonics
Particle morphology will thus influence the collective properties and Optoelectronics group of the
of the assembly structure through various kinds of translational Ludwig-Maximilians-Universität
and orientational ordering, and the interaction and coupling of München (2002–2009). Since 2008, he has been an
the individual nanoparticle building blocks. Assembling, pattern- adjunct professor at the Center for Research on Adaptive
ing, and integration of nanoparticles in functional and ordered Nanostructures and Nanodevices (CRANN) in Dublin,
networks (on suitable surfaces) is of great importance for the Ireland. Presently, he is appointed as professor at the City
fabrication of efficient electronic, photonic, or sensor devices.[19] University of Hong Kong.

3. Chemical Reactivities dissolution and reaction with persulfate and were attributed to the
Researchers have recently started to explore the effects of metal structural metastability of the spheroids.[24–26] It has been
nanoparticle morphology on chemical reactivity. Nanoparticles reported that chemical reactions started at ridges, apexes, or
have several inherent features that change their chemistry particular facets during galvanic replacement reactions between
compared to their bulk counterparts or constituent atoms and silver nanoparticles and HAuCl4, depending on the morphology
molecules, since adsorption and reactivity are highly structure- of the template nanoparticles and reaction conditions.[27,28] Brus
sensitive properties. The large surface of a nanoparticle may be and co-workers reported an interesting physico-chemical con-
structurally and compositionally different from the bulk due to version of sodium-citrate-stabilized colloidal Ag nanocrystals to
surface relaxation and reconstruction, the presence of adsorbed nanoprisms.[29] According to them, irreversible ‘‘hot hole’’
layers of reaction by-products and stabilizing molecules, etc.[20,21] photo-oxidation of citrate anions adsorbed on Ag nanoparticles
Additionally, the surface structure changes as a function of size, builds up a photovoltage under visible excitation. This in turn
shape, and number of components of a particle.[3,22] The large causes the photochemical conversion of spherical 8 nm Ag seeds
particle surface area results in increased interaction with their into 70 nm single-crystal disk prisms under light irradiation.
environment. These effects may lead to a radical alteration in Recently, Tsung et al. reported selective shortening by mild
chemical reactivity. oxidative dissolution of single-crystalline gold nanorods prepared
Long ago, Jang et al. pointed out that the surface geometry using the silver-ion-assisted seed-mediated method.[30] The
influences the photochemical reaction of 1,10-phenanthroline oxidation was carried out by bubbling O2 in the presence of
adsorbed on Ag nanoparticles.[23] Anisotropic chemical reactiv- HCl and a high concentration of cetyltrimethylammonium
ities of spheroidal Au nanoparticles were reported during cyanide bromide (CTAB) maintained at certain temperatures.

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REVIEW
Figure 1. Self-assembly of perfect and truncated cubic Pt nanoparticles
showing the effects of particle morphology on self-assembly. A) TEM image
and B) scheme of self-assembled cubic superlattices formed by perfect
nanocubes. C) TEM image and D) scheme of self-assembled fcc super-
lattices formed by truncated nanocubes. Reproduced with permission from
ref. [16]. Copyright 2008 American Chemical Society.
Figure 2. Oxidation of Au nanorods by O2 in 1 M HCl and concentrated
cetyltrimethylammonium bromide (CTAB) at 70 8C. a) UV–vis spectra
acquired at every 1 min interval during oxidation reaction of nanorods.
Transmission electron microscopy (TEM) studies showed that Au At the beginning of the reaction, the spectra exhibit two extinction peaks, a
higher-energy transverse plasmon band (TPB) and a lower-energy longi-
nanorods decreased in length whereas the diameter remained
tudinal plasmon band (LPB), characteristic of Au nanorod suspension. The
almost constant during oxidation (Fig. 2). Upon further oxidation, TPB stays at 520 nm and decreases in intensity while the LPB blue-shifts
Au nanospheres form, which ultimately dissolve into ionic gold and decreases in intensity with time. Upon further oxidation, the LPB
species. This implies that the oxidation starts at the ends of the Au disappears, indicating the conversion of nanorods into nanospheres.
nanorods. The nanorods stay single-crystalline during oxidation, Finally, the TPB extinction peak at 520 nm vanishes, suggesting the
suggesting that twinning is not involved in the oxidative oxidation of Au nanospheres into ionic Au species. b–d) Typical TEM
images of Au nanoparticles formed at various stages of Au nanorod
shortening process. This approach allows post-synthetic control
oxidation. TEM images of as-synthesized Au nanorods with longitudinal
of the aspect ratio of Au nanorods. plasmon wavelength (LPW) ¼ 785 nm (b), of shortened Au nanorods with
LPW ¼ 595 nm (c), and of final oxidation products showing spherical Au
nanoparticles (d). e) The changes of Au nanorod lengths (~) and
diameters (!) versus LPWs. f) The relationship between LPWs and aspect
4. Catalysis ratios. The line is a linear fit. Error bars in (e) and (f) represent standard
deviations. Reproduced with permission from ref. [30]. Copyright 2006
The use of palladium and platinum particles as catalysts in
American Chemical Society.
numerous chemical reactions is well known.[31] Due to the finely
dispersed states of nanoscale systems, one can obtain large
surface areas for a given quantity of materials. Nonspherical compared the catalytic properties of spherical Pt nanoparticles
particles provide ample corners, vertices, defects, kinks, and and Pt nanowires formed in mesopores of FSM-16 (a mesoporous
steps.[1] Exposure of different crystallographic facets, together silica) respectively.[38] Pt nanowires showed substantially higher
with the increased number of edges, corners, and faces, is of activity in the hydrogenolysis of butane than spherical particles, in
critical importance in controlling the catalytic activity and spite of a smaller total surface area of Pt nanowires. This was
selectivity of metal nanoparticles. Therefore, nanoparticles of attributed to the presence of more electron-deficient sites or
different sizes and shapes are highly desirable as catalysts in fuel preferential exposure of {110} planes. The morphology of Pt
cells, waste reduction, bioprocessing, and the chemical industry. metal nanoparticles significantly affected the catalytic activity in
Effects of NMNP size on the catalytic activity are well terms of product selectivity too. Pt-Rh nanowires that were
documented.[31–34] On the contrary, knowledge about the synthesized in a similar way by co-impregnating RhCl3 with
influence of metallic nanoparticle shapes on the catalytic activity H2PtCl6 also showed similar activities. Telkar et al. observed that
has started to develop only recently. Studies on the catalytic cubic Pd nanoparticles had higher turnover frequencies
activities of platinum nanoparticles showed distinctly different compared to those of spherical particles for the hydrogenation
catalytic activities for different morphologies.[35–37] Fukuoka et al. of butyne-1,4-diol and of styrene oxide.[39] Further, cubic particles

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gave higher selectivity than spherical particles for


REVIEW

the hydrogenation of butyne-1,4-diol into


but-2-ene-1,4-diol. Xu et al. compared the catalytic
activity of truncated triangular silver nanoparticles
with that of cubic and near-spherical silver
nanoparticles in the oxidation of styrene in
colloidal solution.[40] It was found that the rate
of the reaction over the nanocubes was more than
14 times higher than that on nanoplates and four
times higher than that on near-spherical nano-
particles. This has been ascribed to the different
crystal faces of the silver nanoparticles. Chimentao
et al. prepared silver nanoparticles of different
morphologies by using the polyol process and
observed that catalytic activity and selectivity for
the selective oxidation of styrene were strongly
morphology-dependent.[41,42] El-Sayed and co-
workers have investigated catalytic properties of
a number of particle morphologies.[43–46] From a
comparative study of tetrahedral, spherical, and
cubic shaped platinum nanoparticles catalyzing
the electron-transfer reaction between hexa- Figure 3. Effects of particle morphology on the catalytic properties of Pt nanoparticles for the
cyanoferrate(III) ions and thiosulfate ions, these electron transfer reaction between hexacyanoferrate(III) ions and thiosulfate ions. TEM
authors reported a catalytic activity that followed images of dominantly tetrahedral (a), cubic (b), and near spherical (c) Pt nanoparticles used
the order: cubes < spheres < tetrahedral, at the as catalysts and the corresponding activation energies (Ea) are given in the top panel. d) Plot
early stages of the reaction (Fig. 3). The kinetic of the average rate constant versus surface atom fraction on edges and corners of the
parameters were found to correlate with the tetrahedral, cubic, and near spherical Pt nanoparticles. The rate constant increases expo-
nentially as the surface atom fraction on corners and edges increases. e) Plot of ln A versus E
calculated fraction of surface atoms located on of the Arrhenius equation demonstrates that as the activation energy increases, thea
the corners and edges in each size and shape. The pre-exponential factor (A) also increases (compensation effect) in Pt nanoparticle catalysis.
higher catalytic activity of the tetrahedral nano- The activation energies and pre-exponential factors are those obtained when using the
particles is believed to arise from their exposed tetrahedral, cubic, and near spherical Pt nanoparticles to catalyze the electron-transfer
(111) facets and higher fraction of corner and edge reaction in the first 40 min. Reproduced with permission from ref. [43]. Copyright 2004
sites. The lower catalytic activity of cubic nano- American Chemical Society.
particles can be ascribed to their (100) facets and a
very small fraction of surface atoms on edges and
corners. The spherical nanoparticles, which have a combination nanoparticles of unusual tetrahexahedral shape prepared by an
of many (111) and (100) facets with many edges at their interfaces, electrochemical method showed catalytic activity superior to that
show an activity intermediate to that of the tetrahedral and cubic of the spherical Pt nanoparticles for the oxidation of small organic
nanoparticles. However, during the course of the reaction, molecules such as formic acid and ethanol.[36] Lee et al. reported a
distortions occur at the corners and edges of the tetrahedral and synthesis of binary Pt/Pd nanoparticles by localized overgrowth
cubic types of nanoparticles, causing them to lose some of their of Pd on cubic Pt seeds and investigated electrocatalytic formic
catalytic activities.Balint et al. have also observed a conversion of acid oxidation.[50] The binary Pt/Pd nanoparticles exhibited much
the low-index facets of the cubic Pt nanocrystals to higher-index less self-poisoning and a lower activation energy relative to Pt
planes during the reduction of NO with C3H6, causing substantial nanocubes. Recently, Novo et al. studied single Au nanoparticle
changes in the catalytic activity and selectivity to reaction catalyzed reactions by following the change in optical properties of
products.[47] Tsung et al. reported that for pyrrole hydrogenation, single Au nanoparticles via dark-field microscopy.[51] This dark-field
Pt nanocubes enhanced ring-opening ability and thus showed a microscopy-based method may allow one to study the effects of
higher selectivity to n-butylamine as compared to nanopolyhe- different crystal geometries and crystal facets of plasmon resonant
dra.[48] However, ethylene hydrogenation rates were independent nanoparticles on the rates of catalysis.It appears that NMNPs with
of both size and shape of Pt nanocrystals. controlled morphologies have outstanding potential as catalysts and
Recently, researchers have been able to synthesize particles will continue to enrich the area of nanocatalysis.
with even more complex morphologies and have examined their
catalytic properties. For example, Mahmoud et al. prepared multi-
armed Pt nanostars from tetrahedral seed nanoparticles and
observed that Pt nanostars were catalytically more active than the
5. Localized Surface Plasmon Resonance
tetrahedral Pt nanoparticles for the reduction reaction of Light in the UV–vis–near IR (NIR) range impinging on an
ferrricyanide by thiosulfate.[49] This was attributed to the presence interface between a metal and a dielectric excites, if fulfilling all
of multiple arms with more edges and corners as well as the boundary conditions, collective oscillations of the conduction
presence of high-index sites on the nanostar.[49] Platinum electrons, so-called surface plasmon polaritons or short surface

