Phase diagram and stability of mixed-cation lead iodide perovskites: A theory and experiment combined study
Phase diagram and stability of mixed-cation lead iodide perovskites: A theory and experiment combined study
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混合阳离子碘化铅钙钛矿的相图和稳定性：理论与实验相结合的研究
DOI：
10.1103/physrevmaterials.4.095401
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发表时间：
2020-09
影响因子：
3.4
通讯作者：
Yexin Feng
中科院分区：
文献类型：
--
作者：
Zhengwei Xu;Yicheng Zhao;Jiyun Zhang;Keqiu Chen;Christoph J. Brabec;Yexin Feng
Alloying structurally similar perovskites to form mixed-cation lead iodide perovskites, e.g., ${\mathrm{Cs}}_{x}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x)}\mathrm{Pb}{\mathrm{I}}_{3}, \mathrm{M}{\mathrm{A}}_{x}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x)}\mathrm{Pb}{\mathrm{I}}_{3}$, and ${\mathrm{Cs}}_{x}\mathrm{M}{\mathrm{A}}_{y}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x\ensuremath{-}y)}\mathrm{Pb}{\mathrm{I}}_{3}$, could improve the performance of perovskite-based solar cells and light-emitting diodes. However, a phase diagram of them and a clear understanding of the underlying atomic-scale mechanism are still lacking. Using ab initio calculations combined with high-throughput experimentation, we demonstrate the phase diagram of mixed-cation lead iodide perovskites. Only a small proportion of monovalent cations (${\mathrm{Cs}}^{+}/{\mathrm{Rb}}^{+}/{\mathrm{MA}}^{+}$) could be incorporated into the ${\mathrm{FAPbI}}_{3}/{\mathrm{MAPbI}}_{3}$ matrix; otherwise it will be separated into \ensuremath{\delta}-${\mathrm{CsPbI}}_{3}$, \ensuremath{\delta}-${\mathrm{RbPbI}}_{3}$, MAI, etc. The smaller the radius of doping cations, the harder it is to incorporate them into a perovskite lattice and the easier it is to stabilize the perovskite phase. In ${\mathrm{FAPbI}}_{3}$-based multication perovskites, moreover, over 10 mol % alloying is needed to convert \ensuremath{\delta} phase to \ensuremath{\alpha} phase at room temperature. The combined upper and lower limits for doping concentration restrict the appropriate alloying ratio to a narrow window. We further plot the relative energy diagram for triple-cation perovskite ${\mathrm{Cs}}_{x}\mathrm{M}{\mathrm{A}}_{y}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x\ensuremath{-}y)}\mathrm{Pb}{\mathrm{I}}_{3}$, which reveals the ideal doping ratio for uniform stable alloying. This theory-experiment-combined study provides a clear microscopic picture of phase stability and segregation for mixed-cation perovskite solids.
Alloying structurally similar perovskites to form mixed-cation lead iodide perovskites, e.g., ${\mathrm{Cs}}_{x}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x)}\mathrm{Pb}{\mathrm{I}}_{3}, \mathrm{M}{\mathrm{A}}_{x}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x)}\mathrm{Pb}{\mathrm{I}}_{3}$, and ${\mathrm{Cs}}_{x}\mathrm{M}{\mathrm{A}}_{y}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x\ensuremath{-}y)}\mathrm{Pb}{\mathrm{I}}_{3}$, could improve the performance of perovskite-based solar cells and light-emitting diodes. However, a phase diagram of them and a clear understanding of the underlying atomic-scale mechanism are still lacking. Using ab initio calculations combined with high-throughput experimentation, we demonstrate the phase diagram of mixed-cation lead iodide perovskites. Only a small proportion of monovalent cations (${\mathrm{Cs}}^{+}/{\mathrm{Rb}}^{+}/{\mathrm{MA}}^{+}$) could be incorporated into the ${\mathrm{FAPbI}}_{3}/{\mathrm{MAPbI}}_{3}$ matrix; otherwise it will be separated into \ensuremath{\delta}-${\mathrm{CsPbI}}_{3}$, \ensuremath{\delta}-${\mathrm{RbPbI}}_{3}$, MAI, etc. The smaller the radius of doping cations, the harder it is to incorporate them into a perovskite lattice and the easier it is to stabilize the perovskite phase. In ${\mathrm{FAPbI}}_{3}$-based multication perovskites, moreover, over 10 mol % alloying is needed to convert \ensuremath{\delta} phase to \ensuremath{\alpha} phase at room temperature. The combined upper and lower limits for doping concentration restrict the appropriate alloying ratio to a narrow window. We further plot the relative energy diagram for triple-cation perovskite ${\mathrm{Cs}}_{x}\mathrm{M}{\mathrm{A}}_{y}\mathrm{F}{\mathrm{A}}_{(1\ensuremath{-}x\ensuremath{-}y)}\mathrm{Pb}{\mathrm{I}}_{3}$, which reveals the ideal doping ratio for uniform stable alloying. This theory-experiment-combined study provides a clear microscopic picture of phase stability and segregation for mixed-cation perovskite solids.
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混合碘化铅钙钛矿中的质子迁移：从经典跳跃到深量子隧道
影响因子：
5.7
作者：
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通讯作者：
Li Xin Zheng
影响因子：
3.7
作者：
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通讯作者：
L. K. Teles;J. Furthmüller;L. Scolfaro;J. Leite;F. Bechstedt
影响因子：
16.6
作者：
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通讯作者：
Sargent EH
影响因子：
5.7
作者：
Brivio, Federico;Caetano, Clovis;Walsh, Aron
通讯作者：
Walsh, Aron
DOI：
10.1021/jz501896w
发表时间：
2014-10
期刊：
The journal of physical chemistry letters
影响因子：
--
作者：
W. Yin;Yanfa Yan;S. Wei
通讯作者：
W. Yin;Yanfa Yan;S. Wei