CsI-Antisolvent Adduct Formation in All-Inorganic Metal Halide Perovskites
Abstract
The excellent optoelectronic properties shown by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high-performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead-halide precursor salts. These adduct-based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all-inorganic perovskites such as CsPbI3. In this work, inorganic perovskite composition CsPbI3 is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A-site cation salts. These CsI adducts control nucleation more so than the PbI2-dimethyl sulfoxide (DMSO) adduct and demonstrate how the A-site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI-MeOAc adduct and results in solar cellsmore »
- Authors:
-
- National Renewable Energy Laboratory Golden CO 80401 USA
- Department of PhysicsUniversity of Oxford Oxford OX1 3PU UK
- Department of ChemistryColorado School of Mines Golden CO 80401 USA
- National Renewable Energy Laboratory Golden CO 80401 USA; Department of Material Science and EngineeringStanford University Palo Alto CA 94305 USA
- National Renewable Energy Laboratory Golden CO 80401 USA; Department of ChemistryUniversity of Michigan Ann Arbor MI 48109 USA
- National Renewable Energy Laboratory Golden CO 80401 USA; Department of Chemical and Biological EngineeringUniversity of Colorado Boulder CO 80309 USA
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- U.S. Department of Defense (DOD); USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Building Technologies Office; USDOE Office of Science (SC), Office of Workforce Development for Teachers and Scientists, Science Undergraduate Laboratory Internship (SULI) Program
- OSTI Identifier:
- 1598483
- Alternate Identifier(s):
- OSTI ID: 1596387
- Report Number(s):
- NREL/JA-5900-75166
Journal ID: ISSN 1614-6832
- Grant/Contract Number:
- AC36-08GO28308; AC36‐08GO28308
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Energy Materials
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 9; Journal ID: ISSN 1614-6832
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 36 MATERIALS SCIENCE; acid-base complex; adduct antisolvent; CsPbI3; perovskite; solar cells
Citation Formats
Moot, Taylor, Marshall, Ashley R., Wheeler, Lance M., Habisreutinger, Severin N., Schloemer, Tracy H., Boyd, Caleb C., Dikova, Desislava R., Pach, Gregory F., Hazarika, Abhijit, McGehee, Michael D., Snaith, Henry J., and Luther, Joseph M. CsI-Antisolvent Adduct Formation in All-Inorganic Metal Halide Perovskites. United States: N. p., 2020.
Web. doi:10.1002/aenm.201903365.
Moot, Taylor, Marshall, Ashley R., Wheeler, Lance M., Habisreutinger, Severin N., Schloemer, Tracy H., Boyd, Caleb C., Dikova, Desislava R., Pach, Gregory F., Hazarika, Abhijit, McGehee, Michael D., Snaith, Henry J., & Luther, Joseph M. CsI-Antisolvent Adduct Formation in All-Inorganic Metal Halide Perovskites. United States. https://doi.org/10.1002/aenm.201903365
Moot, Taylor, Marshall, Ashley R., Wheeler, Lance M., Habisreutinger, Severin N., Schloemer, Tracy H., Boyd, Caleb C., Dikova, Desislava R., Pach, Gregory F., Hazarika, Abhijit, McGehee, Michael D., Snaith, Henry J., and Luther, Joseph M. Fri .
"CsI-Antisolvent Adduct Formation in All-Inorganic Metal Halide Perovskites". United States. https://doi.org/10.1002/aenm.201903365. https://www.osti.gov/servlets/purl/1598483.