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plasmons. Associated with the excitation of surface plasmons are shape demonstrates that nonspherical nanoparticles will exhibit

REVIEW
strongly enhanced and highly localized electromagnetic fields multiple optical extinction bands due to their anisotropy. For
(i.e., local field enhancement). Surface plasmon can either be particles with shapes more complex than spherical or spheroid,
propagating, for instance at planar bulk metal surfaces, or numerical methods, such as the discrete dipole approximation
localized as in the case of NMNPs. In both cases, the (DDA), the T-matrix method, finite-difference time-domain
electromagnetic field is spatially confined at the interface; i.e., (FDTD) simulations, finite element calculations, the modified
it can be described by evanescent waves in the direction long wavelength approximation (MLWA), the multiple multipole
perpendicular to the interface. The optical properties of colloidal
method, and spectral representation, are used for the calculations
NMNPs in the UV–vis–NIR spectral range are mainly determined
of spectral characteristics.[53,58,63–73] Kuwata et al. have suggested
by localized surface plasmons that give rise to so-called localized
an empirical extension of the quasistatic (analytical) approach to
surface plasmon resonances—LSPRs observable in their extinc-
tion, i.e. absorption and scattering, spectra.[2,52,53] The electro- particles of arbitrary shapes, which can quantitatively predict
magnetic fields are not evenly distributed around nonspherical resonant light scattering from metal nanoparticles of arbitrary
NMNPs, which gives rise to shape-dependent LSPR spectra. Ag shape, whose sizes are too large for the Rayleigh approximation to
and Au nanoparticles are of particular interest in the context of be applicable.[74]
LSPR.
The optical features of the LSPR (e.g., peak absorption,
linewidth) depend on the size, shape, composition of the NMNP,
its surface charge, surface-adsorbed species, interparticle inter- 5.1. LSPR of Rod-Shaped Nanoparticles
actions, and the refractive index of the surrounding medium.[54]
LSPR is particularly pronounced if the imaginary part of the Nonspherical NMNPs offer the possibility of tuning the optical
dielectric constant is small and the real part of the dielectric properties over a broad spectral range. LSPR of gold nanorods are
constant equals twice the negative of the dielectric constant of the one of the most widely studied topics in the field of nanoparticle
surroundings.[55,56] Silver and gold fulfill these criteria and are optical properties. Short gold nanorods exhibit two bands in
commonly used as plasmonic metals. On the other hand, the vis–NIR spectral range. Based on theoretical studies and
colloidal platinum or palladium exhibit only broad absorption optical polarization measurements, the band near 530 nm has
continua extending throughout the near UV and visible range. been assigned to a transverse LSPR, which is polarized across
The effect of deviation from spherical geometry on the (corresponding to electron oscillation perpendicular to) the long
properties of NMNPs is well documented through their optical axis of the nanorod, and the other one, appearing at a longer
property studies. For nonspherical nanoparticles, such as rods, wavelength, has been assigned to a longitudinal LSPR mode,
disks, and triangular prisms, the LSPRs are typically split into which is polarized along (parallel to) the long axis. The
distinctive dipole and quadrupole plasmon modes.[57–60] Optical longitudinal LSPR peak is very sensitive to the aspect ratio
properties of NMNPs can be theoretically predicted for various (length/diameter) of the nanorod and shifts to longer wavelength
shapes. The simplest form of a nonspherical shape is a spheroid. (red-shift) with increasing aspect ratio.[62,75–77] From DDA
For spheroids, a classical quasistatic approach serves well to simulations, Brioude et al. found that thinner nanorods give
describe the spectral position, width, and strength of the dipolar larger lmax shifts than thicker ones for the same difference in
plasmon resonance.[55,59] Based on classical approaches, for a their rod lengths.[77] The morphological anisotropy of gold
metal nanoparticle sufficiently small compared to the wavelength nanorods can influence the width of the absorption band.[78] Hu
of light l, there is a resonance condition associated with each axis et al. synthesized tadpole-shaped gold nanoparticles, showing a
j of a spheroid: broad peak at 583 nm with a full width at half-maximum
(FWHM) of 150 nm.[79] These authors suggest that the electron
  oscillation corresponding to the plasmon absorption along the
1
" ¼ "m 1  (1) long axis is retarded on a reflective path. This is attributed to a
Lj large disparity in size from the tip of the head through the tail of
the tadpole. The tadpole-shaped nanoparticles have yet another
where e is the complex wavelength-dependent dielectric function interesting property: the tails of the tadpoles contain a higher
of the metal, Lj is the geometrical depolarization factor along the negative charge than their heads unlike the usual case of uniform
charge distribution on the surfaces of colloidal nanoparticles, as
axis j, and em is the dielectric function of the surrounding
demonstrated by electrophoresis experiments.
medium.[54,60] L1 ¼ L2 ¼ L3 ¼ 1=3 for spherical particles. For
For small metal particles with dimensions far less than the
prolate spheroidal particles (L1 ¼ L2 < L3), the dipole resonance
wavelength, the conduction electrons are all excited in-phase with
splits into two absorption bands—longitudinal and transverse the incident electromagnetic field, yielding a dipolar oscillation.
modes—where the induced dipole oscillates along and perpen- However, in larger particles, the field across the particle becomes
dicular to the long axis of the spheroid, respectively.[61] The nonuniform and multipolar excitations, such as the quadrupolar
longitudinal resonance band shifts towards longer wavelengths and octupolar, can be observed. This gives rise to multiple
(red-shift) and increases in absorption cross-section as the aspect peaks in the optical spectrum. Such multipole resonances
ratio of the spheroid increases, whereas the transverse resonance have been detected experimentally and theoretically from gold
band remains near the wavelengths of the spherical particle nanorods/nanowires and nanoshells, and silver and gold
absorption band.[55,61,62] This example of the simplest nonspherical nanoprisms.[65,72,73,80–85] The dipolar LSPR is always situated

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at longer wavelengths with respect to the multipolar ones and is


REVIEW

red-shifted by the electric field generated by higher multipolar


charge oscillations.[52] In the case of spherical NMNPs, the LSPR
can be tuned by increasing the particle size. However, the dipolar
LSPR band becomes significantly broadened due to radiation
damping.[86] The LSPR can be tuned more elegantly without
sacrificing the linewidth of the resonance through changing the
nanoparticle geometry.

