Photon-Momentum-Enabled Electronic Raman Scattering in Silicon Glass.

The nature of enhanced photoemission in disordered and amorphous solids is an intriguing question. A point in case is light emission in porous and nanostructured silicon, a phenomenon that is still not fully understood. In this work, we study structural photoemission in heterogeneous cross-linked silicon glass, a material that represents an intermediate state between the amorphous and crystalline phases, characterized by a narrow distribution of structure sizes. This model system shows a clear dependence of photoemission on size and disorder across a broad range of energies. While phonon-assisted indirect optical transitions are insufficient to describe observable emissions, our experiments suggest these can be understood through electronic Raman scattering instead. This phenomenon, which is not commonly observed in crystalline semiconductors, is driven by structural disorder. We attribute photoemission in this disordered system to the presence of an excess electron density of states within the forbidden gap (Urbach bridge) where electrons occupy trapped states. Transitions from gap states to the conduction band are facilitated through electron-photon momentum matching, which resembles Compton scattering but is observed for visible light and driven by the enhanced momentum of a photon confined within the nanostructured domains. We interpret the light emission in structured silicon glass as resulting from electronic Raman scattering. These findings emphasize the role of photon momentum in the optical response of solids that display disorder on the nanoscale.

Light-Controlled Multiphase Structuring of Perovskite Crystal Enabled by Thermoplasmonic Metasurface.

Halide perovskites belong to an important family of semiconducting materials with electronic properties that enable a myriad of applications, especially in photovoltaics and optoelectronics. Their optical properties, including photoluminescence quantum yield, are affected and notably enhanced at crystal imperfections where the symmetry is broken and the density of states increases. These lattice distortions can be introduced through structural phase transitions, allowing charge gradients to appear near the interfaces between phase structures. In this work, we demonstrate controlled multiphase structuring in a single perovskite crystal. The concept uses cesium lead bromine (CsPbBr3) placed on a thermoplasmonic TiN/Si metasurface and enables single-, double-, and triple-phase structures to form on demand above room temperature. This approach promises application horizons of dynamically controlled heterostructures with distinctive electronic and enhanced optical properties.

Designing two-dimensional temperature profiles using tunable thermoplasmonics.

Heat flow generation and manipulation in nanometer-sized solids using light represents one of the up-and-coming tasks in thermonanophotonics. Enhanced light-matter interaction due to plasmon resonance permits metallic nanostructures to absorb light energy efficiently, and it results in extra optical heating. The net temperature increment of nanostructures is directly dependent on heat exchange with a thermostat. However, to the best of our knowledge, precise tailoring of optical heating at a fixed pump power is still of no practical implementation. In this paper, we focus on the tunable optical heating of a plasmonic nanostructure exposed to moderate light intensity (MW cm-2) based on slowing down heat exchange through a 1D waveguide heatsink bridging the nanostructure and the highly thermal conducting thermostat. The rationale for this concept is evidenced through optical heating of a 2D array of stacked titanium nitride (TiN) (plasmonic refractory nanoheater) and height-controlled silicon (Si) (1D waveguide heatsink) cylinders. Depending on the Si pillar height, the temperature rise of a TiN : Si voxel ranges from a few up to thousands of degrees at a fixed pump power. The temperature of the TiN : Si voxel is remotely measured from the Raman shift of the Si pillar. Using ellipsometry, we find a temperature threshold of 400 °C, above which the thin TiN film is chemically degraded due to oxidation. The latter enables fine tailoring of thermal gradients using TiN : Si voxels of equal size but different permittivity. These findings contribute towards the development of tunable thermoplasmonics by demonstrating programmable non-uniform temperature profiles in the steady-state regime under continuous-wave laser illumination for a variety of thermo-optical applications.

Nanoscale Melting of 3D Confined Azopolymers through Tunable Thermoplasmonics.

