Gradient High-Q Dielectric Metasurfaces for Broadband Sensing and Control of Vibrational Light-Matter Coupling.

Surface-enhanced infrared absorption spectroscopy (SEIRA) has emerged as a powerful technique for ultrasensitive chemical-specific analysis. SEIRA can be realized by employing metasurfaces that can enhance light-matter interactions in the spectral bands of molecular vibrations. Increasing sample complexity emphasizes the need for metasurfaces that can operate simultaneously at different spectral bands, both accessing rich spectral information over a broad band, and resolving subtle differences in the absorption fingerprints through narrow-band resonances. Here, a novel concept of resonance-gradient metasurfaces is introduced, where the required spectral selectivity is achieved via local high-quality-factor (high-Q) resonances, while the continuous coverage of a broad band is enabled by the gradual adjustment of the unit-cell dimensions along the planar structure. The highly tailorable design of the gradient metasurfaces provides flexibility for shaping the spectral sampling density to match the relevant bands of target analytes while keeping a compact device footprint. The versatility of the gradient metasurfaces is demonstrated through several sensing scenarios, including polymer mixture deconvolution, detecting a multistep bioassay, and identification of the onset of vibrational strong coupling regime. The proposed gradient-resonance platform significantly contributes to the rapidly evolving landscape of nonlocal metasurfaces, enabling applications in molecular detection and analysis of fundamental light-matter interaction phenomena.

Spectral Tuning of High-Harmonic Generation with Resonance-Gradient Metasurfaces.

High-index dielectric subwavelength structures and metasurfaces are capable of enhancing light-matter interaction by orders of magnitude via geometry-dependent optical resonances. This enhancement, however, comes with a fundamental limitation of a narrow spectral range of operation in the vicinity of one or few resonant frequencies. Here, this limitation is tackled by introducing an innovative and practical approach to achieve spectrally tunable enhancement of light-matter interaction with resonant metasurfaces. Resonance-gradient metasurfaces are designed and fabricated with varying geometrical parameters that translate into resonant frequencies dependence on one of the coordinates of the metasurface. The metasurfaces are composed of bone-like nanoresonators, which are made of germanium and support high-quality optical resonances in the mid-IR spectral range. The concept is applied to observe the resonant enhancement of the third and fifth harmonics generated from the gradient metasurfaces being used in conjunction with a tunable excitation laser to provide a wide spectral coverage of resonantly-enhanced tunable generation of multiple optical harmonics.

Dielectric Tetramer Nanoresonators Supporting Strong Superchiral Fields for Vibrational Circular Dichroism Spectroscopy.

Chirality (C) is a fundamental property of objects, in terms of symmetry. It is extremely important to sense and distinguish chiral molecules in the fields of biochemistry, science, and medicine. Vibrational circular dichroism (VCD) spectroscopy, obtained from the differential absorption of left- and right- circularly polarized light (CPL) in the infrared range, is a promising technique for enantiomeric detection and separation. However, VCD signals are typically very weak for most small molecules. Dielectric metasurfaces are an emerging platform to enhance the sensitivity of VCD spectroscopy of chiral molecules via superchiral field manipulation. Here, we demonstrate a dielectric metasurface consisting of achiral germanium (Ge) tetramer nanoresonators that provide a proper and accessible high C enhancement (CE). We realize a maximum C enhancement (CE_max) with respect to the incident CPL (CE_max = Cmax/CRCP) of more than 750. The volume-averaged C enhancement (CE_ave = Cave/CRCP) is 148 in the 50 nm thick region above the sample surface and 215 in the central region of the structure. Especially, the corresponding CE_ave values are more than 89 and 183 even when a 50 nm thick chiral lossy molecular layer is coated on the metasurface. The metasurface benefits from geometrically achiral nanostructure design to eliminate intrinsic background chiral-optical signal from the substrate, which is useful in chiral sensing, enantioselectivity, and VCD spectroscopy applications in the mid-infrared range.

Vacuum ultraviolet nonlinear metalens.

Vacuum ultraviolet (VUV) light plays an essential role across science and technology, from molecular spectroscopy to nanolithography and biomedical procedures. Realizing nanoscale devices for VUV light generation and control is critical for next-generation VUV sources and systems, but the scarcity of low-loss VUV materials creates a substantial challenge. We demonstrate a metalens that both generates-by second-harmonic generation-and simultaneously focuses the generated VUV light. The metalens consists of 150-nm-thick zinc oxide (ZnO) nanoresonators that convert 394 nm (~3.15 eV) light into focused 197-nm (~6.29 eV) radiation, producing a spot 1.7 µm in diameter with a 21-fold power density enhancement as compared to the wavefront at the metalens surface. The reported metalens is ultracompact and phase-matching free, allowing substantial streamlining of VUV system design and facilitating more advanced applications. This work provides a useful platform for developing low-loss VUV components and increasing the accessibility of the VUV regime.

