Published August 2023 | Version Published
Journal Article Open

Correlated anharmonicity and dynamic disorder control carrier transport in halide perovskites

  • 1. ROR icon Technical University of Munich
  • 2. ROR icon University of California, Berkeley
  • 3. ROR icon Columbia University
  • 4. ROR icon Lawrence Berkeley National Laboratory

Abstract

Halide pervoskites are an important class of semiconducting materials that hold great promise for optoelectronic applications. In this work we investigate the relationship between vibrational anharmonicity and dynamic disorder in this class of solids. Via a multiscale model parametrized from first-principles calculations, we demonstrate that the non-Gaussian lattice motion in halide perovskites is microscopically connected to the dynamic disorder of overlap fluctuations among electronic states. This connection allows us to rationalize the emergent differences in temperature-dependent mobilities of prototypical MAPbI₃ and MAPbBr₃ compounds across structural phase transitions, in agreement with experimental findings. Our analysis suggests that the details of vibrational anharmonicity and dynamic disorder can complement known predictors of electronic conductivity and can provide structure-property guidelines for the tuning of carrier transport characteristics in anharmonic semiconductors.

Copyright and License

© 2023 American Physical Society.

Acknowledgement

We thank Andrew M. Rappe for past collaborations on related work. Funding provided by the Alexander von Humboldt Foundation in the framework of the Sofja Kovalevskaja Award, endowed by the German Federal Ministry of Education and Research, by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) via Germany's Excellence Strategy–EXC 2089/1-390776260, and by TU Munich–IAS, funded by the German Excellence Initiative and the European Union Seventh Framework Programme under Grant Agreement No. 291763, are gratefully acknowledged. The work of D.R.R. was performed with support from the U.S. Department of Energy, Office of Science, Office of Advanced Scientific Computing Research, Scientific Discovery through Advanced Computing (SciDAC) program, under Award No. DE-SC0022088. This work was supported by the user program of the Molecular Foundry, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The Gauss Centre for Supercomputing e.V. is acknowledged for providing computing time through the John von Neumann Institute for Computing on the GCS Supercomputer JUWELS at Jülich Supercomputing Centre. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Data Availability

See Supplemental Material for theoretical and computational details.

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Additional details

Funding

Alexander von Humboldt Foundation
Federal Ministry of Education and Research
Deutsche Forschungsgemeinschaft
EXC 2089/1-390776260
European Research Council
291763
United States Department of Energy
DE-SC0022088
United States Department of Energy
DE-AC02-05CH11231