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.
- Authors:
-
[1];
[1];
[1];
[1];
[1];
[5];
[1];
[1]
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Imperial College, London (United Kingdom)
- Univ. of North Carolina, Chapel Hill, NC (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
- Imperial College, London (United Kingdom); Yonsei Univ., Seoul (Korea, Republic of)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Hybrid Organic-Inorganic Semiconductors for Energy (CHOISE); National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office; USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1506616
- Report Number(s):
- NREL/JA-5900-73083
Journal ID: ISSN 0002-7863
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 14; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 36 MATERIALS SCIENCE; perovskites; 2D structures; perovskite solar cells; transport properties
Citation Formats
Zhang, Fei, Kim, Dong Hoe, Lu, Haipeng, Park, Ji-Sang, Larson, Bryon W., Hu, Jun, Gao, Liguo, Xiao, Chuanxiao, Reid, Obadiah G., Chen, Xihan, Zhao, Qian, Ndione, Paul F., Berry, Joseph J., You, Wei, Walsh, Aron, Beard, Matthew C., and Zhu, Kai. Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b00972.
Zhang, Fei, Kim, Dong Hoe, Lu, Haipeng, Park, Ji-Sang, Larson, Bryon W., Hu, Jun, Gao, Liguo, Xiao, Chuanxiao, Reid, Obadiah G., Chen, Xihan, Zhao, Qian, Ndione, Paul F., Berry, Joseph J., You, Wei, Walsh, Aron, Beard, Matthew C., & Zhu, Kai. Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation. United States. https://doi.org/10.1021/jacs.9b00972
Zhang, Fei, Kim, Dong Hoe, Lu, Haipeng, Park, Ji-Sang, Larson, Bryon W., Hu, Jun, Gao, Liguo, Xiao, Chuanxiao, Reid, Obadiah G., Chen, Xihan, Zhao, Qian, Ndione, Paul F., Berry, Joseph J., You, Wei, Walsh, Aron, Beard, Matthew C., and Zhu, Kai. Mon .
"Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation". United States. https://doi.org/10.1021/jacs.9b00972. https://www.osti.gov/servlets/purl/1506616.
@article{osti_1506616,
title = {Enhanced Charge Transport in 2D Perovskites via Fluorination of Organic Cation},
author = {Zhang, Fei and Kim, Dong Hoe and Lu, Haipeng and Park, Ji-Sang and Larson, Bryon W. and Hu, Jun and Gao, Liguo and Xiao, Chuanxiao and Reid, Obadiah G. and Chen, Xihan and Zhao, Qian and Ndione, Paul F. and Berry, Joseph J. and You, Wei and Walsh, Aron and Beard, Matthew C. and Zhu, Kai},
abstractNote = {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.},
doi = {10.1021/jacs.9b00972},
journal = {Journal of the American Chemical Society},
number = 14,
volume = 141,
place = {United States},
year = {2019},
month = {3}
}
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Works referenced in this record:
Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells
journal, May 2009
- Kojima, Akihiro; Teshima, Kenjiro; Shirai, Yasuo
- Journal of the American Chemical Society, Vol. 131, Issue 17, p. 6050-6051
Efficient planar heterojunction perovskite solar cells by vapour deposition
journal, September 2013
- Liu, Mingzhen; Johnston, Michael B.; Snaith, Henry J.
