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Interstitial Occupancy by Extrinsic Alkali Cations in Perovskites and Its Impact on Ion Migration
Author(s) -
Cao Jie,
Tao Shu Xia,
Bobbert Peter A.,
Wong ChingPing,
Zhao Ni
Publication year - 2018
Publication title -
advanced materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 10.707
H-Index - 527
eISSN - 1521-4095
pISSN - 0935-9648
DOI - 10.1002/adma.201707350
Subject(s) - materials science , halide , perovskite (structure) , alkali metal , chemical physics , ion , lattice (music) , density functional theory , crystallographic defect , hysteresis , inorganic chemistry , computational chemistry , crystallography , condensed matter physics , chemistry , organic chemistry , physics , acoustics
Recent success in achieving highly stable Rb‐containing organolead halide perovskites has indicated the possibility of incorporating small monovalent cations, which cannot fit in the lead‐halide cage with an appropriate tolerance factor, into the perovskite lattice while maintaining a pure stable “black” phase. In this study, through a combined experimental and theoretical investigation by density functional theory (DFT) calculations on the incorporation of extrinsic alkali cations (Rb + , K + , Na + , and Li + ) in perovskite materials, the size‐dependent interstitial occupancy of these cations in the perovskite lattice is unambiguously revealed. Interestingly, DFT calculations predict the increased ion migration barriers in the lattice after the interstitial occupancy. To verify this prediction, ion migration behavior is characterized through hysteresis analysis of solar cells, electrical poling, temperature‐dependent conductivity, and time‐dependent photoluminescence measurements. The results collectively point to the suppression of ion migration after lattice interstitial occupancy by extrinsic alkali cations. The findings of this study provide new material design principles to manipulate the structural and ionic properties of multication perovskite materials.