Abstract
Semiconducting single-walled carbon nanotubes (SWNTs) are considered as building blocks for novel optoelectronic and photonic devices. Energy transport, dissipation and nonlinear optical properties of such devices depend critically on the dynamics of singlet and triplet excitons. However, little is known about triplet excitons in SWNTs despite their important role in photovoltaic, photoelectric and other applications. We present pump–probe and spin-sensitive photoluminescence studies of semiconducting SWNTs that allow the determination of the quantum yield of triplet formation (5 ± 2%), the triplet lifetime (30 ± 10 µs) and the triplet exciton size (0.65 nm). Triplet–triplet annihilation is also found to induce delayed fluorescence. The power-law decay of pump–probe and time-resolved photoluminescence signals is characteristic of diffusion-limited annihilation in one-dimensional systems and allows an estimation of the triplet diffusion constant of 0.1 cm2 s−1. This work suggests that exciton annihilation in SWNTs is reduced by one-dimensional confinement of diffusive exciton motion.
This is a preview of subscription content, access via your institution
Access options
Subscribe to this journal
Receive 12 print issues and online access
$209.00 per year
only $17.42 per issue
Buy this article
- Purchase on Springer Link
- Instant access to full article PDF
Prices may be subject to local taxes which are calculated during checkout
Similar content being viewed by others
References
Hofmann, M. S. et al. Bright, long-lived and coherent excitons in carbon nanotube quantum dots. Nature Nanotech. 8, 502–505 (2013).
Cao, M. S., Parker, I. D., Yu, G., Zhang, C. & Heeger, A. J. Improved quantum eficiency for electroluminescence in semiconducting polymers. Nature 397, 414–417 (1999).
Adachi, C., Baldo, M. A., Thompson, M. E. & Forrest, S. R. Nearly 100% internal phosphorescence efficiency in an organic light-emitting device. J. Appl. Phys. 90, 5048–5051 (2001).
Semonin, O. E. et al. Peak external photocurrent quantum efficiency exceeding 100% via MEG in a quantum dot solar cell. Science 334, 1530–1533 (2011).
Congreve, D. N. et al. External quantum efficiency above 100% in a singlet-exciton-fission-based organic photovoltaic cell. Science 340, 334–337 (2013).
Misewich, J. A. et al. Electrically induced optical emission from a carbon nanotube FET. Science 300, 783–786 (2003).
Arnold, M. S. et al. Broad spectral response using carbon nanotube/organic semiconductor/C-60 photodetectors. Nano Lett. 9, 3354–3358 (2009).
Shao, Y. & Yang, Y. Efficient organic heterojunction photovoltaic cells based on triplet materials. Adv. Mater. 17, 2841–2844 (2005).
Perebeinos, V., Tersoff, J. & Avouris, P. Radiative lifetime of excitons in carbon nanotubes. Nano Lett. 5, 2495–2499 (2005).
Spataru, C. D., Ismail-Beigi, I., Capaz, R. B. & Louie, S. G. Theory and ab initio calculation of radiative lifetime of excitons in semiconducting carbon nanotubes. Phys. Rev. Lett. 95, 247402 (2005).
Ando, T. Effects of valley mixing and exchange on excitons in carbon nanotubes with aharonov-bohm flux. J. Phys. Soc. Jpn 75, 024707 (2006).
Tretiak, S. Triplet state absorption in carbon nanotubes: A TD-DFT study. Nano Lett. 7, 2201–2206 (2007).
Chang, E. et al. Excitons in carbon nanotubes: an ab initio symmetry-based approach. Phys. Rev. Lett. 92, 196401 (2004).
Jones, M. et al. Extrinsic and intrinsic effects on the excited-state kinetics of single-walled carbon nanotubes. Nano Lett. 7, 300–306 (2007).
Aryanpour, K., Mazumdar, S. & Zhao, H. Triplet excitations in carbon nanostructures. Phys. Rev. B 85, 085438 (2012).
Mortimer, I. B. & Nicholas, R. J. Role of bright and dark excitons in the temperature-dependent photoluminescence of carbon nanotubes. Phys. Rev. Lett. 98, 027404 (2007).