- Nature, Vol. 501, Issue 7467, p. 395-398
Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%
journal, August 2012
- Kim, Hui-Seon; Lee, Chang-Ryul; Im, Jeong-Hyeok
- Scientific Reports, Vol. 2, Issue 1
Sequential deposition as a route to high-performance perovskite-sensitized solar cells
journal, July 2013
- Burschka, Julian; Pellet, Norman; Moon, Soo-Jin
- Nature, Vol. 499, Issue 7458, p. 316-319
Polymer-templated nucleation and crystal growth of perovskite films for solar cells with efficiency greater than 21%
journal, September 2016
- Bi, Dongqin; Yi, Chenyi; Luo, Jingshan
- Nature Energy, Vol. 1, Issue 10
Isomer-Pure Bis-PCBM-Assisted Crystal Engineering of Perovskite Solar Cells Showing Excellent Efficiency and Stability
journal, February 2017
- Zhang, Fei; Shi, Wenda; Luo, Jingshan
- Advanced Materials, Vol. 29, Issue 17
Suppressing defects through the synergistic effect of a Lewis base and a Lewis acid for highly efficient and stable perovskite solar cells
journal, January 2018
- Zhang, Fei; Bi, Dongqin; Pellet, Norman
- Energy & Environmental Science, Vol. 11, Issue 12
3D/2D multidimensional perovskites: Balance of high performance and stability for perovskite solar cells
journal, October 2018
- Zhang, Fei; Kim, Dong Hoe; Zhu, Kai
- Current Opinion in Electrochemistry, Vol. 11
Promises and challenges of perovskite solar cells
journal, November 2017
- Correa-Baena, Juan-Pablo; Saliba, Michael; Buonassisi, Tonio
- Science, Vol. 358, Issue 6364
Functionalization of perovskite thin films with moisture-tolerant molecules
journal, January 2016
- Yang, Shuang; Wang, Yun; Liu, Porun
- Nature Energy, Vol. 1, Issue 2
Ligand-Stabilized Reduced-Dimensionality Perovskites
journal, February 2016
- Quan, Li Na; Yuan, Mingjian; Comin, Riccardo
- Journal of the American Chemical Society, Vol. 138, Issue 8
Synthetic Control over Quantum Well Width Distribution and Carrier Migration in Low-Dimensional Perovskite Photovoltaics
journal, February 2018
- Proppe, Andrew H.; Quintero-Bermudez, Rafael; Tan, Hairen
- Journal of the American Chemical Society, Vol. 140, Issue 8
Orientation Regulation of Phenylethylammonium Cation Based 2D Perovskite Solar Cell with Efficiency Higher Than 11%
journal, January 2018
- Zhang, Xinqian; Wu, Gang; Fu, Weifei
- Advanced Energy Materials, Vol. 8, Issue 14
Two-Dimensional Perovskite Solar Cells with 14.1% Power Conversion Efficiency and 0.68% External Radiative Efficiency
journal, August 2018
- Fu, Weifei; Wang, Jian; Zuo, Lijian
- ACS Energy Letters, Vol. 3, Issue 9
Vertically Oriented 2D Layered Perovskite Solar Cells with Enhanced Efficiency and Good Stability
journal, July 2017
- Zhang, Xinqian; Wu, Gang; Yang, Shida
- Small, Vol. 13, Issue 33
2D Perovskites with Short Interlayer Distance for High-Performance Solar Cell Application
journal, April 2018
- Ma, Chunqing; Shen, Dong; Ng, Tsz-Wai
- Advanced Materials, Vol. 30, Issue 22
Two-Dimensional Ruddlesden–Popper Perovskite with Nanorod-like Morphology for Solar Cells with Efficiency Exceeding 15%
journal, August 2018
- Lai, Hongtao; Kan, Bin; Liu, Tingting
- Journal of the American Chemical Society, Vol. 140, Issue 37
Aligned and Graded Type-II Ruddlesden-Popper Perovskite Films for Efficient Solar Cells
journal, May 2018
- Qing, Jian; Liu, Xiao-Ke; Li, Mingjie
- Advanced Energy Materials, Vol. 8, Issue 21
High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells
journal, July 2016
- Tsai, Hsinhan; Nie, Wanyi; Blancon, Jean-Christophe
- Nature, Vol. 536, Issue 7616
Stable high efficiency two-dimensional perovskite solar cells via cesium doping
journal, January 2017
- Zhang, Xu; Ren, Xiaodong; Liu, Bin
- Energy & Environmental Science, Vol. 10, Issue 10
General Post-annealing Method Enables High-Efficiency Two-Dimensional Perovskite Solar Cells
journal, September 2018
- Yan, Liang; Hu, Jun; Guo, Zhenkun
- ACS Applied Materials & Interfaces, Vol. 10, Issue 39
Highly Efficient Ruddlesden–Popper Halide Perovskite PA 2 MA 4 Pb 5 I 16 Solar Cells
journal, July 2018
- Cheng, Peirui; Xu, Zhuo; Li, Jianbo
- ACS Energy Letters, Vol. 3, Issue 8
Improved Photovoltaic Efficiency and Amplified Photocurrent Generation in Mesoporous n = 1 Two-Dimensional Lead–Iodide Perovskite Solar Cells
journal, January 2019
- Febriansyah, Benny; Koh, Teck Ming; Lekina, Yulia
- Chemistry of Materials, Vol. 31, Issue 3
Structure and optical properties of lead iodide based two-dimensional perovskite compounds containing fluorophenethylamines
journal, November 2004
- Kikuchi, K.; Takeoka, Y.; Rikukawa, M.
