DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes

Abstract

Covalent dopants in semiconducting single wall carbon nanotubes (SWCNTs) are becoming important as routes for introducing new photoluminescent emitting states with potential for enhanced quantum yields, new functionality, and as species capable of near-IR room-temperature single photon emission. The origin and behavior of the dopant-induced emission is thus important to understand as a key requirement for successful room-T photonics and optoelectronics applications. Here, we use direct correlated two-color photoluminescence imaging to probe how the interplay between the SWCNT bright E11 exciton and solitary dopant sites yields the dopant-induced emission for three different dopant species: oxygen, 4-methoxybenzene, and 4-bromobenzene. We introduce a route to control dopant functionalization to a low level as a means for introducing spatially well-separated solitary dopant sites. Resolution of emission from solitary dopant sites and correlation to their impact on E11 emission allows confirmation of dopants as trapping sites for localization of E11 excitons following their diffusive transport to the dopant site. Imaging of the dopant emission also reveals photoluminescence intermittency (blinking), with blinking dynamics being dependent on the specific dopant. Density functional theory calculations were performed to evaluate the stability of dopants and delineate the possible mechanisms of blinking. Furthermore, theoretical modeling suggests that the trappingmore » of free charges in the potential well created by permanent dipoles introduced by dopant atoms/groups is likely responsible for the blinking, with the strongest effects being predicted and observed for oxygen-doped SWCNTs.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1255120
Report Number(s):
LA-UR-15-28130
Journal ID: ISSN 2040-3364; NANOHL
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 7; Journal Issue: 48; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY

Citation Formats

Hartmann, Nicolai F., Yalcin, Sibel Ebru, Adamska, Lyudmyla, Haroz, Erik H., Ma, Xuedan, Tretiak, Sergei, Htoon, Han, and Doorn, Stephen K. Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes. United States: N. p., 2015. Web. doi:10.1039/C5NR06343D.
Hartmann, Nicolai F., Yalcin, Sibel Ebru, Adamska, Lyudmyla, Haroz, Erik H., Ma, Xuedan, Tretiak, Sergei, Htoon, Han, & Doorn, Stephen K. Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes. United States. https://doi.org/10.1039/C5NR06343D
Hartmann, Nicolai F., Yalcin, Sibel Ebru, Adamska, Lyudmyla, Haroz, Erik H., Ma, Xuedan, Tretiak, Sergei, Htoon, Han, and Doorn, Stephen K. Wed . "Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes". United States. https://doi.org/10.1039/C5NR06343D. https://www.osti.gov/servlets/purl/1255120.
@article{osti_1255120,
title = {Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes},
author = {Hartmann, Nicolai F. and Yalcin, Sibel Ebru and Adamska, Lyudmyla and Haroz, Erik H. and Ma, Xuedan and Tretiak, Sergei and Htoon, Han and Doorn, Stephen K.},
abstractNote = {Covalent dopants in semiconducting single wall carbon nanotubes (SWCNTs) are becoming important as routes for introducing new photoluminescent emitting states with potential for enhanced quantum yields, new functionality, and as species capable of near-IR room-temperature single photon emission. The origin and behavior of the dopant-induced emission is thus important to understand as a key requirement for successful room-T photonics and optoelectronics applications. Here, we use direct correlated two-color photoluminescence imaging to probe how the interplay between the SWCNT bright E11 exciton and solitary dopant sites yields the dopant-induced emission for three different dopant species: oxygen, 4-methoxybenzene, and 4-bromobenzene. We introduce a route to control dopant functionalization to a low level as a means for introducing spatially well-separated solitary dopant sites. Resolution of emission from solitary dopant sites and correlation to their impact on E11 emission allows confirmation of dopants as trapping sites for localization of E11 excitons following their diffusive transport to the dopant site. Imaging of the dopant emission also reveals photoluminescence intermittency (blinking), with blinking dynamics being dependent on the specific dopant. Density functional theory calculations were performed to evaluate the stability of dopants and delineate the possible mechanisms of blinking. Furthermore, theoretical modeling suggests that the trapping of free charges in the potential well created by permanent dipoles introduced by dopant atoms/groups is likely responsible for the blinking, with the strongest effects being predicted and observed for oxygen-doped SWCNTs.},
doi = {10.1039/C5NR06343D},
journal = {Nanoscale},
number = 48,
volume = 7,
place = {United States},
year = {Wed Nov 11 00:00:00 EST 2015},
month = {Wed Nov 11 00:00:00 EST 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 44 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Chemical doping of graphene
journal, January 2011

