Ershad Mohammadi1, Andreas Tittl2, Kosmas L Tsakmakidis3, T V Raziman1, Alberto G Curto1. 1. Department of Applied Physics and Institute for Photonic Integration, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands. 2. Chair in Hybrid Nanosystems, Nanoinstitute Munich, Faculty of Physics, Ludwig-Maximilians-Universität München, 80539 Munich, Germany. 3. Section of Condensed Matter Physics, Department of Physics, National and Kapodistrian University of Athens, Panepistimioupolis, GR-157 84 Athens, Greece.
Abstract
The discrimination of enantiomers is crucial in biochemistry. However, chiral sensing faces significant limitations due to inherently weak chiroptical signals. Nanophotonics is a promising solution to enhance sensitivity thanks to increased optical chirality maximized by strong electric and magnetic fields. Metallic and dielectric nanoparticles can separately provide electric and magnetic resonances. Here we propose their synergistic combination in hybrid metal-dielectric nanostructures to exploit their dual character for superchiral fields beyond the limits of single particles. For optimal optical chirality, in addition to maximization of the resonance strength, the resonances must spectrally coincide. Simultaneously, their electric and magnetic fields must be parallel and π/2 out of phase and spatially overlap. We demonstrate that the interplay between the strength of the resonances and these optimal conditions constrains the attainable optical chirality in resonant systems. Starting from a simple symmetric nanodimer, we derive closed-form expressions elucidating its fundamental limits of optical chirality. Building on the trade-offs of different classes of dimers, we then suggest an asymmetric dual dimer based on realistic materials. These dual nanoresonators provide strong and decoupled electric and magnetic resonances together with optimal conditions for chiral fields. Finally, we introduce more complex dual building blocks for a metasurface with a record 300-fold enhancement of local optical chirality in nanoscale gaps, enabling circular dichroism enhancement by a factor of 20. By combining analytical insight and practical designs, our results put forward hybrid resonators to increase chiral sensitivity, particularly for small molecular quantities.
The discrimination of enantiomers is crucial in biochemistry. However, chiral sensing faces significant limitations due to inherently weak chiroptical signals. Nanophotonics is a promising solution to enhance sensitivity thanks to increased optical chirality maximized by strong electric and magnetic fields. Metallic and dielectric nanoparticles can separately provide electric and magnetic resonances. Here we propose their synergistic combination in hybrid metal-dielectric nanostructures to exploit their dual character for superchiral fields beyond the limits of single particles. For optimal optical chirality, in addition to maximization of the resonance strength, the resonances must spectrally coincide. Simultaneously, their electric and magnetic fields must be parallel and π/2 out of phase and spatially overlap. We demonstrate that the interplay between the strength of the resonances and these optimal conditions constrains the attainable optical chirality in resonant systems. Starting from a simple symmetric nanodimer, we derive closed-form expressions elucidating its fundamental limits of optical chirality. Building on the trade-offs of different classes of dimers, we then suggest an asymmetric dual dimer based on realistic materials. These dual nanoresonators provide strong and decoupled electric and magnetic resonances together with optimal conditions for chiral fields. Finally, we introduce more complex dual building blocks for a metasurface with a record 300-fold enhancement of local optical chirality in nanoscale gaps, enabling circular dichroism enhancement by a factor of 20. By combining analytical insight and practical designs, our results put forward hybrid resonators to increase chiral sensitivity, particularly for small molecular quantities.
