Graphene/chitosan nanoreactors for ultrafast and precise recovery and catalytic conversion of gold from electronic waste.

The extraction of gold (Au) from electronic waste (e-waste) has both environmental impact and inherent value. Improper e-waste disposal poses environmental and health risks, entailing substantial remediation and healthcare costs. Large efforts are applied for the recovery of Au from e-waste using complex processes which include the dissolution of Au, its adsorption in an ionic state and succeeding reduction to metallic Au. These processes themselves being complex and utilizing harsh chemicals contribute to the environmental impact of e-waste. Here, we present an approach for the simultaneous recovery and reduction of Au3+ and Au+ ions from e-waste to produce solid Au0 forms, thus skipping several technological steps. We develop a nanoscale cross-dimensional composite material via self-assembly of two-dimensional graphene oxide and one-dimensional chitosan macromolecules, capable of acting simultaneously as a scavenger of gold ions and as a reducing agent. Such multidimensional architecture doesn't require to apply any voltage for Au adsorption and reduction and solely relies on the chemisorption kinetics of Au ions in the heterogeneous GO/CS nanoconfinements and their chemical reduction on multiple binding sites. The cooperative phenomena in ionic absorption are responsible for the extremely high efficiency of gold extraction. The extraction capacity reaches 16.8 g/g for Au3+ and 6.2 g/g for Au+, which is ten times larger than any existing gold adsorbents can propose. The efficiency is above 99.5 wt.% (current limit is 75 wt.%) and extraction ability is down to very low concentrations of 3 ppm.

Highly oriented single-crystalline gold quantum-dot metamaterials as prospective materials for photonics.

Miniaturization of optical devices is a modern trend essential for optoelectronics, optical sensing, optical computing and other branches of science and technology. To satisfy this trend, optical materials with a small footprint are required. Here we show that extremely thin, flat, nanostructured gold films made of highly oriented single-crystalline gold quantum-dots can provide elements of topological photonics in visible light and be used as high-index dielectric materials in the infrared part of the spectra. We measure and theoretically confirm the presence of topological darkness and associated phase singularities in studied gold films of thickness of below 10 nm placed on MgO substrates in the red part of the spectrum. At telecom wavelengths, the fabricated gold metasurface behaves as a dielectric with the refractive index of n≈2.75 and the absorption coefficient of k≈0.005.

Label-free optical biosensing: going beyond the limits.

Label-free optical biosensing holds great promise for a variety of applications in biomedical diagnostics, environmental and food safety, and security. It is already used as a key tool in the investigation of biomolecular binding events and reaction constants in real time and offers further potential additional functionalities and low-cost designs. However, the sensitivity of this technology does not match the routinely used but expensive and slow labelling methods. Therefore, label-free optical biosensing remains predominantly a research tool. Here we discuss how one can go beyond the limits of detection provided by standard optical biosensing platforms and achieve a sensitivity of label-free biosensing that is superior to labelling methods. To this end we review newly emerging optical implementations that overcome current sensitivity barriers by employing novel structural architectures, artificial materials (metamaterials and hetero-metastructures) and using phase of light as a sensing parameter. Furthermore, we elucidate the mechanism of plasmonic phase biosensing and review hyper-sensitive transducers, which can achieve detection limits at the single molecule level (less than 1 fg mm-2) and make it possible to detect analytes at several orders of magnitude lower concentrations than so far reported in literature. We finally discuss newly emerging layouts based on dielectric nanomaterials, bound states in continuum, and exceptional points.

Two-Dimensional Covalent Crystals by Chemical Conversion of Thin van der Waals Materials.