  • Liu, Hongtao; Liu, Yunqi; Zhu, Daoben
  • J. Mater. Chem., Vol. 21, Issue 10
  • DOI: 10.1039/C0JM02922J

Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering
journal, November 2014

  • Voiry, Damien; Goswami, Anandarup; Kappera, Rajesh
  • Nature Chemistry, Vol. 7, Issue 1
  • DOI: 10.1038/nchem.2108

Oxygen Doping Modifies Near-Infrared Band Gaps in Fluorescent Single-Walled Carbon Nanotubes
journal, November 2010


Brightening of carbon nanotube photoluminescence through the incorporation of sp3 defects
journal, July 2013

  • Piao, Yanmei; Meany, Brendan; Powell, Lyndsey R.
  • Nature Chemistry, Vol. 5, Issue 10
  • DOI: 10.1038/nchem.1711

Spin-Polarized Mn 2 + Emission from Mn-Doped Colloidal Nanocrystals
journal, August 2011


Stable Solid-State Source of Single Photons
journal, July 2000


Single dopants in semiconductors
journal, January 2011

  • Koenraad, Paul M.; Flatté, Michael E.
  • Nature Materials, Vol. 10, Issue 2
  • DOI: 10.1038/nmat2940

A silicon carbide room-temperature single-photon source
journal, November 2013

  • Castelletto, S.; Johnson, B. C.; Ivády, V.
  • Nature Materials, Vol. 13, Issue 2
  • DOI: 10.1038/nmat3806

Quantum Optical Studies on Individual Acceptor Bound Excitons in a Semiconductor
journal, October 2002


Single photon emitters in exfoliated WSe2 structures
journal, May 2015

  • Koperski, M.; Nogajewski, K.; Arora, A.
  • Nature Nanotechnology, Vol. 10, Issue 6
  • DOI: 10.1038/nnano.2015.67

Room-temperature single-photon generation from solitary dopants of carbon nanotubes
journal, July 2015

  • Ma, Xuedan; Hartmann, Nicolai F.; Baldwin, Jon K. S.
  • Nature Nanotechnology, Vol. 10, Issue 8
  • DOI: 10.1038/nnano.2015.136

Photon Antibunching in the Photoluminescence Spectra of a Single Carbon Nanotube
journal, May 2008


Quantum Light Signatures and Nanosecond Spectral Diffusion from Cavity-Embedded Carbon Nanotubes
journal, January 2012

  • Walden-Newman, William; Sarpkaya, Ibrahim; Strauf, Stefan
  • Nano Letters, Vol. 12, Issue 4
  • DOI: 10.1021/nl204402v

Bright, long-lived and coherent excitons in carbon nanotube quantum dots
journal, June 2013

  • Hofmann, Matthias S.; Glückert, Jan T.; Noé, Jonathan
  • Nature Nanotechnology, Vol. 8, Issue 7
  • DOI: 10.1038/nnano.2013.119

Electronic Structure and Chemical Nature of Oxygen Dopant States in Carbon Nanotubes
journal, October 2014

  • Ma, Xuedan; Adamska, Lyudmyla; Yamaguchi, Hisato
  • ACS Nano, Vol. 8, Issue 10
  • DOI: 10.1021/nn504553y

Brightening of excitons in carbon nanotubes on dimensionality modification
journal, July 2013

  • Miyauchi, Yuhei; Iwamura, Munechiyo; Mouri, Shinichiro
  • Nature Photonics, Vol. 7, Issue 9
  • DOI: 10.1038/nphoton.2013.179

Exciton diffusion, end quenching, and exciton-exciton annihilation in individual air-suspended carbon nanotubes
journal, March 2015


Influences of Exciton Diffusion and Exciton-Exciton Annihilation on Photon Emission Statistics of Carbon Nanotubes
journal, July 2015


Optical Probing of Local pH and Temperature in Complex Fluids with Covalently Functionalized, Semiconducting Carbon Nanotubes
journal, February 2015

