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Light−Matter Interactions in Hybrid Material Metasurfaces

Jun Guan, Jeong-Eun Park, Shikai Deng, Max J. H. Tan, Jingtian Hu, and Teri W. Odom*

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metasurfaces with emissive or stimuli-responsive materials for manipulating light−matter

interactions at the nanoscale. Metasurfaces, engineered planar structures with rationally
designed building blocks, can change the local phase and intensity of electromagnetic waves
at the subwavelength unit level and offers more degrees of freedom to control the flow of
light. A combination of metasurfaces and nanoscale emitters facilitates access to weak and
strong coupling regimes for enhanced photoluminescence, nanoscale lasing, controlled
quantum emission, and formation of exciton−polaritons. In addition to emissive materials,
functional materials that respond to external stimuli can be combined with metasurfaces to
engineer tunable nanophotonic devices. Emerging metasurface designs including surface-
functionalized, chemically tunable, and multilayer hybrid metasurfaces open prospects for
diverse applications, including photocatalysis, sensing, displays, and quantum information.

CONTENTS 3.2.2. Other Mechanical Approaches 15190

3.3. Electrical Tuning of Hybrid Material Meta-
1. Introduction 15178 surfaces 15191
1.1. Metasurfaces: Flat Optics 15179 3.3.1. Graphene and Semiconductors with
1.1.1. Choice of Metasurface Materials 15179 Plasmonic Metasurfaces 15191
1.1.2. Optical Response of a Single Unit 15180 3.3.2. Phase-Change Materials and Liquid
1.1.3. Structural Engineering 15180 Crystals with Metasurfaces 15192
1.1.4. Design Approaches 15180 4. Summary and Outlook 15194
1.2. Light−Matter Interactions with Optical Res- 4.1. Emerging Metasurface Designs 15194
onators: Building toward Metasurfaces 15181 4.1.1. Surface Functionalized Metasurfaces 15194
1.2.1. Fundamentals of Light−Matter Interac- 4.1.2. Chemically Tunable Metasurfaces 15194
tions 15181 4.1.3. Multilayer Hybrid Metasurfaces 15195
1.2.2. Overview of Common Hybrid Cavity- 4.2. Future Prospects 15195
Emitter Systems 15182 4.2.1. Coupling of Metasurfaces and 2D
2. Integration of Emitters and Metasurfaces 15182 Materials 15195
2.1. Weak Coupling in Hybrid Material Meta- 4.2.2. Lasing with Complex Characteristics 15195
surfaces 15182 4.2.3. Polariton Chemistry 15195
2.1.1. Enhanced Photoluminescence 15182 4.2.4. Parity-Time Symmetry 15195
2.1.2. Nanoscale Lasing 15183 4.2.5. Information Processing and Computa-
2.1.3. Quantum Prospects 15185 tion 15195
2.2. Strong Coupling in Hybrid Material Meta- 4.3. Summary 15196
surfaces 15187 Author Information 15196
2.2.1. Strong Coupling with Plasmonic Meta- Corresponding Author 15196
surfaces 15187 Authors 15196
2.2.2. Strong Coupling with Dielectric Meta-
surfaces 15189
3. Combination of Stimuli-Responsive Materials Special Issue: Chemistry of Metamaterials
and Metasurfaces 15189
Received: January 4, 2022
3.1. Static Metasurfaces 15189
Published: June 28, 2022
3.2. Mechanical Control of Hybrid Material
Metasurfaces 15190
3.2.1. Stretching of Elastomeric Substrates 15190

© 2022 American Chemical Society https://doi.org/10.1021/acs.chemrev.2c00011

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Figure 1. Choice of materials for metasurface designs. (a) The material parameters including carrier concentration (maximum doping
concentration for semiconductors), carrier mobility, and interband losses form the optimization space. The labels infrared, near-IR, visible, and UV
indicate the spectral range of the plasma frequency at the given carrier concentration. (b) Table of materials. ωp is the plasma frequency and γ is the
momentum scattering rate that quantifies the loss. Panel a was adapted from ref 31 with permission. Copyright 2011 American Association for the
Advancement of Science (AAAS). Panel b was adapted from ref 38 with permission. Copyright 2018 American Chemical Society (ACS).

Notes 15196 mirrors, metasurfaces can function as open cavity architectures

Biographies 15196
Acknowledgments 15196
References 15197
1. INTRODUCTION
Metasurfaces, engineered substrates with rationally designed
building blocks, enable exquisite control over light propaga-
tion.1,2 Compared to bulk optical components that manipulate
light by refraction, reflection, and diffraction, metasurfaces
control the local phase and intensity of electromagnetic waves
at the unit level, which enables more degrees of freedom for
tailoring optical properties.3−7 As an early demonstration, an
array of plasmonic V-shape nanoantennas with different
geometries was designed to exhibit spatially varying wavefronts
that produced anomalous reflection and refraction.3 Other
recent examples of the engineering of metasurfaces have
resulted in properties important for lensing,8−10 hologra-
phy,11−14 and optical cloaking.15−17
Besides opening opportunities in photonics, metasurfaces
provide a programmable platform for polariton chemistry,
chemical sensing, and photocatalysis. In contrast to conven-
tional Fabry−Perot cavities that trap light between two parallel
15178
where light confinement can be achieved by structural design
of the building units.18,19 Coupling quantum emitters to
metasurfaces can produce hybrid exciton-polariton states that
are promising for improved photochemical reactivity, long-
range energy transfer, and modified charge transport.20,21
Metasurfaces can also be used as chemical and biological
sensors for rapid, label-free, and sensitive detection, where
analyte binding increases the local refractive index, resulting in
a wavelength shift of the optical resonances.22 Recently,
pixelated metasurfaces composed of an array of high-quality-
factor metasurface units has functioned as a mid-infrared
wavelength sensor for enhancing, detecting, and differentiating
the absorption fingerprints of various molecules.23 In addition,
metasurfaces can improve the efficiency of photocatalytic
processes.24,25 Dielectric metasurfaces based on catalytic
materials such as titanium dioxide (TiO2) can accelerate
chemical reactions or improve responses selectively at designer
wavelengths.24 Plasmonic metasurfaces based on Cu/Pt core−
shell nanoparticles (NPs) show increased catalytic activity
under white light illumination compared to dark conditions.25
Depending on the materials of the building blocks, optical
metasurfaces can be broadly divided into two categories:
plasmonic metasurfaces and dielectric metasurfaces. Plasmonic
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Figure 2. Metasurface design. (a) Plasmonic NPs support electric dipole (ED) or electric quadrupole (EQ) modes depending on the size of the
NP. (b) Dielectric NPs support ED, EQ, magnetic dipole (MD), and magnetic quadrupole (MQ) modes. (c) Phase-gradient metasurface where the
antennas operate individually without diffractive coupling. Light steering results from the change of size, shape, and orientation of NPs. (d)
Metasurfaces consisting of diffractively coupled NPs. The photonic band structure and near-field distributions can be manipulated by the size and
shape of NPs and the geometry of the lattice. Panel a was adapted from ref 68 with permission. Copyright 2019 ACS. Panel b was adapted from ref
26 with permission. Copyright 2021 ACS. Panel d was adapted from ref 59, ref 3, and ref 62 with permission. Copyright 2012 ACS, 2011 AAAS,
and 2016 AAAS. Panel f was adapted from ref 100, ref 64, and ref 68 with permission. Copyright 2020 ACS, 2019 Wiley-VCH, 2019 ACS.

