Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation

Fei Zhang; Dong Hoe Kim; Haipeng Lu; Ji Sang Park; Bryon W. Larson; Jun Hu; Liguo Gao; Chuanxiao Xiao; Obadiah G. Reid; Xihan Chen; Qian Zhao; Paul F. Ndione; Joseph J. Berry; Wei You; Aron Walsh; Matthew C. Beard; Kai Zhu

doi:10.1021/jacs.9b00972

Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation

Fei Zhang, Dong Hoe Kim, Haipeng Lu, Ji Sang Park, Bryon W. Larson, Jun Hu, Liguo Gao, Chuanxiao Xiao, Obadiah G. Reid, Xihan Chen, Qian Zhao, Paul F. Ndione, Joseph J. Berry, Wei You, Aron Walsh, Matthew C. Beard, Kai Zhu

Department of Physics

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

325 Scopus citations

Abstract

Organic-inorganic halide perovskites incorporating two-dimensional (2D) structures have shown promise for enhancing the stability of perovskite solar cells (PSCs). However, the bulky spacer cations often limit charge transport. Here, we report on a simple approach based on molecular design of the organic spacer to improve the transport properties of 2D perovskites, and we use phenethylammonium (PEA) as an example. We demonstrate that by fluorine substitution on the para position in PEA to form 4-fluorophenethylammonium (F-PEA), the average phenyl ring centroid-centroid distances in the organic layer become shorter with better aligned stacking of perovskite sheets. The impact is enhanced orbital interactions and charge transport across adjacent inorganic layers as well as increased carrier lifetime and reduced trap density. Using a simple perovskite deposition at room temperature without using any additives, we obtained a power conversion efficiency of >13% for (F-PEA)₂MA₄Pb₅I₁₆-based PSCs. In addition, the thermal stability of 2D PSCs based on F-PEA is significantly enhanced compared to those based on PEA.

Original language	English
Pages (from-to)	5972-5979
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	141
Issue number	14
DOIs	https://doi.org/10.1021/jacs.9b00972
State	Published - 10 Apr 2019

Bibliographical note

Funding Information:
The work was supported by the U.S. Department of Energy under Contract No. DE-AC36-08GO28308 with Alliance for Sustainable Energy, Limited Liability Company (LLC), the Manager and Operator of the National Renewable Energy Laboratory. We acknowledge the support of perovskite synthesis and device fabrication/characterization, and microwave cavity modeling and characterization from the Derisking Halide Perovskite Solar Cells program of the National Center for Photovoltaics, funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office; the support of the in-plane and out-of-plane transport measurement and analysis from the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the U.S. Department of Energy; and the support of density functional theory calculations by supercomputer time awarded through PRACE on the Swiss National Supercomputing Centre (CSCS) under project pr51. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government.

Publisher Copyright:
Copyright © 2019 American Chemical Society.

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10.1021/jacs.9b00972

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Zhang, F., Kim, D. H., Lu, H., Park, J. S., Larson, B. W., Hu, J., Gao, L., Xiao, C., Reid, O. G., Chen, X., Zhao, Q., Ndione, P. F., Berry, J. J., You, W., Walsh, A., Beard, M. C., & Zhu, K. (2019). Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation. Journal of the American Chemical Society, 141(14), 5972-5979. https://doi.org/10.1021/jacs.9b00972

@article{9aa87ecad655447faad172a03c9a6675,

title = "Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation",

abstract = "Organic-inorganic halide perovskites incorporating two-dimensional (2D) structures have shown promise for enhancing the stability of perovskite solar cells (PSCs). However, the bulky spacer cations often limit charge transport. Here, we report on a simple approach based on molecular design of the organic spacer to improve the transport properties of 2D perovskites, and we use phenethylammonium (PEA) as an example. We demonstrate that by fluorine substitution on the para position in PEA to form 4-fluorophenethylammonium (F-PEA), the average phenyl ring centroid-centroid distances in the organic layer become shorter with better aligned stacking of perovskite sheets. The impact is enhanced orbital interactions and charge transport across adjacent inorganic layers as well as increased carrier lifetime and reduced trap density. Using a simple perovskite deposition at room temperature without using any additives, we obtained a power conversion efficiency of >13% for (F-PEA)2MA4Pb5I16-based PSCs. In addition, the thermal stability of 2D PSCs based on F-PEA is significantly enhanced compared to those based on PEA.",

