Acs Chemrev 8b00243
Acs Chemrev 8b00243
copying and redistribution of the article or any adaptations for non-commercial purposes.
Review
ABSTRACT: When metal nanoparticles are arranged in an ordered array, they may
scatter light to produce diffracted waves. If one of the diffracted waves then propagates in
the plane of the array, it may couple the localized plasmon resonances associated with
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3.11. Two Types of SLRs 5925 9.6. Metallic Photonic Crystals for Biosensing 5939
3.12. Section Summary 5926 9.7. SLRs and Spectroscopy 5940
4. Factors Influencing the Properties and Excitation 9.8. SLRs and Solar Cells 5940
of Surface Lattice Resonances 5926 9.9. SLRs and Photocatalysis 5941
4.1. Optical Environment (Refractive Index) 5926 9.10. SLRs and Electrochemistry 5941
4.2. In-Plane vs Out-of-Plane LSPRs 5927 9.11. SLRs and Magneto-Optics 5941
4.3. SLRs at Normal Incidence 5928 9.12. SLRs and Liquid Crystals 5943
4.3.1. Complex Particle Geometries 5928 9.13. Other Applications 5943
4.3.2. Importance of Substrate Conductivity 5928 9.14. Section Summary 5943
4.3.3. Composite Nanoparticles 5929 10. General Summary 5943
4.4. Subwavelength Arrays 5929 Author Information 5944
4.5. Section Summary 5929 Corresponding Authors 5944
5. What Are the Limiting Factors for the Resonance ORCID 5944
Quality? 5929 Notes 5944
5.1. SLRs at Attenuated Total Reflection 5930 Biographies 5944
5.2. High Quality SLRs Using Out-of-Plane Reso- Acknowledgments 5944
nances 5930 References 5944
5.3. Narrow SLRs at High Angles of Incidence in
Nanostripes on a Metallic Film 5930
5.4. High Quality SLRs for High Aspect Ratio 1. INTRODUCTION
Particles 5930 1.1. What Is Plasmonics and Why Is It Interesting/Important?
5.5. Section Summary 5930
6. Phase Singularities under Surface Lattice Reso- Plasmonics is a field that has emerged at the interface of
nances: Optical Sensing 5931 photonics, electronics, and nanotechnology.1 It has seen
6.1. Zero Reflection, Phase Singularities, and spectacular progress in recent years that promises dramatic
Optical Sensing 5931 advances and new developments in nano-optics, nanophotonics,
6.1.1. Zero Reflection and Phase Singularity 5931 and metamaterials.2−7 Plasmonics exploits the collective motion
6.1.2. Phase Singularity and Optical Sensing 5931 of conduction electrons in metals (plasmons), making possible
6.1.3. Sharp Phase Jumps under SPR and SLRs 5931 the coupling of light with nano-objects and the generation of a
6.2. Topological Darkness 5932 range of new optical effects at the nanoscale. The excitation of
6.2.1. Jordan Theorem 5932 plasmons is accompanied by a dramatic localization and
6.3. SLRs and Phase Detection Techniques 5932 enhancement of the electric field associated with light at optical
6.4. SLR and Optical Chirality 5933 frequencies. Field localization and enhancement are central to a
6.5. Section Summary 5934 variety of novel applications in nanoelectronics, optical imaging,
7. Surface Lattice Resonances and the Emission of biomedicine, telecommunications, photovoltaics, photocatalysis,
Light 5934 etc.
7.1. Surface Lattice Resonances and Spontaneous 1.2. Types of Plasmon Modes
Emission and Absorption 5934 Plasmon modes can be subdivided into two classes: propagating
7.1.1. Dye Molecules 5934 surface plasmons and localized surface plasmons.
7.1.2. Inorganic Semiconducting Emitters 5934 1.2.1. Propagating Surface Plasmons (PSP). PSPs have
7.1.3. Light Absorption and SLRs 5934 been extensively studied (for reviews see, e.g., refs 2 and 7) and
7.2. Surface Lattice Resonances and Lasing 5934 are still the focus of interest for numerous research groups, for
7.2.1. Early Work 5935 example, owing to their importance for biosensing/biorecogni-
7.2.2. Tunable Lasing Based on SLRs 5935 tion applications. PSPs are surface electromagnetic waves which
7.2.3. Subwavelength Plasmon Lasers 5935 may be supported at a metal/dielectric interface. They comprise
7.2.4. Hole Arrays and Other Geometries 5935 an electromagnetic wave that is coherently bound with the
7.3. Surface Lattice Resonances and Strong collective motion of mobile charges in the surface of the metal;
Coupling 5936 this coherent interaction leads to the PSP having greater
7.4. SLRs and Nonlinear Effects 5936 momentum than that of a free photon of the same frequency.
7.5. Section Summary 5936 The excitation of PSPs thus requires some kind of momentum
8. SLRs and 2D Materials 5936 matching technique, these include prism coupling8,9 and grating
8.1. Graphene and SLRs 5937 coupling,10 of which nanohole array couplers are an important
8.2. SLRs and Optical Modulators Based on example.11,12 The Turbadar−Kretschmann−Raether prism
Graphene 5937 geometry,8,13 also referred to as surface plasmon resonance
8.3. Other 2D Materials 5937 (SPR), is a prominent example of PSP excitation in which p-
8.4. Section Summary 5937 polarized light is directed into a glass prism and subsequently
9. Miscellaneous: Applications of SLRs in Biosensing/ reflected from a thin (∼50 nm) metal film that has been
Biorecognition, Photovoltaics, Photocatalysis, etc. 5937 deposited on one of the prism’s faces. Light incident in this way
9.1. Biosensing and Biorecognition 5937 leads to the generation of PSPs on the far (opposite to the metal/
9.2. Propagating Surface Plasmons 5938 prism) side of the metal film and occurs for a specific
9.3. SLR vs SPR 5938 combination of angle of incidence and wavelength.2 For a fixed
9.4. Figure of Merit and Sensitivity 5938 angle of incidence, the excitation of PSPs is accompanied by the
9.5. Lower Limit of Detection 5939 appearance of a minimum in the reflectance spectrum. The
5913 DOI: 10.1021/acs.chemrev.8b00243
Chem. Rev. 2018, 118, 5912−5951
Chemical Reviews Review
spectral width of this reflectance dip is typically ∼50 nm full- increase in the polarizability α, when the denominator of the
width at half-maximum (fwhm) for Au films7 and is accompanied right-hand side of (1) approaches zero. Hence, the spectral
by a clear change in the phase of the reflected light near the position of the LSPR can be found from the condition Re[ε(ω)]
minimum of the resonance.14,15 Based on the extremely high = −2. The quality factor of the resonance Q, which is intrinsically
sensitivity of SPR to variations in the refractive index (RI) of the linked to the ratio of energy stored to the energy lost by an
dielectric medium close to the SPP-supporting metal surface,16,17 oscillator, can be estimated as Q = λmin/Δλ (λmin is the resonance
SPR have led to a major advance in the development of wavelength, and Δλ is the width of the resonance) and is large
biosensing methods; indeed, they provide a leading state-of-the- when Im[ε(ω) + 2] is small. For metals, the dielectric constant is
art label-free technology for the detection and study of a complex value so that it is not possible to have a zero value for
biomolecular binding events involving a target analyte (protein, the denominator in (1); Q-factors of ∼10−20 are found to be
DNA, drug, etc.) from a solution and its corresponding receptor typical for most LSPRs.
(ligand, DNA capture, etc.) immobilized on the liquid/metal 1.3.1. Limitations for Simple Nanostructures. An
interface.18,19 improvement in the quality factor of LSPRs was originally
1.2.2. Localized Surface Plasmons (LSPs). LSPs involve expected from appropriate engineering of the shape and size of
the combined oscillation of the free electrons in a metallic nanostructures. However, studies involving various geometries,
nanoparticle and associated oscillations of the electromagnetic including nanotriangles,47,48 nanorods,49 nanostars,50,51 and
field. The resonance frequency depends on the size, shape, nanocrosses,52 did not lead to the anticipated remarkable
composition, and local optical environment of the particle,20,21 narrowing of the LSP resonances associated with these particles.
and typically occurs in the visible to near-infrared part of the Wang and Shen53 showed, in the quasi-static approximation, that
spectrum for nanostructures of noble metals (Au, Ag, Cu). LSPs there is an underlying reason for this behavior. They showed that
have emerged as an attractive alternative to PSPs in a range of the quality factor of the plasmon resonance, Q, depends only on
applications, primarily because momentum matching is not the dielectric function of the metal at the plasmon frequency
required to excite LSPs owing to their lack of translational ω dε′
symmetry; they also benefit from simple fabrication routes for Q ∼ ′′ dω (where ε = ε′ + iε′′). Thus, while the shape and
ε
the metal nanoparticles (e.g., by colloidal chemistry based on environment do influence the LSPR frequency, Wang and Shen’s
reduction of metal salts22) and nanoparticle arrays (e.g., by analysis showed that, to a first order approximation, the quality
nanosphere lithography23) and a series of unique properties and factor Q is independent of the geometric form of the
functionalities, including the possibility of light manipulation and nanostructure and independent of the dielectric medium that
transformation at the nanoscale level,24−29 subwavelength surrounds the nanostructure. A typical LSPR is broader than this
imaging,30−32 nanolensing25,30 and nanolasing,33,34 field concen- simple formula predicts owing to radiative damping and dynamic
trators,35 nanotweezers,36 supersensitive plasmonic nanosen- depolarization (the effect of retardation within the particle). As a
sors,37−40 improved photovoltaic devices,41 active optical result, LSPRs typically have quality factors of order 10, well
elements,42 etc. However, localized surface plasmons are below that desired for many applications.
generally of greater spectral width when compared to 1.3.2. Beyond Single Nanostructure. Fortunately, and at
propagating surface plasmons; as an example, the resonance first sight rather surprisingly, the limitations on the Q-factor of
width typically exceeds ∼80−100 nm fwhm for LSPs for Au LSPs associated with individual nanostructures discussed above
nanostructures, compared to a spectral width of ∼50 nm for PSP. can be largely overcome when nanostructures are arranged in
This increased width significantly limits the potential of LSPs for arrays. The electromagnetic fields related to the LSP mode of one
many applications. Though not within the noble metal list, nanoparticle may then act to influence the response of
aluminum can also be used as viable plasmonic material neighboring nanoparticles. This electromagnetic coupling can
supporting resonances in the UV−visible region.43−45 take several forms: via near-fields and via far-fields.
1.3. Width of Plasmon Resonances Near-Field Coupling. Particles interact via near-field coupling
when they are relatively densely packed, leading to significant
The spectral width of localized surface plasmon resonances
(LSPRs) can be appreciated from the general properties of LSP spectral shifts of the plasmonic resonances and a modification
excitation of a metal nanostructure, or indeed an ensemble of and splitting of their line-shapes due to the hybridization of the
such nanostructures. For a single metallic nanosphere placed in plasmonic modes.54−58 In particular, such hybridization can lead
vacuum, the applied electromagnetic field induces a dipole to the generation of antisymmetric modes,59 which provide
moment p in the sphere whose magnitude is proportional to |E0|, slightly narrower resonances (full width half-maximum (fwhm)
the strength of the applied electric field. The polarizability, α, is ∼ 50 nm). However, these modes are typically dark; that is, they
then defined through p = αE0 and can be derived in the cannot easily be excited by incident light.
quasistatic approach, where the particles are assumed to be Far-Field Coupling. A significant improvement in the quality
smaller than the wavelength of the light involved, as46 of localized plasmon resonances becomes possible with the
involvement of far-field coupling of LSPs, i.e. via their scattered
ε(ω) − 1 radiation fields. When a number of particles are randomly
α = 4πa3 distributed, the scattered fields impinging on a given particle have
ε(ω) + 2 (1)
no particular phase relationship and the effects of the scattered
where ε(ω) is the relative permittivity (dielectric constant) of the fields are relatively minor.60 However, when metal nanoparticles
sphere and a is the particle radius. (In the quasistatic approach, (nanoantennas) are arranged in a periodic array, where the
the analysis is performed as in the static case but the material period is comparable to the wavelength of the incident light, then
parameters of the nanoparticles are taken to be frequency under appropriate conditions the scattered fields impinging on a
dependent. This approach is found to work well in many given particle can arrive in phase with the incident light. The
experimental situations, even at optical frequencies.) The scattered fields correspond to diffraction of the incident light in
localized surface plasmon resonance is associated with a dramatic the plane of the array. By using the right combination of
5914 DOI: 10.1021/acs.chemrev.8b00243
Chem. Rev. 2018, 118, 5912−5951
Chemical Reviews Review
Figure 1. Comparison of LSPR and SLR in transmission spectra. Schematic of structures considered: (a) single particle, (b) a periodic 1D chain. For
both systems the transmission observed at normal incidence is plotted as a function of wavelength; the inset shows a schematic of the particle
arrangement. The electric field of the incident wave was perpendicular to the direction of the chain. The gold particles were 80 nm in radius made in air
environment. The period in the chain was 620 nm and the total number of particles in the chain was 1000. The calculations were performed using
Doyle’s approximation, see section 2 below.
nanoparticle size and shape, together with an appropriate array resonances was not straightforward. Early works recorded a slight
period, one can arrange for the light scattered by each narrowing of the resonances,72−75 but this narrowing was far
nanoparticle into the plane of the array to be in phase with the from that expected from theory.69,70,76,77 The main problem was
plasmon resonance induced in its neighbor by the incident light, related to the high numerical aperture (NA > 0.5) of the focusing
thereby reinforcing the resonance in the neighboring particle. optics used in these works. Such high numerical apertures
Thus, by appropriate tuning of the array period one can resulted in low spatial coherence of the incident light and thus
significantly increase the quality factor of the resonance. This is limited the number of dipoles that could interact in phase with
possible because the scattered fields can act to counter the each other. There were other factors that contributed to the lack
damping of the single particle response. When extended over a of observation of narrow resonances in early experiments. The
large array of nanoparticles,61 such plasmonic surface lattice high NA of the focusing optics also meant that light was collected
resonances (diffractively coupled localized surface plasmon over a range of angles leading to broadening of the observed
resonances) can lead to a remarkable narrowing of the resonance modes due to the dispersive properties of the SLRs. Additionally,
width (down to a few nm), as well as to related phenomena such nanofabrication techniques in early work often led to a large
as a dramatic enhancement of both absorption and the local amount of disorder leading to further broadening. (Subsequent
electric fields near the nanostructures; all of these phenomena are improvements in nanofabrication techniques made it possible to
important for a variety of projected applications. produce metal NP arrays with a uniform period and controlled
1.4. Overview of Early History of Concept of Collective sizes over patterned areas as large as cm2, resulting in stronger
Resonances coherent coupling between NPs and measurements which could
The fundamental ideas behind diffractive coupling of particle be performed without the use of an objective lens.) The
resonances were explored in theoretical works by several research breakthrough in the experimental observation of ultranarrow
groups starting in the 1960s, but the path to their experimental collective plasmon resonances was obtained using optics that
realization was a long one. DeVoe gave the first theoretical provided high spatial coherence to illuminate large arrays of Au
description of an electric dipole model for quasi-stationary nanoparticles.78−80 Kravets et al.78 reported the first observation
aggregations of molecules,62,63 while Purcell and Pennypacker64 of ultranarrow plasmonic resonances (resonant widths down to
completed this description by including phase retardation effects 2−5 nm fwhm, resonances with Q ∼ 100) by illuminating, at a
based on the consideration of propagation of electromagnetic certain angle, a large array (30 × 60 μm) of glass substrate-
waves. Laor and Schatz65 were the first to consider the coupled supported ∼100 nm Au nanopillars. Auguié and Barnes79
dipole approximation (CDA) for aggregations of nanoparticles observed similar resonances using normal incidence light
and to obtain Mie solutions of the dipole sum (for finite size of transmitted through arrays of 50−120 nm Au nanorods, although
nanoparticles), while Meier and co-workers66,67 extended the the resonance features were generated only by placing the
CDA description to structures where retardation effects due to nanostructures in a uniform refractive index environment; very
wave propagation should be taken into account. It is interesting similar results were obtained at the same time by Chu et al.80
to note that the idea of using coupled dipoles to calculate the Later studies led to an improved understanding of the properties
mean polarizability of a molecule in liquids and gases was and conditions necessary for the excitation of ultranarrow
introduced by Silberstein as early as 1917.68 plasmonic resonances, as well exploring a variety of applications
1.4.1. Some Details of Early Work. Markel developed a of these resonances. During the past decade, studies of
CDA-based model for a one-dimensional chain of nanoparticles diffractively coupled ultranarrow resonances have evolved into
and gave the first rigorous mathematical description of a separate, rapidly expanding research area with many tens of
diffraction-based coupling,69 while Schatz and co-workers70,71 groups involved. One result of this expanding community has
clearly explained the physical essence of diffractively coupled been the use of different names for the coupled resonances, these
effects and described conditions for the generation of ultra- include the following: diffractively coupled localized surface
narrow resonances. However, despite a well-developed mathe- plasmon resonances, collective plasmon resonances, lattice
matical description of ultranarrow resonances and clarification of resonances, etc. For simplicity, we refer to them in this article
the physical mechanism, the experimental observation of these as plasmonic surface lattice resonances (SLRs).
