Actively variable-spectrum optoelectronics with black phosphorus.

Room-temperature optoelectronic devices that operate at short-wavelength and mid-wavelength infrared ranges (one to eight micrometres) can be used for numerous applications1-5. To achieve the range of operating wavelengths needed for a given application, a combination of materials with different bandgaps (for example, superlattices or heterostructures)6,7 or variations in the composition of semiconductor alloys during growth8,9 are used. However, these materials are complex to fabricate, and the operating range is fixed after fabrication. Although wide-range, active and reversible tunability of the operating wavelengths in optoelectronic devices after fabrication is a highly desirable feature, no such platform has been yet developed. Here we demonstrate high-performance room-temperature infrared optoelectronics with actively variable spectra by presenting black phosphorus as an ideal candidate. Enabled by the highly strain-sensitive nature of its bandgap, which varies from 0.22 to 0.53 electronvolts, we show a continuous and reversible tuning of the operating wavelengths in light-emitting diodes and photodetectors composed of black phosphorus. Furthermore, we leverage this platform to demonstrate multiplexed nondispersive infrared gas sensing, whereby multiple gases (for example, carbon dioxide, methane and water vapour) are detected using a single light source. With its active spectral tunability while also retaining high performance, our work bridges a technological gap, presenting a potential way of meeting different requirements for emission and detection spectra in optoelectronic applications.

Large-area epitaxial growth of InAs nanowires and thin films on hexagonal boron nitride by metal organic chemical vapor deposition.

Large-area epitaxial growth of III-V nanowires and thin films on van der Waals substrates is key to developing flexible optoelectronic devices. In our study, large-area InAs nanowires and planar structures are grown on hexagonal boron nitride templates using metal organic chemical vapor deposition method without any catalyst or pre-treatments. The effect of basic growth parameters on nanowire yield and thin film morphology is investigated. Under optimised growth conditions, a high nanowire density of 2.1×109cm-2is achieved. A novel growth strategy to achieve uniform InAs thin film on h-BN/SiO2/Si substrate is introduced. The approach involves controlling the growth process to suppress the nucleation and growth of InAs nanowires, while promoting the radial growth of nano-islands formed on the h-BN surface. A uniform polycrystalline InAs thin film is thus obtained over a large area with a dominant zinc-blende phase. The film exhibits near-band-edge emission at room temperature and a relatively high Hall mobility of 399 cm-2/(Vs). This work suggests a promising path for the direct growth of large-area, low-temperature III-V thin films on van der Waals substrates.

Elemental analogues of graphene: silicene, germanene, stanene, and phosphorene.

The fascinating electronic and optoelectronic properties of free-standing graphene has led to the exploration of alternative two-dimensional materials that can be easily integrated with current generation of electronic technologies. In contrast to 2D oxide and dichalcogenides, elemental 2D analogues of graphene, which include monolayer silicon (silicene), are fast emerging as promising alternatives, with predictions of high degree of integration with existing technologies. This article reviews this emerging class of 2D elemental materials - silicene, germanene, stanene, and phosphorene--with emphasis on fundamental properties and synthesis techniques. The need for further investigations to establish controlled synthesis techniques and the viability of such elemental 2D materials is highlighted. Future prospects harnessing the ability to manipulate the electronic structure of these materials for nano- and opto-electronic applications are identified.

Smart mid-infrared metasurface microspectrometer gas sensing system.

Smart, low-cost and portable gas sensors are highly desired due to the importance of air quality monitoring for environmental and defense-related applications. Traditionally, electrochemical and nondispersive infrared (IR) gas sensors are designed to detect a single specific analyte. Although IR spectroscopy-based sensors provide superior performance, their deployment is limited due to their large size and high cost. In this study, a smart, low-cost, multigas sensing system is demonstrated consisting of a mid-infrared microspectrometer and a machine learning algorithm. The microspectrometer is a metasurface filter array integrated with a commercial IR camera that is consumable-free, compact ( ~ 1 cm3) and lightweight ( ~ 1 g). The machine learning algorithm is trained to analyze the data from the microspectrometer and predict the gases present. The system detects the greenhouse gases carbon dioxide and methane at concentrations ranging from 10 to 100% with 100% accuracy. It also detects hazardous gases at low concentrations with an accuracy of 98.4%. Ammonia can be detected at a concentration of 100 ppm. Additionally, methyl-ethyl-ketone can be detected at its permissible exposure limit (200 ppm); this concentration is considered low and nonhazardous. This study demonstrates the viability of using machine learning with IR spectroscopy to provide a smart and low-cost multigas sensing platform.