Chirality plays a vital
role in the functionality of biomolecules
such as proteins, amino acids, and carbohydrates.[1,2] It
also determines the interactions of chiral drugs within the human
body in terms of their healing potency and toxicity.[3,4] Furthermore, chirality could be one of the microscopic origins of
Alzheimer’s, Parkinson’s, and chronic kidney diseases.[5−7] Therefore, the detection and differentiation of chiral molecules
is of great interest in chemistry, biomedicine, and the food and pharmaceutical
industries.Chiral molecules reveal their handedness through
interaction with
another chiral entity such as circularly polarized light. Circular
dichroism (CD) spectroscopy exploits the difference in light absorption
for right- and left-handed circular polarizations.[8] The differential absorbed power of a small volume of a
chiral sample with respect to right and left circularly polarized
light can be expressed as[9]where c0, κ,
and V are the speed
of light, the Pasteur parameter of the chiral sample,[10] and the sample volume, respectively, and CR is the optical chirality under illumination with right-handed
circularly polarized light, which is assumed to be uniform inside
the sample. Optical chirality is defined as[11]where k0 is the
free-space wavevector and E and H are the
complex electric and magnetic fields. For small volumes of biomolecules,
the differential absorbed power (eq ) is exceptionally weak because both the chiral sample
volume and the Pasteur parameter are extremely small (Im(κ)
∼ 10–4–10–7).[12] To push down the detection limit, these weak
chiroptical signals can be compensated by an increase in optical chirality
even above that of a circularly polarized plane wave, motivating a
quest to find nanophotonic platforms for improved chiral sensitivity.[13−20]To increase optical chirality, we need both electric and magnetic
resonances to be as strong as possible. Their resonant peaks should
spectrally match to exploit the capability of such resonances for
optimal superchiral fields. Additionally, the corresponding electric
and magnetic fields in eq must be parallel and π/2 out of phase and spatially overlap.
We refer to this set of requirements as optimal conditions
for optical chirality. As we shall demonstrate, however,
the combination of these optimal conditions with maximal strength
of the resonances restricts the maximum attainable optical chirality
in nanophotonic structures.To date, efforts have focused on
exploiting either metallic[21−23] or dielectric particles,[16,24,25] for which the magnetic or electric
field enhancement is comparatively
weak. Metallic nanostructures can create intense electric dipole fields
thanks to localized surface plasmons.[26,27] On the other
hand, high-refractive-index dielectric nanoparticles offer strong
magnetic dipole response through Mie resonances[28−32] (Figure a). Dielectric nanostructures can create high optical chirality
close to the Kerker condition, where the electric and magnetic dipoles
have equal strengths.[9,33] However, the peaks of the two
resonances do not spectrally match, thus reducing the maximum optical
chirality. On the other hand, tuned resonant peaks destroy the phase
condition, resulting again in suboptimal optical chirality.[9,34]
Figure 1
Dual
nanoresonators for enhanced optical chirality. (a) Dual character
of the fields in individual electric and magnetic resonators. Edip (red) and Hdip (blue)
indicate the analogous dipolar fields associated with electric and
magnetic resonators (yellow and gray spheres, respectively). (b) A
dimer of dual nanoresonators illuminated by circularly polarized light
provides strong resonances with the optimal conditions for optical
chirality. Red and blue indicate electric and magnetic fields, respectively.
(c) Optical chirality enhancement at the center of a symmetric dimer
(eq ) vs the magnitudes
of the effective Mie coefficients, which are constrained to a maximum
value of 2.2. The dimer is made of two nanospheres with a center-to-center
distance of 160 nm. The optical chirality is calculated at the wavelength
λ = 560 nm and increases along the diagonal.
Dual
nanoresonators for enhanced optical chirality. (a) Dual character
of the fields in individual electric and magnetic resonators. Edip (red) and Hdip (blue)
indicate the analogous dipolar fields associated with electric and
magnetic resonators (yellow and gray spheres, respectively). (b) A
dimer of dual nanoresonators illuminated by circularly polarized light
provides strong resonances with the optimal conditions for optical
chirality. Red and blue indicate electric and magnetic fields, respectively.
