First-principles DFT insights into the structural, elastic, and optoelectronic properties of α and β-ZnP2: implications for photovoltaic applications

Binary II–V semiconductors are highly optically active materials, possess high intrinsic mechanical and chemical durability, and have electronic properties ideal for optoelectronic applications. Among them, zinc diphosphide (ZnP2) is a promising earth-abundant absorber material for solar energy conversion. We have investigated the structural, mechanical, and optoelectronic properties of both the tetragonal (α) and monoclinic (β) phases of ZnP2 using standard, Hubbard-corrected and screened hybrid density functional theory methods. Through the analysis of bond character, band gap nature, and absorption spectra, we show that there exist two polymorphs of the β phase (denoted as β1 and β2) with distinct differences in the photovoltaic potential. While β1 exhibits the characteristics of metallic compounds, β2 is a semiconductor with predicted thin-film photovoltaic absorbing efficiency of almost 10%. The α phase is anticipated to be an indirect gap material with a calculated efficiency limited to only 1%. We have also analysed and gained insights into the electron localization function, projected density of states and projected crystal orbital Hamilton populations for the analogue bonds between the α and β-ZnP2. In light of these calculations, a number of previous discrepancies have been solved and a solid ground for future employment of zinc diphosphides in photovoltaics has been established.