Most of the studied two-dimensional (2D) materials have been obtained by exfoliation of van der Waals crystals. Recently, there has been growing interest in fabricating synthetic 2D crystals which have no layered bulk analogues. These efforts have been focused mainly on the surface growth of molecules in high vacuum. Here, we report an approach to making 2D crystals of covalent solids by chemical conversion of van der Waals layers. As an example, we used 2D indium selenide (InSe) obtained by exfoliation and converted it by direct fluorination into indium fluoride (InF3), which has a nonlayered, rhombohedral structure and therefore cannot  possibly be obtained by exfoliation. The conversion of InSe into InF3 is found to be feasible for thicknesses down to three layers of InSe, and the obtained stable InF3 layers are doped with selenium. We study this new 2D material by optical, electron transport, and Raman measurements and show that it is a semiconductor with a direct bandgap of 2.2 eV, exhibiting high optical transparency across the visible and infrared spectral ranges. We also demonstrate the scalability of our approach by chemical conversion of large-area, thin InSe laminates obtained by liquid exfoliation, into InF3 films. The concept of chemical conversion of cleavable thin van der Waals crystals into covalently bonded noncleavable ones opens exciting prospects for synthesizing a wide variety of novel atomically thin covalent crystals.

Nonlinear Light Mixing by Graphene Plasmons.

Graphene is known to possess strong optical nonlinearity which turned out to be suitable for creation of efficient saturable absorbers in mode locked fiber lasers. Nonlinear response of graphene can be further enhanced by the presence of graphene plasmons. Here, we report a novel nonlinear effect observed in nanostructured graphene which comes about due to excitation of graphene plasmons. We experimentally detect and theoretically explain enhanced mixing of near-infrared and mid-infrared light in arrays of graphene nanoribbons. Strong compression of light by graphene plasmons implies that the described effect of light mixing is nonlocal in nature and orders of magnitude larger than the conventional local graphene nonlinearity. Both second and third order nonlinear effects were observed in our experiments with the recalculated third-order nonlinearity coefficient reaching values of 4.5 × 10-6 esu. The suggested effect could be used in variety of applications including nonlinear light modulators, light multiplexers, light logic, and sensing devices.

Maximum modulation of plasmon-guided modes by graphene gating.

The potential of graphene in plasmonic electro-optical waveguide modulators has been investigated in detail by finite-element method modelling of various widely used plasmonic waveguiding configurations. We estimated the maximum possible modulation depth values one can achieve with plasmonic devices operating at telecom wavelengths and exploiting the optical Pauli blocking effect in graphene. Conclusions and guidelines for optimization of modulation/intrinsic loss trade-off have been provided and generalized for any graphene-based plasmonic waveguide modulators, which should help in consideration and design of novel active-plasmonic devices.

Super-narrow, extremely high quality collective plasmon resonances at telecom wavelengths and their application in a hybrid graphene-plasmonic modulator.

We present extremely narrow collective plasmon resonances observed in gold nanostripe arrays fabricated on a thin gold film, with the spectral line full width at half-maximum (fwhm) as low as 5 nm and quality factors Q reaching 300, at important fiber-optic telecommunication wavelengths around 1.5 µm. Using these resonances, we demonstrate a hybrid graphene-plasmonic modulator with the modulation depth of 20% in reflection operated by gating of a single layer graphene, the largest measured so far.

Non-Polaritonic Effects in Cavity-Modified Photochemistry.

Strong coupling of molecules to vacuum fields is widely reported to lead to modified chemical properties such as reaction rates. However, some recent attempts to reproduce infrared strong coupling results have not been successful, suggesting that factors other than strong coupling may sometimes be involved. In the first vacuum-modified chemistry experiment, changes to a molecular photoisomerization process in the ultraviolet-visible spectral range are attributed to strong coupling of the molecules to visible light. Here, this process is re-examined, finding significant variations in photoisomerization rates consistent with the original work. However, there is no evidence that these changes need to be attributed to strong coupling. Instead, it is suggested that the photoisomerization rates involved are most strongly influenced by the absorption of ultraviolet radiation in the cavity. These results indicate that care must be taken to rule out non-polaritonic effects before invoking strong coupling to explain any changes of properties arising in cavity-based experiments.

Versatile Method for Preparing Two-Dimensional Metal Dihalides.

