FOCUS | REVIEW ARTICLES

PUBLISHED ONLINE: 31 OCTOBER 2012 | DOI: 10.1038/NPHOTON.2012.244

Nonlinear plasmonics
Martti Kauranen1 and Anatoly V. Zayats2

When light interacts with metal nanostructures, it can couple to free-electron excitations near the metal surface. The electro-
magnetic resonances associated with these surface plasmons depend on the details of the nanostructure, opening up oppor-
tunities for controlling light confinement on the nanoscale. The resulting strong electromagnetic fields allow weak nonlinear
processes, which depend superlinearly on the local field, to be significantly enhanced. In addition to providing enhanced non-
linear effects with ultrafast response times, plasmonic nanostructures allow nonlinear optical components to be scaled down in
size. In this Review, we discuss the principles of nonlinear plasmonic effects and present an overview of their main applications,
including frequency conversion, switching and modulation of optical signals, and soliton effects.

N
onlinear optical effects (Box  1) have an important role in
modern photonic functionalities, including control over
the frequency spectrum of laser light, generation of ultra-
short pulses, all-optical signal processing and ultrafast switching 1.
Optical nonlinearities are inherently weak, because they are gov-
erned by photon–photon interactions enabled by materials. They
are superlinearly dependent on the electromagnetic field and can
be strengthened in material environments that provide mecha-
nisms for field enhancement.
An increased effective nonlinear optical response can be
achieved through plasmonic effects. Such effects arise from coher-
ent oscillations of conduction electrons near the surface of noble-
metal structures2,3 (Box 2). For extended metal surfaces, this gives
rise to surface plasmon polaritons (SPPs), which are surface elec-
tromagnetic waves propagating at the metal–dielectric interface.
For metal nanoparticles, the response arises from localized sur-
face plasmons (LSPs), whose resonances depend on the particle
size and shape. New concepts, including SPP crystals2 and wave-
guides4, nano-antennas5 and plasmonic metamaterials6, can be
used to tailor the optical responses further through the resonances
of the individual units and their mutual electromagnetic coupling.
Plasmonic excitations can boost nonlinear optical effects in sev-
eral ways. First, the coupling of light to surface plasmons can result
in strong local electromagnetic fields2,5, significantly enhancing
optical processes. A prime example is surface-enhanced Raman
scattering, where plasmonic excitations at rough or engineered
metal surfaces can enhance the inherently weak Raman process by
orders of magnitude, allowing even single-molecule detection7. In
nonlinear optics, this naturally translates to higher effective non-
linearities of the metal itself or the surrounding dielectric material.
Second, plasmonic excitations can be extremely sensitive to
dielectric properties of the metal and the surrounding medium.
This is the basis for label-free plasmonic sensors: minute modifi-
cations of the refractive index near the metal surface result in sig-
nificant modifications of the plasmonic resonance8. In nonlinear
optics, this extraordinary sensitivity can be exploited to control
light with light, using a control beam to induce a nonlinear change
in the dielectric properties of one of the materials, thus modifying
the plasmonic resonances and the propagation of a signal beam.
Finally, plasmonic excitations can respond on the timescale of a
few femtoseconds, allowing ultrafast processing of optical signals3.
Nonlinear effects in plasmonics could therefore lead to several
interesting nanophotonic functionalities, and we are now seeing
the emergence of metal nanostructures designed to favour specific
nonlinear processes.
In this Review, we discuss the principles of nonlinear plasmon-
ics and present an overview of its main areas of application. We
will consider the role of LSPs and SPPs on smooth films, in wave-
guides and on periodically structured surfaces as well as plasmonic
metamaterials. We will focus on the most traditional nonlinear
processes, such as harmonic generation, nonlinear propagation
and optical switching, all of which are important for nanopho-
tonic functionalities. We will therefore exclude processes such as
multiphoton-induced luminescence, which is a tool widely used to
study field localization in metal systems. Lasing and related phe-
nomena, such as spasing, are also inherently nonlinear but are not
discussed here (for a recent review, see ref. 9). The emerging area
of strong-field science in plasmonic systems10 is also beyond the
scope of the present article.
Basic concepts in nonlinear plasmonics
Nonlinear optical effects arise when electronic motion in a strong
electromagnetic field cannot be considered harmonic. Expansion
of the anharmonicity as power series in the field strength1 (Box 1)
mixes the incident fields and produces new fields that oscillate at
the sums and differences of the incident frequencies and can prop-
agate in various directions. For applications, the most important
effects occur at second and third order. The second-order response
typically gives rise to wave-mixing effects that lead to frequency
conversion, the most common example being second-harmonic
generation (SHG), where the incident frequency, ω, is converted
to its second harmonic, 2ω. New frequencies arise also from third-
order nonlinearities. More importantly, however, the third-order
response contains terms at the incident frequencies. This is known
as the optical Kerr effect and results in nonlinear modifications
of the refractive index (Box 1, equation (2)), allowing all-optical
switching and modulation of light. By combining Kerr nonlin-
earities with optical cavities or other systems with feedback, it is
possible to obtain bistability, where one input signal allows two
possible outputs. For optical beams with finite transverse size, dif-
fraction and nonlinear effects can balance each other, giving rise
to optical solitons.
The plasmonic structures can enhance nonlinear effects in
two main ways. First, such structures provide field enhancement
near the metal–dielectric interface, associated with the excitation
of either SPPs or LSPs2,3. This is characterized by the frequency-
dependent local-field factor L(ω, r) = |Eloc(ω, r)/E0(ω)|, where r is
the position vector, Eloc(ω, r) is the local field at frequency ω associ-
ated with the plasmonic excitation, and E0(ω) is the incident field.
The resulting strong fields enhance the nonlinear response locally

Department of Physics, Tampere University of Technology, PO Box 692, FI-33101 Tampere, Finland. Department of Physics, King’s College London, Strand,
London WC2R 2LS, UK. e-mail: martti.kauranen@tut.fi; anatoly.zayats@kcl.ac.uk

