Premium
Pressure‐Dependent Polymorphism and Band‐Gap Tuning of Methylammonium Lead Iodide Perovskite
Author(s) -
Jiang Shaojie,
Fang Yanan,
Li Ruipeng,
Xiao Hai,
Crowley Jason,
Wang Chenyu,
White Timothy J.,
Goddard William A.,
Wang Zhongwu,
Baikie Tom,
Fang Jiye
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201601788
Subject(s) - photoluminescence , orthorhombic crystal system , density functional theory , tetragonal crystal system , perovskite (structure) , band gap , ambient pressure , materials science , synchrotron , crystallography , phase (matter) , chemistry , iodide , crystal structure , computational chemistry , optoelectronics , inorganic chemistry , optics , thermodynamics , physics , organic chemistry
We report the pressure‐induced crystallographic transitions and optical behavior of MAPbI 3 (MA=methylammonium) using in situ synchrotron X‐ray diffraction and laser‐excited photoluminescence spectroscopy, supported by density functional theory (DFT) calculations using the hybrid functional B3PW91 with spin‐orbit coupling. The tetragonal polymorph determined at ambient pressure transforms to a ReO 3 ‐type cubic phase at 0.3 GPa. Upon continuous compression to 2.7 GPa this cubic polymorph converts into a putative orthorhombic structure. Beyond 4.7 GPa it separates into crystalline and amorphous fractions. During decompression, this phase‐mixed material undergoes distinct restoration pathways depending on the peak pressure. In situ pressure photoluminescence investigation suggests a reduction in band gap with increasing pressure up to ≈0.3 GPa and then an increase in band gap up to a pressure of 2.7 GPa, in excellent agreement with our DFT calculation prediction.