Hybrid Perovskite at Full Tilt: Structure and Symmetry Relations of the Incommensurately Modulated Phase of Methylammonium Lead Bromide, MAPbBr3.

Dennis Wiedemann,Joachim Breternitz,Susan Schorr,Daniel W Paley

doi:10.1021/acs.jpclett.0c03722

Abstract

As energy-conversion materials, organic-inorganic hybrid perovskites remain a research- and finance-intensive topic. However, even for the arguably most iconic representatives, methylammonium and formamidinium lead halides, the crystal structures of several polymorphs have remained undetermined. Herein, we describe the incommensurately modulated structure of MAPbBr3 in (3+1)D superspace, as deduced from single-crystal X-ray diffractometry despite systematic twinning. Affirming the published average space group, we determined the superspace group Imma(00γ)s00 with cell parameters of a = 8.4657(9), b = 11.7303(12), c = 8.2388(8) Å, and q = 0.2022(8)c*. Via group-subgroup and mode analyses using irreducible representations, we establish symmetry relationships to the well-known cubic and orthorhombic polymorphs and break down distortions into the average tilt system a-b0a- and modulated contributions to tilt and deformation of the PbBr6 coordination polyhedra. Not only does our model fill a long-standing gap in structural knowledge, but it may also serve as a starting point for elucidating other modulated structures within this substance class.

Highlights

As energy-conversion materials, organic−inorganic hybrid perovskites remain a research- and finance-intensive topic
Organic−inorganic hybrid perovskites, in the strict sense of the word,[3] share the formula ABX3, with A being a molecular organic cation, B a metal cation, and X an anion mixed occupation may occur at any position
The crystal structures of these have been characterized with respect to the orientation/position of the organic cation,[4] their actual spacegroup type,[5] and their symmetry relationships and not all facts go undisputed

Summary

Introduction

As energy-conversion materials, organic−inorganic hybrid perovskites remain a research- and finance-intensive topic. The crystal structures of these have been characterized with respect to the orientation/position of the organic cation,[4] their actual spacegroup type,[5] and their symmetry relationships and not all facts go undisputed.

Results

Conclusion