Band 10, Heft 6

Sunlight and water are among the most plentiful and sustainable resources of energy. Natural photosystem II in the plants uses these resources in ecofriendly manner for the production of atmospheric oxygen and energy. Inspired by this natural process, the development of artificial catalytic system to facilitate the solar-induced water splitting for the continuous production of hydrogen is the holy grail of the chemist and energy experts to meet the future energy demand at minimal environmental cost. Despite considerable research efforts dedicated to this area in the last decade, the development of highly efficient, stable and economic photocatalysts remain a challenging task for the large scale H 2 production from water. Polyoxometalates (POMs)-based materials are emerging photo/photoelectrocatalysts in this quest owing to their multi-electron redox potential and fast reversible charge transfer properties, which are the essential requirements of photo-assisted water splitting catalysis. They are generally soluble in aqueous medium and thus their inherent catalytic/co-catalytic properties can be better exploited by incorporating/immobilizing them over suitable support materials. Therefore, exploration of discrete POM units over the support materials possessing high surface area, functionalizable architecture, flexible pore size and good light harvesting ability is an attractive area of research that has resulted in the generation of a strong library of heterocatalysts. The underlying support not only offers stability and recyclability attributes to the POM units but also provides decent dispersion, easy/maximum accessibility to the active sites, enhanced absorption capability, and synergistically enhances the activity by transfer of electrons and efficient charge/carriers separation by creating POM-support junctions. This mini-review emphasizes on the strategies for the incorporation of POMs on various porous supports like metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), oxide-based semiconductors, carbonaceous materials, etc., and their applications as effective photo/photoelectrocatalysts for water splitting. In addition, the mechanistic study, comparative analysis and the future potential of these novel nanoscale materials is also highlighted. We believe that this review article will provide a new direction and scientific interest at the boundary of materials engineering, and solar-driven chemistry for the sustainable energy conversion/storage processes.

Metallic nanoparticles supporting a localized surface plasmon resonance have emerged as promising platforms for nanoscopic labels, sensors, and (photo-) catalysts. To use nanoparticles in these capacities, and to gain mechanistic insight into the reactivity of inherently heterogeneous nanoparticles, single-particle characterization approaches are needed. Single-particle scattering spectroscopy has become an important, highly sensitive tool for localizing single plasmonic nanoparticles and studying their optical properties, local environment, and reactivity. In this review, we discuss approaches taken for collecting the scattered light from single particles, their advantages and disadvantages, and present some recent applications. We introduce techniques for the excitation and detection of single-particle scattering such as high-angle dark-field excitation, total internal reflection dark-field excitation, scanning near-field microscopy, and interferometric scattering. We also describe methods to achieve polarization-resolved excitation and detection. We then discuss different approaches for scanning, ratiometric, snapshot, and interferometric hyperspectral imaging techniques used to extract spectral information. Finally, we provide a brief overview of specialized setups for in situ measurements of nanoparticles in liquid systems and setups coupled to scanning tip microscopes.

Illumination of noble metal nanostructures by electromagnetic radiation induces coherent oscillations of conductive electrons on their surfaces. These coherent oscillations of electrons, also known as localized surface plasmon resonances (LSPR), are the underlying physical cause of the electromagnetic enhancement of Raman scattering from analytes located in a close proximity to the metal surface. This physical phenomenon is broadly known as surface-enhanced Raman scattering (SERS). LSPR can decay via direct interband, phonon-assisted intraband, and geometry-assisted transitions forming hot carriers, highly energetic species that are responsible for a large variety of chemical transformations. This review critically discusses the most recent progress in mechanistic elucidation of hot carrier-driven chemistry and catalytic processes at the nanoscale. The review provides a brief description of tip-enhanced Raman spectroscopy (TERS), modern analytical technique that possesses single-molecule sensitivity and angstrom spatial resolution, showing the advantage of this technique for spatiotemporal characterization of plasmon-driven reactions. The review also discusses experimental and theoretical findings that reported novel plasmon-driven reactivity which can be used to catalyze redox, coupling, elimination and scissoring reactions. Lastly, the review discusses the impact of the most recently reported findings on both plasmonic catalysis and TERS imaging.

Thanks to the unique molecular fingerprints in the mid-infrared spectral region, absorption spectroscopy in this regime has attracted widespread attention in recent years. Contrary to commercially available infrared spectrometers, which are limited by being bulky and cost-intensive, laboratory-on-chip infrared spectrometers can offer sensor advancements including raw sensing performance in addition to utilization such as enhanced portability. Several platforms have been proposed in the past for on-chip ethanol detection. However, selective sensing with high sensitivity at room temperature has remained a challenge. Here, we experimentally demonstrate an on-chip ethyl alcohol sensor based on a holey photonic crystal waveguide on silicon on insulator-based photonics sensing platform offering an enhanced photoabsorption thus improving sensitivity. This is achieved by designing and engineering an optical slow-light mode with a high group-index of n g  = 73 and a strong localization of the modal power in analyte, enabled by the photonic crystal waveguide structure. This approach includes a codesign paradigm that uniquely features an increased effective path length traversed by the guided wave through the to-be-sensed gas analyte. This PIC-based lab-on-chip sensor is exemplary, spectrally designed to operate at the center wavelength of 3.4 μm to match the peak absorbance for ethanol. However, the slow-light enhancement concept is universal offering to cover a wide design-window and spectral ranges towards sensing a plurality of gas species. Using the holey photonic crystal waveguide, we demonstrate the capability of achieving parts per billion levels of gas detection precision. High sensitivity combined with tailorable spectral range along with a compact form-factor enables a new class of portable photonic sensor platforms when integrated with quantum cascade laser and detectors.