metasurfaces rely on surface plasmon oscillations of sub-
wavelength metal NPs,19 and dielectric metasurfaces are based
on Mie scattering of high-index dielectric particles.26 To
advance the applications of miniaturized flat devices, multi-
functional and tunable photonic architectures are required. In
this Review, we will focus on hybrid material metasurfaces.
These hybrid metasurfaces combine plasmonic and dielectric
metasurfaces with emissive materials such as organic dyes,
upconversion NPs (UCNPs), and quantum dots (QDs), and
can support enhanced photoluminescence (PL), lasing, and
quantum phenomena. In addition, we will discuss stimuli-
responsive hybrid metasurfaces that combine metasurfaces
with functional materials such as stretchable elastomers, 2D
materials, phase-change materials, and liquid crystals.
1.1. Metasurfaces: Flat Optics
1.1.1. Choice of Metasurface Materials. The optical
properties of materials can generally be described by the
parameters permittivity (ε) and permeability (μ) that quantify
the response of the material to electromagnetic waves.27
Because the magnetic responses of natural materials are weak
at optical frequencies (300 GHz to 3000 THz), only the
permittivity is needed to describe optical materials.27 The real
part of the permittivity (ε′) defines the motion of free and
bound charges in the material, and the imaginary part (ε″)
defines the optical losses.28 At optical frequencies, metals have
a negative ε′ and large ε″ because of electronic transitions,29,30
and dielectric materials show a positive ε′, and ε″ can be close
to zero.29
Figure 1a summarizes common metasurface materials and
their corresponding wavelength ranges.31 Among metals, Au
and Ag have received the most attention as plasmonic
materials in the visible and near-infrared (NIR) wavelength
15179
ranges because of their relatively low losses.32 Although Cu has
a permittivity similar to Au, its use has been limited because
Cu is susceptible to oxidation, which results in damping from
inelastic electron scattering at the Cu/CuOx interface.33 In
contrast to noble metals, Al has a d-band above its Fermi
energy, which allows for the plasmon resonances to extend
beyond the visible range into the ultraviolet range.34,35 Alkali
metals, such as Na and K, are predicted to exhibit a strong
plasmonic response at visible wavelengths but cannot easily be
integrated into devices because of their extreme chemical
reactivity.29,36
Doped semiconductors (e.g., InGaAs), transparent oxides
(e.g., ITO, AZO), and nitrides (e.g., TiN, ZrN) have also been
investigated as alternative plasmonic materials.37,38 The
plasmonic properties can be adjusted by doping, where larger
carrier concentrations result in higher plasmon frequen-
cies.39,40 Because of doping density limitations in semi-
conductors (∼1019 carriers cm−3), their plasmonic applications
cannot readily access NIR and visible wavelengths.31 For
operation in the NIR range, higher doping densities (1021
carriers cm−3) are needed and can be realized in transparent
oxides.28 Another category of plasmonic materials includes
ceramics. TiN is a promising example whose dielectric
constants are close to Au at NIR wavelengths (Figure
1b).41,42 Also, TiN has advantages over pure metals, including
CMOS compatibility, high-temperature stability, and mechan-
ical robustness.43
For dielectric metasurfaces, high-refractive-index materials
are often used (Figure 1a). Across the visible and NIR spectral
range, semiconductors such as Si, Ge, and AlGaAs have large
refractive indices.44 In the mid-IR range, narrowband semi-
conductors such as Te and PbTe, and polar crystals such as
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SiC, are of interest.44 TiO2 is another common dielectric
material because of its transparency and relatively high index,45
and TiO2 metasurfaces have enabled dynamic control of
photochemistry processes, including photocatalytic reactions.24
1.1.2. Optical Response of a Single Unit. The optical
properties of a plasmonic NP are determined by the collective
oscillations of their conduction electrons, known as localized
surface plasmons (LSPs)30,46 (Figure 2a). Under light, the
conduction electrons oscillate coherently with the external
electromagnetic field, which results in far-field scattering and
near-field enhancement of electric fields. The resonance
wavelength can be tuned by changing the material, size,
shape, and dielectric environment of the particles.30 When the
particle size is much smaller than the wavelength of light (D ≪
λ, where D is the NP diameter, and λ is the wavelength), only
electric dipole (ED) resonances are supported.47,48 Higher
order LSP resonances such as electric quadrupole (EQ) modes
can be excited by increasing the particle size or tailoring the
shape.49,50 For example, large nanorods or triangular NPs can
show EQ modes where half of the electron cloud moves
parallel to the applied field and half moves antiparallel.30,50
Depending on the polarization of the incident light, in-plane
and out-of-plane LSP modes can be excited selectively to
produce different electric near-field distributions.51
High-index dielectric nanostructures can support Mie-type
resonances with low losses (Figure 2b).26 Mie resonances
occur when the NP size is comparable to the effective
wavelength of light (D ≈ λ/n, where n is the refractive index of
the material). In contrast to plasmonic units, dielectric NPs
support both electric and magnetic modes, and the strong
magnetic response results from field penetration and phase
retardation inside the NPs.52 Four types of fundamental Mie
resonances of dielectric NPs include ED and magnetic dipole
(MD) modes as well as higher order EQ and magnetic
quadrupole (MQ) modes (Figure 2b). Because dielectric NPs
show simultaneous excitation of strong electric and magnetic
resonances, manipulation of constructive or destructive
interferences among these modes can result in unusual spatial
scattering characteristics.26,53 For example, the Kerker effect
resulting from interference between multiple Mie modes can
increase the forward-scattered fields and suppress backward
scattering.54,55
1.1.3. Structural Engineering. Similar to solids, where
the atom type and crystal symmetry affect the electronic
properties,56 artificial solids made of photonic structures can
show unprecedented optical responses determined by the
design of individual units and lattice geometry.57,58 In contrast
to diffractive optical elements such as periodic gratings, a key
distinguishing feature of metasurfaces is that their optical
properties can be significantly influenced by the resonant
characteristics of their building blocks. Hence, metasurfaces
can not only steer light at the lattice level but can also strongly
manipulate local phases by the size, shape, and orientations of
NPs at the individual unit level, which provide more degrees of
freedom to control the near-field and far-field properties.
One category of metasurfaces are phase-gradient meta-
surfaces, where the different antennas operate individually
without coupling1,2 (Figure 2c). Because the antenna units in a
metasurface can provide an abrupt phase jump in response to
an incident wave, Snell’s laws can be generalized:3
d designed analytically based on wave-optics principles or
nt sin t ni sin i =
2 dx (1)
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d
ni sin r ni sin i =
2 dx (2)
where λ is the free space wavelength, ni and nt are the refractive
indices of the two media, θi, θr and θt are the incident, reflected
and refracted angles, respectively, and dϕ/dx is the gradient in
phase discontinuity along the interface. For optimal efficiency,
the units of phase-gradient metasurface need to induce phase
delays that cover the full 0−2π range. Spatially varying the size,
shape, or orientation of the antennas enables the metasurface
to show a phase discontinuity with an arbitrary scattered
wavefront (Figure 2d). For example, incident light can be
steered to a single anomalous reflection channel using NPs
with different sizes59 (Figure 2d, left). Other designs based on
various antenna shapes such as V,3 C,60 and U61 can induce
magnetic moments in the units, which allows full 2π phase
control for desired reflection and transmission (Figure 2d,
middle). Circularly polarized light can be generated from an
array of gold nanorods with spatially varying orientations,
where the amplitude of the scattered waves can be controlled
by nanorod length and phase by orientation62 (Figure 2d,
right).
A second category of metasurfaces exploits diffractive
coupling of nanostructures in a periodic array57 (Figure 2e).
In plasmonic metasurfaces, the coupling of LSP modes from
individual NPs with the diffraction modes from the lattice can
produce surface lattice resonances (SLRs).47,48,63 At resonance,
the collective oscillations of free electrons in plasmonic NPs
enable the formation of a standing wave in the plane of the
lattice. In the coupled dipole theory, each particle is treated as
a single-dipole resonator with polarizability αNP, and the
effective array polarization can be written as the sum (S) of the
incident and radiated fields from all other dipoles. When the
real part of (1/αNP − S) vanishes, the imaginary part of the
dipole sum is also reduced, resulting in a narrow SLR peak in
the extinction spectra. The SLR properties can be controlled
by changing the size and shape of the single units and the
geometry of the lattice49,64,65 (Figure 2f). When the NP size is
much smaller than the lattice periodicity (Figure 2f, left), only
dipolar SLRs are produced;48 increasing the NP size in a given
array can introduce ultrasharp SLR resonances based on
overlapped out-of-plane ED and EQ charge oscillations.49,66
Different types of SLRs can also be generated in a single
structure by changing the NP shape.64,67 For example, a
nanocrescent lattice (Figure 2f, middle) allows the excitation of
either ED or EQ SLR modes depending on the polarization of
incident light.64 Also, hierarchical hybridization�hybridization
of same-order LSPs (ED or EQ) between lattice sites as well as
different-order LSPs (ED and EQ) at the same lattice site�
can result in asymmetric electric near-field distributions in non-
Bravais honeycomb lattices68 (Figure 2f, right). Similar to
plasmonic SLRs, collective coupling of Mie resonances in
dielectric NP lattices can produce Mie-SLRs (M-SLRs).69,70
Interferences of photonic modes, such as ED, MD modes in
dielectric metasurfaces have enabled bound states in the
continuum (BIC), which are optically dark states with high
quality factors (Q > 105).53,71 Different types of symmetry-
protected BICs can be supported at the Γ point from dielectric
metasurfaces, including out-of-plane MD modes, out-of-plane
ED modes, and MQ modes.72
1.1.4. Design Approaches. Metasurfaces have been
inversely by heuristic or machine-learning methods. Typically,
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the design of metasurfaces for a targeted optical response relies where g quantifies the rate of energy exchange between the
on arranging the subwavelength units based on desired emitter and the cavity. The coupling strength can be written as
wavefront phase profiles.1,73 For example, ultrathin beam
g Nf where ℏω is the photon energy, εr is the relative
deflectors can be designed by arranging the meta-units to rV
induce a linear phase variation along the interface,74 and lenses permittivity, V is the mode volume, N is the number of
can be realized by spherical wavefront phases.75 Anisotropic emitters, and f is the oscillator strength (f ∝ μ2, μ is the
phase units can also tailor simultaneously the modulation of transition dipole moment of an emitter).94,95 Without coupling
light76 and enable the generation of all polarization states (g = 0), the eigenstates of the system are the same as those of
based on Pancharatnam−Berry-phase-modulation methods.77 the uncoupled emitter and resonator. A comparison of g with
Analytical methods are straightforward and accurate for simple the cavity decay rate (κ) and spontaneous emission decay rate
structures. However, when the geometry and spatial arrange- (Γ0) determines whether the system is in a weak or strong
ments of the structure are complicated, identification of the coupling regime (Figure 3a).
optimized nanostructures for a desired property becomes
difficult. Although electromagnetic simulations can calculate
the optical responses of complicated structures by discretizing
Maxwell’s equations spatially and temporally,78 fine-tuning of
the NP design and arrangements with iterative simulations are
needed to approach the targeted responses.
The inverse design method can predict structures based on a
desired optical performance.79 Optimization algorithms can
search large design spaces efficiently, and nonintuitive,
irregularly shaped photonic structures have been identified to
show improved properties over empirically designed struc-
tures.80−82 Evolutionary design methods can be used to predict
dielectric units easily because the constituent materials are not
lossy; however, these strategies encounter challenges with
plasmonic materials. A key problem in achieving a desired far-
field optical response from metal nanostructures at visible
wavelengths is how to account for losses at the plasma
frequency.83,84 By combining finite-difference time-domain
methods with genetic algorithms, manipulation of the flow of
visible light into distinct profiles in 3D space has been
achieved.42,85,86
For complex designs in a multiconstrained problem, deep
learning has advantages because of its data-driven method-
ology.87 This approach provides a computational model
consisting of multilayers of processing units to learn multiple
levels of abstraction for any data.88 Compared to case-by-case
numerical simulations, deep-learning-based models can be
used to discover nonintuitive relationships between a metasur-
face and its optical properties from a large number of training
examples, which offers more design flexibility and higher Figure 3. Light−matter interactions. (a) Scheme of a hybrid system
efficiency.89,90 consists of a single emitter and a single resonator. (b) Enhanced
1.2. Light−Matter Interactions with Optical Resonators: radiative decay rate and (c) experimental manifestation of Purcell
Building toward Metasurfaces effect in a weak coupling regime. (d) Hybridization energy diagram
and (e) experimental signatures in a strong coupling regime.
Interactions between light and matter are important for areas
ranging from spectroscopy to sensing to quantum technologies.
Here, we introduce principles of light-emitter coupling with When g < κ or g < Γ0, losses dominate the system, and
single building units and give an overview of different hybrid emitter properties are only modestly perturbed by the presence
metasurface systems. of the cavity. The enhanced spontaneous emission rate (γ) of
1.2.1. Fundamentals of Light−Matter Interactions. an emitter in the cavity compared to an emitter in free space
The simplest hybrid system consists of a single emitter with a (Figure 3b) is described by the Purcell factor, Fp, which defines
two-level electronic transition and a resonator with a single the ratio between the decay rate in the presence and absence of
electromagnetic mode. When the emitter in an excited state an optical cavity
interacts with the optical mode of the cavity, the Hamiltonian Ncav /V 3( /n)3 Q
cav
that described the full system, Htot, can be described by a Fp = = =
combination of three Hamiltonians: Hexcition, the excitonic 0 N0/V 4 2V (4)
excitation Hamiltonian, Hphoton, the light-field excitation
Hamiltonian, and Hint, the Jaynes−Cummings interaction where Q = is the quality factor, and n is the refractive
Hamiltonian that describes the interaction of the field with index of the cavity material.96 This enhancement can also be
the emitter via a coupling strength (g) (eq 3).91−93 understood in the context of cavity quantum electrodynamics,
with the optical resonator providing an increased local density
Htot = Hexciton + Hphoton + Hint (3) of states (LDOS).94 In experiments, the Purcell effect is
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manifested as an increase in emission intensity and a reduced
excited-state lifetime of emitters inside the resonator (Figure
3c).
When g > κ and Γ0, the rate of energy exchange between the
emitter and cavity is faster than the rates of other loss
mechanisms. Reversible energy transfer results in the hybrid-
ization between the photonic mode and the electronic
transition, and two new hybrid modes called exciton−
polaritons form. According to the Jaynes−Cumming model
(eq 3), two new mixed eigenstates (Figure 3d) can be
described as92,96
1 This section will discuss properties of hybrid material
E± = [Ephoton + Eexciton ± 4g 2 + (Ephoton Eexciton)2 ]
2 metasurfaces in two coupling regimes: (1) weak coupling,
(5)
The energy separation between the two eigenstates is called
the Rabi splitting (Ω); at the resonant condition (Ephoton =
Eexciton ≡ E), E± = E ± g then Ω = 2g. Experimental evidence
for the formation of polaritons includes peak splitting and
anticrossing behavior of the two original modes (Figure 3e).
1.2.2. Overview of Common Hybrid Cavity-Emitter
Systems. The earliest hybrid metasurfaces were combined
with organic emitters such as fluorophores97 because of their
large oscillator strengths f (>107 μm−3)98 (Figure 4); however,
Figure 4. Excitonic materials for coupling with metasurfaces. Scheme
illustrates the integration of plasmonic and dielectric metasurfaces
with various excitonic materials such as a organic dye, QD, UCNP,
TMD, and CNT. TMD image taken from ref 170 with permission.
Copyright 2019 ACS. CNT image taken from ref 172 with
permission. Copyright 2019 ACS.
they are prone to photobleaching under optical excitation.99
Higher photostability emitters include transition metal
dichalcogenide (TMD) materials (f ∼ 106 μm−3)98 and
single-walled carbon nanotubes (CNTs). Semiconducting QDs
and UCNPs are also attractive materials because of their
unique emission characteristics such as high PL efficiency or
photon upconversion even though they have relatively small f
compared to other emitters.100−103
Both plasmonic and dielectric metasurfaces offer open cavity
architectures that can be readily integrated with excitonic
materials. As discussed earlier, the mode volume V and quality
factor Q describe the spatial and temporal confinement of light
inside a cavity.94 Canonical Fabry−Perot cavities composed of
two parallel mirrors can support high Q values (>105)104 and
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relatively large volumes (μm3).105 In contrast, plasmonic
cavities confine electromagnetic energy into deep-subwave-
length or nm3-scale volumes.94 Compared to metal films or
single plasmonic NPs, plasmonic metasurfaces provide spatially
delocalized but collective SLRs with both plasmonic and
photonic characteristics.63 In addition, high-index dielectric
NP lattices are promising cavities that can overcome high
absorption and radiation losses in plasmonic metals at optical
frequencies.106
2. INTEGRATION OF EMITTERS AND METASURFACES
where emission is enhanced; and (2) strong coupling, where
exciton-polariton modes are formed. In the weak coupling part,
we will first discuss how metasurfaces enable enhanced PL and
faster exciton decay rates. Next, we will introduce how
metasurfaces can function as optical nanocavities for lasing
action and how the lasing emission direction, wavelength, and
polarization can be manipulated by the structural design of the
metasurfaces. Last, we will discuss metasurfaces in quantum
applications, such as enhancing single-photon generation and
imaging of quantum emitters. In the strong coupling part, we
will review the responses from plasmonic and dielectric
metasurfaces combined with a diverse range of emitters and
exciton−polaritons with different magnitudes of Rabi splitting.
2.1. Weak Coupling in Hybrid Material Metasurfaces
2.1.1. Enhanced Photoluminescence. Metasurfaces
coupled with emitters show enhanced light emission that
follows the dispersive properties of the modes in their photonic
band diagrams.18,107 For plasmonic metasurfaces, the enhanced
PL results from the overlap of the SLR modes with the
emission bandwidth. In early work, rectangular arrays of Au
nanorods were combined with organic dye molecules dispersed
in polymer matrices.108,109 Selective excitation of emitters by
coupling to either dipolar (±1,0) SLR or multipolar (0,±1)
SLR modes was possible based on the polarization of the pump
excitation, with the fluorescence intensity enhanced up to 10-
fold. To improve this enhancement even more, strategies to
orient the transition dipole moments of the emitters have been
pursued. Metal organic frameworks (MOFs) are an ideal
platform to organize organic emitters with specific orientations
and in a denser volume than what can be realized by solubility
methods.110 Figure 5a depicts the PL properties of Zn-
porphyrin MOFs whose Q-band excitons coupled to SLRs
from a plasmonic metasurface (Ag NP square lattice).
Enhancements up to 16-fold were possible when the transition
dipoles of the emitters were aligned with the ED direction of
the NPs in the lattice at the Γ point (θ = 0°). Because of the
dispersive properties of the metasurface, molecular emitters
coupled to propagating SLRs can also exhibit strong enhance-
ments at off-normal angles.
Because dielectric metasurfaces can also support strong
Purcell enhancement,111−113 metasurfaces made from high-
index dielectric NPs (e.g., GaAs, Si, and InAs) combined with
emitters (e.g., QDs, dyes, and TMD monolayers) can also
show enhanced PL.114,107,115−118 Si NP square lattices with
polymer containing dye molecules can show both electric and
magnetic Mie SLRs coupled to the emission, with polarization-
dependent enhanced fluorescence (Figure 5b).118 Multiple
resonances in dielectric metasurfaces that can overlap with the
PL of the emissive material offer flexibility in achieving
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Figure 5. Enhanced PL from organic emitters coupled to metasurfaces. (a) Molecular emitters oriented via MOFs coupled to plasmonic
metasurfaces show strong PL enhancements. (b) Mie-resonant metasurfaces support enhancements through magnetic, electric and hybrid modes.
Panel a was adapted from ref 110 with permissions. Copyright 2019 National Academy of Sciences (NAS). Panel b was adapted from ref 118 with
permissions. Copyright 2020 Wiley-VCH.

