Design of I-II-IV-VI semiconductors through element substitution

C. Wang, S. Chen, J.-H. Yang, L. Lang, H.-J. Xiang, X.-G. Gong, A. Walsh, S.-H. Wei

OAI: oai:purehost.bath.ac.uk:openaire_cris_publications/1a3f0053-ff20-4b68-993f-bee971b58b4f • DOI: https://doi.org/10.1021/cm500598x

Through element substitution in CuZnSnS, a class of kesterite-structured I-II-IV-VI semiconductors can be designed as novel functional materials. Using the first-principles calculations, we show that this element-substitution design is thermodynamically limited, that is, although I-II-IV-VI with I = Cu, Ag, II = Zn, Cd, Hg, IV = Si, Ge, Sn, and VI = S, Se, Te are stable quaternary compounds, those with II = Mg, Ca, Sr, Ba, IV =Ti, Zr, Hf, and VI = O are unstable against the phase-separation into the competing binary and ternary compounds. Three main phase-separation pathways are revealed. In general, we show that if the secondary II-VI or I-IV-VI phases prefer to have nontetrahedral structures, then the I-II-IV-VI semiconductors tend to phase separate. This finding can be used as a guideline for future design of new quaternary semiconductors.