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Title: Mechanistic Exploration of Dodecanethiol-Treated Colloidal CsPbBr 3 Nanocrystals with Photoluminescence Quantum Yields Reaching Near 100%

Abstract

Metal halide perovskite nanocrystals (NCs) are attractive materials for optoelectronics. However, further improvements in stability, reproducibility, and photoluminescence quantum yield (Φ PL) are essential for enabling future applications. Inadequate surface passivation is a major cause of instability, irreproducibility, and less than unity Φ PL. Herein, we probe the influence of multiple ligand binding groups on the colloidal stability and Φ PL of CsPbBr 3 nanocrystals (NCs). Here, we find that post-synthetic treatment with dodecanethiol reproducibly yields highly stable NCs with near-unity Φ PL for a range of synthetic conditions and initial Φ PL of the as-synthesized NCs. A mechanistic investigation shows that thiol addition leads to thioether formation via the thiol–ene reaction with octadecene, oleic acid, and oleylamine. Both thiolates and thioethers are suspected to bind to undercoordinated Pb atoms on the NC surfaces, and this surface binding can be rapidly accelerated through exposure to blue or UV light. Furthermore, we show that metallic Pb nanoparticles appear in many batches of synthesized CsPbBr 3 NCs and that dodecanethiol addition eliminates these metallic Pb particles.

Authors:
 [1]; ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Kentucky, Lexington, KY (United States)
Publication Date:
Research Org.:
Univ. of Kentucky, Lexington, KY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Kentucky Science & Engineering Foundation, Lexington, KY (United States)
OSTI Identifier:
1594889
Grant/Contract Number:  
SC0018208; KSEF-3884-RDE-020; IDBR 1556281; 1355438
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 29; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; 14 SOLAR ENERGY; 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Uddin, Md Aslam, Mobley, Justin K., Masud, Abdullah A., Liu, Tuo, Calabro, Rosemary L., Kim, Doo-Young, Richards, Christopher I., and Graham, Kenneth R. Mechanistic Exploration of Dodecanethiol-Treated Colloidal CsPbBr3 Nanocrystals with Photoluminescence Quantum Yields Reaching Near 100%. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.9b05612.
Uddin, Md Aslam, Mobley, Justin K., Masud, Abdullah A., Liu, Tuo, Calabro, Rosemary L., Kim, Doo-Young, Richards, Christopher I., & Graham, Kenneth R. Mechanistic Exploration of Dodecanethiol-Treated Colloidal CsPbBr3 Nanocrystals with Photoluminescence Quantum Yields Reaching Near 100%. United States. doi:10.1021/acs.jpcc.9b05612.
Uddin, Md Aslam, Mobley, Justin K., Masud, Abdullah A., Liu, Tuo, Calabro, Rosemary L., Kim, Doo-Young, Richards, Christopher I., and Graham, Kenneth R. Fri . "Mechanistic Exploration of Dodecanethiol-Treated Colloidal CsPbBr3 Nanocrystals with Photoluminescence Quantum Yields Reaching Near 100%". United States. doi:10.1021/acs.jpcc.9b05612. https://www.osti.gov/servlets/purl/1594889.
@article{osti_1594889,
title = {Mechanistic Exploration of Dodecanethiol-Treated Colloidal CsPbBr3 Nanocrystals with Photoluminescence Quantum Yields Reaching Near 100%},
author = {Uddin, Md Aslam and Mobley, Justin K. and Masud, Abdullah A. and Liu, Tuo and Calabro, Rosemary L. and Kim, Doo-Young and Richards, Christopher I. and Graham, Kenneth R.},
abstractNote = {Metal halide perovskite nanocrystals (NCs) are attractive materials for optoelectronics. However, further improvements in stability, reproducibility, and photoluminescence quantum yield (ΦPL) are essential for enabling future applications. Inadequate surface passivation is a major cause of instability, irreproducibility, and less than unity ΦPL. Herein, we probe the influence of multiple ligand binding groups on the colloidal stability and ΦPL of CsPbBr3 nanocrystals (NCs). Here, we find that post-synthetic treatment with dodecanethiol reproducibly yields highly stable NCs with near-unity ΦPL for a range of synthetic conditions and initial ΦPL of the as-synthesized NCs. A mechanistic investigation shows that thiol addition leads to thioether formation via the thiol–ene reaction with octadecene, oleic acid, and oleylamine. Both thiolates and thioethers are suspected to bind to undercoordinated Pb atoms on the NC surfaces, and this surface binding can be rapidly accelerated through exposure to blue or UV light. Furthermore, we show that metallic Pb nanoparticles appear in many batches of synthesized CsPbBr3 NCs and that dodecanethiol addition eliminates these metallic Pb particles.},
doi = {10.1021/acs.jpcc.9b05612},
journal = {Journal of Physical Chemistry. C},
issn = {1932-7447},
number = 29,
volume = 123,
place = {United States},
year = {2019},
month = {6}
}

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