Figure 6. Dye lasing at the high-symmetry points of plasmonic metasurfaces. (a) Bright mode lasing at the Γ point. IR140 dye is combined with a
square lattice of Au NPs (periodicity a0 = 600 nm). (b) Dark mode lasing at the Γ point. Rhodamine 6G dye is combined with a square lattice of
Ag NPs (a0 = 375 nm). (c) K-point lasing from a honeycomb lattice. IR-792 dye is combined with a honeycomb lattice of Au NPs (NP separation
p = 576 nm). (d) Δ-, Σ-, and X-point in-plane lasing from light-cone SLR modes of a square lattice. C481 dye is combined with a square lattice of
Al NPs (a0 = 450 nm). Panel a was adapted from ref 131 and ref 134 with permission. Copyright 2017 Nature Publishing Group (NPG) and 2015
NPG. Panel b adapted from ref 135 with permission. Copyright 2017 NPG. Panel c was adapted from ref 136 with permission. Copyright 2019
American Physical Society (APS). Panel d was adapted from ref 138 with permission. Copyright 2021 ACS.

emission enhancements at multiple wavelengths, directions,
and polarizations.118 As an example of a different dielectric
metasurface design for enhanced PL, emitters can also be
designed to be part of the metasurface building unit. InAs QDs
embedded in AlGaO/GaAs/SiO2 nanoposts showed a nearly
70-fold emission enhancement at IR wavelengths observed
because of the MQ modes confined within the posts.107
2.1.2. Nanoscale Lasing. 2.1.2.1. Plasmonic Metasurfa-
ces for Lasing. Plasmonic metasurfaces combined with
quantum emitters can support lasing action.119−126 Organic
dye molecules are common gain media at room temperature
that can be can be dispersed in solvents and polymer blends.
They show a wide range of emission wavelengths, from the
visible to the NIR, with a broad PL bandwidth. By designing
SLR modes to overlap with the PL emission, lasing can be
supported at the SLR wavelength. Unlike surface plasmon
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polariton and localized surface plasmon laser designs that lack
beam directionality,127−129 plasmonic NP lattices as meta-
surfaces can facilitate directional emission with a low
divergence angle, which results from the near-zero group
velocity at photonic band edges.101,130−133
Figure 6a depicts lasing emission from the Γ point (k|| = 0)
of a Au NP square lattice combined with organic dye as
gain.130,134 When the dye is optically pumped at room
temperature, the device shows lasing after a threshold pump
fluence, and a signal that is perpendicular to the lattice plane
and with a narrow line width. Besides the bright SLR mode at
the Γ point, dark SLR modes near the Γ point can support
lasing from finite-sized arrays of Ag NPs (Figure 6b).135 In
dispersion diagrams of an infinite lattice, bright modes appear
at lower energies, and the dark mode corresponding to in-plane
EQ SLRs are absent. However, when the lattice has a finite size
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Figure 7. Tunable lasing wavelengths or thresholds from plasmonic metasurfaces. (a) Dynamic laser with a microfluidic channel. (b) Mechanically
tunable laser based on a stretchable elastomer substrate. (c) Magnetically switchable laser using Co/Pt magnetic NPs. Panel a was adapted from ref
134 with permission. Copyright 2015 NPG. Panel b adapted from ref 66 with permission. Copyright 2018 ACS. Panel c was adapted from ref 139
with permission. Copyright 2021 NPG.