  • Kwon, Hyejin; Kim, Mijin; Meany, Brendan
  • The Journal of Physical Chemistry C, Vol. 119, Issue 7
  • DOI: 10.1021/jp509546d

Bench-top aqueous two-phase extraction of isolated individual single-walled carbon nanotubes
journal, March 2015

  • Subbaiyan, Navaneetha K.; Parra-Vasquez, A. Nicholas G.; Cambré, Sofie
  • Nano Research, Vol. 8, Issue 5, p. 1755-1769
  • DOI: 10.1007/s12274-014-0680-z

Role of Surfactants and Salt in Aqueous Two-Phase Separation of Carbon Nanotubes toward Simple Chirality Isolation
journal, January 2014

  • Subbaiyan, Navaneetha K.; Cambré, Sofie; Parra-Vasquez, A. Nicholas G.
  • ACS Nano, Vol. 8, Issue 2
  • DOI: 10.1021/nn405934y

New Route to Fluorescent Single-Walled Carbon Nanotube/Silica Nanocomposites: Balancing Fluorescence Intensity and Environmental Sensitivity
journal, July 2011

  • Duque, Juan G.; Gupta, Gautam; Cognet, Laurent
  • The Journal of Physical Chemistry C, Vol. 115, Issue 31
  • DOI: 10.1021/jp2012107

Fluorescent Single-Walled Carbon Nanotube Aerogels in Surfactant-free Environments
journal, August 2011

  • Duque, Juan G.; Hamilton, Christopher E.; Gupta, Gautam
  • ACS Nano, Vol. 5, Issue 8
  • DOI: 10.1021/nn202225k

NIH Image to ImageJ: 25 years of image analysis
journal, June 2012

  • Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W.
  • Nature Methods, Vol. 9, Issue 7
  • DOI: 10.1038/nmeth.2089

Avogadro: an advanced semantic chemical editor, visualization, and analysis platform
journal, August 2012

  • Hanwell, Marcus D.; Curtis, Donald E.; Lonie, David C.
  • Journal of Cheminformatics, Vol. 4, Issue 1
  • DOI: 10.1186/1758-2946-4-17

XCrySDen—a new program for displaying crystalline structures and electron densities
journal, June 1999


Excitonic and Vibrational Properties of Single-Walled Semiconducting Carbon Nanotubes
journal, October 2007


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Using redundant internal coordinates to optimize equilibrium geometries and transition states
journal, January 1996


Spontaneous Partition of Carbon Nanotubes in Polymer-Modified Aqueous Phases
journal, April 2013

  • Khripin, Constantine Y.; Fagan, Jeffrey A.; Zheng, Ming
  • Journal of the American Chemical Society, Vol. 135, Issue 18
  • DOI: 10.1021/ja402762e

Isolation of Specific Small-Diameter Single-Wall Carbon Nanotube Species via Aqueous Two-Phase Extraction
journal, January 2014

  • Fagan, Jeffrey A.; Khripin, Constantine Y.; Silvera Batista, Carlos A.
  • Advanced Materials, Vol. 26, Issue 18
  • DOI: 10.1002/adma.201304873

Luminescence Properties of Individual Empty and Water-Filled Single-Walled Carbon Nanotubes
journal, February 2012

  • Cambré, Sofie; Santos, Silvia M.; Wenseleers, Wim
  • ACS Nano, Vol. 6, Issue 3
  • DOI: 10.1021/nn300035y

Energy of K -Momentum Dark Excitons in Carbon Nanotubes by Optical Spectroscopy
journal, October 2008


Single Carbon Nanotubes Probed by Photoluminescence Excitation Spectroscopy: The Role of Phonon-Assisted Transitions
journal, April 2005


Photoluminescence imaging of electronic-impurity-induced exciton quenching in single-walled carbon nanotubes
journal, January 2012

  • Crochet, Jared J.; Duque, Juan G.; Werner, James H.
  • Nature Nanotechnology, Vol. 7, Issue 2
  • DOI: 10.1038/nnano.2011.227

Disorder Limited Exciton Transport in Colloidal Single-Wall Carbon Nanotubes
journal, September 2012

  • Crochet, Jared J.; Duque, Juan G.; Werner, James H.
  • Nano Letters, Vol. 12, Issue 10
  • DOI: 10.1021/nl301739d

Surfactant-Dependent Exciton Mobility in Single-Walled Carbon Nanotubes Studied by Single-Molecule Reactions
journal, May 2010