(c) Optical chirality enhancement at the center of a symmetric dimer
(eq ) vs the magnitudes
of the effective Mie coefficients, which are constrained to a maximum
value of 2.2. The dimer is made of two nanospheres with a center-to-center
distance of 160 nm. The optical chirality is calculated at the wavelength
λ = 560 nm and increases along the diagonal.Here we exploit the complementary strengths of metal and
dielectric
nanostructures to obtain strong chiral hotspots. To understand the
general mechanism of chiral field formation in resonant structures,
we first focus on simple nanodimers and derive analytical expressions
describing the optical chirality at the center of the dimer. Through
this analysis, we classify the resonant systems into two categories:
incident-dipolar and fully dipolar. Then we find the fundamental limits
of optical chirality for each class of resonant systems, with the
highest value obtained for resonant dimers sustaining both electric
and magnetic resonances. On this basis, we introduce an idealized
dimer satisfying perfect duality symmetry.To harness this insight
with realistic materials, we propose a
hybrid dimer consisting of a metallic particle next to a high-refractive-index
dielectric particle (Figure b). In such a system, our theoretical results reveal strong
and decoupled electric and magnetic resonances, which are separately
tunable while meeting all of the other requirements to maximize optical
chirality. Finally, on the basis of the mechanisms identified in simple
nanodimers, we introduce a metal–dielectric metasurface for
practical chiral detection. The proposed structure creates optical
chirality hotspots 300 times stronger than the incident field, which
is a significant enhancement compared with state-of-the-art dielectric
nanostructures. These chiral hotspots are also able to enhance the
average value of optical chirality, resulting in an enhancement of
CD signals by a factor of 20.
Nanodimers in the Electric–Magnetic
Dipole Approximation
To recognize the different mechanisms
governing the formation of
chiral fields in resonant systems, we first analyze a typical dimer
composed of two identical spheres of diameter D separated
by a center-to-center distance l along the y axis (Figure ). The dimer is illuminated by circularly polarized light
propagating along the z axis. For practical applications,
the spherical particles could be replaced by disks on top of a substrate.[35,36] The optical response of this system can be described by replacing
each particle by an electric dipole and a magnetic dipole.[37] This electric–magnetic dipole approximation
is valid as long as the particle dimensions are much smaller than
the wavelength (k0D ≪
1) and the interparticle distance l is larger than
the particle dimensions.[38−40] The electromagnetic interaction
of these dipoles is then given by a self-consistent system of coupled
equations. Solving this system yields the dipole moments induced in
each particle (Supporting Section S1).
Figure 2
The optical
chirality at the gap of symmetric dimers is controlled
by the strength and phase of the effective Mie coefficients. We compare
metallic (gold), dielectric (silicon), and ideal dual dimers with
the same particle diameters of 130 nm and interparticle distance of
160 nm, corresponding to a gap of 30 nm. (a–c) Magnitudes of
the effective electric (red) and magnetic (blue) dipolar Mie coefficients
and the phase coefficient (green). (d–f) Optical chirality
enhancement calculated using eq (black) and full-wave numerical simulations (orange) along
with the fundamental limit for each dimer (red).
The optical
chirality at the gap of symmetric dimers is controlled
by the strength and phase of the effective Mie coefficients. We compare
metallic (gold), dielectric (silicon), and ideal dual dimers with
the same particle diameters of 130 nm and interparticle distance of
160 nm, corresponding to a gap of 30 nm. (a–c) Magnitudes of
the effective electric (red) and magnetic (blue) dipolar Mie coefficients
and the phase coefficient (green). (d–f) Optical chirality
enhancement calculated using eq (black) and full-wave numerical simulations (orange) along
with the fundamental limit for each dimer (red).The dominant dipole components producing chiral fields are those
along the dimer axis. Therefore, we consider only the y components of the dipoles in our analysis (Supporting Section S2). Similarly to conventional gap antennas for electric
field enhancement alone, such parallel dipoles ensure the existence
of parallel field components in the gap as well as their spatial overlap.
