skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes

Abstract

The introduction of sp 3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show that such selectivity can be obtained through aryl functionalization of so-called ‘zigzag’ nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. Finally, we show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [3];  [4]; ORCiD logo [1];  [5]; ORCiD logo [2]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); North Dakota State Univ., Fargo, ND (United States). Dept. of Chemistry and Biochemistry
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Materials Science and Engineering Division
  4. National Inst. of Advanced Industrial Science and Technology (AIST), Tsukuba (Japan). Nanomaterials Research Inst.
  5. North Dakota State Univ., Fargo, ND (United States). Dept. of Chemistry and Biochemistry
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC); LANL Laboratory Directed Research and Development (LDRD) Program; National Science Foundation (NSF); Japan Society for the Promotion of Science (JSPS)
OSTI Identifier:
1480023
Report Number(s):
LA-UR-18-20560
Journal ID: ISSN 1755-4330
Grant/Contract Number:  
AC52-06NA25396; CHE-1413614; JP25220602
Resource Type:
Accepted Manuscript
Journal Name:
Nature Chemistry
Additional Journal Information:
Journal Volume: 10; Journal Issue: 11; Journal ID: ISSN 1755-4330
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Material Science

Citation Formats

Saha, Avishek, Gifford, Brendan J., He, Xiaowei, Ao, Geyou, Zheng, Ming, Kataura, Hiromichi, Htoon, Han, Kilina, Svetlana, Tretiak, Sergei, and Doorn, Stephen K. Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes. United States: N. p., 2018. Web. doi:10.1038/s41557-018-0126-4.
Saha, Avishek, Gifford, Brendan J., He, Xiaowei, Ao, Geyou, Zheng, Ming, Kataura, Hiromichi, Htoon, Han, Kilina, Svetlana, Tretiak, Sergei, & Doorn, Stephen K. Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes. United States. doi:10.1038/s41557-018-0126-4.
Saha, Avishek, Gifford, Brendan J., He, Xiaowei, Ao, Geyou, Zheng, Ming, Kataura, Hiromichi, Htoon, Han, Kilina, Svetlana, Tretiak, Sergei, and Doorn, Stephen K. Mon . "Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes". United States. doi:10.1038/s41557-018-0126-4. https://www.osti.gov/servlets/purl/1480023.
@article{osti_1480023,
title = {Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes},
author = {Saha, Avishek and Gifford, Brendan J. and He, Xiaowei and Ao, Geyou and Zheng, Ming and Kataura, Hiromichi and Htoon, Han and Kilina, Svetlana and Tretiak, Sergei and Doorn, Stephen K.},
abstractNote = {The introduction of sp3 defects into single-walled carbon nanotubes through covalent functionalization can generate new light-emitting states and thus dramatically expand their optical functionality. This may open up routes to enhanced imaging, photon upconversion, and room-temperature single-photon emission at telecom wavelengths. However, a significant challenge in harnessing this potential is that the nominally simple reaction chemistry of nanotube functionalization introduces a broad diversity of emitting states. Precisely defining a narrow band of emission energies necessitates constraining these states, which requires extreme selectivity in molecular binding configuration on the nanotube surface. We show that such selectivity can be obtained through aryl functionalization of so-called ‘zigzag’ nanotube structures to achieve a threefold narrowing in emission bandwidth. Accompanying density functional theory modelling reveals that, because of the associated structural symmetry, the defect states become degenerate, thus limiting emission energies to a single narrow band. Finally, we show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.},
doi = {10.1038/s41557-018-0126-4},
journal = {Nature Chemistry},
number = 11,
volume = 10,
place = {United States},
year = {2018},
month = {9}
}

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

Citation Metrics:
Cited by: 10 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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


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 the Lowest Exciton in Carbon Nanotubes via Chemical Functionalization
journal, April 2012

  • Kilina, Svetlana; Ramirez, Jessica; Tretiak, Sergei
  • Nano Letters, Vol. 12, Issue 5
  • DOI: 10.1021/nl300165w