5915 DOI: 10.1021/acs.chemrev.8b00243
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Chemical Reviews Review
1.5. Aim of this Review retarded fields produced by the other N − 1 dipoles Edipole,i. For a
The aim of this review is to describe the physical phenomena given wavelength, λ, this field may be written as
leading to the appearance of ultranarrow diffractively coupled
Eloc , i = Einc , i + Edipole , i = E0 exp(i k·ri)
resonances and contextualize recent works in the field of narrow
N
plasmon resonances. We also consider different manifestations
and applications of these resonances, including the generation of − ∑ Aij ·Pj (i = 1, 2 , ..., N ),
j=1
an optomagnetic response at visible-light and near-infrared
frequencies, extremely sensitive bio- and chemical sensing, and j≠i (2)
strong electromagnetic field enhancement in composite
where E0 and k = 2π/λ are respectively the amplitude and
plasmonic nanostructures for laser and LED applications.
wavenumber of the incident plane wave. (The choice of a minus
1.5.1. An ExampleTo Convey What Is Involved in
sign in front of the sum is simply a matter of convention.) The
Plasmonic Surface Lattice Resonances. To give an idea of
dipole interaction matrix Aij may be expressed as
the structures that we consider, Figure 1 shows a schematic of (a)
a single particle, and (b) a 1D periodic chain of particles, together rij × (rij × Pj)
with their computed normal incidence transmission spectra (the Aij ·Pj = k 2 exp(ik·rij) + exp(ik·rij)
single particle spectrum was renormalized by the same number of rij3
individual particles as in the chain). These spectra represent the [rij2 Pj − 3rij(rij·Pj)]
essence of the described phenomenon: the plasmonic SLR (1 − ik·rij)
observed in the chain of nanoparticles is much stronger than that rij5 (3)
of individual nanoparticles (the drop in transmission at the
resonance position is 70% compared to 20%) and much (i = 1, 2, ..., N, j = 1, 2, ..., N, i ≠ j), where ri j is a vector from dipole
narrower (HWFM is 14 nm compared to 130 nm, which i to dipole j. To obtain the polarization vectors, the 3N equations
corresponds to an almost 10-fold improvement of resonance of the form Ai,jPi = Ej need to be solved. For an infinite array of
quality). identical particles with polarizability αs, an analytical solution of
eq 3 can be readily found by assuming that in each particle the
1.6. Structure of the Review induced polarization is the same. Doing so one finds the
This review is structured as follows. In section 2 we discuss the polarization, P, of each particle to be,
early theoretical work in more detail. Early experimental work E0
will be described in section 3. Section 4 is devoted to the P=
important role played by the substrate on which the array is 1/αS − S (4)
fabricated. Section 5 describes the importance of out-of-plane where S is the dipole sum (see below). The extinction cross-
modes for excitation of plasmonic SLR, and we discuss what section produced by one particle in such an array can be written
limits the Q-factor of the surface lattice resonances. The as
production of SLR is accompanied by generation of singularities
of phase of light that is important for sensing applications. This Cext = 4πk Im(P /E0) (4*)
phenomenon is described in section 6. The addition of gain can
dramatically alter the optical response associated with SLRs and, For the case when the wavevector is perpendicular to the plane
e.g., offers the prospect of lasing, which is discussed in section 7. of the array, the retarded dipole sum S can be found as follows,82
Section 8 describes combination of SLRs with various 2D ⎡ (1 − ik·r )(3 cos2 θ − 1) exp(ik·r )
materials while other applications of SLRs are discussed in S= ∑⎢ ij ij ij
The main difference between SLR and LSPR lies in the presence 2.1.2. Response of an Array Calculated Using CDA. The
of the dipole sum in the former case. The dipole sum depends on first thing to notice in Figure 2(a) is that the response of the array
array parameters (the period, size of a particle, etc.) and provides is very different from that of the single particle. The array
an additional degree of freedom to improve the quality of resonance is much stronger, is much shaper, and has a longer
plasmonic SLRs as compared to LSPRs. Indeed, the width of wavelength. To help understand these changes, we show in
plasmonic SLRs is governed by Im(1/αs − S) and can be made Figure 2(b) the real and imaginary parts of both 1/α and S. There
small by compensating Im(1/αs) with Im(S). Calculations show are two wavelengths at which the real parts of 1/α and S are
that the dipole sum S becomes large (and comparable with αs) equal, each suggesting the possibility of an SLR; they are shown
only at conditions when some diffracted wave propagates along by the vertical dashed black lines. The long-wavelength crossing
the surface of the array which explains the term diffraction point corresponds to the SLR seen in Figure 2(a). At this point
coupled localized plasmons as an alternative to plasmonic the imaginary parts of 1/α and S are both negative and nearly
SLRs.72 Figure 2 compares the extinction cross section per equal in magnitude. This means that the imaginary part of the
particle, as calculated using the dipole sum procedure adopted polarizability in eq 4 is small, thereby yielding the strong
from ref 83, to that of a single particle. resonance. In contrast, at the short wavelength crossing point for
the real parts of 1/α and S, the imaginary parts of 1/α and S are of
the opposite signs; they contribute additively to the polarizability
so that damping is increased cf. the single particle case and no
SLR is seen at this wavelength.
2.2. Beyond the Dipole Approximation
For the calculations shown in Figure 2(a) slightly extended
version of the approach indicated above has been adopted, this is
so that effects arising from the finite size (radius ∼60 nm) of the
particles may be accounted for; details are given in ref 83. The
two key effects that have to be accounted for are (i) radiation
damping and (ii) dynamic depolarization, i.e. the role of
retardation across the particle. In some cases it is convenient
to use an approach that is known as the modified long-
wavelength approximation,84 in which extra terms are incorpo-
rated into the polarizability to account both for the radiative
damping and the retardation. The dielectric constants for the
silver were taken from Palik.85 As an alternative, a numerical
approach was successfully adopted by Kuwata that achieved a
similar result.86 Doyle also explored how to modify the
polarizability to take account of dynamic (retardation) effects87
by making an approximation that made partial use of the
complete electromagnetic solution for spherical particles in Mie
theory.88 These approximations allow one to include particles
which are not small when compared with the incident
wavelength λ while still staying within the simple dipole
approximation. Figure 1 was calculated using Doyle’s approx-
imation. Frequently, although not always,89 higher multipole
effects can be ignored.
Swiecicki and Sipe90 recently presented an extensive analytic
model of SLRs in 2D arrays of gold spheres that takes into
Figure 2. Comparison of SLR with LSPR. (a) Extinction cross section account electric dipole, electric quadrupole, and magnetic dipole
calculated per particle. (b) Dipole sum for a square array (having period moments of the spheres. They identified “ideal” surface-lattice
480 nm) of silver disks (h = 30 nm, d = 120 nm). Light is incident modes of the array which are characterized by strong interaction
normally, using linearly polarized light where the electric field is parallel between different moments of the nanoparticles and possess
to the array’s y-axis. Index matching was used, with an immersion oil
having n = 1.515; thus, the diffraction edge occurs at 727 nm. The
interesting spectral properties.90
intersection of the real parts of 1/α and S is indicated by dashed lines in 2.3. Effect of Array Period
(a) and (b). Reproduced and adapted with permission from ref 83.
Copyright 2014 American Physical Society.
A primary focus of the early work by Zou et al.70 was to examine
the effect of the array period for chains and square arrays of
particles using the dipole sum approach, and some of their results
are reproduced below. They calculated the extinction efficiency
The calculations were performed for a square array (period (the ratio of the extinction cross section compared to the
480 nm); the particles were silver disks (diameter = 120 nm, geometrical area) of the array of particles for array periods in the
height = 30 nm) immersed in a medium of refractive index 1.515. range 200−700 nm, for arrays containing 400 particles. Their
The SLR resonance is clearly observed at a wavelength of ∼760 results are reproduced in Figure 3, which shows the results of
nm. It shows a ∼5 times increase of extinction cross section per calculations for a 1D chain (a) and for a 2D hexagonal array (b).
particle (compared to LSPR of an isolated particle) and For comparison, the spectrum of an isolated particle is shown in
demonstrates a ∼7 times improvement of resonance quality. Figure 3(a) as a dotted line.
5917 DOI: 10.1021/acs.chemrev.8b00243
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Chemical Reviews Review
Figure 3. Extinction spectra (calculated) of 100 nm (diameter) silver nanoparticles for (a) a 1D chain of 400 particles and (b) a 2D hexagonal array of
400 particles. Data are shown over a range of array periods, as indicated. For the chain, both the polarization vector and the wave vector are perpendicular
to the chain. For the array, the wave vector is perpendicular to the plane, while the polarization vector is in the plane. These results are reproduced and
adapted with permission from ref 70. Copyright 2004 American Institute of Physics.
Zou et al.70 found a remarkable narrowing and shift to the red de Abajo noted that some of the collective effects in nanohole
of the plasmonic SLR when compared to the single particle arrays have the same origin as for particle arrays; that is, that
response as the particle separation was increased for both 1D and resonances associated with individual elements (hole, particle)
2D array types. They established that the linear chain gives the are coherently coupled by scattered fields. Parsons et al.,
sharpest SLR. For the chain of 470 nm period, the calculated demonstrated the presence of the thin metallic film to be
resonance wavelength was 471.4 nm while the calculated HWFM responsible for changes in the interaction between adjacent
was 3.7 nm, yielding a Q-factor of ∼135, which represents at least resonators, due to the propagating surface plasmon mode that
a 10-fold improvement over LSPR of a single particle. The line the thin metal film supported;96 hole arrays will not be
width narrowed further on increasing the period, giving Q > 300, considered further in the present article since they do not
but the strength of the response for these longer periods, where provide a significant increase in the resonance quality. It is worth
the SLR is further from the peak position of the single particle noting that hole arrays can also demonstrate a different type of
response, is also reduced. Figure 3(a) refers to the case when the collective plasmon resonance where individual hole resonances
light wavevector is perpendicular to the chain axis. At the same are coupled together by propagating surface plasmon waves.
time, calculations in the parallel situation also indicate narrow These resonances are normally wider than typical SLRs.
resonances, albeit slightly wider.91 The results in Figure 3(b) 2.5. 3D Arrays
indicate that for a 2D array the spectral position of the resonance Schatz et al.97 described the theoretical methods to calculate the
scales as the particle separation rises in a manner that is similar to optical properties of 1D, 2D, and 3D arrays of plasmonic
that for the 1D chains, albeit with resonances that are slightly nanostructures. They showed that three-dimensional arrays can
broader. Zou et al. also found that other wavevector and exhibit unique effective-medium properties, such as a negative
polarization choices led, for a given spacing, to broader line- permittivity that leads to metallic optical response even when
shapes.70 Gomez et al.92 theoretically considered the effect of there is less than 1% metal content in the array. Thus, the
array period on the formation of SLR and presented a simple collective plasmonic effect in three-dimensional arrays is a
nearest-neighbor approximation to describe the collective promising means for the continued development of visible-light
resonances in terms of superposition of the eigenmodes of metamaterials and for the creation of optoelectronic plasmonic
uncoupled nanostructures that exhibit a standing-wave character devices and sensors. These authors also showed that simple
delocalized across the entire periodic structure of the array. The theoretical methods may be used to describe complex media with
formalism they developed allows one to describe plasmonic edge deliberately designed properties.97
states.92 2.6. Section Summary
2.4. Holes Rather Than Particles To summarize, early theoretical investigations provided the
Nanoholes in thin metal films may also support localized following insights:
plasmon resonances, as one might expect from Babinet’s 1. 1D arrays of metallic nanoparticles may support very
principle, in which the diffraction pattern produced by an narrow surface lattice resonances.
opaque body is identical to that produced by a hole of the same 2. Narrow SLR features having spectral widths less than 1 nm
shape and size, except for the overall intensity of the forward
may occur when the array spacing is somewhat greater
beam.93 There are thus similarities between the modes supported
than the resonance wavelength of the isolated particle
by arrays of metallic nanoparticles, as discussed above, and arrays
of holes in thin metallic films. Ebbesen and colleagues showed plasmon.
enhanced transmission of light through metallic thin films 3. The narrow plasmonic SLRs occur because of the
perforated with periodic arrays of holes; this remarkable result interaction between the localized plasmons associated
was a key step in the very significant expansion of plasmonics with the nanoparticles and light diffracted by the array.
research toward the end of the last century.11 A detailed 4. SLRs can be derived within the electric dipole
discussion of the interaction of light with 2D periodic arrays of approximation when the imaginary part of the dipole
́
holes can be found in the review of Garcia-Vidal et al.94 and that field (retarded) cancels the effect of resonance damping of
́
of particles and holes in the review by Garcia de Abajo.95 Garciá a single particle.
5918 DOI: 10.1021/acs.chemrev.8b00243
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Figure 4. Surface lattice resonances for an array of Au nanoparticles. Experimentally measured spectra of ellipsometric parameters, reflection, and
extinction for the studied 2D arrays. (a) The ellipsometric parameter Ψ. The inset provides a zoom-in of the minimum at θ = 64°. λR_1air and λR_1sub are
given by eq 6 (using the + sign). (b) The phase Δ. The left inset shows the geometry for the p-polarized incident light. The right inset provides a zoom-in
of the jump in phase at θ = 64°. (c) Reflection spectra for p polarization, Rp, and for s polarization, Rs. (d) Extinction spectra for p polarization. An SEM
image is shown in the inset, while the arrow marks the location of the weak and narrow resonance in absorption. Data have been plotted for θ = 62°
(orange), 64° (green), 66° (blue), and 68° (brown). The array period was a = 320 nm, the dot diameter d = 100 nm, while the dot height was h = 90 nm.