The optimal conditions for chiral fields then reduce to achieving
spectral overlap of the resonances and π/2 dephasing of the
electric and magnetic fields. As shown in Supporting Section S1, the optical chirality at the center of the nanodimer
normalized to that of the incident field iswhere Cinc = k0/c0η0, in which η0 is the free-space wave impedance;
ζ(x) = exp(−ix)(ix–2 + x–3)/2π is related to the yy component of the
dyadic Green’s function of dipole radiation in free space;
and the effective electric and magnetic dipolar Mie coefficients for
the nanodimer arewhere a1 and b1 are the electric and magnetic dipolar Mie
coefficients of the individual particles, respectively.[41]The optical chirality enhancement at the
center of a general nanodimer
is given analytically by eq in the electric–magnetic dipole approximation. We
represent it as a function of the effective Mie coefficients in Figure c. First, we consider
purely real values for the effective Mie coefficients and later investigate
the effect of a phase difference between them. The diagonal increase
in the optical chirality confirms the capability of dual electric
and magnetic resonances to achieve strong superchiral fields. To understand
how such resonances give rise to optical chirality, we return to eq to find the origin of
its different terms (Supporting Section S3). The first constant term comes from the y components
of the incident fields. The second term corresponds to the interaction
of incident and dipolar fields, for which ζ(k0l/2)a1,eff and ζ*(k0l/2)b1,eff* express the interaction of the incident magnetic field with the
dipolar electric field and the incident electric field with the dipolar
magnetic field, respectively. Finally, the last term provides the
optical chirality due to the interaction of the dipolar electric and
magnetic fields.On this foundation, we
can classify dimer resonators on the basis
of the origin of optical chirality from incident-dipolar fields or
fully dipolar fields (Supporting Section S3). This classification helps us to find a fundamental upper limit
of optical chirality for different types of resonant systems. For
resonators supporting only electric resonances, such as metallic dimers,
the dominant part of optical chirality in eq is 3π|ζ(k0l/2)||a1,eff |
cos(ΔΦinc–dip), where ΔΦinc–dip = ∠[ζ(k0l/2)a1,eff] –
π/2. The phase coefficient cos(ΔΦinc–dip) indicates the dephasing of the dipolar electric and incident magnetic
fields, where cos(ΔΦinc–dip) = ±1
is the perfect phase condition. On the other hand, for resonators
with both electric and magnetic resonances, such as dielectric dimers,
the dominant term iswhere ΔΦdip–dip = ∠a1,eff – ∠b1,eff. A unity phase coefficient (i.e., cos(ΔΦdip–dip) = 1) guarantees π/2 out of phase dipolar
electric and magnetic fields.For particles without gain, there
is an upper limit of unity to
the Mie coefficients of the individual resonators,[42] which sets a limit of 2.2 on the effective Mie coefficients
of dimers (Figure c and Supporting Section S4). Accordingly,
the fundamental limit of optical chirality is 6.6π|ζ(k0l/2)| for a metallic dimer
and the significantly higher value of 87.12π2|ζ(k0l/2)|2 for a dielectric
dimer. These strikingly different limits prove the promise of electric–magnetic
resonant systems for strong chiral fields, for which |a1,eff||b1,eff| cos(ΔΦdip–dip) should be maximized. Analogously, we can classify
the individual nanoresonators and find the fundamental limits in each
class (Supporting Section S5). Our analysis
shows that the fundamental limits are 2.2 and 2.22 times
higher for the dimers compared with individual nanoparticles for the
incident-dipolar and fully dipolar classes, respectively. We note
that the fundamental limits derived above using the dipolar approximation
for dimers could be generalized to multipolar resonators and higher
numbers of nanoparticles.To investigate the interplay between
the resonance strength and
the optimal conditions for optical chirality, we compare metallic
and dielectric dimers with a hypothetical dimer fulfilling dipolar
duality symmetry (Figure ).[43,44] Such an ideal dual dimer consists
of particles with equal electric and magnetic dipolar responses (a1 = b1). In all
three cases, the diameter of the spherical particles is D = 130 nm and the gap is g = 30 nm (interparticle
distance l = 160 nm). For a fair comparison, we set
the resonance wavelengths of the three systems to the same spectral
range to take into account the increase in the fundamental limit of
optical chirality at longer wavelengths (see eq and red lines in Figures d–f). Hence, for the ideal dual dimer,
we choose the permittivity and the permeability as ϵ = μ
= 4.75 – 0.01i, resulting in a resonance at around λ
= 560 nm. It should be noted that we use the time-harmonic convention
exp(iωt) throughout this article, which determines
the sign of the imaginary part of the permittivity.First, we
calculate the magnitude of the effective dipolar Mie
coefficients and the phase coefficients for metallic, dielectric,
and dual dimers (Figure a–c). The negligible effective magnetic Mie coefficient (blue)
in the metallic dimer results in an electric-resonant system. Consequently,
it has a much lower fundamental limit of optical chirality than the
dielectric and dual dimers (red curves in Figure d–f). Furthermore, the small phase
coefficient around the peak of its effective electric Mie coefficient
(vertical dashed line) prevents using the full strength of the electric
resonance for chirality. In contrast, the dielectric dimer provides
a larger value of a1,eff close to the
resonance peak of b1,eff. Nevertheless,
the phase coefficient is still suboptimal, with cos(ΔΦdip–dip) = 0.5.The ideal dual symmetric dimer
removes the main drawbacks of the
metallic dimer (small fundamental limit) and the dielectric dimer
(imperfect phase coefficient). Duality symmetry provides spectrally
matched effective Mie coefficients higher than 1. The phase coefficient
is also perfect as a consequence of preserving the helicity of the
incident field, which ensures that the scattered light has a π/2
phase difference between the electric and magnetic field components.
