The nature of dynamic local order in CH3NH3PbI3 and CH3NH3PbBr3

Nicholas J. Weadock; Tyler C. Sterling; Julian A. Vigil; Aryeh Gold-Parker; Ian C. Smith; Ballal Ahammed; Matthew J. Krogstad; Feng Ye; David Voneshen; Peter M. Gehring; Andrew M. Rappe; Hans Georg Steinrück; Elif Ertekin; Hemamala I. Karunadasa; Dmitry Reznik; Michael F. Toney

doi:10.1016/j.joule.2023.03.017

The nature of dynamic local order in CH₃NH₃PbI₃ and CH₃NH₃PbBr₃

Nicholas J. Weadock, Tyler C. Sterling, Julian A. Vigil, Aryeh Gold-Parker, Ian C. Smith, Ballal Ahammed, Matthew J. Krogstad, Feng Ye, David Voneshen, Peter M. Gehring, Andrew M. Rappe, Hans Georg Steinrück, Elif Ertekin, Hemamala I. Karunadasa, Dmitry Reznik, Michael F. Toney

Single Crystal Diffraction

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

Hybrid lead-halide perovskites (LHPs) are semiconductors with novel properties that are distinctively governed by structural fluctuations. Diffraction experiments sensitive to long-range order reveal a cubic structure in the device-relevant, high-temperature phase. Local probes find additional short-range order with lower symmetry that may govern structure-function relationships. However, our understanding is impeded by unresolved dimensionality, participating atoms, and dynamics of short-range order. Here, we determine the true structure of two hybrid LHPs, CH₃NH₃PbI₃ and CH₃NH₃PbBr₃, using a combination of single-crystal diffuse scattering, neutron inelastic spectroscopy, and molecular dynamics simulations. The remarkable collective dynamics, not observed in previous studies, consist of a network of local, two-dimensional, circular regions of dynamically tilting lead-halide octahedra (lower symmetry) that induce longer-range intermolecular CH₃NH₃⁺ correlations. The dynamic local structure may introduce transient ferroelectric or antiferroelectric domains that increase charge carrier lifetimes and strongly affect halide migration, a poorly understood degradation mechanism.

Original language	English
Pages (from-to)	1051-1066
Number of pages	16
Journal	Joule
Volume	7
Issue number	5
DOIs	https://doi.org/10.1016/j.joule.2023.03.017
State	Published - May 17 2023

Funding

The authors acknowledge helpful discussions with Xixi Qin, Volker Blum, and Alex Zunger. We thank Maximilian Schilcher and David Egger (both TU Munich) for providing their MD simulations for comparison. This work (X-ray and neutron scattering, interpretation) was supported by the Center for Hybrid Organic Inorganic Semiconductors for Energy and Energy Frontier Research Center funded by the Office of Basic Energy Sciences , an office of science within the US Department of Energy (DOE). J.A.V. acknowledges fellowship support from the Stanford University Office of the Vice Provost of Graduate Education and the National Science Foundation Graduate Research Fellowship Program under grant no. DGE – 1656518 (sample preparation, NDS and XDS data collection). H.I.K. acknowledges funding through the DOE Office of Basic Energy Sciences , Division of Materials Science and Engineering under contract no. DE-AC02-76SF0051 (sample preparation). B.A. and E.E. acknowledge funding from the National Science Foundation award OAC 2118201 (MD simulations). T.C.S. and D.R. acknowledge funding by the DOE Office of Basic Energy Sciences , Office of Science under contract no. DE-SC0006939 (NIS data collection, S(Q,E) calculations, interpretation). A.M.R. acknowledges support from the National Science Foundation , Science and Technology Centers Program under grant number DMR-2019444 (supplemental MD simulations). A portion of this work (S(Q) calculations) used the Summit supercomputer, which is supported by the National Science Foundation (awards ACI-1532235 and ACI-1532236 ), the University of Colorado Boulder, and Colorado State University. The Summit supercomputer is a joint effort of the University of Colorado Boulder and Colorado State University. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy , Office of Science , Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357 . Experiments at the ISIS Pulsed Neutron and Muon Source were supported by a beamtime allocation from the Science and Technology Facilities Council. Any mention of commercial products here is for information only; it does not imply recommendation or endorsement by the National Institute of Standards and Technology. The authors acknowledge helpful discussions with Xixi Qin, Volker Blum, and Alex Zunger. We thank Maximilian Schilcher and David Egger (both TU Munich) for providing their MD simulations for comparison. This work (X-ray and neutron scattering, interpretation) was supported by the Center for Hybrid Organic Inorganic Semiconductors for Energy and Energy Frontier Research Center funded by the Office of Basic Energy Sciences, an office of science within the US Department of Energy (DOE). J.A.V. acknowledges fellowship support from the Stanford University Office of the Vice Provost of Graduate Education and the National Science Foundation Graduate Research Fellowship Program under grant no. DGE – 1656518 (sample preparation, NDS and XDS data collection). H.I.K. acknowledges funding through the DOE Office of Basic Energy Sciences, Division of Materials Science and Engineering under contract no. DE-AC02-76SF0051 (sample preparation). B.A. and E.E. acknowledge funding from the National Science Foundation award OAC 2118201 (MD simulations). T.C.S. and D.R. acknowledge funding by the DOE Office of Basic Energy Sciences, Office of Science under contract no. DE-SC0006939 (NIS data collection, S(Q,E) calculations, interpretation). A.M.R. acknowledges support from the National Science Foundation, Science and Technology Centers Program under grant number DMR-2019444 (supplemental MD simulations). A portion of this work (S(Q) calculations) used the Summit supercomputer, which is supported by the National Science Foundation (awards ACI-1532235 and ACI-1532236), the University of Colorado Boulder, and Colorado State University. The Summit supercomputer is a joint effort of the University of Colorado Boulder and Colorado State University. A portion of this research used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract no. DE-AC02-06CH11357. Experiments at the ISIS Pulsed Neutron and Muon Source were supported by a beamtime allocation from the Science and Technology Facilities Council. Any mention of commercial products here is for information only; it does not imply recommendation or endorsement by the National Institute of Standards and Technology. Conceptualization, N.J.W. H.-G.S. and M.F.T.; methodology, N.J.W. T.C.S. B.A. and E.E.; investigation, N.J.W. T.C.S. J.A.V. H.-G.S. P.M.G. F.Y. M.J.K. D.V. and D.R.; resources, J.A.V. A.G.-P. I.C.S. B.A. A.M.R. H.I.K. E.E. F.Y. M.J.K. and D.V.; data curation, B.A. A.M.R. E.E. F.Y. M.J.K. and D.V.; visualization, N.J.W. and T.C.S.; writing – original draft, N.J.W. T.C.S. and J.A.V.; writing – review & editing, all authors; supervision, D.R. and M.F.T.; funding acquisition, M.F.T. D.R. E.E. H.I.K. and A.M.R. The authors declare no competing interests. We support inclusive, diverse, and equitable conduct of research. One or more of the authors of this paper self-identifies as an underrepresented ethnic minority in their field of research or within their geographical location. One or more of the authors of this paper self-identifies as a gender minority in their field of research. One or more of the authors of this paper received support from a program designed to increase minority representation in their field of research.

