Quasi-bound states in the continuum for electromagnetic induced transparency and strong excitonic coupling.

Advancing on previous reports, we utilize quasi-bound states in the continuum (q-BICs) supported by a metasurface of TiO2 meta-atoms with broken inversion symmetry on an SiO2 substrate, for two possible applications. Firstly, we demonstrate that by tuning the metasurface's asymmetric parameter, a spectral overlap between a broad q-BIC and a narrow magnetic dipole resonance is achieved, yielding an electromagnetic induced transparency analogue with a 50 µs group delay. Secondly, we have found that, due to the strong coupling between the q-BIC and WS2 exciton at room temperature and normal incidence, by integrating a single layer of WS2 to the metasurface, a 37.9 meV Rabi splitting in the absorptance spectrum with 50% absorption efficiency is obtained. These findings promise feasible two-port devices for visible range slow-light characteristics or nanoscale excitonic coupling.

Manipulating Intermetallic Charge Transfer for Switchable External Stimulus-Enhanced Water Oxidation Electrocatalysis.

Electrocatalytic processes involving the oxygen evolution reaction (OER) present a kinetic bottleneck due to the existence of linear-scaling relationships, which bind the energies of the different intermediates in the mechanism limiting optimization. Here, we offer a way to break these scaling relationships and enhance the electrocatalytic activity of a Co-Fe Prussian blue modified electrode in OER by applying external stimuli. Improvements of ≈11 % and ≈57 % were achieved under magnetic field (0.2 T) and light irradiation (100 mW cm-2 ), respectively, when working at fixed overpotential, η=0.6 V at pH 7. The observed enhancements strongly tie in with the intermetallic charge transfer (IMCT) intensity between Fe and Co sites. Density Functional Theory simulations suggest that tuning the IMCT can lead to a change of the OER mechanism to an external stimuli-sensitive spin crossover-based pathway, which opens the way for switchable electrocatalytic devices.

Fano resonance in a dolomite phase-change multilayer design for dynamically tunable omnidirectional monochromatic thermal emission.

In this Letter, we unveil the unprecedented optical phonon response of CaMg(CO3)2 (dolomite) thin film in the design of a planar ultra-narrowband mid-infrared (MIR) thermal emitter. Dolomite (DLM) is a carbonate mineral composed of calcium magnesium carbonate, which can inherently accommodate highly dispersive optical phonon modes. Utilizing strong interference in the Al-DLM bilayer, a lithography-free planar thermal emitter is realized with near-unity omnidirectional emission at a specific resonance wavelength of 7.12 µm. Further incorporation of embedded vanadium dioxide (VO2) phase change material (PCM) enables the excitation of hybrid Fano resonances with dynamic spectral tunability. The findings of this study can have multiple applications, ranging from biosensing and gas sensing to thermal emission.

Light-Driven Water Oxidation with Ligand-Engineered Prussian Blue Analogues.

The elucidation of the ideal coordination environment of a catalytic site has been at the heart of catalytic applications. Herein, we show that the water oxidation activities of catalytic cobalt sites in a Prussian blue (PB) structure could be tuned systematically by decorating its coordination sphere with a combination of cyanide and bidentate pyridyl groups.  K0.1[Co(bpy)]2.9[Fe(CN)6]2 ([Cobpy-Fe]), K0.2[Co(phen)]2.8[Fe(CN)6]2 ([Cophen-Fe]), {[Co(bpy)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 ([Cobpy2-Fe]), and {[Co(phen)2]3[Fe(CN)6]2}[Fe(CN)6]1/3 Cl0.11 ([Cophen2-Fe]) were prepared by introducing bidentate pyridyl groups (phen: 1,10-phenanthroline, bpy: 2,2'-bipyridine) to the common synthetic protocol of Co-Fe Prussian blue analogues. Characterization studies indicate that [Cobpy2-Fe] and [Cophen2-Fe] adopt a pentanuclear molecular structure, while [Cobpy-Fe] and [Cophen-Fe] could be described as cyanide-based coordination polymers with lower-dimensionality and less crystalline nature compared to the regular Co-Fe Prussian blue analogue (PBA), K0.1Co2.9[Fe(CN)6]2 ([Co-Fe]). Photocatalytic studies reveal that the activities of [Cobpy-Fe] and [Cophen-Fe] are significantly enhanced compared to those of [Co-Fe], while molecular [Cobpy2-Fe] and [Cophen2-Fe] are inactive toward water oxidation. [Cobpy-Fe] and [Cophen-Fe] exhibit upper-bound turnover frequencies (TOFs) of 1.3 and 0.7 s-1, respectively, which are ∼50 times higher than that of [Co-Fe] (1.8 × 10-2 s-1). The complete inactivity of [Cobpy2-Fe] and [Cophen2-Fe] confirms the critical role of aqua coordination to the catalytic cobalt sites for oxygen evolution reaction (OER). Computational studies show that bidentate pyridyl groups enhance the susceptibility of the rate-determining Co(IV)-oxo species to the nucleophilic water attack during the critical O-O bond formation. This study opens a new route toward increasing the intrinsic water oxidation activity of the catalytic sites in PB coordination polymers.

