Understanding the Crystal Growth of Bismuth Chalcohalide Nanorods through a Self-Sacrificing Template Process: A...

Bismuth-based semiconductors are promising candidates for applications in photocatalysis, photodetection, solar cells, etc. BiSI in particular is attracting attention. It has anisotropic optoelectronic properties and comprises relatively abundant elements. However, the synthesis of this ternary compound presents several challenges. Here, we delve into the underlying chemical processes that lead to the crystal growth of BiSI nanorods and optimize a solution-based synthesis. The mechanism of formation of BiSI nanocrystals is the self-sacrifice of Bi₂S₃ nanostructures, which also act as templates. The crystallographic similarities between the chalcogenide and the chalcohalide allow for the solid state transformation from one to the other. However, there is also a synergy with the I₃^- species formed in the reaction media needed to obtain BiSI. Our method makes use of a green solvent, avoids complicated media, and drastically reduces the reaction time compared to other methods. The obtained nanorods present a band gap of 1.6 eV, in accordance with the reported values. This work presents insight into the chemistry of bismuth-based semiconductors, while introducing an easy, green, and scalable synthesis of a promising material, which could also be applied to similar compounds and other chalcoiodides, such as SbSI. In addition, the optical properties of the BiSI nanorods show their potential in photovoltaic applications.