Pixelated High-Q Metasurfaces for in Situ Biospectroscopy and Artificial Intelligence-Enabled Classification of Lipid Membrane Photoswitching Dynamics.

Nanophotonic devices excel at confining light into intense hot spots of electromagnetic near fields, creating exceptional opportunities for light-matter coupling and surface-enhanced sensing. Recently, all-dielectric metasurfaces with ultrasharp resonances enabled by photonic bound states in the continuum (BICs) have unlocked additional functionalities for surface-enhanced biospectroscopy by precisely targeting and reading out the molecular absorption signatures of diverse molecular systems. However, BIC-driven molecular spectroscopy has so far focused on end point measurements in dry conditions, neglecting the crucial interaction dynamics of biological systems. Here, we combine the advantages of pixelated all-dielectric metasurfaces with deep learning-enabled feature extraction and prediction to realize an integrated optofluidic platform for time-resolved in situ biospectroscopy. Our approach harnesses high-Q metasurfaces specifically designed for operation in a lossy aqueous environment together with advanced spectral sampling techniques to temporally resolve the dynamic behavior of photoswitchable lipid membranes. Enabled by a software convolutional neural network, we further demonstrate the real-time classification of the characteristic cis and trans membrane conformations with 98% accuracy. Our synergistic sensing platform incorporating metasurfaces, optofluidics, and deep learning reveals exciting possibilities for studying multimolecular biological systems, ranging from the behavior of transmembrane proteins to the dynamic processes associated with cellular communication.

Optically addressable spin defects coupled to bound states in the continuum metasurfaces.

Van der Waals (vdW) materials, including hexagonal boron nitride (hBN), are layered crystalline solids with appealing properties for investigating light-matter interactions at the nanoscale. hBN has emerged as a versatile building block for nanophotonic structures, and the recent identification of native optically addressable spin defects has opened up exciting possibilities in quantum technologies. However, these defects exhibit relatively low quantum efficiencies and a broad emission spectrum, limiting potential applications. Optical metasurfaces present a novel approach to boost light emission efficiency, offering remarkable control over light-matter coupling at the sub-wavelength regime. Here, we propose and realise a monolithic scalable integration between intrinsic spin defects in hBN metasurfaces and high quality (Q) factor resonances, exceeding 102, leveraging quasi-bound states in the continuum (qBICs). Coupling between defect ensembles and qBIC resonances delivers a 25-fold increase in photoluminescence intensity, accompanied by spectral narrowing to below 4 nm linewidth and increased narrowband spin-readout efficiency. Our findings demonstrate a new class of metasurfaces for spin-defect-based technologies and pave the way towards vdW-based nanophotonic devices with enhanced efficiency and sensitivity for quantum applications in imaging, sensing, and light emission.

Multi-band Metasurface-Driven Surface-Enhanced Infrared Absorption Spectroscopy for Improved Characterization of in-Situ Electrochemical Reactions.

Surface-enhanced spectroscopy techniques are the method-of-choice to characterize adsorbed intermediates occurring during electrochemical reactions, which are crucial in realizing a green and sustainable future. Characterizing species with low coverage or short lifetimes has so far been limited by low signal enhancement. Recently, single-band metasurface-driven surface-enhanced infrared absorption spectroscopy (SEIRAS) has been pioneered as a promising technology to monitor a single vibrational mode during electrochemical CO oxidation. However, electrochemical reactions are complex, and their understanding requires the simultaneous monitoring of multiple adsorbed species in situ, hampering the adoption of nanostructured electrodes in spectro-electrochemistry. Here, we develop a multi-band nanophotonic-electrochemical platform that simultaneously monitors in situ multiple adsorbed species emerging during cyclic voltammetry scans by leveraging the high resolution offered by the reproducible nanostructuring of the working electrode. Specifically, we studied the electrochemical reduction of CO2 on a Pt surface and used two separately tuned metasurface arrays to monitor two adsorption configurations of CO with vibrational bands at ∼2030 and ∼1840 cm-1. Our platform provides a ∼40-fold enhancement in the detection of characteristic absorption signals compared to conventional broadband electrochemically roughened platinum films. A straightforward methodology is outlined starting with baselining our system in a CO-saturated environment and clearly detecting both configurations of adsorption. In contrast, during the electrochemical reduction of CO2 on platinum in K2CO3, CO adsorbed in a bridged configuration could not be detected. We anticipate that our technology will guide researchers in developing similar sensing platforms to simultaneously detect multiple challenging intermediates, with low surface coverage or short lifetimes.