Figure 8. QD lasing from plasmonic metasurfaces. (a) Radially or azimuthally polarized lasing controlled by the QD film thickness. (b) Two-color
lasing from a rectangular lattice. (c) Engineered emission angles by lattice periodicity and QD film thickness. (d) NPL lasing that depends on NPL
film thickness. Panel a was adapted from ref 100. Copyright 2020 ACS. Panel b was adapted from ref 102. Copyright 2020 ACS. Panel c was
adapted from ref 101. Copyright 2020 ACS. Panel d was adapted from ref 144. Copyright 2021 ACS.

(<100 μm), the SLR mode contains both EQ modes with
subradiant features in the middle of the lattice and ED modes
at the edges of the lattice. A finite lattice can support both
bright mode and dark mode lasing where the dark mode
emission is slightly off the Γ point in the k space.
High-symmetry points of plasmonic metasurfaces at nonzero
wavevectors can be also used to manipulate lasing emission
angles.136−138 In contrast to surface-normal lasing from the Γ
point, the K-points of a honeycomb plasmonic lattice can
enable six lasing beams at ∼35° along the Γ−K lattice
directions (Figure 6c).136 In addition, M-point lasing from
both hexagonal and honeycomb lattices has been reported with
emission angles near 60°.137 SLR modes that support in-plane
light scattering can facilitate tunability at other lasing emission
angles.138 The 3D light cone boundary, which describes the
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free photon dispersion in the 2D E−k|| relation, corresponds to
light propagation along the in-plane direction (θ = 90°). Using
dye molecules to excite the high-order SLR modes on the light
cone boundary enables multicolor, in-plane lasing emission,
where different colors are along different azimuthal angles
(Figure 6d).
In addition, plasmonic metasurfaces provide a program-
mable platform to manipulate the lasing wavelengths under
different stimuli.66,134 Real-time tunable lasing can be achieved
with SLR cavities because their resonance wavelengths depend
on the refractive index (n).134 By combining a plasmonic NP
lattice within a microfluidic channel, liquid gain with different
n (n1, n2, n3, ...) can be introduced to the same system, with
tunable lasing demonstrated (Figure 7a). The lasing wave-
length can also be controlled by varying the lattice periodicity
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Figure 9. Dielectric metasurface lasers. (a) Mie-resonant metasurfaces coupled with gain enable quasi-BIC lasing based on magnetic dipolar and
multipolar modes that result in donut-shaped beam profiles with azimuthal polarizations. (b) Dielectric metasurfaces acting as flat lenses for
collimating lasing emission by VCSELs with controlled beam profiles. Panel a was adapted from ref 72. Copyright 2020 ACS. Panel b was adapted
from ref 147. Copyright 2020 NPG.
of plasmonic metasurfaces on an elastomeric substrate
surrounded by dye molecules66 (Figure 7b). Stretching and
releasing the substrate can engineer the SLR wavelength by
changing the interparticle separation, enabling reversible
tuning of the lasing output. A higher figure of merit (Δλ =
31 nm for Δε = 0.03, 18 nm) can be achieved in this
stretchable laser design compared with photonic crystals (Δλ =
26 nm for Δε = 0.23, 150 nm).
The magnetic responses of plasmonic Co/Pt NP meta-
surfaces have also been tested for on−off lasing switching139
(Figure 7c). When Co/Pt NPs support a net magnetization,
the Lorentz force on the surface plasmons lifts the spectral
degeneracy of the SLR modes. Despite the weak circular
dichroism effect in altering the optical response (<1%), pump
fluence-sensitive phenomena such as lasing show modest
differences in thresholds (∼4%) and emission wavelengths
(∼0.4 nm) between the different magnetization directions.
This work explores how small magnetic responses can act as a
tunable parameter for tuning metasurfaces of unconventional
materials.
In addition to liquid dye as gain, solid-state emitters have
been used as gain media in plasmonic metasurface lasers.
UCNPs are attractive for their long excited-state lifetimes
(∼100 μs) that support multiphoton absorption and high
stability.140 All-solid-state devices based on Yb3+/ Er3+
sensitizer/emitter UCNPs as gain combined with Ag
plasmonic metasurfaces showed spectrally stable lasing for
more than 6 h.103 The Yb3+ ion enhanced the NIR (980 nm)
continuous wave pump absorption, and the SLR mode coupled
selectively to emission in the red-wavelength manifold of the
Er3+ ions. Ultralow lasing thresholds of 29 W/cm2 represent a
greater than 200-fold reduction compared to dielectric
microbead lasers.141
Colloidal QDs are another type of solid-state gain material
for coherent light sources.142,143 Conformal coating of CdSe/
CdS core−shell QD films on plasmonic metasurfaces enables
the formation of hybrid waveguide-SLR (W-SLR) modes
because of the high refractive index of the QD films.100−102
The sidebands of these hybrid modes at nonzero wavevectors
facilitate directional lasing emission with either radial or
azimuthal polarization depending on the thickness of the QD
film normal to the surface100 (Figure 8a). The manipulation of
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QD laser colors from a single plasmonic metasurface is also
possible,102 where rectangular lattices can support two W-SLRs
and hence two output wavelengths whose color can be selected
by a linear polarizer (Figure 8b). In addition, the direction of
QD-plasmon lasing can be engineered by exploiting high-
symmetry points in the plasmonic metasurfaces101 (Figure 8c).
Changing the periodicity of the plasmonic lattices enables
different high-symmetry points (Δ, Γ, or M) of the lattice to
overlap with the QD shell emission and directional emission.
Lasing from colloidal CdSe nanoplatelets (NPLs) and Al
plasmonic metasurfaces has also been observed144 (Figure 8d).
A critical NPL film thickness of 150 nm was found to support
SLR-mediated lasing, and thinner films exhibited only PL.
2.1.2.2. Dielectric Metasurfaces for Lasing. Dielectric
metasurfaces can also serve as distributed feedback cav-
ities.72,145,146 Recent work of Mie-resonant cavities coupled
with colloidal NPLs has shown lasing from both MD and MQ
modes.72 The high Q-factors (>2590) of the quasi-BICs near
the Γ-point band edges enable surface-emitting lasing (Figure
9a). Because BICs are decoupled from the radiation field at
normal incidence but have leaky sidebands, their beam profiles
are donut-shaped and with polarizations that reflect the nature
of the BIC (Figure 9a, inset). In addition to periodic lattices,
phase-gradient dielectric metasurfaces have been integrated
with microlasers to engineer emission (Figure 9b). Either
replacing or patterning Bragg mirrors with metasurface
structures on vertical cavity surface emitting lasers (VCSELs)
can result in far-field emission with controlled beam profiles in
monolithic devices.147 Spiral-patterned metasurfaces integrated
on electrically pumped VCSELs have demonstrated controlled
collimation of small IR lasers. The spiral patterns provide a
compensating phase that corrects for beam divergence and
shapes the beam with specific intensity (e.g., Bessel and
Gaussian) profiles (Figure 9b). These designs have been
extended to more complicated metasurface architectures that
can accommodate complex beam steering for sensing
applications.148,149
2.1.3. Quantum Prospects. Metasurface designs for
quantum applications are receiving increased attention,
where the quantum states of interest are based on light
polarization, direction, and orbital angular momentum.150−152
Metasurface integration with quantum emitters offers a
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Figure 10. Metasurface-assisted single photon emission. (a) Deterministic coupling of single quantum emitters in 2D hBN with a plasmonic
nanocavity array. (b) Large-scale quantum-emitter arrays in WSe2 or WS2 on top of a dielectric metasurface. (c) Generation of circularly polarized
single photons from a chiral, dielectric metasurface. Panel a was adapted from ref 154. Copyright 2017 ACS. Panel b was adapted from ref 155.
Copyright 2017 NPG. Panel c was adapted from ref 156. Copyright 2020 Wiley-VCH.

Figure 11. Strong coupling between plasmonic NP lattices and organic emitters. (a) Ag NP lattice coupled with a dye-doped polymer layer and
dispersion diagram. (b) Rectangular Ag NP lattice coupled with a dye-doped layer and different dispersion diagrams depending on excitation-
direction. (c) Ag NP lattice coupled with a MOF film and TA spectra at 300 fs of the pristine Pd-P MOF film, Ag NP lattice, and strongly coupled
system. Panel a was adapted from ref 161. Copyright 2014 ACS. Panel b was adapted from ref 97, Copyright 2013 Optica Publishing Group
(OPG), and ref 163. Copyright 2017 ACS. Panel c was adapted from ref 164. Copyright 2021 ACS.

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Figure 12. Strong coupling of plasmonic NP lattices to inorganic emitters. (a) Quantum dots on a Ag NP lattice and concentration-dependent PL
spectra. (b) WS2 layers integrated on a Ag NP lattice, dispersion diagram with mono- and 16-layers of WS2, and Rabi energy as a function of the
number of layer. (c) Polymer-wrapped CNT on top of Au NP lattice where the sample is pumped at a position 5 μm from the edge of the
plasmonic metasurfaces, and spectrum-integrated radiative decay showing upward propagation of the polaritons. Panel a was adapted from ref 165.
Copyright 2020 ACS. Panel b was adapted from ref 170. Copyright 2019 ACS. Panel c was adapted from ref 173. Copyright 2018 ACS.