5.2. LSPR of Nanoprisms

Metal nanoprisms display a range of optical features depending


on their geometry, i.e., lateral size, thickness, and degree of
corner truncation.[65] The optical spectra of silver nanoprisms
show two in-plane resonance bands (one each due to dipole and
quadrupole oscillations): an out-of-plane quadrupole resonance Figure 4. Optical extinction spectra of polyhedral silver nanoparticles.
band and a small shoulder due to out-of-plane dipole resonance. Symmetric truncation is performed on a cube-shaped nanoparticle (with
Their optical spectral positions show high sensitivity towards the six faces) to create various truncated nanocubes (TCs, with 14 faces), then
physical dimension and sharpness of the tips and the change in icosahedron (Ih, with 20 faces) and finally spherical shape (with a qua-
refractive index of the surrounding medium, and therefore, si-infinite number of faces). The degree of truncation (r) in TCs is shown in
nanoprisms can find applications in sensing.[65,85,87–91] Germain parentheses. TCs are obtained by truncating the eight corners of the cube
by r  l, where l is the length of the cube’s side and 0 < r  1/2. A
et al. compared the experimental absorption spectra of silver
cuboctahedron (CO) is obtained for r ¼ 1/2. The optical response below
nanodisks of different sizes with those simulated using the DDA 325 nm is independent of the particle morphology. Reproduced with
method.[70] For smaller nanodisk sizes, simulated spectra of permission from ref. [52]. Copyright 2007 American Chemical Society.
spheroidally shaped particles closely relate to the experimental
spectra. That is, the specific shape of nanodisks can be neglected or pentagonal bipyramid-shaped nanoparticles.[52,94,95] Alekseeva
for smaller nanodisk sizes. However, for larger nanodisks, one et al. demonstrated that the cubic gold nanoparticles have an
has to consider the precise geometries represented by snip and extinction spectrum peaking at a wavelength of 570 nm.[96] Jiang
aspect ratio parameters of the disks for good agreement between et al. showed that a 512 nm peak arises partially due to the
experiments and simulations. Aherne et al. demonstrated that the dipolar resonance of underdeveloped nanocubes, and the other
main LSPR (in-plane dipole) increasingly red-shifts by increasing peak around 570 nm corresponds to that of well-faceted
in the silver nanoprism edge length.[92] Furthermore, the width of cubes.[96,97] McLellan et al. reported that the truncation or
the main LSPR band narrows with increasing nanoprism volume, rounding of the corners and edges of cubes lead to a sharpening
as the resonance energy decreases.[87,92,93] This has been attributed as well as blue-shifting for the LSPR bands.[98]
to a smaller nonradiative plasmon damping with decreasing In addition to geometries, such as rods, prisms, and polyhedra
plasmon resonance energy overcompensating the increased discussed above, LSPR of nanoparticles with more intricate
radiation damping at larger nanoparticle volume. morphologies (e.g., nanocage, branched, multipod, star-shaped,
lumpy) have also been explored. Au–Ag nanocages and
nanoboxes can be prepared by galvanic replacement in Ag
5.3. LSPR of Polyhedral Nanoparticles nanocubes.[99,100] Chen et al. have shown that the extinction
spectra of the Au–Ag nanoboxes can be tuned from the visible to
Noguez and co-workers have theoretically studied the influence of the NIR region by controlling the molar ratio of Ag to HAuCl4 in
morphology on the LSPR of metal nanoparticles.[52,94] For the galvanic replacement reaction.[99] However, the asymmetric
polyhedral (cube, octahedra, cuboctahedra, icosahedra, decahe- shapes and varying tip geometries of branched nanoparticle
dra, with different degrees of truncation) silver nanoparticles, the ensembles sometimes give rise to featureless broad LSPR.[101]
number of LSPR peaks (dipolar and quadrupolar) decreased and Recently, Nehl et al., Kumar et al. and Khoury and Vo-Dinh
the main LSPR peak position blue-shifted as the number of faces demonstrated that Au nanostars/multipods show well-defined
increased or the nanoparticles became more symmetric. This is LSPR extinction spectra comprising a short and a long
exemplified in Figure 4. It shows how the optical extinction wavelength plasmon band, with the latter becoming increasingly
spectra of silver nanoparticles change, when symmetric trunca- broad and red-shifted with enlarging nanostars.[102–105] Kumar
tions are performed on a cube to create various truncated et al. applied the boundary element method (BEM) to a
nanocubes, then an icosahedrons, and finally a spherical shape geometrical model of the nanostar consisting of a central sphere
with a quasi-infinite number of faces. A dramatic change in LSPR with either one or two (located at opposite sides of the sphere)
feature even for small truncations clearly shows the sensitive pseudoconical caps in order to quantify the precise optical
nature of LSPR to particle morphology. These authors have also response of these complex nanoparticles.[102] Their calculations
established similar trends for LSPRs in terms of the faces, demonstrated that plasmon oscillations associated with the tips
vertices, and truncations of other morphologies, such as regular, give rise to the main plasmon band and dominate the overall
rounded, truncated (e.g., Marks-type and star-shaped) decahedral optical response. The number of tips is of minor importance for

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the spectral position of the main, low-energy resonance

REVIEW
wavelength, which is mainly determined by the aperture angle
and the roundness of the tip.

5.4. Single-Particle LSPR

We have mentioned earlier that optical properties depend on


concentration, size, shape, spatial arrangement, and configura-
tion of the nanoparticles. With the availability of improved colloid
chemical synthetic methods, it has been possible to produce
nanoparticles with less heterogeneity in shape and size, and
compare their optical properties with particle morphology.[106]
Although many applications require assembly of nanoparticles,
several future applications will make use of the properties of the
individual nanoparticles (sensors, medical diagnostics, etc.). In
addition to the study of their collective properties, single-particle
studies are also important for determining structure-sensitive
properties as well as the direct relationship between particle
morphology and the resulting properties. One inherent property
of nonspherical metal nanoparticles is their polarization-
dependent response to incident light (Fig. 5). Unlike nano-
spheres, the LSPR wavelength of nonspherical nanoparticles
depends on the orientation of the incident light relative to the
particle. However, when the nonspherical nanoparticles are
randomly oriented in a medium, one observes an orientation-
averaged property. Furthermore, the yield of branched particles
has often been poor and therefore the optical spectra of the
ensemble are dominated by the LSPR of spherical particles. A
clear structure–property relationship in such low-yield cases can
be established by single-particle measurements. The asymmetric
shapes and varying tip-geometries of branched nanoparticle
ensembles sometimes give rise to featureless broad LSPR.[101]
Therefore, the impact of the nanoparticle morphology on the Figure 5. TEM images of an ensemble of nanorods (a) and a single
LSPR is not easily inferred from ensemble spectra for complex nanosphere (b). c) Light-scattering spectra from a gold nanorod (light
polarized along the long rod axis) and a 60 nm gold nanosphere measured
branched nanoparticles. As a matter of fact, single-particle
under identical conditions. The resonance energies Eres and linewidths G
investigations are becoming increasingly important to study are indicated. d) Polar plot of the intensity from the long-axis plasmon
more complex structures. For example, Nehl et al. reported resonance of a nanorod as a function of polarization angle of the exciting
experimental and theoretical scattering spectra of individual gold light (circles: experimental data; line: dipole characteristics). e) TEM image
nanostars by single-particle spectroscopy.[104] Unlike the one of a representative gold nanostar, and f) polarization-dependent white light
major peak in bulk solution spectra, single gold nanostars showed Rayleigh scattering spectra of an individual gold nanostar (208 steps in
multiple peak scattering spectra in the visible and NIR region polarization, and spectra vertically offset for clarity). a–d) Reproduced with
permission from ref. [115]. Copyright 2002 The American Physical Society.
(Fig. 5).[104,107] The nanostar, being an example of an extremely e–f) Reproduced with permission from ref. [107]. Copyright 2009 American
anisotropic nanoparticle, shows polarization dependent, tip Institute of Physics.
specific spectral peaks. An analysis of the near-field enhance-
ments also revealed that the observed resonances are localized nanoparticle shape and size have been investigated using
around the tips of a nanostar.[102,105,108] single-particle experiments.[52,120,121] The LSPRs are red-shifted
A number of experimental methods have been developed to depending on the dielectric constant of the substrate and the
study the plasmonic properties of isolated nanoparticles includ- particle–substrate separation distance. When a particle is in contact
ing white light Rayleigh scattering in a dark-field microscope, with the substrate, the contact area of the particle influences the
scanning near field optical microscopy, two photon photolumi- magnitude of the red-shift. By a combined single-particle
nescence, photoelectron emission microscopy, and electron measurement and theoretical study, Sherry et al. have shown that
energy-loss spectroscopy (EELS).[57,93,100,109–119] From a systema- in addition to a red-shifted LSPR peak, a new blue-shifted peak
tic study of the effect of size and shape on the spectral response of arises, when a silver nanocube interacts with a glass substrate.[120]
individual silver nanoparticles, Mock et al. concluded that specific The sharp blue peak is more advantageous for chemical sensing
geometrical shapes cause distinct spectral responses and subtle applications in comparison to broader spectral features stemming
changes in the particle morphology give rise to shifts in from plasmon resonances of other particle shapes.
the individual particle spectra.[111] Effects of the substrate on Single-particle spectroscopy can provide useful information on
the LSPR of a nanoparticle with a specific focus on the multisegment nanorods and nanowires with alternating metal

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composition. Mock et al. have synthesized homogeneous and


REVIEW

multisegment silver, gold, and nickel nanowires, which exhibit


unique subsection-dependent surface plasmon scattering of
light.[122] These multisegment plasmon resonant nanowires can
find applications as nanoscale plasmon resonant codes or labels
in biological assays. Experimental techniques, such as scanning
near-field optical microscopy (SNOM) and EELS, are tools to map
the localized plasmonic excitations over a single nanoparticle with
high resolution.[57,114,118,123–125] Imura et al. have carried out
near-field optical transmission-spectral measurements (mea-
sured at different points on the sample surface) on single gold
nanorods and have imaged the optical local density of states
(LDOS) and spatial features of the plasmon wave functions
(Fig. 6).[114,125] These authors have found the oscillating behavior
of the LDOS. The longer the rod length is, the larger the number
of oscillations, which is in agreement with the theoretical
predictions by Weber et al.[126] By combining optical near-field
microscopy with a time-resolved technique, they investigated the
ultrafast temporal responses of single gold nanorods.
Interestingly, the spatiotemporal response measurements
revealed a position-dependent energy dissipation (electron–
phonon relaxation) process. It was found that the collective
motion of electrons at the center of the rod was different from that
at the ends. The dispersion relation of a plasmon travelling along
a metal nanowire has been investigated by Schider et al.[127]
Sanders et al. have reported interesting optical properties of
single and overlapping silver nanowires, in which the length
exceeds the wavelength of the incident light.[128] When one end of
a metallic nanowire is irradiated with a focused laser, the laser
light excites plasmons that propagate along the wire and couple to
free-space photons at the other end. Plasmons can be launched
from either end of the nanowire; however, plasmon modes were
not observed to be launched when the laser was focused on the
midsection of the nanowire. Interestingly, in the case of
overlapping nanowires, if one nanowire is excited, then radiation
is emitted at the intersection and visible light is emitted at the
ends of the non-illuminated overlapping nanowire. These
observations indicate that the intersection couples plasmons in
Figure 6. Scanning near-field transmission microscopy images of a single
the excited wire to both photons as well as to plasmons in the gold nanorod. a) The transmission image at 530 nm (resonant with the
crossing wire. These characteristics of metallic nanowires show transverse LSPR) shows a uniform reduction of transmission intensity
that they can serve as effective wave-guides in optical (dark regions indicate less transmission) along the long axis of the
nanodevices.[129,130] nanorod. b) The transmission image taken at 780 nm (resonant with
the longitudinal LSPR) shows a characteristic spatially oscillatory pattern
along the long axis of the nanorod. The images in (a) and (b) correspond to
5.5. Refractive Index Sensitivity of LSPR the squared amplitude mapping of the wave functions for the transverse
and longitudinal LSPs, respectively, as the near-field transmission at a given
position of the sample reflects the optical transition probability, which is
The refractive index sensitivity of the LSPR depends on the proportional to the square modulus of the localized surface plasmon wave
morphology of the nanoparticles.[130,131] Longitudinal and function (or the photonic LDOS) resonant with the observed wavelength.
transverse resonances of nanorods show different sensitivities The longitudinal-plasmon image in (b) with a spatially oscillating structure
towards the change in dielectric environment.[132] The long- was assigned to a localized surface plasmon mode having a node at the
center (mL ¼ 2, next to the dipolar mode). c) The solid curve shows a
itudinal plasmon mode is highly sensitive to the change in the
transmission spectrum taken at a point (marked with T) on the nanorod
refractive index of the environment, and the sensitivity increases (inset in (d)), and the dashed curve gives calculated DOS. d) Polarization
as the aspect ratio of the nanorods increases.[133–137] measurements show that the band at 532 nm is effectively excited when the
Single-particle spectroscopy has been used to show how different light is polarized perpendicular to the long axis of the nanorod, and the
morphologies induce different sensitivities to the change in local band 780 nm is excited by the polarization parallel to the long axis of the
refractive index.[110,138] The LSPR from each of the nanoparticles nanorod. Reproduced with permission from ref. [114]. Copyright 2004
American Chemical Society.
generally undergoes a red-shift as the local refractive index is
increased.[138] The amount of red-shift per unit of refractive index
increase varies depending on the morphology of the