Reproduced and adapted with permission from ref 78. Copyright 2008 American Physical Society.
5. The SLR may disappear either if the particles are too small with a small NA (NA < 0.1) are suitable for the excitation of
or if the array size is too small. In both cases, the dipole SLRs.
sum, S, is insufficient to offset the effect of single particle 3.1. First Report of Experimental Observation of Plasmonic
SLRs
relaxation (decay) effects.
6. 2D arrays also show narrow plasmonic modes; indeed, it is Probably the first report of an experiment in which SLRs were
observed came in 2008.78 The necessary conditions for sufficient
only for the 2D arrays that SLRs have thus-far been seen
spatial coherence of the incident light were achieved by using the
through experiment. focusing optics of an ellipsometer (NA = 0.1), thereby providing
sufficient spatial coherence over the ∼30 × 30 μm focal spot on
3. EXPERIMENTAL OBSERVATIONS OF SLRS AND the sample surface. Arrays of Au nanopillars (200 μm × 200 μm,
CLARIFICATION OF THEIR PROPERTIES containing ≈106 pillars) were fabricated by electron-beam
Early attempts to observe SLRs were not very successful.72−75 lithography on top of a glass substrate. A number of arrays
One of the main obstacles in detecting SLRs was the high with lattice period, a, in the range 270−400 nm were examined.
numerical aperture optics (NA > 0.5) used. Observation of SLRs The pillar dimensions were as follows: height h ≈ 90 nm (first 3
requires the incident light to be spatially coherent over a large nm Cr, then 90 nm of Au), diameter d ≈ 100 nm; these
area (i.e., a sufficient number of particles) to ensure useful dimensions were picked so that the LSPR of an individual pillar
interference of light scattered by different nanoparticles in an appeared in the visible spectrum, specifically the red part.
array. Focused light of wavelength λ has a lateral spatial Figure 4(a) shows some typical very narrow SLRs observed in
coherence of order λ/NA. This means that the number of experiment near λR ≈ 600 nm at angles of incidence, θ, of 62−68°
particles in a 2D array, N, that may interact coherently and thus for a square array of period a = 320 nm.
be involved in a collective resonance is given by N ∼ (λR/(NA· 3.1.1. Use of Ellipsometry. Greater insight can be gained by
a))2̧ where λR is the wavelength at which the collective resonance looking at other parameters that can be determined using a
is excited and a is the array period. Thus, only focusing optics spectroscopic ellipsometer. Ellipsometry routinely provides
5919 DOI: 10.1021/acs.chemrev.8b00243
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Figure 5. SLRs for the Au dimer array. Experimentally measured spectra of ellipsometric parameters, reflection, and extinction for the studied 2D arrays.
(a) The ellipsometric parameter Ψ. Shown in the inset is a zoom-in of the reflection minimum at θ = 64°; λR_1air and λR_1sub are given by eq 6 with using
the “+” sign. (b) The phase Δ. Left inset shows the geometry for the p-polarized incident light. Right inset shows a zoom-in of the jump in phase at θ =
64°. (c) Reflection spectra for p polarization, Rp, and for s polarization, Rs. (d) Extinction for p-polarized light, the incident electric field is perpendicular
to the dimer axis. The inset at left shows an SEM of the array. The inset at right shows a zoom-in of the maximum in extinction for θ = 64°. Data are
shown for θ = 62° (orange), 64° (green), 66° (blue), and 68° (brown). The period of the dimer array was a = 320 nm, the diameter of the particles was d
= 108 nm, the height of the particles was h = 90 nm, the separation of the dimer particles was 140 nm (center-to-center). Reproduced and adapted with
permission from ref 78. Copyright 2008 American Physical Society.
amplitude (Ψ) and phase (Δ) parameters for light reflected from a a
λRair_m = [1 ± sin(θ)] and λRsub
_m = [ns ± sin(θ)]
a sample object, which are related to the reflected field m m
amplitudes Ep (p-polarization) and Es (s-polarizations) of the (6)
incident light (Ei), in the following equation EP/ES = tan(Ψ) where ns is the substrate’s refractive index. These conditions (eq
exp(iΔ).98 In addition, the ellipsometer allows one to measure 6) are sometimes known as “diffraction edges”. The extinction
the intensity reflection and transmission coefficients (Rp, Tp) for only showed a weak feature at the wavelength of interest, λR ≈
p- and (Rs, Ts) for s-polarized light at various incident angles. The 600 nm, and then only at large angles; see Figure 4(d) where the
advantages of using spectroscopic ellipsometry for character- arrow marks a weak and narrow feature at θ = 68°. This was
ization of plasmonic materials are described in ref 99. Figure 4(b) because in-plane diffraction occurs at wavelengths too far from
shows the behavior of Δ (the relative phase) at the same values of the spectral position of LSPR of nanoparticles; see Figure 4(d).
θ while Figure 4(c) shows the spectral dependence of the 3.1.2. SLRs in Extinction. Although the data in Figure 4
polarization specific reflection coefficients Rp and Rs. A very deep show clear evidence of SLRs, they do not show the strong
signature expected in extinction; see Figure 4(d). As noted in the
and narrow SLR with a half-width of 5 nm is seen in reflection for
previous paragraph, this is because the spectral position of the
p-polarization when the first-order diffraction in air is in the plane SLR was too far from the position of LSPR of a single particle.
of the array. In the presence of a substrate, two types of lattice There are several ways to match the LSPR of a nanoparticle with
coupling are possible differentiated by whether the diffraction SLRs: (i) to increase the period of the array, (ii) to decrease the
takes place in the substrate medium (typically glass) or in the particle size, or (iii) to select a different geometry for the array
superstrate (sometimes air). For the experimental conditions unit cell and use it to tune the SLR resonance. The authors of ref
studied in ref 78, two subsets of these conditions are given by 78 selected the third method and designed a two nanoparticle
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3.3. Refractive Index of the Environment particles.76 A comprehensive investigation into the effect of array
A key feature of the system studied by Auguié and Barnes79 was size for 2D arrays was carried out by Rodriguez et al.61 using both
the need for an homogeneous (symmetric) index environment experiments and numerical modeling. Using the coupled dipole
for observation of SLRs at the normal angle of incidence which is model outlined above, they showed that the quality factor of
in contrast to the study discussed above.78 In Figure 7 data from a SLRs increases with array size; see Figure 9. The response
homogeneous environment, upper panel, are compared with an saturates for arrays of a few hundred particles.
inhomogeneous (asymmetric) one, lower panel; the homoge-
neous environment was achieved by replacing the air superstrate
with an index matching oil.
The strong asymmetry between superstrate and substrate acts
to spoil the radiative coupling between the nanorods at normal
angle of light incidence; see the lower panel of Figure 7. (It is
interesting to note that in this case SLR spectral positions are
clearly not matched with the LSPR of the nanorods; see above.)
Several earlier studies recorded a strong impact of the asymmetry
of the environment on the line shape of the resonances
observed.75,77
Chu et al.80 also showed that diffractive coupling between
LSPRs in 2D gold nanoparticle arrays with a superstrate of water
could lead to narrow near-IR resonance peaks in the far-field
extinction spectra. Arrays of gold nanoparticles were made using
e-beam lithography and indium tin oxide (ITO)-coated glass
substrates. The arrays were square lattices of Au disks with array Figure 9. Calculated Q-factor of the surface lattice resonance for arrays
periods in the range 520 to 640 nm, and the gold disks were 40 of gold nanodiscs as a function of the number of particles N along the
nm thick and 180 nm in diameter. The use of water as the side of the square array. Disc dimensions are diameter 120 nm and
superstrate was sufficient to allow the observation of surface height 50 nm. Arrays were of N × N particles in size and were situated in
a homogeneous environment. Figure reproduced with permission from
lattice resonances, Figure 8; the measured extinction spectra are
ref 61. Copyright 2012 American Physical Society.
Figure 14. Electric field distributions (amplitude) |Ey| for the structure with lattice constants ax = 450 nm, ay = 250 nm at the condition of SLRs for two
cases: near the diffraction edge where the field is distributed between nanoparticles (a) and (b) at the SLR condition where the field is distributed on the
nanoparticles (c) and (d). The pictures show two unit cells. Reproduced and adapted with permission from ref 114. Copyright 2012 The Optical Society.
the resonance wavelength to the spatial arrangement of the can indeed lead to strongly enhanced local electric fields near the
plasmonic oscillators produces superradiant coupling. Such nanoparticles.
results might be useful in controlling the optical properties of 3.11. Two Types of SLRs
plasmonic nanostructures, perhaps allowing emitters to be
incorporated so as to yield a strong collective resonance with The question of how the diffraction edge relates to the spectral
enhanced radiative properties.113 position of plasmonic SLR is quite important. Thackray et al.116
considered in detail the properties of SLRs excited by light of
3.10. Field Distributions at SLR normal and oblique angles of incidence and showed that there are
In some applications (e.g., sensing) it is important to know the two generic types of SLRs distinguished by the behavior of the
near-field distributions associated with surface lattice resonances, inverse polarizability, 1/α, and the dipole sum S near the
how the field is distributed across a unit cell of the array. Nikitin resonance; see Figure 15.
et al.114 examined regimes of excitation of SLRs under normal The first type of SLR is observed when the dipole sum is large
illumination of an array of Au nanoparticles located in a and the curve Re(S) intersects the curve Re(1/α), Figure 15(a−
homogeneous refractive index environment, and they deter- c). In this case, two unequal resonances are observed (P and Q)
mined electric near-field distributions using numerical simu- while the location of the diffraction edge corresponds to the
lations. They identified two clear regimes of response from minimum of extinctionthe situation discussed in ref 114. One
lattices under normal incidence. The first is characterized by a of the resonances (Q in Figure 15) is much larger than the other
localization of the electric field between nanoparticles for the (P in Figure 15) due to a much smaller value of Im(1/α − S)
excitation wavelength close to the diffraction edge, leading to which defines the strength of the resonance. (Note that Im(S)
nearly complete transparency of the array, Figure 14(a, b), changes sign near the diffraction edge and combines with Im(1/
(something which was previously discussed by Abajo95). α) either in phase or in antiphase.) This is exactly the case
The second regime corresponds to a SLR for which there is a discussed in section 2 above. It is important to note that the
localization of the electric field on the nanoparticles, combined location of the stronger resonance is shifted from that of the
with a strong absorption/scattering, Figure 14(c, d). All these diffraction edge.
features have a natural explanation in terms of the SLR theory The second type of SLR is observed when Re(S) does not
described above. Finally, the authors in ref 114 optimized the intersect the curve Re(1/α) but comes close to it; see Figure
lattice parameters so as to maximize the electric field enhance- 15(d−f). In this case, a single, extremely narrow Fano-type,
ment on the nanoparticles. It is worth noting that SLRs observed resonance is observed at the location of the diffraction edge and
under oblique incidence could often be characterized by the fact the diffraction edge corresponds to a significant field enhance-
that SLRs and the diffraction edge coincide; for this case (in ment. This SLR normally yields SLRs of the highest resonance
contrast to the normal angle of incidence) the field enhancement quality due to the fact that the imaginary part of Im(1/α − S) is
is observed at a diffraction edge condition; see below. Recently, a smaller in this case. Since the spectral position of this single-peak
finite-element analysis was implemented to determine the SLR coincides with the diffraction edge position, the task of
distribution of electromagnetic fields under conditions that interpreting chemical and biosensing events becomes much
support SLRs with an emphasis on near-field and far-field simpler for SLRs of this second type (there exists an analytical
interference.115 The study confirmed that constructive and expression which gives the spectral position of the diffraction
destructive interferences are possible near SLRs and that SLRs edge.) It is worth noting that the first type of SLR is more often
5925 DOI: 10.1021/acs.chemrev.8b00243
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Figure 15. Spectral behavior of the real and imaginary components of the inverse polarizability 1/α (black) and dipole sum S (red) for a square array of
gold nanospheres on a substrate of glass, and the resulting normal incidence extinction spectra (in air). (a to c) are for period a = 600 nm, and radius r =
80 nm, and (d to f) are for a = 700 nm and r = 75 nm at normal incidence. Figure reproduced with permission from ref 116. Copyright 2014 American
Chemical Society.
observed at normal incidence while the second type is typically 6. For normal incidence SLRs are usually detuned from the
observed at oblique angles. diffraction edge while for oblique incidence SLRs are
3.12. Section Summary usually observed close to the diffraction edge.
To summarize, early experimental investigations provided the 4. FACTORS INFLUENCING THE PROPERTIES AND
following insights: EXCITATION OF SURFACE LATTICE RESONANCES
1. SLRs may be observed in reflection, transmission, Here we discuss the role of various factors that affect the
extinction, and absorption. properties and excitation of surface lattice resonances; these
2. As few as 50 particles in an array are enough to observe include the following: the optical environment (refractive index),
the illumination conditions, and the shape and size of the
SLR. nanoparticles from which the array is made.
