Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites

G. P. Nagabhushana, Radha Shivaramaiah, Alexandra Navrotsky

Research output: Contribution to journalArticlepeer-review

233 Scopus citations

Abstract

Hybrid perovskites, especially methylammonium lead iodide (MAPbI3), 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, 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. 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.

Original languageEnglish (US)
Pages (from-to)7717-7721
Number of pages5
JournalProceedings of the National Academy of Sciences of the United States of America
Volume113
Issue number28
DOIs
StatePublished - Jul 12 2016
Externally publishedYes

Keywords

  • Enthalpy of formation
  • Hybrid halide perovskites
  • Solar cells
  • Thermodynamic instability
  • Tolerance factor

ASJC Scopus subject areas

  • General

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