Unlocking the out-of-plane dimension for photonic bound states in the continuum to achieve maximum optical chirality.

The realization of lossless metasurfaces with true chirality crucially requires the fabrication of three-dimensional structures, constraining experimental feasibility and hampering practical implementations. Even though the three-dimensional assembly of metallic nanostructures has been demonstrated previously, the resulting plasmonic resonances suffer from high intrinsic and radiative losses. The concept of photonic bound states in the continuum (BICs) is instrumental for tailoring radiative losses in diverse geometries, especially when implemented using lossless dielectrics, but applications have so far been limited to planar structures. Here, we introduce a novel nanofabrication approach to unlock the height of individual resonators within all-dielectric metasurfaces as an accessible parameter for the efficient control of resonance features and nanophotonic functionalities. In particular, we realize out-of-plane symmetry breaking in quasi-BIC metasurfaces and leverage this design degree of freedom to demonstrate an optical all-dielectric quasi-BIC metasurface with maximum intrinsic chirality that responds selectively to light of a particular circular polarization depending on the structural handedness. Our experimental results not only open a new paradigm for all-dielectric BICs and chiral nanophotonics, but also promise advances in the realization of efficient generation of optical angular momentum, holographic metasurfaces, and parity-time symmetry-broken optical systems.

Two-Dimensional Chiral Metasurfaces Obtained by Geometrically Simple Meta-atom Rotations.

Two-dimensional chiral metasurfaces seem to contradict Lord Kelvin's geometric definition of chirality since they can be made to coincide by performing rotational operations. Nevertheless, most planar chiral metasurface designs often use complex meta-atom shapes to create flat versions of three-dimensional helices, although the visual appearance does not improve their chiroptical response but complicates their optimization and fabrication due to the resulting large parameter space. Here we present one of the geometrically simplest two-dimensional chiral metasurface platforms consisting of achiral dielectric rods arranged in a square lattice. Chirality is created by rotating the individual meta-atoms, making their arrangement chiral and leading to chiroptical responses that are stronger or comparable to more complex designs. We show that resonances depending on the arrangement are robust against geometric variations and behave similarly in experiments and simulations. Finally, we explain the origin of chirality and behavior of our platform by simple considerations of the geometric asymmetry and gap size.

Probing the micro- and nanoscopic properties of dental materials using infrared spectroscopy: A proof-of-principle study.

The preservation of oral health over a person's lifespan is a key factor for a high quality of life. Sustaining oral health requires high-end dental materials with a plethora of attributes such as durability, non-toxicity and ease of application. The combination of different requirements leads to increasing miniaturization and complexity of the material components such as the composite and adhesives, which makes the precise characterization of the material blend challenging. Here, we demonstrate how modern IR spectroscopy and imaging from the micro- to the nanoscale can provide insights on the chemical composition of the different material sections of a dental filling. We show how the recorded IR-images can be used for a fast and non-destructive porosity determination of the studied adhesive. Furthermore, the nanoscale study allows precise assessment of glass cluster structures and distribution within their characteristic organically modified ceramic (ORMOCER) matrix and an assessment of the interface between the composite and adhesive material. For the study we used a Fourier-Transform-IR (FTIR) microscope and a quantum cascade laser-based IR-microscope (QCL-IR) for the microscale analysis and a scattering-type scanning near-field optical microscopy (s-SNOM) for the nanoscale analysis. The paper ends with an in-depth discussion of the strengths and weaknesses of the different imaging methods to give the reader a clear picture for which scientific question the microscopes are best suited for. STATEMENT OF SIGNIFICANCE: Modern resin-based composites for dental restoration are complex multi-compound materials. In order to improve these high-end materials, it is important to investigate the molecular composition and morphology of the different parts. An emergent method to characterize these materials is infrared spectroscopic imaging, which combines the strength of infrared spectroscopy and an imaging approach known from optical microscopy. In this work, three state of the art methods are compared for investigating a dental filling including FTIR- and quantum cascade laser IR-imaging microscopy for the microscale and scattering-type scanning near-field optical microscopy for the nanoscale.

Intrinsic strong light-matter coupling with self-hybridized bound states in the continuum in van der Waals metasurfaces.