3. The effects of disorder were as follows: positional array 4.1. Optical Environment (Refractive Index)
disorder suppresses SLRs while particle size disorder We begin by looking at the refractive index of the medium
makes SLRs wider. surrounding the particles, and especially whether the refractive
4. SLRs can be observed in a variety of arrays with no array index of the substrate and superstrate need to be matched. In the
geometry showing a distinct advantage. early stages of experimental investigation into plasmonic surface
lattice resonance phenomena there was initially some confusion
5. Field distributions inside the array can radically change as
about the need for a homogeneous (symmetric) refractive index
one sweeps the frequency of the incident light through the environment. The first report78 of ultranarrow SLRs involved
condition of SLR excitation. substrate and superstrate having markedly different refractive
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Figure 16. (a) Two-dimensional square array (schematic) of nanoparticles (gold) situated in a homogeneous semi-infinite medium having refractive
index n1 at a distance d above a substrate that has refractive index n2. The array period is a. Normally incident light is polarized along one of the lattice
vectors (x). (b) Cross section (scattering) of a single gold sphere in water (n = 1.33) and in glass (n = 1.46), as calculated using Mie theory. (c) Same as
(b) but now for an array having period a = 500 nm, as opposed to that of an individual particle; also included is the asymmetric configuration for which
now the spheres are in water and have their surfaces positioned 1 nm away from a glass substrate. Dashed lines (vertical) mark the position of the ⟨0,1⟩
and ⟨1,1⟩ diffraction edges in the various media. Notice how the sharp SLR features adjacent to the ⟨0,1⟩ diffraction edges are absent for the asymmetric
environment (red line). All gold nanospheres were supposed to be of radius 35 nm. Reproduced and adapted with permission from ref 117. Copyright
2010 American Physical Society.
indices, Chu et al.80 observed SLRs in the case of less pronounced For large nanoparticles, the contribution of the substrate
asymmetry between substrate and superstrate, while Auguié et reflection to the total array reflection becomes small and SLRs
al.79 made use of an homogeneous environment; indeed Auguié can again be observed. Also, when oblique light of p-polarization
et al.79 showed that a homogeneous environment was a “soft” is used, the reflection from the substrate becomes small near the
requirement to observe SLRs at normal angles of incidence. We Brewster angle and SLRs can be observed again. It is worth
note that this requirement is not necessary for light of oblique noting that particles of large sizes (or in denser arrays) restore
incidence as SLRs can be easily excited by such light in SLRs in asymmetric environments for light of both s- and p-
inhomogeneous conditions; see ref 78. The following works also polarizations (exciting either in-plane or out-of-plane resonan-
showed that the requirement of homogeneous conditions for the ces), while oblique incidence (and the Brewster phenomenon)
observation of SLRs at normal angle of incidence can be lifted for works only for p-polarization (for out-of-plane resonances).
arrays of larger and composite particles; see below. Mahi et al.118 looked at the dispersion curves of SLRs as a
Auguié et al.117 explored the symmetry/asymmetry problem in function of both the angle of incidence and the polarization
a detailed theoretical investigation. They found that excitation of direction for 2D square arrays of monomers and dimers for gold
SLRs under normal incidence is facilitated by the placement of nanocylinder substrates. They used a Green’s tensor method and
metal nanoparticles into the symmetric environment, for compared it to simulations based on the CDA approach. They
example by adding matching oil in order to remove the refractive confirmed that the substrate interface greatly modifies the shape
index contrast between substrate and superstrate. Using rigorous of the dipole sum around the Rayleigh wavelength, compared to a
electromagnetic simulations they showed that the asymmetric grating embedded in a homogeneous environment.
environment can suppress long-range interactions between the 4.2. In-Plane vs Out-of-Plane LSPRs
particles and thus inhibit lattice resonances for normal incidence Understanding the differing conclusions reached by different
(Figure 16). It was shown that the superstrate-to-substrate index authors is possible by considering the different relevant aspects
contrast together with the distance of the array from the interface involved. In particular, the simple view that an homogeneous
are the key parameters that determine the strength of diffractive medium is a “must” is a view that only strictly applies to arrays of
coupling. particles where the particle height is relatively small (e.g., 35 nm
The effect of a dielectric substrate in terms of the excitation of in79 and 38 nm in105). In this case the dipole moment of the
SLRs can be understood as follows. The substrate affects both the plasmon resonance of the particle that is used is in the plane
polarizability of an individual nanoparticle α (by changing its defined by the array. As a consequence of the close proximity of
environment) and the dipole sum S. These changes, however, the dipole moment to the interface between the substrate and the
can be compensated for by a change in array period and/or a size superstrate, the fields by which neighboring particles interact
of the nanoparticle. The main cause for suppressing SLRs in an span both substrate and superstrate. If these two media have
asymmetric environment is then the additional reflection differing refractive indices then constructive interference is not
produced by the substrate. For a dielectric substrate, this possible. If however taller particles are used and light made
additional reflection is purely real and should be combined with incident at an oblique angle then a dipole moment may be excited
Re(1/α − S), producing no contribution to Im(1/α − S). perpendicular to the plane of the array. In this case, the electric
Therefore, the cancellation of the inverse polarizability (real fields associated with the interaction between neighboring
part) happens at the spectral position where there is no particles are primarily in the superstrate and a refractive index
cancellation of the imaginary part and SLRs become suppressed. mismatch between substrate and superstrate is less important.
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Figure 17. (a) Transmission of arrays of large, 200 nm tall, square nanostructures 200 nm × 200 nm, with periods that vary from 450 to 760 nm. SLRs are
excited in an air environment. (b) SEM image of one array. Figure reproduced with permission from ref 116. Copyright 2014 American Chemical
Society.
Odom et al.119,120 introduced the terms “in-plane” and “out-of- 4.3.1. Complex Particle Geometries. An example of using
plane” resonances in order to characterize excitations of plasmon a complex particle geometry to achieve SLRs under normal
oscillations in the plane of the array and perpendicular to the incidence for an inhomogeneous environment is the specially
array plane. Another way to promote the interaction via fields in designed L-shaped and also rather tall nanostructures employed
just one medium is to bury the particles in the (higher index) by Thackray et al.,116 for use with air/glass and water/glass
substrate. This approach was adopted by Adato et al.121 who interfaces. For these L-shaped (and tall) nanostructures light that
demonstrated strong near-field enhancement and long plasmon is normally incident may excite the oscillation of in-plane
lifetimes by embedding nanoantenna arrays into a dielectric electrons in the base of the structure, which is electrically
substrate. Far-field extinction measurements confirmed the connected to the out-of-plane plasmon, thereby inducing an out-
strong diffractive coupling between the particles and the resulting of-plane dipole moment. Tall nanostructures were found to be
narrow plasmonic line shapes. more effective in generating narrow resonances under normal
The properties (optical) of in-plane and out-of-plane SLRs for incidence than L-shaped ones. Q-factors of ∼45 for a water/
hexagonal and square lattices as determined with the discrete- substrate and Q ∼ 85 for a glycerol/substrate were achieved.116
dipole approximation were studied by Huttenen et al.122 These SLRs excitation in a strongly inhomogeneous situation (air/
authors concluded that out-of-plane SLRs show much stronger glass) was also possible; see Figure 17.
polarization dependence as compared to in-plane SLRs. This 4.3.2. Importance of Substrate Conductivity. The
comes from the fact that out-of-plane oscillations are able to presence of substrate conductivity can strongly influence SLRs
couple in all directions within the array plane. by (i) introducing coupling between nanoparticles due to
4.3. SLRs at Normal Incidence substrate conductivity and suppressing both LSPRs and SLRs
Significant effort was expended to find ways to employ normally and by (ii) absorbing electromagnetic waves propagating near
incident light and yet still observe sharp surface lattice resonances the substrate at grazing angles and hence suppressing diffractive
for asymmetric water/glass or air/glass environments. The coupling (this is relevant when the electric field is parallel to the
motivation to do this stems from the fact that normal incidence surface of substrate). The substrate conductivity is important
observation requires only simple equipment readily based on a since nanofabrication often requires the presence of a thin
standard optical microscope, and an asymmetric environment metallic layer (or ITO sublayer) to avoid charging during
makes the pursuit of applications, such as biosensing, much electron beam lithography. This conductive layer can be kept on
easier.37−40 It was found that it is possible; the key idea is that one the substrate surface after fabrication. Several studies reported a
has to use either composite116 or large119 nanostructures as the key role of the substrate’s electric properties for the excitation of
elementary element in the unit cell of the array so as to enable the SLRs. The suppression of LSPRs and SLRs by a conductive
excitation of out-of-plane dipole moments.78 Several studies sublayer was discussed in Kravets et al.,126 where it was found
reported success in accomplishing this, albeit the narrowing that in-plane SLRs can be completely suppressed by a 5 nm thick
effect was not as pronounced as in a symmetric, homogeneous Cr layer as observed under normal incidence illumination. SLRs
environment.80,123,124 However, narrow SLRs were achieved for (albeit of lower quality) reappeared for oblique incidence of p-
normally incident light. polarized light while s-polarized light still showed no sign of
Zhou et al.120 later showed that out-of-plane SLR modes may SLRs.127 The reason for the suppression of SLRs in arrays that
be thought of as a surface Bloch mode that comprises many had been made on a substrate having a conductive layer under
Bloch harmonics. The out-of-plane dispersion evolves from a light of s-polarization is connected to the strong absorption of the
stationary state as the in-plane wavevector increases to become a diffracted light of s-polarization propagating along the substrate.
propagating state, and as this happens, the nonradiative loss falls This strong absorption comes from the excitation of currents in
since a smaller fraction of the optical energy is stored by the the conductive layer and it suppresses the diffractive coupling of
nanoparticles; in contrast, the radiative loss rises since better the localized resonances by reducing the dipole sum S. For light
coupling between higher-order Bloch harmonics and the leaky of p-polarization, coupling happens via the diffracted beams with
zero-order harmonics takes place. Such a system provides a nice the electric field perpendicular to the substrate (so, connected to
conceptual framework for the dispersive properties of delocalized out-of-plane resonances). These beams do not excite strong
plasmon resonances that may be supported by other kinds of currents in the conductive layer (due to its small thickness), and
plasmonic nanostructures.125 hence SLRs reappear.
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Figure 18. Properties (optical) of the regular arrays of gold dimers on a glass substrate. (a) Reflection spectra of gold dimers for p- polarized light as a
function of the angle of incidence. Array period a = 320 nm, particle diameter d = 110 nm and height h = 90 nm. (b) Reflection spectra of embedded gold
dimers for p- polarized light as a function of incident angle (a = 320 nm, d = 130 nm, h = 90 nm). Shown in the insets are SEMs. Adapted with permission
from ref 127. Copyright 2014 American Physical Society.
Sadeghi et al.128 offered a convenient way to tune SLRs by wavelength periods observed in both homogeneous (matching
controlling the coupling of light with plasmon resonances in oil) and asymmetric environment for large size particles, thus
arrays of metallic nanoantennas with the help of ultrathin layers confirming the theory.
of conducting silicon. This was accomplished by including a thin Finally we note in this section that surface lattice resonances
film of silicon onto a plasmonic array. The authors demonstrated can be observed in nonplasmonic systems. Ghenuche et al.
that some plasmonic arrays on a glass substrate that do not show studied arrays of nanoparticles made of the dielectric silicon
SLRs at normal incidence could nevertheless acquire SLRs after nitride (SiN x).135 In this case, NPs were placed in a
deposition of an ultrathin silicon layer. The authors studied the homogeneous (index-matched) environment. Angle resolved
behavior of these “induced” SLR resonances as a function both of transmission data from polarized light revealed both a shifting
the angle of incidence and of the arrays’ geometrical parameters. and splitting of the resonance peaks as angle of incidence was
4.3.3. Composite Nanoparticles. Composite nanoparticles varied, in good agreement with calculations based on the dipole-
are another way in which SLR quality can be improved in an lattice sum approach described above. These data showed that
asymmetric environment.127 Normally incident light may couple grating-induced effects and symmetrical/asymmetrical environ-
to out-of-plane resonances of composite nanostructures, e.g., ments could play an important role in the optical response of
dimers,127,129 and generate SLRs. Figure 18(a) shows the regular arrays of nonplasmonic nanoparticles. Lattice resonances
dependence (angular) of the reflection spectra for p- polarized have also been predicted for arrays of particles that support
light for arrays of Au nanodimers, with a particle diameter d = 110 exciton-polariton modes, thus opening a pathway to the
nm, where collective resonances result in the reflection peak exploitation of lattice effects in organic material systems.136
(instead of reflection drop). One of the narrowest SLR 4.5. Section Summary
resonances in visible light was recorded in reflection mode for To summarize, factors that influence SLRs are as follows:
gold dimer arrays made using electron beam lithography but
without using a lift-off process; see Figure 18(b).127 A strong 1. A homogeneous (symmetric) refractive index environ-
decrease of p-polarized reflectivity was recorded at λ ∼ 600−650 ment is necessary for the observation of SLRs at the
nm with fwhm of resonances lower than 3−5 nm. The origin of normal angle of incidence for arrays of relatively short
such a small width of SLRs in this system is still an open question. nanoparticles.
4.4. Subwavelength Arrays 2. SLRs for tall nanostructures or under oblique incidence
can be observed in an inhomogeneous (asymmetric)
It is also interesting to note the importance of out-of-plane dipole environment.
moments for profoundly subwavelength arrays of nanoparticles. 3. Out-of-plane plasmon modes can facilitate the generation
Such arrays are involved in remarkable effects such as the
of high quality SLRs.
emergence of collective plasmonic, Dirac-like modes,130−132
4. Substrate conductivity may suppress SLRs at normal angle
where predictions involve honeycomb arrays with periods that
are smaller than the resonance wavelength by an order of of incidence.
magnitude.131 With such small separations, near-field inter- 5. For arrays fabricated on conductive substrates, SLRs
actions take on an important role. The collective tunable reappear for p-polarization under oblique illumination.
excitations in graphene-like nanostructures exhibit some of the
special features that electrons exhibit in graphene and can be 5. WHAT ARE THE LIMITING FACTORS FOR THE
accompanied by a variety of effects such as, e.g., a nontrivial Berry RESONANCE QUALITY?
phase behavior.133 For example, particle arrays made from the Improving the quality of localized surface plasmon resonances is
metal tin (Sn)134 showed pronounced resonances for sub- important for many applications, from nanolasers to biosensing.
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Figure 19. (a) Surface lattice resonance seen using ellipsometry in reflection in an attenuated total reflection geometry (Q ≈ 150 where water was used
as a buffer layer). (b) SEM image of Au nanodots arrays. Figure reproduced with permission from ref 104. Copyright 2010 The Optical Society.
We have already seen that the early reports of plasmonic surface 5.3. Narrow SLRs at High Angles of Incidence in Nanostripes
lattice resonances achieved quality factors of Q ∼ 40−60.78,79 on a Metallic Film
This was nearly a factor of 10 improvement over typical LSP The third method moved away from the use of particle arrays and
resonances of individual gold nanoparticles.37,47 The width of an explored a related structure, that of a metallic grating. In this
SLR mode depends on the relation between the particle study140 the authors observed very narrow SLRs in the near IR
susceptibility and the dipole sum; from Markel’s theory it may with a spectral width below 5 nm fwhm and associated Q-factors
even be exponentially small.69 At the same time, the width of an of ∼300 using a grating structure comprising gold nanostripe
SLR depends on the number of particles that interact coherently. arrays fabricated above a thin gold film. Measured quality factors
This number might in turn be limited by the spatial coherence of of up to 300 are among the highest reported from arrays of
diffractively coupled nanostructures at telecom wavelengths
the illumination, the physical size of the array area, disorder,
around 1.5 μm.137,138,140
substrate curvature, etc. In this section we look at several different
5.4. High Quality SLRs for High Aspect Ratio Particles
approaches that have been explored to further improve the
quality factor. In the fourth and last example discussed here, Zilio et al.141
experimentally investigated the optical properties of high-aspect-
5.1. SLRs at Attenuated Total Reflection
ratio out-of-plane metallic slanted silver nanorod dimers standing
The first method we discuss was that of modifying the excitation on a metallic substrate. The proposed architecture mimics a 3D
geometry by making use of attenuated total reflection (ATR) in split-ring resonator with a nanometric gap. High-quality-factor
prism coupling (Turbadar−Kretschmann−Raether) geome- resonances with Q ≈ 390 were reported in the mid-IR (10−12
try;104 a Q of ∼150 was achieved in this way for a deep red μm) because of the efficient excitation of collective modes in
resonance; see Figure 19. An asymmetric index arrangement was dimer arrays. It was shown that the tiny gap between the
used, with the two media being water and glass. This high quality nanorods renders possible an effective near-field coupling
between the rods that leads to the splitting of the single rod
SLR was achieved in the ATR geometry using 90° prism of
resonance into two hybrid dimer modes (called bonding and
refractive index 1.5 for the array parameters as follows: a = 318 antibonding ones). The tilt of the structure on the other hand is
nm, d = 132 nm, and s = 140 nm at the incidence angle of 45°. demonstrated to be the important feature that enables the
This is an order of magnitude better compared to that of excitation of the bonding resonance of the structure using far-
conventional LSPRs in gold where Q ∼ 10.18,19 field illumination. By optimizing the grating pitch and
5.2. High Quality SLRs Using Out-of-Plane Resonances illumination conditions, the value of Q could be further raised
up to 500. It is easy to see the trend that the longer the SLR
Out-of-plane resonances have been used in an interesting way to wavelength observed in the array, the higher the quality of SLR
realize high quality SLRsin the form of arrays of monopole that can be achieved (∼100 for visible light, ∼300 for telecom
oscillators, being achieved by making use of the metallic mirror wavelengths, ∼500 for mid-IR). The reason for this trend is the
plane immediately below the metal particles.137,138 For large decrease of the imaginary part of susceptibility of nanoparticles
angles of incidence Q-factors of over 200 were achieved. These and the dipole sum at larger wavelengths (physically connected
results were achieved in the infrared (λ ∼ 5 μm); the resonators with the fact that larger nanoparticles mostly scatter light instead
were made of indium tin oxide (a good plasmonic material in the of absorbing it). Note that high resonance quality does not have
IR,139 the metallic ground plane being made of gold). Note that to mean high field enhancement for SLRs.116
the sharpness of SLRs depends on Im(1/α − S) which can be 5.5. Section Summary
made smaller for larger particles and for resonances at longer To summarize, the quality of SLRs follows the following trends:
wavelengths (where both Im(1/α) and Im(S) become small). 1. The longer the SLR wavelength, the higher the quality of
Out-of-plane resonances may be used to increase the height
SLR that can be achieved.