promising platform for quantum photon sources and
manipulation of quantum light.150,153 In the weak coupling
regime, the Purcell enhancement of quantum emitters via
enhanced spontaneous emission rates can facilitate efficient
generation of single-photon sources for optical technologies.154
2D materials such as hexagonal boron nitride (hBN) and
TMDs are promising single-photon sources. Defects in 2D
hBN can function as quantum emitters and have been
deterministically coupled to a plasmonic metasurface154
(Figure 10a). Emission rates are enhanced and fluorescent
lifetimes reduced from the Purell effect. The second-order
correlation function g2(τ) shows a dip at zero delay time,
which indicates that the single-photon statistics are largely
preserved. In addition, arrays of single-photon quantum
emitters in WSe2 and quantum-like emitters in WS2 have
been realized using a dielectric silica metasurface155 (Figure
10b). The NPs generated local deformations in the TMD
materials, which resulted in quantum confinement of excitons.
This approach allows the placement of emitters in photonic
metasurfaces in a scalable way.
Moreover, dielectric metasurfaces have been designed to
produce directional circularly polarized single photons156
(Figure 10c). A nanodiamond (ND) containing a single
nitrogen-vacancy center in the center of a bull’s eye design
(circular nanoridges with azimuthally varying widths) on a thin
SiO2 film on a Ag substrate could exhibit single-photon
chirality. This quantity representing the degree of left-/right-
handed polarization of 0.8 was achieved, and the metasurface
increased the collection efficiency from 75% to 92%. Other
recent work demonstrated how accurately integrating a QD
and its mirror image onto the two foci of a Si metalens can
result in on-demand generation and separation of the spin
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states of the single photons.157 Using the metasurface, photon
streams with different spin states can be flexibly manipulated to
propagate along arbitrarily designed directions. In addition to
the generation of single photons, metasurfaces have been used
to image quantum emitters.150 A metasurface composed of ND
pillars has served as an immersion lens to collect and collimate
the emission of a nitrogen-vacancy center.158 This work
provides a pathway to packaging quantum devices by
eliminating the need for an objective and to realizing room-
temperature operation of quantum devices.
2.2. Strong Coupling in Hybrid Material Metasurfaces
2.2.1. Strong Coupling with Plasmonic Metasurfaces.
The most common emitters for strong coupling studies that
involve plasmonic metasurfaces are organic fluorophores
embedded in a matrix (Figure 11a).97,159,160 Measured
extinction spectra of bare Ag NP lattices support an avoided
crossing between the LSP of the NPs and the SLR.161 The
addition of a 50 nm layer of poly(methyl methacrylate)
(PMMA) with Rhodamine 6G introduced additional anti-
crossings at the two absorption peaks of the dye, and the Rabi
splitting ranged between 100 and 150 meV. Because of the
collective nature of the SLRs, the polaritons from excitons
hybridized with SLRs also displayed long-range coherence
even when the polaritons were 80% excitonic.162 Exciton-SLR
coupling in rectangular NP lattices can produce polaritons with
two different energy-momentum dispersions and group
velocities (vg = ℏ−1(dE/dk)) depending on excitation direction
(Figure 11b).97,163
Strong coupling was recently demonstrated between organic
linkers arranged in a MOF and Ag NP lattices.164 When the
thin-film MOF was grown on the plasmonic metasurface
(Figure 11c), Q1 band excitons of Pd-metalated porphyrin
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Figure 13. Strong coupling with dielectric metasurfaces. (a) Simulations of the spatial distribution of the field intensity of ED and MD Mie SLR
and angle-resolved extinction spectra of the of Si NP lattice covered by a PMMA layer doped with dye molecules. (b) Dispersion of the WS2-Si NP
lattice coupled system under different polarizations. (c) Fabrication of a 2D perovskites pillar lattice, simulated dispersion diagram of passive
structures where the perovskite is replaced by a dielectric medium, simulated and experimental dispersion diagram of hybrid metasurfaces. Panel a
was adapted from ref 70. Copyright 2020 ACS. Panel b was adapted from ref 69. Copyright 2020 ACS. Panel c was adapted from ref 175. Copyright
2020 ACS.

ligands could be strongly coupled with SLRs, even though the
oscillator strength f is relatively low because the framework
enables a high density of emitters. A Rabi splitting of 110 meV
was determined from the transmission spectra. Ultrafast
transient absorption (TA) spectroscopy was used to reveal
polariton dynamics, which are important in understanding the
photophysical properties of the hybrid states. In time-resolved
TA spectra at 300 fs, both pristine MOFs and the Ag NP
lattice exhibited single bleach signals from the Q1 band and
SLR, respectively (Figure 11c). In the strongly coupled system,
two bleach signals were evident and whose energy separation
matched that of the Rabi splitting. A kinetic profile analysis
showed that the lower polaritons decayed faster than pristine
MOF excitons at shorter time scales (<500 ps), while their
decay became slower at longer time scales (0.5−3 ns) because
of energy transfer from the upper polaritons. Notable, the
upper polariton lifetime was more than 10 times longer than
the uncoupled MOF exciton.
Colloidal QDs have also been used to investigate how
emitter concentration affects strong coupling with plasmonic
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metasurfaces.165 At the low-density limit, where one or two
CdSe/ZnS core−shell QDs were placed within the measure-
ment area, the system showed only weak coupling. As the
concentration increased (from 57 to 142 mM), peak splitting
started to appear in the PL spectra (Figure 12a), which
indicates the hybridization between the SLR and excitons.
When closely packed films of QDs were strongly coupled with
2D lattices, the Rabi splitting was ∼100 meV, and long-range
energy propagation up to 600 μm was observed based on real-
space imaging of the radiative decay of polaritons.166
Another excitonic material used for strong coupling is mono-
and few-layer TMDs because of their strongly bound excitons
in 2D. Compared to weak coupling between MoS2 and Ag NP
lattices at room temperature and intermediate coupling at 77
K,167 the same combination of materials achieved strong
coupling (Rabi splitting of 11 meV) at cryogenic temper-
atures.168 In contrast, WS2 enables strong coupling at room
temperature because of its larger oscillator strength (Figure
12b).169 Interestingly, increasing the number of WS2 layers
from one to 16 resulted in increased Rabi splitting from 50 to
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100 meV even though the in-plane dipole moments were
reduced beyond the monolayer because in-plane electric field
distributions extended into the surrounding dielectric
medium.170
Single-walled CNTs support strong exciton binding energies
(∼300 meV) and prominent charge transport properties.171
When CNTs embedded in a polymer layer were combined
with plasmonic metasurfaces, the interaction strength seemed
to correlate with the CNT layer thickness (100−300 nm), and
Rabi splitting up to ∼120 meV was observed.172 To investigate
polariton propagation, radiative decay was measured in real
space by exciting the sample position 5 μm from the edge of
the lattice (Figure 12c).173 The PL position and intensity
could be directly translated into the spatial distribution and
population of polaritons; propagation lengths of ∼20 μm were
possible for polaritons with higher photonic fractions. In
contrast, the more excitonic polaritons near the CNT
absorption decayed within a few micrometers. Note that
CNTs show much shorter polariton propagation lengths
compared to semiconductor QD layers (∼600 μm),166 which
may be attributed to differences in waveguide effects and
packing density of materials in emitter layers.
2.2.2. Strong Coupling with Dielectric Metasurfaces.
Incorporating high-index dielectric NPs that support both
electric and magnetic Mie modes with emitters results in
additional light−matter coupling. The first observation of
strong coupling with Mie SLRs was reported from amorphous
Si NP lattices covered by a PMMA film doped with organic
dye (IR-792), exhibiting a Rabi splitting of 253 meV.174 For
polycrystalline Si NPs, near-field simulations of the Mie SLRs
under TE polarization showed strong electric-field confine-
ment in the y-direction,70 which indicates that these Mie SLRs
have ED character (Figure 13a). In contrast, under TM
polarization, the electric field circulates inside the NPs, which
corresponds to a Mie SLR with MD nature. When these two
types of SLRs with similar line widths were combined with a
PMMA layer doped with a rylene dye, the Rabi splitting based
on the electronic transition X1 was ∼200 meV for both ED and
MD (Figure 13a).
When Si NP lattices were integrated with monolayer WS2
and excited under TM polarization, strong coupling between
the in-plane electric field of the ED Mie SLR and the in-plane
excitonic dipoles resulted in a Rabi splitting of 32 meV (Figure
13b).69 When the same WS2 layers were coupled with MD Mie
SLRs, however, the out-of-plane electromagnetic distribution
of the magnetic SLRs were orthogonal to dipole modes of the
emitter, which precluded formation of exciton−polaritons
(Figure 13b). Note that although coupling with Mie SLRs
benefits from the low absorption of dielectric materials, the
Rabi splitting observed in dielectric metasurfaces is similar to
or even slightly smaller than that in plasmonic systems. For
example, Rabi splitting of organic dyes and monolayer TMDs,
respectively, coupled to metasurfaces was 253 and 32 meV for
dielectric NP lattices, and 293 and 50 meV for plasmonic NP
lattices.174
Direct patterning of high-index, excitonic materials is an
additional strategy to achieve strong coupling. 2D hybrid
organic−inorganic perovskites patterned into a pillar lattice
structure support both exciton and photonic Bloch modes
simultaneously (Figure 13c).175 Angle-resolved reflectivity
spectra show polaritons with different group velocities as the
lattice periodicity and pillar diameter changed; lower polar-
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|vg|
itons had 0.42 with a linear dispersion when kx > ± 5
c
|vg |
μm−1, and c 0.08 with a parabolic dispersion at kx ≈ ± 5
μm−1. The lower polariton from coupling with the W-shaped
multivalley dispersion resulted in a near zero group velocity at
nonzero kx (≈ ± 1.5 μm−1). Thus, direct emitter-based
metasurface patterning allows a facile approach to tailor the
polariton characteristics while offering the potential for large-
scale fabrication based on imprint and solution spin-coating
techniques.
3. COMBINATION OF STIMULI-RESPONSIVE
MATERIALS AND METASURFACES
This section reviews the hybrid materials platforms that enable
adaptive responses from optical metasurfaces. First, we will
describe typical applications of static metasurfaces, including
imaging, holographic displaying, and spectroscopy as well as
their limitations in realizing dynamic optical responses. To
address these drawbacks, we will review elastomer materials
that enable mechanical actuation of the metasurface properties
such as their focal lengths and beam deflection angles. We will
further discuss electrically tunable materials including 2D
materials, semiconductors, phase-change materials, and liquid
crystals for modulating the polarization and reflection of
metasurfaces by electronic devices.
3.1. Static Metasurfaces
Metasurfaces have contributed to the miniaturization of optical
elements ranging from lenses to spectrometers to holographic
displays. For example, low-loss dielectric metalenses can
function as compact monochromatic imaging devices with
high focusing efficiencies (up to 86%) and numerical apertures
(NA = 0.8) comparable to commercial objective lenses.75 To
expand to full-color imaging, a single dielectric metalens
designed by dispersion engineering strategies can show
achromatic focusing for the entire visible range (λ = 400−
660 nm).176 Also, dielectric metasurface doublets that can
compensate for comatic aberrations and astigmatism177 have
been used in compact wide-angle cameras.178 In addition,
miniaturized endoscopes for in vivo optical coherence
tomography have been demonstrated with superior resolution
and imaging depth.179 Compared to refractive lenses,
metasurfaces with subwavelength phase elements can capture
optical information beyond intensity. Complex lens designs
consisting of four stacked Si metasurfaces can capture spatially
resolved phase information rapidly.180
Full control over phase profiles using subwavelength units
enables metasurfaces to be used in portable spectrometer
designs not possible for refractive optics.181 Compact
spectrometers constructed from three dielectric metasurfa-
ces181 are 20 times more compact than conventional
spectrometers. Also, effective spatial separation of spectral
components by reflections from the metasurfaces and
propagation in the glass substrate can be realized.181 This
folded approach further contributes to hyperspectral imaging
in the same wavelength range with an angular resolution of
0.075°. Metasurfaces also play a key role in holography, a 3D
imaging technique that stores and recovers the amplitude and
phase of light.182 Their control over amplitude and phase can
generate high-resolution low-noise images for image displays at
visible wavelengths. In reflection mode, metasurface holograms
can reach an efficiency of 80%, which is 2-fold higher than the
optics for computer-generated holograms.183 Lastly, meta-
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Figure 14. Reconfigurable metasurfaces by mechanical stimuli. (a) Metalens consisting of amorphous silica nanoposts (a0 = 380 nm, h = 690 nm, λ
= 915 nm) in a PDMS slab demonstrates dynamic focusing. Metasurfaces based on plasmonic nanorodsin a PDMS enable (b) beam deflection with
tunable angle (square lattice a0 = 400−520 nm, l = 240 nm, w = 100 nm, λ = 632.8 nm) and (c) holograms with switchable images (square lattice
a0 = 340−360 nm, l = 220 nm, w = 90 nm, λ = 632.8 nm). Panel a was adapted from ref 187 with permission. Copyright 2016 Wiley-VCH. Panel b
adapted from ref 188 with permission. Copyright 2016 ACS. Panel c was adapted from ref 189 with permission. Copyright 2017 ACS.