Solid-state single-photon emitters
journal, September 2016


Electrolyte Tuning of Surfactant Interfacial Behavior for Enhanced Density-Based Separations of Single-Walled Carbon Nanotubes
journal, January 2009

  • Niyogi, Sandip; Densmore, Crystal G.; Doorn, Stephen K.
  • Journal of the American Chemical Society, Vol. 131, Issue 3
  • DOI: 10.1021/ja807785e

Efficient near-infrared up-conversion photoluminescence in carbon nanotubes
journal, November 2015

  • Akizuki, Naoto; Aota, Shun; Mouri, Shinichiro
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9920

SDS Surfactants on Carbon Nanotubes: Aggregate Morphology
journal, February 2009

  • Tummala, Naga Rajesh; Striolo, Alberto
  • ACS Nano, Vol. 3, Issue 3
  • DOI: 10.1021/nn8007756

Industrial-scale separation of high-purity single-chirality single-wall carbon nanotubes for biological imaging
journal, June 2016

  • Yomogida, Yohei; Tanaka, Takeshi; Zhang, Minfang
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms12056

Correction Scheme for Comparison of Computed and Experimental Optical Transition Energies in Functionalized Single-Walled Carbon Nanotubes
journal, April 2018

  • Gifford, Brendan J.; Sifain, Andrew E.; Htoon, Han
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 10
  • DOI: 10.1021/acs.jpclett.8b00653

Chemistry of Single-Walled Carbon Nanotubes
journal, December 2002

  • Niyogi, S.; Hamon, M. A.; Hu, H.
  • Accounts of Chemical Research, Vol. 35, Issue 12
  • DOI: 10.1021/ar010155r

Low-Temperature Single Carbon Nanotube Spectroscopy of sp 3 Quantum Defects
journal, September 2017


Saturation of Surfactant Structure at the Single-Walled Carbon Nanotube Surface
journal, November 2010

  • Duque, Juan G.; Densmore, Crystal G.; Doorn, Stephen K.
  • Journal of the American Chemical Society, Vol. 132, Issue 45
  • DOI: 10.1021/ja106836f

Structure-Assigned Optical Spectra of Single-Walled Carbon Nanotubes
journal, November 2002


Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals
journal, September 1969

  • Hehre, W. J.; Stewart, R. F.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 51, Issue 6
  • DOI: 10.1063/1.1672392

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

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


Molecularly Tunable Fluorescent Quantum Defects
journal, May 2016

  • Kwon, Hyejin; Furmanchuk, Al’ona; Kim, Mijin
  • Journal of the American Chemical Society, Vol. 138, Issue 21
  • DOI: 10.1021/jacs.6b03618

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

Quantum emission from hexagonal boron nitride monolayers
journal, October 2015

  • Tran, Toan Trong; Bray, Kerem; Ford, Michael J.
  • Nature Nanotechnology, Vol. 11, Issue 1
  • DOI: 10.1038/nnano.2015.242

Near infrared photoluminescence modulation by defect site design using aryl isomers in locally functionalized single-walled carbon nanotubes
journal, January 2017

  • Shiraki, Tomohiro; Uchimura, Shunsuke; Shiraishi, Tomonari
  • Chemical Communications, Vol. 53, Issue 93
  • DOI: 10.1039/C7CC06663E

Single-photon emission at 1.5 μm from an InAs/InP quantum dot with highly suppressed multi-photon emission probabilities
journal, September 2016

  • Miyazawa, T.; Takemoto, K.; Nambu, Y.
  • Applied Physics Letters, Vol. 109, Issue 13
  • DOI: 10.1063/1.4961888

Emergence of new red-shifted carbon nanotube photoluminescence based on proximal doped-site design
journal, June 2016

  • Shiraki, Tomohiro; Shiraishi, Tomonari; Juhász, Gergely
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep28393

Quantum correlation among photons from a single quantum dot at room temperature
journal, August 2000

  • Michler, P.; Imamoğlu, A.; Mason, M. D.
  • Nature, Vol. 406, Issue 6799
  • DOI: 10.1038/35023100

Voltage-controlled quantum light from an atomically thin semiconductor
journal, May 2015

