American Chemical Society
cm7b02638_si_001.pdf (7.77 MB)

I2–II–IV–VI4 (I = Cu, Ag; II = Sr, Ba; IV = Ge, Sn; VI = S, Se): Chalcogenides for Thin-Film Photovoltaics

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journal contribution
posted on 2017-08-21, 00:00 authored by Tong Zhu, William P. Huhn, Garrett C. Wessler, Donghyeop Shin, Bayrammurad Saparov, David B. Mitzi, Volker Blum
Recent work has identified a non-zinc-blende-type quaternary semiconductor, Cu2BaSnS4–xSex (CBTSSe), as a promising candidate for thin-film photovoltaics (PVs). CBTSSe circumvents difficulties of competing PV materials regarding (i) toxicity (e.g., CdTe), (ii) scarcity of constituent elements (e.g., Cu­(In,Ga)­(S,Se)2/CdTe), and (iii) unavoidable antisite disordering that limits further efficiency improvement (e.g., in Cu2ZnSnS4–xSex). In this work, we build on the CBTSSe paradigm by computationally scanning for further improved, earth-abundant and environmentally friendly thin-film PV materials among the 16 quaternary systems I2–II–IV–VI4 (I = Cu, Ag; II = Sr, Ba; IV = Ge, Sn; VI = S, Se). The band structures, band gaps, and optical absorption properties are predicted by hybrid density-functional theory calculations. We find that the Ag-containing compounds (which belong to space groups I222 or I4̅2m) show indirect band gaps. In contrast, the Cu-containing compounds (which belong to space group P31/P32 and Ama2) show direct or nearly direct band gaps. In addition to the previously considered Cu2BaSnS4–xSex system, two compounds not yet considered for PV applications, Cu2BaGeSe4 (P31) and Cu2SrSnSe4 (Ama2), show predicted quasi-direct/direct band gaps of 1.60 and 1.46 eV, respectively, and are therefore most promising with respect to thin-film PV application (both single- and multijunction). A Cu2BaGeSe4 sample, prepared by solid-state reaction, exhibits the expected P31 structure type. Diffuse reflectance and photoluminescence spectrometry measurements yield an experimental band gap of 1.91(5) eV for Cu2BaGeSe4, a value slightly smaller than that for Cu2BaSnS4.