Ever since the ground-breaking isolation of graphene, numerous two-dimensional (2D) materials have emerged with 2D metal dihalides gaining significant attention due to their intriguing electrical and magnetic properties. In this study, we introduce an innovative approach via anhydrous solvent-induced recrystallization of bulk powders to obtain crystals of metal dihalides (MX2, with M = Cu, Ni, Co and X = Br, Cl, I), which can be exfoliated to 2D flakes. We demonstrate the effectiveness of our method using CuBr2 as an example, which forms large layered crystals. We investigate the structural properties of both the bulk and 2D CuBr2 using X-ray diffraction, along with Raman scattering and optical spectroscopy, revealing its quasi-1D chain structure, which translates to distinct emission and scattering characteristics. Furthermore, microultraviolet photoemission spectroscopy and electronic transport reveal the electronic properties of CuBr2 flakes, including their valence band structure. We extend our methodology to other metal halides and assess the stability of the metal halide flakes in controlled environments. We show that optical contrast can be used to characterize the flake thicknesses for these materials. Our findings demonstrate the versatility and potential applications of the proposed methodology for preparing and studying 2D metal halide flakes.

Topological Darkness in Optical Heterostructures: Prediction and Confirmation.

Topological darkness is a new phenomenon that guarantees zero reflection/transmission of light from an optical sample and hence provides topologically nontrivial phase singularities. Here we consider topological darkness in an optical heterostructure that consists of an (unknown) layer placed on a composite substrate and suggest an algorithm that can be used to predict and confirm the presence of topological darkness. The algorithm is based on a combination of optical measurements and the Fresnel equations. We apply this algorithm to ultrathin Pd films fabricated on a Si/SiO2/Cr substrate and extract four different points of topological darkness. Our results will be useful for topological photonics and label-free optical biosensing based on phase interrogation.

Topological Darkness: How to Design a Metamaterial for Optical Biosensing with Ultrahigh Sensitivity.

Due to the absence of labels and fast analyses, optical biosensors promise major advances in biomedical diagnostics, security, environmental, and food safety applications. However, the sensitivity of the most advanced plasmonic biosensor implementations has a fundamental limitation caused by losses in the system and/or geometry of biochips. Here, we report a "scissor effect" in topologically dark metamaterials which is capable of providing ultrahigh-amplitude sensitivity to biosensing events, thus solving the bottleneck sensitivity limitation problem. We explain how the "scissor effect" can be realized via the proper design of topologically dark metamaterials and describe strategies for their fabrication. To validate the applicability of this effect in biosensing, we demonstrate the detection of folic acid (vitamin important for human health) in a wide 3-log linear dynamic range with a limit of detection of 0.22 nM, which is orders of magnitude better than those previously reported for all optical counterparts. Our work provides possibilities for designing and realizing plasmonic, semiconductor, and dielectric metamaterials with ultrasensitivity to binding events.

"Dead" Exciton Layer and Exciton Anisotropy of Bulk MoS2 Extracted from Optical Measurements.

Excitons (electron-hole pairs bound by the Coulomb potential) play an important role in optical and electronic properties of layered materials. They can be used to modulate light with high frequencies due to the optical Pauli blocking. The properties of excitons in 2D materials are extremely anisotropic. However, due to nanometre sizes of excitons and their short life times, reliable tools to study this anisotropy are lacking. Here, we show how direct optical reflection measurements can be used to evaluate anisotropy of excitons in transition metal dichalcogenides MoS2. Using focused beam spectroscopic ellipsometry, we have measured the polarized optical reflection of bulk MoS2 for two crystal orientations: c-axis being perpendicular to the surface from which reflection is measured and c-axis being parallel to the surface from which reflection is measured. We found that for the parallel configuration the optical reflection near excitonic transitions is strongly affected by the presence of the exciton "dead" layer such that the excitonic reflection peaks become the excitonic dips due to light interference. At the same time, the optical reflection for the perpendicular orientation is not significantly altered by the exciton "dead" layer due to large anisotropy of exciton properties. Performing simultaneous Fresnel fitting for both geometries, we were able to evaluate exciton anisotropy in layered materials from simple optical measurements.

