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Title: Ultrashort Carbon Nanotubes That Fluoresce Brightly in the Near-Infrared

Abstract

The intrinsic near-infrared photoluminescence observed in long single-walled carbon nanotubes is known to be quenched in ultrashort nanotubes due to their tiny size as compared to the exciton diffusion length in these materials (>100 nm). Here in this study, we show that intense photoluminescence can be created in ultrashort nanotubes (~40 nm length) upon incorporation of exciton-trapping sp3 defect sites. Using super-resolution photoluminescence imaging at <25 nm resolution, we directly show the preferential localization of excitons at the nanotube ends, which separate by less than 40 nm and behave as independent emitters. Lastly, this unexpected observation opens the possibility to synthesize fluorescent ultrashort nanotubes—a goal that has been long thought impossible—for bioimaging applications, where bright near-infrared photoluminescence and small size are highly desirable, and for quantum information science, where high quality and well-controlled near-infrared single photon emitters are needed.

Authors:
 [1];  [2];  [1];  [2];  [1];  [2]; ORCiD logo [3]; ORCiD logo [3];  [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. Bordeaux (France); Institut d’Optique & CNRS (France)
  2. Univ. of Maryland, College Park, MD (United States)
  3. 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 Office of Science (SC); USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1479935
Report Number(s):
LA-UR-18-20557
Journal ID: ISSN 1936-0851
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 6; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; doping; emission centers; exciton localization; photoluminescence; single molecules; super-resolution microscopy; ultrashort carbon nanotube

Citation Formats

Danné, Noémie, Kim, Mijin, Godin, Antoine G., Kwon, Hyejin, Gao, Zhenghong, Wu, Xiaojian, Hartmann, Nicolai F., Doorn, Stephen K., Lounis, Brahim, Wang, YuHuang, and Cognet, Laurent. Ultrashort Carbon Nanotubes That Fluoresce Brightly in the Near-Infrared. United States: N. p., 2018. Web. doi:10.1021/acsnano.8b02307.
Danné, Noémie, Kim, Mijin, Godin, Antoine G., Kwon, Hyejin, Gao, Zhenghong, Wu, Xiaojian, Hartmann, Nicolai F., Doorn, Stephen K., Lounis, Brahim, Wang, YuHuang, & Cognet, Laurent. Ultrashort Carbon Nanotubes That Fluoresce Brightly in the Near-Infrared. United States. https://doi.org/10.1021/acsnano.8b02307
Danné, Noémie, Kim, Mijin, Godin, Antoine G., Kwon, Hyejin, Gao, Zhenghong, Wu, Xiaojian, Hartmann, Nicolai F., Doorn, Stephen K., Lounis, Brahim, Wang, YuHuang, and Cognet, Laurent. Mon . "Ultrashort Carbon Nanotubes That Fluoresce Brightly in the Near-Infrared". United States. https://doi.org/10.1021/acsnano.8b02307. https://www.osti.gov/servlets/purl/1479935.
@article{osti_1479935,
title = {Ultrashort Carbon Nanotubes That Fluoresce Brightly in the Near-Infrared},
author = {Danné, Noémie and Kim, Mijin and Godin, Antoine G. and Kwon, Hyejin and Gao, Zhenghong and Wu, Xiaojian and Hartmann, Nicolai F. and Doorn, Stephen K. and Lounis, Brahim and Wang, YuHuang and Cognet, Laurent},
abstractNote = {The intrinsic near-infrared photoluminescence observed in long single-walled carbon nanotubes is known to be quenched in ultrashort nanotubes due to their tiny size as compared to the exciton diffusion length in these materials (>100 nm). Here in this study, we show that intense photoluminescence can be created in ultrashort nanotubes (~40 nm length) upon incorporation of exciton-trapping sp3 defect sites. Using super-resolution photoluminescence imaging at <25 nm resolution, we directly show the preferential localization of excitons at the nanotube ends, which separate by less than 40 nm and behave as independent emitters. Lastly, this unexpected observation opens the possibility to synthesize fluorescent ultrashort nanotubes—a goal that has been long thought impossible—for bioimaging applications, where bright near-infrared photoluminescence and small size are highly desirable, and for quantum information science, where high quality and well-controlled near-infrared single photon emitters are needed.},
doi = {10.1021/acsnano.8b02307},
journal = {ACS Nano},
number = 6,
volume = 12,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
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Cited by: 17 works
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Figures / Tables:

Figure 1 Figure 1: Brightening of ultrashort SWCNTs through fluorescent quantum defects. (a) Cumulative distribution of ultrashort nanotubes lengths measured by AFM (N=88, median= 43 nm, 1st /3rd quartile= 24/69 nm). (b), Distribution of ultrashort nanotubes absorption signals measured by PhI (N=472) which also reflects the nanotube lengths distribution but with bettermore » statistics. (c) 2D PL map of ultrashort nanotubes shows no luminescence. (d) single molecule imaging of ultrashort nanotubes is not observed. (e) 2D PL map of fluorescent ultrashort nanotubes reveals bright luminescence. (f) single molecule imaging of fluorescent ultrashort nanotubes is clearly observed. (g) Distribution of fluorescent ultrashort nanotubes PL signals (N=265) mirrors nanotube length distributions in (a) and (b).« less