- Current Applied Physics, Vol. 4, Issue 6
Quantitative analysis of time-resolved microwave conductivity data
journal, November 2017
- Reid, Obadiah G.; Moore, David T.; Li, Zhen
- Journal of Physics D: Applied Physics, Vol. 50, Issue 49
Revealing the Dynamics of Charge Carriers in Polymer:Fullerene Blends Using Photoinduced Time-Resolved Microwave Conductivity
journal, October 2013
- Savenije, Tom J.; Ferguson, Andrew J.; Kopidakis, Nikos
- The Journal of Physical Chemistry C, Vol. 117, Issue 46
Examining the Effect of the Dipole Moment on Charge Separation in Donor–Acceptor Polymers for Organic Photovoltaic Applications
journal, December 2011
- Carsten, Bridget; Szarko, Jodi M.; Son, Hae Jung
- Journal of the American Chemical Society, Vol. 133, Issue 50
Silaindacenodithiophene-Based Low Band Gap Polymers - The Effect of Fluorine Substitution on Device Performances and Film Morphologies
journal, February 2012
- Schroeder, Bob C.; Huang, Zhenggang; Ashraf, Raja Shahid
- Advanced Functional Materials, Vol. 22, Issue 8
The Curious Case of Fluorination of Conjugated Polymers for Solar Cells
journal, August 2017
- Zhang, Qianqian; Kelly, Mary Allison; Bauer, Nicole
- Accounts of Chemical Research, Vol. 50, Issue 9
The influence of molecular orientation on organic bulk heterojunction solar cells
journal, April 2014
- Tumbleston, John R.; Collins, Brian A.; Yang, Liqiang
- Nature Photonics, Vol. 8, Issue 5
Correlation between Crystal Structure and Mobility in Organic Field-Effect Transistors Based on Single Crystals of Tetrathiafulvalene Derivatives
journal, July 2004
- Mas-Torrent, Marta; Hadley, Peter; Bromley, Stefan T.
- Journal of the American Chemical Society, Vol. 126, Issue 27
Charge Transport in Organic Semiconductors
journal, April 2007
- Coropceanu, Veaceslav; Cornil, Jérôme; da Silva Filho, Demetrio A.
- Chemical Reviews, Vol. 107, Issue 4
Hybrid Dion–Jacobson 2D Lead Iodide Perovskites
journal, February 2018
- Mao, Lingling; Ke, Weijun; Pedesseau, Laurent
- Journal of the American Chemical Society, Vol. 140, Issue 10
Two-Dimensional Hybrid Halide Perovskites: Principles and Promises
journal, November 2018
- Mao, Lingling; Stoumpos, Constantinos C.; Kanatzidis, Mercouri G.
- Journal of the American Chemical Society, Vol. 141, Issue 3
Conducting tin halides with a layered organic-based perovskite structure
journal, June 1994
- Mitzi, D. B.; Feild, C. A.; Harrison, W. T. A.
