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

Duyen H. Cao; Peijun Guo; Arun Mannodi-Kanakkithodi; Gary P. Wiederrecht; David J. Gosztola; Nari Jeon; Richard Daniel Schaller; Maria K.Y. Chan; Alex B.F. Martinson

doi:10.1021/acsami.8b20928

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

Duyen H. Cao, Peijun Guo, Arun Mannodi-Kanakkithodi, Gary P. Wiederrecht, David J. Gosztola, Nari Jeon, Richard Daniel Schaller, Maria K.Y. Chan, Alex B.F. Martinson^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

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-1 Pb _n I _3n+1 (n = 3, 2, and 1) perovskites, which also remain phase-separated.

Original language	English (US)
Pages (from-to)	9583-9593
Number of pages	11
Journal	ACS Applied Materials and Interfaces
Volume	11
Issue number	9
DOIs	https://doi.org/10.1021/acsami.8b20928
State	Published - Mar 6 2019

Funding

This work was performed at Argonne National Laboratory and supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility was supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. This work was performed at Argonne National Laboratory and supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility was supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Centera DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.

Keywords

2D perovskites
CH NH PbCl
charge transfer dynamics
halide perovskites
phase-segregated

ASJC Scopus subject areas

General Materials Science

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1021/acsami.8b20928

Cite this

Cao, D. H., Guo, P., Mannodi-Kanakkithodi, A., Wiederrecht, G. P., Gosztola, D. J., Jeon, N., Schaller, R. D., Chan, M. K. Y., & Martinson, A. B. F. (2019). Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH ₃ NH ₃ PbCl ₃ and CH ₃ NH ₃ PbI ₃ or (C ₄ H ₉ NH ₃ ) ₂ (CH ₃ NH ₃ ) _n-1 Pb _n I _{3 n+1} Mixtures. ACS Applied Materials and Interfaces, 11(9), 9583-9593. https://doi.org/10.1021/acsami.8b20928

Cao, Duyen H. ; Guo, Peijun ; Mannodi-Kanakkithodi, Arun et al. / Charge Transfer Dynamics of Phase-Segregated Halide Perovskites : CH ₃ NH ₃ PbCl ₃ and CH ₃ NH ₃ PbI ₃ or (C ₄ H ₉ NH ₃ ) ₂ (CH ₃ NH ₃ ) _n-1 Pb _n I _{3 n+1} Mixtures. In: ACS Applied Materials and Interfaces. 2019 ; Vol. 11, No. 9. pp. 9583-9593.

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title = "Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH 3 NH 3 PbCl 3 and CH 3 NH 3 PbI 3 or (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) n-1 Pb n I 3 n+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-1 Pb n I 3n+1 (n = 3, 2, and 1) perovskites, which also remain phase-separated.",

keywords = "2D perovskites, CH NH PbCl, charge transfer dynamics, halide perovskites, phase-segregated",

author = "Cao, {Duyen H.} and Peijun Guo and Arun Mannodi-Kanakkithodi and Wiederrecht, {Gary P.} and Gosztola, {David J.} and Nari Jeon and Schaller, {Richard Daniel} and Chan, {Maria K.Y.} and Martinson, {Alex B.F.}",

note = "Funding Information: This work was performed at Argonne National Laboratory and supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility was supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Funding Information: This work was performed at Argonne National Laboratory and supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility was supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Centera DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = mar,

day = "6",

doi = "10.1021/acsami.8b20928",

language = "English (US)",

volume = "11",

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journal = "ACS Applied Materials and Interfaces",

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Cao, DH, Guo, P, Mannodi-Kanakkithodi, A, Wiederrecht, GP, Gosztola, DJ, Jeon, N, Schaller, RD , Chan, MKY & Martinson, ABF 2019, 'Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH ₃ NH ₃ PbCl ₃ and CH ₃ NH ₃ PbI ₃ or (C ₄ H ₉ NH ₃ ) ₂ (CH ₃ NH ₃ ) _n-1 Pb _n I _{3 n+1} Mixtures', ACS Applied Materials and Interfaces, vol. 11, no. 9, pp. 9583-9593. https://doi.org/10.1021/acsami.8b20928

Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH ₃ NH ₃ PbCl ₃ and CH ₃ NH ₃ PbI ₃ or (C ₄ H ₉ NH ₃ ) ₂ (CH ₃ NH ₃ ) _n-1 Pb _n I _{3 n+1} Mixtures. / Cao, Duyen H.; Guo, Peijun; Mannodi-Kanakkithodi, Arun et al.
In: ACS Applied Materials and Interfaces, Vol. 11, No. 9, 06.03.2019, p. 9583-9593.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Charge Transfer Dynamics of Phase-Segregated Halide Perovskites

T2 - CH 3 NH 3 PbCl 3 and CH 3 NH 3 PbI 3 or (C 4 H 9 NH 3 ) 2 (CH 3 NH 3 ) n-1 Pb n I 3 n+1 Mixtures

AU - Cao, Duyen H.

AU - Guo, Peijun

AU - Mannodi-Kanakkithodi, Arun

AU - Wiederrecht, Gary P.

AU - Gosztola, David J.

AU - Jeon, Nari

AU - Schaller, Richard Daniel

AU - Chan, Maria K.Y.

AU - Martinson, Alex B.F.

N1 - Funding Information: This work was performed at Argonne National Laboratory and supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility was supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Funding Information: This work was performed at Argonne National Laboratory and supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE-AC02-06CH11357. Use of the Center for Nanoscale Materials, a U.S. Department of Energy Office of Science User Facility was supported by the U.S. Department of Energy, Office of Science, under Contract No. DE-AC02-06CH11357. This research used resources of the National Energy Research Scientific Computing Centera DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/3/6

Y1 - 2019/3/6

N2 - 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-1 Pb n I 3n+1 (n = 3, 2, and 1) perovskites, which also remain phase-separated.

AB - 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-1 Pb n I 3n+1 (n = 3, 2, and 1) perovskites, which also remain phase-separated.

KW - 2D perovskites

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KW - halide perovskites

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Cao DH, Guo P, Mannodi-Kanakkithodi A, Wiederrecht GP, Gosztola DJ, Jeon N et al. Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH ₃ NH ₃ PbCl ₃ and CH ₃ NH ₃ PbI ₃ or (C ₄ H ₉ NH ₃ ) ₂ (CH ₃ NH ₃ ) _n-1 Pb _n I _{3 n+1} Mixtures. ACS Applied Materials and Interfaces. 2019 Mar 6;11(9):9583-9593. doi: 10.1021/acsami.8b20928