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The Role of Chlorine in the Formation Process of “CH 3 NH 3 PbI 3‐x Cl x ” Perovskite
Author(s) -
Yu Hui,
Wang Feng,
Xie Fangyan,
Li Wenwu,
Chen Jian,
Zhao Ni
Publication year - 2014
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.201401872
Subject(s) - halide , perovskite (structure) , materials science , annealing (glass) , crystallization , chlorine , crystal structure , inorganic chemistry , crystallography , chemistry , organic chemistry , metallurgy , composite material
CH 3 NH 3 PbI 3‐x Cl x is a commonly used chemical formula to represent the methylammonium lead halide perovskite fabricated from mixed chlorine‐ and iodine‐containing salt precursors. Despite the rapid progress in improving its photovoltaic efficiency, fundamental questions remain regarding the atomic ratio of Cl in the perovskite as well as the reaction mechanism that leads to its formation and crystallization. In this work we investigated these questions through a combination of chemical, morphological, structural and thermal characterizations. The elemental analyses reveal unambiguously the negligible amount of Cl atoms in the CH 3 NH 3 PbI 3‐x Cl x perovskite. By studying the thermal characteristics of methylammonium halides as well as the annealing process in a polymer/perovskite/FTO glass structure, we show that the formation of the CH 3 NH 3 PbI 3‐x Cl x perovskite is likely driven by release of gaseous CH 3 NH 3 Cl (or other organic chlorides) through an intermediate organometal mixed halide phase. Furthermore, the comparative study on CH 3 NH 3 I/PbCl 2 and CH 3 NH 3 I/PbI 2 precursor combinations with different molar ratios suggest that the initial introduction of a CH 3 NH 3 + rich environment is critical to slow down the perovskite formation process and thus improve the growth of the crystal domains during annealing; accordingly, the function of Cl − is to facilitate the release of excess CH 3 NH 3 + at a relatively low annealing temperatures.