Search

Laterally large (≈3 µm), atomically thin 2D Bi2O2CO3 nanosheets (2D bismuth oxycarbonate, 2D bismutite) are fabricated via sonochemically assisted, template‐free synthesis. Keys to the synthesis of the freestanding, laterally large 2D Bi2O2CO3 nanosheets from bulk Bi powder are choice of suspension medium, controlled reaction temperatures, and several hours processing time. Lateral sizes of 2D Bi2O2CO3 can be controlled between µm‐sized nanosheets and tens of nm sized nanoflakes solely based on the choice of suspension medium. The here introduced 2D Bi2O2CO3 nano‐sheets/‐flakes are then hybridized by a simple mix‐and‐match approach with TiO2 nanoparticles for testing in suspension‐type photocatalytic hydrogen production via water splitting. This introduces the 2D Bi2O2CO3 as a prospective noble‐metal‐free catalyst component with TiO2 for photocatalytic hydrogen evolution, beyond Bi2O2CO3's current use as photocatalyst for organic pollutant degradation. These results enrich the fabrication toolbox of emerging 2D pnictogen oxycarbonates toward large 2D nanosheets and demonstrate the potential of 2D Bi2O2CO3 as a catalyst component for hydrogen evolution in photocatalytic water splitting. [ABSTRACT FROM AUTHOR]

Many applications of 2D materials require deposition of non‐2D metals and metal‐oxides onto the 2D materials. Little is however known about the mechanisms of such non‐2D/2D interfacing, particularly at the atomic scale. Here, atomically resolved scanning transmission electron microscopy (STEM) is used to follow the entire physical vapor deposition (PVD) cycle of application‐relevant non‐2D In/In2O3 nanostructures on graphene. First, a "quasi‐in‐situ" approach with indium being in situ evaporated onto graphene in oxygen‐/water‐free ultra‐high‐vacuum (UHV) is employed, followed by STEM imaging without vacuum break and then repeated controlled ambient air exposures and reloading into STEM. This allows stepwise monitoring of the oxidation of specific In particles toward In2O3 on graphene. This is then compared with conventional, scalable ex situ In PVD onto graphene in high vacuum (HV) with significant residual oxygen/water traces. The data shows that the process pathway difference of oxygen/water feeding between UHV/ambient and HV fabrication drastically impacts not only non‐2D In/In2O3 phase evolution but also In2O3/graphene out‐of‐plane texture and in‐plane rotational van‐der‐Waals epitaxy. Since non‐2D/2D heterostructures' properties are intimately linked to their structure and since influences like oxygen/water traces are often hard to control in scalable fabrication, this is a key finding for non‐2D/2D integration process design. [ABSTRACT FROM AUTHOR]

Organic–inorganic halide perovskites are intrinsically unstable when exposed to moisture and/or light. Additionally, the presence of lead in many perovskites raises toxicity concerns. Herein, a thin film of barium zirconium sulfide (BaZrS3), a lead‐free chalcogenide perovskite, is reported. Photoluminescence and X‐ray diffraction measurements show that BaZrS3 is far more stable than methylammonium lead iodide (MAPbI3) in moist environments. Moisture‐ and light‐induced degradations in BaZrS3 and MAPbI3 are compared by using simulations and calculations based on density functional theory. The simulations reveal drastically slower degradation in BaZrS3 due to two factors—weak interaction with water and very low rates of ion migration. BaZrS3 photodetecting devices with photoresponsivity of ≈46.5 mA W−1 are also reported. The devices retain ≈60% of their initial photoresponse after 4 weeks under ambient conditions. Similar MAPbI3 devices degrade rapidly and show a ≈95% decrease in photoresponsivity in just 4 days. The findings establish the superior stability of BaZrS3 and strengthen the case for its use in optoelectronics. New possibilities for thermoelectric energy conversion using these materials are also demonstrated. [ABSTRACT FROM AUTHOR]

Abstract: Rhenium disulfide (ReS2) differs fundamentally from other group‐VI transition metal dichalcogenides (TMDs) due to its low structural symmetry, which results in its optical and electrical anisotropy. Although vertical growth is observed in some TMDs under special growth conditions, vertical growth in ReS2 is very different in that it is highly spontaneous and substrate‐independent. In this study, the mechanism that underpins the thermodynamically favorable vertical growth mode of ReS2 is uncovered. It is found that the governing mechanism for ReS2 growth involves two distinct stages. In the first stage, ReS2 grows parallel to the growth substrate, consistent with conventional TMD growth. However, subsequent vertical growth is nucleated at points on the lattice where Re atoms are “pinched” together. At such sites, an additional Re atom binds with the cluster of pinched Re atoms, leaving an under‐coordinated S atom protruding out of the ReS2 plane. This under‐coordinated S is “reactive” and binds to free Re and S atoms, initiating growth in a direction perpendicular to the ReS2 surface. The utility of such vertical ReS2 arrays in applications where high surface‐to‐volume ratio and electric‐field enhancement are essential, such as surface enhanced Raman spectroscopy, field emission, and solar‐based disinfection of bacteria, is demonstrated. [ABSTRACT FROM AUTHOR]

It is understood that defects of the atomic arrangement of the lattice in 2D molybdenum disulfide (MoS2) grown by chemical vapor deposition (CVD) can have a profound effect on the electronic and optical properties. Beyond these it is a major prerequisite to also understand the fundamental effect of such defects on phonon transport, to guarantee the successful integration of MoS2 into the solid-state devices. A comprehensive joint experiment-theory investigation to explore the effect of lattice defects on the thermal transport of the suspended MoS2 monolayer grown by CVD is presented. The measured room temperature thermal conductivity values are 30 ± 3.3 and 35.5 ± 3 W m−1 K−1 for two samples, which are more than two times smaller than that of their exfoliated counterpart. High-resolution transmission electron microscopy shows that these CVD-grown samples are polycrystalline in nature with low angle grain boundaries, which is primarily responsible for their reduced thermal conductivity. Higher degree of polycrystallinity and aging effects also result in smoother temperature dependency of thermal conductivity (κ) at temperatures below 100 K. First-principles lattice dynamics simulations are carried out to understand the role of defects such as isotopes, vacancies, and grain boundaries on the phonon scattering rates of our CVD-grown samples. [ABSTRACT FROM AUTHOR]