CVD-Grown Monolayer MoS2 and GaN Thin Film Heterostructure for a Self-Powered and Bidirectional Photodetector with an Extended Active Spectrum.

Photodetector technology has evolved significantly over the years with the emergence of new active materials. However, there remain trade-offs between spectral sensitivity, operating energy, and, more recently, an ability to harbor additional features such as persistent photoconductivity and bidirectional photocurrents for new emerging application areas such as switchable light imaging and filter-less color discrimination. Here, we demonstrate a self-powered bidirectional photodetector based on molybdenum disulfide/gallium nitride (MoS2/GaN) epitaxial heterostructure. This fabricated detector exhibits self-powered functionality and achieves detection in two discrete wavelength bands: ultraviolet and visible. Notably, it attains a peak responsivity of 631 mAW-1 at a bias of 0V. The device's response to illumination at these two wavelengths is governed by distinct mechanisms, activated under applied bias conditions, thereby inducing a reversal in the polarity of the photocurrent. This work underscores the feasibility of self-powered and bidirectional photocurrent detection but also opens new vistas for technological advancements for future optoelectronic, neuromorphic, and sensing applications.

Deep Eutectic Solvent Eutectogels for Delivery of Broad-Spectrum Antimicrobials.

Gel-based wound dressings have gained popularity within the healthcare industry for the prevention and treatment of bacterial and fungal infections. Gels based on deep eutectic solvents (DESs), known as eutectogels, provide a promising alternative to hydrogels as they are non-volatile and highly tunable and can solubilize therapeutic agents, including those insoluble in hydrogels. A choline chloride:glycerol-cellulose eutectogel was loaded with numerous antimicrobial agents including silver nanoparticles, black phosphorus nanoflakes, and commercially available pharmaceuticals (octenidine dihydrochloride, tetracycline hydrochloride, and fluconazole). The eutectogels caused >97% growth reduction in Gram-positive methicillin-resistant Staphylococcus aureus and Gram-negative Pseudomonas aeruginosa bacteria and the fungal species Candida albicans.

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.

Repairing and Preventing Photooxidation of Few-Layer Black Phosphorus with ß-Carotene.

Few-layer black phosphorus (FLBP), a technologically important 2D material, faces a major hurdle to consumer applications: spontaneous degradation under ambient conditions. Blocking the direct exposure of FLBP to the environment has remained the key strategy to enhance its stability, but this can also limit its utility. In this paper, a more ambitious approach to handling FLBP is reported where not only is FLBP oxidation blocked, but it is also repaired postoxidation. Our approach, inspired by nature, employs the antioxidant molecule ß-carotene that protects plants against photooxidative damages to act as a protecting and repairing agent for FLBP. The mechanistic role of ß-carotene is established by a suite of spectro-microscopy techniques, in combination with computational studies and biochemical assays. Transconductance studies on FLBP-based field effect transistor (FET) devices further affirm the protective and reparative effects of ß-carotene. The outcomes indicate the potential for deploying a plethora of natural antioxidant molecules to enhance the stability of other environmentally sensitive inorganic nanomaterials and expedite their translation for technological and consumer applications.

Nitrogen-Doped Porous Nickel Molybdenum Phosphide Sheets for Efficient Seawater Splitting.

Hydrogen is emerging as an alternative clean fuel; however, its dependency on freshwater will be a threat to a sustainable environment. Seawater, an unlimited source, can be an alternative, but its salt-rich nature causes corrosion and introduces several competing reactions, hindering its use. To overcome these, a unique catalyst composed of porous sheets of nitrogen-doped NiMo3 P (N-NiMo3 P) having a sheet size of several microns is designed. The presence of large homogenous pores in the basal plane of these sheets makes them catalytically more active and ensures faster mass transfer. The introduction of N and Ni into MoP significantly tunes the electronic density of Mo, surface chemistry, and metal-non-metal bond lengths, optimizing surface energies, creating new active sites, and increasing electrical conductivity. The presence of metal-nitrogen bonds and surface polyanions increases the stability and improves anti-corrosive properties against chlorine chemistry. Ultimately, the N-NiMo3 P sheets show remarkable performance as it only requires overpotentials of 23 and 35 mV for hydrogen evolution reaction, and it catalyzes full water splitting at 1.52 and 1.55 V to achieve 10 mA cm-2 in 1 m KOH and seawater, respectively. Hence, structural and compositional control can make catalysts effective in realizing low-cost hydrogen directly from seawater.

Gas sensors based on the oxide skin of liquid indium.