Broadband long-wavelength infrared (LWIR) optical absorbers have important applications in thermal emission and imaging, infrared camouflaging, and waste heat and biothermal energy utilization. However, the practical application of broadband LWIR optical absorbers requires low-cost and facile fabrication of large-area structures with limited thickness. This paper reports the design and fabrication of an ultrathin, broadband, omnidirectional, and polarization-independent LWIR optical absorber composed of anodized aluminum oxide and highly doped Si using the gradient refractive index strategy. The average absorption of the broadband optical absorber is higher than 95% in the 8–15 μm wavelength range, and it has wide incident angle and polarization tolerances. More than 95% of the optical energy in the wavelength range from 8 to 13 μm was absorbed within a depth of 8 μm, making this absorber the thinnest broadband LWIR dielectric absorber so far. The absorption remained above 90% after annealing at 800 °C in air. The infrared camouflage of the proposed absorber was successfully demonstrated with a human body background. With the advantages of facile fabrication, low-cost materials, restricted absorption thickness, and excellent thermal stability, the developed broadband LWIR optical absorber is very promising for the practical applications mentioned above.

We theoretically study the nature of parametrically driven dissipative Kerr soliton (PD-DKS) in a doubly resonant degenerate micro-optical parametric oscillator (DR-DμOPO) with the cooperation of χ (2) and χ (3) nonlinearities. Lifting the assumption of close-to-zero group velocity mismatch (GVM) that requires extensive dispersion engineering, we show that there is a threshold GVM above which single PD-DKS in DR-DμOPO can be generated deterministically. We find that the exact PD-DKS generation dynamics can be divided into two distinctive regimes depending on the phase matching condition. In both regimes, the perturbative effective third-order nonlinearity resulting from the cascaded quadratic process is responsible for the soliton annihilation and the deterministic single PD-DKS generation. We also develop the experimental design guidelines for accessing such deterministic single PD-DKS state. The working principle can be applied to different material platforms as a competitive ultrashort pulse and broadband frequency comb source architecture at the mid-infrared spectral range.

We investigate the photovoltaic behaviors of magnetic graphene interconnect junctions, which are constructed by zigzag graphene nanoribbons (ZGNRs), with the aim to produce pure spin current by photogalvanic effect (PGE). Two kinds of interconnect junctions are designed by connecting two 6-ZGNR with a carbon hexagon (C6) and a carbon tetragon (C4), respectively. It is found that zero charge current is produced under irradiation of light in both structures due to the presence of spatial inversion symmetry. Nevertheless, behind the zero charge current, net pure spin current is produced in the structure with a C6, but not in the structure with a C4. This difference originates from their different edge state distribution and different spatial inversion symmetry of the spin density. However, interestingly, local edge pure spin current can be obtained in both structures. More importantly, the pure spin current generation is independent of the photon energy, polarization type or polarization angle, suggesting a robust way of generating pure spin current with PGE and new possibility of graphene’s applications in spintronics.

When solving, modeling or reasoning about complex problems, it is usually convenient to use the knowledge of a parallel physical system for representing it. This is the case of lumped-circuit abstraction, which can be used for representing mechanical and acoustic systems, thermal and heat-diffusion problems and in general partial differential equations. Integrated photonic platforms hold the prospective to perform signal processing and analog computing inherently, by mapping into hardware specific operations which relies on the wave-nature of their signals, without trusting on logic gates and digital states like electronics. Here, we argue that in absence of a straightforward parallelism a homomorphism can be induced. We introduce a photonic platform capable of mimicking Kirchhoff’s law in photonics and used as node of a finite difference mesh for solving partial differential equation using monochromatic light in the telecommunication wavelength. Our approach experimentally demonstrates an arbitrary set of boundary conditions, generating a one-shot discrete solution of a Laplace partial differential equation, with an accuracy above 95% with respect to commercial solvers. Our photonic engine can provide a route to achieve chip-scale, fast (10 s of ps), and integrable reprogrammable accelerators for the next generation hybrid high-performance computing. Summary A photonic integrated platform which can mimic Kirchhoff’s law in photonics is used for approximately solve partial differential equations noniteratively using light, with high throughput and low-energy levels.

