Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics
Abstract
The ability to manipulate quantum dot (QD) surfaces is foundational to their technological deployment. Surface manipulation of metal halide perovskite (MHP) QDs has proven particularly challenging in comparison to that of more established inorganic materials due to dynamic surface species and low material formation energy; most conventional methods of chemical manipulation targeted at the MHP QD surface will result in transformation or dissolution of the MHP crystal. In previous work, we have demonstrated record-efficiency QD solar cells (QDSCs) based on ligand-exchange procedures that electronically couple MHP QDs yet maintain their nanocrystalline size, which stabilizes the corner-sharing structure of the constituent PbI64-octahedra with optoelectronic properties optimal for solar energy conversion. In this work, we employ a variety of spectroscopic techniques to develop a molecular-level understanding of the MHP QD surface chemistry in this system. We individually target both the anionic (oleate) and cationic (oleylammonium) ligands. We find that atmospheric moisture aids the process by hydrolysis of methyl acetate to generate acetic acid and methanol. Acetic acid then replaces native oleate ligands to yield QD surface-bound acetate and free oleic acid. The native oleylammonium ligands remain throughout this film deposition process and are exchanged during a final treatment step employing smaller cationsmore »
- Authors:
-
- National Renewable Energy Lab. (NREL), Golden, CO (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Washington, Seattle, WA (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
- National Renewable Energy Lab. (NREL), Golden, CO (United States); Inst. Photovoltaique d’Île de France (IPVF), Palaiseau (France)
- Univ. of Texas, Austin, TX (United States)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Univ. of Washington, Seattle, WA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Advanced Solar Photophysics (CASP); National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Workforce Development for Teachers and Scientists (WDTS); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Renewable Power Office. Solar Energy Technologies Office
- OSTI Identifier:
- 1466557
- Report Number(s):
- NREL/JA-5900-71521
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: 140; Journal Issue: 33; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 14 SOLAR ENERGY; 77 NANOSCIENCE AND NANOTECHNOLOGY; atmospheric moisture; chemical manipulation; film-deposition process; nanocrystalline size; optoelectronic properties; photovoltaic performance; spectroscopic technique; surface manipulation
Citation Formats
Wheeler, Lance M., Sanehira, Erin M., Marshall, Ashley R., Schulz, Philip, Suri, Mokshin, Anderson, Nicholas C., Christians, Jeffrey A., Nordlund, Dennis, Sokaras, Dimosthenis, Kroll, Thomas, Harvey, Steven P., Berry, Joseph J., Lin, Lih Y., and Luther, Joseph M. Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b04984.
Wheeler, Lance M., Sanehira, Erin M., Marshall, Ashley R., Schulz, Philip, Suri, Mokshin, Anderson, Nicholas C., Christians, Jeffrey A., Nordlund, Dennis, Sokaras, Dimosthenis, Kroll, Thomas, Harvey, Steven P., Berry, Joseph J., Lin, Lih Y., & Luther, Joseph M. Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics. United States. doi:https://doi.org/10.1021/jacs.8b04984
Wheeler, Lance M., Sanehira, Erin M., Marshall, Ashley R., Schulz, Philip, Suri, Mokshin, Anderson, Nicholas C., Christians, Jeffrey A., Nordlund, Dennis, Sokaras, Dimosthenis, Kroll, Thomas, Harvey, Steven P., Berry, Joseph J., Lin, Lih Y., and Luther, Joseph M. Wed .
"Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics". United States. doi:https://doi.org/10.1021/jacs.8b04984. https://www.osti.gov/servlets/purl/1466557.