Phase transitions that are thermally induced by using light at the nanoscale play a vital role in material science. Enhanced optical heating sustained by resonant nanostructures can turn out to be insignificant when a higher thermal conductivity of a heatsink, regardless of the pumping intensity. In this Letter, we demonstrate an approach to control an operating temperature range due to excess heating of a structured heatsink. A design rationale has been performed by using a 2D array of TiN:Si voxels, consisting of stacked TiN and Si pillars. All the TiN nanoheaters responsible for enhanced light absorption at plasmon resonance are of equal size, and the height of the Si pillars varies to control heat localization. A height-dependent temperature rise of the Si pillars is found from Raman thermometry. Herein, for the first time, we have determined the melting temperature of azobenzene-functionalized polymers at the nanoscale using the tunable plasmonic metasurface.

Disordered Nonlinear Metalens for Raman Spectral Nanoimaging.

Over the past decades, considerable progress has been made toward far-field optical imaging beyond the diffraction limit. However, most working proof-of-concepts are based on either time-consuming scanning of a subdiffraction focal spot over a sample or postrecovery treatment using a priori information on a sought image. To our knowledge, none of these can be regarded as being close to a perfect far-field superlensing system capable of real-time color imaging with subwavelength resolution. In this paper, we suggest a proof-of-concept for far-field nonlinear metalens that is made of a disordered metal-dielectric nanocomposite. Postoxidation of a refractory titanium nitride (TiN) thin film, used as a nonlinear plasmonic material, results in the formation of a titanium oxynitride (TiON) film comprising a mixture of multiple phases of TiOxNy. Due to a double epsilon-near-zero behavior near the percolation threshold, the TiON favors supercoupling of the incident light to surface plasmon resonance within the visible and near-infrared range. Point spread function narrowing is achieved owing to the multiplicative nature of stimulated Raman scattering (SRS) and enhanced third-order optical nonlinearity in TiN and TiO2 particle chains through plasmon resonances and Anderson localization of light, respectively. Combined with a conventional confocal optical microscope, the multimode metalens shows subwavelength resolution of λ/6NA at different visible wavelengths (SRS overtones) using multiwalled carbon nanotubes as a test sample. We are confident that our finding will bring us one step closer to developing a robust and versatile far-field super-resolution color imaging system and, eventually, implementing "eye-on-a-chip" technology.

Superresolution stimulated Raman scattering microscopy using 2-ENZ nano-composites.

Superlensing plays a crucial role in near- and far-field optical imaging with sub-wavelength resolution. One of the ways to expand optical bandwidth is surface plasmon resonances in layered metal-dielectric nanostructures. These resonances are commonly excited at a tunable single frequency. In this study, we propose the concept of a multimode far-field superlens made of a titanium oxynitride (TiON) thin film, that is a disordered metal-dielectric refractory nano-composite. These films exhibit a double epsilon-near-zero (2-ENZ) behavior near the percolation threshold and, therefore, favor super-coupling the incident laser light to surface plasmon resonances, not using such couplers as a prism, a grating, etc. We experimentally observe stimulated Raman gain emission from nano-structured TiON thin films exposed to low-power continuous-wave laser light. It is shown that superresolution of <λ/80 (near-field) and <λ/8 (far-field) is achieved due to both the enhanced third-order optical nonlinearity and the multiplicative nature of four-wave mixing. The multimode tunable far-field superlens will impact emerging diffraction-free far-field optical microscopy, random Raman lasing on meta-atoms and broadband thermophotovoltaics.

Far-field Raman color superlensing based on disordered plasmonics.

Plasmon multiple scattering within a disordered metal-dielectric medium allows one to enhance a cubic susceptibility drastically, and thus stimulated Raman scattering (SRS) can occur in highly confined media exposed to the continuous-wave low-powered pump. In this study, a percolated 50 nm titanium oxynitride thin film is used as a disordered nonlinear metalens that meets epsilon-near-zero (ENZ) wavelengths in the visible and near infrared region. We experimentally demonstrate a far-field Raman superlensing effect by showing a subwavelength resolution of λ/6NA at different SRS overtones using multiwalled carbon nanotubes directly dispersed on the metalens.