@article{osti_1598483,
title = {CsI-Antisolvent Adduct Formation in All-Inorganic Metal Halide Perovskites},
author = {Moot, Taylor and Marshall, Ashley R. and Wheeler, Lance M. and Habisreutinger, Severin N. and Schloemer, Tracy H. and Boyd, Caleb C. and Dikova, Desislava R. and Pach, Gregory F. and Hazarika, Abhijit and McGehee, Michael D. and Snaith, Henry J. and Luther, Joseph M.},
abstractNote = {The excellent optoelectronic properties shown by hybrid organic/inorganic metal halide perovskites are all predicated on precisely controlling the exact nucleation and crystallization dynamics that occur during film formation. In general, high-performance thin films are obtained by a method commonly called solvent engineering (or antisolvent quench) processing. The solvent engineering method removes excess solvent, but importantly leaves behind solvent that forms chemical adducts with the lead-halide precursor salts. These adduct-based precursor phases control nucleation and the growth of the polycrystalline domains. There has not yet been a comprehensive study comparing the various antisolvents used in different perovskite compositions containing cesium. In addition, there have been no reports of solvent engineering for high efficiency in all-inorganic perovskites such as CsPbI3. In this work, inorganic perovskite composition CsPbI3 is specifically targeted and unique adducts formed between CsI and precursor solvents and antisolvents are found that have not been observed for other A-site cation salts. These CsI adducts control nucleation more so than the PbI2-dimethyl sulfoxide (DMSO) adduct and demonstrate how the A-site plays a significant role in crystallization. The use of methyl acetate (MeOAc) in this solvent engineering approach dictates crystallization through the formation of a CsI-MeOAc adduct and results in solar cells with a power conversion efficiency of 14.4%.},
doi = {10.1002/aenm.201903365},
journal = {Advanced Energy Materials},
number = 9,
volume = 10,
place = {United States},
year = {Fri Jan 31 00:00:00 EST 2020},
month = {Fri Jan 31 00:00:00 EST 2020}
}
Web of Science
Works referenced in this record:
In Situ Real-Time Study of the Dynamic Formation and Conversion Processes of Metal Halide Perovskite Films
journal, January 2018
- Meng, Ke; Wu, Longlong; Liu, Zhou
- Advanced Materials, Vol. 30, Issue 11
Stabilizing Perovskite Structures by Tuning Tolerance Factor: Formation of Formamidinium and Cesium Lead Iodide Solid-State Alloys
journal, December 2015
- Li, Zhen; Yang, Mengjin; Park, Ji-Sang
- Chemistry of Materials, Vol. 28, Issue 1
Surface passivation of perovskite film for efficient solar cells
journal, April 2019
- Jiang, Qi; Zhao, Yang; Zhang, Xingwang
- Nature Photonics, Vol. 13, Issue 7
NMR Chemical Shifts of Trace Impurities: Industrially Preferred Solvents Used in Process and Green Chemistry
journal, February 2016
- Babij, Nicholas R.; McCusker, Elizabeth O.; Whiteker, Gregory T.
- Organic Process Research & Development, Vol. 20, Issue 3
Solvent-controlled growth of inorganic perovskite films in dry environment for efficient and stable solar cells
journal, June 2018
- Wang, Pengyang; Zhang, Xingwang; Zhou, Yuqin
- Nature Communications, Vol. 9, Issue 1
Tailored interfaces of unencapsulated perovskite solar cells for >1,000 hour operational stability
journal, January 2018
- Christians, Jeffrey A.; Schulz, Philip; Tinkham, Jonathan S.
- Nature Energy, Vol. 3, Issue 1
Fabrication of Efficient and Stable CsPbI 3 Perovskite Solar Cells through Cation Exchange Process
journal, August 2019
- Lau, Cho Fai Jonathan; Wang, Zhiping; Sakai, Nobuya
- Advanced Energy Materials, Vol. 9, Issue 36
23.6%-efficient monolithic perovskite/silicon tandem solar cells with improved stability
journal, February 2017
- Bush, Kevin A.; Palmstrom, Axel F.; Yu, Zhengshan J.
- Nature Energy, Vol. 2, Issue 4
Reversible photo-induced trap formation in mixed-halide hybrid perovskites for photovoltaics
journal, January 2015
- Hoke, Eric T.; Slotcavage, Daniel J.; Dohner, Emma R.
- Chemical Science, Vol. 6, Issue 1
Selective Stabilization and Photophysical Properties of Metastable Perovskite Polymorphs of CsPbI 3 in Thin Films
journal, September 2017
- Fu, Yongping; Rea, Morgan T.; Chen, Jie
- Chemistry of Materials, Vol. 29, Issue 19
Manipulating the Mixed‐Perovskite Crystallization Pathway Unveiled by In Situ GIWAXS
journal, April 2019
- Qin, Minchao; Tse, Kinfai; Lau, Tsz‐Ki
- Advanced Materials, Vol. 31, Issue 25
Processing Solvent-Dependent Electronic and Structural Properties of Cesium Lead Triiodide Thin Films
journal, August 2017
- Ramadan, Alexandra J.; Rochford, Luke A.; Fearn, Sarah
- The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
Improving the Stability and Monodispersity of Layered Cesium Lead Iodide Perovskite Thin Films by Tuning Crystallization Dynamics
journal, June 2019
- Hadi, Atefe; Ryan, Bradley J.; Nelson, Rainie D.