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nanoparticle.[104,131,139] By comparing the refractive index It should be pointed out here that there are factors, such as

REVIEW
sensitivities of a number of Au nanoparticles, Chen et al. surface-induced relaxation (surface scattering) and radiative
observed an increase in the index sensitivities when Au decay (radiation damping) of LSPRs, which impose upper limits
nanoparticles become elongated or their apexes becomes to the strength of the field enhancement in metal nanoparti-
sharper.[131] Accordingly, Au nanospheres exhibit the smallest cles.[141] Surface scattering is a function of the surface-to-volume
refractive index sensitivity of 44 nm/RIU (refractive index unit), ratio; hence, it scales with 1/r where r is the typical dimension of
and branched Au nanoparticles exhibit the largest index the particle, the radius in the case of a sphere. Thus, the degree of
sensitivity of 703 nm/RIU (Table 1). These authors also found plasmon damping is largely influenced by the nanoparticle shape.
that the sensitivities of Au nanobipyramids were higher than The radiation damping can in principle be reduced by decreasing
those of the corresponding Au nanorods with increasing the particle volume. However, in the case of very small particles,
longitudinal plasmon wavelengths. This suggests that the the plasmon is damped due to surface scattering. In the latter
nanoparticle morphology is an important factor in determining case, electrons can be scattered at the particle surface, when the
the refractive index sensitivity. However, Miller and Lazarides dimensions of the particle become comparable to or smaller than
have theoretically predicted that for any gold nanoparticle of the free-electron mean free path. The surface electron scattering
moderate size in a homogeneous dielectric environment, the depends on both the particle size and shape.[145] As the radiation
refractive index sensitivity is a function of only the LSPR band damping is larger at larger size and the surface scattering is
position, and independent of particle shape, size, or composi- stronger at smaller size, there will be an optimum volume for
tion.[133] That is, the refractive index sensitivity of all arbitrarily which the highest enhancement is achieved, depending on the
shaped nanoparticles in a homogeneous dielectric environment particle shape.[141]
will be the same if they have the same plasmon band location. It In addition to radiative damping and surface scattering, there
should be pointed out here that nanoparticles are often present in are two important size-independent damping mechanisms.
an inhomogeneous dielectric environment due to asymmetric Plasmon polaritons may either decay via single-electron excita-
surface adsorption or substrate interaction. tions where electrons of the sp band are excited to empty states
in the sp band (intraband excitation), or d band electrons are
excited to empty states in the sp band (interband excitation).[54]
6. Local Field Enhancement The latter is a particularly severe damping mechanism of Cu
Plasmon resonant particles are surrounded by strongly enhanced nanoparticles and still disturbs the plasmon resonance of
and highly localized electromagnetic fields when excited at their spherical gold nanoparticles. Yet, any nanoparticle morphology
LSPR. These fields are the direct result of the polarization which shifts the plasmon resonance away from the onset of
associated with the collective electron oscillation in the metal interband excitation automatically leads to a narrowing of the
particles. The local field (Eloc) on or near the nanoparticle will be a plasmon spectra. A narrow plasmon spectrum (or equivalently,
sum of the incident field (E) and the induced field from the a long plasmon lifetime) is beneficial for all effects that rely
oscillating electrons; i.e., Eloc is usually higher than the original on a huge field enhancement. For instance, the third-order
field E.[54,140] The local field enhancement factor, f(v), is defined susceptibility of metal nanoparticles[146] and the effective SERS
by f(v) ¼ Eloc/E. Earlier electrodynamic calculations have shown cross-section[147] are proportional to the fourth power of the
that the local field enhancement factor depends on the particle inverse of the homogeneous linewidth Ghom of the plasmon
eccentricity.[68,141–144] The field enhancement at the tip of a resonance. Knowledge of the damping mechanisms is therefore
spheroid is larger than the one created by a resonant sphere of vital for a deep understanding of the performance of metal
similar dimensions.[141–144] nanostructures.

Table 1. Sizes, plasmon wavelengths, and refractive index sensitivities (RIU: refractive index unit) of variously shaped Au nanoparticles. The numbers in the
parentheses following values are standard deviations. Reproduced with permission from ref. [131]. Copyright 2008 American Chemical Society.

Au nanoparticles Length Diameter Aspect Plasmon wavelength Index sensitivity Figure of merit
[nm] [a] [nm] [b] ratio [c] [nm] [d] [nm/RIU] [e]

Nanospheres 15(1) 527 44(3) 0.6


Nanocubes 44(2) 538 83(2) 1.5
Branched nanoparticles 80(14) 1141 703(19) 0.8
Nanorods 40(6) 17(2) 2.4(0.3) 653 195(7) 2.6
Nanorods 55(7) 16)(2) 3.4(0.5) 728 224(4) 2.1
Nanorods 74(6) 17(2) 4.6(0.8) 846 288(8) 1.7
Nanobipyramids 27(4) 19(7) 1.5(0.3) 645 150(5) 1.7
Nanobipyramids 50(6) 18(1) 2.7(0.2) 735 212(6) 2.8
Nanobipyramids 103(7) 26(2) 3.9(0.2) 886 392(7) 4.2
Nanobipyramids 189(9) 40(2) 4.7(0.2) 1096 540(6) 4.5

[a] Length for nanocubes is the edge length, and for branched nanoparticles, it is the distance from the center to the branch tip of the particle. [b] The diameter for nanobipyramid
is the central width. [c] The ratio between the length and diameter. [d] Plasmon wavelength of Au nanoparticles dispersed in aqueous solutions. For branched nanoparticles, it is
the longer plasmon wavelength; for nanorods and nanobipyramids, it is the longitudinal plasmon wavelengths. [e] For nanobranches, it is the refractive index sensitivity of the
longer-wavelength plasmon peak, and for nanorods and nanobipyramids, it is that of the longitudinal plasmon resonance peaks.

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The main obstacle for measurements of Ghom or, alternatively,


REVIEW

the plasmon lifetime T2, is the inhomogeneous broadening of the


plasmon resonances due to broad size and shape distributions in
ensembles of colloidal nanoparticle dispersions. In order to
overcome the inhomogeneous broadening due to the shape
distribution and different crystalline structures, several line width
measurements on single metallic nanoparticles have been
performed in recent years, reporting a dephasing time T2 in
the range of a few femtoseconds (i.e., only a few cycles of the
dipolar electronic oscillation occurs).[93,100,115,118,148–151]
Sönnichsen et al. investigated the dephasing of particle plasmons
in single gold nanoparticles as a function of particle size and
shape using light-scattering spectroscopy.[115] The line widths for
Rayleigh scattering spectra of single gold nanorods were much
narrower than the line widths obtained from the ensemble
spectrum, and close to the value expected from the dielectric
constants of bulk gold.[115] Novo et al. claim that the line width of
the longitudinal surface plasmon mode depends critically on the
width of the rod, and the line width broadening behavior is
essentially the same as that of gold spheres.[149] The line widths
observed in the scattering spectra of the Ag-Au nanobox particles
were narrower than those observed for Au spheres, but much
broader than those of either the pure Au nanorods or the Au–Ag
core–shell nanorods.[115,150,151] A comparison with theoretically
calculated spectra indicated that both surface scattering of
electrons at the particle–solution interface and radiation damping
were responsible for line width broadening. According to
Sönnichsen et al., the dephasing rate of nanospheres increases
for more red-shifted (i.e., larger) particles.[115] This was attributed
to the increased radiation damping with increased particle
volume. On the contrary, the dephasing rate of nanorods
decreased drastically with increasing red-shift, i.e., for increasing
nanorod aspect ratios. The reduction of the plasmon dephasing
rate in nanorods was shown to be due to the suppression of
interband damping and weaker radiation damping as compared Figure 7. Contour plots showing relative local field enhancements for
excitation of the a) 804, b) 717, and c) 594 nm nanostar plasmon
to nanospheres.
resonances. The polarization angles are indicated by the insets to the
In addition to LSPR spectra, analytical as well as numerical right of the panels. The maximum field enhancements are indicated on top
methods including DDA, finite element, and FDTD methods of each panel. Reproduced with permission from ref. [105]. Copyright 2007
have been used to predict the field enhancements in the American Chemical Society.
vicinity of single metal nanoparticles of a variety of
shapes.[53,58,74,84,105,152,153] Numerical calculations by Jain et al. Further, for nanoparticle dimers, larger enhancements were
showed that gold nanorods have higher local field enhancement generally observed for dimers with longer-wavelength dipole
factors than nanoshells and nanospheres.[153] Li et al. performed plasmon resonances. However, structural properties of the dimer
FDTD calculations on similarly sized Au nanorods and Au/Ag (such as local curvature) were found to play a less important role
nanoshuttles, and concluded that the maximum field enhance- in determining field enhancements.
ment of the Au/Ag nanoshuttle is about 5.1 times that of the Au Nonspherical metal nanoparticles may show another kind of
nanorod.[152] Simulating triangular nanoparticles, Kottmann et al. field enhancement, termed ‘‘lightning-rod effect.’’ The term owes
have shown that sub-wavelength nonspherical metal nanoparti- its origin to the sharply pointed conductor poles that are used to
cles exhibit multiple resonances and the field amplitudes protect buildings from the destroying power of lightning. In
associated with these resonances can be extremely large, up to nanoparticle systems, the term refers to an enhanced charge
several hundred times the incoming field amplitude.[84] These density localization at a tip or vertex of a nanoparticle. When an
large electromagnetic fields are strongly localized at particular electromagnetic field (e.g., laser light) excites the free electrons of
positions on the particle surface (Fig. 7). Therefore, nonspherical a metallic tip, a highly localized, strong electric field develops at
nanoparticles can be very useful for applications where extremely surfaces of large curvatures (such as a tip or vertex) of the
large electromagnetic fields at different wavelengths are required. nanoparticle, leading to large field enhancement in those regions
However, it is interesting to note that according to DDA-based without the need of nanoplasmonic resonances.[143,154] Recently,
calculations of Hao and Schatz on silver particles, the largest field based on experimental and theoretical studies on triangular silver
enhancement values were very similar for different shapes, such nanoprisms, Rang et al. claimed that particle morphology and the
as triangular prisms, oblate spheroids, or cylindrical rods.[58] associated LSPR do not uniquely reflect the details of the local