Various non-stratified two-dimensional (2D) materials can be obtained from liquid metal surfaces that are not naturally accessible. Homogenous nucleation on atomically flat interfaces of liquid metals with air produces unprecedented high-quality oxide layers that can be transferred onto desired substrates. The atomically flat and large areas provide large surface-to-volume ratios ideal for sensing applications. Versatile crucial applications of the liquid metal-derived 2D oxides have been realized; however, their gas-sensing properties remain largely underexplored. The cubic In2O3 structure, which is nonlayered, can be formed as an ultrathin layer on the surface of liquid indium during the self-limiting Cabrera-Mott oxidation process in the air. The morphology, crystal structure, and band structure of the harvested 2D In2O3 nanosheets from liquid indium are characterized. Sensing capability toward several gases, both inorganic and organic, entailing NO2, O2, NH3, H2, H2S, CO, and Methyl ethyl ketone (MEK) are explored. A high ohmic resistance change of 1974% at 10 ppm, fast response, and recovery times are observed for NO2 at an optimum temperature of 200 °C. The sensing fundamentals are investigated for NO2, and its performances and cross-selectivity to different gases are analyzed. The NO2 sensing response from room temperature to 300 °C has been measured and discussed, and stability after 24 hours of continuous operation is presented. The results demonstrate liquid metal-derived 2D oxides as promising materials for gas sensing applications.

Metal-Air Field Emission Devices - Nano Electrode Geometries Comparison of Performance and Stability.

Air-channel devices have a special advantage due to the promise of vacuum-like ballistic transport in air, radiation insensitivity, and nanoscale size. Here, achieving high current at low voltage along with considerable mechanical stability is a primary issue. The comparative analysis of four planar and metallic electrode-pair geometries at 10 nm channel length is presented. The impact of nano-electrode-pair geometries on overall device performance is investigated. Air-channel devices are operated at the ultra-low voltage of 5 mV to demonstrate the device dynamics of air-channel devices at low power. Investigations focus on the direct tunneling (DT) mechanism which is dominant in the low-voltage regime. Comparative analysis of different electrode-pair geometries reveals two orders of magnitude increment in the current just by modulating the electrode-pair structure. Theoretical analysis suggests that the emission current is directly related to the active junction area within the metal-air-metal interface at the direct tunneling regime. The geometry-dependent mechanical stability of different electrode pairs is compared by imaging biasing triggered nanoscale structural changes and pulsed biasing stress analysis. The results and claims are confirmed and consolidated with the statistical analysis. Experimental investigations provide strong directions for high-performance and stable devices. In-depth theoretical discussions will enable the accurate modeling of emerging low-power, high-speed, radiation-hardened nanoscale vacuum electronics.

GS-2: A Novel Broad-Spectrum Agent for Environmental Microbial Control.

The environmental control of microbial pathogens currently relies on compounds that do not exert long-lasting activity on surfaces, are impaired by soil, and contribute to the growing problem of antimicrobial resistance. This study presents the scientific development and characterization of GS-2, a novel, water-soluble ammonium carboxylate salt of capric acid and L-arginine that demonstrates activity against a range of bacteria (particularly Gram-negative bacteria), fungi, and viruses. In real-world surface testing, GS-2 was more effective than a benzalkonium chloride disinfectant at reducing the bacterial load on common touch-point surfaces in a high-traffic building (average 1.6 vs. 32.6 CFUs recovered from surfaces 90 min after application, respectively). Toxicology testing in rats confirmed GS-2 ingredients were rapidly cleared and posed no toxicities to humans or animals. To enhance the time-kill against Gram-positive bacteria, GS-2 was compounded at a specific ratio with a naturally occurring monoterpenoid, thymol, to produce a water-based antimicrobial solution. This GS-2 with thymol formulation could generate a bactericidal effect after five minutes of exposure and a viricidal effect after 10 min of exposure. Further testing of the GS-2 and thymol combination on glass slides demonstrated that the compound retained bactericidal activity for up to 60 days. Based on these results, GS-2 and GS-2 with thymol represent a novel antimicrobial solution that may have significant utility in the long-term reduction of environmental microbial pathogens in a variety of settings.

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.

Doped 2D SnS materials derived from liquid metal-solution for tunable optoelectronic devices.

