Dramatically Enhanced Valley-Polarized Emission by Alloying and Electrical Tuning of Monolayer WTe2 x S2(1- x ) Alloys at Room Temperature with 1T'-WTe2 -Contact.

Monolayer ternary tellurides based on alloying different transition metal dichalcogenides (TMDs) can result in new two-dimensional (2D) materials ranging from semiconductors to metals and superconductors with tunable optical and electrical properties. Semiconducting WTe2 x S2(1- x ) monolayer possesses two inequivalent valleys in the Brillouin zone, each valley coupling selectively with circularly polarized light (CPL). The degree of valley polarization (DVP) under the excitation of CPL represents the purity of valley polarized photoluminescence (PL), a critical parameter for opto-valleytronic applications. Here, new strategies to efficiently tailor the valley-polarized PL from semiconducting monolayer WTe2 x S2(1- x ) at room temperature (RT) through alloying and back-gating are presented. The DVP at RT is found to increase drastically from < 5% in WS2 to 40% in WTe0.12 S1.88 by Te-alloying to enhance the spin-orbit coupling. Further enhancement and control of the DVP from 40% up to 75% is demonstrated by electrostatically doping the monolayer WTe0.12 S1.88 via metallic 1T'-WTe2 electrodes, where the use of 1T'-WTe2 substantially lowers the Schottky barrier height (SBH) and weakens the Fermi-level pinning of the electrical contacts. The demonstration of drastically enhanced DVP and electrical tunability in the valley-polarized emission from 1T'-WTe2 /WTe0.12 S1.88 heterostructures paves new pathways towards harnessing valley excitons in ultrathin valleytronic devices for RT applications.

Atomic-Layer Controlled Interfacial Band Engineering at Two-Dimensional Layered PtSe2/Si Heterojunctions for Efficient Photoelectrochemical Hydrogen Production.

Platinum diselenide (PtSe2) is a group-10 two-dimensional (2D) transition metal dichalcogenide that exhibits the most prominent atomic-layer-dependent electronic behavior of "semiconductor-to-semimetal" transition when going from monolayer to bulk form. This work demonstrates an efficient photoelectrochemical (PEC) conversion for direct solar-to-hydrogen (H2) production based on 2D layered PtSe2/Si heterojunction photocathodes. By systematically controlling the number of atomic layers of wafer-scale 2D PtSe2 films through chemical vapor deposition (CVD), the interfacial band alignments at the 2D layered PtSe2/Si heterojunctions can be appropriately engineered. The 2D PtSe2/p-Si heterojunction photocathode consisting of a PtSe2 thin film with a thickness of 2.2 nm (or 3 atomic layers) exhibits the optimized band alignment and delivers the best PEC performance for hydrogen production with a photocurrent density of -32.4 mA cm-2 at 0 V and an onset potential of 1 mA cm-2 at 0.29 V versus a reversible hydrogen electrode (RHE) after post-treatment. The wafer-scale atomic-layer controlled band engineering of 2D PtSe2 thin-film catalysts integrated with the Si light absorber provides an effective way in the renewable energy application for direct solar-to-hydrogen production.

High-Quality Conformal Homogeneous All-Vacuum Deposited CsPbCl3 Thin Films and Their UV Photodiode Applications.

A sensitive and fast ultraviolet (UV) photodetector is strongly desirable because of its wide range of applications in chemical/biological sensing and imaging. CsPbCl3-based thin film photodetectors have not been constructed previously owing to their extremely poor precursor solubility; however, vapor deposition allows for thin film fabrication without the limitation of solubility. Therefore, this work is the first to demonstrate the optoelectronic properties of inorganic CsPbCl3 perovskite thin films and UV photodiodes using all-vacuum deposition. The perovskites annealed at 120 °C exhibited outstanding performance, including a notable external quantum efficiency value of 797.1% with an applied bias of -2 V, an outstanding detectivity of 1.4 × 1013 Jones, a short response time as low as ∼ 50 µs, and a large linear dynamic range of up to 136 dB. CsPbCl3 thin films manufactured by this vacuum-deposited approach were also found to be moisture-resistant and demonstrated high durability. The devices maintained excellent performance and demonstrated less than 10% degradation after 30 days. Thus, thin film visible-blind UV detectors can potentially be used in transparent smart displays, window-integrated electronic circuits, and sensor applications.

KSCN-induced Interfacial Dipole in Black TiO2 for Enhanced Photocatalytic CO2 Reduction.

