Color Tunable, Lithography-Free Refractory Metal-Oxide Metacoatings with a Graded Refractive Index Profile.

The refractory metal-oxide semiconductors are an overlooked platform for nanophononics that offer alloys with high melting points and tunable optical constants through stoichiometry changes and ion intercalation. We show that these semiconductors can form metamaterial coatings (metacoatings) made from a set of highly subwavelength, periodic metal-oxide layers (≤20 nm) with a varying and graded refractive index profile that includes a combination of high and low refractive indices and plasmonic layers. These metacoatings exhibit vibrant, structural color arising from the periodic index profile that can be tuned across the visible spectrum, over ultralarge lateral areas through bottom-up thermal annealing techniques.

On-chip sub-wavelength Bragg grating design based on novel low loss phase-change materials.

We propose a reconfigurable and non-volatile Bragg grating in the telecommunication C-band based on the combination of novel low-loss phase-change materials (specifically Ge2Sb2Se4Te1 and Sb2S3) with a silicon nitride platform. The Bragg grating is formed by arrayed cells of phase-change material, whose crystallisation fraction modifies the Bragg wavelength and extinction ratio. These devices could be used in integrated photonic circuits for optical communications applications in smart filters and Bragg mirrors and could also find use in tuneable ring resonators, Mach-Zehnder interferometers or frequency selectors for future laser on chip applications. In the case of Ge2Sb2Se4Te1, crystallisation produces a Bragg resonance shift up to ∼ 15 nm, accompanied with a large amplitude modulation (insertion loss of 22 dB). Using Sb2S3, low losses are presented in both states of the phase change material, obtaining a ∼ 7 nm red-shift in the Bragg wavelength. The gratings are evaluated for two period numbers, 100 and 200 periods. The number of periods determines the bandwidth and extinction ratio of the filters. Increasing the number of periods increases the extinction ratio and reflected power, also narrowing the bandwidth. This results in a trade-off between device size and performance. Finally, we combine both phase-change materials in a single Bragg grating to provide both frequency and amplitude modulation. A defect is introduced in the Sb2S3 Bragg grating, producing a high quality factor resonance (Q ∼ 104) which can be shifted by 7 nm via crystallisation. A GSST cell is then placed in the defect which can modulate the transmission amplitude from low loss to below -16 dB.

Optical-resonance-enhanced nonlinearities in a MoS2-coated single-mode fiber.

Few-layer molybdenum disulfide (MoS2) has an electronic band structure that is dependent on the number of layers and, therefore, is a very promising material for an array of optoelectronic, photonic, and lasing applications. In this Letter, we make use of a side-polished optical fiber platform to gain access to the nonlinear optical properties of the MoS2 material. We show that the nonlinear response can be significantly enhanced via resonant coupling to the thin film material, allowing for the observation of optical modulation and spectral broadening in the telecom band. This route to access the nonlinear properties of two-dimensional materials promises to yield new insights into their photonic properties.

High speed chalcogenide glass electrochemical metallization cells with various active metals.

We fabricated electrochemical metallization cells using a GaLaSO solid electrolyte, an InSnO inactive electrode and active electrodes consisting of various metals (Cu, Ag, Fe, Cu, Mo, Al). Devices with Ag and Cu active metals showed consistent and repeatable resistive switching behaviour, and had a retention of 3 and >43 days, respectively; both had switching speeds of <5 ns. Devices with Cr and Fe active metals displayed incomplete or intermittent resistive switching, and devices with Mo and Al active electrodes displayed no resistive switching ability. Deeper penetration of the active metal into the GaLaSO layer resulted in greater resistive switching ability of the cell. The off-state resistivity was greater for more reactive active metals which may be due to a thicker intermediate layer.

Enhanced light-matter interaction in atomically thin MoS2 coupled with 1D photonic crystal nanocavity.

Engineering the surrounding electromagnetic environment of light emitters by photonic engineering, e.g. photonic crystal cavity, can dramatically enhance its spontaneous emission rate through the Purcell effect. Here we report an enhanced spontaneous emission rate of monolayer molybdenum disulfide (MoS2) by coupling it to a 1D silicon nitride photonic crystal. A four times stronger photoluminescence (PL) intensity of MoS2 in a 1D photonic crystal cavity than un-coupled emission is observed. Considering the relative ease of fabrication and the natural integration with a silicon-based system, the high Purcell factor renders this device as a highly promising platform for applications such as visible solid-state cavity quantum electrodynamics (QED).

Nonlinear refractive index of ultrafast laser inscribed waveguides in gallium lanthanum sulphide.