Metasurface-Based Abrupt Autofocusing Beam for Biomedical Applications.

Manipulation and precise delivery of optical energies in the regions of interest within specimens require different strategies. Hence, proper control of input beam parameters is a prerequisite. One of the prominent methods is metasurface optics, capable of crafting properties of light at nanoscales. Here, the generation of an abrupt autofocusing (AAF) beam by a nanophotonic metasurface for biomedical applications is demonstrated. Fluorescence guided laser microprofiling of mouse cardiac samples is experimentally investigated, using the AAF beam to deliver optical energy selectively to specific locations. In addition, photocoagulation of ex vivo swine skin tissue is performed and observed through optical coherence tomography. The results show great potentials for integrating metasurface optics to realize miniature laser surgery instruments for wide applications in biomedicine.

Wafer-Scale Functional Metasurfaces for Mid-Infrared Photonics and Biosensing.

Metasurfaces have emerged as a breakthrough platform for manipulating light at the nanoscale and enabling on-demand optical functionalities for next-generation biosensing, imaging, and light-generating photonic devices. However, translating this technology to practical applications requires low-cost and high-throughput fabrication methods. Due to the limited choice of materials with suitable optical properties, it is particularly challenging to produce metasurfaces for the technologically relevant mid-infrared spectral range. These constraints are overcome by realizing functional metasurfaces on almost completely transparent free-standing metal-oxide membranes. A versatile nanofabrication process is developed and implemented for highly efficient dielectric and plasmonic mid-infrared metasurfaces with wafer-scale and complementary metal-oxide-semiconductor (CMOS)-compatible manufacturing techniques. The advantages of this method are revealed by demonstrating highly uniform and functional metasurfaces, including high-Q structures enabling fine spectral selectivity, large-area metalenses with diffraction-limited focusing capabilities, and birefringent metasurfaces providing polarization control at record-high conversion efficiencies.  Aluminum plasmonic devices and their integration into microfluidics for real-time and label-free mid-infrared biosensing of proteins and lipid vesicles are further demonstrated. The versatility of this approach and its compatibility with mass-production processes bring infrared metasurfaces markedly closer to commercial applications, such as thermal imaging, spectroscopy, and biosensing.

Generating Third Harmonic Vacuum Ultraviolet Light with a TiO2 Metasurface.

Dielectric metasurfaces have recently been shown to provide an excellent platform for the harmonic generation of light due to their low optical absorption and to the strong electromagnetic field enhancement that can be designed into their constituent meta-atoms. Here, we demonstrate vacuum ultraviolet (VUV) third harmonic generation from a specially designed dielectric metasurface consisting of a titanium dioxide (TiO2) nanostructure array. The metasurface was designed to enhance the generation of VUV light at a wavelength of 185 nm by tailoring its geometric design parameters to achieve an optical resonance at the fundamental laser wavelength of 555 nm. The metasurface exhibits an enhancement factor of nominally 180 compared to an unpatterned TiO2 thin film of the same thickness, evidence of strong field enhancement at the fundamental wavelength. Mode analysis reveals that the origin of the enhancement is an anapole resonance near the pump wavelength. This work demonstrates an effective strategy for the compact generation of VUV light that could enable expanded access to this useful region of the electromagnetic spectrum.

Vacuum Ultraviolet Light-Generating Metasurface.

Vacuum ultraviolet (VUV) light has important applications in many fields, ranging from device fabrication to photochemistry, from environmental remediation to microscopy and spectroscopy. Methods to produce coherent VUV light frequently utilize high harmonic generation in media such as rare gases or atomic vapors; nonlinear optical crystals that support second harmonic generation into the VUV are quite rare. Here, we demonstrate an all-dielectric metasurface designed for the nonlinear optical generation of VUV light. Consisting of an array of zinc oxide nanoresonators, the device exhibits a magnetic dipole resonance at a wavelength of 394 nm. When excited with ultrafast laser pulses at this wavelength, the second harmonic at 197 nm is readily generated. Manipulation of the metasurface design enables control over the radiation pattern. This work has the potential to open the door toward simple and compact VUV sources for new applications.

Ultrathin Planar Cavity Metasurfaces.