surfaces based on anisotropic units can tailor the polarization77
and spectral components184 of light to replace existing
waveplates, polarizers, and band-pass filters.
3.2. Mechanical Control of Hybrid Material Metasurfaces
Applications of static metasurfaces are limited because their
optical responses are fixed after fabrication. However, devices
based on flat optics such as cameras and microscopes need
dynamic operations, including zooming and focusing, and
reconfigurable metasurfaces are needed.
3.2.1. Stretching of Elastomeric Substrates. Active
optical responses can be realized by mechanical control of
metasurfaces fabricated on flexible substrates.185,186 For
example, the phase profile of a static metalens with a focal
distance f is defined by the following equation:187
L2
(L , )
f (6)
where L is the distance to the lens axis, and λ is the wavelength
of light. By applying a uniform biaxial strain Δε to this
substrate, the focal distance is increased to f(1+ Δε)2 with the
phase profile:
L2
(L , )
f (1 + )2 (7)
Figure 14a shows a mechanically controlled dielectric Si
metalens on an elastic substrate with tunable focal lengths at λ
= 915 nm. 187 By applying a biaxial strain to the
polydimethylsiloxane (PDMS) substrate of up to 50%, the
focal length can be tailored from f = 600 to f = 1400 μm. The
full-width half-maximum (fwhm) of the focal points broadens
with increasing strain because of the decrease in NA. A similar
strategy based on plasmonic nanorods in PDMS also realized
stretchable metalenses in the visible range.188 The ability to
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adjust focal lengths allows a single flexible metalens to image
objects on different imaging planes beyond the depth of the
focus.
Mechanical approaches can also be used for beam steering
by metasurfaces based on the generalized law of refraction:74
d (x)
nt sin t ni sin i
2 dx (8)
where nt(i) and θt(i) are the index of medium and angle for the
transmitted (incident) light. To steer an incoming beam at
normal incidence (θt = 0) in the air (nt = 1), the phase profile
is defined by a linear function of x as ϕ(x) ≈ 2πx/ma0, where
a0 is the spacing between phase units in x, and m is an arbitrary
number that tailors the deflection. The resulting refraction
angle can be predicted as θt = sin−1(λ/ma), which decreases
when the substrate is stretched.
Figure 14b shows a reconfigurable metasurface deflector
consisting of plasmonic nanorods in a PDMS slab that can
steer normal incident light to a tunable angle θt.188 As the
substrate is stretched, the spatial phase gradient is reduced, and
θt is decreased from 15.3° (Figure 14b, lower left) to 11.7°
(Figure 14b, lower right). In contrast to spectrometers
consisting of gratings, this metasurface deflector on a flexible
substrate can enable compact spectrometers with tunable
spectral range detection and resolution. The flexible materials
platform can be extended to construct holograms that can
switch between multiple images on a targeted plane (Figure
14c).189 In this demonstration, the metasurface is programmed
to display different holograms optimized at three separated
image planes that move away from the metasurface upon
stretching the substrate. Application of biaxial strain can adjust
the position of each hologram and reconfigure the displayed
image on a fixed plane.
3.2.2. Other Mechanical Approaches. In adaptive
devices, tunable metasurfaces need integration with electro-
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Figure 15. Tunable metasurface devices by mechanical control. (a) Adaptive metalens on dielectric elastomer actuators that enable electrical
control of focal length, astigmatism, and shift. (b) MEMS system for controlling the focal length of a lens doublet by adjusting their distances. (c)
Scalable, unit-level reconfiguration of lattice-resonance metasurfaces by SANE on arrays of Ag NPs (a0 = 400 nm). Phase units of (a) are
amorphous Si posts with h = 950 nm, diameters d = 810−990 nm, and edge-to-edge spacing of 650 nm. Panel a was adapted from ref 190 with
permission. Copyright 2018 AAAS. Panel b adapted from ref 192 with permission. Copyright 2018 NPG. Panel c was adapted from ref 193 with
permission. Copyright 2019 ACS.

mechanical controllers that can modulate the strain accurately
in real-time. A dielectric elastomer actuator has been used to
control the focal length and astigmatism of a metalens using
electrical signals (Figure 15a).190 The metasurface embedded
in an electro-active elastomer could be stretched independently
along two axes as a voltage is applied to electrodes. This hybrid
metalens allows a tunable focal length f = 50−65 mm as well as
lateral shifts up to 0.39 mm. This device has a response time of
∼33 ms, where the focusing is tailored upon electric stimuli. In
comparison, a varifocal refractive objective lens tuned can only
achieve a tunable focal length f = 2.13−2.77 mm at a similar
modulation speed (32 ms).191 A slightly faster response of 0.25
ms has been realized by a metalens doublet controlled by a
microelectromechanical system (Figure 15b).192 This lens
complex consists of (1) a dynamic metalens on a SiNx
membrane that can be displaced along the lens axis by an
electrostatic actuator; and (2) a stationary metalens on fused
silica below the SiNx membrane. By adjusting the distance
between the two lenses from 10 to 9 μm, the focal distance can
be tailored between f = 781 and 817 μm. With an additional
refractive lens, the device enabled the tuning of the effective
focal length from 44 to 122 mm.
One major limitation of mechanical approaches is that long-
range modulation lacks tunability at the single-unit level. A
metalens platform with unit-level reconfiguration has been
demonstrated for programmable 3D imaging at visible
wavelengths (Figure 15c).193 Wavefront phase profiles can be
tailored on arrays of Ag NPs that support SLRs by patterning
the superstrate refractive index by solvent-assisted nanoscale
embossing (SANE).194 This method can reversibly switch the
substrate between two (or more) lens designs and demon-
strates adaptive imaging by evolving a metalens sequentially
from single- to multifocal-point configurations during the same
15191
experiment. A drawback of the technique for tuning the
refractive index is its inability to realize more than 2 phase
levels for higher diffraction efficiency. To address this
limitation, a reconfigurable metasurface that allows single-
unit switching between four phases has been realized by
patterning superstrate index on a 2 × 2 supercell of phase
elements with phase delays of 0, π/2, π, 3π/2;195 however, the
patterns of indices achieved by removal of PMMA resist with
e-beam lithography, which is slow and unscalable.
3.3. Electrical Tuning of Hybrid Material Metasurfaces
Compared to mechanical control of metasurfaces, electrical
tuning has advantages in terms of operational speed,
compactness, compatibility with semiconductor technology,
and large-scale fabrication. The key to achieve electrically
tunable metasurfaces is to integrate components whose optical
properties can be dynamically modulated upon an external
electrical stimulus.
3.3.1. Graphene and Semiconductors with Plasmonic
Metasurfaces. Hybrid metasurface structures composed of
plasmonic metasurfaces and graphene can result in the
manipulation of amplitude, phase, and polarization of
light.196−202 Graphene is an ideal platform for optoelectronics
and transformational optics203−205 because the sp2-hybridized
material can be electrically controlled with a tunable Fermi
energy and optical response.206 The gate-controlled light
response in graphene can be greatly enhanced by integration
with a plasmonic metasurface.207 For example, an electrically
tunable perfect absorber was prepared by incorporating a
metasurface on graphene into an asymmetric Fabry−Perot
resonator.208 These metasurfaces can function as ultrathin
(thickness < λ0/10), high speed (up to 20 GHz) optical
modulators with a broad range of tunable absorption
wavelengths by controlling the applied voltage (Figure 16a).
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Figure 16. Electrically tunable graphene and semiconductors with plasmonic metasurfaces. (a) Schematic of the optical modulator based on a
graphene/metasurface absorber and simulated reflection spectra at different gate voltages. (b) Schematics of graphene-integrated anisotropic
metasurfaces for polarization control. (c) Schematic of graphene-tuned antenna arrays for phase control. (d) Schematic and scanning electron
microscopy (SEM) images of the electrically tunable metamaterial/ENZ hybrid device and measured transmission spectra at different voltages,
scale bar is 5 μm. Panel a was adapted from ref 208 with permission. Copyright 2014 ACS. Panel b was adapted from ref 209 with permission.
Copyright 2017 Royal Society. Panel c was adapted from ref 211 with permission. Copyright 2017 ACS. Panel d was adapted from ref 214 with
permission. Copyright 2013 ACS.

