The effect of elevated temperatures on excitonic emission and degradation processes of WS2 monolayers.

Controlled heating experiments in an inert environment have been performed on WS2 monolayers, in order to clarify the conflicting reports on the high-temperature photoluminescent response of 2D TMDs. We find that in contrast to some previous results on both WS2 and MoS2, the photoluminescent intensity shows a consistent reduction above room temperature. This is accompanied by an almost linear redshift of the peak maximum, and a nearly linear increase in the peak width, which is attributed to an enhanced interaction with optical phonons. Moreover, by fitting the photoluminescence integral intensity with an Arrhenius type dependence, we demonstrate that the center of the WS2 monolayer flake starts to undergo irreversible degradation at a temperature of 573 K in an inert environment. Regions close to flake edges in contrast, with a more intense room temperature PL response, remain stable. The macroscopic PL signal is largely recovered in these regions following subsequent cooling to room temperature.

Efficient Defect-Driven Cation Exchange beyond the Nanoscale Semiconductors toward Antibacterial Functionalization.

Defect engineering is an exciting tool for customizing semiconductors' structural and optoelectronic properties. Elaborating programmable methodologies to circumvent energy constraints in multievent inversions expands our understanding of the mechanisms governing the functionalization of nanomaterials. Herein, we introduce a novel strategy based on defect incorporation and solution rationalization, which triggers energetically unfavorable cation exchange reactions in extended solids. Using Sb2X3 + Ag (I) → Ag: Sb2X3 (X= S, Se) as a system to model, we demonstrate that incorporating chalcogen vacancies and AgSbVX complex defects into initial thin films (TFs) is crucial for activating long-range solid-state ion diffusion. Additional regulation of the Lewis acidity of auxiliary chemicals provides an exceptional conversion yield of the Ag precursor into a solid-state product up to 90%, simultaneously transforming upper matrix layers into AgSbX2. The proposed strategy enables tailoring radiative recombination processes, offers efficiency to invert TFs at moderate temperatures quickly, and yields structures of large areas with substantial antibacterial activity in visible light for a particular inversion system. Similar customization can be applied to most sulfides/selenides with controlled reaction yields.

Unusual Defect-Related Room-Temperature Emission from WS2 Monolayers Synthesized through a Potassium-Based Precursor.

Alkali-metal-based synthesis of transition metal dichalcogenide (TMD) monolayers is an established strategy for both ultralarge lateral growth and promoting the metastable 1T phase. However, whether this can also lead to modified optical properties is underexplored, with reported photoluminescence (PL) spectra from semiconducting systems showing little difference from more traditional syntheses. Here, we show that the growth of WS2 monolayers from a potassium-salt precursor can lead to a pronounced low-energy emission in the PL spectrum. This is seen 200-300 meV below the A exciton and can dominate the signal at room temperature. The emission is spatially heterogeneous, and its presence is attributed to defects in the layer due to sublinear intensity power dependence, a noticeable aging effect, and insensitivity to washing in water and acetone. Interestingly, statistical analysis links the band to an increase in the width of the A1g Raman band. The emission can be controlled by altering when hydrogen is introduced into the growth process. This work demonstrates intrinsic and intense defect-related emission at room temperature and establishes further opportunities for tuning TMD properties through alkali-metal precursors.

Cu2ZnSnS4 monograin layer solar cells for flexible photovoltaic applications.

Monograin powder technology is one possible path to developing sustainable, lightweight, flexible, and semi-transparent solar cells, which might be ideal for integration with various building and product elements. In recent years, the main research focus of monograin technology has centered around understanding the synthesis and optoelectronic properties of kesterite-type absorber materials. Among these, Cu2ZnSnS4 (CZTS) stands out as a promising solar cell absorber due to its favorable optical and electrical characteristics. CZTS is particularly appealing as its constituent elements are abundant and non-toxic, and it currently holds the record for highest power conversion efficiency (PCE) among emerging inorganic thin-film PV candidates. Despite its advantages, kesterite solar cells' PCE still falls significantly behind the theoretical maximum efficiency due to the large VOC deficit. This review explores various strategies aimed at improving VOC losses to enhance the overall performance of CZTS monograin layer solar cells. It was found that low-temperature post-annealing of CZTS powders reduced Cu-Zn disordering, increasing Eg by ∼100 meV and VOC values; however, achieving the optimal balance between ordered and disordered regions in kesterite materials is crucial for enhancing photovoltaic device performance due to the coexistence of ordered and disordered phases. CZTS alloying with Ag and Cd suppressed non-radiative recombination and increased short-circuit current density. Optimizing Ag content at 1% reduced CuZn antisite defects, but higher Ag levels compensated for acceptor defects, leading to reduced carrier density and decreased solar cell performance. Co-doping with Li and K resulted in an increased bandgap (1.57 eV) and improved VOC, but further optimization is required due to a relatively large difference between measured and theoretical VOC. Heterojunction modifications led to the most effective PCE improvement in CZTS-based solar cells, achieving an overall efficiency of 12.06%.

