Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites
- Peter A. Rock Thermochemistry Laboratory and Nanomaterials in the Environment, Agriculture, and Technology Organized Research Unit, University of California, Davis, CA 95616
Hybrid perovskites, especially methylammonium lead iodide (MAPbI3), exhibit excellent solar power conversion efficiencies. However, their application is plagued by poor chemical and structural stability. In this paper, using direct calorimetric measurement of heats of formation, MAPbI3 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 MAPbCl3, MAPbBr3, MAPbI3, with only the chloride having a negative heat of formation. Finally, 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.
- Research Organization:
- Univ. of California, Davis, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- FG02-03ER46053
- OSTI ID:
- 1259914
- Alternate ID(s):
- OSTI ID: 1470072
- Journal Information:
- Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 113 Journal Issue: 28; ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of SciencesCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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