Tuning the electronic band structure of black titania to improve photocatalytic performance through conventional band engineering methods has been challenging because of the defect-induced charge carrier and trapping sites. In this study, KSCN-modified hydrogenated nickel nanocluster-modified black TiO2 (SCN-H-Ni-TiO2) exhibits enhanced photocatalytic CO2 reduction due to the interfacial dipole effect. Upon combining the experimental and theoretical simulation approach, the presence of an electrostatic interfacial dipole associated with chemisorption of SCN has dramatic effects on the photocatalyst band structure in SCN-H-Ni-TiO2. An interfacial dipole possesses a more negative zeta potential shift of the isoelectric point from 5.20 to 3.20, which will accelerate the charge carrier separation and electron transfer process. Thiocyanate ion passivation on black TiO2 demonstrated an increased work function around 0.60 eV, which was induced by the interracial dipole effect. Overall, the SCN-H-Ni-TiO2 photocatalyst showed an enhanced CO2 reduction to solar fuel yield by 2.80 times higher than H-Ni-TiO2 and retained around 88% product formation yield after 40 h.

Cytotoxicity and in Vitro Degradation Kinetics of Foundry-Compatible Semiconductor Nanomembranes and Electronic Microcomponents.

Foundry-compatible materials and processing approaches serve as the foundations for advanced, active implantable microsystems that can dissolve in biofluids into biocompatible reaction products, with broad potential applications in biomedicine. The results reported here include in vitro studies of the dissolution kinetics and nanoscale bioresorption behaviors of device-grade thin films of Si, SiN x, SiO2, and W in the presence of dynamic cell cultures via atomic force microscopy and X-ray photoemission spectroscopy. In situ investigations of cell-extracellular mechanotransduction induced by cellular traction provide insights into the cytotoxicity of these same materials and of microcomponents formed with them using foundry-compatible processes, indicating potential cytotoxicity elicited by W at concentrations greater than 6 mM. The findings are of central relevance to the biocompatibility of modern Si-based electronics technologies as active, bioresorbable microsystems that interface with living tissues.

Amino-Acid-Induced Preferential Orientation of Perovskite Crystals for Enhancing Interfacial Charge Transfer and Photovoltaic Performance.

Interfacial engineering of perovskite solar cells (PSCs) is attracting intensive attention owing to the charge transfer efficiency at an interface, which greatly influences the photovoltaic performance. This study demonstrates the modification of a TiO2 electron-transporting layer with various amino acids, which affects charge transfer efficiency at the TiO2 /CH3 NH3 PbI3 interface in PSC, among which the l-alanine-modified cell exhibits the best power conversion efficiency with 30% enhancement. This study also shows that the (110) plane of perovskite crystallites tends to align in the direction perpendicular to the amino-acid-modified TiO2 as observed in grazing-incidence wide-angle X-ray scattering of thin CH3 NH3 PbI3 perovskite film. Electrochemical impedance spectroscopy reveals less charge transfer resistance at the TiO2 /CH3 NH3 PbI3 interface after being modified with amino acids, which is also supported by the lower intensity of steady-state photoluminescence (PL) and the reduced PL lifetime of perovskite. In addition, based on the PL measurement with excitation from different side of the sample, amino-acid-modified samples show less surface trapping effect compared to the sample without modification, which may also facilitate charge transfer efficiency at the interface. The results suggest that appropriate orientation of perovskite crystallites at the interface and trap-passivation are the niche for better photovoltaic performance.

Ultrahigh Responsivity and Detectivity Graphene-Perovskite Hybrid Phototransistors by Sequential Vapor Deposition.

In this work, graphene-methylammonium lead iodide (MAPbI3) perovskite hybrid phototransistors fabricated by sequential vapor deposition are demonstrated. Ultrahigh responsivity of 1.73 × 107 A W-1 and detectivity of 2 × 1015 Jones are achieved, with extremely high effective quantum efficiencies of about 108% in the visible range (450-700 nm). This excellent performance is attributed to the ultra-flat perovskite films grown by vapor deposition on the graphene sheets. The hybrid structure of graphene covered with uniform perovskite has high exciton separation ability under light exposure, and thus efficiently generates photocurrents. This paper presents photoluminescence (PL) images along with statistical analysis used to study the photo-induced exciton behavior. Both uniform and dramatic PL intensity quenching has been observed over entire measured regions, consistently demonstrating excellent exciton separation in the devices.