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Title: Coupling between Emissive Defects on Carbon Nanotubes: Modeling Insights

Abstract

Covalent functionalization of single-walled carbon nanotubes (SWCNTs) with organic molecules results in red-shifted emissive states associated with sp3-defects in the tube lattice, which facilitate their improved optical functionality, including single-photon emission. The energy of the defect-based electronic excitations (excitons) depends on the molecular adducts, the configuration of the defect, and concentration of defects. In this work, we model the interactions between two sp3-defects placed at various distances in the (6,5) SWCNT using time-dependent density functional theory. Calculations reveal that these interactions conform to the effective model of J-aggregates for well-spaced defects (>2 nm), leading to a red-shifted and optically allowed (bright) lowest energy exciton. H-aggregate behavior is not observed for any defect orientations, which is beneficial for emission. The splitting between the lowest energy bright and optically forbidden (dark) excitons and the pristine excitonic band are controlled by the single-defect configurations and their axial separation. These findings enable a synthetic design strategy for SWCNTs with tunable near-infrared emission.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [3]
+ Show Author Affiliations
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Univ. of Rochester, NY (United States); North Dakota State Univ., Fargo, ND (United States)
  2. Army Research Lab., Adelphi, MD (United States)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. North Dakota State Univ., Fargo, ND (United States)
Publication Date:
Research Org.:
North Dakota State Univ., Fargo, ND (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1839862
Grant/Contract Number:  
SC0021287; AC02-05CH11231; 86678
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 12; Journal Issue: 32; Related Information: The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.1c01631.Array of spectra for all geometries studied in this work, real-space projected transition density for single-defect and angular-dependent geometries, as well as an analysis of a model HJ-aggregate system; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
77 NANOSCIENCE AND NANOTECHNOLOGY; covalent functionalization; single-walled carbon nanotubes

Citation Formats

Weight, Braden M., Sifain, Andrew E., Gifford, Brendan J., Kilin, Dmitri, Kilina, Svetlana, and Tretiak, Sergei. Coupling between Emissive Defects on Carbon Nanotubes: Modeling Insights. United States: N. p., 2021. Web. doi:10.1021/acs.jpclett.1c01631.
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Weight, Braden M., Sifain, Andrew E., Gifford, Brendan J., Kilin, Dmitri, Kilina, Svetlana, & Tretiak, Sergei. Coupling between Emissive Defects on Carbon Nanotubes: Modeling Insights. United States. https://doi.org/10.1021/acs.jpclett.1c01631
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Weight, Braden M., Sifain, Andrew E., Gifford, Brendan J., Kilin, Dmitri, Kilina, Svetlana, and Tretiak, Sergei. Wed . "Coupling between Emissive Defects on Carbon Nanotubes: Modeling Insights". United States. https://doi.org/10.1021/acs.jpclett.1c01631. https://www.osti.gov/servlets/purl/1839862.
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@article{osti_1839862,
title = {Coupling between Emissive Defects on Carbon Nanotubes: Modeling Insights},
author = {Weight, Braden M. and Sifain, Andrew E. and Gifford, Brendan J. and Kilin, Dmitri and Kilina, Svetlana and Tretiak, Sergei},
abstractNote = {Covalent functionalization of single-walled carbon nanotubes (SWCNTs) with organic molecules results in red-shifted emissive states associated with sp3-defects in the tube lattice, which facilitate their improved optical functionality, including single-photon emission. The energy of the defect-based electronic excitations (excitons) depends on the molecular adducts, the configuration of the defect, and concentration of defects. In this work, we model the interactions between two sp3-defects placed at various distances in the (6,5) SWCNT using time-dependent density functional theory. Calculations reveal that these interactions conform to the effective model of J-aggregates for well-spaced defects (>2 nm), leading to a red-shifted and optically allowed (bright) lowest energy exciton. H-aggregate behavior is not observed for any defect orientations, which is beneficial for emission. The splitting between the lowest energy bright and optically forbidden (dark) excitons and the pristine excitonic band are controlled by the single-defect configurations and their axial separation. These findings enable a synthetic design strategy for SWCNTs with tunable near-infrared emission.},
doi = {10.1021/acs.jpclett.1c01631},
journal = {Journal of Physical Chemistry Letters},
number = 32,
volume = 12,
place = {United States},
year = {Wed Aug 11 00:00:00 EDT 2021},
month = {Wed Aug 11 00:00:00 EDT 2021}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.1c01631
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