Thermodynamic origin of photoinstability in the CH3NH3Pb(I1-xBrx)3 hybrid halide perovskite alloy

Federico Brivio, Clovis Caetano, Aron Walsh

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179 Citations (Scopus)


The formation of solid-solutions of iodide, bromide, and chloride provides the means to control the structure, band gap, and stability of hybrid halide perovskite semiconductors for photovoltaic applications. We report a computational investigation of the CH3NH3PbI3/CH3NH3PbBr3 alloy from density functional theory with a thermodynamic analysis performed within the generalized quasi-chemical approximation. We construct the phase diagram and identify a large miscibility gap, with a critical temperature of 343 K. The observed photoinstability in some mixed-halide solar cells is explained by the thermodynamics of alloy formation, where an initially homogeneous solution is subject to spinodal decomposition with I and Br-rich phases, which is further complicated by a wide metastable region defined by the binodal line.

Original languageEnglish
Pages (from-to)1083-1087
Number of pages5
JournalJournal of Physical Chemistry Letters
Issue number6
Publication statusPublished - 17 Mar 2016

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