Besides spectral modulation, graphene hybrid metasurfaces
show more sophisticated functions,198 including control over
the polarization states of mid-infrared light (Figure 16b)197,209
and highly tunable reflected phase at multiple wavelengths and
with high (up to 237° compared to up to 180° in ITO/
plasmonic metasurfaces210) phase modulation (Figure 16c).211
Electrically tunable metasurfaces can also be designed based
on heavily doped semiconductors or conducting oxide
semiconductors with a large variety of complex refractive
indexes and carrier densities.212,213 An electrically tunable
planar metasurface was made by a hybrid structure consisting
of a plasmonic metasurface composed of gold split-ring
resonators and a GaAs nanolayer (Figure 16d). The split
ring resonator strongly coupled to the epsilon-near-zero
(ENZ) modes in the doped semiconductor GaAs layer and
showed large spectral splitting at the resonance frequency of
the Au resonators; the coupling can be dynamically modulated
by depleting the doped GaAs nanolayer electrically.214
Conducting ITO layers can also be combined with gold stripe
antenna arrays to form another type of hybrid plasmonic
metasurface. The ITO layer with a gate-tunable refractive index
is the active layer that can couple to optical near fields of the
plasmonic metasurface for electrically controlled spectral
tunability.215,216
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3.3.2. Phase-Change Materials and Liquid Crystals
with Metasurfaces. Electrically tunable metasurfaces can also
be designed from phase-change materials (PCMs) (e.g., alloys
containing Ge, Sb, and Te) that support reversible transitions
between amorphous and crystalline phases accompanied by a
large change in refractive index.217,218 PCMs can transform
between an amorphous state and a crystalline state by heating
and melt-quenching processes, and electrical biases are widely
used to generate heat in PCMs.219,220 Switchable PCM
metasurfaces have been designed from large-scale (up to 0.4
× 0.4 mm) electrothermal arrays on a heater with curved
boundaries (Figure 17a). Smooth control of the PCM phases
with different crystallinity was demonstrated by modulating the
electrical pulse duration and amplitude. Besides amplitude and
wavelength tuning of resonances, this PCM-based metasurface
also enables facile control over optical phase and wavefront.
These on-chip electrical metasurfaces showed binary switching
and ultrabroadband tuning of metasurface resonances across a
record half-octave spectral regime.221 Similar work has also
been reported on electrically switchable phase-change
metasurfaces based on PCM nanobeam arrays placed on an
optically thick silver strip.83 These hybrid metasurfaces showed
strong, reversible, nonvolatile, multiphase switching and
spectral tuning. Utilizing destructive interference between
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Figure 17. Electrically tunned phase-change and liquid crystal metasurfaces. (a) Schematic reconfigurable configuration and schematic rendering of
beam deflector; measured reflectance spectra of the phase-changed materials based metasurface. (b) Schematic of the electrically tunable
multifunctional polarization-dependent liquid crystal hybrid metasurfaces. (c) Schematic of hybrid metasurfaces of liquid crystal and gold arrays
and experimental transmittance spectra of the metasurfaces with no voltage applied (OFF) and for V = 6 V (ON). (d) Design and operational
principle of a liquid crystal/zigzag gold pattern hybrid metasurface and its measured transmission spectra at various voltages. Panel a was adapted
from ref 221 with permission. Copyright 2021 NPG. Panel b was adapted from ref 226 with permission. Copyright 2021 ACS. Panel c was adapted
from ref 227 with permission. Copyright 2013 OPG. Panel d was adapted from ref 228 with permission. Copyright 2013 OPG.

Figure 18. Molecule arrangement in hybrid metasurfaces. (a) Scheme and atomic force microscopy (AFM) characterization of the MOF coated on
Ag NP arrays. (b) Left: a single-stranded M13mp18 scaffold is annealed with staples to form origami triangles with single-stranded linkers (black
squiggles). Bottom: fluid AFM of origami without (leftmost image) and with (rightmost image). Right: AFM images of DNA origami placement.
Panel a was adapted from ref 229 with permission. Copyright 2019 NAS. Panel b was adapted from ref 232 with permission. Copyright 2016 NPG.

two pathways, an electrical modulation of the reflectance by
more than 4-fold at 755 nm was demonstrated.83 Notably,
applications of PCM devices operating at visible and NIR
wavelengths are still sparse because of their high optical losses
(large extinction coefficient κ) in this spectral regime;
development of PCMs with high-index modulation and low
optical losses are needed for further PCM/plasmonic
metasurfaces.
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Liquid crystals (LCs) are another platform for designing
tunable hybrid metasurfaces because their optical properties
such as nonlinearity and optical anisotropy can be controlled
by applied fields.222−224 Electrical tuning of the spectral
response was demonstrated in a dielectric metasurface of Si
nanodisks surrounded by LCs. This hybrid metasurface
achieved an absolute transmission modulation of up to 75%
by switching the voltage on and off.225 Recently, birefringent
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Figure 19. Hybrid metasurfaces with 2D materials. (a) Schematic illustration and SEM images of gold heptamers sandwiched between two
monolayer graphene sheets. (b) Schematic Berry-phase defective photonic crystal covered with a WSe2 monolayer. (c) Scheme of CVD process for
fabrication, SEM image of Cu@G NP lattices with a 45° tilting angle, transmission electron microscopy image of a single Cu@G NP, and
transmission spectra of Cu@G NP lattices after 1 month of exposure in air. Panel a was adapted from ref 232 with permission. Copyright 2012
ACS. Panel b was adapted from ref 239 with permission. Copyright 2020 NPG. Panel c was adapted from ref 240 with permission. Copyright 2020
NAS.

