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Title: Excitations Partition into Two Distinct Populations in Bulk Perovskites

Abstract

Organolead halide perovskites convert optical excitations to charge carriers with remarkable efficiency in optoelectronic devices. Previous research predominantly documents dynamics in perovskite thin films; however, extensive disorder in this platform may obscure the observed carrier dynamics. Here in this study, carrier dynamics in perovskite single-domain single crystals is examined by performing transient absorption spectroscopy in a transmissive geometry. Two distinct sets of carrier populations that coexist at the same radiation fluence, but display different decay dynamics, are observed: one dominated by second-order recombination and the other by third-order recombination. Based on ab initio simulations, this observation is found to be most consistent with the hypothesis that free carriers and localized carriers coexist due to polaron formation. Lastly, the calculations suggest that polarons will form in both CH 3NH 3PbBr 3 and CH 3NH 3PbI 3 crystals, but that they are more pronounced in CH 3NH 3PbBr 3. Single-crystal CH 3NH 3PbBr 3 could represent the key to understanding the impact of polarons on the transport properties of perovskite optoelectronic devices.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [4];  [5]; ORCiD logo [1]
  1. Univ. of Chicago, IL (United States). James Franck Inst., and Inst. for Biophysical Dynamics
  2. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  4. Argonne National Lab. (ANL), Argonne, IL (United States).Chemical Sciences and Engineering Division
  5. Univ. of Chicago, IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Alfred P. Sloan Foundation; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); U.S. Department of Defense (DOD). National Security Science and Engineering Faculty Fellowship (NSSEFF)
OSTI Identifier:
1427475
Alternate Identifier(s):
OSTI ID: 1416406
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Optical Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 5; Journal ID: ISSN 2195-1071
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; organolead halide perovskites; bulk carrier dynamics; transient absorption; polaron formation

Citation Formats

Wang, Lili, Brawand, Nicholas P., Voros, Marton, Dahlberg, Peter D., Otto, John P., Williams, Nicholas E., Tiede, David M., Galli, Giulia, and Engel, Gregory S. Excitations Partition into Two Distinct Populations in Bulk Perovskites. United States: N. p., 2018. Web. doi:10.1002/adom.201700975.
Wang, Lili, Brawand, Nicholas P., Voros, Marton, Dahlberg, Peter D., Otto, John P., Williams, Nicholas E., Tiede, David M., Galli, Giulia, & Engel, Gregory S. Excitations Partition into Two Distinct Populations in Bulk Perovskites. United States. doi:10.1002/adom.201700975.
Wang, Lili, Brawand, Nicholas P., Voros, Marton, Dahlberg, Peter D., Otto, John P., Williams, Nicholas E., Tiede, David M., Galli, Giulia, and Engel, Gregory S. Tue . "Excitations Partition into Two Distinct Populations in Bulk Perovskites". United States. doi:10.1002/adom.201700975.
@article{osti_1427475,
title = {Excitations Partition into Two Distinct Populations in Bulk Perovskites},
author = {Wang, Lili and Brawand, Nicholas P. and Voros, Marton and Dahlberg, Peter D. and Otto, John P. and Williams, Nicholas E. and Tiede, David M. and Galli, Giulia and Engel, Gregory S.},
abstractNote = {Organolead halide perovskites convert optical excitations to charge carriers with remarkable efficiency in optoelectronic devices. Previous research predominantly documents dynamics in perovskite thin films; however, extensive disorder in this platform may obscure the observed carrier dynamics. Here in this study, carrier dynamics in perovskite single-domain single crystals is examined by performing transient absorption spectroscopy in a transmissive geometry. Two distinct sets of carrier populations that coexist at the same radiation fluence, but display different decay dynamics, are observed: one dominated by second-order recombination and the other by third-order recombination. Based on ab initio simulations, this observation is found to be most consistent with the hypothesis that free carriers and localized carriers coexist due to polaron formation. Lastly, the calculations suggest that polarons will form in both CH3NH3PbBr3 and CH3NH3PbI3 crystals, but that they are more pronounced in CH3NH3PbBr3. Single-crystal CH3NH3PbBr3 could represent the key to understanding the impact of polarons on the transport properties of perovskite optoelectronic devices.},
doi = {10.1002/adom.201700975},
journal = {Advanced Optical Materials},
number = 5,
volume = 6,
place = {United States},
year = {Tue Jan 09 00:00:00 EST 2018},
month = {Tue Jan 09 00:00:00 EST 2018}
}

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