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Colloidal semiconductor nanoparticles (NPs) have long been used as a reliable method for depositing thin films of semiconductor materials for applications, such as photovoltaics via solution-processed means. Traditional methods for synthesizing colloidal NPs often utilize heavy, long-chain organic species to serve as surface ligands, which, during the fabrication of selenized chalcogenide films, leaves behind an undesirable carbonaceous residue in the film. In an effort to minimize these residues, this work looks at using N-methyl-2-pyrrolidone (NMP) as an alternative to the traditional species used as surface ligands. In addition to serving as a primary ligand, NMP also serves as the reaction medium and coating solvent for fabricating CuInS2 (CIS) NPs and thin-film solar cells. Through the use of the NMP-based synthesis, a substantial reduction in the number of carbonaceous residues was observed in selenized films. Additionally, the resulting fine-grain layer at the bottom of the film was observed to exhibit a larger average grain size and increased chalcopyrite character over those of traditionally prepared films, presumably as a result of the reduced carbon content. As a result, a gallium-free CuIn(S,Se)2 device was shown to achieve power-conversion efficiencies of over 11% as well as possessing exceptional carrier generation capabilities with a short-circuit current density (JSC) of 41.6 mA/cm2, which is among the highest for the CIGSSe family of devices fabricated from solution-processed methods. 

The solution-processing of metal chalcogenides offers a promising route to improve the manufacturing of semiconductor devices. The amine–thiol solvent system has been deemed an “alkahest” for its ability to dissolve a wide range of metals and metal chalcogenides. Therefore, it enables convenient synthesis of metal sulfides. However, in the literature there are limited reports of analogous selenium-based “alkahest” chemistry. Here we show that solutions containing n-alkylammonium polyselenides can dissolve a wide range of metals and metal compounds through the formation of soluble metal polyselenides. These metal polyselenides can subsequently be utilized as precursors for the synthesis of a wide range of binary and multinary metal selenide thin films and nanoparticles, including Cu(In,Ga)Se2, Cu2ZnSnSe4, and Ag2ZnSnSe4. 

Chalcogenide perovskites have recently attracted significant attention for renewable energy applications due to their predicted combination of air, moisture, and thermal stability, which has been experimentally validated, along with their excellent optoelectronic properties, which are still under experimental investigation. While historically requiring high synthesis temperatures, some solution-processed routes have recently emerged for synthesizing chalcogenide perovskites, such as BaZrS3 and BaHfS3, at temperatures below 600 °C. This study discusses several experimental challenges associated with the moderate-temperature synthesis of solution-deposited chalcogenide perovskites. Firstly, we identify Ruddlesden–Popper (RP) phases as thermodynamically stable competing secondary phases in perovskite synthesis. High sulfur pressures favor the formation of BaZrS3 or BaHfS3, whereas lower sulfur pressures result in a mixture of perovskite and RP phases. Additionally, we briefly discuss the mechanism of moderate-temperature synthesis of chalcogenide perovskites, including some of the morphological and optoelectronic challenges it presents, such as grain overgrowth, secondary phase contamination entrapment, and the presence of mid-band gap emissions. Finally, we address the importance of substrate selection and the potential presence of Ca- and Na-based impurities originating from cation out-diffusion from glass substrates. Addressing these challenges will be crucial as these unique materials continue to be investigated for applications in optoelectronic devices.