An ultrathin planar cavity metasurface is proposed based on ultrathin film interference and its practicability for light manipulation in visible region is experimentally demonstrated. Phase of reflected light is modulated by finely adjusting the thickness of amorphous silicon (a-Si) by a few nanometers on an aluminum (Al) substrate via nontrivial phase shifts at the interfaces and interference of multireflections generated from the planar cavity. A phase shift of π, the basic requirement for two-level phase metasurface systems, can be accomplished with an 8 nm thick difference. For proof of concept, gradient metasurfaces for beam deflection, Fresnel zone plate metalens for light focusing, and metaholograms for image reconstruction are presented, demonstrating polarization-independent and broadband characteristics. This novel mechanism for phase modulation with ultrathin planar cavity provides diverse routes to construct advanced flat optical devices with versatile applications.

Two-Dimensional Active Tuning of an Aluminum Plasmonic Array for Full-Spectrum Response.

Color pixels composed of plasmonic nanostructures provide a highly promising approach for new display technologies, capable of vivid, robust coloration and incorporating the use of low-cost plasmonic materials, such as aluminum. Here we report a plasmonic device that can be tuned continuously across the entire visible spectrum, based on integrating a square array of aluminum nanostructures into an elastomeric substrate. By stretching the substrate in either of its two dimensions, the period and therefore the scattering color can be modified to the blue or the red of the at-rest structure, spanning the entire visible spectrum. The unique two-dimensional design of this structure enables active mechanical color tuning, under gentle elastic modulation with no more than 35% strain. We also demonstrate active image switching with this structure. This design strategy has the potential to open the door for next-generation flexible photonic devices for a wide variety of visible-light applications.

Nanogapped Au Antennas for Ultrasensitive Surface-Enhanced Infrared Absorption Spectroscopy.

Surface-enhanced infrared absorption (SEIRA) spectroscopy has outstanding potential in chemical detection as a complement to surface-enhanced Raman spectroscopy (SERS), yet it has historically lagged well behind SERS in detection sensitivity. Here we report a new ultrasensitive infrared antenna designed to bring SEIRA spectroscopy into the few-molecule detection range. Our antenna consists of a bowtie-shaped Au structure with a sub-3 nm gap, positioned to create a cavity above a reflective substrate. This three-dimensional geometry tightly confines incident mid-infrared radiation into its ultrasmall junction, yielding a hot spot with a theoretical SEIRA enhancement factor of more than 107, which can be designed to span the range of frequencies useful for SEIRA. We quantitatively evaluated the IR detection limit of this antenna design using mixed monolayers of 4-nitrothiophenol (4-NTP) and 4-methoxythiolphenol (4-MTP). The optimized antenna structure allows the detection of as few as ∼500 molecules of 4-NTP and ∼600 molecules of 4-MTP with a standard commercial FTIR spectrometer. This strategy offers a new platform for analyzing the IR vibrations of minute quantities of molecules and lends insight into the ultimate limit of single-molecule SEIRA detection.

Coherent selection of invisible high-order electromagnetic excitations.

Far-field spectroscopy and mapping of electromagnetic near-field distribution are the two dominant tools for analysis and characterization of the electromagnetic response in nanophotonics. Despite the widespread use, these methods can fail at identifying weak electromagnetic excitations masked by stronger neighboring excitations. This is particularly problematic in ultrafast nanophotonics, including optical sensing, nonlinear optics and nanolasers, where the broad resonant modes can overlap to a significant degree. Here, using plasmonic metamaterials, we demonstrate that coherent spectroscopy can conveniently isolate and detect such hidden high-order photonic excitations. Our results establish that the coherent spectroscopy is a powerful new tool. It complements the conventional methods for analysis of the electromagnetic response, and provides a new route to designing and characterizing novel photonic devices and materials.

Enhanced sensitivity of surface plasmon resonance phase-interrogation biosensor by using oblique deposited silver nanorods.

Sensitivity of surface plasmon resonance phase-interrogation biosensor is demonstrated to be enhanced by oblique deposited silver nanorods. Silver nanorods are thermally deposited on silver nanothin film by oblique angle deposition (OAD). The length of the nanorods can be tuned by controlling the deposition parameters of thermal deposition. By measuring the phase difference between the p and s waves of surface plasmon resonance heterodyne interferometer with different wavelength of incident light, we have demonstrated that maximum sensitivity of glucose detection down to 7.1 × 10(-8) refractive index units could be achieved with optimal deposition parameters of silver nanorods.

Multi-level surface enhanced Raman scattering using AgOx thin film.

Ag nanostructures with surface-enhanced Raman scattering (SERS) activities have been fabricated by applying laser-direct writing (LDW) technique on silver oxide (AgOx) thin films. By controlling the laser powers, multi-level Raman imaging of organic molecules adsorbed on the nanostructures has been observed. This phenomenon is further investigated by atomic-force microscopy and electromagnetic calculation. The SERS-active nanostructure is also fabricated on transparent and flexible substrate to demonstrate our promising strategy for the development of novel and low-cost sensing chip.