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field distribution.[155] According to their report, the tips of the Raman intensity is thereby enhanced by the square of the product

REVIEW
triangles in general do not represent regions of highest local field of the field (amplitude) enhancement factors at the excitation
enhancement. frequency nL and Stokes Raman frequency nS.[141,148,166,176] When
Experimental determinations of field enhancements have been nL and nS are near the LSPR frequency, the observed Raman
performed using two-photon photoluminescence (TPPL) from scattering intensity is approximately proportional to the fourth
gold bowtie nanoantennas, and a comparison with the TPPL power of the local electric field enhancement.[181] Even a modest
emission from smooth gold films was made.[119] The determina- local field enhancement near the metal particle leads to
tion of field enhancements from SERS appears to be more substantial electromagnetic enhancements of Raman scattering
difficult since the total Raman enhancement factors can also intensities. The chemical enhancement mechanism arises due to
include nonelectromagnetic contributions, as discussed below. specific, localized analyte–substrate interactions upon analyte
The optical local field enhancement provides the basis for adsorption. These interactions include the electronic resonance-
many applications in molecular detection, sensing, and nano- charge transfer between the molecule and metal surface, and
photonic devices. A molecule residing on or near a metal adsorption-induced changes in the analyte polarizability.[168,179]
nanoparticle may experience a light intensity far stronger than The Stokes Raman signal is proportional to the Raman
just the intensity of the incident light due to the enhanced local cross-section of the molecule s, the excitation laser intensity, I(nL),
fields.[156] This has been exploited for a variety of applications, and the number of molecules N which are involved in the
such as the above-mentioned SERS, surface-enhanced fluores- process.[166] The surface-enhanced Stokes Raman signal ISERS can
cence (SEF), SNOM, etc.[157–164] Nonspherical nanoparticles of be written as follows:
silver and gold are attractive as SERS and SEF substrates, because
the LSPR wavelengths of these particles can be tuned over a broad
range in the UV–vis–NIR region.[159,160,165] ISERS ðnS Þ ¼ N  IðnL Þ  jf ðnL Þj2 jf ðnS Þj2 s ads (2)

where sads describes the increased Raman cross-section of the


7. NMNPs and Surface-Enhanced Raman adsorbed molecule (this includes chemical enhancement), and
Scattering f(nL) and f(nS) are the field enhancement factors at the laser and
Stokes frequency, respectively.[166] SERS enhancement due to the
Raman spectroscopy reveals the inelastic scattering of photons by
resonance of the incoming radiation with the LSPR is sometimes
molecules or solids. The energy difference between the incident
distinguished from the nonresonant lightning-rod effect.
and scattered photons, detected via observation of the red-shifted
We have discussed above that the optical polarization of the
inelastically scattered photons, is used to excite vibrational (Raman)
modes of the molecule in the IR spectral region. This spectroscopic anisotropic metal nanoparticles with highly curved, sharp surface
technique is non-invasive, and provides rich structural informa- features will show lightning-rod effects at surface protrusions. A
tion leading to chemically highly specific and sensitive detection molecule situated in the vicinity of protrusions will experience an
and identification of analyte molecules. However, it suffers from enhanced localized electromagnetic field, which gives rise to an
low scattering intensity since Raman scattering cross-sections enhanced Raman scattering.[108,143,154] Further, the surface
of molecules are usually extremely small, typically protrusions can also play a role in the chemical enhancement
1030–1025 cm2/molecule, compared to fluorescence cross- mechanism, since they may act as preferred binding sites for
sections, which are in the order of 1016 cm2/molecule for analyte molecules.[143,182,183]
high-quantum-yield fluorophores.[166] In the presence of plas- All enhancement mechanisms discussed above can be
monic nanoparticles or rough metal surfaces, the Raman considered as functions of the nanoparticle morphology, since
intensity is greatly enhanced under certain conditions.[167,168] it determines the LSPR, local curvature, local field enhancement,
This phenomenon is known as surface-enhanced Raman surface characteristics, and bonding nature. Researchers have
scattering—SERS.[169–171] In surface-enhanced resonance been trying to find out, both theoretically and experimentally,
Raman scattering (SERRS), the same approach is taken to which particle shapes and/or assemblies would result in the
achieve surface enhancement, but additional enhancement is strongest SERS enhancement.[144] The electromagnetic enhance-
obtained through the excitation of electronic transitions in the ment is greatest when the LSPR lmax falls between the excitation
analyte by using a laser source with an appropriate excitation wavelength and the wavelength of the scattered photon.[181] As the
frequency.[167,168] Similar to fluorescence, SE(R)RS can achieve nanoparticles with nonspherical morphology offer tunable LSPR
single-molecule sensitivity and still maintain its chemical wavelengths, they are ideal candidates for SERS substrates. Peak
specificity.[172–174] enhancement values, which are important for single-molecule
The intensity enhancement of SERS from an analyte has SERS, have been found to be significantly larger for spheroids
been shown to occur through mainly two mechanisms: and nanoprisms compared to spheres due in part to red-shifted
electromagnetic[175–178] and chemical enhancement.[168,179,180] plasmon excitation and to sharp points that produce stronger
The electromagnetic enhancement in SERS results from the lightning-rod effects.[58,141,184,185] El-Sayed and co-workers com-
coupling of the LSPR of nanoparticles (individual or aggregated) pared the Raman spectra of a few molecules adsorbed on gold
with Raman excitation and emission. Under plasmonic resonant nanospheres and nanorods, using an off-plasmon resonance
excitation condition, the enhanced local field at the location of the excitation condition.[183] Enhancement factors of the order of
analyte molecule near the metal nanoparticle amplifies both the 104–105 were observed for the adsorbed molecules on the
excitation field as well as the Raman scattered field. The scattered nanorods, whereas no such enhancement was observed on

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spherical gold nanoparticles under similar conditions. These gold nanostars coated with self-assembled monolayers of 4-MBA
REVIEW