Photoreflectance and Photoluminescence Study of Antimony Selenide Crystals.

Among inorganic, Earth-abundant, and low-toxicity photovoltaic technologies, Sb2Se3 has emerged as a strong material contender reaching over 10% solar cell power conversion efficiency. Nevertheless, the bottleneck of this technology is the high deficit of open-circuit voltage (V OC) as seen in many other emerging chalcogenide technologies. Commonly, the loss of V OC is related to the nonradiative carrier recombination through defects, but other material characteristics can also limit the achievable V OC. It has been reported that in isostructural compound Sb2S3, self-trapped excitons are readily formed leading to 0.6 eV Stokes redshift in photoluminescence (PL) and therefore significantly reducing the obtainable V OC. However, whether Sb2Se3 has the same limitations has not yet been examined. In this work, we aim to identify main radiative carrier recombination mechanisms in Sb2Se3 single crystals and estimate if there is a fundamental limit for obtainable V OC. Optical transitions in Sb2Se3 were studied by means of photoreflectance and PL spectroscopy. Temperature, excitation intensity, and polarization-dependent optical characteristics were measured and analyzed. We found that at low temperature, three distinct radiative recombination mechanisms were present and were strongly influenced by the impurities. The most intensive PL emissions were located near the band edge. In conclusion, no evidence of emission from self-trapped excitons or band-tails was observed, suggesting that there is no fundamental limitation to achieve high V OC, which is very important for further development of Sb2Se3-based solar cells.

Postdeposition Processing of SnS Thin Films and Solar Cells: Prospective Strategy To Obtain Large, Sintered, and Doped SnS Grains by Recrystallization in the Presence of a Metal Halide Flux.

Postdeposition treatments (PDTs) are common technological approaches to achieve high-efficiency chalcogenide solar cells. For SnS, a promising solar cell material, most PDT strategies to control the SnS properties are overwhelmingly based on an annealing in sulfur-containing ambient atmosphere that is described by condensed-state reactions and vapor-phase transport. In this work, a systematic study of the impact of PDTs in a N2 atmosphere, ampules at temperatures between 400 and 600 °C, and a SnCl2 treatment at 250-500 °C on the properties of SnS films and SnS/CdS solar cells prepared by close-spaced sublimation is reported. The ampule and N2 annealing conditions do not affect the grain size of the SnS layers but significantly impact the concentration of intrinsic point defects, carrier density, and mobility. Annealing at 500-600 °C strongly enhances the hole concentration and decreases the carrier mobility, having detrimental impacts on the device performance. SnCl2 treatment promotes grain growth, sintering, and doping by mass transport through the melted phase; it adjusts the hole density and improves the carrier mobility in the SnS layers. SnS/CdS solar cells with an efficiency of 2.8% are achieved in the SnCl2 treatment step, opening new possibilities to further improve the performance of SnS-based devices.

Photoluminescence of spray pyrolysis deposited ZnO nanorods.

Photoluminescence of highly structured ZnO layers comprising well-shaped hexagonal rods is presented. The ZnO rods (length 500-1,000 nm, diameter 100-300 nm) were grown in air onto a preheated soda-lime glass (SGL) or ITO/SGL substrate by low-cost chemical spray pyrolysis method using zinc chloride precursor solutions and growth temperatures in the range of 450-550°C. We report the effect of the variation in deposition parameters (substrate type, growth temperature, spray rate, solvent type) on the photoluminescence properties of the spray-deposited ZnO nanorods. A dominant near band edge (NBE) emission is observed at 300 K and at 10 K. High-resolution photoluminescence measurements at 10 K reveal fine structure of the NBE band with the dominant peaks related to the bound exciton transitions. It is found that all studied technological parameters affect the excitonic photoluminescence in ZnO nanorods.PACS: 78.55.Et, 81.15.Rs, 61.46.Km.