- Chemistry of Materials, Vol. 31, Issue 14
Microstructures of Organometal Trihalide Perovskites for Solar Cells: Their Evolution from Solutions and Characterization
journal, November 2015
- Zhou, Yuanyuan; Game, Onkar S.; Pang, Shuping
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 23
Challenges for commercializing perovskite solar cells
journal, September 2018
- Rong, Yaoguang; Hu, Yue; Mei, Anyi
- Science, Vol. 361, Issue 6408
Bifunctional Stabilization of All-Inorganic α-CsPbI 3 Perovskite for 17% Efficiency Photovoltaics
journal, September 2018
- Wang, Yong; Zhang, Taiyang; Kan, Miao
- Journal of the American Chemical Society, Vol. 140, Issue 39
Thermodynamically stabilized β-CsPbI 3 –based perovskite solar cells with efficiencies >18%
journal, August 2019
- Wang, Yong; Dar, M. Ibrahim; Ono, Luis K.
- Science, Vol. 365, Issue 6453
Lewis-Adduct Mediated Grain-Boundary Functionalization for Efficient Ideal-Bandgap Perovskite Solar Cells with Superior Stability
journal, August 2018
- Zong, Yingxia; Zhou, Zhongmin; Chen, Min
- Advanced Energy Materials, Vol. 8, Issue 27
Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide
journal, July 2015
- Ahn, Namyoung; Son, Dae-Yong; Jang, In-Hyuk
- Journal of the American Chemical Society, Vol. 137, Issue 27
Morphological Control for High Performance, Solution-Processed Planar Heterojunction Perovskite Solar Cells
journal, September 2013
- Eperon, Giles E.; Burlakov, Victor M.; Docampo, Pablo
- Advanced Functional Materials, Vol. 24, Issue 1, p. 151-157
Myths and reality of HPbI3 in halide perovskite solar cells
journal, November 2018
- Ke, Weijun; Spanopoulos, Ioannis; Stoumpos, Constantinos C.
- Nature Communications, Vol. 9, Issue 1
Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells
journal, July 2014
- Jeon, Nam Joong; Noh, Jun Hong; Kim, Young Chan
- Nature Materials, Vol. 13, Issue 9, p. 897-903
Carrier lifetimes of >1 μs in Sn-Pb perovskites enable efficient all-perovskite tandem solar cells
journal, April 2019
- Tong, Jinhui; Song, Zhaoning; Kim, Dong Hoe
- Science, Vol. 364, Issue 6439
High Performance of Planar Perovskite Solar Cells Produced from PbI 2 (DMSO) and PbI 2 (NMP) Complexes by Intramolecular Exchange
journal, February 2016
- Jo, Yimhyun; Oh, Kyoung Suk; Kim, Minjin
- Advanced Materials Interfaces, Vol. 3, Issue 10
Influence of Solvent Coordination on Hybrid Organic–Inorganic Perovskite Formation
journal, November 2017
- Hamill, J. Clay; Schwartz, Jeffrey; Loo, Yueh-Lin
- ACS Energy Letters, Vol. 3, Issue 1
Visualization and suppression of interfacial recombination for high-efficiency large-area pin perovskite solar cells
journal, July 2018
- Stolterfoht, Martin; Wolff, Christian M.; Márquez, José A.
- Nature Energy, Vol. 3, Issue 10
Application of Cesium on the Restriction of Precursor Crystallization for Highly Reproducible Perovskite Solar Cells Exceeding 20% Efficiency
journal, February 2018
- Zhou, Gen; Wu, Jionghua; Zhao, Yanhong
- ACS Applied Materials & Interfaces, Vol. 10, Issue 11
Entropic stabilization of mixed A-cation ABX 3 metal halide perovskites for high performance perovskite solar cells
journal, January 2016
- Yi, Chenyi; Luo, Jingshan; Meloni, Simone
- Energy & Environmental Science, Vol. 9, Issue 2
Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics
journal, October 2016
- Swarnkar, A.; Marshall, A. R.; Sanehira, E. M.
- Science, Vol. 354, Issue 6308
Power and Technology Scaling into the 5 nm Node with Stacked Nanosheets
journal, January 2018
- Hook, Terence B.
- Joule, Vol. 2, Issue 1
Mayer Bond Order as a Metric of Complexation Effectiveness in Lead Halide Perovskite Solutions
journal, November 2016
- Stevenson, James; Sorenson, Blaire; Subramaniam, Varun Hari
- Chemistry of Materials, Vol. 29, Issue 6
Scalable fabrication of perovskite solar cells
journal, March 2018
- Li, Zhen; Klein, Talysa R.; Kim, Dong Hoe
- Nature Reviews Materials, Vol. 3, Issue 4
The mechanism of toluene-assisted crystallization of organic–inorganic perovskites for highly efficient solar cells
journal, January 2016
- Sakai, Nobuya; Pathak, Sandeep; Chen, Hsin-Wei
- Journal of Materials Chemistry A, Vol. 4, Issue 12
Perovskite Quantum Dot Photovoltaic Materials beyond the Reach of Thin Films: Full-Range Tuning of A-Site Cation Composition
journal, September 2018
- Hazarika, Abhijit; Zhao, Qian; Gaulding, E. Ashley
- ACS Nano, Vol. 12, Issue 10
Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics
journal, July 2018
- Wheeler, Lance M.; Sanehira, Erin M.; Marshall, Ashley R.