(effective) of the nanostructures fabricated on a metal substrate
as explained below and hence to improve the resonance quality 2. A substrate metal mirror layer can significantly improve
even further. SLR quality for large angles of incidence.
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Figure 20. Experimental spectra for the phase and amplitude of reflected light under resonant plasmonic conditions: (a) Excitation of SPPs for a 50 nm
gold film in the Turbadar−Kretschmann−Raether prism geometry (classical SPR). Owing to the finite roughness of the gold film surface, the Ψ value is
well away from zero, leading to a smooth phase change in the minimum of the resonance curve. (b) Diffractively coupled array of gold nanodots (SLRs).
The SLR is seen to be much narrower, and the value of Ψ is close to zero, leading to a very sharp jump in the phase close to the resonance minimum.
Reproduced and adapted with permission from 149. Copyright 2016 The International Society for Optical Engineering.
3. The ATR geometry, monopole emitters, and composite Kretschmann−Raether SPR biosensing geometry.14,15,144,145 In
particles can be used to improve SLR quality. terms of the minimum-detectable bulk refractive index change,
4. It is difficult at the present state of knowledge to determine the sensitivity of phase-sensitive SPR schemes can reach down
an upper limit on the maximum quality factor of SLRs that to10−8 refractive index units (RIU), which is at least a factor of 10
lower than with amplitude-based parameters (these include the
might be possible.
spectral or angular position of the SPR reflectivity dip, together
6. PHASE SINGULARITIES UNDER SURFACE LATTICE with its depth).15,145 The lower detection limit of conventional
sensitive SPR devices is typically estimated to be 1 pg/mm2 of
RESONANCES: OPTICAL SENSING
biomaterial accumulated on the surface of the sensor.146
An interesting and alternative way to view the nanoparticle arrays Therefore, the employment of phase sensitivity gives access to
that support surface lattice resonances is to see if one can sub-100 fg/mm2 level sensitivity.
consider them as thin films of an effective medium. In this section 6.1.3. Sharp Phase Jumps under SPR and SLRs. As noted
we do just this, and in doing so make a connection with another above, in practice the phase jump is not perfectly sharp
topical area, that of metasurfaces. (Heaviside-like) under SPR excitation because of the unavoid-
6.1. Zero Reflection, Phase Singularities, and Optical able roughness of the Au film surface, which limits the resulting
Sensing improvement of the detection limit of phase-sensitive SP devices.
6.1.1. Zero Reflection and Phase Singularity. The An example of the behavior of the phase and amplitude
absorption of light under conditions for which plasmons are parameters under SPR excitation for a high quality gold film
excited leads to a drop of the reflected (or transmitted) light having the optimal thickness in the Turbadar−Kretschmann−
intensity. A general property of the light intensity falling toward a Raether geometry (∼50 nm) is shown in Figure 20(a). One can
zero value (something we refer to as darkness) is that the phase of see that under nearly optimal width of the resonance (30 nm
the light experiences a sharp jump with a magnitude of up to π; fwhm), the parameter Ψ exceeds 8° at the resonance minimum
the phase is undefined for a zero value of intensity.15,142 In corresponding to ∼5% of the optical intensity when compared
general, the lower the intensity of the minimum, the sharper the with off-resonance conditions. As a result, the jump of phase of
associated phase jump. It is worth noting that while it is easy to the light is considerably smoothed out; such a phase smoothing
achieve a theoretical zero reflection in, e.g., the surface plasmon effect limits the sensitivity of this approach. It was recently shown
resonance (SPR) configuration, sufficient loss (e.g., scattering that the intensity at the minimum of the resonance may be
due to roughness, or indeed sufficient absorption143) could reduced by using alternative graphene/copper147 or graphene/
suppress darkness and spoil observation of a phase singularity. gold148 structures for plasmon excitation; however these
6.1.2. Phase Singularity and Optical Sensing. When alternative geometries need their own functionalizing protocols
employed in optical sensing tasks that rely on refractive-index- to be developed.
based monitoring of binding-recognition events (see Introduc- The employment of diffractively coupled nanoparticles, SLRs,
tion), these sharp characteristics (singularities) of the phase of enables one to revisit the use of phase properties and their
light enable orders of magnitude better sensitivity when sensing applications. Indeed, in addition to the above-mentioned
compared with more conventional amplitude-based approaches. drastic narrowing of plasmonic resonances, diffractive coupling
In particular, a significant gain in sensitivity may be obtained may also lead to a dramatic fall in intensity at the resonance
when phase is used as the sensing parameter in the Turbadar− minimum and an associated sharpening of the phase
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Figure 22. Spectral dependence (measured) of the spectral position of the resonance (a) and the phase angle (b) to variations in the refractive index for
diffractive coupled SLR (red) and for conventional SPR with a 50 nm gold film (black). Figure adapted with permission from 149. Copyright 2016 The
International Society for Optical Engineering.
darkness using an inexpensive fabrication technique based upon period). It is clear that to achieve such a low detection limit
self-assembly, thereby enhancing the prospects for phase- requires the development of low-noise phase detection schemes,
sensitive plasmonic measurements in device applications. such as those based on interferometry14,144 or polarimetry.15,154
Note that phase and amplitude sensitivities do not always 6.4. SLR and Optical Chirality
correlate with each other in different plasmonic geometries.
Indeed, the spectral sensitivity of SLRs in nanoperiodic arrays is The previous sections focused on how plasmonic arrays could be
typically much lower when compared to that of surface plasmons effectively used to manipulate the reflected/transmitted light
(PSPs), while the phase sensitivity is higher. This situation is amplitude and phase. When arrays are made of chiral elements,
illustrated by Figure 22(a), where a change in SLR (red) and PSP more subtle optical effects are possible with light propagation
(black) features is shown as a function of the refractive index of being different for light of left and right circular polarizations.
the medium; these changes were accomplished through the use This asymmetry leads to circular dichroism, characterized by
different concentrations of glycerin. different levels of optical absorption for the two circular light
polarizations, and optical activity, where linearly polarized light
The increase of RI produces a shift to longer resonance
rotates polarization during its propagation.155 Chirality can be
wavelengths for both configurations. The gradient of the linear fit
introduced either through a careful design of the shape of
yields a sensitivity of 400 nm/RIU for SLRs, this is similar to the
constituent elements or through an arrangement of these
best reported values of sensitivity for localized plasmons37 but
elements into chiral superstructures.156 At the same time, the
about an order of magnitude lower than that obtained using thin
optical effects associated with chirality can be strongly enhanced
film-based PSP sensing in the Turbadar−Kretschmann−Raether with the help of plasmonics.157−161 The fascinating world of
prism geometry (∼3,600 nm/RIU). The limitation in using SLRs chiral metasurfaces and their optical properties have been
concerns the diffractively coupled nature of localized plasmons; extensively reviewed.138,156,162−164 Chiral materials are often
diffractively based phenomena have sensitivity that is typically of made in the form of 2D structures (metasurfaces) which are
the order of the array lattice constant Δλ/Δn ∼ a152 (unless the arranged in regular arrays in order to avoid scattering.157−161
arrays are 3D153). However, the same considerations do not hold Therefore, one can expect that plasmonic surface lattice
for phase sensitivities. Indeed, as shown in Figure 22(b), PSPs resonances could enhance further the optical effects of chirality
have a rather moderate phase sensitivity (2.3 × 104 deg of phase (e.g., circular dichroism and optical activity). An enhancement
per RIU), while the SLR phase sensitivity may easily exceed 105 has been indeed observed for chiroptical effectscircular
deg of phase per RIU; see Figure 22(b). This is due to the dichroism in particularin plasmonic arrays under oblique
significantly lower light intensity in the minima associated with light illumination where SLR modes can be excited more
diffractively coupled resonances, compare Figure 20(b) with easily.165 The dependence of SLR modes on the angle of
Figure 20(a). Thus, despite a poorer amplitude sensitivity for incidence was used in ref 166 to realize spectrally tunable and
SLRs, the use of phase sensitivity more than compensates for this. strong chirality in diffractive metasurfaces. In this case, the
The best sensitivities to-date of SLRs to refractive index diffraction-assisted chiralitycircular polarization dependent
variations in gaseous and aqueous media were reported in ref light transmission and circular dichroismwas very large near
104. It was shown that the SLR phase sensitivity may be more the main SLR modes of the plasmonic chiral array. Cotrufo et
than 2 orders of magnitude greater than the best amplitude al.167 showed that lattice resonances play a primary role in
sensitivity for the same nanodot array and an order of magnitude controlling the spin-dependent emission of light from planar
better than the PSP sensitivity in the Turbadar−Kretschmann− chiral metallic nanoparticle arrays embedded in a light-emitting
Raether configuration. In experiments involving gaseous media it dye-doped slab. They found that the photoluminescence
was found that the best SLR phase sensitivity (5.2 × 105 degrees observed from these arrays showed a high degree of circular
of phase shift per RIU) is better by more than 2 orders of polarization near the position of the SLR, which emphasizes the
magnitude than the corresponding SPR amplitude sensitiv- important role that diffractive coupling may have for optical
ity.144,145 It seems realistic to develop a phase sensitive SLR spin−orbit effects. It is worth noting that investigations of SLR
sensor with the threshold at subnanolevel of 10−10 RIU by modes in chiral arrays started only recently and could bring new
appropriate optimization of array parameters (e.g., the lattice surprises.
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6.5. Section Summary authors noted that this approach might also enable control over
To summarize, SLRs can lead to the following: the color of solid-state lighting devices. The scope for making use
of different nanostructure designs for the antennas was
1. Zero reflection and singular behavior in the phase of the
demonstrated through the use of nanopyramid arrays, with the
reflected light.
shape of these particles allowing control over the balance
2. Topologically protected darkness (zero reflectivity) with between forward and backward emission of emitters of light.174
improved phase sensitivity toward binding events. The physics underlying this effect was discussed in terms of the
3. Optical sensors based on SLRs with surface area sensitivity enhanced magnetic and magnetoelectric response of the
at the level of <10 fg/mm2 (better than conventional SPR nanopyramids.
by several orders of magnitude). 7.1.2. Inorganic Semiconducting Emitters. Surface lattice
4. Phase sensitive SLRs with 10−10 RIU detection limit resonances can be used to control the emission of inorganic
(better than conventional SPR sensors by 4 orders of semiconducting emitters. Diffractive arrays comprising nano-
magnitude). cylinders made of silver were used to enhance the efficiency of
5. Strong enhancement of chiroptical effects in chiral radiation from InGaN/GaN quantum wells whose visible
plasmonic arrays. emission was in the blue/green part of the spectrum (around
495 nm).175 Significant enhancements in the luminescence
7. SURFACE LATTICE RESONANCES AND THE output (a factor 5 or more) were found when the period of the
EMISSION OF LIGHT array exceeded the wavelength of the emission in the
semiconductor material. The results, from both experiment
Array structures may effectively couple light from nearby and associated numerical simulations, were indicative of an
emitters (dye molecules, quantum dots, etc.) to light, and as a underlying mechanism based upon a strong resonant coupling
result their use is a subject of active investigation for applications between the SLR of the arrays and the light-emitting quantum
potential in light-emitting diodes, lasing, and strong coupling; we well excitons. Rodriguez et al. demonstrated that SLRs in an array
explore each of these below. of silver nanoantennas may be used to modify the emission from
7.1. Surface Lattice Resonances and Spontaneous Emission a thin layer of CdSe/CdS core/shell quantum rods (QRs)176
and Absorption (randomly oriented) yielding a highly directional and enhanced
Interest in using SLRs to control the emission of light is perhaps polarized light source. By tailoring the spectral/angular depend-
the most explored of these three areas of potential. Here we look ence between the emission spectra and the SLR, it has been
at two classes of emitting source: dye molecules and inorganic shown that a Lambertian source can be converted into a
semiconductors. directional emitter of polarized light.176 Strong modifications of
7.1.1. Dye Molecules. Vecchi et al. initiated much of the the emission characteristics of quantum dots in the presence of
work concerning the coupling of emitters of light via SLRs with plasmonic nanoarrays were also demonstrated in ref 177, where
their 2009 article on shaping the fluorescent emission from dye coupling with the plasmonic modes was found to boost the
molecules using an array of nanoantennas produced by spontaneous emission decay rate of quantum dots. Murai et al.178
nanoimprint lithography.110 They showed that the emission studied the mechanism where photoluminescence from a thin
direction could be controlled by making use of SLRs. The same Eu(III)-complex that would otherwise suffer total internal
group reported a ∼10-fold enhancement of emission from dye reflection and be trapped in the film could instead be recovered
molecules as a result of coupling to SLRs, again making use of as emission into free space using SLRs. Periodic arrays of Al
arrays made by nanoimprint lithography.168 Interestingly, they nanocylinders nanoparticles were used, and it was shown that
exploited the multipolar plasmonic resonances of their antennas, directional photoluminescence enhancement as large as 5-fold
as nicely revealed by simulations of the field profiles associated can be achieved by excitation of SLRs.
with the modes involved. The same group explored the 7.1.3. Light Absorption and SLRs. Surface lattice
sensitivity of the emission via SLRs to the spatial location of resonances can also be used to control the absorption of light.
the emitting sources169 and investigated other aspects important Perhaps building on earlier ideas concerning the coherent
to the design of useful structures through combined control of absorption,179,180 coherent control was used to modify
experimental/numerical work.170 In a separate study, ring- the absorption of light by a layer of dye molecules.181 Of
shaped nanoantennas were used to illustrate the potential to particular interest was the finding that absorption by molecules
control the line width, shape, and amplitude of the emission.171 residing in the regions between the metal particles could be
The concept of using SLRs as intermediaries to control the controlled, something that may prove useful for light-harvesting
emission of light was extended to the UV part of the spectrum by devices.
making use of an array of Al nanoantennas produced by focused
7.2. Surface Lattice Resonances and Lasing
ion-beam lithography.172
Further work with a specific focus on exploiting SLRs in the The idea of trying to harness periodic arrays of plasmonic
context of solid-state lighting has also been reported.173 In this scatterers for lasing is a natural one, there is a long and
work, the authors sought to control the directionality of the successfully history of using periodic dielectric structures to
emission from a phosphor layer pumped by a blue LED. By provide lasing feedback.182,183 A priori it is not obvious that
placing a large-area nanoimprinted hexagonal array of aluminum plasmonic modes will make good candidates for lasing structures
nanoparticles between the blue LED and the phosphor, they because although they are efficient scatterers they are also
were able to couple phosphor emission to SLRs and thereby absorptive.184 The combination of gain and plasmonics is a
control the directionality of the emission from the phosphor. For topical one,185 and a significant amount of recent research has
the phosphor, they used a 700 nm thick layer of polymer doped been directed at lasing from individual plasmonic structures.
with the light-emitting molecules Lumogen F Red (BASF); the That work is reviewed elsewhere186 and will not be considered
emission was characterized using Fourier microscopy. The here; instead, we focus on periodic plasmonic structures.