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© 2012 Macmillan Publishers Limited. All rights reserved.
REVIEW ARTICLES | FOCUS
Box 1 | Nonlinear optics
c the permittivity and, thus, refractive index depend on intensity
ω1
ω1
a b
ω ω ω
ω2
ω 2ω ω ω
Figure B1 | Photon diagrams for common nonlinear processes. The
solid horizontal lines correspond to real quantum-mechanical states
of the material system, whereas the dashed lines are so-called virtual
states, where the system resides only instantaneously. The thick
arrows correspond to the input fields that can drive the material
system up or down in energy as indicated. The thin downward arrow
corresponds to the generated field, which returns the material to
the initial state. a, SHG; b, degenerate FWM; c, coherent anti-Stokes
Raman scattering (CARS). Degenerate FWM gives rise to an intensity-
dependent refractive index, and CARS forms a basis for molecular
vibrational spectroscopy.
The response of materials to an optical field E is described by the
material polarization P:
P = ε0 χ(1) E + χ(2) E2 + χ(3) E3 + ∙∙∙
Here, ε0 is the vacuum permittivity and χ(s) is the sth-order sus-
ceptibility of the material1. In general, the field E consists of time-
harmonic at several frequencies, ωn. For moderate light intensities,
only the first term in equation (1) is important, and each compo-
nent gives rise to polarization oscillating at the corresponding
frequency. Such a linear response describes conventional optical
effects, such as refraction, absorption and scattering.
For strong fields, the higher-order (s>1) terms in equa-
tion  (1) need to be considered. They contain sums and differ-
ences of the incident light frequencies and give rise to radiation
at these new frequencies. The way the various positive and nega-
tive frequencies combine is often described in terms of photon
diagrams (Fig.  B1). The most important effects arise from sec-
ond- and third-order interactions. In second order, we obtain
SHG, sum- and difference-frequency generation, and an elec-
tro-optic response. Even more possibilities exist in third order,
with third-harmonic generation and FWM as specific examples.
Importantly, the third-order response contains oscillations also
and, when carefully designed, even when the response is inte-
grated over the whole sample. This concept is equally applicable to
increasing the nonlinearity of the metal itself (intrinsic response)
or of a material adjacent to the metal (extrinsic response). Second,
the plasmonic excitation parameters, including the SPP wavevec-
tor and the LSP or metamaterial resonance frequency, are very
sensitive to the refractive indices of the metal and the surrounding
dielectric. A nonlinear change in the index of either material can
therefore significantly modify plasmonic resonances and associ-
ated reflection, transmission or absorption of light.
Nonlinear effects are constrained by material symmetry 1.
Whereas all materials support third-order effects, second-order
effects are possible only in non-centrosymmetric materials within
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NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244
at the original frequencies. This is known as the Kerr effect, where
ε = ε0 χ(1) + 3χ(3)|E| 2 or (2)
ω3 n = n0 + n2I
Here, ε is the permittivity of the material, n0 is its linear refractive
index, n2 is the nonlinear index and I is the field intensity. In self-
modulation, a beam modifies the index it experiences, leading to
self-focusing or defocusing of beams of finite transverse size. In
cross-modulation, a control beam modifies the index at the signal
beam frequency, allowing all-optical modulation and switching.
A more complete description takes into account the vectorial
character of the electric field and polarization. The susceptibilities
are therefore tensorial quantities, which depend on material sym-
metry. Third-order processes can occur in all materials. Second-
order processes, however, are forbidden in centrosymmetric
materials within the dipolar approximation, and a response can
occur only at surfaces where centrosymmetry is broken. Beyond
this, second-order effects can occur even in the bulk of centrosym-
metric materials when higher-multipole (magnetic-dipole and
electric-quadrupole) interactions are considered11,12.
The nonlinear response leads to strong, coherent signals only
when individual nonlinear sources add up in phase. Such phase
matching is important for frequency conversion and samples
(1) much larger than the wavelength. Otherwise, the nonlinear effects
grow only over the coherence length of the interaction, typically
on the order of 10  μm. For subwavelength nonlinear sources,
phase-matching considerations are not important and the nonlin-
ear signals can be emitted in all directions. The same is true for
random ensembles of subwavelength sources, which lead to inco-
herent signals emitted in all directions (hyper-scattering).
The basic formalism needs to be corrected by the fact that the opti-
cal field experienced by a given dipole in the material is not the same
as the macroscopic field. The local field at frequency ωn and point r is123
Σ L (ω,r ) E (ω )
Eloc, i(ω,rn) = (3)
ij n j n
j
where i and j refer to Cartesian components of the field. For clarity,
the frequencies are shown as arguments of the fields. The local-
field factor, Lij(ωn, r), is tensorial, as the field direction may also
change through local-field effects. Such effects are particularly
important for nanostructured materials, which can strongly mod-
ify the local-field distribution, for example when a surface plas-
mon is excited.
the electric-dipole approximation of the light–matter interaction.
Although magnetic and quadrupole effects allow second-order
effects even in centrosymmetric materials (Box  1), such effects
are difficult to achieve. Centrosymmetry is therefore expected to
be detrimental to second-order response even in the presence of
local-field enhancement.
Intrinsic (ohmic) losses are always present in plasmonic sys-
tems. They limit both the SPP propagation distance and the achiev-
able local-field factors. For propagating waves, the nonlinear effect
on the field amplitude scales linearly with the interaction length,
typically up to 1  cm for phase-matched wave mixing (Box  1) in
bulk materials and waveguides. For typical loss-limited field-
enhancement factors of 10 for all interacting fields, the interaction
NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244
Box 2 | Plasmonics
a b
θSP
c d
Figure B2 | Examples of plasmonic structures. a, schematic of SPP on
a planar metal film excited through a prism b, Electric field distribution
of the SPP mode in a dielectric-loaded plasmonic waveguide-splitter.
c, Dipolar LSP mode intensity distribution for nanorod-shaped particle.
Brighter colour corresponds to higher intensity. d, SEM image of a