@article{osti_1466557,
title = {Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics},
author = {Wheeler, Lance M. and Sanehira, Erin M. and Marshall, Ashley R. and Schulz, Philip and Suri, Mokshin and Anderson, Nicholas C. and Christians, Jeffrey A. and Nordlund, Dennis and Sokaras, Dimosthenis and Kroll, Thomas and Harvey, Steven P. and Berry, Joseph J. and Lin, Lih Y. and Luther, Joseph M.},
abstractNote = {The ability to manipulate quantum dot (QD) surfaces is foundational to their technological deployment. Surface manipulation of metal halide perovskite (MHP) QDs has proven particularly challenging in comparison to that of more established inorganic materials due to dynamic surface species and low material formation energy; most conventional methods of chemical manipulation targeted at the MHP QD surface will result in transformation or dissolution of the MHP crystal. In previous work, we have demonstrated record-efficiency QD solar cells (QDSCs) based on ligand-exchange procedures that electronically couple MHP QDs yet maintain their nanocrystalline size, which stabilizes the corner-sharing structure of the constituent PbI64-octahedra with optoelectronic properties optimal for solar energy conversion. In this work, we employ a variety of spectroscopic techniques to develop a molecular-level understanding of the MHP QD surface chemistry in this system. We individually target both the anionic (oleate) and cationic (oleylammonium) ligands. We find that atmospheric moisture aids the process by hydrolysis of methyl acetate to generate acetic acid and methanol. Acetic acid then replaces native oleate ligands to yield QD surface-bound acetate and free oleic acid. The native oleylammonium ligands remain throughout this film deposition process and are exchanged during a final treatment step employing smaller cations - namely, formamidinium. This final treatment has a narrow processing window; initial treatment at this stage leads to a more strongly coupled QD regime followed by transformation into a bulk MHP film after longer treatment. These insights provide chemical understanding to the deposition of high-quality, electronically coupled MHP QD films that maintain both quantum confinement and their crystalline phase and attain high photovoltaic performance.},
doi = {10.1021/jacs.8b04984},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 140,
place = {United States},
year = {2018},
month = {7}
}
Web of Science
Figures / Tables:

Works referencing / citing this record:
Inorganic CsPbI 3 Perovskites toward High‐Efficiency Photovoltaics
journal, June 2019
- Shi, Jielin; Wang, Yong; Zhao, Yixin
- ENERGY & ENVIRONMENTAL MATERIALS, Vol. 2, Issue 2
High efficiency perovskite quantum dot solar cells with charge separating heterostructure
journal, June 2019
- Zhao, Qian; Hazarika, Abhijit; Chen, Xihan
- Nature Communications, Vol. 10, Issue 1
Inorganic CsPbI 3 Perovskites toward High‐Efficiency Photovoltaics
journal, June 2019
- Shi, Jielin; Wang, Yong; Zhao, Yixin
- ENERGY & ENVIRONMENTAL MATERIALS, Vol. 2, Issue 2
High efficiency perovskite quantum dot solar cells with charge separating heterostructure
journal, June 2019
- Zhao, Qian; Hazarika, Abhijit; Chen, Xihan
- Nature Communications, Vol. 10, Issue 1
Short‐Chain Ligand‐Passivated Stable α‐CsPbI 3 Quantum Dot for All‐Inorganic Perovskite Solar Cells
journal, April 2019
- Chen, Keqiang; Zhong, Qiaohui; Chen, Wen
- Advanced Functional Materials, Vol. 29, Issue 24
Spray‐Coated Colloidal Perovskite Quantum Dot Films for Highly Efficient Solar Cells
journal, September 2019
- Yuan, Jifeng; Bi, Chenghao; Wang, Shixun
- Advanced Functional Materials, Vol. 29, Issue 49
A Small‐Molecule “Charge Driver” enables Perovskite Quantum Dot Solar Cells with Efficiency Approaching 13%
journal, July 2019
- Xue, Jingjing; Wang, Rui; Chen, Lan
- Advanced Materials, Vol. 31, Issue 37
Dual Interfacial Design for Efficient CsPbI 2 Br Perovskite Solar Cells with Improved Photostability
journal, March 2019
- Tian, Jingjing; Xue, Qifan; Tang, Xiaofeng
- Advanced Materials, Vol. 31, Issue 23
Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI 3 Nanocrystal Films
journal, May 2019
- Gaulding, E. Ashley; Hao, Ji; Kang, Hyun Suk
- Advanced Materials, Vol. 31, Issue 27
Review on Recent Progress of All‐Inorganic Metal Halide Perovskites and Solar Cells
journal, September 2019
- Xiang, Wanchun; Tress, Wolfgang
- Advanced Materials, Vol. 31, Issue 44
Managing Energy Loss in Inorganic Lead Halide Perovskites Solar Cells
journal, September 2019
- Liu, Chongming; Zeng, Qingsen; Yang, Bai
- Advanced Materials Interfaces, Vol. 6, Issue 22
14.1% CsPbI 3 Perovskite Quantum Dot Solar Cells via Cesium Cation Passivation
journal, June 2019
- Ling, Xufeng; Zhou, Sijie; Yuan, Jianyu
- Advanced Energy Materials, Vol. 9, Issue 28
Rational Core–Shell Design of Open Air Low Temperature In Situ Processable CsPbI 3 Quasi‐Nanocrystals for Stabilized p‐i‐n Solar Cells
journal, July 2019
- Xi, Jun; Piao, Chengcheng; Byeon, Junseop
- Advanced Energy Materials, Vol. 9, Issue 31
CsI‐Antisolvent Adduct Formation in All‐Inorganic Metal Halide Perovskites
journal, January 2020
- Moot, Taylor; Marshall, Ashley R.; Wheeler, Lance M.
