H-Glass Supported Hybrid Gold Nano-Islands for Visible-Light-Driven Hydrogen Evolution.

Flat panel reactors, coated with photocatalytic materials, offer a sustainable approach for the commercial production of hydrogen (H2) with zero carbon footprint. Despite this, achieving high solar-to-hydrogen (STH) conversion efficiency with these reactors is still a significant challenge due to the low utilization efficiency of solar light and rapid charge recombination. Herein, hybrid gold nano-islands (HGNIs) are developed on transparent glass support to improve the STH efficiency. Plasmonic HGNIs are grown on an in-house developed active glass sheet composed of sodium aluminum phosphosilicate oxide glass (H-glass) using the thermal dewetting method at 550 °C under an ambient atmosphere. HGNIs with various oxidation states (Au0, Au+, and Au-) and multiple interfaces are obtained due to the diffusion of the elements from the glass structure, which also facilitates the lifetime of the hot electron to be ≈2.94 ps. H-glass-supported HGNIs demonstrate significant STH conversion efficiency of 0.6%, without any sacrificial agents, via water dissociation. This study unveils the specific role of H-glass-supported HGNIs in facilitating light-driven chemical conversions, offering new avenues for the development of high-performance photocatalysts in various chemical conversion reactions for large-scale commercial applications.

Multi-Functional Applications of H-Glass Embedded with Stable Plasmonic Gold Nanoislands.

Metal nanoparticles (MNPs) are synthesized using various techniques on diverse substrates that significantly impact their properties. However, among the substrate materials investigated, the major challenge is the stability of MNPs due to their poor adhesion to the substrate. Herein, it is demonstrated how a newly developed H-glass can concurrently stabilize plasmonic gold nanoislands (GNIs) and offer multifunctional applications. The GNIs on the H-glass are synthesized using a simple yet, robust thermal dewetting process. The H-glass embedded with GNIs demonstrates versatility in its applications, such as i) acting as a room temperature chemiresistive gas sensor (70% response for NO2 gas); ii) serving as substrates for surface-enhanced Raman spectroscopy for the identifications of Nile blue (dye) and picric acid (explosive) analytes down to nanomolar concentrations with enhancement factors of 4.8 × 106 and 6.1 × 105 , respectively; and iii) functioning as a nonlinear optical saturable absorber with a saturation intensity of 18.36 × 1015 W m-2 at 600 nm, and the performance characteristics are on par with those of materials reported in the existing literature. This work establishes a facile strategy to develop advanced materials by depositing metal nanoislands on glass for various functional applications.

Iridium-Based Selective Emitters for Thermophotovoltaic Applications.

The long-term operation of refractory-metal-based metamaterials is crucial for applications such as thermophotovoltaics. The metamaterials based on refractory metals like W, Mo, Ta, Nb, and Re fail primarily by oxidation. Here, the use of the noble metal Ir is proposed, which is stable to oxidation and has optical properties comparable to gold. The thermal endurance of Ir in a 3-layer-system, consisting of HfO2 /Ir/HfO2 , by performing annealing experiments up to 1240 °C in a pressure range from 2 × 10-6  mbar to 1 bar, is demonstrated. The Ir layer shows no oxidation in a vacuum and inert gas atmosphere. At temperatures above 1100 °C, the Ir layer starts to agglomerate due to the degradation of the confining HfO2 layers. An in situ X-ray diffraction experimental comparison between 1D multilayered Ir/HfO2 and W/HfO2 selective emitters annealed at 1000 °C, 2 × 10-6  mbar, over 100 h, confirms oxidation stability of Ir while W multilayers gradually disappear. The results of this work show that W-based metamaterials are not long-term stable even at 1000 °C. However, the oxidation resistance of Ir can be leveraged for refractory plasmonic metamaterials, such as selective emitters in thermophotovoltaic systems with strong suppression of long wavelength radiation.

Structural degradation of tungsten sandwiched in hafnia layers determined by in-situ XRD up to 1520 °C.