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dependence of both lasing threshold and line width.196,197 A from rectangular arrays of split-ring resonators at oblique
number of alternative structures have also been investigated. In incidence and found the conditions which provide more than
one example, a dye-doped polymer layer (PMMA) was situated 30-fold enhancement of the emitted second harmonics
above a silver film of 20 nm thickness. A square lattice (2D) of compared with light incident normally. They showed that
gold nanopillars having period 865 nm was then fabricated on these conditions agree well with the existence of a SLR at the
top of the doped polymer layer to provide the feedback element. wavelength of SHG.
The authors of ref 198 investigated how the fields supported by It has also been shown213−216 that enhanced nonlinear
SLRs are modified by the inclusion realistic optical gain. interactions in plasmonic/dielectric structures may be associated
Recently, the amplification of out-of-plane SLRs in gain- with the excitation of SLRs, with their origin connected to
assisted nanoparticle arrays has been predicted.199 These out-of- nonlinearity in the metal and field enhancement in the
plane SLRs demonstrated lower thresholds for lasing compared surrounding material. In the future, the nonlinear susceptibilities
with in-plane lattice plasmons, due to enhancement and more of plasmonic nanostructures are expected to become part of the
efficient localization of the electric field. The results199 also design of nonlinear integrated devices and optical information
suggest that gain thresholds for SLRs are much lower than those processing applications.
of individual nanoparticles. A consequence of the low radiative Kolmychek et al.217 demonstrated magnetic modulation of
loss of surface lattice modes is to give active nanoparticle arrays a SHG from 100 nm diameter gold NPs arranged in a square array
clear advantage of a lower lasing threshold than gain-assisted of 400 nm period, covered by an iron-garnet layer (90 nm) doped
nanoparticles. Such active nanoarrays may also find application in with Bi. They observed that SHG generation is resonantly
luminescence and Raman scattering studies, in photocatalysis, enhanced under the excitation of SLRs and studied the
and in nonlinear optics. magnetization-induced change of SHG in their system.
7.3. Surface Lattice Resonances and Strong Coupling In another study,218 a single bow-tie nanoantenna embedded
in an array of scattering nanoparticles was presented. The authors
Strong coupling between cavity modes and quantum emitters is a demonstrated the possibility for implementing multifrequency
rapidly emerging field in which an ensemble of light emitters (several mid-IR wavelengths) operation through the use of
(e.g., dye molecules, quantum dots, etc.) exchanges energy with nested particle arrays having multiple periodicities, possibly
an electromagnetic resonance, e.g. light confined (and thereby paving the way for broadband nanoantennas to be developed that
enhanced) in a microcavity.200 Surface plasmon modes are also may be used as near-field probes for nanoimaging, biosensing,
suitable optical resonances;201−203 indeed, the extent of the field and spectroscopy.218
confinement they offer has recently led to the report of single
molecule strong coupling.204 7.5. Section Summary
The combination of strong coupling between confined optical To summarize, SLRs can strongly affect the process of light
fields and molecular resonances is a fascinating one because it emission:
offers the prospect of control over chemical processes. As an 1. SLRs can enhance directional output of light from dye
example, control over photoswitching of spiropyran molecules molecules by at least an order of magnitude.
was demonstrated using a planar optical microcavity.205 Similar
switching behavior was also achieved using the localized surface 2. SLRs can be used to control the following characteristrics
plasmon modes on metal nanoparticles, again with spiropyran of light emitted by LED: direction, wavelength, and
molecules as described in ref 206. Strong coupling of excitons polarization.
with PSPs was also achieved using resonances with excitons of
3. Absorption of light by dye molecules can also be modified
organic semiconductors, specifically J-aggregates of TDBC dye
molecules.207 by SLRs.
Strong coupling involving surface lattice modes and dye 4. SLRs can reduce lasing thresholds and provide control
molecules was explored and achieved in 2013 by two groups, over lasing wavelength and direction.
both making use of the standard laser dye molecule R6G and 5. Strong coupling of emitters with light can be achieved
silver nanoparticle arrays. In one report the authors used
conformal imprint lithography;208 in the other particle arrays through surface lattice modes.
were produced by electron beam lithography.209 Taken together 6. SLR modification of nonlinear effects is possible, although
these results show that SLRs offer a powerful means by which much more work is required to assess the potential.
light−matter interactions may be manipulated.
7.4. SLRs and Nonlinear Effects 8. SLRS AND 2D MATERIALS
Nonlinear optics at the nanoscale is attracting increasing interest, As we have seen elsewhere in this review (section 6), the
and this applies to arrays of plasmonic particles.210 An interesting confined and enhanced optical fields associated with plasmonic
study concerning the role of SLRs in second-harmonic resonances, including surface lattice resonances, make these
generation (SHG) was carried out by Czaplicki et al.,211 where modes sensitive to their immediate environment. That sensitivity
arrays of metal nanoparticles were employed. They demon- extends to atomically thin 2D materials, including graphene,219
strated that by altering the incident angle it was possible to tune and van der Waals materials such as MoS2 (semiconducting) and
the SLR to match the fundamental wavelength for SHG and NbSe2 (superconducting).130,220 Another important reason for
thereby improve the quality of the resonance for better using plasmonic surface lattice modes vs propagating “flat”
enhancement of the SHG process. When compared with results plasmons lies in the field distribution: PSPs often provide
obtained at normal incidence, an enhancement by a factor of ∼10 enhanced electromagnetic fields which are perpendicular to the
was observed. However, the authors concluded that more studies plane of 2D materials and hence do not interact strongly with
are needed if the SLR-enhanced nonlinear response is to be fully them.221 Here we look at the combination of surface lattice
understood. Michaeli et al.212 experimentally demonstrated SHG resonances and these 2D materials.
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Figure 25. Monolayer MoS2-bowtie resonator array and associated optical properties. (a) Schematic of device indicating parameters of bowtie array:
metal thickness (h), gap separation (g), triangle size (s), and pitch of unit cell (p = (px, py)). (b) Photoluminescence spectra of bare MoS2, bowtie array
and bowtie-MoS2. Reproduced and adapted with permission from ref 229. Copyright 2015 American Chemical Society.
refractive index (RI) of most biological molecules, nbio, is usually achieve sensitive control of their position and thus limits the
larger than that of water; nbio ∼ 1.45−1.55, compared to nwater = precision of sensing measurements. It is natural to consider using
1.33. Consequently, when molecules bind to a surface, the local SLRs to reduce the line width of the resonances and thereby see if
refractive index rises. Surface optical phenomena, such as surface they can be used to improve the sensitivity.
plasmons (both propagating and localized), are sensitive to this 9.3. SLR vs SPR
local refractive index, and their properties, e.g. spectral position
of resonance, change.231 Central to the success of this approach is The involvement of SLRs enables one to make significant
the use of a layer of biorecognition molecules on the sensor advances to state-of-the-art biosensing technology using
surface. The idea is that the biorecognition molecules only allow plasmonics, although sensing tasks require the adaptation of
the analyte molecules of interest to bind, thus providing the SLR excitation geometries for the operation in an essentially
specificity of the sensor. A successful sensor requires specificity asymmetric (w.r.t. refractive index) environment when metal
nanoparticles are located at a substrate/water or substrate/air
(through appropriate biochemistry) and sensitivity; it is
interface. In general, geometries enabling the excitation of SLRs
sensitivity that plasmonic techniques offer (we note that there
that make use of out-of-plane dipole moments are well suited for
are many other approaches, see e.g. ref 232 for a review). Any
these tasks.78,119 Under these conditions, the characteristics of
biological binding event of target analyte from the solution with
SLRs are almost independent of the asymmetry of the
its associated receptor (immobilized on the surface) is
environment,78 while SLRs can be efficiently excited even
accompanied by a change of RI of a thin near-surface layer;
under the attenuated total reflection geometry in which light
typically this layer is between a few nm and a few tens of nm. This
does not propagate through the sample liquid/air medium
approach conveniently avoids the use of labels, convenient
(important if the effect of bulk refractive index on the desired
because labels often reduce the activity of target molecules by
signal is to be avoided).104 Danilov et al.238 compared the
occluding the binding site. In addition, in optical transduction
conditions for excitation of SLRs involving array Au nano-
one can follow biomolecular interactions in real time and thus particles (size ∼100−200 nm, period 320 nm) supported on
obtain information on kinetic constants of reactions, which is glass substrates, both in the direct and in the attenuated total
hardly possible with labeling methods.232 reflection (ATR) geometries, and they assessed their perform-
Biological sensing based on the transition from LSPRs to SLRs ance relevant for biosensing. They showed that the spectral
was studied in arrays of gold nanoantennas covered by an sensitivities to modes located predominantly in liquid medium
ultrathin silicon layer by Gutha et al.233 They showed that SLRs were dictated by the period of the lattice in both direct and ATR
may lead to very high sensitivities to small changes of refractive geometries (∼320 nm per RIU change), while the substrate
index; they did this by detecting biomonolayers and streptavidin- mode demonstrated, as expected, a much lower sensitivity. They
conjugated semiconducting quantum dots. Sadeghi et al.234 also demonstrated that the phase sensitivity does not depend on
investigated the application of SLRs of arrays of large metal the periodicity of the structure and may exceed 105 degrees of
nanodisks to chemical and biological sensing. They demon- phase shift per RIU change, thereby outperforming the relevant
strated that narrow SLRs could be shifted from the visible (∼650 parameter for all other plasmonic sensing approaches.
nm) through to the infrared (∼900 nm) range by altering the The oblique incidence arrangement is rather complicated in
environment’s refractive index. Gutha et al.235 confirmed that 2D terms of experimental setup when compared with the simple
arrays of large gold metallic nanodisks may have a greater transmission geometry.79 Therefore, significant efforts have been
sensitivity to changes in the superstrate’s refractive index in the applied to enable the excitation of SLRs under normal incidence
near IR region. The authors tuned the SLRs modes, using illumination while still employing an asymmetric environment.
ultrathin layers of silicon, in the range from 1 to 1.7 μm and Partial success in narrowing the resonances for a water/substrate
achieved a reasonably high refractive index sensitivity of ∼795 interface was achieved through control of the shape and size of
nm/RIU. Lee et al.236 studied the optical properties of a 1D chain suitable nanostructures.80,123,124 More recently, Thackray et
of silver capped nanoslits under oblique illumination and al.116 demonstrated efficient excitation of very narrow SLRs,
compared the sensing performance of these structures for a down to a width of several nm fwhm under normal incidence, via
range of plasmonic modes, including SLRs. They detected the the employment of a specially designed array of Au nanocubes
reaction involving bovine serum albumin and anti-bovine serum (area 200 nm x 200 nm, height 200 nm). Compatibility with
albumin, and they obtained a lower detectable limit of 1 ng/mL standard microscope systems is important since it removes the
(0.14 pg/mm2), comparable with that of the standard SPR need for specialist optics, making the technique much more
technique. accessible for bio- and chemical sensing.
9.2. Propagating Surface Plasmons 9.4. Figure of Merit and Sensitivity
Surface plasmon resonance techniques are at the heart of existing The reduced spectral width of SLRs helps to improve the
label-free optical sensing technology, offering superior sensitivity precision of biosensing tests using plasmonic nanostructures. To
due to the enhanced electric field.237 The rapid and widespread take account of the sharp nature of the resonance and thus
progress of SPR technology over the past few years has been examine the effectiveness of a system to sensitively measure small
assisted by the development of many affinity models and the wavelength changes, one normally uses a characteristic “Figure of
establishment of many preparation protocols for gold surfaces. Merit” (FOM) parameter:239 FOM = (Δλ/Δn)(1/Δω), where
However, SPR biosensors could still benefit from improved Δω is the full-width of the resonance (e.g., reflectivity) at half-
sensitivity in the detection of small analytes (typically less than maximum and Δλ is the resonance wavelength shift for a Δn
500 Da). Localized plasmon resonances of metallic nanostruc- change in refractive-index. The wavelength shift of an LSP peak
tures seem better suited and bring added functionalities, for with the refractive index of the surrounding medium is nearly
example spectral tunability; however, these resonances have linear so that the refractive index sensitivity, S, associated with a
nearly an order of magnitude lower sensitivity. In addition, LSPR particular type of nanoparticle is usually stated in nanometers of
are typically spectral very broad,37 which makes it difficult to peak shift per refractive index unit (nm/RIU): S = dλR/dn. The
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spectral sensitivities of LSPR and SLR features are typically of by diffraction phenomena and is typically similar to the period of
order 100−450 nm/RIU.37,238 the array Δλ/Δn ∼ d (200−450 nm/RIU), while the phase
The sensitivity S is usually normalized to give the FOM by sensitivity may reach 5 × 105 deg of phase shift per RIU,104 due to
dividing by the fwhm of the resonance dip (a sharper peak gives a very low reflectivity on resonance.39 To assess the applicability of
more precise indication of the resonance minimum posi- phase-sensitive SLRs for biosensing, Kravets et al.39 used a
tion).240,241 This FOM adequately quantifies the sensing calibrated and established protocol that employs the streptavi-
potential of plasmonic modes in configurations similar to those din−biotin system.247 Functionalization of the surface of a
used in commercial instruments, where the angular shift of the plasmonic (nanodot) structure with carboxylate groups was
resonance angle of incidence is changing quickly with angle and is carried out, and biotin was then attached to the resulting
used to detect changes in the refractive index at the surface. It carboxylate binding sites. Lastly, the biotin-covered nanodots
should be noted that SLRs do not exactly fit the Lorentzian were exposed to 10 pM of streptavidin (SA) solution in 10 mM
profile, which complicates the measurement of the width of the phosphate-buffered saline for a period of 3 h; this led to SA being
SLR. Recently an alternative figure of merit was suggested by bound to all the biotin sites. The binding of SA altered the phase
Becker et al.,242 termed FOM*, as another metric for comparison of the reflected light by ∼25° (at 710 nm) and incident at 53°.
of the sensing capabilities of different nanostructures. Complex This phase change corresponds to 20−100 SA molecules being
plasmonic nanostructures often do not have a simple, single line bound to each nanodot, so that the experimental LOD is just 1−4
shape so that FOM* is defined instead in terms of the relative molecules per nanodot. For a thermally stabilized system the
change in intensity dI/I at a given wavelength λ that results from resolution of phase measurements can exceed 5 × 10−3 deg;15
a small change dn in the local refractive index, thereby avoiding thus, in principle one might resolve the attachment of 0.004−
the line-width. This approach allows sensors based on changes in 0.02 SA molecules per nanodot or resolve <1 molecule being
intensity to be compared with those making use of peak shifts. bound to each square micron of device, with the total number of
For the latter (peak shift) type, FOM* can be written in terms of molecules detected in the illuminated area being ∼2000.39 This
the refractive index sensitivity S as FOM* = [S dI/dλ)/I]max = detection limit was 100−1000× better than achieved before
[(dI/dn)/I]max. Note that FOM* is based on the wavelength that using conventional plasmonic nanosensors where optical
yields the greatest intensity change with refractive index. intensity rather than phase is monitored37 and nearly 100×
It is known that typical FOMs and FOM*s do not exceed 8 lower than for the PSP approach.17−19
and 23, respectively, for the sensors based on LSP37,243 and Finally, SLRs open up access for novel and promising
PSP,244 respectively. The employment of SLRs enables one to nanoarchitectures for biosensing. As an example, Yanik et al.248
increase these parameters up to a factor of 100 or more. proposed an interesting architecture based on combining a very
Offermans et al.240 showed that SLRs in ordered arrays of gold dispersive Fano resonance with dark (subradiant) modes; they
NPs provide a sensing performance more than an order of employed a hole rather than a particle array (see section 7). The
magnitude better than the LSPRs associated with disordered observed resonances were due to incident light coupling to the
particle arrays. They found that the FOM scales similarly for Au, subradiant multipolar modes. Naked eye detection of just one
Ag, and Cu particles because the losses (Ohmic) in these metals monolayer of antibodies (mouse IgG antibody) was reported.
are all small. They used calculations based on arrays of coupled The lift-off free fabrication approach adopted by Yanik et al.248
dipoles to reproduce this universal scaling and further explained allows the frequency regime to be easily tuned by varying the
their results on the basis of a simple coupled oscillator model.240 structural parameters of the array. Arrays of rectangular metallic
Later studies245,246 experimentally demonstrated a high- antennas suitable for THz SLRs have also been suggested for a
performance refractive index sensor using a double-layered sensor-on-chip approach to liquid sensing,249 Such arrays could
metal grating (DMG) having FOM and FOM* values reaching perhaps be combined with a microfluidic system for in situ
38 and 40, respectively, for normal illumination. These high sensing.