Scalable Fabrication of Black Phosphorous Films for Infrared Photodetector Arrays.

Bulk black phosphorous (bP) exhibits excellent infrared (IR) optoelectronic properties, but most reported bP IR photodetectors are fabricated from single exfoliated flakes with lateral sizes of < 100 µm. Here, scalable thin films of bP suitable for IR photodetector arrays are realized through a tailored solution-deposition method. The properties of the bP film and their protective capping layers are optimized to fabricate bP IR photoconductors exhibiting specific detectivities up to 4.0 × 108 cm Hz1/2 W-1 with fast 30/60 µs rise/fall times under λ = 2.2 µm illumination. The scalability of the bP thin film fabrication is demonstrated by fabricating a linear array of 25 bP photodetectors and obtaining 25 × 25 pixel IR images at ≈203 ppi with good spatial fidelity. This research demonstrates a commercially viable method of fabricating scalable bP thin films for optoelectronic devices including room temperature-operable IR photodetector arrays.

Improved Efficiency in WSe2 Solar Cells Using Amorphous InOx Heterocontacts.

van der Waals (vdW) layered materials have been shown to have excellent optoelectronic properties relevant to photovoltaics. Despite their promise, the demonstrated efficiencies of vdW material solar cells remain low and are seldom supported by statistics or spectral quantum efficiency analysis. In this study, we utilize a p-type WSe2 absorber, forming a solar cell with a transparent front InOx electron contact, and a rear Pd reflector/hole contact. We fabricate multiple devices providing statistics for 10 devices with an average 1 sun conversion efficiency above 5%, among which a champion efficiency of 6.37% is achieved. This is the highest AM 1.5G 1 sun efficiency reported for a vdW material solar cell, with a current density supported by external quantum efficiency analysis. This cell is also shown to have near unity quantum efficiency around λ = 600 nm. This work provides support to vdW materials being considered as serious candidates for future thin-film solar cells.

Engineering electrodeposited ZnO films and their memristive switching performance.

We report the influence of zinc oxide (ZnO) seed layers on the performance of ZnO-based memristive devices fabricated using an electrodeposition approach. The memristive element is based on a sandwich structure using Ag and Pt electrodes. The ZnO seed layer is employed to tune the morphology of the electrodeposited ZnO films in order to increase the grain boundary density as well as construct highly ordered arrangements of grain boundaries. Additionally, the seed layer also assists in optimizing the concentration of oxygen vacancies in the films. The fabricated devices exhibit memristive switching behaviour with symmetrical and asymmetrical hysteresis loops in the absence and presence of ZnO seed layers, respectively. A modest concentration of oxygen vacancy in electrodeposited ZnO films as well as an increase in the ordered arrangement of grain boundaries leads to higher switching ratios in Ag/ZnO/Pt devices.

Room Temperature Bias-Selectable, Dual-Band Infrared Detectors Based on Lead Sulfide Colloidal Quantum Dots and Black Phosphorus.

A single photodetector capable of switching its peak spectral photoresponse between two wavelength bands is highly useful, particularly for the infrared (IR) bands in applications such as remote sensing, object identification, and chemical sensing. Technologies exist for achieving dual-band IR detection with bulk III-V and II-VI materials, but the high cost and complexity as well as the necessity for active cooling associated with some of these technologies preclude their widespread adoption. In this study, we leverage the advantages of low-dimensional materials to demonstrate a bias-selectable dual-band IR detector that operates at room temperature by using lead sulfide colloidal quantum dots and black phosphorus nanosheets. By switching between zero and forward bias, these detectors switch peak photosensitive ranges between the mid- and short-wave IR bands with room temperature detectivities of 5 × 109 and 1.6 × 1011 cm Hz1/2 W-1, respectively. To the best of our knowledge, these are the highest reported room temperature values for low-dimensional material dual-band IR detectors to date. Unlike conventional bias-selectable detectors, which utilize a set of back-to-back photodiodes, we demonstrate that under zero/forward bias conditions the device's operation mode instead changes between a photodiode and a phototransistor, allowing additional functionalities that the conventional structure cannot provide.

The Acoustophotoelectric Effect: Efficient Phonon-Photon-Electron Coupling in Zero-Voltage-Biased 2D SnS2 for Broad-Band Photodetection.