Wang, F., Dukovic, G., Brus, L. E. & Heinz, T. F. The optical resonances in carbon nanotubes arise from excitons. Science 308, 838–841 (2005).
Maultzsch, J. et al. Exciton binding energies in carbon nanotubes from two-photon photoluminescence. Phys. Rev. B 72, 241402 (2005).
Lefebvre, J. & Finnie, P. Excited excitonic states in single-walled carbon nanotubes. Nano Lett. 8, 1890–1895 (2009).
Hagen, A. et al. Exponential decay lifetimes of excitons in individual single-walled carbon nanotubes. Phys. Rev. Lett. 95, 197401 (2005).
Graham, M. W. et al. Pure optical dephasing dynamics in semiconducting single-walled carbon nanotubes. J. Chem. Phys. 134, 034504 (2011).
Zhu, Z. P. et al. Pump–probe spectroscopy of exciton dynamics in (6,5) carbon nanotubes. J. Phys. Chem. C 111, 3831–3835 (2007).
Wang, F., Dukovic, G., Knoesel, E., Brus, L. E. & Heinz, T. F. Observation of rapid Auger recombination in optically excited semiconducting carbon nanotubes. Phys. Rev. B 70, 241403 (2004).
Ma, Y. Z. et al. Ultrafast carrier dynamics in single-walled carbon nanotubes probed by femtosecond spectroscopy. J. Chem. Phys. 120, 3368–3373 (2004).
Manzoni, C. et al. Intersubband exciton relaxation dynamics in single-walled carbon nanotubes. Phys. Rev. Lett. 94, 207401 (2005).
Cognet, L. et al. Stepwise quenching of exciton fluorescence in carbon nanotubes by single-molecule reactions. Science 316, 1465–1468 (2007).
Hertel, T., Himmelein, S., Ackermann, T., Stich, D. & Crochet, J. Diffusion limited photoluminescence quantum yields in 1-D semiconductors: single-wall carbon nanotubes. ACS Nano 4, 7161–7168 (2010).
Murakami, Y. & Kono, J. Nonlinear photoluminescence excitation spectroscopy of carbon nanotubes: exploring the upper density limit of one-dimensional excitons. Phys. Rev. Lett. 102, 037401 (2009).
Santos, S. M. et al. All-optical trion generation in single-walled carbon nanotubes. Phys. Rev. Lett. 107, 187401 (2011).
Gosh, S., Bachilo, S. M., Simonette, R. A., Beckingham, K. M. & Weisman, R. B. Oxygen doping modifies near-infrared band gaps in fluorescent single-walled carbon nanotubes. Science 330, 1656–1659 (2010).
Nagatsu, K., Chiashi, S., Konabe, S. & Homma, Y. Brightening of triplet dark excitons by atomic hydrogen adsorption in single-walled carbon nanotubes observed by photoluminescence spectroscopy. Phys. Rev. Lett. 105, 157403 (2010).
Kanemitsu, Y. Excitons in semiconducting carbon nanotubes: diameter-dependent photoluminescence spectra. Phys. Chem. Chem. Phys. 13, 14879–14888 (2011).
Park, J., Deria, P. & Therien, M. J. Dynamics and transient absorption spectral signatures of the single-wall carbon nanotube electronically excited triplet state. J. Am. Chem. Soc. 133, 17156–17159 (2011).
Mohite, A. D., Santos, T. S., Moodera, J. S. & Alphenaar, B. W. Observation of the triplet exciton in EuS-coated single-walled nanotubes. Nature Nanotech. 4, 425–429 (2009).
Lebedkin, S., Hennrich, F., Kiowski, O. & Kappes, M. M. Photophysics of carbon nanotubes in organic polymer–toluene dispersions: emission and excitation satellites and relaxation pathways. Phys. Rev. B 77, 165429 (2008).
Crochet, J., Clemens, M. & Hertel, T. Quantum yield heterogeneities of aqueous single-wall carbon nanotube suspensions. J. Am. Chem. Soc. 129, 8058–8059 (2007).
