Acoustic phonon lifetimes limit thermal transport in methylammonium lead iodide
File(s)pnas_mapi_18.pdf (906.33 KB)
Published version
Author(s)
Type
Journal Article
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.
Date Issued
2018-11-20
Date Acceptance
2018-10-16
Citation
Proceedings of the National Academy of Sciences of the United States of America, 2018, 115 (47), pp.11905-11910
ISSN
0027-8424
Publisher
National Academy of Sciences
Start Page
11905
End Page
11910
Journal / Book Title
Proceedings of the National Academy of Sciences of the United States of America
Volume
115
Issue
47
Copyright Statement
© 2018 the Author(s). This open access article is distributed under Creative Commons Attribution-NonCommercial-NoDerivatives License 4.0 (CC BY-NC-ND - https://creativecommons.org/licenses/by-nc-nd/4.0/).
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000450642800037&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Multidisciplinary Sciences
Science & Technology - Other Topics
hybrid perovskite
thermal conductivity
inelastic neutron spectroscopy
lattice dynamics
solar cells
INELASTIC NEUTRON-SCATTERING
HALIDE PEROVSKITES
CONDUCTIVITY
DECAY
SEMICONDUCTORS
TRANSITIONS
CH3NH3PBI3
Publication Status
Published
Date Publish Online
2018-11-06