Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites
Abstract
Intrinsic photophysical origin of lead halide perovskites (LHPs) succeeding in optolectronic applications still remains hotly debated. In this study, by using the ultrafast X-ray transient absorption spectroscopy, we successfully tracked the fate of photogenerated charge carriers at room temperature within the thin films of two classic LHPs, namely MAPbBr3 (MA: CH3NH3) and FAPbBr3 (FA: CH(NH2)2). We clearly observed in both thin films that the hole polaron is formed by localizing the photogenerated hole at Br 4p orbital and concurrently distorting the local structure surrounding Br atom after the photoexcitation. Furthermore, the bigger cation FA in the cavity of [PbBr6]4- octahedral framework induces larger hole polaron effect due to its p orbital hybridization into valence and conduction bands, correlating with the slower charge carrier recombination dynamics. Our direct experimental observation of the localized hole polaron in perovskites should advance the fundamental comprehension of charge carrier behavior within LHPs and their related devices.
- Authors:
-
[2];
[2];
[3];
[1]
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Center for Integrated Nanotechnologies (CINT)
- Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1726211
- Alternate Identifier(s):
- OSTI ID: 1674972
- Report Number(s):
- LA-UR-20-24148
Journal ID: ISSN 1948-7185
- Grant/Contract Number:
- AC02-06CH11357; 89233218CNA000001
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry Letters
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 15; Journal ID: ISSN 1948-7185
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; polarons; thin films; carrier dynamics; electrical conductivity; perovskites
Citation Formats
Liu, Cunming, Tsai, Hsinhan, Nie, Wanyi, Gosztola, David J., and Zhang, Xiaoyi. Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites. United States: N. p., 2020.
Web. doi:10.1021/acs.jpclett.0c01708.
Liu, Cunming, Tsai, Hsinhan, Nie, Wanyi, Gosztola, David J., & Zhang, Xiaoyi. Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites. United States. https://doi.org/10.1021/acs.jpclett.0c01708
Liu, Cunming, Tsai, Hsinhan, Nie, Wanyi, Gosztola, David J., and Zhang, Xiaoyi. Mon .
"Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites". United States. https://doi.org/10.1021/acs.jpclett.0c01708. https://www.osti.gov/servlets/purl/1726211.
@article{osti_1726211,
title = {Direct Spectroscopic Observation of the Hole Polaron in Lead Halide Perovskites},
author = {Liu, Cunming and Tsai, Hsinhan and Nie, Wanyi and Gosztola, David J. and Zhang, Xiaoyi},
abstractNote = {Intrinsic photophysical origin of lead halide perovskites (LHPs) succeeding in optolectronic applications still remains hotly debated. In this study, by using the ultrafast X-ray transient absorption spectroscopy, we successfully tracked the fate of photogenerated charge carriers at room temperature within the thin films of two classic LHPs, namely MAPbBr3 (MA: CH3NH3) and FAPbBr3 (FA: CH(NH2)2). We clearly observed in both thin films that the hole polaron is formed by localizing the photogenerated hole at Br 4p orbital and concurrently distorting the local structure surrounding Br atom after the photoexcitation. Furthermore, the bigger cation FA in the cavity of [PbBr6]4- octahedral framework induces larger hole polaron effect due to its p orbital hybridization into valence and conduction bands, correlating with the slower charge carrier recombination dynamics. Our direct experimental observation of the localized hole polaron in perovskites should advance the fundamental comprehension of charge carrier behavior within LHPs and their related devices.},
doi = {10.1021/acs.jpclett.0c01708},
journal = {Journal of Physical Chemistry Letters},
number = 15,
volume = 11,
place = {United States},
year = {Mon Jul 13 00:00:00 EDT 2020},
month = {Mon Jul 13 00:00:00 EDT 2020}
}
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