plasmonic metamaterial consisting of an array of SRRs (from ref. 103).
The optical properties of metal films and nanostructures are gov-
erned by the coupling of the incident electromagnetic field to the
coherent motion of free-electron plasma near the metal surface.
Such systems can be classified on the basis of which type of plas-
monic excitations they support2,3.
A surface plasmon polariton (SPP) is a propagating surface wave
at the continuous metal–dielectric interface (Fig. B2). The electro-
magnetic field decays exponentially on both sides of the interface,
providing subwavelength confinement near the metal surface. On
two-dimensional planar interfaces, an SPP is a longitudinal wave
with electric field components both perpendicular to the metal inter-
face and parallel to the wavevector. Light therefore needs to have an
electric field component in the plane of incidence for SPP excitation.
The SPP wavevector is larger than the wavevector of light propa-
gating in the adjacent dielectric medium. Coupling of light from free
space to SPPs, in analogy with any type of guided photonic modes,
therefore requires special arrangements such as a prism or diffrac-
tion grating coupler. Owing to its dispersion, an SPP is a slow wave
accumulating energy from the incoming light and providing field
enhancement near the metal interface. As a result of ohmic losses in
metal, SPPs have a finite propagation distance that depends on the
geometry of the supporting structure.
The SPP dispersion and, therefore, the field confinement and
enhancement, can be modified by structuring the interface (either
the metal or the dielectric medium). By doing so, it is possible to
make plasmonic waveguides2,4 and plasmonic crystals2 (periodi-
cally structured plasmonic surfaces or films). In the latter case,
one-dimensional (slits, grooves or ribs) or two-dimensional (holes,
protrusions or nanoparticle arrays) nanostructures on the surface
length can thus be reduced by a factor of at least 1,000 (second-
order process with three fields) to achieve an equivalent nonlin-
ear response. The resulting lengths of 10  μm or less are shorter
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FOCUS | REVIEW ARTICLES
or in the metal film, with period comparable to the SPP wavelength,
are used. The SPP dispersion in plasmonic crystals exhibits a struc-
ture of allowed and forbidden bands, similar to photon dispersion
in two-dimensional photonic crystals.
Localized surface plasmons (LSPs) are associated with the elec-
tron plasma oscillations in confined (subwavelength) geometries,
for example metal nanoparticles. LSP resonances depend on the
particle size, shape and refractive index of their surroundings. LSPs
can be resonantly excited with light of the appropriate frequency
and polarization irrespective of the excitation light wavevector.
Because its field is confined near the nanoparticle, an LSP has a
small mode volume and therefore provides significant electromag-
netic field enhancement, which is limited by ohmic and radiative
losses3 as well as quantum121 and nonlocal122 effects in the case of
ultrasmall sizes.
LSPs can also be supported by subwavelength features on a metal
surface. LSP resonances therefore have a considerable role in the
behaviour of SPPs on rough surfaces if their frequency is close to
the SPP frequency. The spectrum of LSPs associated with an ensem-
ble of metallic particles (or voids) is determined by the interaction
between the individual LSP resonances. The resulting spectrum and
the field enhancement depend strongly on the shape and size of the
individual particles and the distance between them. In such ensem-
bles of interacting small metallic particles, a very strong enhance-
ment of the electromagnetic field can be observed.
Recently plasmonic antennas based on pairs of, or several,
plasmonic particles have been developed to control near-field-to-
far-field light transformations5. Furthermore, sharp metal tips can
produce strong local electromagnetic fields through the ‘lightning-
rod’ effect 2, even when LSPs are not resonantly excited. In all cases, a
source of radiation localized to a subwavelength LSP mode can emit
a signal in essentially all directions, independently of the direction
of propagation of the incident field.
Plasmonic metamaterials consist of ensembles of electromag-
netically coupled, subwavelength metal nanostructures6. Their
optical properties can often be described by effective medium
parameters. Typical metamaterials can be achieved with SRRs of
different geometries, fishnets or nanoparticles. The optical response
of plasmonic metamaterials can be designed by tailoring the
response of individual units as well as the electromagnetic coupling
between them. Of particular interest are properties that naturally
occurring materials do not have. For example, certain resonances
of plasmonic metamaterials can be interpreted to have a magnetic
character even when the constituent materials are non-magnetic.
Some metamaterials can be designed to exhibit ‘hyperbolic’ dis-
persion, when the diagonal components of the permittivity tensor
have opposite signs. In addition, the permittivity can be tailored to
be very small at certain wavelengths giving rise to ‘epsilon-near-
zero’ metamaterials104,105.
Universal properties of all types of plasmonic nanostructure are
field enhancement near the metal surface, compared with the free-
space field of the incident light; strong sensitivity to refractive index
changes near the metal surface; and the possibility of engineering
the dispersion and resonances by controlling the nanostructure
geometry and dielectric surroundings. The resonances can thus be
tuned to the operation wavelength where the nonlinear response
needs to be enhanced.
than SPP propagation distance at most spectral ranges and are
comparable to typical coherence lengths of photonic non-phase-
matched interactions. For higher-order processes, the interaction
REVIEW ARTICLES | FOCUS
length can be reduced even more. For both wave mixing at the
nanoscale and Kerr-type processes involving LSP resonances, no
phase matching is needed (Box 1), and the effect of losses is in lim-
iting achievable local-field factors. Nevertheless, compared with
other structures, the ratio of the resonance quality to the mode
volume in plasmonic nanostructures is unsurpassed3. In all cases,
however, to utilize the field enhancement at all frequencies, the
structures must be designed with great care for good overlap of
plasmonic modes at all frequencies.
To achieve optical signal modulation in plasmonic structures,
either the plasmonic resonance can be shifted using control light
(induced refractive index change) or absorption at the plasmonic
resonance can be increased or decreased. Plasmonic nanostruc-
tures can be beneficial here owing to the high sensitivity of their
resonances to refractive index changes and because they localize