enhancement factors were two orders of magnitude larger than (Fig. 8) and estimated a total Raman enhancement factor of 107
the calculated values. This was, therefore, attributed to the for individual nanostars.[107] This wide range of enhancement
chemical enhancement contributions on the gold nanorod factors reported for rather similar structures demonstrate the
surface. Murphy and co-workers reported the effects of aspect difficulty in determining reliable estimates for total Raman
ratios of silver and gold nanorods on SERS in colloidal enhancement factors. The difficulties may include changing
solution.[186] The optical properties of these nanorods have been analyte–particle interactions if different analytes are employed,
tailored to have variable degrees of overlap of their longitudinal different experimental situations (i.e., ensemble versus single
plasmon mode with the excitation source in the absence of objects, or geometry), or potentially different amounts of analyte
interparticle plasmon coupling effects. According to these due to different initial surface functionalization, which hinders a
authors, silver and gold nanorods of an aspect ratio of 10 and precise determination of the number of molecules contributing to
1.7, respectively, show total Raman enhancement factors in the the signal. Recently, Uji-i et al. demonstrated remote excitation of
range of 103–107, when the plasmon resonance overlaps with the SERS by forming a hotspot between a silver nanoparticle and a
excitation frequency. These enhancement factor are 10–100 times silver nanowire. SERS in the hotspot region could be observed
greater than the ones of particles with aspect ratios that lack the after launching a propagating plasmon in the wire through laser
spectral overlap between their plasmon resonance and the excitation several micrometers away from the hotspot.[190]
excitation wavelength.[186] Similarly, Xia and co-workers demon- According to Xu et al., single spherical or regular crystal
strated that for a given size, the sharper cubes gave stronger shaped nanoparticles are likely inefficient as substrates for
Raman peaks than truncated ones.[98] The difference in single-molecule SERS due to their comparatively weak electro-
enhancement factor was attributed to the variation in overlap magnetic enhancement effect.[144] Strongly coupled structures,
between the particle LSPR and the laser frequency. such as dimer configurations or particles with sharp surface
Kottmann et al. studied the relation between the nonregular protrusions, may be suitable for single-molecule SERS due to
cross-sectional shape of a nanowire, its resonance spectrum, and large and spatially confined electromagnetic enhancement
the resulting field enhancement by numerical calculations.[187] effects.[144,191,192] It should be noted however, that in dimer
According to them, the maximum field and Raman enhance- structures at very small interparticle distances (<1 nm) electro-
ments depend on the cross-sectional shapes of silver nanowires, magnetic enhancements will be limited by quantum mechanical
among others. The maximum Raman enhancement should effects such as interparticle electron tunneling.[193] Though
exceed 106 for a triangular cross-section; for a square, it is about electromagnetic enhancement is likely to produce the dominant
105, whereas it is below 104 for the hexagonal, pentagonal, and contribution to single-molecule sensitivity in SERS in these cases,
circular cross-sections. Calculations of Xu et al. indicate that the an additional chemical or electronical resonant enhancement
maximum enhancement factor achievable through electromag-
netic mechanisms is on the order of 1011.[144] This can be realized
only under special circumstances, such as for strongly coupled
structures (such as dimer configurations) or at locations close to
sharp surface protrusions.[102,107,144] From the extensive literature
that reports estimates and measurements of Raman enhance-
ment factors, we limit ourselves to mentioning a few: Tian et al.
have reported that platinum nanothorns prepared by an
electrochemical method exhibit considerably higher SERS activity
than smooth spherical platinum nanoparticles possibly due to the
lightning-rod effect.[188] The SERS signal significantly decreases
with the decrease in nanothorn tip sharpness and nanothorn
density. Murphy and co-workers reported surface enhancement
factors in the range of 107–109 for 4-mercaptobenzoic acid
(4-MBA) molecules sandwiched between a smooth gold substrate
and gold nanoparticles of several different morphologies.[182]
Recently, star-shaped gold nanoparticles received increasing
attention due to the potentially large field enhancements in the
vicinity of their tips.[105] Khoury and Vo-Dinh have reported an
enhancement factor 5  103 for SERS of 4-MBA molecules on
gold nanoparticles with such sharp surface protrusions in
solution ensemble measurements.[103] Nalbant-Esenturk et al.
estimated the Raman enhancement factors of gold nanostars to Figure 8. a) Sketch of the combined dark-field scattering and Raman
exceed 105 using 2-mercaptopyridine and crystal violet as microscope used for single-particle spectroscopy. b) Scanning force micros-
analytes.[189] Rodriguez-Lorenzo et al. recently demonstrated that copy height image of an individual gold nanostar deposited on a glass
coverslip and coated with self-assembled monolayers of 4-mercaptobenzoic
a SERS signal amplification of 1010 can be achieved in junctions acid. c) Raman spectrum of a self-assembled monolayer (SAM) of
between a gold nanostar tip and a gold surface for 4-mercaptobenzoic acid on the single gold nanostar shown in (b) (60 s
1,5-naphtalenedithiol which allows zeptomolar analyte detec- integration time and 240 kW/cm2 at the sample). Reproduced with per-
tion.[108] Hrelescu et al. reported Raman scattering from single mission from ref. [107]. Copyright 2009 American Institute of Physics.

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effect has to be invoked in order to explain the SERS moment relative to the particle surface.[159,203,204] For example, the

REVIEW
enhancement factors of the order 1014 reported in the fluorescence intensity depends on whether a fluorophore is located
literature.[144,172–174,180,191] Based on DDA calculations of the near the tip of an ellipsoid (on the major axis), or along the minor
field enhancement factors for various different silver axis of the ellipsoid. The fluorophore will experience two different
particle sizes, shapes, orientations, and interparticle spacings, modes of the LSPR. Further, there is a difference whether the
Hao and Schatz also concluded that not all of the single-molecule fluorophore dipole moment is perpendicular or parallel to the
SERS enhancement factor of 1012 can be ascribed to purely particle surface. Fluorescence is either enhanced or quenched
electromagnetic effects.[58] Wokaun et al. have shown that since the molecular transition dipole is enhanced or canceled by
radiation damping limits the values of the attainable electric the corresponding image dipole induced in the metal.[203]
field intensity at the tip of small metal rods and hence limits the Depending on the aspect ratio, a radiative rate enhancement by
enhancement factors found in SERS.[141] According to them, the a factor of 103 or greater can be found for a fluorophore (transition
difference between various shapes is virtually eliminated for moment) orientation perpendicular to the surface of an
larger volumes due to radiation damping. ellipsoid.[203] Therefore, quenching or enhancement of the
fluorescence and changes of fluorescence lifetime are dependent
on the morphology of the metal particles.
Gold nanoparticles have also been observed to show weak
8. NMNPs and Fluorescence intrinsic photoemission via an interband transition mechan-
Fluorescence, the spontaneous radiative decay of electronically ism.[205] This effect can be enhanced by many orders of
excited molecules, is widely used as a signal transduction tool for magnitude in the presence of plasmon resonances.For example,
the detection of trace levels of analytes, imaging, and El-Sayed and co-workers have shown that the photoluminescence
single-molecule studies of biological systems. Metal nanoparti- quantum efficiency from gold nanorods can be enhanced by 6 to 7
cles have been found to either quench or enhance fluorescence orders of magnitude compared to bulk metal.[206] Li et al. have
intensity of a fluorophore.[156,162–164,194–196] The quenching and demonstrated that sufficiently long gold nanorods (aspect
enhancement are determined by interactions between fluoro- ratio > 13) exhibit intense fluorescence.[160] The emission
phores and metal surfaces depending on the location of the observed in gold nanorods of different aspect ratios is a function
fluorophore around the particle, the orientation of its transition of local field enhancement factors and is therefore enhanced in
dipole moment relative to the particle surface, and the the spectral vicinity of the LSPR.[160,206–208] Enhanced emission of
particle–fluorophore distance.[156,162–164,194–198] Quenching may the rod is more than 1 order of magnitude larger compared to that
occur by Förster resonant energy transfer (FRET) to the surface for the nanosphere.[207] Under pulsed laser excitation, Au
plasmon absorption of the metal particle. FRET is a dipole–dipole nanorods were observed to emit a strong TPPL, which is many
interaction mechanism in which a donor fluorophore in its times brighter than the TPPL from single dye molecules.[209,210]
excited state transfers its energy radiationless to an acceptor. The strong TPPL is thought to arise from the plasmon-enhanced
FRET has been widely used to measure the distance between sites two-photon absorption cross-section due to coupling of weak
or biomolecules due to its 1/R6 distance dependence (R is the electronic transitions in the metal to the particle plasmons.[210,211]
distance between the dipoles concerned).[199–201] When donors TPPL has been recently used as a nonlinear optical imaging
and acceptors are present in proximity with sub-wavelength mode, which will be discussed below.
metal particles, the rates of energy transfer increase at distances
up to 70 nm, which is 10-fold larger than typical Förster
distances.[199,200] 9. Applications of Nonspherical NMNPs
Enhancement occurs through the increase of the strength of
the incident light field which increases the rate of excitation, and 9.1. Analytical Applications
an increase in the radiative decay rate of the fluorophore.[194] The
resonantly enhanced local field of metal nanoparticles can NMNPs, and in particular gold nanoparticles, possess large
increase or suppress the rate of excitation. Metal particles can scattering cross-sections, high degree of biocompatibility, rich
greatly enhance local excitation intensities, since the light surface functionalization chemistry, and high photostability.
intensity is proportional to the square of the field. Another Therefore, these particles have been shown to be very useful for
important effect of metal particles is that they can modify the biomolecular manipulation, labeling, and detection.[212–214]
intrinsic radiative decay rate of a fluorophore. An appropriate Further, for several (in vivo) applications, nonspherical gold
proximity and orientation of fluorophores to metal particles nanoparticles are also advantageous because their LSPR can be
modifies the photonic mode density around the fluorophore and tuned to the NIR wavelength range, the so-called biological
will lead to a radiative rate outranging the rate of losses under window, where the absorption, scattering, and fluorescence from
favorable circumstances.[194,197] Theoretical calculations show an endogenous biological chromophores are minimal.[215]
increase of the radiative decay rate of up to two orders of Sensitivity and specificity are two critical issues in modern
magnitude for a fluorophore near a prolate silver nanoparticle, biomedical diagnosis research. Yguerabide and Yguerabide
unlike the radiative rate increase in case of a spherically or a demonstrated that single NMNP can be used as optical reporters
nonresonantly shaped nanoparticle.[202] in clinical and biological applications by using the strong elastic
The shape of a nanoparticle exerts its influence on the light scattering properties of these particles.[86,117,216] Plasmon
fluorescence of a fluorophore depending on the location of resonant particles have very high scattering cross-sections
the fluorophore around the particle and the orientation of its dipole compared to other optical labeling entities under the same