We demonstrate ultrafast all-optical switching in femtosecond laser inscribed nonlinear directional couplers in gallium lanthanum sulphide operated at 1.55 µm. We report on the evaluation of the nonlinear refractive index of the waveguides forming the directional couplers by making use of the switching parameters. The nonlinear refractive index is reduced by the inscription process to about 4-5 times compared to bulk material.

Refractive index and dispersion control of ultrafast laser inscribed waveguides in gallium lanthanum sulphide for near and mid-infrared applications.

The powerful ultrafast laser inscription technique is used to fabricate optical waveguides in gallium lanthanum sulphide substrates. For the first time the refractive index profile and the dispersion of such ultrafast laser inscribed waveguides are experimentally measured. In addition the Zero Dispersion Wavelength of both the waveguides and bulk substrate is experimentally determined. The Zero Dispersion Wavelength was determined to be between 3.66 and 3.71 µm for the waveguides and about 3.61 µm for the bulk. This work paves the way for realizing ultrafast laser inscribed waveguide devices in gallium lanthanum sulphide glasses for near and mid-IR applications.

On the analogy between photoluminescence and carrier-type reversal in Bi- and Pb-doped glasses.

Reaction order in Bi-doped oxide glasses depends on the optical basicity of the glass host. Red and NIR photoluminescence (PL) bands result from Bi(2+) and Bin clusters, respectively. Very similar centers are present in Bi- and Pb-doped oxide and chalcogenide glasses. Bi-implanted and Bi melt-doped chalcogenide glasses display new PL bands, indicating that new Bi centers are formed. Bi-related PL bands have been observed in glasses with very similar compositions to those in which carrier-type reversal has been observed, indicating that these phenomena are related to the same Bi centers, which we suggest are interstitial Bi(2+) and Bi clusters.

Spin-orbit splitting in single-layer MoS2 revealed by triply resonant Raman scattering.

Although new spintronic devices based on the giant spin-orbit splitting of single-layer MoS(2) have been proposed, such splitting has not been studied effectively in experiments. This Letter reports the valence band spin-orbit splitting in single-layer MoS(2) for the first time, probed by the triply resonant Raman scattering process. We found that upon 325 nm laser irradiation, the second order overtone and combination Raman modes of single-layer MoS(2) are dramatically enhanced. Such resonant Raman enhancement arises from the electron-two-phonon triple resonance via the deformation potential and Fröhlich interaction. As a sensitive and precise probe for the spin-orbit splitting, the triply resonant Raman scattering will provide a new and independent route to study the spin characteristics of MoS(2).

Conformal CVD-Grown MoS2 on Three-Dimensional Woodpile Photonic Crystals for Photonic Bandgap Engineering.

To achieve the modification of photonic band structures and realize the dispersion control toward functional photonic devices, composites of photonic crystal templates with high-refractive-index material are fabricated. A two-step process is used: 3D polymeric woodpile templates are fabricated by a direct laser writing method followed by chemical vapor deposition of MoS2. We observed red-shifts of partial bandgaps at the near-infrared region when the thickness of deposited MoS2 films increases. A ∼10 nm red-shift of fundamental and high-order bandgap is measured after each 1 nm MoS2 thin film deposition and confirmed by simulations and optical measurements using an angle-resolved Fourier imaging spectroscopy system.

Thermo-optic tuning of silicon nitride microring resonators with low loss non-volatile [Formula: see text] phase change material.

A new family of phase change material based on antimony has recently been explored for applications in near-IR tunable photonics due to its wide bandgap, manifested as broadband transparency from visible to NIR wavelengths. Here, we characterize [Formula: see text] optically and demonstrate the integration of this phase change material in a silicon nitride platform using a microring resonator that can be thermally tuned using the amorphous and crystalline states of the phase change material, achieving extinction ratios of up to 18 dB in the C-band. We extract the thermo-optic coefficient of the amorphous and crystalline states of the [Formula: see text] to be 3.4 x [Formula: see text] and 0.1 x 10[Formula: see text], respectively. Additionally, we detail the first observation of bi-directional shifting for permanent trimming of a non-volatile switch using continuous wave (CW) laser exposure ([Formula: see text] to 5.1 dBm) with a modulation in effective refractive index ranging from +5.23 x [Formula: see text] to [Formula: see text] x 10[Formula: see text]. This work experimentally verifies optical phase modifications and permanent trimming of [Formula: see text], enabling potential applications such as optically controlled memories and weights for neuromorphic architecture and high density switch matrix using a multi-layer PECVD based photonic integrated circuit.

Low Energy Switching of Phase Change Materials Using a 2D Thermal Boundary Layer.