Fabrication of three-dimensional plasmonic cavity by femtosecond laser-induced forward transfer.

We fabricated a three-dimensional five-layered plasmonic resonant cavity by low-cost, efficient and high-throughput femtosecond laser-induced forward transfer (fs-LIFT) technique. The fabricated cavity was characterized by optical measurements, showing two different cavity modes within the measured wavelength region which is in good agreement with numerical simulations. The mode volume corresponding to each resonance is found to be squeezed over 10(4) smaller than the cube of incident wavelength. This property may facilitate many applications in integrated optics, optical nonlinearities, and luminescence enhancement, etc.

Plasmonic ZnO/Ag embedded structures as collecting layers for photogenerating electrons in solar hydrogen generation photoelectrodes.

A new fabrication strategy in which Ag plasmonics are embedded in the interface between ZnO nanorods and a conducting substrate is experimentally demonstrated using a femtosecond-laser (fs-laser)-induced plasmonic ZnO/Ag photoelectrodes. This fs-laser fabrication technique can be applied to generate patternable plasmonic nanostructures for improving their effectiveness in hydrogen generation. Plasmonic ZnO/Ag nanostructure photoelectrodes show an increase in the photocurrent of a ZnO nanorod photoelectrodes by higher than 85% at 0.5 V. Both localized surface plasmon resonance in metal nanoparticles and plasmon polaritons propagating at the metal/semiconductor interface are available for improving the capture of sunlight and collecting charge carriers. Furthermore, in-situ X-ray absorption spectroscopy is performed to monitor the plasmonic-generating electromagnetic field upon the interface between ZnO/Ag nanostructures. This can reveal induced vacancies on the conduction band of ZnO, which allow effective separation of charge carriers and improves the efficiency of hydrogen generation. Plasmon-induced effects enhance the photoresponse simultaneously, by improving optical absorbance and facilitating the separation of charge carriers.

Fabrication of plasmonic devices using femtosecond laser-induced forward transfer technique.

Using femtosecond laser-induced forward transfer techniques we have fabricated gold dots and nanoparticles on glass substrates, as well as nanobumps on gold thin film. The surface morphologies of these structures with different laser fluences and film thicknesses are investigated. We also study the focusing and defocusing properties of the nanofence-an arranged nanobump pattern-by the total-internal reflection microscope. Observations reveal that surface plasmon waves can be highly directed and focused via this nanofence pattern. Results are in good agreement with the simulation results using the finite-element method and demonstrate the potential applications of these nanophotonic devices. Furthermore, we utilize high laser energy to fabricate plasmonic waveguides, and also succeed in transferring the waveguides to another substrate. The attenuation rates of the light propagating in the waveguides are observed to achieve 0.31 dB µm(-1) and 0.48 dB µm(-1) on the target and receiver sides, respectively.

Plasmon inducing effects for enhanced photoelectrochemical water splitting: X-ray absorption approach to electronic structures.

Artificial photosynthesis using semiconductors has been investigated for more than three decades for the purpose of transferring solar energy into chemical fuels. Numerous studies have revealed that the introduction of plasmonic materials into photochemical reaction can substantially enhance the photo response to the solar splitting of water. Until recently, few systematic studies have provided clear evidence concerning how plasmon excitation and which factor dominates the solar splitting of water in photovoltaic devices. This work demonstrates the effects of plasmons upon an Au nanostructure-ZnO nanorods array as a photoanode. Several strategies have been successfully adopted to reveal the mutually independent contributions of various plasmonic effects under solar irradiation. These have clarified that the coupling of hot electrons that are formed by plasmons and the electromagnetic field can effectively increase the probability of a photochemical reaction in the splitting of water. These findings support a new approach to investigating localized plasmon-induced effects and charge separation in photoelectrochemical processes, and solar water splitting was used herein as platform to explore mechanisms of enhancement of surface plasmon resonance.

Fast fabrication of a Ag nanostructure substrate using the femtosecond laser for broad-band and tunable plasmonic enhancement.

Using a femtosecond laser, we have transformed the laser-direct-writing technique into a highly efficient method that can process AgO(x) thin films into Ag nanostructures at a fast scanning rate of 2000 µm(2)/min. The processed AgO(x) thin films exhibit broad-band enhancement of optical absorption and effectively function as active SERS substrates. Probing of the plasmonic hotspots with dyed polymer beads indicates that these hotspots are uniformly distributed over the treated area.