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Title: 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 » - 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.« less

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [5];  [1]; ORCiD logo [1];  [6];  [6];  [6]; ORCiD logo [1];  [1]; ORCiD logo [7]; ORCiD logo [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Washington, Seattle, WA (United States)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States); Inst. Photovoltaique d’Île de France (IPVF), Palaiseau (France)
  5. Univ. of Texas, Austin, TX (United States)
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  7. 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}
}

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Cited by: 41 works
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Figures / Tables:

Scheme 1 Scheme 1: (a) Hydrolysis of an Ester To Yield a Carboxylic Acid and an Alcohol; (b) Anionic Carboxylate Ligand-Exchange Reaction Observed in CsPbI3 Thin Films and Solutions; (c) Cationic Ligand Exchange Observed in CsPbI3 Thin Films

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Works referencing / citing this record:

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  • Shi, Jielin; Wang, Yong; Zhao, Yixin
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  • DOI: 10.1002/eem2.12039

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  • ENERGY & ENVIRONMENTAL MATERIALS, Vol. 2, Issue 2
  • DOI: 10.1002/eem2.12039

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  • Chen, Keqiang; Zhong, Qiaohui; Chen, Wen
  • Advanced Functional Materials, Vol. 29, Issue 24
  • DOI: 10.1002/adfm.201900991

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  • Yuan, Jifeng; Bi, Chenghao; Wang, Shixun
  • Advanced Functional Materials, Vol. 29, Issue 49
  • DOI: 10.1002/adfm.201906615

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journal, March 2019

  • Tian, Jingjing; Xue, Qifan; Tang, Xiaofeng
  • Advanced Materials, Vol. 31, Issue 23
  • DOI: 10.1002/adma.201901152

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journal, May 2019

  • Gaulding, E. Ashley; Hao, Ji; Kang, Hyun Suk
  • Advanced Materials, Vol. 31, Issue 27
  • DOI: 10.1002/adma.201902250

Review on Recent Progress of All‐Inorganic Metal Halide Perovskites and Solar Cells
journal, September 2019


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
  • DOI: 10.1002/admi.201901136

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journal, June 2019

  • Ling, Xufeng; Zhou, Sijie; Yuan, Jianyu
  • Advanced Energy Materials, Vol. 9, Issue 28
  • DOI: 10.1002/aenm.201900721

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
  • DOI: 10.1002/aenm.201901787

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
  • DOI: 10.1002/aenm.201903365

Anorganische CsPbX 3 ‐Perowskit‐Solarzellen: Fortschritte und Perspektiven
journal, August 2019


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
  • DOI: 10.1002/anie.201901081

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journal, May 2019

  • Cho, Yuljae; Pak, Sangyeon; An, Geon‐Hyoung
  • Israel Journal of Chemistry, Vol. 59, Issue 8
  • DOI: 10.1002/ijch.201900035

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
  • DOI: 10.1002/ppsc.201900391

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
  • DOI: 10.1002/pssr.201900387

Halide Perovskite Nanocrystals for Next‐Generation Optoelectronics
journal, April 2019


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
  • DOI: 10.1002/wnan.1567

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
  • DOI: 10.1039/c8nr08445a

Observation and implication of halide exchange beyond CsPbX 3 perovskite nanocrystals
journal, January 2019


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
  • DOI: 10.1039/c8se00315g

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
  • DOI: 10.1039/c8ta10901j

Colloidal metal halide perovskite nanocrystals: a promising juggernaut in photovoltaic applications
journal, January 2019


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
  • DOI: 10.1039/c8tc05545a

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
  • DOI: 10.1039/c9nr03707a

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
  • DOI: 10.1039/c9ta07143a

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
  • DOI: 10.1063/1.5129261

Synthesis and optical applications of low dimensional metal-halide perovskites
journal, January 2020


Resurfacing halide perovskite nanocrystals
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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.