The switchable optical and electrical properties of phase change materials (PCMs) are finding new applications beyond data storage in reconfigurable photonic devices. However, high power heat pulses are needed to melt-quench the material from crystalline to amorphous. This is especially true in silicon photonics, where the high thermal conductivity of the waveguide material makes heating the PCM energy inefficient. Here, we improve the energy efficiency of the laser-induced phase transitions by inserting a layer of two-dimensional (2D) material, either MoS2 or WS2, between the silica or silicon substrate and the PCM. The 2D material reduces the required laser power by at least 40% during the amorphization (RESET) process, depending on the substrate. Thermal simulations confirm that both MoS2 and WS2 2D layers act as a thermal barrier, which efficiently confines energy within the PCM layer. Remarkably, the thermal insulation effect of the 2D layer is equivalent to a ∼100 nm layer of SiO2. The high thermal boundary resistance induced by the van der Waals (vdW)-bonded layers limits the thermal diffusion through the layer interface. Hence, 2D materials with stable vdW interfaces can be used to improve the thermal efficiency of PCM-tuned Si photonic devices. Furthermore, our waveguide simulations show that the 2D layer does not affect the propagating mode in the Si waveguide; thus, this simple additional thin film produces a substantial energy efficiency improvement without degrading the optical performance of the waveguide. Our findings pave the way for energy-efficient laser-induced structural phase transitions in PCM-based reconfigurable photonic devices.

Facilitating Uniform Large-Scale MoS2, WS2 Monolayers, and Their Heterostructures through van der Waals Epitaxy.

The fabrication process for the uniform large-scale MoS2, WS2 transition-metal dichalcogenides (TMDCs) monolayers, and their heterostructures has been developed by van der Waals epitaxy (VdWE) through the reaction of MoCl5 or WCl6 precursors and the reactive gas H2S to form MoS2 or WS2 monolayers, respectively. The heterostructures of MoS2/WS2 or WS2/MoS2 can be easily achieved by changing the precursor from WCl6 to MoCl5 once the WS2 monolayer has been fabricated or switching the precursor from MoCl5 to WCl6 after the MoS2 monolayer has been deposited on the substrate. These VdWE-grown MoS2, WS2 monolayers, and their heterostructures have been successfully deposited on Si wafers with 300 nm SiO2 coating (300 nm SiO2/Si), quartz glass, fused silica, and sapphire substrates using the protocol that we have developed. We have characterized these TMDCs materials with a range of tools/techniques including scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), micro-Raman analysis, photoluminescence (PL), atomic force microscopy (AFM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and selected-area electron diffraction (SAED). The band alignment and large-scale uniformity of MoS2/WS2 heterostructures have also been evaluated with PL spectroscopy. This process and resulting large-scale MoS2, WS2 monolayers, and their heterostructures have demonstrated promising solutions for the applications in next-generation nanoelectronics, nanophotonics, and quantum technology.

Nonvolatile programmable silicon photonics using an ultralow-loss Sb2Se3 phase change material.

The next generation of silicon-based photonic processors and neural and quantum networks need to be adaptable, reconfigurable, and programmable. Phase change technology offers proven nonvolatile electronic programmability; however, the materials used to date have shown prohibitively high optical losses, which are incompatible with integrated photonic platforms. Here, we demonstrate the capability of the previously unexplored material Sb2Se3 for ultralow-loss programmable silicon photonics. The favorable combination of large refractive index contrast and ultralow losses seen in Sb2Se3 facilitates an unprecedented optical phase control exceeding 10π radians in a Mach-Zehnder interferometer. To demonstrate full control over the flow of light, we introduce nanophotonic digital patterning as a previously unexplored conceptual approach with a footprint orders of magnitude smaller than state-of-the-art interferometer meshes. Our approach enables a wealth of possibilities in high-density reconfiguration of optical functionalities on silicon chip.

Laser printed two-dimensional transition metal dichalcogenides.

Laser processing is a highly versatile technique for the post-synthesis treatment and modification of transition metal dichalcogenides (TMDCs). However, to date, TMDCs synthesis typically relies on large area CVD growth and lithographic post-processing for nanodevice fabrication, thus relying heavily on complex, capital intensive, vacuum-based processing environments and fabrication tools. This inflexibility necessarily restricts the development of facile, fast, very low-cost synthesis protocols. Here we show that direct, spatially selective synthesis of 2D-TMDCs devices that exhibit excellent electrical, Raman and photoluminescence properties can be realized using laser printing under ambient conditions with minimal lithographic or thermal overheads. Our simple, elegant process can be scaled via conventional laser printing approaches including spatial light modulation and digital light engines to enable mass production protocols such as roll-to-roll processing.