Photonic bound states in the continuum (BICs) provide a standout platform for strong light-matter coupling with transition metal dichalcogenides (TMDCs) but have so far mostly been implemented as traditional all-dielectric metasurfaces with adjacent TMDC layers, incurring limitations related to strain, mode overlap and material integration. Here, we demonstrate intrinsic strong coupling in BIC-driven metasurfaces composed of nanostructured bulk tungsten disulfide (WS2) and exhibiting resonances with sharp, tailored linewidths and selective enhancement of light-matter interactions. Tuning of the BIC resonances across the exciton resonance in bulk WS2 is achieved by varying the metasurface unit cells, enabling strong coupling with an anticrossing pattern and a Rabi splitting of 116 meV. Crucially, the coupling strength itself can be controlled and is shown to be independent of material-intrinsic losses. Our self-hybridized metasurface platform can readily incorporate other TMDCs or excitonic materials to deliver fundamental insights and practical device concepts for polaritonic applications.

Permittivity-Asymmetric Quasi-Bound States in the Continuum.

Breaking the in-plane geometric symmetry of dielectric metasurfaces allows us to access a set of electromagnetic states termed symmetry-protected quasi-bound states in the continuum (qBICs). Here we demonstrate that qBICs can also be accessed by a symmetry breaking in the permittivity of the comprising materials. While the physical size of atoms imposes a limit on the lowest achievable geometrical asymmetry, weak permittivity modulations due to carrier doping, and electro-optical Pockels and Kerr effects, usually considered insignificant, open the possibility of infinitesimal permittivity asymmetries for on-demand, dynamically tunable resonances of extremely high quality factors. As a proof-of-principle, we probe the excitation of permittivity-asymmetric qBICs (ε-qBICs) using a prototype Si/TiO2 metasurface, in which the asymmetry in the unit cell is provided by the permittivity contrast of the materials. ε-qBICs are also numerically demonstrated in 1D gratings, where quality-factor enhancement and tailored interference phenomena of qBICs are shown via the interplay of geometrical and permittivity asymmetries.

Metasurface-Enhanced Infrared Spectroscopy: An Abundance of Materials and Functionalities.

Infrared spectroscopy provides unique information on the composition and dynamics of biochemical systems by resolving the characteristic absorption fingerprints of their constituent molecules. Based on this inherent chemical specificity and the capability for label-free, noninvasive, and real-time detection, infrared spectroscopy approaches have unlocked a plethora of breakthrough applications for fields ranging from environmental monitoring and defense to chemical analysis and medical diagnostics. Nanophotonics has played a crucial role for pushing the sensitivity limits of traditional far-field spectroscopy by using resonant nanostructures to focus the incident light into nanoscale hot-spots of the electromagnetic field, greatly enhancing light-matter interaction. Metasurfaces composed of regular arrangements of such resonators further increase the design space for tailoring this nanoscale light control both spectrally and spatially, which has established them as an invaluable toolkit for surface-enhanced spectroscopy. Starting from the fundamental concepts of metasurface-enhanced infrared spectroscopy, a broad palette of resonator geometries, materials, and arrangements for realizing highly sensitive metadevices is showcased, with a special focus on emerging systems such as phononic and 2D van der Waals materials, and integration with waveguides for lab-on-a-chip devices. Furthermore, advanced sensor functionalities of metasurface-based infrared spectroscopy, including multiresonance, tunability, dielectrophoresis, live cell sensing, and machine-learning-aided analysis are highlighted.

High-Q Nanophotonics over the Full Visible Spectrum Enabled by Hexagonal Boron Nitride Metasurfaces.

All-dielectric optical metasurfaces with high quality (Q) factors have been hampered by the lack of simultaneously lossless and high-refractive-index materials over the full visible spectrum. In fact, the use of low-refractive-index materials is unavoidable for extending the spectral coverage due to the inverse correlation between the bandgap energy (and therefore the optical losses) and the refractive index (n). However, for Mie resonant photonics, smaller refractive indices are associated with reduced Q factors and low mode volume confinement. Here, symmetry-broken quasi bound states in the continuum (qBICs) are leveraged to efficiently suppress radiation losses from the low-index (n ≈ 2) van der Waals material hexagonal boron nitride (hBN), realizing metasurfaces with high-Q resonances over the complete visible spectrum. The rational use of low- and high-refractive-index materials as resonator components is analyzed and the insights are harnessed to experimentally demonstrate sharp qBIC resonances with Q factors above 300, spanning wavelengths between 400 and 1000 nm from a single hBN flake. Moreover, the enhanced electric near fields are utilized to demonstrate second-harmonic generation with enhancement factors above 102 . These results provide a theoretical and experimental framework for the implementation of low-refractive-index materials as photonic media for metaoptics.