FOM and FOM* values arise because of the sharp SLRs 9.6. Metallic Photonic Crystals for Biosensing
associated with coherent interference between the LSP of each
gold stripe and the diffracted light. It is important for sensing that Arrays of nanoparticles can also be combined with dielectric
such a hybrid guided mode confines a large proportion of the cavities to form metallic photonic (plasmonic) crystals
optical field between the upper and lower gold structures, leading (MPCs).213,250−253 Different optical sensors based on MPC
to remarkably narrow line widths. These authors additionally waveguides were reported to offer a sensitive test for
noted245,246 that DMGs may be made using a cost-effective and biomolecular interactions, potentially providing a practical
simple approach employing a combination of thin-film metal approach for label-free detection of specific bioreactions. The
deposition and two-beam optical interference lithography. In improvement in sensitivity was due to coupling of the waveguide
general, the employment of SLRs makes possible a very resonance mode and SLR.213,250−253 Giessen et al.250 proposed a
significant enhancement in both FOM and FOM* for plasmonic design of MPCs and explained its operation by a waveguide-
biosensing. As an example, Thackray et al.116 reported FOM*s mediated collective interaction process between light and gold
up to 120 under normal incidence of illuminating light together NPs. This approach offers a compact design when compared
with the analysis of resonant features in the transmitted light. with conventional devices based on arrays of NPs.37 The concept
of such sensors is based on the combination of a photonic
9.5. Lower Limit of Detection microcavity and nanostructures supporting SLRs; for example,
Surface lattice resonances may lead to substantial improvements metal nanorods placed appropriately above a metal mirror form a
in the lower limit of detection (LOD) for plasmonic biosensors. microcavity. The combination is thus a coupled photonic-
However, to record these LOD one must pass from spectral to plasmonic system.253 MPCs combined with waveguides have
phase sensitivity. As noted above in section 6, spectral and phase been demonstrated to enable efficient and sensitive detection of
sensitivities do not correlate with each other as they have the HIV-1 virus.254 A hybrid waveguide−plasmon system
different origins. For SLR the spectral sensitivity is conditioned consisting of a waveguide layer of ZrO2 upon which was placed
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Figure 26. (a) Atomic force microscope measurement of silk film thickness, for a 4 nm thick film. (b) Protein backbone vibrational modes associated
with Amide-I and II. (c) Reflectance spectra from the 1.6 μm periodic array before (dashed line) and after (solid line) coating with a 2 nm film of protein.
Vertical lines (dashed) mark the positions of the amide-I and II peak absorptions. (d) Spectral characteristics of the arrays before and after protein
coating, recorded as difference reflection spectra. Reproduced and adapted with permission from ref 257. Copyright 2009 National Academy of Sciences.
gold nanopillar arrays was also proposed.214,215 The momentum a biocompatible system. SERS Raman spectra from living cells
coupling between the PSPs and the waveguide modes comes were obtained with a near-IR laser source at very low pump
from the periodic arrangement of the metallic nanoparticles. On intensities. Spectra were obtained showing an enhancement of
passing from normal incidence to oblique incidence measure- the amplitude of the incident field of approximately 45 times.
ments, an increase in the FOM of up to 5 times was achieved. 9.8. SLRs and Solar Cells
New architectures based on nanocavity perfect absorbers were
proposed, which may also be integrated in biosensors to increase Plasmonics offers a novel means to improve the efficiency of solar
their FOM.255,256 In these works, metal−insulator−metal cells,41,260−266 especially through increased absorption of
(MIM) nanocavity arrays demonstrated good performance, incident sunlight.252 In particular, enhanced coupling of light
with a sensitivity to bulk refractive index changes equal to 300− from the sun into the active region of a semiconductor solar cell
400 nm/RIU at the near IR wavelengths. can be achieved via guiding and localization light at the nanoscale
9.7. SLRs and Spectroscopy using plasmonic nanoparticles covering such structures. Out-of-
plane lattice plasmons have been proposed as a way to bring
Another promising approach for biosensing brings together the together the advantage of LSPRs in individual nanoparticles
combination of SLRs and spectroscopic techniques. In particular, (high field-confinement) and the advantage of PSPs on
an approach based on the SLRs of metallic nanoantenna arrays continuous metal films (tunability of dispersion) in 2D metal−
was proposed for the direct detection of vibrational signatures insulator (MI) and metal−insulator−metal (MIM) struc-
using infrared absorption spectroscopy of a single protein tures;262−264 such architectures may also offer potential for
monolayer.248,257 Here the vibrational spectra from proteins chemical and biological sensing, photocatalysis, surface enhanced
were investigated at low concentration (zeptomole) and for spectroscopies, and photovoltaics. Moreover, plasmonic crystals
sensitivities amounting to <155 molecules per antenna. The composed of materials with more than one functionality, e.g. Ag,
plasmonic (near-field) character of the absorption enhancement Au, Pt, Pd, and metal/dielectric stacks, have been demon-
was shown using a ramped increase in protein film thicknesses,257
strated199 that may be useful for practical photonic applications.
and ultrasensitive collectively enhanced IR absorption (CEIRA)
Zhukovsky et al.265 demonstrated the SLRs could enhance and
spectroscopy was employed to identify the vibrational signature
control photoelectron emission in solar cells and Schottky barrier
of protein monolayers (silk fibroin). Figure 26(c) shows that the
photodetectors when plasmonic nanoparticle arrays are included.
protein absorption bands were resolved in spectra collected from
They showed that the interaction between broad-band LSPs and
the protein coated arrays (period 1.6 μm). Minima in the
reflectivity are associated with the plasmonic response, and narrow-band SLRs leads to a stronger local field enhancement. A
absorption due to the presence of amide II and I are indicated in notable increase in the photocurrent when compared with the
Figure 26(c) at 1,537 and 1,660 cm−1, respectively; the protein excitation of individual particles was found. These findings may
layer also produced a slight red-shift of the plasmonic resonance. be used to help design photodetectors having a tunable spectral
An ultrahigh FOM refractive index sensor based on a near- response and may detect photons whose energy is below the
infrared narrow-band plasmonic absorber was designed and bandgap of the semiconductor and to develop solar cells with
analyzed in ref 258. The system featured a good signal-to-noise improved efficiency.265 Crystalline Si nanopillar arrays on a Si
ratio (>250) together with a useful range of refractive indices; it substrate have huge potential in surface enhanced spectroscopy
also had a quality factor >110 and a wavelength tunability from and thin film solar cells.267 These SLR resonances are due to
800 nm to 1,500 nm. The design featured arrays of gold bowtie coherent oscillations in the nanopillars and can be tuned
nanoantennas with a metal−insulator−metal (MIM) config- spectrally via the nanopillar diameter and lattice period; they
uration. Such nanoantennas might be of use in a range of strongly suppress reflection from the Si surface. Further, the
applications, including reflective filtering, label-free biochemical reduced reflectivity is accompanied by an increased electro-
detection, optical trapping, heat-assisted magnetic recording, and magnetic field in the Si. The physical nature of the SLRs suggests
hot-electron generation. that not only does more electromagnetic energy becomes
Recently it was shown that a chemical analysis of living cells available for harvesting due to the suppressed scattering losses,
may be undertaken using out-of-plane plasmonic antennas.259 but it is also efficiently confined in a thin layer of the solar cell. It
The good adhesion between antennas and biological cells is worth noting that SLRs in a Si array system rely on localized
enables sensitive SERS analysis of cell membrane components in Mie resonances rather than plasmon modes.267
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Using a metal−dielectric composite “black-body” composed semiconductor alone. The Au core also leads to strong near-field
of a properly selected mixture of nanostructured plasmonic and enhancement, thus helping to increase the optical absorption
dielectric films, one can ensure that impedances are matched and efficiency. For the core−shell nanostructure based on the metal−
that substantial absorption of light over a wide optical frequency semiconductor combination, the thickness of semiconductor
range is achieved.260,261,266 In this case, the fact that the light shell should be carefully tuned because it significantly alters the
interacts with metal only within the skin depth looks promising, LSPR characteristics of photocatalysts.258 Other studies271,273
since only the electronic surface states of semiconductors also confirm that hybrid metal−dielectric nanostructures may
contribute to solar cell performance. In such blackbody help to enhance charge separation in a semiconductor and
nanostructures, plasmonic nanoparticles embedded in a improve the operation of photovoltaic and photocatalytic
dielectric matrix effectively enhance the optical path length for devices.
incident light by a factor of ∼50 due to the scattering of light by The authors of ref 275 demonstrated that a combination of
nanoparticles and subsequent total internal reflection. Recent near- and far-field coupling of LSPRs associated with nano-
investigations showed that the optical path enhancement can particles of aluminum deposited on titania (TiO2) films
break the limit for Lambertian surfaces due to the plasmonic significantly enhances (by 2 orders of magnitude) the photo-
trapping in structures inspired by the human eye retina.266 catalytic activity under visible light illumination of the semi-
conductor material. The excitations of SLRs result in enhanced
9.9. SLRs and Photocatalysis
rates of production of hot-electrons and thus lead to higher redox
The use of plasmonic structures to enable efficient combination reaction rates. Further, the authors of ref 276 show a correlation
of light-harvesting and catalytic functions in one material is between photocatalytic activity and waveguide-plasmon polar-
another distinctive feature of plasmonic nanostructures, one that iton excitation in Al nanowire gratings produced on thin TiO2
renders possible relatively high photocatalytic reaction rates. films. It was suggested that this may be due to hot-electron
Detailed descriptions of a wide range of photochemical reactions injection from aluminum nanowires into TiO2, a process that is
enhanced by surface plasmons can be found in the review by strengthened because of the increased absorption of visible light
Ueno and Misawa.268 The review summarized recent results on and a decreased radiative damping associated with the wave-
the application of plasmonic nanostructures for the development guide-plasmon polaritons.
of novel photochemical schemes, including photocatalysis, Recent work from Linic’s group277,278 demonstrates advances
nanolithography, water-splitting systems, and photovoltaic in photochemical catalysis on nanostructures of plasmonic
cells. In these systems, the plasmon-enhanced electric field metals. These authors pointed out that when optically excited the
plays a crucial role in both excitation and photochemical reaction plasmonic modes of metallic nanoparticles may promote
(e.g., photoinduced electron transfer reaction) processes.268 In chemical reactions directly on their surfaces. Furthermore, it
the near future we hope to find out whether a useful reduction of was shown277 that the process of charge transfer from plasmonic
carbon dioxide via photocatalytic reaction using near-infrared nanoparticles to photocatalytic materials causes specific and
light is possible in this way. direct excitation of electrons from occupied to unoccupied
The addition of metallic nanoparticles is now a widely adopted orbitals of the molecule−nanoparticle complex. These findings
approach to boost the phocatalytic performance of semi- indicate that the role of the local electronic structure in
conducting photoanodes.258,268−271 Regular arrays of metallic plasmonic photocatalysis is to a degree decoupled from the
nanoparticles located on the surface of the semiconductor role of LSPRs and that plasmonic nanomaterials may be tuned so
capture electrons produced by photoexcitation, thereby that when illuminated, selective enhancement of particular
increasing the electron−hole pair separation. It is hoped that chemical pathways occurs. The work of Linic’s group277,278
the use of plasmonic nanostructures to confine sunlight in small demonstrates ways to engineer plasmonic nanomaterials having
volumes will be an important element that promotes their use in resonance wavelengths that correspond to the charge excitation
the design of complex solar fuel photocatalysts.272 By altering the energies of photocatalytic structures. Perhaps plasmonic catalysts
shape and size of plasmonic nanostructures, the absorption band that selectively activate targeted chemical bonds could be
of composite photocatalysts may be extended into regions that produced, thereby opening several opportunities in the area of
are not accessible for standard semiconductors.269,270 As an selective chemical synthesis.
example, by adjusting the size of gold nanospheres (30−100 nm) 9.10. SLRs and Electrochemistry
fabricated on arrays of TiO2 nanowires, the absorption of
Frank et al.279 presented a nanostructure based on double-
photocatalysts in the spectral region 300 to 800 nm may be
layered NP stacks suitable for spectra-electrochemical applica-
enhanced, leading to increased incident photon-to-electron
tions. Their structure was based on a continuous gold layer upon
conversion efficiencies (IPCE).273 Plasmon-assisted water
which periodic arrays of tantalum pentoxide (Ta2O5) nanodisks
splitting was also verified by using gold nanorods (220 nm ×
were formed. On top of these dielectric discs, a further disc of
110 nm × 40 nm) arrayed on the surface of a single crystal
gold was added. To demonstrate the applicability of this structure
photoanode.274 The geometric arrangement of plasmonic for electrochemical analysis, potassium ferricyanide was used as a
nanostructures exerts a measurable influence on plasmonic standard redox compound and cyclic voltammetry (CV)
photocatalysts. Lin et al.258 designed Au@SiO2@CuO2 core− measurements undertaken. This area is largely unexplored and
shell nanostructures with the aim of enhancing broadband solar would benefit from further investigation.
absorption. In such nanostructures, the Au core converts the
incident light into LSPRs and then acts to transfer this energy to 9.11. SLRs and Magneto-Optics
the semiconducting shell (CuO2) via a process of resonant SLRs may also be used to enhance magnetic effects by (i) directly
energy transfer, thereby inducing charge separation in the using magnetic materials and (ii) indirectly using nano-
semiconductor. The dipole−dipole interaction between the metamaterials structures that exhibit magnetic dipole moments.