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Works referenced in this record:

Nanoscale magnetic sensing with an individual electronic spin in diamond
journal, October 2008

  • Maze, J. R.; Stanwix, P. L.; Hodges, J. S.
  • Nature, Vol. 455, Issue 7213
  • DOI: 10.1038/nature07279

Molecular-sized fluorescent nanodiamonds
journal, December 2013

  • Vlasov, Igor I.; Shiryaev, Andrey A.; Rendler, Torsten
  • Nature Nanotechnology, Vol. 9, Issue 1
  • DOI: 10.1038/nnano.2013.255

Room-temperature entanglement between single defect spins in diamond
journal, February 2013

  • Dolde, F.; Jakobi, I.; Naydenov, B.
  • Nature Physics, Vol. 9, Issue 3
  • DOI: 10.1038/nphys2545

The properties and applications of nanodiamonds
journal, December 2011

  • Mochalin, Vadym N.; Shenderova, Olga; Ho, Dean
  • Nature Nanotechnology, Vol. 7, Issue 1
  • DOI: 10.1038/nnano.2011.209

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

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

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

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

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


Band Gap Fluorescence from Individual Single-Walled Carbon Nanotubes
journal, July 2002

  • O'Connell, Michael J.; Bachilo, Sergei M.; Huffman, Chad B.
  • Science, Vol. 297, Issue 5581, p. 593-596
  • DOI: 10.1126/science.1072631

Phonon and Electronic Nonradiative Decay Mechanisms of Excitons in Carbon Nanotubes
journal, July 2008


Stepwise Quenching of Exciton Fluorescence in Carbon Nanotubes by Single-Molecule Reactions
journal, June 2007


Luminescence Decay and the Absorption Cross Section of Individual Single-Walled Carbon Nanotubes
journal, August 2008


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

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

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

Length-Dependent Optical Effects in Single Walled Carbon Nanotubes
journal, May 2008

  • Rajan, Aruna; Strano, Michael S.; Heller, Daniel A.
  • The Journal of Physical Chemistry B, Vol. 112, Issue 19
  • DOI: 10.1021/jp077144l

Optical detection of individual ultra-short carbon nanotubes enables their length characterization down to 10 nm
journal, November 2015

  • Gao, Zhenghong; Oudjedi, Laura; Faes, Romain
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep17093

Sub-10 nm Carbon Nanotube Transistor
journal, January 2012

  • Franklin, Aaron D.; Luisier, Mathieu; Han, Shu-Jen
  • Nano Letters, Vol. 12, Issue 2
  • DOI: 10.1021/nl203701g

In Vivo Behavior of Large Doses of Ultrashort and Full-Length Single-Walled Carbon Nanotubes after Oral and Intraperitoneal Administration to Swiss Mice
journal, February 2010

  • Kolosnjaj-Tabi, Jelena; Hartman, Keith B.; Boudjemaa, Sabah
  • ACS Nano, Vol. 4, Issue 3
  • DOI: 10.1021/nn901573w

Stochastic transport through carbon nanotubes in lipid bilayers and live cell membranes
journal, October 2014

  • Geng, Jia; Kim, Kyunghoon; Zhang, Jianfei
  • Nature, Vol. 514, Issue 7524
  • DOI: 10.1038/nature13817

Tube length and cell type-dependent cellular responses to ultra-short single-walled carbon nanotube
journal, March 2014


Fluorescent Carbon Nanotube Defects Manifest Substantial Vibrational Reorganization
journal, May 2016

  • Kim, Mijin; Adamska, Lyudmyla; Hartmann, Nicolai F.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 20
  • DOI: 10.1021/acs.jpcc.6b02538

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

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

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

Length- and Defect-Dependent Fluorescence Efficiencies of Individual Single-Walled Carbon Nanotubes
journal, December 2011

  • Cherukuri, Tonya K.; Tsyboulski, Dmitri A.; Weisman, R. Bruce
  • ACS Nano, Vol. 6, Issue 1
  • DOI: 10.1021/nn2043516

Diffusion Limited Photoluminescence Quantum Yields in 1-D Semiconductors: Single-Wall Carbon Nanotubes
journal, November 2010

  • Hertel, Tobias; Himmelein, Sabine; Ackermann, Thomas
  • ACS Nano, Vol. 4, Issue 12
  • DOI: 10.1021/nn101612b

Metrological Investigation of the (6,5) Carbon Nanotube Absorption Cross Section
journal, April 2013

  • Oudjedi, Laura; Parra-Vasquez, A. Nicholas G.; Godin, Antoine G.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 9
  • DOI: 10.1021/jz4003372