Plasmonic bound states in the continuum to tailor light-matter coupling.

Plasmon resonances play a pivotal role in enhancing light-matter interactions in nanophotonics, but their low-quality factors have hindered applications demanding high spectral selectivity. Here, we demonstrate the design and 3D laser nanoprinting of plasmonic nanofin metasurfaces, which support symmetry-protected bound states in the continuum up to the fourth order. By breaking the nanofins' out-of-plane symmetry in parameter space, we achieve high-quality factor (up to 180) modes under normal incidence. The out-of-plane symmetry breaking can be fine-tuned by the nanofins' triangle angle, opening a pathway to precisely control the ratio of radiative to intrinsic losses. This enables access to the under-, critical, and over-coupled regimes, which we exploit for pixelated molecular sensing. We observe a strong dependence of the sensing performance on the coupling regime, demonstrating the importance of judicious tailoring of light-matter interactions. Our demonstration provides a metasurface platform for enhanced light-matter interaction with a wide range of applications.

Radial bound states in the continuum for polarization-invariant nanophotonics.

All-dielectric nanophotonics underpinned by the physics of bound states in the continuum (BICs) have demonstrated breakthrough applications in nanoscale light manipulation, frequency conversion and optical sensing. Leading BIC implementations range from isolated nanoantennas with localized electromagnetic fields to symmetry-protected metasurfaces with controllable resonance quality (Q) factors. However, they either require structured light illumination with complex beam-shaping optics or large, fabrication-intense arrays of polarization-sensitive unit cells, hindering tailored nanophotonic applications and on-chip integration. Here, we introduce radial quasi-bound states in the continuum (radial BICs) as a new class of radially distributed electromagnetic modes controlled by structural asymmetry in a ring of dielectric rod pair resonators. The radial BIC platform provides polarization-invariant and tunable high-Q resonances with strongly enhanced near fields in an ultracompact footprint as low as 2 µm2. We demonstrate radial BIC realizations in the visible for sensitive biomolecular detection and enhanced second-harmonic generation from monolayers of transition metal dichalcogenides, opening new perspectives for compact, spectrally selective, and polarization-invariant metadevices for multi-functional light-matter coupling, multiplexed sensing, and high-density on-chip photonics.

Catalytic Metasurfaces Empowered by Bound States in the Continuum.

Photocatalytic platforms based on ultrathin reactive materials facilitate carrier transport and extraction but are typically restricted to a narrow set of materials and spectral operating ranges due to limited absorption and poor energy-tuning possibilities. Metasurfaces, a class of 2D artificial materials based on the electromagnetic design of nanophotonic resonators, allow optical absorption engineering for a wide range of materials. Moreover, tailored resonances in nanostructured materials enable strong absorption enhancement and thus carrier multiplication. Here, we develop an ultrathin catalytic metasurface platform that leverages the combination of loss-engineered substoichiometric titanium oxide (TiO2-x) and the emerging physical concept of optical bound states in the continuum (BICs) to boost photocatalytic activity and provide broad spectral tunability. We demonstrate that our platform reaches the condition of critical light coupling in a TiO2-x BIC metasurface, thus providing a general framework for maximizing light-matter interactions in diverse photocatalytic materials. This approach can avoid the long-standing drawbacks of many naturally occurring semiconductor-based ultrathin films applied in photocatalysis, such as poor spectral tunability and limited absorption manipulation. Our results are broadly applicable to fields beyond photocatalysis, including photovoltaics and photodetectors.

Optical Metasurfaces for Energy Conversion.

Nanostructured surfaces with designed optical functionalities, such as metasurfaces, allow efficient harvesting of light at the nanoscale, enhancing light-matter interactions for a wide variety of material combinations. Exploiting light-driven matter excitations in these artificial materials opens up a new dimension in the conversion and management of energy at the nanoscale. In this review, we outline the impact, opportunities, applications, and challenges of optical metasurfaces in converting the energy of incoming photons into frequency-shifted photons, phonons, and energetic charge carriers. A myriad of opportunities await for the utilization of the converted energy. Here we cover the most pertinent aspects from a fundamental nanoscopic viewpoint all the way to applications.