- Nature, Vol. 369, Issue 6480, p. 467-469
Lead-Free, Air-Stable All-Inorganic Cesium Bismuth Halide Perovskite Nanocrystals
journal, August 2017
- Yang, Bin; Chen, Junsheng; Hong, Feng
- Angewandte Chemie International Edition, Vol. 56, Issue 41
Lead-Free Silver-Bismuth Halide Double Perovskite Nanocrystals
journal, March 2018
- Yang, Bin; Chen, Junsheng; Yang, Songqiu
- Angewandte Chemie International Edition, Vol. 57, Issue 19
Intrinsic White-Light Emission from Layered Hybrid Perovskites
journal, September 2014
- Dohner, Emma R.; Jaffe, Adam; Bradshaw, Liam R.
- Journal of the American Chemical Society, Vol. 136, Issue 38
Optical properties of natural quantum-well compounds (C6H5-CnH2n-NH3)2PbBr4 (n=1–4)
journal, May 2010
- Kitazawa, Nobuaki; Watanabe, Yoshihisa
- Journal of Physics and Chemistry of Solids, Vol. 71, Issue 5
Suppressing defects through thiadiazole derivatives that modulate CH 3 NH 3 PbI 3 crystal growth for highly stable perovskite solar cells under dark conditions
journal, January 2018
- Zhu, Hongwei; Zhang, Fei; Xiao, Yin
- Journal of Materials Chemistry A, Vol. 6, Issue 12
Ion Migration in Organometal Trihalide Perovskite and Its Impact on Photovoltaic Efficiency and Stability
journal, January 2016
- Yuan, Yongbo; Huang, Jinsong
- Accounts of Chemical Research, Vol. 49, Issue 2
2D Ruddlesden-Popper Perovskites for Optoelectronics
journal, October 2017
- Chen, Yani; Sun, Yong; Peng, Jiajun
- Advanced Materials, Vol. 30, Issue 2
Atomistic Origins of High-Performance in Hybrid Halide Perovskite Solar Cells
journal, April 2014
- Frost, Jarvist M.; Butler, Keith T.; Brivio, Federico
- Nano Letters, Vol. 14, Issue 5
Tuning the crystal growth of perovskite thin-films by adding the 2-pyridylthiourea additive for highly efficient and stable solar cells prepared in ambient air
journal, January 2017
- Sun, Mengna; Zhang, Fei; Liu, Hongli
- Journal of Materials Chemistry A, Vol. 5, Issue 26
Enhanced stability and optoelectronic properties of MAPbI 3 films by a cationic surface-active agent for perovskite solar cells
journal, January 2018
- Zhao, He; Wang, Shirong; Sun, Mengna
- Journal of Materials Chemistry A, Vol. 6, Issue 23
Impact of Peripheral Groups on Phenothiazine-Based Hole-Transporting Materials for Perovskite Solar Cells
journal, April 2018
- Zhang, Fei; Wang, Shirong; Zhu, Hongwei
- ACS Energy Letters, Vol. 3, Issue 5
Novel dopant-free metallophthalocyanines based hole transporting materials for perovskite solar cells: The effect of core metal on photovoltaic performance
journal, October 2017
- Guo, Jun-Jie; Bai, Zheng-Chen; Meng, Xian-Fang
- Solar Energy, Vol. 155
Over 20% PCE perovskite solar cells with superior stability achieved by novel and low-cost hole-transporting materials
journal, November 2017
- Zhang, Fei; Wang, Zhiqiang; Zhu, Hongwei
- Nano Energy, Vol. 41
Works referencing / citing this record:
Addressing the Reliability and Electron Transport Kinetics in Halide Perovskite Film via Pulsed Laser Engineering
journal, November 2019
- Song, Chunpeng; Tong, Lei; Liu, Feng
- Advanced Functional Materials, Vol. 30, Issue 5
High‐Performance Perovskite Light‐Emitting Diode with Enhanced Operational Stability Using Lithium Halide Passivation
journal, January 2020
- Wu, Tian; Li, Junnan; Zou, Yatao
- Angewandte Chemie International Edition, Vol. 59, Issue 10