- Advanced Energy Materials, Vol. 10, Issue 9
Anorganische CsPbX 3 ‐Perowskit‐Solarzellen: Fortschritte und Perspektiven
journal, August 2019
- Zhang, Jingru; Hodes, Gary; Jin, Zhiwen
- Angewandte Chemie, Vol. 131, Issue 44
All‐Inorganic CsPbX 3 Perovskite Solar Cells: Progress and Prospects
journal, August 2019
- Zhang, Jingru; Hodes, Gary; Jin, Zhiwen
- Angewandte Chemie International Edition, Vol. 58, Issue 44
Quantum Dots for Hybrid Energy Harvesting: From Integration to Piezo‐Phototronics
journal, May 2019
- Cho, Yuljae; Pak, Sangyeon; An, Geon‐Hyoung
- Israel Journal of Chemistry, Vol. 59, Issue 8
Room Temperature Synthesis of Phosphine‐Capped Lead Bromide Perovskite Nanocrystals without Coordinating Solvents
journal, November 2019
- Ambroz, Filip; Xu, Weidong; Gadipelli, Srinivas
- Particle & Particle Systems Characterization, Vol. 37, Issue 1
Role of Capped Oleyl Amine in the Moisture‐Induced Structural Transformation of CsPbBr 3 Perovskite Nanocrystals
journal, May 2019
- Sandeep, K.; Gopika, K. Y.; Revathi, M. R.
- physica status solidi (RRL) – Rapid Research Letters, Vol. 13, Issue 11
Halide Perovskite Nanocrystals for Next‐Generation Optoelectronics
journal, April 2019
- Liu, Maning; Zhang, Haichang; Gedamu, Dawit
- Small, Vol. 15, Issue 28
Quantum dots from microfluidics for nanomedical application
journal, July 2019
- Bian, Feika; Sun, Lingyu; Cai, Lijun
- Wiley Interdisciplinary Reviews: Nanomedicine and Nanobiotechnology, Vol. 11, Issue 5
Ligand-assisted cation-exchange engineering for high-efficiency colloidal Cs1−xFAxPbI3 quantum dot solar cells with reduced phase segregation
journal, January 2020
- Hao, Mengmeng; Bai, Yang; Zeiske, Stefan
- Nature Energy, Vol. 5, Issue 1
Charge transfer dynamics in CsPbBr 3 perovskite quantum dots–anthraquinone/fullerene (C 60 ) hybrids
journal, January 2019
- Mandal, Sadananda; George, Lijo; Tkachenko, Nikolai V.
- Nanoscale, Vol. 11, Issue 3
Observation and implication of halide exchange beyond CsPbX 3 perovskite nanocrystals
journal, January 2019
- Jia, Chao; Li, Hui; Tan, Longfei
- Nanoscale, Vol. 11, Issue 7
Building bridges between halide perovskite nanocrystals and thin-film solar cells
journal, January 2018
- Yang, Hanjun; Zhang, Yi; Hills-Kimball, Katie
- Sustainable Energy & Fuels, Vol. 2, Issue 11
Convenient preparation of CsSnI 3 quantum dots, excellent stability, and the highest performance of lead-free inorganic perovskite solar cells so far
journal, January 2019
- Wang, Yangyang; Tu, Jin; Li, Tianhao
- Journal of Materials Chemistry A, Vol. 7, Issue 13
Colloidal metal halide perovskite nanocrystals: a promising juggernaut in photovoltaic applications
journal, January 2019
- Fu, Huiying
- Journal of Materials Chemistry A, Vol. 7, Issue 24
Luminescent perovskite quantum dots: synthesis, microstructures, optical properties and applications
journal, January 2019
- Chen, Daqin; Chen, Xiao
- Journal of Materials Chemistry C, Vol. 7, Issue 6
Hybrid light emitting diodes based on stable, high brightness all-inorganic CsPbI 3 perovskite nanocrystals and InGaN
journal, January 2019
- Zhang, Chengxi; Turyanska, Lyudmila; Cao, Haicheng
- Nanoscale, Vol. 11, Issue 28
Efficient and stable CsPbI 3 perovskite quantum dots enabled by in situ ytterbium doping for photovoltaic applications
journal, January 2019
- Shi, Junwei; Li, Fangchao; Yuan, Jianyu
- Journal of Materials Chemistry A, Vol. 7, Issue 36
Enhanced photoredox activity of CsPbBr 3 nanocrystals by quantitative colloidal ligand exchange
journal, November 2019
- Lu, Haipeng; Zhu, Xiaolin; Miller, Collin
- The Journal of Chemical Physics, Vol. 151, Issue 20
Synthesis and optical applications of low dimensional metal-halide perovskites
journal, January 2020
- Liu, Jingying; Chen, Keqiang; Khan, Sayed Ali
- Nanotechnology, Vol. 31, Issue 15
Resurfacing halide perovskite nanocrystals
journal, May 2019
- Almeida, Guilherme; Infante, Ivan; Manna, Liberato
- Science, Vol. 364, Issue 6443
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