the interaction volume below the diffraction limit. The small mode
volume of plasmonic excitations provides the advantage for a low
power requirement despite being lossy. Intrinsic metal nonlineari-
ties also provide very high switching rates, limited only by the elec-
tron relaxation time in metal: the response times range from tens
of femtoseconds to a few picoseconds, depending on the electron
plasma relaxation processes involved.
The nonlinear response can be described theoretically in terms
of real and virtual electronic transitions in a material1. In metals,
intraband transitions of conduction electrons—the crucial differ-
ence from non-plasmonic materials—are essential, but interband
transitions from the valence band to the conduction band can also
be important. The conduction electrons can be treated as an iso-
tropic electron gas in the hydrodynamic model11, an extension of
the Drude model, where the electron velocity, v, obeys
дv v en
mn дt + (v• )v + τ = − enE − c v × B − p
∆
∆ (1)
Here m is the electron effective mass, n the density and e is the elec-
tron charge. The electric and magnetic components of the electro-
magnetic field are denoted E and B, p is the pressure of the electron
gas and c denotes the speed of light. On the left-hand side of equa-
tion (1), the second term represents convection and the third term
represents damping. The terms on the right-hand side are the electric
and magnetic parts of the Lorentz force and the pressure gradient,
respectively. Damping was neglected in the original hydrodynamic
model11 but has proved to be important in more recent treatments
of the nonlinear response12, especially for Kerr-type nonlinearity 13.
The various nonlinear effects can be described by expanding all
quantities to different orders of the interaction. Interestingly, the
convective and magnetic terms give rise to a second-order response
of higher-multipolar character even in the bulk of the electron gas12.
The surface nonlinearities can be treated in the selvedge model11,
where the electron density changes in a thin transition layer between
the two bulk media.
The Kerr-type nonlinearity of metals is usually described by
changes in the distribution of conduction-band electrons by the
excitation light 13, which can arise from the heating of the conduc-
tion-band electrons and from the interband excitation of electrons
from the d band to the conduction band. The change of the elec-
tron distribution modifies both the real and the imaginary parts
of the permittivity. The intraband part of the nonlinear response
is modelled with the Drude-like response with modified param-
eters13. The interband contribution is described within the random
phase approximation14. Additionally, conservative ponderomo-
tive potentials may also lead to third-order nonlinearities of the
electron gas15.
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NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244
Wave mixing in nanoplasmonic structures
Surface-enhanced nonlinear effects. Surface-enhanced SHG
was first studied using electrochemically roughened silver sur-
faces16. The SHG signal was found to be diffuse, but increased by
four orders of magnitude relative to a flat reference surface when
integrated over all detection directions. The results suggested that
the signals are incoherent and enhanced by LSP resonances of the
nanoscale surface features. Further support for the role of LSP
resonances was obtained from SHG experiments on metal-island
films and lithographic nanostructures17.
More-recent work has addressed surface-enhanced SHG from
a number of viewpoints. Near-field SHG measurements have been
performed using near-field detection18 and excitation19, the latter
also correlated with surface topography. Far-field SHG micros-
copy has emphasized the spatial overlap of the local fundamen-
tal and SHG modes20. These and additional studies show that the
SHG signals depend on the polarization of the fundamental field
even if the light is focused down to the achievable resolution of a
few hundreds of nanometres. The SHG emission, however, is inco-
herent and depolarized21, theoretically down to the scale of a few
nanometres22. Furthermore, semicontinuous metal-island films
near the percolation threshold support LSP resonances over broad
spectral ranges23.
LSP resonances can also enhance nonlinear processes other
than SHG. In particular, surface-enhanced third-harmonic gen-
eration has also been observed and its different symmetry rules,
relative to those of SHG, discussed24.
Enhancement of SHG by propagating SPPs was also demon-
strated early on25, and SPPs have been used to enhance four-wave
mixing 26 (FWM). Very recently, the roles of photonic and plas-
monic modes in SHG from metal films have been addressed by
momentum-space spectroscopy 27.
Nonlinear scattering from individual nano-objects. The first
formal electromagnetic description of incoherent second-har-
monic scattering (hyper-Rayleigh scattering (HRS)) from small
spherical particles was based on Mie theory but included only the
local surface response28. This formalism and its extension to the
local bulk response29 provided selection rules for signals arising
from the various multipolar Mie terms at the fundamental and
second-harmonic wavelengths.
Experiments on HRS30 from 13-nm gold particles yielded a
very high hyperpolarizability of 2,000–3000 × 10−30 e.s.u. per atom,
greatly exceeding that of the best molecular materials. Interference
between dipolar and quadrupolar HRS was subsequently observed
using 32-nm silver particles31. More detailed studies using parti-
cles ranging in size from 20 to 150  nm have shown that small,
non-spherical particles have a dipolar response arising from their
lack of centrosymmetry 32. For large particles, field retardation
across the particle enhances the quadrupole interaction, allowing
HRS even from spherical particles. Most recently, this interplay
between multipoles has also been extended to octupoles33. Since
these ensemble experiments, HRS from individual gold nanopar-
ticles has been observed34.
The various multipoles are important in HRS because of their
different resonance characteristics. Quadrupole resonances, for
example, are weaker but have narrower linewidths than the usual
dipole resonances. Unfortunately, the quadrupole resonance often
occurs at the spectral onset of the dipole resonance and hence can-
not be easily resolved. In HRS, however, the selection rules can be
used to isolate the quadrupolar signal. This opens a possibility for
nonlinear sensing of the refractive index of the surroundings with
properties superior to those of traditional approaches35.
Non-spherical plasmonic objects have also been investigated.
SHG from the sharp tip of a gold nanocone was strongest for
NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244 FOCUS | REVIEW ARTICLES
a d V(t) Fundamental f Enhanced
wave, Iω NIR field

