Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide

Aryeh Gold-Parker, Peter M. Gehring, Jonathan M. Skelton, Ian C. Smith, Dan Parshall, Jarvist M. Frost, Hemamala I. Karunadasa, Aron Walsh, Michael F. Toney

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

Hybrid organic–inorganic perovskites (HOIPs) have become an important class of semiconductors for solar cells and other optoelectronic applications. Electron–phonon coupling plays a critical role in all optoelectronic devices, and although the lattice dynamics and phonon frequencies of HOIPs have been well studied, little attention has been given to phonon lifetimes. We report high-precision momentum-resolved measurements of acoustic phonon lifetimes in the hybrid perovskite methylammonium lead iodide (MAPI), using inelastic neutron spectroscopy to provide high-energy resolution and fully deuterated single crystals to reduce incoherent scattering from hydrogen. Our measurements reveal extremely short lifetimes on the order of picoseconds, corresponding to nanometer mean free paths and demonstrating that acoustic phonons are unable to dissipate heat efficiently. Lattice-dynamics calculations using ab initio third-order perturbation theory indicate that the short lifetimes stem from strong three-phonon interactions and a high density of low-energy optical phonon modes related to the degrees of freedom of the organic cation. Such short lifetimes have significant implications for electron–phonon coupling in MAPI and other HOIPs, with direct impacts on optoelectronic devices both in the cooling of hot carriers and in the transport and recombination of band edge carriers. These findings illustrate a fundamental difference between HOIPs and conventional photovoltaic semiconductors and demonstrate the importance of understanding lattice dynamics in the effort to develop metal halide perovskite optoelectronic devices.

Original languageEnglish
Pages (from-to)11905-11910
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume115
Issue number47
DOIs
Publication statusPublished - 2018 Nov 20

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Phonons
Iodides
Acoustics
Hot Temperature
Semiconductors
Equipment and Supplies
Neutrons
Genetic Recombination
Lead
methylamine
Cations
Hydrogen
Spectrum Analysis
Metals

All Science Journal Classification (ASJC) codes

  • General

Cite this

Gold-Parker, A., Gehring, P. M., Skelton, J. M., Smith, I. C., Parshall, D., Frost, J. M., ... Toney, M. F. (2018). Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide. Proceedings of the National Academy of Sciences of the United States of America, 115(47), 11905-11910. https://doi.org/10.1073/pnas.1812227115
Gold-Parker, Aryeh ; Gehring, Peter M. ; Skelton, Jonathan M. ; Smith, Ian C. ; Parshall, Dan ; Frost, Jarvist M. ; Karunadasa, Hemamala I. ; Walsh, Aron ; Toney, Michael F. / Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide. In: Proceedings of the National Academy of Sciences of the United States of America. 2018 ; Vol. 115, No. 47. pp. 11905-11910.
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Gold-Parker, A, Gehring, PM, Skelton, JM, Smith, IC, Parshall, D, Frost, JM, Karunadasa, HI, Walsh, A & Toney, MF 2018, 'Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide', Proceedings of the National Academy of Sciences of the United States of America, vol. 115, no. 47, pp. 11905-11910. https://doi.org/10.1073/pnas.1812227115

Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide. / Gold-Parker, Aryeh; Gehring, Peter M.; Skelton, Jonathan M.; Smith, Ian C.; Parshall, Dan; Frost, Jarvist M.; Karunadasa, Hemamala I.; Walsh, Aron; Toney, Michael F.

In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 115, No. 47, 20.11.2018, p. 11905-11910.

Research output: Contribution to journalArticle

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T1 - Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide

AU - Gold-Parker, Aryeh

AU - Gehring, Peter M.

AU - Skelton, Jonathan M.

AU - Smith, Ian C.

AU - Parshall, Dan

AU - Frost, Jarvist M.

AU - Karunadasa, Hemamala I.

AU - Walsh, Aron

AU - Toney, Michael F.

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AB - Hybrid organic–inorganic perovskites (HOIPs) have become an important class of semiconductors for solar cells and other optoelectronic applications. Electron–phonon coupling plays a critical role in all optoelectronic devices, and although the lattice dynamics and phonon frequencies of HOIPs have been well studied, little attention has been given to phonon lifetimes. We report high-precision momentum-resolved measurements of acoustic phonon lifetimes in the hybrid perovskite methylammonium lead iodide (MAPI), using inelastic neutron spectroscopy to provide high-energy resolution and fully deuterated single crystals to reduce incoherent scattering from hydrogen. Our measurements reveal extremely short lifetimes on the order of picoseconds, corresponding to nanometer mean free paths and demonstrating that acoustic phonons are unable to dissipate heat efficiently. Lattice-dynamics calculations using ab initio third-order perturbation theory indicate that the short lifetimes stem from strong three-phonon interactions and a high density of low-energy optical phonon modes related to the degrees of freedom of the organic cation. Such short lifetimes have significant implications for electron–phonon coupling in MAPI and other HOIPs, with direct impacts on optoelectronic devices both in the cooling of hot carriers and in the transport and recombination of band edge carriers. These findings illustrate a fundamental difference between HOIPs and conventional photovoltaic semiconductors and demonstrate the importance of understanding lattice dynamics in the effort to develop metal halide perovskite optoelectronic devices.

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