The high-temperature stability of thermal emitters is one of the critical properties of thermophotovoltaic (TPV) systems to obtain high radiative power and conversion efficiencies. W and HfO2 are ideal due to their high melting points and low vapor pressures. At high temperatures and given vacuum conditions, W is prone to oxidation resulting in instantaneous sublimation of volatile W oxides. Herein, we present a detailed in-situ XRD analysis of the morphological changes of a 3-layer-system: HfO2/W/HfO2 layers, in a high-temperature environment, up to 1520 °C. These samples were annealed between 300 °C and 1520 °C for 6 h, 20 h, and 40 h at a vacuum pressure below 3 × 10-6 mbar using an in-situ high-temperature X-ray diffractometer, which allows investigation of crucial alterations in HfO2 and W layers. HfO2 exhibits polymorphic behavior, phase transformations and anisotropy of thermal expansion leads to formation of voids above 800 °C. These voids serve as transport channels for the residual O2 present in the annealing chamber to access W, react with it and form volatile tungsten oxides. An activation energy of 1.2 eV is calculated. This study clarifies the limits for the operation of W-HfO2 spectrally selective emitters for TPV in high-temperature applications.

Thermal stability of tungsten based metamaterial emitter under medium vacuum and inert gas conditions.

Commercial deployment of thermophotovoltaics (TPV) is lacking behind the implementation of solar PV technology due to limited thermal stability of the selective emitter structures. Most of the TPV emitters demonstrated so far are designed to operate under high vacuum conditions (~10-6 mbar vacuum pressure), whereas under medium vacuum conditions (~10-2 mbar vacuum pressure), which are feasible in technical implementations of TPV, these emitters suffer from oxidation due to significant O2 partial pressure. In this work, the thermal stability of 1D refractory W-HfO2 based multilayered metamaterial emitter structure is investigated under different vacuum conditions. The impact of the O2 partial pressure on thermal stability of the emitters is experimentally quantified. We show that, under medium vacuum conditions, i.e. ~10-2 mbar vacuum pressure, the emitter shows unprecedented thermal stability up to 1300 °C when the residual O2 in the annealing chamber is minimized by encapsulating the annealing chamber with Ar atmosphere. This study presents a significant step in the experimental implementation of high temperature stable emitters under medium vacuum conditions, and their potential in construction of economically viable TPV systems. The high TPV efficiency, ~50% spectral efficiency for GaSb PV cell at 1300 °C, and high temperature stability make this platform well suited for technical application in next-generation TPV systems.

Metamaterial emitter for thermophotovoltaics stable up to 1400 °C.

High temperature stable selective emitters can significantly increase efficiency and radiative power in thermophotovoltaic (TPV) systems. However, optical properties of structured emitters reported so far degrade at temperatures approaching 1200 °C due to various degradation mechanisms. We have realized a 1D structured emitter based on a sputtered W-HfO2 layered metamaterial and demonstrated desired band edge spectral properties at 1400 °C. To the best of our knowledge the temperature of 1400 °C is the highest reported for a structured emitter, so far. The spatial confinement and absence of edges stabilizes the W-HfO2 multilayer system to temperatures unprecedented for other nanoscaled W-structures. Only when this confinement is broken W starts to show the well-known self-diffusion behavior transforming to spherical shaped W-islands. We further show that the oxidation of W by atmospheric oxygen could be prevented by reducing the vacuum pressure below 10-5 mbar. When oxidation is mitigated we observe that the 20 nm spatially confined W films survive temperatures up to 1400 °C. The demonstrated thermal stability is limited by grain growth in HfO2, which leads to a rupture of the W-layers, thus, to a degradation of the multilayer system at 1450 °C.

Near-infrared tailored thermal emission from wafer-scale continuous-film resonators.

We experimentally investigate the near-infrared emission from simple-to-fabricate, continuous-film Fabry-Perot-type resonators, consisting only of unstructured dielectric and metallic films. We show that the proposed configuration is suitable for realization of narrowband emitters, tunable in ranges from mid- to near-infrared, and demonstrate emission centered at the wavelength of 1.7 µm, which corresponds to the band gap energy of GaSb-based photodetectors. The emission is measured at 748 K and follows well the emissivity as predicted from reflection measurements and Kirchhoff's reciprocity. The considered emitter configuration is spectrally highly tunable and, consisting of only few unstructured layers, is amenable to wafer-scale fabrication at low cost by use of standard deposition procedures.

Bimetallic 3D nanostar dimers in ring cavities: recyclable and robust surface-enhanced Raman scattering substrates for signal detection from few molecules.