χ (2), χ (3)

x
z EUV
EFISH signal, I2ω (t) output

e 2ω 2ω
Tapered silver
waveguide
b
– – –

+p
ε1
ω r1 d
E0
r2 ts
–
c
NIR input
+++
Gold ε3
Silica Glass Ti4+
Silica Ba2+
O2– 2ω 2ω

Figure 1 | Examples of individual metal nanostructures for enhancing nonlinear effects. a, Nano-aperture in a silver film, surrounded by a circular grating
for enhanced SHG (adapted from ref. 38). b, Gold bowtie antenna for third-harmonic generation (adapted from ref. 41). c, Non-centrosymmetric gold
nanocup for SHG (adapted from ref. 42). d, Plasmonic grating and nanoslit filled with nonlinear polymer for electric-field-induced SH (EFISH) generation
(adapted from Ref. 43). e, Barium titanate nanoparticle of radius r1 and nonlinear coefficient tensor of d coated by gold shell of thickness ts and outer radius
of r2, which enhances the nonlinear polarization p for SHG (adapted from Ref. 44). f, Tapered plasmonic silver waveguide that focuses near-infrared (NIR)
light to the tip for enhanced high-harmonic generation into the extreme-ultraviolet (EUV) regime (adapted from ref. 45).

incoming light polarized along the tip axis36, as expected, as a
result of the lowered symmetry relative to the sphere37. A rela-
tively advanced structure for SHG consisted of a nano-aperture
in a silver film surrounded by a concentric grating 38 (Fig. 1a). The
grating directed the incident light towards the aperture, whose
SHG response was enhanced by four orders of magnitude com-
pared with the aperture in the absence of the grating. The role
of the nanogap between two nanospheres was investigated by
FWM39. The signal increased as the gap size decreased to the ång-
ström regime, where quantum effects start limiting the local-field
enhancement 40. The geometry of nanoantennas (one example
shown in Fig. 1b) has also been shown to affect radiative damping
of their LSP resonances, playing thereby a crucial role in efficiency
third-harmonic generation41.
Recent work has utilized three-dimensional nanostructures.
Non-centrosymmetric gold nanocups were proposed for SHG
enhancement (Fig. 1c) and shown to be as efficient as traditional
nonlinear materials42. The nonlinearity of an organic polymer
has been combined with a plasmonic gap to allow tuning of SHG
by voltage43 (Fig.  1d). SHG from non-centrosymmetric barium
titanate nanoparticles has been enhanced by a factor of more
than 500 by coating the particle with a gold shell44 (Fig. 1e), with
possible applications as nonlinear labels in biological imaging.
Furthermore, a tapered, hollow, plasmonic waveguide channelling
energy to the narrow end yielded high-harmonic generation from
xenon up to the forty-third harmonic45 (Fig. 1f).
Structured plasmonic surfaces for enhanced nonlinear effects.
The first extended plasmonic structure designed for SHG was a
metal grating that enhanced the local field at the SHG wavelength
and gave rise to SHG emission into the first diffraction order 17.
A comprehensive theory of nonlinear metal gratings was subse-
quently formulated46 and experimentally tested47.
The first example of a surface designed to be non-centrosym-
metric consisted of an array of L-shaped nanoparticles48, fabri-
cated to determine the femtosecond plasmon dephasing time by
SHG autocorrelation measurements. Similar arrays of L-shaped
gold particles were then investigated for their SHG properties
(Fig. 2a). The efficiency was found to depend strongly on particle
ordering in the array 49, with the strongest signals when the funda-
mental wavelength was at plasmonic resonance of the structure.
It soon became evident, however, that the expected symmetry
rules of the linear and nonlinear responses of similar samples are
not obeyed50.
The split-ring resonators51 (SRR; Fig. 2b) have similar symme-
try to the L-shaped nanoparticles. The plasmonic resonances of
SRRs can be interpreted to have electric or magnetic character,
although the constituent materials themselves are non-magnetic6.
The initial measurements on arrays of SRRs suggested that the
magnetic resonances are favourable for SHG52. However, no signif-
icant difference between SHG from SRRs and that from comple-
mentary SRRs, which consist of holes in a metal film, was found53.
Because the roles of the electric and magnetic resonances of SRRs
and complementary SRRs are reversed, the importance of mag-
netic resonances in nonlinear responses has not been unambigu-
ously confirmed.
SHG has also been discussed for centrosymmetric samples,
including arrays of nanoparticles54 and nano-apertures55,56. In all
cases, the strongest SHG was found when at least the fundamen-
tal or SHG beam propagated at an oblique angle of incidence. An
exception is the work on rectangular apertures at normal inci-
dence57. There the origin of SHG was assigned to the focused
beams that give rise to longitudinal field components, which
results in coupling with the surface nonlinearity. The SHG effi-
ciency correlated well with the cut-off of a waveguide mode within
individual apertures.

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REVIEW ARTICLES | FOCUS NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244

a b c

d e f
E1 E2

ω1 ω2 ω4WM

Λg
Au d
w
z
x

Figure 2 | Examples of structured metal surfaces for nonlinear plasmonics. a–c, Some of the basic cases investigated for SHG: L-shaped gold particles
(a; adapted from ref. 59); gold SRRs (b; adapted from ref. 51); G-shaped chiral particles ordered in different ways (c; adapted from ref. 61). d–f, Recent,
more advanced, structures for enhanced nonlinear effects: Gold grating for enhanced FWM. The blue part represents the incident fields E1 and E2 at the
respective frequencies ω1 and ω2 as well as the generated FWM signal at frequency ω4WM. The yellow part is the gold grating with critical dimensions
indicated (d; adapted from ref. 67); gold nanocavities for enhanced CARS (e; adapted from ref. 68); a change in the ordering of L-shaped particles can
suppress or enhance SHG compared with the case shown in a (f; adapted from ref. 71).

Detailed inspection of refs  50, 52 and 54–57, however, shows
that not L shapes, SRRs nor more symmetric shapes satisfied the
symmetry rules of SHG. The results were thus modified by the
extreme sensitivity of SHG to symmetry breaking, arising from the
deviation of the shape from design or surface defects. The role of
defects can also be interpreted in terms of multipole interference,
which affects the directional properties of SHG58. This problem
was resolved only recently when samples of much higher quality
yielded SHG from the desired dipolar response59.
An attempt was also made to utilize nanodimers for SHG. Its
dependence on the gap size of T-shaped nanodimers, however,
was highly non-trivial60. In contrast to FWM from nanodimers39,
which is not constrained by symmetry, the results for SHG were
explained by the requirement that the strong local fields need to
be asymmetrically distributed around the dimer.
The role of deliberate symmetry lowering in SHG has also been
investigated. Modifying the arrangement of chiral G-shaped gold
particles in an array (Fig. 2c) was shown to switch on or off the chi-
ral nonlinearity 61. There the particle size exceeded one micrometre,
such that the arrays were well in the diffractive regime. A benefit
of the large scale structures is that the hot spots within individual
particles could be resolved by SHG microscopy. SHG microscopy
has also been used to address magnetic domain ordering, which
also modifies symmetry rules, in metal nanostructures62.
Nanostructured plasmonic surfaces have also been used to
enhance the response of known nonlinear materials. One interest-
ing sample consisted of arrays of coaxial holes in a 70-nm-thick
gold film on a gallium arsenide (GaAs) substrate63. The structures
exhibited the SHG response near the cut-off of a coaxial wave-
guide mode. GaAs has also been used with SRR arrays64: samples
were designed so that certain SHG signals were forbidden for both
GaAs and SRRs alone but the combined structure gave rise to a
strong signal. Furthermore, arrays of silver nanoparticles have
been used with a self-assembled film of organic molecules65, yield-
ing an SHG enhancement factor of 1,600.
Very recent work has demonstrated more advanced plasmonic
surfaces with enhanced nonlinear properties. The apparent cen-
trosymmetry of dielectric gratings was broken for SHG by metal
deposition at an oblique angle66. FWM from a gold grating was
enhanced by a factor of 2,000 relative to FWM from a flat film, by
tailoring the individual grating grooves to support cavity modes,
which were further coupled by surface waves67 (Fig. 2d). Similarly,
an array of spherical nanocavities in a gold film is beneficial for
CARS spectroscopy 68 (Fig.  2e). Arrays of bowtie antennas were
used for high-harmonic generation up to the seventeenth har-
monic69 and for enhancing several other nonlinear processes when
the bowtie and array resonances were coupled70. Finally, SHG
from arrays of L-shaped particles was tailored by subtle details of
particle ordering (Fig. 2f), resulting in a 50-fold difference in SHG
signals expected to be equivalent 71.
Controlling light with light in plasmonic nanostructures
LSP and SPP nonlinear effects. The use of plasmonic structures
for all-optical modulation or switching, or to achieve optically tun-
able photonic properties, relies on enhancing Kerr-type nonlin-
earities (Box 1, equation (2)) and detecting the modified refractive
index of either the metal itself or the adjacent dielectric. Examples
of such plasmon-enhanced nonlinear materials are metal nano-
particles72,73 and bulk materials doped with such particles74–76. The
excitation of such composites at the wavelength of the nanoparti-
cle LSP leads to an increase in the effective nonlinear susceptibility
compared with both materials separately 77,78 (Fig.  3a). Similarly,
the coverage of metal nanoparticle arrays, for example nanosphere
or nanorod assemblies, with nonlinear material enhances the

