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Title: Dynamics of charged excitons in electronically and morphologically homogeneous single-walled carbon nanotubes

Abstract

The trion, a three-body charge-exciton bound state, offers unique opportunities to simultaneously manipulate charge, spin, and excitation in one-dimensional single-walled carbon nanotubes (SWNTs) at room temperature. Effective exploitation of trion quasi-particles requires fundamental insight into their creation and decay dynamics. Such knowledge, however, remains elusive for SWNT trion states, due to the electronic and morphological heterogeneity of commonly interrogated SWNT samples, and the fact that transient spectroscopic signals uniquely associated with the trion state have not been identified. Here, we prepare length-sorted SWNTs and precisely control charge-carrier-doping densities to determine trion dynamics using femtosecond pump–probe spectroscopy. Identification of the trion transient absorptive hallmark enables us to demonstrate that trions ( i ) derive from a precursor excitonic state, ( ii ) are produced via migration of excitons to stationary hole-polaron sites, and ( iii ) decay in a first-order manner. Importantly, under appropriate carrier-doping densities, exciton-to-trion conversion in SWNTs can approach 100% at ambient temperature. Our findings open up possibilities for exploiting trions in SWNT optoelectronics, ranging from photovoltaics and photodetectors to spintronics.

Authors:
; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1416093
Alternate Identifier(s):
OSTI ID: 1527123
Grant/Contract Number:  
SC0001517
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 4; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; trion; exciton; single-walled carbon nanotube; dynamics; charge

Citation Formats

Bai, Yusong, Olivier, Jean-Hubert, Bullard, George, Liu, Chaoren, and Therien, Michael J. Dynamics of charged excitons in electronically and morphologically homogeneous single-walled carbon nanotubes. United States: N. p., 2018. Web. doi:10.1073/pnas.1712971115.
Bai, Yusong, Olivier, Jean-Hubert, Bullard, George, Liu, Chaoren, & Therien, Michael J. Dynamics of charged excitons in electronically and morphologically homogeneous single-walled carbon nanotubes. United States. doi:10.1073/pnas.1712971115.
Bai, Yusong, Olivier, Jean-Hubert, Bullard, George, Liu, Chaoren, and Therien, Michael J. Mon . "Dynamics of charged excitons in electronically and morphologically homogeneous single-walled carbon nanotubes". United States. doi:10.1073/pnas.1712971115.
@article{osti_1416093,
title = {Dynamics of charged excitons in electronically and morphologically homogeneous single-walled carbon nanotubes},
author = {Bai, Yusong and Olivier, Jean-Hubert and Bullard, George and Liu, Chaoren and Therien, Michael J.},
abstractNote = {The trion, a three-body charge-exciton bound state, offers unique opportunities to simultaneously manipulate charge, spin, and excitation in one-dimensional single-walled carbon nanotubes (SWNTs) at room temperature. Effective exploitation of trion quasi-particles requires fundamental insight into their creation and decay dynamics. Such knowledge, however, remains elusive for SWNT trion states, due to the electronic and morphological heterogeneity of commonly interrogated SWNT samples, and the fact that transient spectroscopic signals uniquely associated with the trion state have not been identified. Here, we prepare length-sorted SWNTs and precisely control charge-carrier-doping densities to determine trion dynamics using femtosecond pump–probe spectroscopy. Identification of the trion transient absorptive hallmark enables us to demonstrate that trions ( i ) derive from a precursor excitonic state, ( ii ) are produced via migration of excitons to stationary hole-polaron sites, and ( iii ) decay in a first-order manner. Importantly, under appropriate carrier-doping densities, exciton-to-trion conversion in SWNTs can approach 100% at ambient temperature. Our findings open up possibilities for exploiting trions in SWNT optoelectronics, ranging from photovoltaics and photodetectors to spintronics.},
doi = {10.1073/pnas.1712971115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 4,
volume = 115,
place = {United States},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1712971115

Citation Metrics:
Cited by: 3 works
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Figures / Tables:

Fig. 1 Fig. 1: Structure, morphology, and ultrafast pump–probe spectra of polymer-wrapped SWNTs. (A) Structural schematic of a chiral [arylene]ethynylene polymer-wrapped SWNT (Top); the polymer wraps the SWNT in an exclusive left-handed helical configuration that features a constant pitch length of 10 nm. Molecular structure of the binaphthalene-based polyanionic semiconducting polymer, S-PBN(b)-Ph5more » (Bottom). (B) Transmission electron microscopy image of an S-PBN(b)-Ph5-[(6,5) SWNT] obtained from aqueous suspension highlighting the individualized and helically wrapped nature of the polymer-SWNT superstructure. (Inset) A 3D topographic intermittent contact atomic force microscopy image of an S-PBN(b)-Ph5-[(6,5) SWNT] on a Si surface, underscoring the periodic surface morphology. (C) Representative 2D plot of transient absorption spectra for neutral S-PBN(b)-Ph5-[(6,5) SWNTs]; the horizontal axis, vertical axis, and color scale represent the probe wavelength (photon energy), pump–probe time delay, and the transient absorption signal, respectively. Positive signals indicate a pump-induced increase in absorption, while negative signals indicate pump-induced decrease in absorption; dotted lines highlight major transition manifolds. Experimental conditions: λexc = 1,000 nm; solvent = D2O; T = 293 K; magic angle polarization; excitation pump power = 140 μJ/cm2.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.