Two-dimensional (2D) layered metal dichalcogenides constitute a promising class of materials for photodetector applications due to their excellent optoelectronic properties. The most common photodetectors, which work on the principle of photoconductive or photovoltaic effects, however, require either the application of external voltage biases or built-in electric fields, which makes it challenging to simultaneously achieve high responsivities across broad-band wavelength excitation─especially beyond the material's nominal band gap─while producing low dark currents. In this work, we report the discovery of an intricate phonon-photon-electron coupling─which we term the acoustophotoelectric effect─in SnS2 that facilitates efficient photodetection through the application of 100 MHz order propagating surface acoustic waves (SAWs). This effect not only reduces the band gap of SnS2 but also provides the requisite momentum for indirect band gap transition of the photoexcited charge carriers, to enable broad-band photodetection beyond the visible light range, while maintaining pA-order dark currents─ without the need for any external voltage bias. More specifically, we show in the infrared excitation range that it is possible to achieve up to 8 orders of magnitude improvement in the material's photoresponsivity compared to that previously reported for SnS2-based photodetectors, in addition to exhibiting superior performance compared to most other 2D materials reported to date for photodetection.

Reconfigurable hyperbolic polaritonics with correlated oxide metasurfaces.

Polaritons enable subwavelength confinement and highly anisotropic flows of light over a wide spectral range, holding the promise for applications in modern nanophotonic and optoelectronic devices. However, to fully realize their practical application potential, facile methods enabling nanoscale active control of polaritons are needed. Here, we introduce a hybrid polaritonic-oxide heterostructure platform consisting of van der Waals crystals, such as hexagonal boron nitride (hBN) or alpha-phase molybdenum trioxide (α-MoO3), transferred on nanoscale oxygen vacancy patterns on the surface of prototypical correlated perovskite oxide, samarium nickel oxide, SmNiO3 (SNO). Using a combination of scanning probe microscopy and infrared nanoimaging techniques, we demonstrate nanoscale reconfigurability of complex hyperbolic phonon polaritons patterned at the nanoscale with high resolution. Hydrogenation and temperature modulation allow spatially localized conductivity modulation of SNO nanoscale patterns, enabling robust real-time modulation and nanoscale reconfiguration of hyperbolic polaritons. Our work paves the way towards nanoscale programmable metasurface engineering for reconfigurable nanophotonic applications.

Long-Wave Infrared Photodetectors Based on 2D Platinum Diselenide atop Optical Cavity Substrates.

Long-wave infrared (LWIR) photodetection is of high technological importance, having a wide range of applications that include thermal imaging and spectroscopy. Two-dimensional (2D) noble-transition-metal dichalcogenides, platinum diselenide (PtSe2) in particular, have recently shown great promise for infrared detection. However, previous studies have mainly focused on wavelengths up to the short-wave infrared region. In this work, we demonstrate LWIR photodetectors based on multilayer PtSe2. In addition, we present an optical cavity substrate that enhances the light-matter interaction in 2D materials and thus their photodetection performance in the LWIR spectral region. The PtSe2 photoconductors fabricated on the TiO2/Au optical cavity substrate exhibit responsivities up to 54 mA/W to LWIR illumination at a wavelength of 8.35 µm. Moreover, these devices show a fast photoresponse with a time constant of 54 ns to white light illumination. The findings of this study reveal the potential of multilayer PtSe2 for fast and broadband photodetection from visible to LWIR wavelengths.

Visible to Short-Wave Infrared Photodetectors Based on ZrGeTe4 van der Waals Materials.

The self-terminated, layered structure of van der Waals materials introduces fundamental advantages for infrared (IR) optoelectronic devices. These are mainly associated with the potential for low noise while maintaining high internal quantum efficiency when reducing IR absorber thicknesses. In this study, we introduce a new van der Waals material candidate, zirconium germanium telluride (ZrGeTe4), to a growing family of promising IR van der Waals materials. We find the bulk form ZrGeTe4 has an indirect band edge around ∼0.5 eV, in close agreement with previous theoretical predictions. This material is found to be stable up to 140 °C and shows minimal compositional variation even after >30 days storage in humid air. We demonstrate simple proof-of-concept broad spectrum photodetectors with responsivities above 0.1 AW-1 across both the visible and short-wave infrared wavelengths. This corresponds to a specific detectivity of ∼109 cm Hz1/2 W-1 at λ = 1.4 µm at room temperature. These devices show a linear photoresponse vs illumination intensity relationship over ∼4 orders of magnitude, and fast rise/fall times of ∼50 ns, also verified by a 3 dB roll-off frequency of 5.9 MHz. As the first demonstration of photodetection using ZrGeTe4, these characteristics measured on a simple proof-of-concept device show the exciting potential of the ZrGeTe4 for room temperature IR optoelectronic applications.