Near-field depolarization of tip-enhanced Raman scattering by single azo-chromophores.

The intrinsic symmetry and orientation of single molecules play a crucial role in enhanced optical spectroscopy and nanoscopic imaging. Unlike bulk materials, in which all molecular orientations are unavoidably averaged in the far-field, intensities of vibrational modes in tip-enhanced Raman scattering (TERS) depend greatly on the polarization direction of near-field light. It means that a near-field Raman "dichroism" becomes possible for anisotropic single molecules. Quantitative evaluation of the molecular orientation gets complicated by the depolarization of TERS intensities. Clearly, the depolarization effect is enhanced with an optical antenna and/or a substrate due to their anisotropic origin. In this study, we provide theoretical and experimental insights into Raman tensors of a single azobenzene chromophore, a Disperse Orange 3 (DO3) molecule, supported with a glass base. It is shown that the Raman intensities of the spectral bands corresponding to symmetric and antisymmetric vibrations of the DO3 molecule, for example, -NO2 and -NH2 moieties, behave differently on the nanoscale. In particular, three-dimensional far- and near-field Raman diagrams indicate that antisymmetric vibrations become highly depolarized, whereas symmetric vibrations remain unchangeable but intensities of their spectral bands are enhanced. Here, we introduce a near-field depolarization factor defined as a normalized discrepancy of longitudinal and transverse TERS signals. We believe that our first steps will ultimately lead to advanced facilities of TERS spectroscopy and nanoscopy, related to the orientation of anisotropic single molecules and their symmetries.

Nonlinear Raman Effects Enhanced by Surface Plasmon Excitation in Planar Refractory Nanoantennas.

We consider a nonlinear mechanism of localized light inelastic scattering within nanopatterned plasmonic and Raman-active titanium nitride (TiN) thin films exposed to continuous-wave (cw) modest-power laser light. Owing to the strong third-order nonlinear interaction between optically excited broadband surface plasmons and localized Stokes and anti-Stokes waves, both stimulated and inverse Raman effects can be observed. We provide experimental evidence for coherent amplification of the localized Raman signals using a planar square-shaped refractory antenna.

Near-field Raman dichroism of azo-polymers exposed to nanoscale dc electrical and optical poling.

Azobenzene-functionalized polymer films are functional materials, where the (planar vs. homeotropic) orientation of azo-dyes can be used for storing data. In order to characterize the nanoscale 3D orientation of the pigments in sub-10 nm thick polymer films we use two complementary techniques: polarization-controlled tip-enhanced Raman scattering (TERS) microscopy and contact scanning capacity microscopy. We demonstrate that the homeotropic and planar orientations of the azo-dyes are produced by applying a local dc electrical field and a resonant longitudinal optical near-field, respectively. For a non-destructive probe of the azo-dye orientation we apply a non-resonant optical near-field and compare the intensities of the Raman-active vibrational modes. We show that near-field Raman dichroism, a characteristic similar to the absorption dichroism used in far-field optics, can be a quantitative indicator of the 3D molecular orientation of the azo-dye at the nanoscale. This study directly benefits the further development of photochromic near-field optical memory that can lead to ultrahigh density information storage.

Near-field optical taper antennas fabricated with a highly replicable ac electrochemical etching method.

This paper describes a novel chemical etching method to fabricate high quality near-field optical antennas-tapered metallic tips-from gold wire in a reproducible way for optically probing a specimen on the nanoscale. A new type of an electrochemical cell is introduced and different dc and ac etching regimes are studied in detail. The formation and dynamics of a meniscus around a gold wire immersed in an electrolyte when supplying a square wave voltage are considered. We show that in situ etching current kinetics allows one to improve a yield of tips with a well-defined geometry up to 95% by filtering these on the basis of a cutoff current and a power spectrum of etching current fluctuations. As a quantitative measure for estimating the yield we introduce a probability to find tips with curvature radii falling in the range of interest. Testing the tips for a plasmonic effect is implemented with tip-enhanced Raman spectroscopy and sub-wavelength imaging of a thin fullerene film.