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Chalcogenides in the perovskite and related crystal structures (“chalcogenide perovskites” for brevity) may be useful for future optoelectronic and energy-conversion technologies inasmuch as they have good excited-state, ambipolar transport properties. In recent years, several studies have suggested that semiconductors in the Ba–Zr–S system have slow non-radiative recombination rates. Here, we present a time-resolved photoluminescence (TRPL) study of excited-state carrier mobility and recombination rates in the perovskite-structured material BaZrS 3 , and the related Ruddlesden–Popper phase Ba 3 Zr 2 S 7 . We measure state-of-the-art single crystal samples, to identify properties free from the influence of secondary phases and random grain boundaries. We model and fit the data using a semiconductor physics simulation, to enable more direct determination of key material parameters than is possible with empirical data modeling. We find that both materials have Shockley–Read–Hall recombination lifetimes on the order of 50 ns and excited-state diffusion lengths on the order of 5 μm at room temperature, which bodes well for ambipolar device performance in optoelectronic technologies including thin-film solar cells. 

We report the synthesis of large-area, high-Ti-content, Mo 1−x Ti x S 2 alloy thin films in the 2H phase at temperature as low as 500 °C using a scalable two-step method of metal film deposition, followed by sulfurization in H 2 S. Film processing at higher temperature accelerates Ti segregation, film coarsening, and the formation of TiS 2 in the 1T phase. Crystal growth at higher temperature results in the formation of multiple binary sulfide phases, in agreement with the equilibrium phase diagram. Making highly metastable, smooth, and uniform single-phase alloy films, therefore, hinges on developing low-temperature processing. Our results are relevant to the development of technologies based on designer transition metal dichalcogenide alloys, including in photonic integrated circuits and gas sensing. 

Abstract AimClimate change is transforming mountain summit plant communities worldwide, but we know little about such changes in the High Andes. Understanding large‐scale patterns of vegetation changes across the Andes, and the factors driving these changes, is fundamental to predicting the effects of global warming. We assessed trends in vegetation cover, species richness (SR) and community‐level thermal niches (CTN) and tested whether they are explained by summits' climatic conditions and soil temperature trends. LocationHigh Andes. Time periodBetween 2011/2012 and 2017/2019. Major taxa studiedVascular plants. MethodsUsing permanent vegetation plots placed on 45 mountain summits and soil temperature loggers situated along a ~6800 km N‐S gradient, we measured species and their relative percentage cover and estimated CTN in two surveys (intervals between 5 and 8 years). We then estimated the annual rate of changes for the three variables and used generalized linear models to assess their relationship with annual precipitation, the minimum air temperatures of each summit and rates of change in the locally recorded soil temperatures. ResultsOver time, there was an average loss of vegetation cover (mean = −0.26%/yr), and a gain in SR across summits (mean = 0.38 species m²/yr), but most summits had significant increases in SR and vegetation cover. Changes in SR were positively related to minimum air temperature and soil temperature rate of change. Most plant communities experienced shifts in their composition by including greater abundances of species with broader thermal niches and higher optima. However, the measured changes in soil temperature did not explain the observed changes in CTN. Main conclusionsHigh Andean vegetation is changing in cover and SR and is shifting towards species with wider thermal niche breadths. The weak relationship with soil temperature trends could have resulted from the short study period that only marginally captures changes in vegetation through time. 

Abstract The synthesis of BaZr(S,Se)₃chalcogenide perovskite alloys is demonstrated by selenization of BaZrS₃thin films. The anion‐exchange process produces films with tunable composition and band gap without changing the orthorhombic perovskite crystal structure or the film microstructure. The direct band gap is tunable between 1.5 and 1.9 eV. The alloy films made in this way feature one‐hundred‐times stronger photoconductive response and a lower density of extended defects, compared to alloy films made by direct growth. The perovskite structure is stable in high‐selenium‐content thin films with and without epitaxy. The manufacturing‐compatible process of selenization in H₂Se gas may spur the development of chalcogenide perovskite solar cell technology. 

The dielectric response of materials underpins electronics and photonics. At high frequencies, dielectric polarizability sets the scale for optical density and absorption. At low frequencies, dielectric polarizability determines the band diagram of junctions and devices, and nonlinear effects enable tunable capacitors and electro-optic modulators. More complicated but no less important is the role of dielectric response in screening bound and mobile charges. These effects control defect charge capture and recombination rates, set the scale for insulator-metal transitions, and mediate interactions among charge carriers and between charge carriers and phonons. In this perspective, we motivate the discovery of highly polarizable semiconductors by highlighting their potential to improve existing and enable new optoelectronic device technologies. We then suggest discovery strategies based on solid state chemical principles and building on recent efforts in computational materials screening.