Tunable structural colors on display.

Structural coloration takes inspiration from the bright hues found in nature to control the reflection and transmission of light from artificially structured materials. Combining them with active electrical tuning heralds breakthrough applications in optical displays.

Dual Nanoresonators for Ultrasensitive Chiral Detection.

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.

Angle-multiplexed all-dielectric metasurfaces for broadband molecular fingerprint retrieval.

Infrared spectroscopy resolves the structure of molecules by detecting their characteristic vibrational fingerprints. Subwavelength light confinement and nanophotonic enhancement have extended the scope of this technique for monolayer studies. However, current approaches still require complex spectroscopic equipment or tunable light sources. Here, we introduce a novel metasurface-based method for detecting molecular absorption fingerprints over a broad spectrum, which combines the device-level simplicity of state-of-the-art angle-scanning refractometric sensors with the chemical specificity of infrared spectroscopy. Specifically, we develop germanium-based high-Q metasurfaces capable of delivering a multitude of spectrally selective and surface-sensitive resonances between 1100 and 1800 cm-1. We use this approach to detect distinct absorption signatures of different interacting analytes including proteins, aptamers, and polylysine. In combination with broadband incoherent illumination and detection, our method correlates the total reflectance signal at each incidence angle with the strength of the molecular absorption, enabling spectrometer-less operation in a compact angle-scanning configuration ideally suited for field-deployable applications.

Metasurface-Based Molecular Biosensing Aided by Artificial Intelligence.

Molecular spectroscopy provides unique information on the internal structure of biological materials by detecting the characteristic vibrational signatures of their constituent chemical bonds at infrared frequencies. Nanophotonic antennas and metasurfaces have driven this concept towards few-molecule sensitivity by confining incident light into intense hot spots of the electromagnetic fields, providing strongly enhanced light-matter interaction. In this Minireview, recently developed molecular biosensing approaches based on the combination of dielectric metasurfaces and imaging detection are highlighted in comparison to traditional plasmonic geometries, and the unique potential of artificial intelligence techniques for nanophotonic sensor design and data analysis is emphasized. Because of their spectrometer-less operation principle, such imaging-based approaches hold great promise for miniaturized biosensors in practical point-of-care or field-deployable applications.

Resolving molecule-specific information in dynamic lipid membrane processes with multi-resonant infrared metasurfaces.

A multitude of biological processes are enabled by complex interactions between lipid membranes and proteins. To understand such dynamic processes, it is crucial to differentiate the constituent biomolecular species and track their individual time evolution without invasive labels. Here, we present a label-free mid-infrared biosensor capable of distinguishing multiple analytes in heterogeneous biological samples with high sensitivity. Our technology leverages a multi-resonant metasurface to simultaneously enhance the different vibrational fingerprints of multiple biomolecules. By providing up to 1000-fold near-field intensity enhancement over both amide and methylene bands, our sensor resolves the interactions of lipid membranes with different polypeptides in real time. Significantly, we demonstrate that our label-free chemically specific sensor can analyze peptide-induced neurotransmitter cargo release from synaptic vesicle mimics. Our sensor opens up exciting possibilities for gaining new insights into biological processes such as signaling or transport in basic research as well as provides a valuable toolkit for bioanalytical and pharmaceutical applications.

Imaging-based molecular barcoding with pixelated dielectric metasurfaces.

Metasurfaces provide opportunities for wavefront control, flat optics, and subwavelength light focusing. We developed an imaging-based nanophotonic method for detecting mid-infrared molecular fingerprints and implemented it for the chemical identification and compositional analysis of surface-bound analytes. Our technique features a two-dimensional pixelated dielectric metasurface with a range of ultrasharp resonances, each tuned to a discrete frequency; this enables molecular absorption signatures to be read out at multiple spectral points, and the resulting information is then translated into a barcode-like spatial absorption map for imaging. The signatures of biological, polymer, and pesticide molecules can be detected with high sensitivity, covering applications such as biosensing and environmental monitoring. Our chemically specific technique can resolve absorption fingerprints without the need for spectrometry, frequency scanning, or moving mechanical parts, thereby paving the way toward sensitive and versatile miniaturized mid-infrared spectroscopy devices.