Gas-liquid reaction phenomena on liquid-metal solvents can be used to form intriguing 2D materials with large lateral dimensions, where the free energies of formation determine the final product. A vast selection of elements can be incorporated into the liquid metal-based nanostructures, offering a versatile platform for fabricating novel optoelectronic devices. While conventional doping techniques of semiconductors present several challenges for 2D materials. Liquid metals provide a facile route for obtaining doped 2D semiconductors. In this work, we successfully demonstrate that the doping of 2D SnS can be realized in a glove box containing a diluted H2S gas. Low melting point elements such as Bi and In are alloyed with base liquid Sn in varying concentrations, resulting in the doping of 2D SnS layers incorporating Bi and In sulphides. Optoelectronic properties for photodetectors and piezoelectronics can be fine-tuned through the controlled introduction of selective migration doping. The structural modification of 2D SnS results in a 22.6% enhancement of the d11 piezoelectric coefficient. In addition, photodetector response times have increased by several orders of magnitude. Doping methods using liquid metals have significantly changed the photodiode and piezoelectric device performances, providing a powerful approach to tune optoelectronic device outputs.

Illuminating the biochemical interaction of antimicrobial few-layer black phosphorus with microbial cells using synchrotron macro-ATR-FTIR.

In the fight against drug-resistant pathogenic bacterial and fungal cells, low-dimensional materials are emerging as a promising alternative treatment method. Specifically, few-layer black phosphorus (BP) has demonstrated its effectiveness against a wide range of pathogenic bacterial and fungal cells with studies suggesting low cytotoxicity towards healthy mammalian cells. However, the antimicrobial mechanism of action of BP is not well understood. Before new applications for this material can be realised, further in-depth investigations are required. In this work, the biochemical interaction between BP and a series of microbial cells is investigated using a variety of microscopy and spectroscopy techniques to provide a greater understanding of the antimicrobial mechanism. Synchrotron macro-attenuated total reflection-Fourier transform infrared (ATR-FTIR) micro-spectroscopy is used to elucidate the chemical changes occurring outside and within the cell of interest after exposure to BP nanoflakes. The ATR-FTIR data, coupled with high-resolution microscopy, reveals major physical and bio-chemical changes to the phospholipids and amide I and II proteins, as well as minor chemical changes to the structural polysaccharides and nucleic acids when compared to untreated cells. These changes can be attributed to the physical interaction of the BP nanoflakes with the cell membranes, combined with the oxidative stress induced by the degradation of the BP nanoflakes. This study provides insight into the biochemical interaction of BP nanoflakes with microbial cells, allowing for a better understanding of the antimicrobial mechanism of action that will be important for the next generation of applications such as implant coatings, wound dressings, or medical surfaces.

Rapid Conductometric Detection of SARS-CoV-2 Proteins and Its Variants Using Molecularly Imprinted Polymer Nanoparticles.

Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) biosensors have captured more attention than the conventional methodologies for SARS-CoV-2 detection due to having cost-effective platforms and fast detection. However, these reported SARS-CoV-2 biosensors suffer from drawbacks including issues in detection sensitivity, degradation of biomaterials on the sensor's surface, and incapability to reuse the biosensors. To overcome these shortcomings, molecularly imprinted polymer nanoparticles (nanoMIPs) incorporated conductometric biosensor for highly accurate, rapid, and selective detection of two model SARS-CoV-2 proteins: (i) receptor binding domain (RBD) of the spike (S) glycoprotein and (ii) full length trimeric spike protein are introduced. In addition, these biosensors successfully responded to several other SARS-CoV-2 RBD spike protein variants including Alpha, Beta, Gamma, and Delta. Our conductometric biosensor selectively detects the two model proteins and SARS-CoV-2 RBD spike protein variant samples in real-time with sensitivity to a detection limit of 7 pg mL-1 within 10 min of sample incubation. A battery-free, wireless near-field communication (NFC) interface is incorporated with the biosensor for fast and contactless detection of SARS-CoV-2 variants. The smartphone enabled real-time detection and on-screen rapid result for SARS-CoV-2 variants can curve the outbreak due to its ability to alert the user to infection in real time.

Nicotine Sensors for Wearable Battery-Free Monitoring of Vaping.

Nicotine, an addictive substance in tobacco products and electronic cigarettes (e-cigs), is recognized for increasing the risk of cardiovascular and respiratory disorders. Careful real-time monitoring of nicotine exposure is critical in alleviating the potential health impacts of not just smokers but also those exposed to second-hand and third-hand smoke. Monitoring of nicotine requires suitable sensing material to detect nicotine selectively and testing under free-living conditions in the standard environment. Here, we experimentally demonstrate a vanadium dioxide (VO2)-based nicotine sensor and explain its conductometric mechanisms with compositional analysis and density functional theory (DFT) calculations. For real-time monitoring of nicotine vapor from e-cigarettes in the air, the sensor is integrated with an epidermal near-field communication (NFC) interface that enables battery-free operation and data transmission to smart electronic devices to record and store sensor data. Collectively, the technique of sensor development and integration expands the use of wearable electronics for real-time monitoring of hazardous elements in the environment and biosignals wirelessly.