The dual symmetric dimer thus offers stronger chiral fields than the
dielectric and plasmonic dimers as a result of optimal utilization
of the fundamental limit. To conclude the study of eq , we calculate the optical chirality
for the three cases both analytically and through full-wave numerical
simulations (Figures d–f, black and orange curves). The good agreement proves the
validity of the approximations.
Hybrid Metal–Dielectric
Nanodimers
To tap into the insight gained so far from symmetric
dimers, we
propose asymmetric metal–dielectric dimers with realistic materials
as a new type of electric–magnetic resonator. Such systems
offer a fundamental limit of optical chirality that is as high as
that of the dielectric and dual dimers while leveraging the stronger
effective electric Mie coefficients of plasmonic dimers. Furthermore,
this hybrid route allows a simple approach to obtain decoupled electric
and magnetic resonances with controllable spectral matching and a
perfect phase condition.To understand the physical origin of
these unique opportunities,
we study a hybrid dimer composed of gold and silicon nanospheres (Figure a). They have diameters DAu and DSi and are
placed at y = −lAu = −(g + DAu)/2
and y = lSi = (g + DSi)/2, respectively, where g is the gap. The resulting self-consistent system is similar
to that of the symmetric dimer, but now the metal particle sustains
only an electric dipole. Solving this system of equations yields the
effective electric and magnetic dipolar Mie coefficients of the hybrid
dimer (Supporting Section S6):where l = lAu + lSi, a1Au and a1Si are the electric dipolar Mie coefficients of the single
plasmonic
and dielectric particles, respectively, and b1Si is the magnetic
dipolar Mie coefficient of the dielectric particle.
Figure 3
Hybrid metal–dielectric
dimers. (a) A dimer consisting of
a metallic sphere and a dielectric sphere separated by a distance l = lAu + lSi is illuminated with a circularly polarized plane wave
propagating along the z axis. (b, c) Investigation
of resonance strength and optimal conditions for optical chirality
by comparison of the magnitudes (red and blue) and the phase coefficient
(green) of the effective electric and magnetic dipolar Mie coefficients
in eqs and 8. We fix the diameter of the dielectric particle
at 130 nm and sweep the size of the metallic sphere to maximize |a1,eff||b1,eff| cos(ΔΦ) for the highest
optical chirality.
(d) Simulated electric and magnetic field enhancements (purple and
blue), (e) phase factor, and (f) optical chirality enhancement at
the center of the hybrid dimer for different diameters of the metallic
particle. The vertical dashed line indicates the magnetic resonance
of the dimer. The thickest line in each panel highlights the diameter
with the highest optical chirality.
Hybrid metal–dielectric
dimers. (a) A dimer consisting of
a metallic sphere and a dielectric sphere separated by a distance l = lAu + lSi is illuminated with a circularly polarized plane wave
propagating along the z axis. (b, c) Investigation
of resonance strength and optimal conditions for optical chirality
by comparison of the magnitudes (red and blue) and the phase coefficient
(green) of the effective electric and magnetic dipolar Mie coefficients
in eqs and 8. We fix the diameter of the dielectric particle
at 130 nm and sweep the size of the metallic sphere to maximize |a1,eff||b1,eff| cos(ΔΦ) for the highest
optical chirality.