Optimization of the annealed proton exchange method with controlled annealing for multifunctional integrated optical chip production.

The main objective of our study is to develop a new approach to the annealed proton exchange (APE) method for the fabrication of the multifunctional integrated optical chip (MIOC) used in fiber-optic gyro systems and to eliminate the loss of time and material, especially in mass production applications. In this work, self-polarized waveguides, which are the basic components of a MIOC device, were produced by the APE method and studied. With the developed method, controlled annealing trials have been carried out from a certain region on the LiNbO3 substrate used in waveguide production, and the annealing time specific to the annealing process was determined. By utilizing a special setup for the hot acid process, the proton exchange process was accomplished without a sudden temperature change of the substrate. Using prism coupling measurements of the fabricated waveguides, annealing times were determined to obtain index change values suitable for 45%-50% optical throughput. Mode profiles of devices with high optical throughput that were produced by the proposed method were measured, and it was seen that devices from different proton exchange runs had similar profiles. As a result, many undamaged substrates were fabricated, and their optical quality was found to be within the expected values.

Adaptive visible and short-wave infrared camouflage using a dynamically tunable metasurface.

In this Letter, a dynamically tunable metasurface, which is based on antimony trisulfide, is introduced. In this structure, first a metal-insulator-metal (MIM) nanocavity is optimized in a way that, upon phase change, the visible response switches from a transmissive colored window into a reflective mirror. Later, an indium tin oxide nanoantenna is integrated on the MIM cavity to provide antireflection in the short-wave infrared (SWIR) range for SWIR mode thermal camouflage. The MIM host acts as a thermally tunable substrate to tune the SWIR response of the design.

Multi-spectral infrared camouflage through excitation of plasmon-phonon polaritons in a visible-transparent hBN-ITO nanoantenna emitter.

In an ideal platform for camouflage compatible cooling, the thermal emitter should be a spectrally selective antenna to radiate its heat buildup without being detected by thermal cameras. Moreover, to keep its visual appearance and to minimize solar induced heating, the structure should be visibly transparent. In this Letter, to achieve the visually invisible mid-infrared (MIR) camouflage-cooling feature, a metasurface design based on an indium-doped tin oxide (ITO)-hexagonal boron nitride (hBN) heterostructure is proposed. The proposed ITO-hBN nanoantenna shows spectrally selective broadband absorptions in near-infrared (NIR) and non-transmissive (MIR) windows, while it is dominantly non-emissive in other ranges. The camouflage ability of the structure in the targeted wavelengths is demonstrated using power calculations.

Generation of additive colors with near unity amplitude using a multilayer tandem Fabry-Perot cavity.

In this paper, the generation of additive red-green-blue (RGB) colors in reflectance mode with near unity amplitude is demonstrated. For this purpose, a multilayer structure made of metal-insulator-metal-semiconductor-insulator stacks is designed to achieve >0.9 reflection peaks with full-width-at-half-maximum values <0.3λpeak. The proposed design also shows near zero reflection in off-resonance spectral ranges, and this, in turn, leads to high color purity. The optimized designs are fabricated, and simulation and theoretical results are verified with characterization findings. This work demonstrates the potential of multilayer tandem cavity designs in the realization of lithography-free large-scale compatible functional optical coatings.

Multifunctional tunable gradient metasurfaces for terahertz beam splitting and light absorption.

Obtaining functional devices with tunable features is beneficial to advance terahertz (THz) science and technology. Here, we propose multifunctional gradient metasurfaces that are composed of a periodic array of binary Si microcylinders integrated with VO2 and graphene. The metasurfaces act as transmittive (reflective) beamsplitters for the dielectric (metallic) phase of VO2 with a switchable characteristic. Moreover, by integrating the metasurfaces with graphene and modifying its chemical potential, one can tune the intensity of the split beam as well as obtain nearly perfect resonant absorptions. Consequently, the proposed metasurfaces can find potential applications in THz interferometers, multiplexers, and light absorbers.

Fiber-optic gyroscope for the suppression of a Faraday-effect-induced bias error.