LCs integrated with Pancharatnam−Berry-phase metasurfaces
showed variable wave plates with different phase retardations
by controlling molecular orientation through electric regu-
lation (Figure 17b). On the basis of the phase modulation,
electrically tunable mono- and multicolor switchable meta-
holograms and dynamic varifocal metalenses were demon-
strated.226 Besides dielectric metasurfaces, LCs have also been
combined with plasmonic metasurfaces for electrical switching
of off and on images (Figure 17c).227 Furthermore, 5-fold
hysteresis-free modulation of metamaterial transmission was
also realized from patterned zigzag plasmonic metasurfaces
with LCs (Figure 17d).228
4. SUMMARY AND OUTLOOK
4.1. Emerging Metasurface Designs
4.1.1. Surface Functionalized Metasurfaces. This
Review has focused on plasmonic and dielectric metasurfaces
whose building units are not modified after fabrication.
Because the units support strong localized modes, surface
engineering is emerging as a new design parameter to
manipulate the properties of hybrid metasurfaces. Here we
describe recent strategies for surface modification of
metasurfaces with functional molecules and 2D materials.
MOFs can be conformally grown on plasmonic NP lattices
to generate hybrid metasurfaces with control over the spatial
organization of emitters relative to the surface of the
resonators. Because of their crystalline structure, MOFs can
provide dense, organized, and separated arrangements of
molecular emitters without self-quenching at high molecule
concentrations (Figure 18a). As discussed earlier, thin films of
Zn-porphyrin MOFs assembled by dip coating on lattices of Ag
NPs showed up to 16-fold PL enhancement compared with
pristine Zn-porphyrin (Figure 5a).229 All-dielectric metasurfa-
ces can enhance the absorption of various molecules,230,231 and
surface modification can assist in molecular organization. For
example, DNA origami can function as a surface layer to place
molecular emitters at specific locations in Si photonic crystals
(Figure 18b). This template enables reliable and controllable
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spatial arrangement of emitters, including visualization of the
local density of states with a resolution of about one-tenth of a
wavelength. The programmability and scalability of DNA can
also achieve multiple antinodes within a single photonic
crystal.232 Furthermore, other biomolecules such as proteins
on dielectric metasurfaces can modify the surface composition
and lead to selective chemical interactions for enhancement of
molecular circular dichroism and antibody detection.233,234
2D materials can also realize conformal contact with
metasurfaces by transferring or direct synthesis (Figure
19).235−237 Because of the strong near fields around plasmonic
NPs, sandwich structures of monolayer graphene and Au
antennas can show enhanced photocurrent (Figure 19a). WSe2
monolayers grown by chemical vapor deposition (CVD) and
transferred to a photonic crystal can support Berry-phase
defective modes (Figure 19b). The valley excitons of WSe2
interact with defects in the metasurface for site-controlled
excitation, PL enhancement, and spin-dependent manipula-
tion, and lead to a demonstration of a photonic Rashba effect
(spin-dependent splitting of directional emission in momen-
tum space).238,239 Besides being transferred after synthesis, 2D
materials can be directly grown on the resonator units. Cu is a
widely used substrate to grow graphene because of its catalytic
reactivity and low carbon solubility. A modified CVD process
grew graphene on plasmonic Cu NP lattices and transformed
the NPs into graphene encapsulated Cu (Cu@G) NPs (Figure
19c). Cu@G NP lattices exhibited an ultrasharp SLR with
fwhm = 2 nm, a more than 90% reduction of line width
compared to as-fabricated Cu NPs. These SLR modes
remained narrow for at least three months under ambient
conditions with a high quality factor (Q = 290−430).240
4.1.2. Chemically Tunable Metasurfaces. As discussed
in Section 3, most work on tunable metasurfaces relies on
mechanical or electrical approaches. Dynamic modulation is
also possible through chemical control of the environment.
Chemical tuning in gel-based systems enables in situ
modification to metasurface elements such as the composition
or size of individual units.184 One example is electrodeposition-
mediated growth and stripping of Ag/Au core−shell NPs
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embedded in a periodic SiO2 nanohole template that can
achieve reversibly tunable materials within the visible range.
When a voltage is applied across the gel superstrate, Ag metal
ions are reduced on the NPs, which shifts the LSPs to higher
energies and absorption of blue light. Arrays of these devices
with controlled voltages and electrodeposition times can
produce color effects that mimic camouflage. As another
example, chemical modulation of the metasurface substrates
can achieve tunable optical responses. By leveraging the rich
phase transition characteristics of VO2 in response to
temperature, hydrogenation, and electron doping, the optical
properties of Al NPs on VO2 substrates can be continuously
and reversibly tuned.241
4.1.3. Multilayer Hybrid Metasurfaces. Compared to a
single metasurface, multilayer metasurfaces can expand the
engineering space of additional control over optical properties.
For example, in twisted multilayer metasurfaces consisting of
Au nanorods, manipulating the relative orientation of the
nanorods in each layer can result in strong broadband
effects242 (Figure 20a). The metasurfaces are fabricated using
Figure 20. Fabrication of multilayer hybrid metasurfaces. (a) A
multilayer stack of twisted metasurfaces. The scale bars from left to
right are 2 and 1 μm. (b) A sandwiched architecture based on two
plasmonic lattices with different periodicities and a mixed dye
solution. Panel a was adapted from ref 242. Copyright 2012 NPG.
Panel b was adapted from ref 243. Copyright 2021 Wiley-VCH.
e-beam lithography, and a SiO2 spacer layer (100 nm) is
deposited between each metasurface. Because of coupling
between the closely spaced plasmonic metasurfaces, the
structure can effectively operate as a 3D helical structure
with a bianisotropic optical response.
Recently, a sandwich architecture based on two Al NP
metasurfaces and a liquid gain layer has shown white-light
lasing.243 The device consisted of two Al NP lattices on two
separate quartz substrates separated by a droplet of mixed dye
solution (Figure 20b). Because of the micrometer-scale spatial
separation of the two metasurfaces, interlayer coupling is
negligible. The two lattices with appropriately designed
periodicities can support three different SLR modes at blue,
green, and red wavelengths, which facilitated a white-light
emission profile. Multiplayer metasurfaces also enable
opportunities for applications such as multiwavelength metal-
ens and ultrasensitive sensors.244−246
4.2. Future Prospects
4.2.1. Coupling of Metasurfaces and 2D Materials.
Hybrid metasurfaces integrated with atomically thin 2D
materials can provide a platform for valleytronics, where a
new valley degree of freedom can be encoded and detected
with the spin angular momentum of light.247 Control over
valley polarization and the spatial separation of valley excitons
was recently achieved by incorporating monolayer TMDs with
plasmonic metasurfaces.237,248,249 Because interlayer excitons
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in multilayer TMD materials show reduced electron−hole
exchange interactions,250 multilayer materials could be more
promising for valleytronics than monolayers. In addition, two
stacked monolayers with a twist angle can form moiré patterns
with modulated electronic band structures251,252 and result in
unconventional moiré excitons.253,254 Integrating layered 2D
materials with metasurfaces is expected to modify exciton
dynamics and result in robust valley excitons, enhanced
absorption, and tunable emission. Despite their promise,
hybrid metasurfaces still require the development of new
technologies, including wafer-scale growth and dry transfer of
high-quality 2D materials, fabrication of scalable low-loss
metasurfaces, and structural design of 2D materials and
metasurface resonators.
4.2.2. Lasing with Complex Characteristics. Hybrid
material metasurfaces offer important engineering advances for
miniaturized lasers. Although control over lasing characteristics
such as beam profiles, polarizations, and thresholds has been
demonstrated in Bravais-lattice metasurface lasers, more
complex features such as orbital angular momentum lasing255
and quantum-entangled photon generation256 remain a
challenge. By concurrent optimization of the metasurface
cavity design and gain materials, we anticipate that such
unusual lasing emission properties will be possible. In addition,
we expect that low-threshold polariton lasing can result from
hybrid metasurfaces with gain that support oriented transition
dipoles that overlap with spatially localized fields in metasur-
face cavities.
4.2.3. Polariton Chemistry. Polariton chemistry has been
proposed as a means to tailor chemical reactivity by modifying
both global and local energy landscapes.20 Hence, the kinetics
and thermodynamics of polaritonic systems are expected to
have distinct physicochemical properties compared to their
uncoupled counterparts.257−259 The open architecture nature
of hybrid material metasurfaces may enable in situ probing of
vibrational strong coupling, which will provide spatial and
temporal information on how polaritons accelerate or suppress
particular reactive pathways. Exploration of different types of
reactions will also open prospects for electronic strong
coupling in underexplored applications such as catalysis and
energy harvesting.
4.2.4. Parity-Time Symmetry. Hybrid material meta-
surfaces also offer opportunities to explore parity-time (PT)
symmetry.260 In optical systems, PT symmetry can be
established by a balanced gain and loss profile, such as using
two coupled microdisks of identical geometries, where one has
gain and the other has an equal amount of loss.261 As the
coupling strength between gain and loss changes, a phase
transition can occur at an exceptional point.260 Exceptional
points have enabled unusual optical phenomena, including
loss-induced transparency,262 unidirectional invisibility,263,264
and nonreciprocal transmission.265,266 By investigating PT
symmetry in hybrid material metasurfaces, we expect that more
flexible tuning of gain, loss, and the coupling strength can be
realized in open architectures that will enable switchable
devices capable of unidirectional transport for optical
communications. Because exceptional points are sensitive to
small parameter changes,267 PT-symmetric metasurfaces may
also open prospects for chemical and biological sensing
applications.
4.2.5. Information Processing and Computation.
Hybrid metasurfaces can also be used as an optical platform
for information processing and computation. The encryption
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of optical information can be achieved by separating an image
into the phase profile of the incident light and the phase delay
of the metasurface. The original image can only be
reconstructed from incident light when the correct metasurface
key illuminated.268 With the design of hybrid material
metasurfaces, information encryption can potentially be
tailored by the external environment, where multimaterials
meta-units can adjust their optical responses after exposure to
chemical species.269 Hybrid metasurfaces are also promising
for visible-range deep diffractive networks, the next-generation
hardware for artificial intelligence.270 Currently, 3D-printed
diffractive networks can perform machine-learning tasks using
THz waves.270 However, the design of networks still requires a
computer-based training process based on optical simulations,
which can be slow and inaccurate. Hybrid reconfigurable
metasurfaces will allow on-the-fly tuning of meta-units during
training based on the measured network responses that
guarantee accuracy. We anticipate that fabricated metasurface
networks can contribute to a new regime for machine learning,
computer vision, and computational imaging.
4.3. Summary
In conclusion, this Review described how hybrid metasurfaces
provide expanded opportunities to manipulate light. Depend-
ing on the wavelength of interest and application, metasurfaces
can be constructed using plasmonic or dielectric materials. The
arrangement of building units enables either phase-gradient
metasurfaces with a phase discontinuity or diffractive coupled
metasurfaces supporting long-range coupling between units.
Integrating emitters with passive metasurfaces allows access to
two different coupling regimes: weak and strong coupling.
Under weak coupling, enhanced PL or nanoscale lasing is
observed, and the emissive properties can be manipulated by
the structural design of the metasurfaces. Under strong
coupling, metasurfaces serve as the photonic for producing
exciton−polaritons with controlled photophysical properties.
Moreover, combining metasurfaces with stimuli-responsive
materials enables mechanical and electrical tuning. Very
recently, emerging metasurface designs such as surface
functionalized metasurfaces and chemically tunable metasurfa-
ces have enabled materials engineering at the single-unit level
of a metasurface. Multilayer metasurface designs also offer an
approach to expand functionalities by introducing an addi-
tional physical dimension. We expect that future research in
hybrid material metasurfaces will significantly broaden
chemistry and photonics and will open applications in optical
devices, biological systems, quantum communication, and
energy generation and storage.
AUTHOR INFORMATION
Corresponding Author
Teri W. Odom − Department of Chemistry and Department
of Materials Science and Engineering, Northwestern
University, Evanston, Illinois 60208, United States;
orcid.org/0000-0002-8490-292X; Email: todom@
northwestern.edu
Authors
Jun Guan − Department of Chemistry, Northwestern
University, Evanston, Illinois 60208, United States;
orcid.org/0000-0001-8667-1611
Jeong-Eun Park − Department of Chemistry, Northwestern
University, Evanston, Illinois 60208, United States; Present
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Address: Department of Chemistry, Gwangju Institute of
Science and Technology (GIST), Gwangju 61005, Korea;
orcid.org/0000-0002-6926-2696
Shikai Deng − Department of Chemistry, Northwestern
University, Evanston, Illinois 60208, United States;
orcid.org/0000-0002-1895-2072
Max J. H. Tan − Department of Chemistry, Northwestern
University, Evanston, Illinois 60208, United States
Jingtian Hu − Department of Chemistry, Northwestern
University, Evanston, Illinois 60208, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.chemrev.2c00011
Notes
The authors declare no competing financial interest.
Biographies
Jun Guan is a postdoctoral fellow in the Department of Chemistry at
Northwestern University. She received her B.S. degree in Physics at
Sichuan University in 2016 and her Ph.D. degree in Applied Physics
at Northwestern University in 2021. Her research focuses on
integrating plasmonic lattices with quantum emitters and engineering
the light−matter interactions at the nanoscale.
Jeong-Eun Park is a postdoctoral fellow in the Department of
Chemistry at Northwestern University. She received her B.S. degree
in Chemistry at Pusan National University and her Ph.D. degree in
Chemistry at Seoul National University. Her research focuses on the
light−matter interactions in single and collective plasmonic
nanostructures.
Shikai Deng was a postdoctoral fellow in the Department of
Chemistry at Northwestern University. He obtained his B.S. degree
in Chemical Engineering at Beijing University of Chemical
Technology and his Ph.D. in Chemical Engineering at the University
of Illinois, Chicago. He is currently an associate professor at Shanghai
Institute of Microsystem and Information Technology, Chinese
Academy of Sciences. His research focuses on nanofabrication and
device application of plasmonic and thin-film nanomaterials.
Max Tan is a Ph.D. candidate in the Department of Chemistry at
Northwestern University. He received his B.S. degree in Chemistry at
the National University of Singapore 2019. His research focuses on
integrating plasmonic lattices with perovskite emitters for laser
engineering.
Jingtian Hu is a postdoctoral fellow in the Department of Electrical
and Computer Engineering at University of California, Los Angeles.
He received his B.S. degree in Materials Science and Engineering from
University of Illinois at Urbana−Champaign in 2013 and his Ph.D.
degree in Materials Science and Engineering at Northwestern
University. His research focuses on developing intelligent nano-
photonic platforms for all-optical machine learning.
Teri W. Odom is the Joan Husting Madden and William H. Madden,
Jr. Professor of Chemistry and Chair of the Department of Chemistry
at Northwestern University. She obtained her B.S. degree in
Chemistry at Stanford University and her Ph.D. in Chemical Physics
at Harvard University. Her research focuses on designing structured
multiscale nanoscale materials that exhibit extraordinary size- and
shape-dependent optical and physical properties.
ACKNOWLEDGMENTS
This work was supported by the Vannevar Bush Faculty
Fellowship from the U.S. Department of Defense (DOD
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Chemical Reviews
N00014-17-1-3023), the Office of Naval Research (ONR
N00014-21-1-2289), and the National Science Foundation
under DMR-1904385. S.D. gratefully thanks the Cottrell
Fellowship from the Research Corporation for Science
Advancement (ID 27464) and the National Science
Foundation (CHE-2039044).
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