(d) Simulated electric and magnetic field enhancements (purple and
blue), (e) phase factor, and (f) optical chirality enhancement at
the center of the hybrid dimer for different diameters of the metallic
particle. The vertical dashed line indicates the magnetic resonance
of the dimer. The thickest line in each panel highlights the diameter
with the highest optical chirality.The electric resonances of the metallic and dielectric particles
are thus coupled and form an effective electric resonance (eq ). Remarkably, the effective
magnetic resonance of the system is determined only by the dielectric
particle and is decoupled from the effective electric resonance (eq ). As a result, we can
maximize the product |a1,eff||b1,eff| by tailoring the effective electric dipolar
Mie coefficient to be as strong as possible while spectrally matching
the magnetic resonance. However, the phase coefficient should also
be taken into account for optimal optical chirality.To demonstrate
such tunability, we consider a hybrid metal–dielectric
system with a fixed diameter of the dielectric particle providing
a magnetic resonance at λ = 550 nm (Figure b, blue). We sweep the diameter of the metallic
particle to control the effective electric dipolar Mie coefficient
of the hybrid dimer (red). The metal–dielectric system can
be engineered to provide high values of |a1,eff|, comparable to that of metallic dimers (Figure a), and spectrally coincide with the magnetic
resonance. The phase coefficient cos(ΔΦdip–dip) is also close to unity around the magnetic resonance of the dimer
(Figure c).We examine next the electromagnetic fields, the phase condition,
and the optical chirality enhancement at the center of the hybrid
dimer using numerical simulations (Figure d–f). To evaluate the phase condition,
we define the phase factor Fϕ =
sin(Δϕ), where Δϕ = ∠E – ∠H is the phase difference between dominant
field components. The strongest electric field that overlaps with
the magnetic resonance occurs for DAu =
110 nm (Figure d,
thicker purple line). For this diameter, the phase factor Fϕ vanishes 10 nm away from the magnetic
resonance (Figure e inset). This perfect phase condition cannot be found in metallic
or dielectric dimers, but it is realized by a hybrid nanodimer. The
optical chirality is thus maximized at the wavelength λ = 560
nm, yielding a 14-fold enhancement (Figure f). For smaller gaps, the attainable optical
chirality can be even higher as a result of enhanced electric hotspots
(Supporting Section S7).
Hybrid Metasurface
for Chiral Sensing
In nanophotonics-enhanced chiral sensing,
the sample is usually
uniformly dispersed over the nanostructures. The CD signal is then
proportional to the optical chirality averaged over the volume of
the chiral sample.[9,14] It is therefore highly desirable
to increase the average value of the optical chirality, which is restricted
by the small volume of the chiral hotspots. To remedy this limitation
of simple nanodimers, we propose a hybrid metal–dielectric
metasurface for practical chiral sensing by leveraging multiple chiral
hotspots.The basic constituent element of the proposed metasurface
is a
metallic nanorod next to a silicon disk (Figure a). Similar to our analysis above for spherical
dimers, the strategy is to realize a strong electric hotspot with
perfect phase close to a fixed magnetic resonance of the silicon disk
(λ = 710 nm in Figure b). We vary the nanorod length to control the electric resonances
and to achieve a phase factor of unity. Under illumination with circularly
polarized light, we calculate the electric and magnetic field enhancements
at the center of the gap (Figure b). The magnetic field enhancement is constant for
different nanorod lengths (Figure b, all shown by a single blue curve), which confirms
the decoupling of the magnetic resonance from the electric resonance.