Inertial rotation sensors, interferometric fiber-optic gyroscopes (IFOGs), are widely used in military and industrial applications due to their high sensitivity and stability. In this Letter, a new, to the best of our knowledge, fiber coil design is proposed to reduce magnetic field sensitivity without adding any optical components or electronic algorithms to the IFOG system. It is shown that this design can be applied without disturbing the simplest IFOG structure. Considering the fact that the magnetic field has an invertible effect on polarization, the compensation of the Faraday-effect-induced bias error has been demonstrated theoretically and experimentally by allowing two different polarizations to travel inside the fiber coil. According to the experimental results, the bias error was reduced approximately 20 times from ±9.6∘/h/mT to ±0.5∘/h/mT.

Strong light emission from a defective hexagonal boron nitride monolayer coupled to near-touching random plasmonic nanounits.

In this Letter, we demonstrate strong light emission from defective hexagonal boron nitride (hBN) defect centers upon their coupling with disorder near-touching plasmonic units. Based on numerical simulations and characterization results, the plasmonic design at thin layer thicknesses of 20 nm can provide above 2 orders of magnitude enhancement in photoluminescence (PL) spectra. Moreover, this plasmonic platform shortens the luminescence lifetime of the emitters. The proposed design can be easily extended to other plasmonic-emitter combinations where strong light-matter interaction can be achieved using large-scale compatible routes.

How to Build Prussian Blue Based Water Oxidation Catalytic Assemblies: Common Trends and Strategies.

Prussian blue (PB) and its analogues (PBAs) have at least a three-century-long history in coordination chemistry. Recently, cobalt-based PBAs have been acknowledged as efficient and robust water oxidation catalysts. Given the flexibility in their synthesis, the structure and morphology of cobalt-based PBAs have been modified for enhanced catalytic activity under electrochemical (EC), photocatalytic (PC), and photoelectrochemical (PEC) conditions. Here, in this review, the work on cobalt-based PBAs is presented in four sections: i) electrocatalytic water oxidation with bare PBAs, ii) photocatalytic processes in the presence of a photosensitizer (PS), iii) photoelectrochemical water oxidation by coupling PBAs to proper semiconductors (SCs), and iv) the utilization of PBA-PS assemblies coated on SCs for the dye-sensitized photoelectrochemical water oxidation. This review will guide readers through the structure and catalytic activity relationship in cobalt-based PBAs by describing the role of each structural component. Furthermore, this review aims to provide insight into common strategies to enhance the catalytic activity of PBAs.

Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation.

The replacement of traditional ruthenium-based photosensitizers with low-cost and abundant iron analogs is a key step for the advancement of scalable and sustainable dye-sensitized water splitting cells. In this proof-of-concept study, a pyridinium ligand coordinated pentacyanoferrate(II) chromophore is used to construct a cyanide-based CoFe extended bulk framework, in which the iron photosensitizer units are connected to cobalt water oxidation catalytic sites through cyanide linkers. The iron-sensitized photoanode exhibits exceptional stability for at least 5 h at pH 7 and features its photosensitizing ability with an incident photon-to-current conversion capacity up to 500 nm with nanosecond scale excited state lifetime. Ultrafast transient absorption and computational studies reveal that iron and cobalt sites mutually support each other for charge separation via short bridging cyanide groups and for injection to the semiconductor in our proof-of-concept photoelectrochemical device. The reorganization of the excited states due to the mixing of electronic states of metal-based orbitals subsequently tailor the electron transfer cascade during the photoelectrochemical process. This breakthrough in chromophore-catalyst assemblies will spark interest in dye-sensitization with robust bulk systems for photoconversion applications.

Building an Iron Chromophore Incorporating Prussian Blue Analogue for Photoelectrochemical Water Oxidation.

Invited for the cover of this issue is the Ferdi Karadas and Ekmel Ozbay groups at Bilkent University and co-workers. The image presents an utopic city in Iron Age, which is powered by an iron photosensitizer that bridges semiconductor buildings (TiO2 nanowires) and the catalyst (cobalt site). Read the full text of the article at 10.1002/chem.202100654.

Lithography-free disordered metal-insulator-metal nanoantennas for colorimetric sensing.

The colorimetric detection of bio-agent targets has attracted considerable attention in nanosensor designs. This platform provides an easy to use, real-time, and rapid sensing approach, as the color change can be easily distinguished by the naked eye. In this Letter, we propose a large scale compatible fabrication route to realize colorimetric optical nanosensors with a novel configuration. For this purpose, we design and fabricate a tightly packed disordered arrangement of Fabry-Perot based metal-insulator-metal nanoantennas with a resonance frequency at visible light wavelengths. In this design, the adsorbed bio-agent changes the effective refractive index of the cavity, and this causes a shift in the resonance wavelength. The experimental data show that the proposed design can have sensitivity values >70nm/refractive index unit. Unlike other optical sensing schemes that rely mainly on hot spot formation and field enhancement, this design has a large active area with relatively uniform patterns that make it a promising approach for low-level and reliable bio-detection.