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 NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244 FOCUS | REVIEW ARTICLES
a b
a g'2
8
g"2
NLO index enhancement factor

0
90
120 60
a
-4 150 30
b c
180 2 6 10 0
-8
210 b 330

c 240 300
-12 270
380 400 420 440 460 480 500
λ nm

c Pump d Control (pump) pulse Objective

532 nm

Polarization
Pump
Decoupled signal 200 fs
200 fs
Au –
–
– –
– – Grating
–
SPP signal
ITO Fused silica

Grating
Al film cross-section

Probe
700–1,400 nm

Figure 3 | Plasmonic systems for enhancing nonlinear optical Kerr effect. a, Controlling nonlinearity with metal nanoparticles: real (g’2 ) and imaginary
(g’’2) parts of the nonlinear optical (NLO) refractive index enhancement factor with 10 nm diameter silver par-ticles embedded in carbon disulfide (from
ref. 78) b, 500 × 440 nm2 nonlinear waveguide-ring resonator: the signal (red) and control (green) light are shown. Incorporated in the sketch is the
simulated SPP field distribution 10 nm above the metal interface (adapted from ref. 92). c, Nonlinear gold nanoantenna with 20 nm gap embedded in high-
conductivity indium tin oxide (ITO). Control (pump) changes the scattering efficiency of the antenna for probe light by modifying electron concentration
near the Au/ITO interface (adapted from ref. 81). d, Direct modulation of the SPP signal: the signal beam is coupled to and from the waveguide by gratings
at an aluminium–silica interface and modulated by the control pulses. Both the change in the SPP coupling efficiency and the induced absorption contribute
to the modulation (adapted from ref. 91).

nonlinear response of the dielectric while also lowering the light intensity-dependent refractive index of the liquid crystal illumi-
intensities required for nonlinear action79,80. Specifically designed nated by the evanescent field of the SPP wave.
plasmonic nano-antenna resonances (Fig.  3c) have been con-
trolled using the indium tin oxide free-carrier nonlinearity in the All-optical switching and modulation in plasmonic wave-
picosecond regime81. guides. To modulate and switch SPP signals by optical means
The field enhancement associated with LSP modes has also in a waveguiding geometry, changes can be induced in the real
allowed controlled photon tunnelling through nanoscale pinholes or imaginary part of the permittivity by control light, and these
in metal films covered with a nonlinear polymer 82,83. In particular, changes can occur in the metal or the adjacent dielectric (Fig. 3d).
measurements of photon tunnelling through individual, naturally Light-induced absorption modulation has been explored with the
occurring, nanometre-scale pinholes have provided evidence of intrinsic metal (Au and Ga) nonlinearity 85–87 as well as the die-
‘photon blockade’, similar to Coulomb blockade in single-electron lectric component in a plasmonic waveguide88,89. An integrated
tunnelling 82. Observations of photon tunnelling gated by light at geometry has also been proposed, with signal SPP absorption
a different wavelength have also been reported with somewhat modulation and stimulated emission controlled by an SPP beam
larger pinholes83. at a different frequency 90.
Propagating SPPs also can be used as the signal carrier. This The intrinsic nonlinearity of gold is related to the interband
was first shown with smooth metal films in the Kretschmann excitation of non-equilibrium electrons and results in small
geometry, using thermal liquid-crystal phase transformations changes in the real part of the permittivity but in more consider-
induced by light. Both switching of the reflected light and bistabil- able changes in the imaginary part. The associated relaxation time
ity were observed with the increase of the intensity of the incident is on the picosecond scale72,73,85, and terahertz-rate direct modula-
light84. The latter was explained by positive feedback due to the tion of SPP signals in plasmonic gold waveguides is thus possible.

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a b 0.6 c 10
λ = 890 nm
488 nm 1 β (× 50)

Differntial transmission (ΔT/T)

0.4 514 nm 8 Theory β̃
|E| Experiment β̃
6

β (10–6 m/W)
0.2 0
4
0.0
2
–0.2
0

–0.4
600 700 800 800 850 900 950 1,000
Wavelength (nm) Wavelength (nm)

d 20 e 4
τ (ps)

y µm
10 0

0 –4
500 600 700 0 2.5 5 0 2.5 5
Wavelength (nm) z µm z µm

Figure 4 | Controlling light with light in plasmonic nanostructures. a, Typical geometry of pump–probe experiments: signal (red) and control (green) light
are coupled to plasmonic excitations and the effective nonlinearity is enhanced as a result (from ref. 94). b, Differential transmission spectra of a hybrid
plasmonic crystal (a periodically structured gold film covered with 3BCMU polymer) for control light of wavelengths 488 nm and 514 nm. Depending on
the nature of the plasmonic resonances, either more or less nonlinear transmission is observed (from ref. 97). c, Nonlinearity in a SRR-based metamaterial:
the spectra of the effective two-photon absorption coefficient in the metamaterial (β̃, blue and red) and an unstructured gold reference film (β, green). The
inset shows a map of the electric field magnitude simulated 10 nm below the gold surface at the resonant wavelength (adapted from Ref. 103).”
d, The spectra of the transient nonlinear changes of optical density, recorded at different time delay τ after the excitation, of the gold nanorod
metamaterial shown in the inset. The red and blue colour scales correspond to positive and negative changes in optical density, respectively (adapted
from Ref. 105). e, SPP soliton. Magnetic field distribution of the SPP beam at the metal–dielectric interface for linear diffraction at low power (left) and for a
soliton generated with the increase of the incident power (right) (adapted from ref. 114).

