Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)
DOI: https://doi.org/10.29363/nanoge.matsus.2023.023
Publication date: 22nd December 2022
Although lead-halide perovskites have demonstrated astonishing increases in efficiency in solar cells, they contain lead in a soluble form and are processed with toxic solvents. Bismuth-based compounds have gained increasing attention as a non-toxic alternative because bismuth is a heavy-metal cation that can replicate many of the features of lead thought to enable defect-tolerance. Defect-tolerance is the ability of materials to achieve long charge-carrier transport lengths despite the presence of defects, potentially enabling efficient performance to be achieved in materials made by low-cost methods. This talk explores our recent work on two such materials, bismuth oxyiodide (BiOI) and sodium bismuth sulfide (NaBiS2). We demonstrate BiOI to be tolerant towards its most common point defects, and develop an all-inorganic device structure to achieve external quantum efficiencies up to 80% in photovoltaics [1]. Next, we develop this into a photocathode, making use of a graphite epoxy to further protect the devices from degradation. In doing so, we show that we can improve the stability of the devices from a couple of minutes (BiOI in direct contact with the electrolyte) to a couple of months of operation for water splitting [2]. We further show that integrating these BiOI photocathodes in tandem with BiVO4 photoanodes leads to fully oxide-based photoelectrochemical tandems capable of self-driven water splitting and syngas production [2]. Finally, we cover our recent work on NaBiS2, demonstrating this material to be stable in air for at least 11 months, and a stronger light harvester than established thin-film absorbers, such that a 30 nm thick film has a spectroscopic limited maximum efficiency of 26% [3]. Through detailed computations, we rationalise the cause behind this strong light absorption as resulting from cation disorder. We further show that cation disorder has significant consequences on charge-carrier transport by enabling the formation of small hole polarons.
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