Lead-free low-dimensional tin halide perovskites with functional organic spacers: breaking the charge-transport bottleneck
journal, January 2019
- Ju, Ming-Gang; Dai, Jun; Ma, Liang
- Journal of Materials Chemistry A, Vol. 7, Issue 28
Steric Mixed‐Cation 2D Perovskite as a Methylammonium Locker to Stabilize MAPbI 3
journal, December 2019
- Wang, Xingtao; Wang, Yong; Zhang, Taiyang
- Angewandte Chemie, Vol. 132, Issue 4
Enhanced Charge Transport by Incorporating Formamidinium and Cesium Cations into Two‐Dimensional Perovskite Solar Cells
journal, July 2019
- Gao, Liguo; Zhang, Fei; Chen, Xihan
- Angewandte Chemie, Vol. 131, Issue 34
Vertical Orientated Dion–Jacobson Quasi‐2D Perovskite Film with Improved Photovoltaic Performance and Stability
journal, December 2019
- Li, Fengzhu; Zhang, Jie; Jo, SaeByeok
- Small Methods, Vol. 4, Issue 5
Fine Multi‐Phase Alignments in 2D Perovskite Solar Cells with Efficiency over 17% via Slow Post‐Annealing
journal, September 2019
- Wu, Guangbao; Li, Xing; Zhou, Jiyu
- Advanced Materials, Vol. 31, Issue 42
Steric Mixed‐Cation 2D Perovskite as a Methylammonium Locker to Stabilize MAPbI 3
journal, January 2020
- Wang, Xingtao; Wang, Yong; Zhang, Taiyang
- Angewandte Chemie International Edition, Vol. 59, Issue 4
An Effective Strategy for Photoelectric Performance Enhancement of 2D Perovskite via Halogenating Organic Cation: A Theoretical Prediction
journal, January 2020
- Tang, Yong; Zhou, Yingtang; Zhong, Xiangli
- physica status solidi (b), Vol. 257, Issue 5
Chirality control in white-light emitting 2D perovskites
journal, January 2020
- Trujillo-Hernández, Karla; Rodríguez-López, Germán; Espinosa-Roa, Arian
- Journal of Materials Chemistry C, Vol. 8, Issue 28
High‐Performance Perovskite Light‐Emitting Diode with Enhanced Operational Stability Using Lithium Halide Passivation
journal, January 2020
- Wu, Tian; Li, Junnan; Zou, Yatao
- Angewandte Chemie, Vol. 132, Issue 10
Interlayer Cross‐Linked 2D Perovskite Solar Cell with Uniform Phase Distribution and Increased Exciton Coupling
journal, April 2020
- Wang, Han; Chan, Christopher C. S.; Chu, Ming
- Solar RRL, Vol. 4, Issue 4
Nanostructured Perovskite Solar Cells
journal, October 2019
- McDonald, Calum; Ni, Chengsheng; Maguire, Paul
- Nanomaterials, Vol. 9, Issue 10
Space‐Confined Growth of Individual Wide Bandgap Single Crystal CsPbCl 3 Microplatelet for Near‐Ultraviolet Photodetection
journal, August 2019
- Gui, Pengbin; Zhou, Hai; Yao, Fang
- Small, Vol. 15, Issue 39
Manipulation of Dipolar Polarization at Steady States for a Quasi‐2D Organic–Inorganic Hybrid Perovskite with a Nanorod Network
journal, November 2019
- Yang, Hanjun; Wang, Kai; Deng, Liangliang
- Solar RRL, Vol. 4, Issue 3
Emerging Conductive Atomic Force Microscopy for Metal Halide Perovskite Materials and Solar Cells
journal, March 2020
- Si, Haonan; Zhang, Suicai; Ma, Shuangfei
- Advanced Energy Materials, Vol. 10, Issue 10
Additive Engineering for Efficient and Stable Perovskite Solar Cells
journal, October 2019
- Zhang, Fei; Zhu, Kai
- Advanced Energy Materials
Enhanced Charge Transport by Incorporating Formamidinium and Cesium Cations into Two-Dimensional Perovskite Solar Cells
journal, July 2019
- Gao, Liguo; Zhang, Fei; Chen, Xihan
- Angewandte Chemie International Edition, Vol. 58, Issue 34