Topological phase singularities in atomically thin high-refractive-index materials.

Atomically thin transition metal dichalcogenides (TMDCs) present a promising platform for numerous photonic applications due to excitonic spectral features, possibility to tune their constants by external gating, doping, or light, and mechanical stability. Utilization of such materials for sensing or optical modulation purposes would require a clever optical design, as by itself the 2D materials can offer only a small optical phase delay - consequence of the atomic thickness. To address this issue, we combine films of 2D semiconductors which exhibit excitonic lines with the Fabry-Perot resonators of the standard commercial SiO2/Si substrate, in order to realize topological phase singularities in reflection. Around these singularities, reflection spectra demonstrate rapid phase changes while the structure behaves as a perfect absorber. Furthermore, we demonstrate that such topological phase singularities are ubiquitous for the entire class of atomically thin TMDCs and other high-refractive-index materials, making it a powerful tool for phase engineering in flat optics. As a practical demonstration, we employ PdSe2 topological phase singularities for a refractive index sensor and demonstrate its superior phase sensitivity compared to typical surface plasmon resonance sensors.

Fluorographene: a two-dimensional counterpart of Teflon.

A stoichiometric derivative of graphene with a fluorine atom attached to each carbon is reported. Raman, optical, structural, micromechanical, and transport studies show that the material is qualitatively different from the known graphene-based nonstoichiometric derivatives. Fluorographene is a high-quality insulator (resistivity >10(12) Ω) with an optical gap of 3 eV. It inherits the mechanical strength of graphene, exhibiting a Young's modulus of 100 N m(-1) and sustaining strains of 15%. Fluorographene is inert and stable up to 400 °C even in air, similar to Teflon.

Plasmonic resonances in optomagnetic metamaterials based on double dot arrays.

We study optical properties of optomagnetic metamaterials produced by regular arrays of double gold dots (nanopillars). Using combined data of spectroscopic ellipsometry, transmission and reflection measurements, we identify localized plasmon resonances of a nanopillar pair and measure their dependences on dot sizes. We formulate the necessary condition at which an effective field theory can be applied to describe optical properties of a composite medium and employ interferometry to measure phase shifts for our samples. A negative phase shift for transmitted green light coupled to an antisymmetric magnetic mode of a double-dot array is observed.

Phase and amplitude sensitivities in surface plasmon resonance bio and chemical sensing.

We consider amplitude and phase characteristics of light reflected under the Surface Plasmon Resonance (SPR) conditions and study their sensitivities to refractive index changes associated with biological and chemical sensing. Our analysis shows that phase can provide at least two orders of magnitude better detection limit due to the following reasons: (i) Maximal phase changes occur in the very dip of the SPR curve where the vector of probing electric field is maximal, whereas maximal amplitude changes are observed on the resonance slopes: this provides a one order of magnitude larger sensitivity of phase to refractive index variations; (ii) Under a proper design of a detection scheme, phase noises can be orders of magnitude lower compared to amplitude ones, which results in a much better signal-to-noise ratio; (iii) Phase offers much better possibilities for signal averaging and filtering, as well as for image treatment. Applying a phase-sensitive SPR polarimetry scheme and using gas calibration model, we experimentally demonstrate the detection limit of 10(-8) RIU, which is about two orders of magnitude better compared to amplitude-sensitive schemes. Finally, we show how phase can be employed for filtering and treatment of images in order to improve signal-to-noise ratio even in relatively noisy detection schemes. Combining a much better physical sensitivity and a possibility of imaging and sensing in micro-arrays, phase-sensitive methodologies promise a substantial upgrade of currently available SPR technology.

Ultra-narrow surface lattice resonances in plasmonic metamaterial arrays for biosensing applications.