  • Chakraborty, Chitraleema; Kinnischtzke, Laura; Goodfellow, Kenneth M.
  • Nature Nanotechnology, Vol. 10, Issue 6
  • DOI: 10.1038/nnano.2015.79

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

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

Single quantum emitters in monolayer semiconductors
journal, May 2015

  • He, Yu-Ming; Clark, Genevieve; Schaibley, John R.
  • Nature Nanotechnology, Vol. 10, Issue 6
  • DOI: 10.1038/nnano.2015.75

Differentiating Left- and Right-Handed Carbon Nanotubes by DNA
journal, December 2016

  • Ao, Geyou; Streit, Jason K.; Fagan, Jeffrey A.
  • Journal of the American Chemical Society, Vol. 138, Issue 51
  • DOI: 10.1021/jacs.6b09135

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

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


Chirality dependence of the K -momentum dark excitons in carbon nanotubes
journal, April 2010


Optical Excitation of Carbon Nanotubes Drives Localized Diazonium Reactions
journal, September 2016

  • Powell, Lyndsey R.; Piao, Yanmei; Wang, YuHuang
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 18
  • DOI: 10.1021/acs.jpclett.6b01771

Exciton Localization and Optical Emission in Aryl-Functionalized Carbon Nanotubes
journal, November 2017

  • Gifford, Brendan J.; Kilina, Svetlana; Htoon, Han
  • The Journal of Physical Chemistry C, Vol. 122, Issue 3
  • DOI: 10.1021/acs.jpcc.7b09558

Effect of Covalent Chemistry on the Electronic Structure and Properties of Carbon Nanotubes and Graphene
journal, September 2012

  • Bekyarova, Elena; Sarkar, Santanu; Wang, Feihu
  • Accounts of Chemical Research, Vol. 46, Issue 1
  • DOI: 10.1021/ar300177q

Covalent chemistry on graphene
journal, January 2013

  • Chua, Chun Kiang; Pumera, Martin
  • Chemical Society Reviews, Vol. 42, Issue 8
  • DOI: 10.1039/c2cs35474h

Photoluminescence Dynamics of Aryl sp 3 Defect States in Single-Walled Carbon Nanotubes
journal, August 2016

  • Hartmann, Nicolai F.; Velizhanin, Kirill A.; Haroz, Erik H.
  • ACS Nano, Vol. 10, Issue 9
  • DOI: 10.1021/acsnano.6b02986

Electronic Structure Control of Single-Walled Carbon Nanotube Functionalization
journal, September 2003


( n , m )-Specific Absorption Cross Sections of Single-Walled Carbon Nanotubes Measured by Variance Spectroscopy
journal, October 2016


A Low Energy Route to DNA-Wrapped Carbon Nanotubes via Replacement of Bile Salt Surfactants
journal, September 2017


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

Scanning Tunneling Microscopy of DNA-Wrapped Carbon Nanotubes
journal, January 2009

  • Yarotski, Dzmitry A.; Kilina, Svetlana V.; Talin, A. Alec
  • Nano Letters, Vol. 9, Issue 1, p. 12-17
  • DOI: 10.1021/nl801455t

A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

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

Photoluminescence imaging of solitary dopant sites in covalently doped single-wall carbon nanotubes
journal, January 2015

  • Hartmann, Nicolai F.; Yalcin, Sibel Ebru; Adamska, Lyudmyla
  • Nanoscale, Vol. 7, Issue 48
  • DOI: 10.1039/C5NR06343D

DNA sequence motifs for structure-specific recognition and separation of carbon nanotubes
journal, July 2009

  • Tu, Xiaomin; Manohar, Suresh; Jagota, Anand
  • Nature, Vol. 460, Issue 7252, p. 250-253
  • DOI: 10.1038/nature08116

Optically active quantum dots in monolayer WSe2
journal, May 2015

  • Srivastava, Ajit; Sidler, Meinrad; Allain, Adrien V.
  • Nature Nanotechnology, Vol. 10, Issue 6
  • DOI: 10.1038/nnano.2015.60

Sorting Carbon Nanotubes
journal, January 2017


    Works referencing / citing this record:

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


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