Funders	Funder number
Alex Zunger
ISIS
National Science Foundation , Science and Technology Centers Program	ACI-1532235, ACI-1532236, DMR-2019444
National Science Foundation, Science and Technology Centers Program
National Science Foundation	DGE – 1656518
U.S. Department of Energy
National Institute of Standards and Technology
Office of Science	DE-SC0006939
Basic Energy Sciences
Oak Ridge National Laboratory
Colorado State University	DE-AC02-06CH11357
University of Colorado Boulder
Division of Materials Sciences and Engineering	OAC 2118201, DE-AC02-76SF0051
Office of the Vice Provost for Graduate Education, Stanford University
Science and Technology Facilities Council

Keywords

diffuse scattering
ion migration
local structure
metal halide perovskites
molecular dynamics simulations

Access to Document

10.1016/j.joule.2023.03.017

Cite this

Weadock, N. J., Sterling, T. C., Vigil, J. A., Gold-Parker, A., Smith, I. C., Ahammed, B., Krogstad, M. J., Ye, F., Voneshen, D., Gehring, P. M., Rappe, A. M., Steinrück, H. G., Ertekin, E., Karunadasa, H. I., Reznik, D., & Toney, M. F. (2023). The nature of dynamic local order in CH₃NH₃PbI₃ and CH₃NH₃PbBr₃. Joule, 7(5), 1051-1066. https://doi.org/10.1016/j.joule.2023.03.017

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abstract = "Hybrid lead-halide perovskites (LHPs) are semiconductors with novel properties that are distinctively governed by structural fluctuations. Diffraction experiments sensitive to long-range order reveal a cubic structure in the device-relevant, high-temperature phase. Local probes find additional short-range order with lower symmetry that may govern structure-function relationships. However, our understanding is impeded by unresolved dimensionality, participating atoms, and dynamics of short-range order. Here, we determine the true structure of two hybrid LHPs, CH3NH3PbI3 and CH3NH3PbBr3, using a combination of single-crystal diffuse scattering, neutron inelastic spectroscopy, and molecular dynamics simulations. The remarkable collective dynamics, not observed in previous studies, consist of a network of local, two-dimensional, circular regions of dynamically tilting lead-halide octahedra (lower symmetry) that induce longer-range intermolecular CH3NH3+ correlations. The dynamic local structure may introduce transient ferroelectric or antiferroelectric domains that increase charge carrier lifetimes and strongly affect halide migration, a poorly understood degradation mechanism.",

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AU - Ahammed, Ballal

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