Surface Functionalization of WS2 Nanosheets with Alkyl Chains for Enhancement of Dispersion Stability and Tribological Properties.

Tungsten disulfide (WS2) exhibits intriguing tribological properties and has been explored as an excellent lubricious material in thin-film and solid lubricants. However, the poor dispersibility of WS2 has been a major challenge for its utilization in liquid lubricant applications. Herein, a top-down integrated approach is presented to synthesize oxygenated WS2 (WS2-O) nanosheets via strong acid-mediated oxidation and ultrasound-assisted exfoliation. The ultrathin sheets of WS2-O, comprising 4-7 molecular lamellae, exhibit oxygen/hydroxyl functionalities. The organosilanes having variable surface-active leaving groups (chloro and ethoxy) are covalently grafted, targeting the hydroxyl/oxygen functionalities on the surface of WS2-O nanosheets. The grafting of organosilanes is governed by the reactivity of chloro and ethoxy leaving groups. The DFT calculations further support the covalent interaction between the WS2-O nanosheets and organosilanes. The alkyl chain-functionalized WS2-O nanosheets displayed excellent dispersibility in mineral lube base oil. A minute dose of chemically functionalized-WS2 (0.2 mg.mL-1) notably enhanced the tribological properties of mineral lube oil by reducing the friction coefficient (52%) and wear volume (79%) for a steel tribopair. Raman analysis of worn surfaces revealed WS2-derived lubricious thin film formation. The improved tribological properties are attributed to ultralow thickness, stable dispersion, and low shear strength of chemically functionalized WS2 nanosheets, along with protective thin film formation over the contact interfaces of a steel tribopair. The present work opens a new avenue toward exploiting low-dimensional nanosheets for minimizing energy losses due to high friction.

High-k 2D Sb2O3 Made Using a Substrate-Independent and Low-Temperature Liquid-Metal-Based Process.

High dielectric constant (high-k) ultrathin films are required as insulating gate materials. The well-known high-k dielectrics, including HfO2, ZrO2, and SrTiO3, feature three-dimensional lattice structures and are thus not easily obtained in the form of distinct ultrathin sheets. Therefore, their deposition as ultrathin layers still imposes challenges for electronic industries. Consequently, new high-k nanomaterials with k in the range of 40 to 100 and a band gap exceeding 4 eV are highly sought after. Antimony oxide nanosheets appear as a potential candidate that could fulfill these characteristics. Here, we report on the stoichiometric cubic polymorph of 2D antimony oxide (Sb2O3) as an ideal high-k dielectric sheet that can be synthesized via a low-temperature, substrate-independent, and silicon-industry-compatible liquid metal synthesis technique. A bismuth-antimony alloy was produced during the growth process. Preferential oxidation caused the surface of the melt to be dominated by α-Sb2O3. This ultrathin α-Sb2O3 was then deposited onto desired surfaces via a liquid metal print transfer. A tunable sheet thickness between ∼1.5 and ∼3 nm was achieved, while the lateral dimensions were within the millimeter range. The obtained α-Sb2O3 exhibited high crystallinity and a wide band gap of ∼4.4 eV. The relative permittivity assessment revealed a maximum k of 84, while a breakdown electric field of ∼10 MV/cm was observed. The isolated 2D α-Sb2O3 nanosheets were utilized in top-gated field-effect transistors that featured low leakage currents, highlighting that the obtained material is a promising gate oxide for conventional and van der Waals heterostructure-based electronics.

Antipathogenic properties and applications of low-dimensional materials.

A major health concern of the 21st century is the rise of multi-drug resistant pathogenic microbial species. Recent technological advancements have led to considerable opportunities for low-dimensional materials (LDMs) as potential next-generation antimicrobials. LDMs have demonstrated antimicrobial behaviour towards a variety of pathogenic bacterial and fungal cells, due to their unique physicochemical properties. This review provides a critical assessment of current LDMs that have exhibited antimicrobial behaviour and their mechanism of action. Future design considerations and constraints in deploying LDMs for antimicrobial applications are discussed. It is envisioned that this review will guide future design parameters for LDM-based antimicrobial applications.

UV Photochromism in Transition Metal Oxides and Hybrid Materials.

