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Title: Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH 3NH 3PbCl 3 and CH 3 NH 3PbI 3 or (C 4 H 9NH 3) 2(CH 3NH 3) n-1 Pb nI 3n+1 Mixtures

Abstract

Lead halide perovskites present a versatile class of solution-processable semiconductors with highly tunable bandgaps that span ultraviolet, visible, and near-infrared portions of the spectrum. We explore phase-separated chloride and iodide lead perovskite mixtures as candidate materials for intermediate band applications in future photovoltaics. X-ray diffraction and scanning electron microscopy reveal that deposition of precursor solutions across the MAPbCl 3/MAPbI 3 composition space affords quasi-epitaxial cocrystallized films, in which the two perovskites do not alloy but instead remain phase-segregated. First-principle calculations further support the formation of an epitaxial interface and predict energy offsets in the valence band and conduction band edges that could result in intermediate energy absorption. The charge dynamics of variable mixtures of the relatively narrow bandgap (1.57 eV) MAPbI 3 perovskite and wide bandgap (3.02 eV) MAPbCl 3 are probed to map charge and energy flow direction and kinetics. Time-resolved photoluminescence and transient absorption measurements reveal charge transfer of photoexcited carriers in MAPbCl 3 to MAPbI 3 in tens of picoseconds. The rate of quenching can be further tuned by replacing MAPbI 3 with two-dimensional Ruddlesden-Popper (BA) 2(MA) n-1Pb nI 3n+1 (n = 3, 2, and 1) perovskites, which also remain phase-separated.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1505163
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 11; Journal Issue: 9; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 2D perovskites; CH3NH3PbCl; charge transfer dynamics; halide perovskites; phase segregated

Citation Formats

Cao, Duyen H., Guo, Peijun, Mannodi-Kanakkithodi, Arun, Wiederrecht, Gary P., Gosztola, David J., Jeon, Nari, Schaller, Richard D., Chan, Maria K. Y., and Martinson, Alex B. F. Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH3NH3PbCl3 and CH3 NH 3PbI 3 or (C4 H 9NH3)2(CH 3NH3)n-1 PbnI3n+1 Mixtures. United States: N. p., 2019. Web. doi:10.1021/acsami.8b20928.
Cao, Duyen H., Guo, Peijun, Mannodi-Kanakkithodi, Arun, Wiederrecht, Gary P., Gosztola, David J., Jeon, Nari, Schaller, Richard D., Chan, Maria K. Y., & Martinson, Alex B. F. Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH3NH3PbCl3 and CH3 NH 3PbI 3 or (C4 H 9NH3)2(CH 3NH3)n-1 PbnI3n+1 Mixtures. United States. doi:10.1021/acsami.8b20928.
Cao, Duyen H., Guo, Peijun, Mannodi-Kanakkithodi, Arun, Wiederrecht, Gary P., Gosztola, David J., Jeon, Nari, Schaller, Richard D., Chan, Maria K. Y., and Martinson, Alex B. F. Thu . "Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH3NH3PbCl3 and CH3 NH 3PbI 3 or (C4 H 9NH3)2(CH 3NH3)n-1 PbnI3n+1 Mixtures". United States. doi:10.1021/acsami.8b20928.
@article{osti_1505163,
title = {Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH3NH3PbCl3 and CH3 NH 3PbI 3 or (C4 H 9NH3)2(CH 3NH3)n-1 PbnI3n+1 Mixtures},
author = {Cao, Duyen H. and Guo, Peijun and Mannodi-Kanakkithodi, Arun and Wiederrecht, Gary P. and Gosztola, David J. and Jeon, Nari and Schaller, Richard D. and Chan, Maria K. Y. and Martinson, Alex B. F.},
abstractNote = {Lead halide perovskites present a versatile class of solution-processable semiconductors with highly tunable bandgaps that span ultraviolet, visible, and near-infrared portions of the spectrum. We explore phase-separated chloride and iodide lead perovskite mixtures as candidate materials for intermediate band applications in future photovoltaics. X-ray diffraction and scanning electron microscopy reveal that deposition of precursor solutions across the MAPbCl3/MAPbI3 composition space affords quasi-epitaxial cocrystallized films, in which the two perovskites do not alloy but instead remain phase-segregated. First-principle calculations further support the formation of an epitaxial interface and predict energy offsets in the valence band and conduction band edges that could result in intermediate energy absorption. The charge dynamics of variable mixtures of the relatively narrow bandgap (1.57 eV) MAPbI3 perovskite and wide bandgap (3.02 eV) MAPbCl3 are probed to map charge and energy flow direction and kinetics. Time-resolved photoluminescence and transient absorption measurements reveal charge transfer of photoexcited carriers in MAPbCl3 to MAPbI3 in tens of picoseconds. The rate of quenching can be further tuned by replacing MAPbI3 with two-dimensional Ruddlesden-Popper (BA)2(MA)n-1PbnI3n+1 (n = 3, 2, and 1) perovskites, which also remain phase-separated.},
doi = {10.1021/acsami.8b20928},
journal = {ACS Applied Materials and Interfaces},
number = 9,
volume = 11,
place = {United States},
year = {2019},
month = {2}
}

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This content will become publicly available on February 21, 2020
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