Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite

Shaojie Jiang; Yanan Fang; Ruipeng Li; Hai Xiao; Jason Crowley; Chenyu Wang; Timothy J White; William A Goddard 3rd; Zhongwu Wang; Tom Baikie; Jiye Fang

doi:10.1002/anie.201601788

Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite

Angew Chem Int Ed Engl. 2016 May 23;55(22):6540-4. doi: 10.1002/anie.201601788. Epub 2016 Apr 21.

Authors

Shaojie Jiang¹, Yanan Fang², Ruipeng Li³, Hai Xiao⁴, Jason Crowley⁴, Chenyu Wang⁵, Timothy J White⁶, William A Goddard 3rd⁷, Zhongwu Wang³, Tom Baikie⁸, Jiye Fang^{9

10}

Affiliations

¹ Materials Science and Engineering Program, State University of New York at Binghamton, Binghamton, NY, 13902, USA.
² Energy Research Institute@NTU (ERI@N), Nanyang Technological University, 50 Nanyang Drive, Singapore, 637553, Republic of Singapore.
³ Cornell High Energy Synchrotron Source, Cornell University, Ithaca, NY, 14853, USA.
⁴ Materials and Process Simulation Center (MSC) and Joint Center for Artificial Photosynthesis (JCAP), California Institute of Technology, Pasadena, CA, 91125, USA.
⁵ Department of Chemistry, State University of New York at Binghamton, Binghamton, NY, 13902, USA.
⁶ School of Materials Science and Engineering, Nanyang Technological University, Nanyang Avenue, Singapore, 639798, Republic of Singapore.
⁷ Materials and Process Simulation Center (MSC) and Joint Center for Artificial Photosynthesis (JCAP), California Institute of Technology, Pasadena, CA, 91125, USA. wag@wag.caltech.edu.
⁸ Energy Research Institute@NTU (ERI@N), Nanyang Technological University, 50 Nanyang Drive, Singapore, 637553, Republic of Singapore. tbaikie@ntu.edu.sg.
⁹ Materials Science and Engineering Program, State University of New York at Binghamton, Binghamton, NY, 13902, USA. jfang@binghamton.edu.
¹⁰ Department of Chemistry, State University of New York at Binghamton, Binghamton, NY, 13902, USA. jfang@binghamton.edu.

PMID: 27101324
DOI: 10.1002/anie.201601788

Abstract

We report the pressure-induced crystallographic transitions and optical behavior of MAPbI3 (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 ReO3 -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.

Keywords: band gap; halide perovskite; high-pressure chemistry; phase transitions; photoluminescence.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.