Copper Tetracyanoquinodimethane (CuTCNQ): A Metal-Organic Semiconductor for Room-Temperature Visible to Long-Wave Infrared Photodetection.

Mid-wave and long-wave infrared (MWIR and LWIR) detection play vital roles in applications that include health care, remote sensing, and thermal imaging. However, detectors in this spectral range often require complex fabrication processes and/or cryogenic cooling and are typically expensive, which motivates the development of simple alternatives. Here, we demonstrate broadband (0.43-10 µm) room-temperature photodetection based on copper tetracyanoquinodimethane (CuTCNQ), a metal-organic semiconductor, synthesized via a facile wet-chemical reaction. The CuTCNQ crystals are simply drop-cast onto interdigitated electrode chips to realize photoconductors. The photoresponse is governed by a combination of interband (0.43-3.35 µm) and midgap (3.35-10 µm) transitions. The devices show response times (∼365 µs) that would be sufficient for many infrared applications (e.g., video rate imaging), with a frequency cutoff point of 1 kHz.

Spectrally Selective Mid-Wave Infrared Detection Using Fabry-Pérot Cavity Enhanced Black Phosphorus 2D Photodiodes.

Thin two-dimensional (2D) material absorbers have the potential to reduce volume-dependent thermal noise in infrared detectors. However, any reduction in noise must be balanced against lower absorption from the thin layer, which necessitates advanced optical architectures. Such architectures can be particularly effective for applications that require detection only within a specific narrow wavelength range. This study presents a Fabry-Pérot cavity enhanced bP/MoS2 midwave infrared (MWIR) photodiode. This simple structure enables tunable narrow-band (down to 0.42 µm full width at half-maximum) photodetection in the 2-4 µm range by adjusting the thickness of the Fabry-Pérot cavity resonator. This is achieved while maintaining room-temperature performance metrics comparable to previously reported 2D MWIR detectors. Zero bias specific detectivity and responsivity values of up to 1.7 × 109 cm Hz1/2 W-1 and 0.11 A W-1 at λ = 3.0 µm are measured with a response time of less than 3 ns. These results introduce a promising family of 2D detectors with applications in MWIR spectroscopy.

Edge-oriented and steerable hyperbolic polaritons in anisotropic van der Waals nanocavities.

Highly confined and low-loss polaritons are known to propagate isotropically over graphene and hexagonal boron nitride in the plane, leaving limited degrees of freedom in manipulating light at the nanoscale. The emerging family of biaxial van der Waals materials, such as α-MoO3 and V2O5, support exotic polariton propagation, as their auxiliary optical axis is in the plane. Here, exploiting this strong in-plane anisotropy, we report edge-tailored hyperbolic polaritons in patterned α-MoO3 nanocavities via real-space nanoimaging. We find that the angle between the edge orientation and the crystallographic direction significantly affects the optical response, and can serve as a key tuning parameter in tailoring the polaritonic patterns. By shaping α-MoO3 nanocavities with different geometries, we observe edge-oriented and steerable hyperbolic polaritons as well as forbidden zones where the polaritons detour. The lifetime and figure of merit of the hyperbolic polaritons can be regulated by the edge aspect ratio of nanocavity.

Electrically Activated UV-A Filters Based on Electrochromic MoO3-x.

Chromism-based optical filters is a niche field of research, due to there being only a handful of electrochromic materials. Typically, electrochromic transition metal oxides such as MoO3 and WO3 are utilized in applications such as smart windows and electrochromic devices (ECD). Herein, we report MoO3-x-based electrically activated ultraviolet (UV) filters. The MoO3-x grown on indium tin oxide (ITO) substrate is mechanically assembled onto an electrically activated proton exchange membrane. Reversible H+ injection/extraction in MoO3-x is employed to switch the optical transmittance, enabling an electrically activated optical filter. The devices exhibit broadband transmission modulation (325-800 nm), with a peak of ∼60% in the UV-A range (350-392 nm). Comparable switching times of 8 s and a coloration efficiency of up to 116 cm2 C-1 are achieved.

Liquid-Metal Synthesized Ultrathin SnS Layers for High-Performance Broadband Photodetectors.