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illumination conditions. For example, the cross-section for elastic LSPR biosensor for the binding of streptavidin to biotin.[235] The
REVIEW

light scattering from an 80 nm plasmon resonant particle is lowest streptavidin concentration that was experimentally mea-
equivalent to the absorption cross-section of 500 000 individual sured was 1 nM, which was substantially lower than that detected
fluorescein molecules or >105-fold that from typical semicon- by biotinylated single gold nanospheres.[109,235,236]
ductor quantum dots.[217] The impressive signal of ultrabright Sönnichsen and Alivisatos reported that gold nanorods could
plasmon resonant particles allows them to be individually be exploited for the study of rotational motion in biomole-
identified and counted relatively easily, pushing the analyte cules.[237] Murphy and co-workers demonstrated the use of optical
detection limit to a dramatically low value. This, being aided by patterns, produced by resonant Rayleigh scattering from gold
the high photostability and absence of blinking, promises an nanorods, as markers by which local deformations of stretchable
ultrasensitive assay format based on single-target molecule polymers could be measured using image correlation techniques.
detection. NMNPs can replace or complement the colorimetric, These authors proposed that modified gold nanorods could be
fluorescent, or radioactive labels routinely used in immunoassays used for examining mechanical effects in biological tissues.[238] Li
and cellular imaging.[86,216–219] et al. suggested the use of relatively intense fluorescence of
Single or aggregated NMNPs can also act as transducers that sufficiently long gold nanorods (aspect ratio >13) as probes in
convert the changes in the interparticle distance or local refractive fluorescence-based microarray assays and optical biosensor
index into spectral shifts in their absorption and scattering development, and demonstrated the application of this concept
spectra. Thus the plasmon resonant nanoparticles have very by monitoring DNA hybridization events by measuring the
promising applications as label-free biosensors.[109,137,220–223] concomitant change in fluorescence intensity.[160] Nishizawa et al.
This sensing property uses the spectral change or the LSPR have demonstrated that hollow Au nanotubules support
brought in by the biomolecular event occurring in the vicinity of selective ion transport analogous to that observed in ion-exchange
the plasmon resonant nanoparticles. The biomolecular event can polymers, when the inside radius of the tubule is small relative to
either change the interparticle distance and thereby the coupling the thickness of the electrical double layer.[239] The metal
of surface plasmons between the particles or the local refractive nanotubule membranes can be cation-permselective, anion-
index of the nano-environment of the nanoparticle. When permselective, or nonselective, depending on the potential
the plasmon resonant particles are very close to each other, the applied to the membrane. Metal nanotubule membranes have
plasmon oscillations from adjacent particles can couple giving potential for applications as universal ion-exchange membranes,
rise to hybridized plasmon modes derived from the modes of the and in chemical separations, such as biomedical separations or
individual particles.[224–226] The occurrence of a strongly industrial gas separations.[240]
distance-dependent red-shifted mode has been utilized by NMNPs have been used for the detection of inorganic ions,
researchers to develop colorimetric sensors for the detection of organic molecules, and biomolecules. One of the major
DNA as well as insertions, deletions, and mismatches at a mechanisms of detection involves the change in the LSPR due
single-base resolution.[227–229] Similarly, Dujardin et al. reported to interaction between the particle and adsorbed analyte. Sudeep
self-assembly of oligonucleotide-functionalized short gold nanor- et al. reported selective detection of micromolar concentrations of
ods.[14] As discussed earlier in Section 5.5, the LSPR peak position cysteine and glutathione in the presence of various other a-amino
and intensity are sensitive to the local refractive index acids by exploiting the interparticle plasmon coupling in Au
surrounding the nanoparticle. The binding of biomolecular nanorods.[241] Rex et al. have demonstrated the analytical potential
targets to receptor-functionalized nanoparticles results in a of Au nanorods for monitoring Hg in water samples with
change in the local refractive index and hence spectrally shifts outstanding selectivity and sensitivity based on amalgamation
the LSPR of nanoparticles. These changes enable monitoring of without previous separation or preconcentration of the original
molecular binding in real time with high sensitivity by simple sample.[242]
spectrophotometric techniques.[109,230,231] Chen et al. have shown
that for gold nanorods the longitudinal LSPR band sensing mode
exhibits much higher sensitivity and linearity to the concentration 9.2. Photothermal Therapy
of the target biomolecules compared to that of the gold
nanospheres.[137] Marinakos et al. have also observed that the Large absorption cross-sections and the decay of plasmons into
nanorod-based sensors have advantages over gold nanosphere- electronic excitations with subsequent electron–phonon relaxa-
based sensors.[220,232,233] In addition to a significantly lower tion make metal nanoparticles very efficient heat sources. Metal
detection limit, the signal of the nanorod sensor provides the particles normally show rather poor light emitting ability.
internal self-reference due to the measurement of wavelength Therefore, they can efficiently convert the absorbed light into
shift of the plasmon bands.[220,232,233] The peak wavelength shift heat via nonradiative electron relaxation dynamics, known as
is solely determined by changes in the dielectric properties (i.e., photothermal effect, and serve as nanometric local heat
refractive indices) in the immediate vicinity of the nanoparticles, sources.[243–248] As the light absorption cross-section is greatly
and concentration change has minimal or no effect on this enhanced under plasmonic resonance conditions (the spectrum
parameter. Spectral changes induced by changes in the refractive of the heat generation rate demonstrates a typical plasmon peak at
index in the vicinity of individual gold nanorods due to target the LSPR frequency), the magnitude of generated heat will
binding have been utilized by Yu and Irudayaraj for multiplex depend on the particle size and shape, in addition to the nature of
biosensing by using the longitundinal plasmon mode of nanorods the metal and the number of nanoparticles present in the system.
of different length functionalized with different specific analyte As optical and thermal responses are closely related, metal
acceptors.[234] Recently, Nusz et al. reported a single-gold nanorod nanoparticles can be used as nanometric heat sources and probes

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for local temperature variations via their optical beha-

REVIEW
vior.[229,243,249,250] For example, heat-induced changes in optical
properties (e.g., refractive index) of the surrounding inhomoge-
neous medium can be recorded in photothermal imaging.[251]
The heat generated in metal nanoparticles may also induce phase
transformations in their surrounding matrix and can be used to
release drugs from polymer capsules or to release the contents of
small containers inside living cells.[252–255] The importance of
nanoparticle shape in the photothermal effect has been
demonstrated in photothermal therapy.[256,257] In these applica-
tions, after attaching to tumor cells, the nanoparticles are
irradiated by short laser pulses and the absorbed light energy is
quickly transformed into heat. The heat generated may reach
thresholds which result in desired target damage through
thermal denaturation and coagulation or through mechanical
stress caused by microbubble formation, acoustic, and shock
wave generation.[258,259] The photothermal therapy is relatively
simple to perform and has the potential of treating tumors
embedded in vital regions without surgical resection. In order to
effectively absorb light in biological medium, the metallic
nanoparticles should show a LSPR in the biological window
(650–900 nm). LSPR of several kinds of nonspherical Ag and Au
particles, such as nanorods, nanoshells, nanocages, and
nanostars, can be tailored to this range.[107,153,260] Suitable Figure 9. Photothermal destruction of SK-BR-3 breast cancer cells (in
selection of the experimental parameters, therefore, promises vitro) treated with immunogold nanocages (45 nm size) and irradiated
highly localized and controlled destruction or treatment of the by an 810 nm laser at a power density of 1.5 W/cm2 for 5 min. A well-
targets varying from a few nanometer to tens of micrometers defined circular zone of dead cells is revealed by A) calcein AM assay, and
(such as from bacteria to (cancer) cells).[256,257,261–266] B) ethidium homodimer-1 (EthD-1) assay. In the control experiment, cells
Experimentally, it has been observed that 30–40 nm particles irradiated under the same conditions, but without immunogold nanocage
treatment maintained viability, as indicated by C) calcein fluorescence
are most effective for photothermal therapy.[267] According to
assay and D) the lack of intracellular EthD-1 uptake. Reproduced with
some calculations, silica core–gold nanoshells (core diameter: permission from ref. [274]. Copyright 2007 American Chemical Society.
50–100 nm, shell thickness: 3–8 nm) and gold nanorods (aspect
ratio ¼ {15–20 nm}/{50–70 nm}) are more efficient photothermal
labels and sensitizers than solid single gold spheres of equivalent other components that allow additional functionalities to be
volume.[268] Gold nanoparticles, especially nanorods, are emer- introduced (such as an extra segment that binds to an
ging as one of the most promising candidates for photothermal endosomolytic agent) to create a versatile synthetic gene delivery
applications since they are strong absorbers, biocompatible, easily system. Takahashi et al. have reported that Au nanorods can be
conjugated to antibodies or proteins, and have adjustable optical used as carriers for a phototriggered gene delivery, with 1064 nm
properties.[153,269] Owing to the large plasmon resonance laser irradiation triggering the release of plasmid DNA from
absorption efficiency of nanorods, the threshold energy density phosphatidylcholine-modified nanorod–DNA (PC-NR–DNA) com-
for photothermolysis can be sufficiently small.[265] Further, due to plexes via morphological transformation of Au nanorods into
their large scattering cross-section, nanorods can be used spherical nanoparticles.[277] Kitagawa et al. have reported controlled
simultaneously for imaging and photothermal therapy.[261,270–273] release of myoglobin protein from the myoglobin–gold nanorod
Gold nanoparticles of other morphologies such as nanocages and complexes by NIR (pulsed) laser irradiation.[278]
nanoshells, whose optical properties can be tuned to the vis–NIR
spectral region, have also been tested for their photothermal
therapeutic properties (Fig. 9).[266,274] Chen et al. reported that 9.3. Cellular Uptake and Imaging
immunogold nanocages had lower power density threshold of
1.5 W cm2 for selective destruction of cancer cells than those Chithrani et al. have studied the size- and shape-dependence of
reported for gold nanorods (10 W cm2) or gold nanoshells the uptake of gold nanoparticles into mammalian cells.[279] These
(35 W cm2).[257,261] However, in addition to the morphology authors found that 50 nm spheres were taken up more effectively
effect, other parameters such as the density of nanocages on each by the cells compared to both smaller and larger spheres in the
cell could also contribute to the lowering of the thermal damage 10–100 nm size range. On the other hand, uptake of lower-
threshold. aspect-ratio (1:3) nanorods was greater than that of those with
Salem et al. have demonstrated a new nonviral gene therapy higher aspect ratio (1:5). Interestingly, nanospheres were taken
approach by using multisegment metal nanorods.[275,276] up more efficiently than nanorods with dimensions in the
Differential molecular binding strategies were used to attach 10–100 nm range. However, the difference in surface chemistry
plasmids and a cell-targeting protein to spatially separated regions could be partly responsible for the difference in uptake between
of the delivery system. This approach can be extended to include spherical and rod-shaped NMNPs. Still very little is known about

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the independent role of particle size, shape, and surface physical and chemical properties of nonspherical NMNPs, which
REVIEW

chemistry on cellular uptake.[280] show their promising application potentials.