Nonlinear Photoluminescence Spectroscopy of Carbon Nanotubes with Localized Exciton States
journal, October 2014

  • Iwamura, Munechiyo; Akizuki, Naoto; Miyauchi, Yuhei
  • ACS Nano, Vol. 8, Issue 11
  • DOI: 10.1021/nn503803b

The 2015 super-resolution microscopy roadmap
journal, October 2015


Subdiffraction Far-Field Imaging of Luminescent Single-Walled Carbon Nanotubes
journal, February 2008

  • Cognet, Laurent; Tsyboulski, Dmitri A.; Weisman, R. Bruce
  • Nano Letters, Vol. 8, Issue 2
  • DOI: 10.1021/nl0725300

Super-resolution Microscopy Approaches for Live Cell Imaging
journal, October 2014


Position measurement with a resolution and noise‐limited instrument
journal, June 1986

  • Bobroff, Norman
  • Review of Scientific Instruments, Vol. 57, Issue 6
  • DOI: 10.1063/1.1138619

Optimized localization analysis for single-molecule tracking and super-resolution microscopy
journal, April 2010

  • Mortensen, Kim I.; Churchman, L. Stirling; Spudich, James A.
  • Nature Methods, Vol. 7, Issue 5
  • DOI: 10.1038/nmeth.1447

Confined propagation of covalent chemical reactions on single-walled carbon nanotubes
journal, July 2011

  • Deng, Shunliu; Zhang, Yin; Brozena, Alexandra H.
  • Nature Communications, Vol. 2, Issue 1
  • DOI: 10.1038/ncomms1384

Propagative Sidewall Alkylcarboxylation that Induces Red-Shifted Near-IR Photoluminescence in Single-Walled Carbon Nanotubes
journal, February 2013

  • Zhang, Yin; Valley, Nicholas; Brozena, Alexandra H.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 5
  • DOI: 10.1021/jz400167d

Toward the suppression of cellular toxicity from single-walled carbon nanotubes
journal, January 2016

  • Gao, Zhenghong; Varela, Juan A.; Groc, Laurent
  • Biomaterials Science, Vol. 4, Issue 2
  • DOI: 10.1039/C5BM00134J

Evaluation of Different Single-Walled Carbon Nanotube Surface Coatings for Single-Particle Tracking Applications in Biological Environments
journal, November 2017

  • Gao, Zhenghong; Danné, Noémie; Godin, Antoine
  • Nanomaterials, Vol. 7, Issue 11
  • DOI: 10.3390/nano7110393

Single-nanotube tracking reveals the nanoscale organization of the extracellular space in the live brain
journal, November 2016

  • Godin, Antoine G.; Varela, Juan A.; Gao, Zhenghong
  • Nature Nanotechnology, Vol. 12, Issue 3
  • DOI: 10.1038/nnano.2016.248

Works referencing / citing this record:

Fluorescent Single-Walled Carbon Nanotubes for Protein Detection
journal, December 2019

  • Hendler-Neumark, Adi; Bisker, Gili
  • Sensors, Vol. 19, Issue 24
  • DOI: 10.3390/s19245403

Single-defect spectroscopy in the shortwave infrared
journal, June 2019


Super-resolution fluorescence imaging of carbon nanotubes using a nonlinear excitonic process
journal, January 2019

  • Otsuka, Keigo; Ishii, Akihiro; Kato, Yuichiro K.
  • Optics Express, Vol. 27, Issue 13
  • DOI: 10.1364/oe.27.017463

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

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


Electronic and optical characteristics of phosphorus-doped carbon nanotubes: a first principle study
journal, February 2019


Semiconducting Single-Walled Carbon Nanotubes or Very Rigid Conjugated Polymers: A Comparison
journal, November 2018


Photophysical deactivation behaviour of Rhodamine B using different graphite materials
journal, January 2019

  • Prakash, Varnika; Bhar, Rekha; Sharma, Shweta
  • RSC Advances, Vol. 9, Issue 39
  • DOI: 10.1039/c9ra03325d

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

Photoswitchable single-walled carbon nanotubes for super-resolution microscopy in the near-infrared
journal, September 2019

  • Godin, Antoine G.; Setaro, Antonio; Gandil, Morgane
  • Science Advances, Vol. 5, Issue 9
  • DOI: 10.1126/sciadv.aax1166

Self‐Sorting of 10‐µm‐Long Single‐Walled Carbon Nanotubes in Aqueous Solution
journal, June 2019

  • Wang, Peng; Barnes, Benjamin; Wu, Xiaojian
  • Advanced Materials, Vol. 31, Issue 33
  • DOI: 10.1002/adma.201901641

Fluorescent sp3 Defect-Tailored Carbon Nanotubes Enable NIR-II Single Particle Imaging in Live Brain Slices at Ultra-Low Excitation Doses
journal, March 2020


Photoswitchable single-walled carbon nanotubes for super-resolution microscopy in the near-infrared
text, January 2019


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