When excited over a periodic metamaterial lattice of gold nanoparticles (~ 100nm), localized plasmon resonances (LPR) can be coupled by a diffraction wave propagating along the array plane, which leads to a drastic narrowing of plasmon resonance lineshapes (down to a few nm full-width-at-half-maximum) and the generation of singularities of phase of reflected light. These phenomena look very promising for the improvement of performance of plasmonic biosensors, but conditions of implementation of such diffractively coupled plasmonic resonances, also referred to as plasmonic surface lattice resonances (PSLR), are not always compatible with biosensing arrangement implying the placement of the nanoparticles between a glass substrate and a sample medium (air, water). Here, we consider conditions of excitation and properties of PSLR over arrays of glass substrate-supported single and double Au nanoparticles (~ 100-200nm), arranged in a periodic metamaterial lattice, in direct and Attenuated Total Reflection (ATR) geometries, and assess their sensitivities to variations of refractive index (RI) of the adjacent sample dielectric medium. First, we identify medium (PSLRair, PSLRwat for air and water, respectively) and substrate (PSLRsub) modes corresponding to the coupling of individual plasmon oscillations at medium- and substrate-related diffraction cut-off edges. We show that spectral sensitivity of medium modes to RI variations is determined by the lattice periodicity in both direct and ATR geometries (~ 320nm per RIU change in our case), while substrate mode demonstrates much lower sensitivity. We also show that phase sensitivity of PSLR can exceed 105 degrees of phase shift per RIU change and thus outperform the relevant parameter for all other plasmonic sensor counterparts. We finally demonstrate the applicability of surface lattice resonances in plasmonic metamaterial arrays to biosensing using standard streptavidin-biotin affinity model. Combining advantages of nanoscale architectures, including drastic concentration of electric field, possibility of manipulation at the nanoscale etc, and high phase and spectral sensitivities, PSLRs promise the advancement of current state-of-the-art plasmonic biosensing technology toward single molecule label-free detection.

Solid-State Electrolyte-Gated Graphene in Optical Modulators.

The gate-tunable wide-band absorption of graphene makes it suitable for light modulation from terahertz to visible light. The realization of graphene-based modulators, however, faces challenges connected with graphene's low absorption and the high electric fields necessary to change graphene's optical conductivity. Here, a solid-state supercapacitor effect with the high-k dielectric hafnium oxide is demonstrated that allows modulation from the near-infrared to shorter wavelengths close to the visible spectrum with remarkably low voltages (≈3 V). The electroabsorption modulators are based on a Fabry-Perot-resonator geometry that allows modulation depths over 30% for free-space beams.

Strong coupling of diffraction coupled plasmons and optical waveguide modes in gold stripe-dielectric nanostructures at telecom wavelengths.

We propose a hybrid plasmonic device consisting of a planar dielectric waveguide covering a gold nanostripe array fabricated on a gold film and investigate its guiding properties at telecom wavelengths. The fundamental modes of a hybrid device and their dependence on the key geometric parameters are studied. A communication length of 250 µm was achieved for both the TM and TE guided modes at telecom wavelengths. Due to the difference between the TM and TE light propagation associated with the diffractive plasmon excitation, our waveguides provide polarization separation. Our results suggest a practical way of fabricating metal-nanostripes-dielectric waveguides that can be used as essential elements in optoelectronic circuits.

Plasmon-induced nanoscale quantised conductance filaments.

Plasmon-induced phenomena have recently attracted considerable attention. At the same time, relatively little research has been conducted on electrochemistry mediated by plasmon excitations. Here we report plasmon-induced formation of nanoscale quantized conductance filaments within metal-insulator-metal heterostructures. Plasmon-enhanced electromagnetic fields in an array of gold nanodots provide a straightforward means of forming conductive CrOx bridges across a thin native chromium oxide barrier between the nanodots and an underlying metallic Cr layer. The existence of these nanoscale conducting filaments is verified by transmission electron microscopy and contact resistance measurements. Their conductance was interrogated optically, revealing quantised relative transmission of light through the heterostructures across a wavelength range of 1-12 µm. Such plasmon-induced electrochemical processes open up new possibilities for the development of scalable devices governed by light.