Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

Luo, Yanqi; Khoram, Parisa; Brittman, Sarah; Zhu, Zhuoying; Lai, Barry; Ong, Shyue Ping; Garnett, Erik C.; Fenning, David P.

doi:10.1002/adma.201703451

Title: Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

Journal Article · Fri Sep 29 00:00:00 EDT 2017 · Advanced Materials

DOI:https://doi.org/10.1002/adma.201703451· OSTI ID:1468624

Luo, Yanqi ^[1]; Khoram, Parisa ^[1]; Brittman, Sarah ^[2]; Zhu, Zhuoying ^[1]; Lai, Barry ^[3]; Ong, Shyue Ping ^[1]; Garnett, Erik C. ^[2];

^[1]

Univ. of California, San Diego, CA (United States). Dept. of Nanoengineering
FOM Inst. for Atomic and Molecular Physics (AMOLF), Amsterdam (Netherlands). Center for Nanophotonics
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Optoelectronic devices based on hybrid perovskites have demonstrated outstanding performance within a few years of intense study. However, commercialization of these devices requires barriers to their development to be overcome, such as their chemical instability under operating conditions. In order to investigate this instability and its consequences, the electric field applied to single crystals of methylammonium lead bromide (CH₃NH₃PbBr₃) is varied, and changes are mapped in both their elemental composition and photo-luminescence. Synchrotron-based nanoprobe X-ray fluorescence (nano-XRF) with 250 nm resolution reveals quasi-reversible field-assisted halide migration, with corresponding changes in photoluminescence. It is observed that higher local bromide concentration is correlated to superior optoelectronic performance in CH₃NH₃PbBr₃. A lower limit on the electromigration rate is calculated from these experiments and the motion is interpreted as vacancy-mediated migration based on nudged elastic band density functional theory (DFT) simulations. The XRF mapping data provide direct evidence of field-assisted ionic migration in a model hybrid-perovskite thin single crystal, while the link with photoluminescence proves that the halide stoichiometry plays a key role in the optoelectronic properties of the perovskite.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Netherlands Organization for Scientific Research (NWO); European Research Council (ERC); Koninklijke Philips N.V., Amsterdam (Netherlands); National Science Foundation (NSF)

Contributing Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Grant/Contract Number:: AC02-06CH11357; FP/2007‐2013; 337328; SC0012118; ACI‐1053575

OSTI ID:: 1468624

Alternate ID(s):: OSTI ID: 1395604

Journal Information:: Advanced Materials, Vol. 29, Issue 43; ISSN 0935-9648

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 71 works

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36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
nudged elastic band (NEB)
DFT computation
halide migration
hybrid perovskites
nanoprobe x-ray fluorescence
spatially resolved photoluminescence mapping

Title: Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

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