Furthermore, there is a strong electric hotspot that spectrally overlaps
with the magnetic resonance for an optimal length of 80 nm. In this
case, the phase factor is close to perfect around the magnetic resonance
(Figure c inset, orange),
resulting in a 375-fold enhancement of the optical chirality. To the
best of our knowledge, this is the highest enhancement of local optical
chirality in the visible and near-infrared reported to date.[45]
Figure 4
Basic building block for a realistic metasurface exploiting
dual
resonators. (a) A gold nanorod next to a silicon disk. The diameter D and height h of the silicon disk are
both 160 nm. The width and the thickness of the nanorod are w = 30 and t = 15 nm, respectively, and
its length l is varied to tune the electric resonance
independently of the magnetic resonance of the silicon disk. (b) Electric
and magnetic field enhancements and (c) optical chirality enhancement
at the center of the gap under illumination with circularly polarized
light propagating along the disk axis. The inset in (c) shows the
corresponding phase factors.
Basic building block for a realistic metasurface exploiting
dual
resonators. (a) A gold nanorod next to a silicon disk. The diameter D and height h of the silicon disk are
both 160 nm. The width and the thickness of the nanorod are w = 30 and t = 15 nm, respectively, and
its length l is varied to tune the electric resonance
independently of the magnetic resonance of the silicon disk. (b) Electric
and magnetic field enhancements and (c) optical chirality enhancement
at the center of the gap under illumination with circularly polarized
light propagating along the disk axis. The inset in (c) shows the
corresponding phase factors.To increase the total volume of the chiral hotspots, we use multiple
nanorods arranged as a hybrid oligomer. This approach is suitable
as long as the coupling between nanorods does not disturb the main
mechanism of chiral field formation. We surround a central silicon
disk by eight identical gold nanorods equally spaced around the disk
equator (see the metasurface unit cell in Figure a). The metasurface is covered by a chiral
thin film with a thickness of 20 nm that coats the substrate and the
outer surfaces of the structures. Because of the presence of a glass
substrate and a buffer superstrate, we adjust the dimensions of the
nanorods to an optimal length of 60 nm. The chiral sample on the metasurface
displays a small difference in the transmission spectra for illumination
with right- and left-handed circularly polarized light, IR and IL (Figure b, including a close-up around
the resonance). The coupled electric resonances in the nanorods and
the disk provide strong electric hotspots at the magnetic resonance
wavelength of the disk (Figure c,d). These spectrally overlapping resonances provide electric
and magnetic fields that are dephased by π/2, leading to a 300-fold
enhancement in optical chirality in every nanogap (Figure e).
Figure 5
Hybrid metal–dielectric
metasurface for enhanced chiral
molecular detection. (a) Unit cell with a silicon disk surrounded
by gold nanorods. Above the substrate, there is a buffer solution
with a refractive index of 1.33. A planar chiral layer with a thickness
of 20 nm covers the metasurface. The refractive index and the Pasteur
parameter of the chiral sample are 1.46 – 0.01i and κ
= 0 ± 0.001i, respectively. (b) Transmission spectra for right
and left circularly polarized light. The inset shows the difference
in transmission around the resonance. (c–e) Electric field,
magnetic field, and optical chirality enhancements at resonance (λ
= 720 nm) on a plane at the center of the nanorods. (f) Enhanced circular
dichroism signals for positive (red) and negative (blue) Pasteur parameters
as retrieved from the transmission spectra in (b), compared with the
theoretical prediction obtained using eq . The inset shows the CD of the chiral layer alone.
