Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 113, Issue 28, Pages 7717-7721Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.1607850113
Keywords
hybrid halide perovskites; thermodynamic instability; solar cells; tolerance factor; enthalpy of formation
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Funding
- US Department of Energy [DE-FG02-03ER46053]
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Hybrid perovskites, especially methylammonium lead iodide (MAPbI(3)), exhibit excellent solar power conversion efficiencies. However, their application is plagued by poor chemical and structural stability. Using direct calorimetric measurement of heats of formation, MAPbI(3) is shown to be thermodynamically unstable with respect to decomposition to lead iodide and methylammonium iodide, even in the absence of ambient air or light or heat-induced defects, thus limiting its long-term use in devices. The formation enthalpy from binary halide components becomes less favorable in the order MAPbCl(3), MAPbBr(3), MAPbI(3), with only the chloride having a negative heat of formation. Optimizing the geometric match of constituents as measured by the Goldschmidt tolerance factor provides a potentially quantifiable thermodynamic guide for seeking chemical substitutions to enhance stability.
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