Intrinsic thermal decomposition pathways of lead halide perovskites APbX3

Azat F. Akbulatov, Vyacheslav M. Martynenko, Lyubov A. Frolova, Nadezhda N. Dremova, Ivan Zhidkov, Sergey A. Tsarev, Sergey Yu Luchkin, Ernst Z. Kurmaev, Sergey M. Aldoshin, Keith J. Stevenson, Pavel A. Troshin

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27 Citations (Scopus)

Abstract

We present a systematic study on intrinsic thermal stability of a series of complex lead halides APbX3, used as absorber materials in perovskite solar cells. Mechanistically, the perovskites APbX3 were shown to decompose under thermal stress conditions initially to form PbX2 and AX salts. Thermolysis of the latter yields multiple volatile products, which were analyzed by mass spectrometry. We reconfirmed the CH3I + NH3 decomposition route for MAPbI3 and observed for the first time CH4, ethylene and HI (formed from CH3I). In case of FAPbI3, the formation of 2-aminomalononitrile (not 1,3,5-triazine as reported recently) was revealed along with NH4I and HCN. Importantly, the stability of the lead halide perovskites shows a good correlation with the volatility of univalent cation halides (or their decomposition products) incorporated in their structure. In particular, MAPbX3 have the lowest stability since they incorporate the most volatile (or easy to decompose) methylammonium halides MAX. On the contrary, all-inorganic CsPbX3 show remarkable compositional stability since CsBr and CsI are non-volatile under the solar cell operation conditions. The established relationship and material decomposition pathways provide important guidelines for rational design of novel absorber materials for perovskite solar cells with improved thermal stability suitable for terrestrial and space applications.

Original languageEnglish
Article number110559
JournalSolar Energy Materials and Solar Cells
Volume213
DOIs
Publication statusPublished - 15 Aug 2020

Keywords

  • Decomposition pathways
  • Mass spectrometry
  • Perovskite solar cells
  • Prebiotic HCN chemistry
  • Thermal decomposition

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