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Title: Exciton–Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands

Abstract

Some ligand-nanocrystal combinations exhibit rapid cooling of highly excited electronic states while other nanocrystal/shell combinations do not appear to have this effect. There remains a need to identify the distinguishing properties of ligand-nanocrystal interactions that avoid such rapid relaxation processes to guide the design of colloidal quantum dots (QDs) that take advantage of multiple exciton generation or hot-carrier extraction processes. Here, we use mid-infrared transient absorption spectroscopy to investigate the influence that carboxylate ligands with distinct excited state surface chemistries has on exciton-phonon coupling and hot exciton relaxation in PbS quantum dot (QD) films. Our findings reveal that despite significant differences in the excited state surface chemistry of oleate (OA) and iodide/mercaptopropionic acid (I-/MPA) ligands, PbS QD films passivated with both ligand types exhibit identical electronic relaxation rates and exciton-phonon coupling strengths within experimental precision. The data suggest that the inorganic lattice is the principal source of exciton-phonon coupling that influences hot exciton relaxation, rather than the vibronic modes of carboxylate ligands. The size-dependent nature of the exciton-phonon coupling strength is consistent with the localization of charge on the QD surfaces, which enhances the mixing of electronic and nuclear coordinates particularly when the electronic states are more quantum confined inmore » smaller nanocrystals.« less

Authors:
 [1];  [2];  [1];  [2];  [3]; ORCiD logo [3]; ORCiD logo [2]
+ Show Author Affiliations
  1. Magnitude Instruments, State College, PA (United States); Pennsylvania State Univ., University Park, PA (United States)
  2. Pennsylvania State Univ., University Park, PA (United States)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)
Publication Date:
Research Org.:
Pennsylvania State Univ., University Park, PA (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1839362
Alternate Identifier(s):
OSTI ID: 1832229
Report Number(s):
NREL/JA-5900-80431
Journal ID: ISSN 1932-7447; DGE1255832
Grant/Contract Number:  
SC0019349; DGE1255832; AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 125; Journal Issue: 41; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 14 SOLAR ENERGY; Quantum dots; Light absorption; Ligands; Excited states; Nanocrystals; Carrier dynamics; Ligand chemistry; QDs; Solar-photochemistry

Citation Formats

Kennehan, Eric R., Munson, Kyle T., Grieco, Christopher, Doucette, Grayson S., Marshall, Ashley R., Beard, Matthew C., and Asbury, John B. Exciton–Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands. United States: N. p., 2021. Web. doi:10.1021/acs.jpcc.1c05803.
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Kennehan, Eric R., Munson, Kyle T., Grieco, Christopher, Doucette, Grayson S., Marshall, Ashley R., Beard, Matthew C., & Asbury, John B. Exciton–Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands. United States. https://doi.org/10.1021/acs.jpcc.1c05803
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Kennehan, Eric R., Munson, Kyle T., Grieco, Christopher, Doucette, Grayson S., Marshall, Ashley R., Beard, Matthew C., and Asbury, John B. Fri . "Exciton–Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands". United States. https://doi.org/10.1021/acs.jpcc.1c05803. https://www.osti.gov/servlets/purl/1839362.
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@article{osti_1839362,
title = {Exciton–Phonon Coupling and Carrier Relaxation in PbS Quantum Dots: The Case of Carboxylate Ligands},
author = {Kennehan, Eric R. and Munson, Kyle T. and Grieco, Christopher and Doucette, Grayson S. and Marshall, Ashley R. and Beard, Matthew C. and Asbury, John B.},
abstractNote = {Some ligand-nanocrystal combinations exhibit rapid cooling of highly excited electronic states while other nanocrystal/shell combinations do not appear to have this effect. There remains a need to identify the distinguishing properties of ligand-nanocrystal interactions that avoid such rapid relaxation processes to guide the design of colloidal quantum dots (QDs) that take advantage of multiple exciton generation or hot-carrier extraction processes. Here, we use mid-infrared transient absorption spectroscopy to investigate the influence that carboxylate ligands with distinct excited state surface chemistries has on exciton-phonon coupling and hot exciton relaxation in PbS quantum dot (QD) films. Our findings reveal that despite significant differences in the excited state surface chemistry of oleate (OA) and iodide/mercaptopropionic acid (I-/MPA) ligands, PbS QD films passivated with both ligand types exhibit identical electronic relaxation rates and exciton-phonon coupling strengths within experimental precision. The data suggest that the inorganic lattice is the principal source of exciton-phonon coupling that influences hot exciton relaxation, rather than the vibronic modes of carboxylate ligands. The size-dependent nature of the exciton-phonon coupling strength is consistent with the localization of charge on the QD surfaces, which enhances the mixing of electronic and nuclear coordinates particularly when the electronic states are more quantum confined in smaller nanocrystals.},
doi = {10.1021/acs.jpcc.1c05803},
journal = {Journal of Physical Chemistry. C},
number = 41,
volume = 125,
place = {United States},
year = {Fri Oct 08 00:00:00 EDT 2021},
month = {Fri Oct 08 00:00:00 EDT 2021}
}
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