Chalcogenide glass microsphere laser.

Laser action has been demonstrated in chalcogenide glass microsphere. A sub millimeter neodymium-doped gallium lanthanum sulphide glass sphere was pumped at 808 nm with a laser diode and single and multimode laser action demonstrated at wavelengths between 1075 and 1086 nm. The gallium lanthanum sulphide family of glass offer higher thermal stability compared to other chalcogenide glasses, and this, along with an optimized Q-factor for the microcavity allowed laser action to be achieved. When varying the pump power, changes in the output spectrum suggest nonlinear and/or thermal effects have a strong effect on laser action.

Solution-Based Synthesis of Few-Layer WS2 Large Area Continuous Films for Electronic Applications.

Unlike MoS2 ultra-thin films, where solution-based single source precursor synthesis for electronic applications has been widely studied, growing uniform and large area few-layer WS2 films using this approach has been more challenging. Here, we report a method for growth of few-layer WS2 that results in continuous and uniform films over centimetre scale. The method is based on the thermolysis of spin coated ammonium tetrathiotungstate ((NH4)2WS4) films by two-step high temperature annealing without additional sulphurization. This facile and scalable growth method solves previously encountered film uniformity issues. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) were used to confirm the few-layer nature of WS2 films. Raman and X-Ray photoelectron spectroscopy (XPS) revealed that the synthesized few-layer WS2 films are highly crystalline and stoichiometric. Finally, WS2 films as-deposited on SiO2/Si substrates were used to fabricate a backgated Field Effect Transistor (FET) device for the first time using this precursor to demonstrate the electronic functionality of the material and further validate the method.

Ultrabroad emission from a bismuth doped chalcogenide glass.

We report emission from a bismuth doped chalcogenide glass which is flattened, has a full width at half maximum (FWHM) of 600 nm, peaks at 1300 nm and covers the entire telecommunications window. At cryogenic temperatures the FWHM reaches 850 nm. The quantum efficiency and lifetime were as high as 32% and 175 mus, respectively. We also report two new bismuth emission bands at 2000 and 2600 nm. Absorption bands at 680, 850, 1020 and 1180 nm were observed. The 1180 nm absorption band was previously unobserved. We suggest that the origin of the emission in Bi:GLS is Bi22- dimers.

Mechanochromic Reconfigurable Metasurfaces.

The change of optical properties that some usually natural compounds or polymeric materials show upon the application of external stress is named mechanochromism. Herein, an artificial nanomechanical metasurface formed by a subwavelength nanowire array made of molybdenum disulfide, molybdenum oxide, and silicon nitride changes color upon mechanical deformation. The aforementioned deformation induces reversible changes in the optical transmission (relative transmission change of 197% at 654 nm), thus demonstrating a giant mechanochromic effect. Moreover, these types of metasurfaces can exist in two nonvolatile states presenting a difference in optical transmission of 45% at 678 nm, when they are forced to bend rapidly. The wide optical tunability that photonic nanomechanical metasurfaces, such as the one presented here, possess by design, can provide a valuable platform for mechanochromic and bistable responses across the visible and near infrared regime and form a new family of smart materials with applications in reconfigurable, multifunctional photonic filters, switches, and stress sensors.

High-throughput physical vapour deposition flexible thermoelectric generators.

Flexible thermoelectric generators (TEGs) can provide uninterrupted, green energy from body-heat, overcoming bulky battery configurations that limit the wearable-technologies market today. High-throughput production of flexible TEGs is currently dominated by printing techniques, limiting material choices and performance. This work investigates the compatibility of physical vapour deposition (PVD) techniques with a flexible commercial process, roll-to-roll (R2R), for thermoelectric applications. We demonstrate, on a flexible polyimide substrate, a sputtered Bi2Te3/GeTe TEG with Seebeck coefficient (S) of 140 µV/K per pair and output power (P) of 0.4 nW per pair for a 20 °C temperature difference. For the first time, thermoelectric properties of R2R sputtered Bi2Te3 films are reported and we demonstrate the ability to tune the power factor by lowering run times, lending itself to a high-speed low-cost process. To further illustrate this high-rate PVD/R2R compatibility, we fabricate a TEG using Virtual Cathode Deposition (VCD), a novel high deposition rate PVD tool, for the first time. This Bi2Te3/Bi0.5Sb1.5Te3 TEG exhibits S = 250 µV/K per pair and P = 0.2 nW per pair for a 20 °C temperature difference.