  • Siitonen, Anni J.; Tsyboulski, Dmitri A.; Bachilo, Sergei M.
  • Nano Letters, Vol. 10, Issue 5
  • DOI: 10.1021/nl9039845

Probing exciton propagation and quenching in carbon nanotubes with near-field optical microscopy: Probing exciton propagation and quenching in carbon nanotubes
journal, October 2009

  • Georgi, Carsten; Böhmler, Miriam; Qian, Huihong
  • physica status solidi (b), Vol. 246, Issue 11-12
  • DOI: 10.1002/pssb.200982306

Precisely and accurately localizing single emitters in fluorescence microscopy
journal, February 2014

  • Deschout, Hendrik; Zanacchi, Francesca Cella; Mlodzianoski, Michael
  • Nature Methods, Vol. 11, Issue 3
  • DOI: 10.1038/nmeth.2843

Facts and Artifacts in the Blinking Statistics of Semiconductor Nanocrystals
journal, May 2010

  • Crouch, Catherine H.; Sauter, Orion; Wu, Xiaohua
  • Nano Letters, Vol. 10, Issue 5
  • DOI: 10.1021/nl100030e

Effect of Solvent Polarity and Electrophilicity on Quantum Yields and Solvatochromic Shifts of Single-Walled Carbon Nanotube Photoluminescence
journal, July 2012

  • Larsen, Brian A.; Deria, Pravas; Holt, Josh M.
  • Journal of the American Chemical Society, Vol. 134, Issue 30
  • DOI: 10.1021/ja2114618

Mechanism of Electrolyte-Induced Brightening in Single-Wall Carbon Nanotubes
journal, February 2013

  • Duque, Juan G.; Oudjedi, Laura; Crochet, Jared J.
  • Journal of the American Chemical Society, Vol. 135, Issue 9
  • DOI: 10.1021/ja4001757

Electromigration of bivalent functional groups on graphene
journal, April 2014


Prolonged spontaneous emission and dephasing of localized excitons in air-bridged carbon nanotubes
journal, July 2013

  • Sarpkaya, Ibrahim; Zhang, Zhengyi; Walden-Newman, William
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3152

Strong Acoustic Phonon Localization in Copolymer-Wrapped Carbon Nanotubes
journal, May 2015

  • Sarpkaya, Ibrahim; Ahmadi, Ehsaneh D.; Shepard, Gabriella D.
  • ACS Nano, Vol. 9, Issue 6
  • DOI: 10.1021/acsnano.5b01997

Single dopants in semiconductors
journal, March 2015


Doping in III-V Semiconductors
journal, January 1994


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
text, January 1988

  • Robert, Parr,; Chengteh, Lee,; Weitao, Yang,
  • The University of North Carolina at Chapel Hill University Libraries
  • DOI: 10.17615/zrp0-ry04

Prolonged spontaneous emission and dephasing of localized excitons in air-bridged carbon nanotubes
text, January 2013


Works referencing / citing this record:

New Light on Molecule–Nanotube Hybrids
journal, September 2019

  • Chen, Yani; Marty, Laëtitia; Bendiab, Nedjma
  • Advanced Materials, Vol. 31, Issue 48
  • DOI: 10.1002/adma.201902917

Tunable room-temperature single-photon emission at telecom wavelengths from sp3 defects in carbon nanotubes
journal, July 2017


Creating fluorescent quantum defects in carbon nanotubes using hypochlorite and light
journal, June 2019


Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes
journal, September 2018


Carbon nanotubes as emerging quantum-light sources
journal, June 2018


Controlling the optical properties of carbon nanotubes with organic colour-centre quantum defects
journal, June 2019

  • Brozena, Alexandra H.; Kim, Mijin; Powell, Lyndsey R.
  • Nature Reviews Chemistry, Vol. 3, Issue 6
  • DOI: 10.1038/s41570-019-0103-5

Intrinsic limits of defect-state photoluminescence dynamics in functionalized carbon nanotubes
journal, January 2019

  • He, Xiaowei; Sun, Liuyang; Gifford, Brendan J.
  • Nanoscale, Vol. 11, Issue 18
  • DOI: 10.1039/c9nr02175b

Quantum light sources from semiconductor
journal, July 2019