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

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

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 (US)
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

Keywords

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

ASJC Scopus subject areas

General Energy

Online availability

10.1016/j.joule.2023.03.017

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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 - Weadock, Nicholas J.

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AU - Smith, Ian C.

AU - Ahammed, Ballal

AU - Krogstad, Matthew J.

AU - Ye, Feng

AU - Voneshen, David

AU - Gehring, Peter M.

AU - Rappe, Andrew M.

AU - Steinrück, Hans Georg

AU - Ertekin, Elif

AU - Karunadasa, Hemamala I.

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AU - Toney, Michael F.

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N2 - 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.

AB - 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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