Similarly, the relaxation time of the interband transitions in alu-
minium is much shorter and can provide even faster modulation
speeds in aluminium-based plasmonic waveguides91.
The variation of the real part of the metal or dielectric per-
mittivity will influence the propagation of SPP modes via modi-
fication of their phase velocity and, thus, the phase of the wave.
To convert this to intensity modulation, various phase-sensitive
configurations, including Mach–Zehnder interferometers and
waveguide-ring resonators, are needed. Both these configurations
can be realized using various types of plasmonic waveguides, such
as metal–insulator–metal, V-groove or dielectric-loaded wave-
guides4. A dielectric refractive index variation of 0.001 can provide
a 50% change in the transmission of a nonlinear, polymer-loaded,
plasmonic waveguide-ring resonator (Fig. 3b), which needs only
a 2.5-μm ring radius for operation at telecommunications wave-
lengths92. The figures of merit (the ratio of modulation perfor-
mance to size) of plasmon-based resonant nonlinear components
are intrinsically better than those of photonic ones owing to the
stronger changes in the effective refractive index of the mode,
which is facilitated by the mode field distribution and the field-
enhancement effects93.
Nonlinear plasmonic crystals: switching and bistability.
Periodically structured metal films and surfaces, the so-called plas-
monic or surface plasmon polaritonic crystals (SPPCs), provide
considerable versatility for tailoring the wavelength-dependent
plasmonic resonances and the electromagnetic field enhancement
in devices a few tens of wavelengths in size2,94. SPPCs have opti-
cal properties analogous to those of two-dimensional photonic
crystals. The spectral positions of their resonances, their disper-
sion, and the phase and group velocities of SPP Bloch modes can
be engineered by controlling the size and shape of the unit cell
and its period. In particular, relatively flat SPP modes with low
group velocity are possible, resulting in the high field enhance-
ment beneficial for high effective nonlinearity. Moreover, with flat
SPP bands, it is much easier to observe the shift of the resonance
when nonlinear effects are induced, and the modulation contrast
is higher. All the optical properties of plasmonic crystals, such as
reflection, absorption and transmission, are determined to a large
extent by the SPP Bloch modes, which can be easily excited, with-
out any special arrangements, as a result of the periodic structure.
All-optical control of the Bloch SPP mode structure by modifi-
cation of the refractive index of the metal or adjacent dielectric
therefore provides a very useful way of changing the reflection or
transmission of signal light through SPPCs. Coupling of both con-
trol and signal light to SPP Bloch modes further helps to enhance
the nonlinear interaction94 (Fig. 4a).
These effects have been demonstrated using the nonlinearity
of gold gratings to control SPP excitation at speeds determined
by the subpicosecond response time of the gold nonlinearity 95.
Hybridization of SPPCs with nonlinear polymers and use of the
strong electromagnetic field enhancement in cylindrical channels
allowed efficient modulation of light transmission through the
crystals by controlling the Bloch mode resonances96.