Tsyboulski, D. A., Rocha, J. D. R., Bachilo, S. M., Cognet, L. & Weisman, R. B. Structure-dependent fluorescence efficiencies of individual single-walled cardon nanotubes. Nano Lett. 7, 3080–3085 (2007).
Russo, R. M. et al. One-dimensional diffusion-limited relaxation of photoexcitations in suspensions of single-walled carbon nanotubes. Phys. Rev. B 74, 041405 (2006).
Toussaint, D. & Wilczek, F. Particle antiparticle annihilation in diffusive motion. J. Chem. Phys. 78, 2642–2647 (1983).
Suna, A. Kinematics of exciton–exciton annihilation in molecular crystals. Phys. Rev. B 1, 1716–1739 (1970).
Merrifield, R. Magnetic effects on triplet exciton interactions. Pure Appl. Chem. 27, 481–498 (1970).
Dyakonov, V., Rosler, G., Schwoerer, M. & Frankevich, L. E. Evidence for triplet interchain polaron pairs and their transformations in polyphenylenevinylene. Phys. Rev. B 56, 3852–3862 (1997).
van Kampen, N. Stochastic Processes in Physics and Chemistry (North-Holland, 1992).
Capaz, R. B., Spataru, C. D., Ismail-Beigi, S. & Louie, S. G. Diameter and chirality dependence of exciton properties in carbon nanotubes. Phys. Rev. B 74, 121401 (2006).
Weiland, J. A. & Bolton, J. R. Electron Paramagnetic Resonance. Elementary Theory and Practical Applications 2nd edn (Wiley-Interscience, 2006).
Epshtein, O., Nakhmanovich, G., Eichen, Y. & Ehrenfreund, E. Dispersive dynamics of photoexcitations in conjugated polymers measured by photomodulation spectroscopy. Phys. Rev. B 63, 125206 (2001).
Schoppler, F. et al. Molar extinction coefficient of single-wall carbon nanotubes. J. Phys. Chem. C 115, 14682–14686 (2011).
Habenicht, B. & Prezhdo, O. Ab initio time-domain study of the triplet state in a semiconducting carbon nanotube: intersystem crossing, phosphorescence time, and line width. J. Am. Chem. Soc. 134, 15648–15651 (2012).
Masser, T. & ben Avraham, D. Kinetics of coalescence, annihilation, and the q-state Potts model in one dimension. Phys. Lett. A 275, 382–385 (2000).
Ozawa, H., Ide, N., Fujigaya, T., Niidome, Y. & Nakashima, N. One-pot separation of highly enriched (6,5)-single-walled carbon nanotubes using a fluorene-based copolymer. Chem. Lett. 40, 239–241 (2011).
Acknowledgements
V.D. acknowledges financial support through ZAE Bayern, funded through the Bavarian Ministry of Economic Affairs, Infrastructure, Transport and Technology. T.H. acknowledges stimulating discussions with J. Allam.
Author information
Authors and Affiliations
Contributions
D.S. and F.S. carried out the time-resolved photoluminescence measurements and prepared samples. H.K., A.S. and V.D. were responsible for ODMR experiments, their interpretation and design. T.H. and F.S. developed the kinetic model. All authors contributed to the interpretation of the results and writing of the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary information
Supplementary information (PDF 768 kb)
Rights and permissions
About this article
Cite this article
Stich, D., Späth, F., Kraus, H. et al. Triplet–triplet exciton dynamics in single-walled carbon nanotubes. Nature Photon 8, 139–144 (2014). https://doi.org/10.1038/nphoton.2013.316
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1038/nphoton.2013.316
This article is cited by
-
Probing the ultrafast dynamics of excitons in single semiconducting carbon nanotubes
Nature Communications (2022)
-
Formation of organic color centers in air-suspended carbon nanotubes using vapor-phase reaction
Nature Communications (2022)
-
Measurement of complex optical susceptibility for individual carbon nanotubes by elliptically polarized light excitation
Nature Communications (2018)
-
Bandgap renormalization in single-wall carbon nanotubes
Scientific Reports (2017)
-
Photoinduced spontaneous free-carrier generation in semiconducting single-walled carbon nanotubes
Nature Communications (2015)