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Title: Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites

Abstract

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.

Authors:
; ;
Publication Date:
Research Org.:
Univ. of California, Davis, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1259914
Alternate Identifier(s):
OSTI ID: 1470072
Grant/Contract Number:  
FG02-03ER46053
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 113 Journal Issue: 28; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; hybrid halide perovskites; thermodynamic instability; solar cells; tolerance factor; enthalpy of formation

Citation Formats

Nagabhushana, G. P., Shivaramaiah, Radha, and Navrotsky, Alexandra. Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites. United States: N. p., 2016. Web. doi:10.1073/pnas.1607850113.
Nagabhushana, G. P., Shivaramaiah, Radha, & Navrotsky, Alexandra. Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites. United States. doi:10.1073/pnas.1607850113.
Nagabhushana, G. P., Shivaramaiah, Radha, and Navrotsky, Alexandra. Tue . "Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites". United States. doi:10.1073/pnas.1607850113.
@article{osti_1259914,
title = {Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites},
author = {Nagabhushana, G. P. and Shivaramaiah, Radha and Navrotsky, Alexandra},
abstractNote = {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.},
doi = {10.1073/pnas.1607850113},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 28,
volume = 113,
place = {United States},
year = {2016},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1607850113

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Cited by: 44 works
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