Strong optical response, coupled with photo- and chemical Silver has been known for a long time for its bactericidal
stability, biocompatibility, and easy surface conjugation chem- properties. In the recent past, silver nanoparticles had been
istry, make NIR-absorbing nonspherical Au nanoparticles reported to show antibacterial properties that find immediate
attractive contrast agents compared to molecular dyes for NIR applications in biomedical science and household appliances.
imaging applications.[281] A number of optical imaging techni- Chemisorbed Agþ ions on the nanoparticle surface are thought to
ques, such as dark-field microscopy (DFM), TPPL microscopy, be responsible for the antibacterial action of silver nanoparticles.
and optical coherence tomography (OCT), are used to image Recently, Pal et al. reported a particle morphology-dependent
living tissue with subcellular resolution. From numerical antibacterial activity for a number of silver nanoparticles.[303]
calculations, El-Sayed and co-workers have concluded that gold According to this report, truncated silver nanotriangles showed
nanorods offer the superior NIR absorption and scattering at bactericidal properties at much lower total silver content than
much smaller particle sizes compared to nanospheres and spherical nanoparticles, which in turn showed better bactericidal
nanoshells.[153] Their calculations further showed that Au properties at lower total silver concentration than silver nanorods.
nanorods with a large aspect ratio along with a small effective The degree of antibacterial activity is believed to depend on the
radius were the best photoabsorbing nanoparticles, whereas the availability of atom-dense {111} faces on the surface of the
largest scattering contrast could be obtained from nanorods of particles. Berry et al. have reported that CTAB-capped Au
high aspect ratio with a larger effective radius.[153] Gold nanorods nanorods can be deposited on the surface of gram-positive
have been demonstrated to be promising contrast agents for bacteria more easily than peptide and nucleic-acid-capped
dark-field imaging studies.[261,281–285] Dark-field microscopy has nanoparticles.[304] The strong electrostatic interaction between
been the most common means for plasmon resonant nanopar- the rod and bacterium surface results in bending of the nanorods
ticle imaging. However, strong background signal in the case of and formation of a percolating–conducting network on the
intracellular imaging often impairs the detection of low bacterium surface. This gives an enhancement of four orders of
concentrations of plasmon resonant particles by this technique. magnitude, in the conductivity of the rod network compared to a
TPPL microscopy is an alternative imaging option under such network of nanospheres. The authors believe that the high
conditions. There are a few advantages associated with TPPL conductivity at only 10% coverage (which is well below the
imaging. For example, in TPPL NIR frequencies in the biological percolation threshold of 45%) can open the possibility of
window can be used at power densities well below the damage fabricating electronic circuitry on bacteria without suffocating
threshold of biological tissue. Further, TPPL can provide 3D the microorganism.
spatial resolution avoiding tissue autofluorescence. TPPL of Laicer et al. have reported that alkanethiol-functionalized gold
nonspherical Au nanoparticles has been used to image the nanorods can act as morphological seeds that specifically
location of these particles both in in-vitro and in-vivo target template the growth and direction of large, uniform, cylindri-
cells.[123,210,286–288] Nonspherical Au nanoparticles have also been cal-phase domains from a polystyrene-block-polyisoprene
reported to improve the imaging performance when they are used (PS-b-PI) copolymer solution, whereas spherical gold nanopar-
as exogenous contrast agents in OCT and photoacoustic ticles and other materials, which are commonly used as
tomography (PAT), two other noninvasive imaging tech- heterogeneous nucleants in crystallization, fail to promote
niques.[99,289–298] OCT detects the depth of reflections of light single-crystalline domain growth in the same material.[305]
of low coherence. It can produce real-time, high-resolution Sanders et al. and Dickson and Lyon have demonstrated that
(typically 1–15 mm) images in vivo of biological tissues with a high-aspect-ratio metal nanostructures, such as Au and Ag
spatial resolution that is many times greater than that produced nanorods/nanowires, can be used to transport optical signals over
by ultrasound imaging or magnetic resonance imaging.[299] In distances of several micrometers.[128,306] When plasmon propa-
PAT, photoinduced thermalization of conduction electrons in the gation is launched parallel to the long axis of nanorods/wires, the
NIR-active particles results in a temperature increase of hundreds incident optical energy passes down the length as a surface-bound
of degrees.[300] This leads to plasma formation, microbubble plasmon mode and re-emerges from the end as a photon (via
expansion, and collapse. The expansion and collapse of cavitation plasmon scattering). By constructing a composite nanowire with
bubbles produce an acoustic shockwave which can be detected by two discrete segments of Au and Ag, they have demonstrated that
ultrasonic transducers. PAT has the advantage over pure optical a unidirectional plasmon transmission through the composite
imaging. PAT combines the intrinsic optical contrast character- nanowire can be obtained; i.e., an electro-optic heterojunction can
istics with the capability of the diffraction-limited high spatial be constructed by controlling rod orientation, composition, and
resolution of ultrasound.[301,302] incident wavelength. With much higher bandwidths than
electronic devices and smaller spatial constraints than conven-
tional light guides, plasmon-mediated transport of optical
9.4. Other Applications information on the scale of tens of micrometers and controlling
the directional flow of optical information show great promise for
The range of applications of nonspherical NMNPs encompasses future optical devices, high-density optical information proces-
several fields, from science and engineering to technology, and is sing, and nanoscale optical sensing methods. Zijlstra et al.
expanding rapidly. Progress in nanoparticle synthesis and recently demonstrated the use of gold nanorods for five-
modification has fueled enormous advances in applications dimensional data storage based on thermal reshaping of
recently. In the following, we mention several other interesting nanorods by pulsed laser irradiation for writing and TPPL

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imaging for reading.[307] Due to the strongly anisotropic will be to make them multifunctional and to control their

REVIEW
plasmonic response of the nanorods only a small subpopulation properties via the local environment or external stimuli. This is
is thermally reshaped for a given laser wavelength and essential for construction of future nanodevices. Looking further
polarization. The use of five wavelengths and two polarization to future potential applications, one can expect that the NMNPs of
orientations, therefore, allowed the authors to write and read controlled morphologies will find applications as in vivo force
18 images in three layers spaced by 10 mm (Fig. 10). They sensors; morphological seeds for aligned block copolymer/
estimated that the storage density can reach 1 Tbit cm3 which inorganic nanocomposites with anisotropic properties; smart
would result in a capacity of about 1.6 Tbyte for a DVD-sized disk. catalysts (for fuel cells, waste treatment, bioprocessing, etc);
Pan et al. have studied the optical limiting properties of a number enhancers in photovoltaics and other energy conversion devices;
of metal (Cu, Co, Ni, Pd, Pt, and Ag) nanowires.[308] They have better therapeutic and imaging agents; probes for single-molecule
found that the nanowires have broadband optical limiting sensing of drugs, toxins, and environmental pollutants; and key
capability and that the optical limiting performances of some components in energy transport and novel opto-electronic
metal wires are comparable to or better than those of carbon devices.
nanotubes. Thus, metal nanowires can find
applications as cheap and efficient optical
limiters. Recently, Selhuber-Unkel et al. have
shown that gold nanorods can be used as
efficient optical handles in nanoscale experi-
ments.[309] These authors anticipate that gold
nanorods can be employed as force sensors
in future in vitro and in vivo studies as well
as force transducers in single-molecule
experiments.

10. Conclusions and Outlook


Understanding the properties and exploring
applications of nonspherical NMNPs have
made great progress in recent years.
Advances in theory and computational tech-
niques for quantitative understanding of the
morphology-dependent properties have been
satisfactory. Scientists around the world have
shown tremendous interest in a variety of
applications of NMNPs ranging from efficient
catalysis to improved methods for diagnostics
and the treatment of diseases. This review
attempted to highlight properties and applica-
tions of chemically synthesized colloidal
NMNPs with nonsperical morphologies.
Both physical and chemical properties of
nanoparticles are affected by subtle aspects
of particle morphology. This gives an oppor-
tunity to generate novel properties, which in Figure 10. Gold nanorod surface plasmon-mediated optical recording and readout. a) A sche-
turn offers numerous innovative possibilities matic illustration of the patterning mechanism. The patterning is achieved by the photothermal
for technological applications. Anisotropic reshaping of the gold nanorods in the focal volume of the focusing objective. The nanorod
features in nonspherical nanoparticles make reshaping is selective in terms of aspect ratio and orientation of the nanorod. A linear polarized
laser pulse will only be absorbed by gold nanorods that are aligned to the laser light polarization
them ideal candidates for enhanced chemical,
and exhibit an absorption cross-section that matches the laser wavelength. Top panel of (a):
catalytic, and local field related applications. s-polarized laser light with a wavelength of 840 nm will only affect the nanorods with an
Nonspherical plasmon resonant nanoparticles intermediate aspect ratio that are aligned to the laser polarization (encircled spheres indicate
offer favorable properties for their use as (in rod reshaping). Bottom panel of (a): p-polarized laser light with a wavelength of 980 nm only
vivo) analytical tools, transport vehicles, as well reshapes the high-aspect-ratio gold nanorods aligned with the laser light polarization.
as diagnostic and therapeutic agents. b) Normalized two-photon photoluminescence (TPPL) raster scans of 18 patterns encoded
New applications of NMNPs are bound to in the same area using two laser light polarizations and three different laser wavelengths. Patterns
were written in three layers spaced by 10 mm. The recording laser pulse properties are indicated
evolve rapidly as more and more particles with
(wavelength at left, polarization at bottom). The recordings were retrieved by detecting the TPPL
well-controlled morphologies become avail- excited with the same wavelength and polarization as employed for the recording. The size of all
able. One of the major trends in further images is 100 mm  100 mm, and the patterns are 75 pixels 75 pixels. Reproduced with
development of nonspherical nanoparticles permission from ref. [307]. Copyright 2009 Macmillan Publishers Limited.

Adv. Mater. 2010, 22, 1805–1825 ß 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1821
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105, 15241.
through the Excellence Cluster ‘‘Nanosystems Initiative Munich’’ (NIM)
[38] A. Fukuoka, N. Higashimoto, Y. Sakamoto, S. Inagaki, Y. Fukushima,
and the LMUexcellent program, and the Alexander-von-Humboldt
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