Hybrid metal–dielectric
metasurface for enhanced chiral
molecular detection. (a) Unit cell with a silicon disk surrounded
by gold nanorods. Above the substrate, there is a buffer solution
with a refractive index of 1.33. A planar chiral layer with a thickness
of 20 nm covers the metasurface. The refractive index and the Pasteur
parameter of the chiral sample are 1.46 – 0.01i and κ
= 0 ± 0.001i, respectively. (b) Transmission spectra for right
and left circularly polarized light. The inset shows the difference
in transmission around the resonance. (c–e) Electric field,
magnetic field, and optical chirality enhancements at resonance (λ
= 720 nm) on a plane at the center of the nanorods. (f) Enhanced circular
dichroism signals for positive (red) and negative (blue) Pasteur parameters
as retrieved from the transmission spectra in (b), compared with the
theoretical prediction obtained using eq . The inset shows the CD of the chiral layer alone.From the transmission spectra, we calculate the
CD as a function
of differential transmittance as tan–1[(TR – TL)/(TR + TL)] (Figure f).[46] The CD enhancement[14] can be
expressed aswhere CD0 is the CD of the chiral
film without nanostructures and T and Cav denote the transmittance and the average optical chirality
over the sample, respectively, when the system is illuminated with
either right- or left-handed circularly polarized light (Supporting Section S8). Apart from the average
optical chirality, the CD depends on the transmission in a similar
way as the dissymmetry factor for chiral molecules, which is inversely
proportional to the electric energy density.[11] In most relevant studies exploiting transmission (absorption), the
circular dichroism (dissymmetry factor) enhancement is achieved by
suppressing the transmittance (electric energy density), which degrades
the signal-to-noise ratio. In contrast, our hybrid metasurface retains
40% of the transmission near the resonance. The CD enhancement predicted
by eq shows good agreement
with numerical simulations (Figure f, pink and red). The hybrid metasurface creates a
20-fold enhancement of CD compared with the chiral layer without nanostructures.
The enhanced CD is due to the higher average value of chiral fields
over the volume of the chiral sample aided by the stronger local optical
chirality in the hotspots (Figure e). Reversing the handedness of the chiral molecules
reverses the CD as well, confirming that the structure does not introduce
any chiroptical background.
Conclusions
We have presented metal–dielectric
nanostructures as dual
electric–magnetic resonators for achieving strong chiral fields.
We derived closed-form expressions for the optical chirality in a
symmetric nanodimer. On the basis of the dominant term, we classified
the resonant systems into distinct incident-dipolar and fully dipolar
categories. We then extracted the fundamental upper limits of optical
chirality for each class, demonstrating values for dimers beyond those
of single nanoparticles. Through our analytical treatment, we merged
different requirements for the optical chirality into only two conditions:
the magnitude and the phase retardation of the effective Mie coefficients
of the dimers. On the basis of these observations for symmetric dimers,
we exploited a combination of the electric and magnetic resonances
found in metallic and high-index dielectric nanoparticles. We showed
that hybrid nanosphere dimers can provide larger values of the effective
Mie coefficients. Together with spectral overlap of the resonances
and a perfect phase, the asymmetric dual dimers result in superchiral
light in nanoscale gaps.To obtain a practical metasurface for
chiral sensing, we adapted
the spherical nanodimers into an array of disk–rod oligomers
sustaining two strong but decoupled electric and magnetic resonances.
The decoupling of the resonances provides design flexibility and enables
a straightforward realization of maximal electric hotspots at the
same wavelength as the magnetic resonance of the dielectric particle.
We demonstrated that the proposed metasurface improves the CD by a
factor of 20 relative to a chiral thin film thanks to the formation
of hotspots with extreme local optical chirality. The possibility
of obtaining strong fields for enhanced circular dichroism in metal–dielectric
nanogap antennas will push the sensitivity of chiral molecular detection
to the few- and single-molecule regimes.
Methods
We perform
full-wave numerical simulations using the finite element
method in COMSOL Multiphysics 5.5. To incorporate the Pasteur parameter
into the simulations, we modified the built-in default wave equations
in COMSOL according to the constitutive relations for a chiral medium.[14] In Figures and 5, the width and height
of the nanorods are 30 and 15 nm, respectively. The diameter and the
height of the silicon disk are both 160 nm. The ends of the nanorods
are rounded with a radius of 15 nm for a realistic geometry and to
avoid numerical errors.[47] For maximum access
to the magnetic fields outside of the dielectric particle, the nanorods
should be aligned around the equator of the silicon disk. The gap
between the each nanorod and the disk is 5 nm. The metallic and dielectric
nanostructures are made of gold and silicon with realistic permittivities.[48,49] In Figure , the
length of the nanorods is 45 nm. The lattice constant of the metasurface
is 440 nm, and the refractive index of the glass substrate is 1.5.