author = "Fei Zhang and Kim, {Dong Hoe} and Haipeng Lu and Park, {Ji Sang} and Larson, {Bryon W.} and Jun Hu and Liguo Gao and Chuanxiao Xiao and Reid, {Obadiah G.} and Xihan Chen and Qian Zhao and Ndione, {Paul F.} and Berry, {Joseph J.} and Wei You and Aron Walsh and Beard, {Matthew C.} and Kai Zhu",

note = "Funding Information: The work was supported by the U.S. Department of Energy under Contract No. DE-AC36-08GO28308 with Alliance for Sustainable Energy, Limited Liability Company (LLC), the Manager and Operator of the National Renewable Energy Laboratory. We acknowledge the support of perovskite synthesis and device fabrication/characterization, and microwave cavity modeling and characterization from the Derisking Halide Perovskite Solar Cells program of the National Center for Photovoltaics, funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office; the support of the in-plane and out-of-plane transport measurement and analysis from the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the U.S. Department of Energy; and the support of density functional theory calculations by supercomputer time awarded through PRACE on the Swiss National Supercomputing Centre (CSCS) under project pr51. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

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T1 - Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation

AU - Zhang, Fei

AU - Kim, Dong Hoe

AU - Lu, Haipeng

AU - Park, Ji Sang

AU - Larson, Bryon W.

AU - Hu, Jun

AU - Gao, Liguo

AU - Xiao, Chuanxiao

AU - Reid, Obadiah G.

AU - Chen, Xihan

AU - Zhao, Qian

AU - Ndione, Paul F.

AU - Berry, Joseph J.

AU - You, Wei

AU - Walsh, Aron

AU - Beard, Matthew C.

AU - Zhu, Kai

N1 - Funding Information: The work was supported by the U.S. Department of Energy under Contract No. DE-AC36-08GO28308 with Alliance for Sustainable Energy, Limited Liability Company (LLC), the Manager and Operator of the National Renewable Energy Laboratory. We acknowledge the support of perovskite synthesis and device fabrication/characterization, and microwave cavity modeling and characterization from the Derisking Halide Perovskite Solar Cells program of the National Center for Photovoltaics, funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office; the support of the in-plane and out-of-plane transport measurement and analysis from the Center for Hybrid Organic Inorganic Semiconductors for Energy (CHOISE), an Energy Frontier Research Center funded by the Office of Basic Energy Sciences, Office of Science within the U.S. Department of Energy; and the support of density functional theory calculations by supercomputer time awarded through PRACE on the Swiss National Supercomputing Centre (CSCS) under project pr51. The views expressed in the article do not necessarily represent the views of the DOE or the U.S. Government. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/4/10

Y1 - 2019/4/10

N2 - Organic-inorganic halide perovskites incorporating two-dimensional (2D) structures have shown promise for enhancing the stability of perovskite solar cells (PSCs). However, the bulky spacer cations often limit charge transport. Here, we report on a simple approach based on molecular design of the organic spacer to improve the transport properties of 2D perovskites, and we use phenethylammonium (PEA) as an example. We demonstrate that by fluorine substitution on the para position in PEA to form 4-fluorophenethylammonium (F-PEA), the average phenyl ring centroid-centroid distances in the organic layer become shorter with better aligned stacking of perovskite sheets. The impact is enhanced orbital interactions and charge transport across adjacent inorganic layers as well as increased carrier lifetime and reduced trap density. Using a simple perovskite deposition at room temperature without using any additives, we obtained a power conversion efficiency of >13% for (F-PEA)2MA4Pb5I16-based PSCs. In addition, the thermal stability of 2D PSCs based on F-PEA is significantly enhanced compared to those based on PEA.

AB - Organic-inorganic halide perovskites incorporating two-dimensional (2D) structures have shown promise for enhancing the stability of perovskite solar cells (PSCs). However, the bulky spacer cations often limit charge transport. Here, we report on a simple approach based on molecular design of the organic spacer to improve the transport properties of 2D perovskites, and we use phenethylammonium (PEA) as an example. We demonstrate that by fluorine substitution on the para position in PEA to form 4-fluorophenethylammonium (F-PEA), the average phenyl ring centroid-centroid distances in the organic layer become shorter with better aligned stacking of perovskite sheets. The impact is enhanced orbital interactions and charge transport across adjacent inorganic layers as well as increased carrier lifetime and reduced trap density. Using a simple perovskite deposition at room temperature without using any additives, we obtained a power conversion efficiency of >13% for (F-PEA)2MA4Pb5I16-based PSCs. In addition, the thermal stability of 2D PSCs based on F-PEA is significantly enhanced compared to those based on PEA.

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SN - 0002-7863

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 14

ER -

Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation

Abstract

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