CaltechAUTHORS
  A Caltech Library Service

Correlating Broadband Photoluminescence with Structural Dynamics in Layered Hybrid Halide Perovskites

Koegel, Alexandra A. and Mozur, Eve M. and Oswald, Iain W. H. and Jalarvo, Niina H. and Prisk, Timothy R. and Tyagi, Madhusudan and Neilson, James R. (2022) Correlating Broadband Photoluminescence with Structural Dynamics in Layered Hybrid Halide Perovskites. Journal of the American Chemical Society, 144 (3). pp. 1313-1322. ISSN 0002-7863. doi:10.1021/jacs.1c11217. https://resolver.caltech.edu/CaltechAUTHORS:20220216-31310748

This is the latest version of this item.

[img] PDF - Supplemental Material
See Usage Policy.

5MB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20220216-31310748

Abstract

The emission of white light from a single material is atypical and is of interest for solid-state lighting applications. Broadband light emission has been observed in some layered perovskite derivatives, A₂PbBr₄ (A = R-NH₃⁺), and correlates with static structural distortions corresponding to out-of-plane tilting of the lead bromide octahedra. While materials with different organic cations can yield distinct out-of-plane tilts, the underlying origin of the octahedral tilting remains poorly understood. Using high energy resolution (e.g., quasi-elastic) neutron scattering, this contribution details the rotational dynamics of the organic cations in A₂PbBr₄ materials where A = n-butylammonium (nBA), 1,8-diaminooctammonium (ODA), and 4-aminobutyric acid (GABA). The organic cation dynamics differentiate (nBA)₂PbBr₄ from (ODA)PbBr₄ or (GABA)₂PbBr₄ in that the larger spatial extent of dynamics of nBA yields a larger effective cation radius. The larger effective volume of the nBA cation in (nBA)₂PbBr₄ yields a closer to ideal A-site geometry, preventing the out-of-plane tilt and broadband luminescence. In all three compounds, we observe hydrogen dynamics attributed to rotation of the ammonium headgroup and at a time scale faster than the white light photoluminescence studied by time-correlated single photon counting spectroscopy. This supports a previous assignment of the broadband emission as resulting from a single ensemble, such that the emissive excited state experiences many local structures faster than the emissive decay. The findings presented here highlight the role of the organic cation and its dynamics in hybrid organic–inorganic perovskites and white light emission.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.1c11217DOIArticle
ORCID:
AuthorORCID
Koegel, Alexandra A.0000-0001-8045-3226
Mozur, Eve M.0000-0002-7960-4135
Jalarvo, Niina H.0000-0003-0644-6866
Neilson, James R.0000-0001-9282-5752
Additional Information:© 2022 American Chemical Society. Received 22 October 2021. Published online 14 January 2022. Published in issue 26 January 2022. The work at Colorado State University was supported by grant DE-SC0016083 funded by the U.S. Department of Energy, Office of Science. J.R.N. and A.A.K. acknowledge support from Research Corporation for Science Advancement through a Cottrell Scholar Award, and J.R.N. thanks the A.P. Sloan Foundation for assistance provided from a Sloan Research Fellowship. A portion of this research used resources at the Center for Neutron Research, operated by the National Institute of Standards and Technology (NIST) and the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. Access to the High Flux Backscattering Spectrometer was provided by the Center for High Resolution Neutron Scattering, a partnership between the National Institute of Standards and Technology and the National Science Foundation under Agreement No. DMR-2010 792. The computing resources for the QENS calculations were made available through the ICEMAN project, funded by the Laboratory Directed Research and Development program at Oak Ridge National Laboratory. The authors wish to thank the Analytical Resources Core at Colorado State University for instrument access, training and assistance with sample analysis. The authors thank Dr. Matthew D. Smith and Professor Hemamala Karunadasa of Stanford University (Department of Chemistry, Stanford, CA) for openly sharing their photoluminescence data, in addition to Dr. A. J. Ramireza-Cuesta (Oak Ridge National Laboratory), Professor Annalise E. Maughan (Colorado School of Mines), and Dr. Allison Wustrow (Colorado State University) for many helpful discussions. The identification of any commercial product or trade name does not imply endorsement or recommendation by NIST. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0016083
Cottrell Scholar of Research CorporationUNSPECIFIED
Alfred P. Sloan FoundationUNSPECIFIED
NSFDMR-2010 792
Issue or Number:3
DOI:10.1021/jacs.1c11217
Record Number:CaltechAUTHORS:20220216-31310748
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220216-31310748
Official Citation:Correlating Broadband Photoluminescence with Structural Dynamics in Layered Hybrid Halide Perovskites Alexandra A. Koegel, Eve M. Mozur, Iain W. H. Oswald, Niina H. Jalarvo, Timothy R. Prisk, Madhusudan Tyagi, and James R. Neilson Journal of the American Chemical Society 2022 144 (3), 1313-1322 DOI: 10.1021/jacs.1c11217
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:113470
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:16 Feb 2022 10:04
Last Modified:16 Feb 2022 22:37

Available Versions of this Item

  • Correlating Broadband Photoluminescence with Structural Dynamics in Layered Hybrid Halide Perovskites. (deposited 16 Feb 2022 10:04) [Currently Displayed]

Commentary/Response Threads

  • Koegel, Alexandra A. and Mozur, Eve M. and Oswald, Iain W. H. and Jalarvo, Niina H. and Prisk, Timothy R. and Tyagi, Madhusudan and Neilson, James R. Correlating Broadband Photoluminescence with Structural Dynamics in Layered Hybrid Halide Perovskites. (deposited 16 Feb 2022 10:04) [Currently Displayed]

Repository Staff Only: item control page