Limited levels of UV exposure can be beneficial to the human body. However, the UV radiation present in the atmosphere can be damaging if levels of exposure exceed safe limits which depend on the individual the skin color. Hence, UV photochromic materials that respond to UV light by changing their color are powerful tools to sense radiation safety limits. Photochromic materials comprise either organic materials, inorganic transition metal oxides, or a hybrid combination of both. The photochromic behavior largely relies on charge transfer mechanisms and electronic band structures. These factors can be influenced by the structure and morphology, fabrication, composition, hybridization, and preparation of the photochromic materials, among others. Significant challenges are involved in realizing rapid photochromic change, which is repeatable, reversible with low fatigue, and behaving according to the desired application requirements. These challenges also relate to finding the right synergy between the photochromic materials used, the environment it is being used for, and the objectives that need to be achieved. In this review, the principles and applications of photochromic processes for transition metal oxides and hybrid materials, photocatalytic applications, and the outlook in the context of commercialized sensors in this field are presented.

Broad-Spectrum Solvent-free Layered Black Phosphorus as a Rapid Action Antimicrobial.

Antimicrobial resistance has rendered many conventional therapeutic measures, such as antibiotics, ineffective. This makes the treatment of infections from pathogenic micro-organisms a major growing health, social, and economic challenge. Recently, nanomaterials, including two-dimensional (2D) materials, have attracted scientific interest as potential antimicrobial agents. Many of these studies, however, rely on the input of activation energy and lack real-world utility. In this work, we present the broad-spectrum antimicrobial activity of few-layered black phosphorus (BP) at nanogram concentrations. This property arises from the unique ability of layered BP to produce reactive oxygen species, which we harness to create this unique functionality. BP is shown to be highly antimicrobial toward susceptible and resistant bacteria and fungal species. To establish cytotoxicity with mammalian cells, we showed that both L929 mouse and BJ-5TA human fibroblasts were metabolically unaffected by the presence of BP. Finally, we demonstrate the practical utility of this approach, whereby medically relevant surfaces are imparted with antimicrobial properties via functionalization with few-layer BP. Given the self-degrading properties of BP, this study demonstrates a viable and practical pathway for the deployment of novel low-dimensional materials as antimicrobial agents without compromising the composition or nature of the coated substrate.

Rapid and Selective Biomarker Detection with Conductometric Sensors.

The biomarker detection in human body fluids is crucial as biomarkers are important in diagnosing diseases. Conventional invasive techniques for biomarker detection are associated with infection, tissue damage, and discomfort. Non-invasive devices are an attractive alternative. Here, metal oxide (oxygen-deficient zinc oxide, ZnO) based conductometric sensors with two-terminal electrodes for rapid detection of biomarkers in real-time, are presented. This platform can be engineered for non-invasive, sensitive, and on-demand selective detection of biomarkers based on surface functionalization. The three novelties in this biosensing technique include an on-demand target selection device platform, short (<10 min) incubation times, and real-time monitoring of the biomarker of interest by electrical (resistance change) measurements. Cardiac inflammatory biomarkers interleukin 6 (IL-6) and C-reactive protein (CRP) are used as the model antigens. The devices can detect 100× lower concentration of IL-6 than healthy levels in human saliva and sweat and 1000× and ≈50× lower CRP concentrations than healthy levels in human saliva and sweat, respectively. The devices show high selectivity for IL-6 and CRP antigens when tested with a mixture of biomarkers. This sensor platform can be extended to selective measurements for viruses or DNA screening, which enables a new category of compact and rapid point-of-care medical devices.

Fully Light-Controlled Memory and Neuromorphic Computation in Layered Black Phosphorus.

Imprinting vision as memory is a core attribute of human cognitive learning. Fundamental to artificial intelligence systems are bioinspired neuromorphic vision components for the visible and invisible segments of the electromagnetic spectrum. Realization of a single imaging unit with a combination of in-built memory and signal processing capability is imperative to deploy efficient brain-like vision systems. However, the lack of a platform that can be fully controlled by light without the need to apply alternating polarity electric signals has hampered this technological advance. Here, a neuromorphic imaging element based on a fully light-modulated 2D semiconductor in a simple reconfigurable phototransistor structure is presented. This standalone device exhibits inherent characteristics that enable neuromorphic image pre-processing and recognition. Fundamentally, the unique photoresponse induced by oxidation-related defects in 2D black phosphorus (BP) is exploited to achieve visual memory, wavelength-selective multibit programming, and erasing functions, which allow in-pixel image pre-processing. Furthermore, all-optically driven neuromorphic computation is demonstrated by machine learning to classify numbers and recognize images with an accuracy of over 90%. The devices provide a promising approach toward neurorobotics, human-machine interaction technologies, and scalable bionic systems with visual data storage/buffering and processing.