We study how nanophotonic structures can be used for determining the position of a nearby nanoscale object with subwavelength accuracy. Through perturbing the near-field environment of a metasurface transducer consisting of nano-apertures in a metallic film, the location of the nanoscale object is transduced into the transducer’s far-field optical response. By monitoring the scattering pattern of the nanophotonic near-field transducer and comparing it to measured reference data, we demonstrate the two-dimensional localization of the object accurate to 24 nm across an area of 2 × 2 μm. We find that adding complexity to the nanophotonic transducer allows localization over a larger area while maintaining resolution, as it enables encoding more information on the position of the object in the transducer’s far-field response.

We demonstrate a simple, cost-effective method to enhance the photoluminescence intensity of monolayer MoS 2 . A hexagonal symmetric Au metasurface, made by polystyrene nanosphere lithography and metal coating, is developed to enhance the photoluminescence intensity of monolayer MoS 2 . By using nanospheres of different sizes, the localized surface plasmon resonances of the Au metasurfaces can be effectively tuned. By transferring monolayer MoS 2 onto the Au metasurface, the photoluminescence signal of the monolayer MoS 2 can be significantly enhanced up to 12-fold over a square-centimeter area. The simple, large-area, cost-effective fabrication technique could pave a new way for plasmon-enhanced light-mater interactions of atomically thin two-dimensional materials.

Metallic 2D materials can be promising saturable absorbers for ultrashort pulsed laser production in the long wavelength regime. However, preparing and manipulating their 2D structures without layer stacking have been nontrivial. Using a combined experimental and theoretical approach, we demonstrate here that a metallic titanium carbide (Ti 3 C 2 T x ), the most popular MXene 2D material, can have excellent nonlinear saturable absorption properties even in a highly stacked state due to its intrinsically existing surface termination, and thus can produce mode-locked femtosecond pulsed lasers in the 1.9-μm infrared range. Density functional theory calculations reveal that the electronic and optical properties of Ti 3 C 2 T x MXene can be well preserved against significant layer stacking. Indeed, it is experimentally shown that 1.914-μm femtosecond pulsed lasers with a duration of 897 fs are readily generated within a fiber cavity using hundreds-of-layer stacked Ti 3 C 2 T x MXene saturable absorbers, not only being much easier to manufacture than mono- or few-layered ones, but also offering character-conserved tightly-assembled 2D materials for advanced performance. This work strongly suggests that as-obtained highly stacked Ti 3 C 2 T x MXenes can serve as superb material platforms for versatile nanophotonic applications, paving the way toward cost-effective, high-performance photonic devices based on MXenes.

In the quest to realize analog signal processing using subwavelength metasurfaces, in this paper, we present the first demonstration of programmable time-modulated metasurface processors based on the key properties of spatial Fourier transformation. Exploiting space-time coding strategy enables local, independent, and real-time engineering of not only amplitude but also phase profile of the contributing reflective digital meta-atoms at both central and harmonic frequencies. Several illustrative examples are demonstrated to show that the proposed multifunctional calculus metasurface is capable of implementing a large class of useful mathematical operators, including 1st- and 2nd-order spatial differentiation, 1st-order spatial integration, and integro-differential equation solving accompanied by frequency conversions. Unlike the recent proposals based on the Green’s function (GF) method, the designed time-modulated signal processor effectively operates for input signals containing wide spatial frequency bandwidths with an acceptable gain level. Proof-of-principle simulations are also reported to demonstrate the successful realization of image processing functions like edge detection. This time-varying wave-based computing system can set the direction for future developments of programmable metasurfaces with highly promising applications in ultrafast equation solving, real-time and continuous signal processing, and imaging.

We design and demonstrate an asymmetric Ge/SiGe coupled quantum well (CQW) waveguide modulator for both intensity and phase modulation with a low bias voltage in silicon photonic integration. The asymmetric CQWs consisting of two quantum wells with different widths are employed as the active region to enhance the electro-optical characteristics of the device by controlling the coupling of the wave functions. The fabricated device can realize 5 dB extinction ratio at 1446 nm and 1.4 × 10 −3 electrorefractive index variation at 1530 nm with the associated modulation efficiency V π L π of 0.055 V cm under 1 V reverse bias. The 3 dB bandwidth for high frequency response is 27 GHz under 1 V bias and the energy consumption per bit is less than 100 fJ/bit. The proposed device offers a pathway towards a low voltage, low energy consumption, high speed and compact modulator for silicon photonic integrated devices, as well as opens possibilities for achieving advanced modulation format in a more compact and simple frame.

The optical elements comprised of sub-diffractive light scatterers, or metasurfaces, hold a promise to reduce the footprint and unfold new functionalities of optical devices. A particular interest is focused on metasurfaces for manipulation of phase and amplitude of light beams. Characterisation of metasurfaces can be performed using interferometry, which, however, may be cumbersome, specifically in the infrared (IR) range. Here, we realise a new method for characterising metasurfaces operating in the telecom IR range using accessible components for visible light. Correlated IR and visible photons are launched into a non-linear interferometer so that the phase profile, imposed by the metasurface on the IR photons, modifies the interference at the visible photon wavelength. Furthermore, we show that this concept can be used for broadband manipulation of the intensity profile of a visible beam using a single IR metasurface. Our method unfolds the potential of quantum interferometry for the characterization of advanced optical elements.