Electron–Phonon-Mediated Temperature-Dependent Optical Bandgap of MAPbCl_<i>x</i>Br_3–<i>x</i> Single Crystals

Methylammonium-lead-halide compounds have emerged as promising bandgap engineering materials due to their ability to fine-tune the energy gap through halogen element mixing. We present a comprehensive investigation of the temperature-dependent photoluminescence (PL) transition characteristics exhibited by single crystals of chlorine- and bromine-based methylammonium lead halides. MAPbCl3 and MAPbBr3 crystals exhibit a distinct, sharp, free exciton transition with an abrupt transition behavior associated with the structural phase transition as the temperature varies. However, when the two halogen elements are mixed within the crystals, no structural phase transition is observed. This study explores the temperature-dependent variations in integrated PL intensity, full width at half-maximum, and peak transition energy of the crystals. The obtained results discuss the intricate interplay between temperature, crystal structure, and composition, providing valuable insights into the optical properties and potential applications of organic–inorganic hybrid methylammonium lead halide single crystals as tunable energy gap semiconductor materials

In Situ Analyses of Carbon Dissolution into Ni-YSZ Anode Materials

A combination of in situ analyses, including measurement of both electrical resistance and volumetric expansion, and thermogravimetric analysis (TGA) was employed to elucidate the deactivation process of a nickel-yttria-stabilized zirconia (Ni-YSZ) cermet (60 wt % NiO-YSZ) upon exposure to methane at 750 °C. In conjunction with the aforementioned in situ techniques, a number of ex situ analyses, including scanning electron microscopy (SEM), electron probe microanalysis (EPMA), X-ray diffraction (XRD), and Raman spectroscopy, revealed that carbon deposition initially occurred at the Ni centers, followed by carbon dissolution into the Ni-YSZ cermet after an induction period of 200 min, which then led to three-dimensional expansion. The structural change of the Ni-based cermet induced increases in electrical resistance of the material. The increased electrical resistance likely originated from the breakage of the Ni–Ni conducting network as well as from the formation of microscopic cracks within the Ni-YSZ material, resulting from the observed process of carbon dissolution. Moreover, a combination of TGA involving measurements of electrical resistance was demonstrated to be useful for determining amounts of carbon deposits critical for carbon dissolution. These results strongly suggest that changes in electrical resistance can be utilized to monitor the extent of carbon dissolution into the Ni-YSZ catalysts in situ, which would be helpful for the development of an efficient curing system for solid oxide fuel cells (SOFCs)

Effect of Activating a Nickel–Molybdenum Catalyst in an Anion Exchange Membrane Water Electrolyzer

Water electrolysis using anion exchange membranes is promising for hydrogen production, and Ni–Mo catalysts have shown high activity for alkaline hydrogen evolution reaction (HER). However, their performance has been mostly tested in a half-cell setup and rarely studied in a single-cell setup with a membrane electrode assembly (MEA) structure, which is used for practical applications. With Ni3Mo as the cathode, a single cell was fabricated using non-noble metal catalysts exclusively. Interestingly, the activation procedure significantly affected the cell performance. The single cell performed better than that with the Pt/C catalyst when the Ni3Mo catalyst was mildly activated. The distribution of Mo in electrodes, membrane, and electrolytes was estimated, confirming Mo dissolution from the cathode. Once the cell was activated, the cell performance was stable without degradation in long-term chronopotentiometry operation, but the performance was degraded by sudden voltage change such as imposing open circuit voltage (OCV). The surface structure and reaction mechanism were studied with density functional theory: the Mo-dissolved Ni3Mo(101) surface could promote H2O dissociation, while MoO3 stably adsorbed on the surface weakened H* adsorption, promoting HER. This study provides important insights into the development of efficient catalysts for large-scale hydrogen production

Relating Electronic and Geometric Structure of Atomic Layer Deposited BaTiO₃ to its Electrical Properties

Atomic layer deposition allows the fabrication of BaTiO₃ (BTO) ultrathin films with tunable dielectric properties, which is a promising material for electronic and optical technology. Industrial applicability necessitates a better understanding of their atomic structure and corresponding properties. Through the use of element-specific X-ray absorption near edge structure (XANES) analysis, O K-edge of BTO as a function of cation composition and underlying substrate (RuO₂ and SiO₂) is revealed. By employing density functional theory and multiple scattering simulations, we analyze the distortions in BTO’s bonding environment captured by the XANES spectra. The spectral weight shifts to lower energy with increasing Ti content and provides an atomic scale (microscopic) explanation for the increase in leakage current density. Differences in film morphologies in the first few layers near substrate–film interfaces reveal BTO’s homogeneous growth on RuO₂ and its distorted growth on SiO₂. This work links structural changes to BTO thin-film properties and provides insight necessary for optimizing future BTO and other ternary metal oxide-based thin-film devices

Plasma-Enhanced Atomic Layer Deposition of SiN–AlN Composites for Ultra Low Wet Etch Rates in Hydrofluoric Acid

The continued scaling in transistors and memory elements has necessitated the development of atomic layer deposited (ALD) of hydrofluoric acid (HF) etch resistant and electrically insulating films for sidewall spacer processing. Silicon nitride (SiN) has been the prototypical material for this need and extensive work has been conducted into realizing sufficiently lower wet etch rates (WERs) as well as leakage currents to meet industry needs. In this work, we report on the development of plasma-enhanced atomic layer deposition (PEALD) composites of SiN and AlN to minimize WER and leakage current density. In particular, the role of aluminum and the optimum amount of Al contained in the composite structures have been explored. Films with near zero WER in dilute HF and leakage currents density similar to pure PEALD SiN films could be simultaneously realized through composites which incorporate ≥13 at. % Al, with a maximum thermal budget of 350 °C