Chalcogenide perovskites, including BaZrS3, have been suggested as highly stable alternatives to halide perovskites. However, the synthesis of chalcogenide perovskites has proven to be a significant challenge, often relying on excessively high temperatures and methods that are incompatible with device integration. In this study, we developed a solution-based approach to the deposition of BaZrS3. This method utilizes a combination of a soluble barium thiolate and nanoparticulate zirconium hydride. Following solution-based deposition of the precursors and subsequent sulfurization, BaZrS3 can be obtained at temperatures as low as 500 °C. Furthermore, this method was extended to other chalcogenide perovskite (BaHfS3) and perovskite-related (BaTiS3) materials.

Chalcogenide perovskites have garnered interest for applications in semiconductor devices due to their excellent predicted optoelectronic properties and stability. However, high synthesis temperatures have historically made these materials incompatible with the creation of photovoltaic devices. Here, we demonstrate the solution processed synthesis of luminescent BaZrS3 and BaHfS3 chalcogenide perovskite films using single‐phase molecular precursors at sulfurization temperatures of 575 °C and sulfurization times as short as one hour. These molecular precursor inks were synthesized using known carbon disulfide insertion chemistry to create Group 4 metal dithiocarbamates, and this chemistry was extended to create species, such as barium dithiocarboxylates, that have never been reported before. These findings, with added future research, have the potential to yield fully solution processed thin films of chalcogenide perovskites for various optoelectronic applications.

In this work, we report the first-ever fabrication of solution-processed Se–Te alloy thin films for photovoltaic applications using an amine–thiol solvent system. By controlling the relative quantity of Se and Te in ethylenediamine–ethanethiol (EN–ET) solution mixtures, films with different Se/Te ratios were fabricated at temperatures as low as 200 °C with phase-pure material synthesis and uniform homogenous alloying. These composition variations then successfully demonstrated band gap variation from 1.80 eV for pure Se to 1.18 eV for a film with 60% Se and 40% Te that closely matches the theoretical values calculated from Vegard’s law for these materials. Using the evaporation process, the isolation of chalcogen complexes from the EN–ET solution was performed, which was followed by the addition of foreign solvents like dimethyl sulfoxide, dimethyl formamide, and ethanolamine, which enabled the fabrication of better quality films using the spin coating process, minimizing the porosity and increasing the uniformity of the film. A preliminary device fabricated from these films showed diode characteristics with encouraging photovoltaic performance (a power conversion efficiency of 1.11%) that demands further optimization with film fabrication, selection of device architecture, and detailed defect analysis for this material.

Enargite (ENG) Cu3AsS4 is a promising material for photovoltaic applications due to its constituent earth abundant elements of differing ionic radii, ideal predicted optoelectronic properties, and demonstrated use in a working thin-film solar cell. However, little is known about ENG's defect properties; such knowledge is necessary to assess its potential for future use in high-efficiency devices. One indicator of a material's quality is its photogenerated carrier lifetime, which can be related to its bulk defect properties. Here, we use a combination of time-resolved terahertz spectroscopy and time-resolved photoluminescence to assess carrier dynamics in ENG thin films processed from nanoparticle precursors. The Shockley–Read–Hall (SRH) lifetimes are on the multi-nanosecond scale, which exceed those reported in more mature systems and represent promising values for a candidate photovoltaic material. These results suggest that ENG is worthy of further research and development effort with an eye toward future photovoltaic applications.

Chalcogenide perovskites have garnered interest for applications in semiconductor devices due to their excellent predicted optoelectronic properties and stability. However, high synthesis temperatures have historically made these materials incompatible with the creation of photovoltaic devices. Here, we demonstrate the solution processed synthesis of luminescent BaZrS3 and BaHfS3 chalcogenide perovskite films using single‐phase molecular precursors at sulfurization temperatures of 575 °C and sulfurization times as short as one hour. These molecular precursor inks were synthesized using known carbon disulfide insertion chemistry to create Group 4 metal dithiocarbamates, and this chemistry was extended to create species, such as barium dithiocarboxylates, that have never been reported before. These findings, with added future research, have the potential to yield fully solution processed thin films of chalcogenide perovskites for various optoelectronic applications.