Numerical analysis of a thermally tunable spectrally selective absorber enabled by an all-dielectric metamirror.

In this Letter, we numerically propose a temperature-tunable, ultra-narrowband one-way perfect near-infrared radiation absorber with high transmission in the longer wavelength neighboring spectral range. We obtained this functionality by using a guided-mode resonance-based grating-waveguide metamirror that is comprised of silicon, a spacer dielectric, an absorbing semiconductor, and germanium. Within the ultra-narrow bandwidth of the guided-mode resonance excited at 1.16 µm with a full width at half-maximum of 3.3 nm, we confirmed perfect absorption when light is incident from one of the two opposite directions. Excitation from the opposite direction resulted in perfect reflection. The thickness of the entire structure is limited to about one third the operating wavelength. Furthermore, due to the temperature tunability of silicon and germanium the thermo-optical sensitivity was found to be approximately 0.068 nm/K. In addition to this spectral tunability, our proposed device supports transparency windows with 80% transmission in the higher wavelength ranges. Our device is highly promising in the applications of thermo-tunable modulators and obtaining single frequency near-infrared signals from broadband sources.

Dynamic beam splitter employing an all-dielectric metasurface based on an elastic substrate.

Beam splitters are an indispensable part of optical measurements and applications. We propose a dynamic beam splitter incorporating all-dielectric metasurface in an elastic substrate under external mechanical stimulus of stretching. The optical behavior at 720 nm wavelength shows that it can be changed from a pure optical-diode-like behavior to a dynamic beam splitter. Although the structure is designed running at 720 nm, the design approach with appropriate materials can be used at any wavelength. Various cases, including wavelength and polarization dependencies, are thoroughly investigated to demonstrate the principles of operating conditions of two different regimes of the designed metasurface.

One-way and near-absolute polarization insensitive near-perfect absorption by using an all-dielectric metasurface.

In this Letter, we numerically propose the one-way perfect absorption of near-infrared radiation in a tunable spectral range with high transmission in the neighboring spectral ranges. This functionality is obtained by using a two-dimensional, guided-mode resonance-based grating-waveguide metasurface that acts as a frequency-selective reflector, a spacer dielectric, and an absorbing oxide layer. Within the bandwidth of the excited guided-mode resonance excited at 1.82 µm (with a full-width at half-maximum of 19 nm), we confirmed perfect absorption when light was incident from one of the two opposite directions, whereas in the other direction, perfect reflection was observed. The forward-to-backward absorption ratio reached as high as 60, while the thickness of the entire structure was on the order of the operating wavelength. In addition to the spectral tunability of the excited resonances and their bandwidths, our proposed device supports transparency windows with 65% transmission in the adjacent frequency bands. Our 2D grating is also verified to enable near-absolute insensitivity to the polarization state of incident light. Geometrical parameter modification also gives our design great tunability, as we also designed a device with a 300 nm absorption/reflection linewidth.

Thermally induced bias error due to strain inhomogeneity through the fiber optic gyroscope coil.

One of the performance limits of a navigation grade fiber optic gyroscope is the bias error due to the thermal sensitivity of the fiber coil. Thermal stress inside the fiber coil is an important source of the bias error. The reduction of the total stress inside the fiber coil can be limited. In this paper, it is shown that further improvement can be achieved by controlling the strain inhomogeneity through the fiber coil. A validated simulation environment is presented for strain distribution analysis. Thermally induced bias error formation mechanisms are compared. The effect of the strain inhomogeneity is reduced by presenting a different coil cross section and spool material. Experiments utilizing a coil design with better performance are presented for the verification of the approach.

A Robust, Precious-Metal-Free Dye-Sensitized Photoanode for Water Oxidation: A Nanosecond-Long Excited-State Lifetime through a Prussian Blue Analogue.

Herein, we establish a simple synthetic strategy affording a heterogeneous, precious metal-free, dye-sensitized photoelectrode for water oxidation, which incorporates a Prussian blue (PB) structure for the sensitization of TiO2 and water oxidation catalysis. Our approach involves the use of a Fe(CN)5 bridging group not only as a cyanide precursor for the formation of a PB-type structure but also as an electron shuttle between an organic chromophore and the catalytic center. The resulting hetero-functional PB-modified TiO2 electrode demonstrates a low-cost and easy-to-construct photoanode, which exhibits favorable electron transfers with a remarkable excited state lifetime on the order of nanoseconds and an extended light absorption capacity of up to 500 nm. Our approach paves the way for a new family of precious metal-free robust dye-sensitized photoelectrodes for water oxidation, in which a variety of common organic chromophores can be employed in conjunction with CoFe PB structures.