Lone pair driven anisotropy in antimony chalcogenide semiconductors

• Published in: Physical chemistry chemical physics : PCCP Vol. 24; no. 12; pp. 7195 - 722
• Main Authors: Wang, Xinwei, Li, Zhenzhu, Kavanagh, Seán R, Ganose, Alex M, Walsh, Aron
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 23.03.2022
• Subjects: Anisotropy; Carrier transport; Crystal structure; Current carriers; Electronic structure; Fermi surfaces; First principles; Optical properties; Photovoltaic cells; Semiconductors; Solar cells; Structural analysis; Thin films
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d1cp05373f

Antimony sulfide (Sb 2 S 3 ) and selenide (Sb 2 Se 3 ) have emerged as promising earth-abundant alternatives among thin-film photovoltaic compounds. A distinguishing feature of these materials is their anisotropic crystal structures, which are composed of quasi-one-dimensional (1D) [Sb 4 X 6 ] n ribbons. The interaction between ribbons has been reported to be van der Waals (vdW) in nature and Sb 2 X 3 are thus commonly classified in the literature as 1D semiconductors. However, based on first-principles calculations, here we show that inter-ribbon interactions are present in Sb 2 X 3 beyond the vdW regime. The origin of the anisotropic structures is related to the stereochemical activity of the Sb 5s lone pair according to electronic structure analysis. The impacts of structural anisotropy on the electronic, dielectric and optical properties relevant to solar cells are further examined, including the presence of higher dimensional Fermi surfaces for charge carrier transport. Our study provides guidelines for optimising the performance of Sb 2 X 3 -based photovoltaics via device structuring based on the underlying crystal anisotropy. The unique electronic and optical properties of Sb 2 S 3 and Sb 2 Se 3 are connected to their underlying crystal structures and chemical bonding.