Design of I2鈥揑I鈥揑V鈥揤I4 Semiconductors through Element Substitution: The Thermodynamic Stability Limit and Chemical Trend

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• 作者：Congcong Wang ; Shiyou Chen ; Ji-Hui Yang ; Li Lang ; Hong-Jun Xiang ; Xin-Gao Gong ; Aron Walsh ; Su-Huai Wei
• 刊名：Chemistry of Materials
• 出版年：2014
• 出版时间：June 10, 2014
• 年：2014
• 卷：26
• 期：11
• 页码：3411-3417
• 全文大小：321K
• 年卷期：v.26,no.11(June 10, 2014)
• ISSN：1520-5002

文摘

Through element substitution in Cu₂ZnSnS₄, a class of kesterite-structured I₂鈥揑I鈥揑V鈥揤I₄ 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 I₂鈥揑I鈥揑V鈥揤I₄ 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鈥揤I or I₂鈥揑V鈥揤I₃ phases prefer to have nontetrahedral structures, then the I₂鈥揑I鈥揑V鈥揤I₄ semiconductors tend to phase separate. This finding can be used as a guideline for future design of new quaternary semiconductors.