semiconductor CuO2 charge displacements and the Au plasmons Adopting the first of these approaches, Kataja et al. studied arrays
enhances the photovoltaic activity when compared with the of magnetic nanoparticles with a view to enhancing magneto-
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Figure 27. (a) Comparison between the extinction spectra of a single 60 nm diameter spherical Ag NP (orange line), a 60 nm spherical Co NP (blue
line), and the extinction spectra of a dimer (green line) formed by the interaction of these two NPs separated by a 1 nm gap as illustrated in the schematic
below. The dimer exhibits two peaks, one at 2.20 and the other at 2.89 eV; the first is at a much lower energy than the peaks associated with the isolated
Co NP and Ag NP, and the second is also lower in energy than the Co NP but at almost the same energy of the isolated Ag NP. (b) Electromagnetic field
enhancement (E/E0) distribution around the nanoparticle dimer at the two peak energies produced by the interaction of a plasmonic NP and a
nonoplasmonic ferromagnetic Co NP shown in panel A. The insets in the figure show higher resolution views of the field enhancement around the NP
dimer marked by the squares. Figure reproduced with permission from ref 282. Copyright 2014 American Chemical Society.
optical (MO) responses and so use magnetic fields to control tion would allow one to create new composite plasmonic
plasmonic systems and to tune the MO properties of individual nanomaterials with extremely promising magnetic function-
nanostructures.280 In a combined experimental and theoretical alities. From the technological point of view, one could envision
investigation, they found that rectangular magnetic nanoparticle several potential applications employing such magnetic meta-
arrays exhibit SLR modes and that the two lattice directions were materials, and one of these applications is in the field of magnetic
coupled by spin−orbit coupling in nanoparticles that may be data storage. Current hard disk devices (HDDs) with capacities
controlled via the magnetic field. The authors investigated the of several terabits of information have data storage cells with
interplay between the single-particle optical and magneto-optical dimensions of around 100 nm × 100 nm. The reduction of grain
response of magnetic nickel (Ni) particles on the one hand and sizes of magnetic materials to minimize the bit cell size could
their periodic arrangement on the other. Rectangular arrays of Ni increase the capacities of current HDDs; a problem, however, is
particles displayed SLRs, and this produced a strong and that storage for materials with grains below a certain size
spectrally narrow MO response. The polar Kerr effect and Kerr becomes unstable, while their magnetization may undergo
rotation were enhanced, at a specific wavelength, 4- and 3-fold, arbitrary changes due to thermal effects.283 The combination
respectively, when compared with a system of randomly oriented of plasmon-induced heating by light with ferromagnetic Co
particles. nanoislands (heat-assisted magnetic recording) enables one to
To enhance the MO response, Sachan et al.281 looked at a overcome limitations imposed by the grain size. As an example,
novel way to boost the strength of the response of individual Stipe et al.284 developed a recording device having a data density
nanoparticles by combining two materials, one plasmonic of 1.5 Pb m−2 by employing an integrated plasmonic antenna. It
(metallic) and the other ferromagnetic, to make individual is expected that the reports of ferroplasmons281,282 will inspire
nanostructures: they called the resulting resonance a “ferroplas- future work in this direction.
mon”. Hybridized resonances associated with these hetero- Arrays of elliptical nickel nanoantennas were studied by
dimers, formed by noble metal nanoparticles and ferromagnetic Maccaferri et al.285 They showed that the diffractive coupling in
metal nanoparticles, were also discussed in ref 281 and 282. The these arrays is dictated by two orthogonal and spectrally detuned
authors reported281,282 the excitation of sharp resonance modes in-plane plasmonic responses of the individual elements, one
in materials with nonexistent/highly damped surface plasmon directly induced by the incident light, the other produced
modes. Here, the hybridization of the Ag plasmonic mode at 2.89 through an external magnetic field being applied. This led to
eV with a strongly damped plasmon mode of Co located at 3.74 highly tunable and enhanced magneto-optical effects when
eV generated a lower energy LSPR mode at 2.2 eV, as soon as the compared with a continuous Ni film or compared with surfaces
nanospheres approach each other at close distances and another made from disordered noninteracting anisotropic magneto-
one at 2.89 eV with almost identical energy to that one of the plasmonic antennas. In another very interesting approach, Kataja
isolated Ag plasmon mode (Figure 27). The near-field et al.286 recently investigated the magneto-optical and optical
enhancement generated in the gap between the spheres, response of Au and Ni nanoparticles organized in a checker
determined at each of the peak energies, was ∼30 times bigger board configuration. Analysis of the optical fields indicate that
than the enhancement produced using isolated Ag spheres both the Au and Ni nanoparticles contribute to SLRs and thus to
excited at the lower (2.2 eV) energy modes, and 10 times bigger the magneto-optical activity of these hybrid arrays, the approach
than the enhancement at the higher (2.89 eV) energy modes may thus lead to new possibilities for the realization of tunable
(Figure 27). and sensitive magneto-plasmonic nanostructures. In addition, it
It would be interesting to see how arrays of these was shown that both the magneto-optical and the optical
ferroplasmonic heterodimers behave in terms of the SLRs they response of the hybrid arrays could be adjusted by altering the
support. We anticipate that high quality arrays of ordered size of the gold (nonmagnetic) nanoparticles. The concepts
nanoparticle structures with magnetic and plasmonic composi- presented in refs 171 and 285 show that novel magneto-
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plasmonic designs may lead to a variety of attractive effects based plasmonic nanodots is a very important factor for building
on SLRs including magnetic tunability of light polarization and metamaterials not only in the visible but also in the IR and
label-free sensing.287 terahertz regions. Singh et al.292 concluded that there is an
We mentioned at the beginning of this section that there is an optimal packaging density in metamaterials to induce the
alternative approach to achieving magnetic effects, that is strongest dispersion. Adjusting the period involved enables the
employing metamaterials; such an approach was investigated design of frequency selective surfaces that have an adjustable Q
by Tang et al.288 They used pairs of magnetic rods as the factor and may lead to the development of terahertz devices and
elements in their arrays. Such particles are known to exhibit components having a tunable refractive index of the substrate.292
magnetic effects owing to the displacement currents they Yang et al.293 realized SLRs in the terahertz range using a
support.129 Tang et al. suggested a way to enhance the magnetic metamaterial that comprised two particular split-ring resonators
fields at optical frequencies by using diffractive coupling of that supported extremely sharp trapped-modes. Their unit cell
magnetic surface plasmon resonances in 2D periodic arrays of structure dramatically reduced the radiative damping and
paired metal rods, a kind of metamaterial. The authors predicted improved the resonance quality. New designs of metamaterials
narrow-band hybrid plasmon/magnetic modes that occur for the terahertz region based on arrays of split ring resonators
because of the strong interaction between magnetic resonances were suggested by Manjappa et al.294 where a lattice-induced
and the collective surface lattice resonances of the array. transparency has been observed and explained through coupling
Magnetic fields in the pairs of metal rods were 5-fold greater of the first-order lattice mode to a structural resonance. Banon et
than the relevant fields of isolated individual pairs of metal rods. al.295 developed a method of calculating the angle-resolved
This strong magnetic field enhancement indicates there is much spectroscopic Mueller matrix describing SLRs of two-dimen-
potential for metamaterials; indeed, Tang et al. suggested that it sional plasmonic photonic crystals. Their method could be
may be possible to enhance the second-harmonic generation inverted to extract geometrical parameters of a rectangular array
using magnetic nonlinearities.288 (for a known geometrical shape of nanoparticles) from
9.12. SLRs and Liquid Crystals experimentally measured ellipsometry data. Wang et al.296 also
made use of Mueller matrix spectra to investigate complex
Another promising external field modulation can be provided anisotropic optical nanostructures in the presence of SLRs. They
using liquid crystals (LCs) in combination with plasmonic suggested that Mueller matrix spectroscopic ellipsometry is ideal
nanoarrays. Li et al.289 proposed devices consisting of a 1D for fast, noninvasive, and precise metrology of all plasmonic
periodic Au nanoparticle array immersed in an aligned nematic modes existing in plasmonic metasurfaces. Yang et al.45 have
LC cell. In such a cell, the spectral position of SLR may be demonstrated programmable engineering of ultranarrow reso-
controlled through the application of a voltage so as to change nances across the visible regime. They made arrays of aluminum
the relative orientation between the optical axis of the LC and the nanoparticles immersed in an elastomeric slab that showed high-
incident light. The spectral tunability was proportional to the quality SLRs features with line widths down to 3 nm. Such
index difference Δn = ne − no of the LC and the interparticle elastomeric slabs allow dynamic modulation of interparticle
distance, which was as large as 100 nm. It was shown that the spacing, allowing selective access to and optimization of either
resonance could shift by as high as 100 nm, leading to high dipolar or quadrupolar lattice modes. This offers a new approach
sensitivity when the system is used for sensing or switching for real-time tunable materials, of interest for biosensing,
operations. An electrically tunable if rather complex plasmonic fluorescence enhancement, photocatalysis, and plasmonic nano-
crystal with a nematic LC layer on its surface was reported in ref lasers.
290. The associated coupled surface lattice mode has its electric
field mostly normal to the surface, making the coupled resonance 9.14. Section Summary
sensitive to molecular reorientation of the LC. It was shown that SLRs provide a generic platform for research in a number of
the SLRs could be red-shifted by 8 nm with an associated 35% topical areas of science and technology.
change in the relative transmission light intensity through the
application of external voltages to the LC layer, thereby 10. GENERAL SUMMARY
producing an SLR-LC optical modulator.
To summarize, metal nanoparticles arranged in ordered 1D or
9.13. Other Applications 2D arrays can produce remarkably narrow plasmon resonances
Liu et al.272 demonstrated that a pair of orthogonal electric down to 1−2 nm in spectral width due to diffractive coupling of
dipolar and optically induced magnetic dipolar resonances can be the localized plasmon resonances associated with individual
excited in arrays of various configurations of metal-core/ nanoparticles. These coupled resonances can be understood
dielectric-shell NPs. These two resonant modes can interfere reasonably well within the framework of the coupled dipole
simultaneously with SLRs of the periodic array via diffractive approximation (modified if necessary). SLRs manifest them-
coupling, opening new opportunities for near-field manipu- selves in reflection, transmission, extinction, and absorption with
lations, which may find applications in nonlinear switching in as little as 50 particles required to achieve narrowing of the
plasmonic nanostructures and metamaterials. Collective effects plasmonic resonances. Positional disorder in the array suppresses
in arrays of meta-molecules based on plasmonic double antennas SLRs while particle size disorder makes them wider. SLRs are an
were also studied.291 Collective behavior in this structure was important consequence of the interaction of nanoparticle arrays
observed through experiment and found to differ substantially with light: they were observed for various array geometries and
from that observed using single-antenna counterparts. These various shapes and forms of the nanoparticles. In general,
results indicate that plasmonic metamaterials that exhibit diffraction edge phenomena accompany the formation of SLRs.
collective effects are very sensitive to the topology and design An homogeneous (symmetric) refractive index environment is
of the meta-molecules they comprise and perhaps offer the helpful but not necessary for the observation of SLRs; indeed,
prospect new approaches to the design of metamaterials with SLRs have been observed in asymmetric environments for
engineered optical properties. Dense packing of arrays of oblique light incidence and/or relatively large nanoparticles
5943 DOI: 10.1021/acs.chemrev.8b00243
Chem. Rev. 2018, 118, 5912−5951
Chemical Reviews Review
(where out-of-plane modes could be important). The longer the Director position of the French National Center of Scientific Research
SLR wavelength, then the higher the resonance quality that may (CNRS) in Aix-Marseille Univ, Marseille, France. He is also a scientific
be achieved, with quality factors reaching 300 in the near-infrared supervisor of Institute of Engineering Physics for Biomedicine and of
and 500 in the mid-infrared. One of the many useful properties of International Laboratory “Bionanophotonics” in MEPHI, Moscow,
SLRs is the fact that they can provide topologically protected Russia, as well as holding faculty positions in the Institute of Lasers,
zero refection of light with improved phase sensitivity to binding Photonics and Biophotonics in State University of New York at Buffalo
events. At the same time, the directional properties of SLRs (USA) and the University of Sherbrooke (Canada).
combined with spectral selectivity could provide a platform to
Bill Barnes is Professor of Photonics at the Department of Physics and
enhance the directional emission of light and to control LEDs
Astronomy at the University of Exeter, UK. He leads a research group
and lasers. In addition, SLRs present a natural way to couple light
that is now focused on light−matter interactions, especially those
to 2D materials and heterostructures which is an active and
exciting area of research. involving molecular materials. He was awarded B.Sc. (1983) and Ph.D.
The success story for surface lattice resonances comes from an (1987) degrees by the University of Exeter before spending several years
intriguing redistribution of the electromagnetic field associated as a postdoc at the University of Southampton, UK, working on optical
with an incident wave through the use of diffractive coupling fiber lasers and amplifiers. He is fortunate to currently hold a European
from ordered plasmonic arrays in such a way that the field is Research Council Advanced Investigator Award (AdG-photmat-
concentrated near the plane of the array. This leads to a range of 742222).
characteristic properties for SLRs: stronger field enhancement as Alexander Grigorenko is Professor of Physics at the School of Physics
compared to LSPR, ultranarrow widths of plasmon resonances, and Astronomy at the University of Manchester, UK. He leads a nano-
strong light extinction at SLR, and the absence of reflection optics lab which studies light−matter interactions at the nanoscale. He
under some conditions. From the many applications discussed was awarded MPhys (1986) and Ph.D. (1989) degrees by the Moscow
above it is clear that plasmonic arrays supporting SLRs strongly Institute of Physics and Technology. Before Manchester, he worked as a
enhance light−matter interaction in 2D. By coupling surface senior researcher at the A.M. Prokhorov General Physics Institute,
lattice modes with various types of molecules and media, one can Moscow, Russia, and as PDRA at Bath and Plymouth Universities. His
achieve ultrasensitive biodetection, improved photovoltaic cells, research interests include optics, magnetism, superconductors,
new optoelectronic and communication devices, more efficient plasmonics, hybrid 2D materials, and photochemisty.
photocatalysis, enhanced magneto-optical signals, advanced
liquid crystal devices, and new metamaterials. This list is growing
quickly, with new applications of SLRs emerging to tackle various ACKNOWLEDGMENTS
scientific and technological problems. WLB would like to acknowledge support from the EPSRC (EP/
K041150/1) and ERC-AdG-742222(photmat). ANG acknowl-
AUTHOR INFORMATION edges the support from the European Union’s Horizon 2020
Corresponding Authors research and innovation programme under grant agreement No.
*A.N.G.: E-mail, [email protected]. 696656 “GrapheneCore1”, the EPSRC (EP/K011022/1), and
*W.L.B.: E-mail, [email protected]. SONY research grant agreement. AVK acknowledges the
support from Excellence Initiative of Aix-Marseille Univ -
ORCID
A*MIDEX, a French “Investissements d’Avenir” program,
A. V. Kabashin: 0000-0003-1549-7198 ITMO “Plan Cancer 2014−2019” INSERM program and
W. L. Barnes: 0000-0002-9474-5534 Competitiveness Program of MEPHI.
A. N. Grigorenko: 0000-0002-4109-2672
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