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NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244
Investigations of the spectral response of the SPPC switching
in pump–probe configuration has shown that differential trans-
mission of up to 60% can be achieved in some of the resonances
with both increased and reduced transmission possible (Fig. 4b),
depending on the origin of the plasmonic resonances, which can
be related to either pure SPP Bloch mode or can involve interplay
between Bloch modes and LSPs of the holes forming the crystal97.
The observed SPP bandgap shift suggests that the control-light-
induced changes in the average effective refractive index of the
polymer are 10−3–10−4 and that local changes can be higher 94. The
spatial distribution of the control field intensity on the metal sur-
face is also important. Owing to the feedback loop between the
nonlinear changes in the refractive index of the polymer as the
control intensity is varied, it is possible to observe bistable behav-
iour in the transmission of signal light through the structure97.
The self-action of light of varying intensity has also been observed
in plasmonic structures hybridized with liquid-crystal mol-
ecules98, showing good intensity-limiting properties of the plas-
monic device. The response times of the above nonlinear effects in
hybrid dielectric–metal systems are determined by the relaxation
time of both the metal and the dielectric and is usually limited by
the latter.
Full numerical simulations of nonlinear SPPCs in various
geometries have been performed99,100. In particular, they have been
modelled for one-dimensional structures (slit arrays) in relatively
thin metal films, with nonlinear Kerr materials in the slits and
on top of the metallic structures. In both cases, nonlinear trans-
mission and its bistability were predicted in full agreement with
experiments. Earlier modelling of gratings in a thick, perfect metal
with the slits filled with Kerr-type nonlinear dielectric also pre-
dicted bistability owing to waveguide modes in the slits101.
Nonlinear plasmonic metamaterials. Plasmonic metamaterials
provide additional possibilities for all-optical switching, because
their optical properties can be tailored through the plasmonic
resonances of the constituents, for example SRRs or nanorods,
and the electromagnetic coupling between them6. A change in the
refractive index of the embedding dielectric or substrate there-
fore leads to the modification of both individual plasmonic reso-
nances and their interaction, resulting in an enhanced nonlinear
response.
These properties have been demonstrated in nanorod-based
metamaterials where the spectral position of the plasmonic mode
was controlled by modifying the refractive index of an adjacent
polymer layer 79. Similarly, the dielectric and metal nonlinearity of
SRR-based metamaterials has been explored. Using carbon nano-
tubes as the nonlinear material hybridized with an SRR-based
metamaterial, efficient all-optical modulation has been demon-
strated102. Very short relaxation times, of less than 100 fs, may be
achievable for bare gold SRR metamaterials, using the intrinsic
nonlinearity of gold under two-photon excitation103 (Fig. 4c).
Plasmonic metamaterials also provide a new approach to
enhancing nonlinearity by utilizing ‘nonlocal’ effects arising in
the epsilon-near-zero regime104,105. The nonlocal effects depend
strongly on losses and can be considerably modified by control-
ling losses in gold nanorods105. The nonlinearity of gold under
interband excitation leads to pronounced changes in the imagi-
nary part of the permittivity. This gives rise to very large changes
in the metamaterial transmission owing to the modification of the
nonlocal response, with transmission changes of up to 80% with
subpicosecond response times (Fig. 4d). For such performance in
100 × 100 nm2 devices, 10-fJ control pulses are sufficient.
Efficient all-optical modulation can also be achieved by con-
trolling the coupling strength between molecular excitons
and plasmonic excitations in metamaterials. This is extremely
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FOCUS | REVIEW ARTICLES
sensitive to any perturbation of the system, including changes in
the metal permittivity 106,107.
Nonlinear SPP propagation
Nonlinearity is often used to control spatial and temporal charac-
teristics of light pulses1. For SPP signals, it was initially proposed
that the nonlinear effects be applied to diffraction management
using self-focusing or defocusing nonlinearities and spatial soliton
effects108–110. Owing to the short SPP propagation length, these
effects are important only for strongly diffracting SPP beams. The
problem of diffraction management may, however, become impor-
tant if SPP amplification is considered to increase the SPP propa-
gation distance.
The gain media for amplification often possess intrinsic
nonlinearities that lead to self-focusing or defocusing. This is
largely undesirable, for instance in lasers, but is sometime use-
ful, for example to achieve diffractionless propagation. In plas-
monic structures, the field enhancement may lead to this effect at
smaller light intensities than in conventional photonic structures.
Although no experimental observations of these nonlinear effects
have been made so far, extensive theoretical treatments have been
developed. Nonlinear propagation has been studied in both SPP-
and nanoparticle-based waveguides, and a wealth of interesting
effects has been predicted.
Light-intensity-dependent, and, thus, optically controlled, dis-
persion can be achieved in plasmonic waveguides by relying on
dielectric materials with Kerr nonlinearity 111 or by utilizing the
‘ponderomotive’ nonlinearity of the metal112. These effects can be
tailored so as to produce effective intensity limiters. Nonlinear
waveguides consisting of silver nanoparticles have also been pre-
dicted to show, under different conditions, bistability and modula-
tional instability due to the nonlinearity of silver itself 113.
In principle, plasmonic soliton-like excitation is possible by
choosing the correct balance between the gain and the nonlin-
earity. This has been demonstrated with single-interface SPPs114
(Fig. 4e) and asymmetric, dielectric-clad metal films115. In the lat-
ter, stable spatial solitons have been realized with the gain near one
interface compensating the loss near the other.
In the absence of gain, self-trapping has been observed, but
losses result in slowly decaying spatial SPP solitons. The self-
trapping dimensions of about 100 nm have been predicted for
plasmon-solitons115 which is much smaller than for solitons in
dielectric waveguides with Kerr-type nonlinear medium. Discrete
solitons have also been predicted in the case of plasmonic wires in
a nonlinear medium116 as well as in planar plasmonic–dielectric
multilayers117, requiring a relatively small gain of about 100 cm−1
for their observation.
Discussion and outlook
Nonlinear plasmonics is still a young research field, but its basic
concepts have already been demonstrated in a wide variety of
ways. Most structures so far have been based on relatively sim-
ple concepts, yet their experimental implementation often pushed
the limits of the nanofabrication techniques of the day. Great
improvements in the quality of state-of-the-art samples now allow
the principles of nonlinear effects to be tested ever more pre-
cisely. At the same time, more sophisticated sample designs and
functional concepts are emerging, and the activity in the field is
increasing markedly.
The role of plasmonics in nonlinear optics is threefold. First,
by enhancing the effective nonlinearity, plasmonic nanostructures
contribute to conventional photonics by allowing nonlinear effects
to be utilized with reduced optical power. Second, they make it
possible to scale down nonlinear components in size, which is
important for the development of integrable photonic devices
REVIEW ARTICLES | FOCUS
and, ultimately, fully functional nanophotonic circuitry. Third, the
response time of plasmonic excitations is ultrafast, allowing opti-
cal signals to be manipulated on femtosecond timescales.
A large fraction of the work on nonlinear plasmonics has stud-
ied SHG, because it is straightforward to implement experimen-
tally. Results on more complicated processes, such as FWM and
CARS, are beginning to appear. However, with few exceptions the
majority of experiments have involved free-space beams at least
for signal or control light, even if they interact with each other
through plasmonic excitations. For certain applications, it is nec-
essary to design systems where all beams are maintained within
the integrated plasmonic circuitry. The theoretical treatments of
nonlinear propagation and soliton effects in plasmonic structures
call for experiments and, if practically realized, will contribute a
significant tool for all-optical signal manipulation.
Inherent losses in plasmonic systems are a notable challenge, as
they limit the propagation length of SPPs to the range from 10 μm
to several millimetres, depending on wavelength and geometry.
As already mentioned, however, plasmonic field enhancement
can ideally even overcompensate for the reduced nonlinear inter-
action length. Losses are also important in the context of LSPs,
where the local-field enhancement must be carefully balanced
with radiative and ohmic losses to optimize the nonlinear inter-
action. Nevertheless, it will be challenging to design structures
where the local-field factors at all interacting frequencies are fully
utilized. The design will also depend on the particular application
and whether far- or near-field (integrated) devices are considered.
The requirements on plasmonic resonances may indeed be differ-
ent for integrated nonlinear components, allowing dark plasmonic
modes with low radiative loss to be used.
Nonlinear plasmonics faces significant theoretical challenges.
Although theoretical treatments exist for bulk metals and planar
surfaces11, they need to be applied to nanoparticle geometries
where the fields, nonlinear responses and nonlinear sources vary
locally. For second-order effects, it is not even clear what the role
of surface and bulk terms in the local response is. Experiments on
planar metal films suggest that surface terms dominate12, whereas
initial theories emphasized bulk terms118. Other theories have sug-
gested that the importance of surface and bulk terms depends on
the experimental details119. All these approaches12,118–120 need to be
made mutually compatible if we are to understand how the non-
linear responses can be optimized. In addition, quantum40,121 and
nonlocal122 effects should be considered for structures with critical
dimensions on the scale of single nanometres, as they may limit
the attainable field enhancement.
In principle, a nonlinear response is enhanced when any
combination of the interacting frequencies is resonant with the
material. Unlike in conventional materials, where the resonances
of the atomic-scale constituents are important, in plasmonic sys-
tems the resonances occur mainly in the local-field factors123.
For harmonic generation, a resonance at the fundamental fre-
quency and its quality are crucial41,51,123,124. Recent work, how-
ever, has shown that resonances at multiple wavelengths can also
be utilized125,126.
For all-optical signal processing, the ultrafast nonlinearity
of free electrons in plasmonic nanostructures provides record
switching speeds, at switching rates greater than a terahertz. The
switching energy per bit can also be low (down to 10 fJ), approach-
ing the requirements for viable all-optical signal processing.
Reduction of this energy to a few femtojoules would make all-
optical switches competitive with electronic switches. Advanced
tailoring of plasmonic resonances in metamaterials and utilization
of their properties not available in conventional materials will be
important for the development of next-generation, low-power, all-
optical switches and all-optically-tunable plasmonic devices. Such
746 NATURE PHOTONICS | VOL 6 | NOVEMBER 2012 | www.nature.com/naturephotonics
© 2012 Macmillan Publishers Limited. All rights reserved.
NATURE PHOTONICS DOI: 10.1038/NPHOTON.2012.244
concepts have numerous applications as integrated and stand-
alone photonic components.
Significant challenges need to be overcome and new types of
nanostructure design investigated before the functional concepts
of nonlinear plasmonics will be fully ready to move towards appli-
cations. Nevertheless, we expect the field to become increasingly
important in the development of the future nanophotonics, just as
traditional nonlinear optics was in shaping the landscape of mod-
ern photonics.
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