- Journal of the American Chemical Society, Vol. 140, Issue 33
Identifying the Molecular Structures of Intermediates for Optimizing the Fabrication of High-Quality Perovskite Films
journal, August 2016
- Cao, Jing; Jing, Xiaojing; Yan, Juanzhu
- Journal of the American Chemical Society, Vol. 138, Issue 31
Perovskite ink with wide processing window for scalable high-efficiency solar cells
journal, March 2017
- Yang, Mengjin; Li, Zhen; Reese, Matthew O.
- Nature Energy, Vol. 2, Issue 5
Stabilizing the α-Phase of CsPbI3 Perovskite by Sulfobetaine Zwitterions in One-Step Spin-Coating Films
journal, October 2017
- Wang, Qi; Zheng, Xiaopeng; Deng, Yehao
- Joule, Vol. 1, Issue 2
Surface passivation engineering strategy to fully-inorganic cubic CsPbI3 perovskites for high-performance solar cells
journal, March 2018
- Li, Bo; Zhang, Yanan; Fu, Lin
- Nature Communications, Vol. 9, Issue 1
A Green Anti-Solvent Process for High Performance Carbon-Based CsPbI 2 Br All-Inorganic Perovskite Solar Cell
journal, July 2018
- Dong, Chen; Han, Xiuxun; Zhao, Yun
- Solar RRL, Vol. 2, Issue 9
Solution-Phase Synthesis of Cesium Lead Halide Perovskite Nanowires
journal, July 2015
- Zhang, Dandan; Eaton, Samuel W.; Yu, Yi
- Journal of the American Chemical Society, Vol. 137, Issue 29
Enabling Flexible All-Perovskite Tandem Solar Cells
journal, September 2019
- Palmstrom, Axel F.; Eperon, Giles E.; Leijtens, Tomas
- Joule, Vol. 3, Issue 9
Cesium-containing triple cation perovskite solar cells: improved stability, reproducibility and high efficiency
journal, January 2016
- Saliba, Michael; Matsui, Taisuke; Seo, Ji-Youn
- Energy & Environmental Science, Vol. 9, Issue 6
Antisolvent processing of lead halide perovskite thin films studied by in situ X-ray diffraction
journal, January 2018
- Bruening, Karsten; Tassone, Christopher J.
- Journal of Materials Chemistry A, Vol. 6, Issue 39
Cesium Lead Halide Perovskites with Improved Stability for Tandem Solar Cells
journal, February 2016
- Beal, Rachel E.; Slotcavage, Daniel J.; Leijtens, Tomas
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 5
Perovskite precursor solution chemistry: from fundamentals to photovoltaic applications
journal, January 2019
- Jung, Minsu; Ji, Sang-Geun; Kim, Gwisu
- Chemical Society Reviews, Vol. 48, Issue 7
Solvent Engineering for Ambient-Air-Processed, Phase-Stable CsPbI 3 in Perovskite Solar Cells
journal, August 2016
- Luo, Paifeng; Xia, Wei; Zhou, Shengwen
- The Journal of Physical Chemistry Letters, Vol. 7, Issue 18
A vibrational assignment for methyl formate and methyl acetate
journal, January 1957
- Wilmshurst, J. K.
- Journal of Molecular Spectroscopy, Vol. 1, Issue 1-4
Hard and Soft Acids and Bases
journal, November 1963
- Pearson, Ralph G.
- Journal of the American Chemical Society, Vol. 85, Issue 22
From Nano- to Micrometer Scale: The Role of Antisolvent Treatment on High Performance Perovskite Solar Cells
journal, April 2017
- Paek, S.; Schouwink, P.; Athanasopoulou, E. Nefeli
- Chemistry of Materials, Vol. 29, Issue 8
A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016
- McMeekin, D. P.; Sadoughi, G.; Rehman, W.
- Science, Vol. 351, Issue 6269
Kinetic Stabilization of the Sol-Gel State in Perovskites Enables Facile Processing of High-Efficiency Solar Cells
journal, June 2019
- Wang, Kai; Tang, Ming-Chun; Dang, Hoang X.
- Advanced Materials, Vol. 31, Issue 32