Role of lattice distortion and A site cation in the phase transitions of methylammonium lead halide perovskites

Journal article

Harwell, Jonathon R, Payne, Julia L, Sajjad, T., Heutz, Frank JL, Dawson, Daniel M, Whitfield, Pamela S, Irvine, John TS, Samuel, Ifor DW and Carpenter, Michael A (2018). Role of lattice distortion and A site cation in the phase transitions of methylammonium lead halide perovskites. Physical Review Materials. 2 (6), pp. 065404-065404. https://doi.org/https://www.doi.org/10.1103/PhysRevMaterials.2.065404
AuthorsHarwell, Jonathon R, Payne, Julia L, Sajjad, T., Heutz, Frank JL, Dawson, Daniel M, Whitfield, Pamela S, Irvine, John TS, Samuel, Ifor DW and Carpenter, Michael A
Abstract

The rapid increase in power conversion efficiencies of photovoltaic devices incorporating lead halide perovskites has resulted in intense interest in the cause of their excellent properties. In the present paper, resonant ultrasound spectroscopy has been used to determine the elastic and anelastic properties of
CH3NH3PbX3(where X=Cl, Br, or I) and CD3ND3PbI3 perovskites in the 5–380 K temperature range. This is coupled with differential scanning calorimetry, variable temperature neutron powder diffraction, and variable temperature photoluminescence studies to provide insights into the underlying processes and structural instabilities in the crystal structure. By comparing measurements on CH3NH3PbI3
with the deuterated equivalent, it has been possible to distinguish processes which are related to the hydrogen bonding between the methylammonium cation and the perovskite framework. We observe that replacing hydrogen with deuterium has a significant impact on both the elastic and photophysical properties, which shows that hydrogen bonding plays a crucial role in the material performance. Temperature-dependent photoluminescence studies show that the light emission is unaffected by the tetragonal-orthorhombic phase transition, but a blueshift in the emission and a steep increase in photoluminescence quantum yield are seen at temperatures below 150 K. Finally, observations of peaks in acoustic loss occurring in CH3NH3PbCl3 have revealed freezing processes in the vicinity of ∼150−170K, with activation energies in the range of 300 to 650 meV. These processes are attributed to freezing of the motion of methylammonium cations, and could explain the changes in photoluminescence seen in CH3NH3PbI3 at the same temperature.

© 2018 American Physical Society. This work has been made available online in accordance with the publisher’s policies. This is the author created, accepted version manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at: https://doi.org/10.1103/PhysRevMaterials.2.065404

Year2018
JournalPhysical Review Materials
Journal citation2 (6), pp. 065404-065404
PublisherAPS
ISSN2475-9953
Digital Object Identifier (DOI)https://doi.org/https://www.doi.org/10.1103/PhysRevMaterials.2.065404
Publication dates
Print20 Jun 2018
Online20 Jun 2018
Publication process dates
Accepted02 Feb 2018
Deposited04 Feb 2020
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