Atomically thin materials face an ongoing challenge of scalability, hampering practical deployment despite their fascinating properties. Tin monosulfide (SnS), a low-cost, naturally abundant layered material with a tunable bandgap, displays properties of superior carrier mobility and large absorption coefficient at atomic thicknesses, making it attractive for electronics and optoelectronics. However, the lack of successful synthesis techniques to prepare large-area and stoichiometric atomically thin SnS layers (mainly due to the strong interlayer interactions) has prevented exploration of these properties for versatile applications. Here, SnS layers are printed with thicknesses varying from a single unit cell (0.8 nm) to multiple stacked unit cells (≈1.8 nm) synthesized from metallic liquid tin, with lateral dimensions on the millimeter scale. It is reveal that these large-area SnS layers exhibit a broadband spectral response ranging from deep-ultraviolet (UV) to near-infrared (NIR) wavelengths (i.e., 280-850 nm) with fast photodetection capabilities. For single-unit-cell-thick layered SnS, the photodetectors show upto three orders of magnitude higher responsivity (927 A W-1 ) than commercial photodetectors at a room-temperature operating wavelength of 660 nm. This study opens a new pathway to synthesize reproduceable nanosheets of large lateral sizes for broadband, high-performance photodetectors. It also provides important technological implications for scalable applications in integrated optoelectronic circuits, sensing, and biomedical imaging.

Dual Selective Gas Sensing Characteristics of 2D α-MoO3-x via a Facile Transfer Process.

Metal oxide-based gas sensor technology is promising due to their practical applications in toxic and hazardous gas detection. Orthorhombic α-MoO3 is a planar metal oxide with a unique layered structure, which can be obtained in a two-dimensional (2D) form. In the 2D form, the larger surface area-to-volume ratio of the material facilitates significantly higher interaction with gas molecules while exhibiting exceptional transport properties. The presence of oxygen vacancies results in nonstoichiometric MoO3 (MoO3-x), which further enhances the charge carrier mobility. Here, we study dual gas sensing characteristics and mechanism of 2D α-MoO3-x. Herein, conductometric dual gas sensors based on chemical vapor deposited 2D α-MoO3-x are developed and demonstrated. A facile transfer process is established to integrate the material into any arbitrary substrate. The sensors show high selectivity toward NO2 and H2S gases with response and recovery rates of 295.0 and 276.0 kΩ/s toward NO2 and 28.5 and 48.0 kΩ/s toward H2S, respectively. These gas sensors also show excellent cyclic endurance with a variation in ΔR ∼ 112 ± 1.64 and 19.5 ± 1.13 MΩ for NO2 and H2S, respectively. As such, this work presents the viability of planar 2D α-MoO3-x as a dual selective gas sensor.

Reversible resistive switching behaviour in CVD grown, large area MoOx.

Non-volatile resistive memory devices are theorized to be the most promising pathway towards analog memory and neuromorphic computing. Two-dimensional MoO3 is a versatile planar transition metal oxide, whose properties can be readily tuned, making it anywhere from a wide bandgap semiconductor to a semi-metal. Successful integration of such a planar metal oxide into resistive memory can enable adaptive and low power memory applications. Here, we investigate the non-volatile and reversible resistive switching behaviour of oxygen deficient MoOx in a cross-point metal/insulator/metal (MIM) architecture. Layered MoOx films are synthesised using chemical vapour deposition (CVD) and reveal excellent resistive switching performance with relatively low electroforming and operating voltages. Switching ratios of ∼103 and stable data retention of >104 s are achieved. As such, this work demonstrates the viability of MoOx as a resistive memory element and paves the way for future two-dimensional resistive memory technologies.

Ambient Protection of Few-Layer Black Phosphorus via Sequestration of Reactive Oxygen Species.

Few-layer black phosphorous (BP) has emerged as a promising candidate for next-generation nanophotonic and nanoelectronic devices. However, rapid ambient degradation of mechanically exfoliated BP poses challenges in its practical deployment in scalable devices. To date, the strategies employed to protect BP have relied upon preventing its exposure to atmospheric conditions. Here, an approach that allows this sensitive material to remain stable without requiring its isolation from the ambient environment is reported. The method draws inspiration from the unique ability of biological systems to avoid photo-oxidative damage caused by reactive oxygen species. Since BP undergoes similar photo-oxidative degradation, imidazolium-based ionic liquids are employed as quenchers of these damaging species on the BP surface. This chemical sequestration strategy allows BP to remain stable for over 13 weeks, while retaining its key electronic characteristics. This study opens opportunities to practically implement BP and other environmentally sensitive 2D materials for electronic applications.