Antimony sulfide (Sb2S3) and selenide (Sb2Se3) 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) [Sb4X6]n ribbons. The interaction between ribbons has been reported to be van der Waals (vdW) in nature and Sb2X3 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 Sb2X3 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 Sb2X3-based photovoltaics via device structuring based on the underlying crystal anisotropy.
Bibliographical noteFunding Information:
We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1 and EP/T022213/1). Xinwei Wang acknowledges Imperial College London for the funding of a President's PhD Scholarship. Seán R. Kavanagh acknowledges the EPSRC Centre for Doctoral Training in the Advanced Characterisation of Materials (CDT-ACM) (EP/S023259/1) for funding a PhD studentship. Alex M. Ganose was supported by EPSRC Fellowship EP/T033231/1. Xinwei Wang thanks Chengcheng Xiao and Sunghyun Kim for advice on the computational analysis.
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