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 here 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. We show that this behaviour can only result from a predominant selectivity for ortho binding configurations of the aryl groups on the nanotube lattice.
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This work was conducted in part at the Center for Integrated Nanotechnologies, a US Department of Energy, Office of Science user facility, and supported in part by the Center for Nonlinear Studies and by Los Alamos National Laboratory Directed Research and Development funds. S.K. acknowledges financial support from NSF Grant CHE-1413614 for studies of functionalized carbon nanotubes. For computational resources and administrative support, the authors thank the Center for Computationally Assisted Science and Technology (CCAST) at North Dakota State University. The authors also acknowledge the LANL Institutional Computing (IC) Program for providing computational resources. H.K. acknowledges support from JSPS KAKENHI grant no. JP25220602. Correspondence and requests for materials should be addressed to S.K.D. or S.T.
The authors declare no competing interests.
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Saha, A., Gifford, B.J., He, X. et al. Narrow-band single-photon emission through selective aryl functionalization of zigzag carbon nanotubes. Nature Chem 10, 1089–1095 (2018). https://doi.org/10.1038/s41557-018-0126-4
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