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  4. Direct observation of dynamic symmetry breaking above room temperature in methylammonium lead iodide perovskite
 
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Direct observation of dynamic symmetry breaking above room temperature in methylammonium lead iodide perovskite
File(s)
acsenergy_notcubic_16.pdf (2.65 MB)
Published version
Author(s)
Beecheri, AN
Semonin, OE
Skelton, JM
Frost, JM
Terban, MW
more
Type
Journal Article
Abstract
Lead halide perovskites such as methylammonium lead triiodide (CH3NH3PbI3) have outstanding optical and electronic properties for photovoltaic applications, yet a full understanding of how this solution-processable material works so well is currently missing. Previous research has revealed that CH3NH3PbI3 possesses multiple forms of static disorder regardless of preparation method, which is surprising in light of its excellent performance. Using high energy resolution inelastic X-ray (HERIX) scattering, we measure phonon dispersions in CH3NH3PbI3 and find direct evidence for another form of disorder in single crystals: large-amplitude anharmonic zone edge rotational instabilities of the PbI6 octahedra that persist to room temperature and above, left over from structural phase transitions that take place tens to hundreds of degrees below. Phonon calculations show that the orientations of the methylammonium (CH3NH3+) couple strongly and cooperatively to these modes. The result is a noncentrosymmetric, instantaneous local structure, which we observe in atomic pair distribution function (PDF) measurements. This local symmetry breaking is unobservable by Bragg diffraction but can explain key material properties such as the structural phase sequence, ultralow thermal transport, and large minority charge carrier lifetimes despite moderate carrier mobility. From the PDF we estimate the size of the fluctuating symmetry broken domains to be between 1 and 3 nm in diameter.
Date Issued
2016-09-21
Date Acceptance
2016-09-21
Citation
ACS Energy Letters, 2016, 1 (4), pp.880-887
URI
http://hdl.handle.net/10044/1/44227
DOI
https://www.dx.doi.org/10.1021/acsenergylett.6b00381
ISSN
2380-8195
Publisher
American Chemical Society
Start Page
880
End Page
887
Journal / Book Title
ACS Energy Letters
Volume
1
Issue
4
Copyright Statement
© 2016 The Authors.This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html), which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000389620400038&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
AUGMENTED-WAVE METHOD
HALIDE PEROVSKITES
SOLAR-CELLS
PHASE-TRANSITIONS
HIGH-PERFORMANCE
ORGANIC CATIONS
SCATTERING
SPECTROSCOPY
CH3NH3PBI3
CRYSTAL
cond-mat.mtrl-sci
Publication Status
Published
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