Top-down fabrication of electron-beam lithography (EBL)-defined metallic nanostructures is a successful route to obtain extremely high electromagnetic field enhancement via plasmonic effects in well-defined regions. To this aim, various geometries have been introduced such as disks, triangles, dimers, rings, self-similar lenses, and more. In particular, metallic dimers are highly efficient for surface-enhanced Raman spectroscopy (SERS), and their decoupling from the substrate in a three-dimensional design has proven to further improve their performance. However, the large fabrication time and cost has hindered EBL-defined structures from playing a role in practical applications. Here we present three-dimensional nanostar dimer devices that can be recycled via maskless metal etching and deposition processes, due to conservation of the nanostructure pattern in the 3D geometry of the underlying Si substrate. Furthermore, our 3D-nanostar-dimer-in-ring structures (3D-NSDiRs) incorporate several advantageous aspects for SERS by enhancing the performance of plasmonic dimers via an external ring cavity, by efficient decoupling from the substrate through an elevated 3D design, and by bimetallic AuAg layers that exploit the increased performance of Ag while maintaining the biocompatibility of Au. We demonstrate SERS detection on rhodamine and adenine at extremely low density up to the limit of few molecules and analyze the field enhancement of the 3D-NSDiRs with respect to the exciting wavelength and metal composition.

Plasmon resonance tuning in metal nanostars for surface enhanced Raman scattering.

We report the fabrication of Au nanostar arrays by means of electron beam lithography, in which the plasmon resonance energy can be tuned via the nanostar size from the visible into the near-infrared region. The spectral response of the nanostar arrays was investigated by optical extinction (transmittance) experiments, and their surface enhanced Raman scattering performance has been tested at two different excitation wavelengths, 633 nm and 830 nm, using chemisorbed Cresyl violet molecules as analyte. The experimental results are supported by numerical simulations of the spatial and spectral electric field enhancement.

3D nanostar dimers with a sub-10-nm gap for single-/few-molecule surface-enhanced raman scattering.

Plasmonic nanostar-dimers, decoupled from the substrate, have been fabricated by combining electron-beam lithography and reactive-ion etching techniques. The 3D architecture, the sharp tips of the nanostars and the sub-10 nm gap size promote the formation of giant electric-field in highly localized hot-spots. The single/few molecule detection capability of the 3D nanostar-dimers has been demonstrated by Surface-Enhanced Raman Scattering.

Plasmon based biosensor for distinguishing different peptides mutation states.

Periodic and reproducible gold nanocuboids with various matrix dimensions and with different inter-particle gaps were fabricated by means of top-down technique. Rhodamine 6G was used as a probe molecule to optimize the design and the fabrication of the cuboid nanostructures. The electric field distribution for the nanocuboids with varying matrix dimensions/inter-particle gap was also investigated. These SERS devices were employed as biosensors through the investigation of both myoglobin and wild/mutated peptides. The results demonstrate the probing and the screening of wild/mutated BRCA1 peptides, thus opening a path for the fabrication of simple and cheap SERS device capable of early detection of several diseases.

Interplay between electric and magnetic effect in adiabatic polaritonic systems.

We report on the possibility of realizing adiabatic compression of polaritonic wave on a metallic conical nano-structure through an oscillating electric potential (quasi dynamic regime). By comparing this result with an electromagnetic wave excitation, we were able to relate the classical lighting-rod effect to adiabatic compression. Furthermore, we show that while the magnetic contribution plays a marginal role in the formation of adiabatic compression, it provides a blue shift in the spectral region. In particular, magnetic permeability can be used as a free parameter for tuning the polaritonic resonances. The peculiar form of adiabatic compression is instead dictated by both the source and the metal permittivity. The analysis is performed by starting from a simple electrostatic system to end with the complete electromagnetic one through intermediate situations such as the quasi-electrostatic and quasi-dynamic regimes. Each configuration is defined by a particular set of equations which allows to clearly determine the individual role played by the electric and magnetic contribution in the generation of adiabatic compression. We notice that these findings can be applied for the realization of a THz nano-metric generator.

Terahertz Dipole Nanoantenna Arrays: Resonance Characteristics.

Resonant dipole nanoantennas promise to considerably improve the capabilities of terahertz spectroscopy, offering the possibility of increasing its sensitivity through local field enhancement, while in principle allowing unprecedented spatial resolutions, well below the diffraction limit. Here, we investigate the resonance properties of ordered arrays of terahertz dipole nanoantennas, both experimentally and through numerical simulations. We demonstrate the tunability of this type of structures, in a range (∼1-2 THz) that is particularly interesting and accessible by means of standard zinc telluride sources. We additionally study the near-field resonance properties of the arrays, finding that the resonance shift observed between near-field and far-field spectra is predominantly ascribable to ohmic damping.