Abstract Incorporating fluorescent quantum defects in the sidewalls of semiconducting single-wall carbon nanotubes (SWCNTs) through chemical reaction is an emerging route to predictably modify nanotube electronic structures and develop advanced photonic functionality. Applications such as room-temperature single-photon emission and high-contrast bio-imaging have been advanced through aryl-functionalized SWCNTs, in which the binding configurations of the aryl group define the energies of the emitting states. However, the chemistry of binding with atomic precision at the single-bond level and tunable control over the binding configurations are yet to be achieved. Here, we explore recently reported photosynthetic protocol and find that it can control chemical binding configurations of quantum defects, which are often referred to as organic color centers, through the spin multiplicity of photoexcited intermediates. Specifically, photoexcited aromatics react with SWCNT sidewalls to undergo a singlet-state pathway in the presence of dissolved oxygen, leading to ortho binding configurations of the aryl group on the nanotube. In contrast, the oxygen-free photoreaction activates previously inaccessible para configurations through a triplet-state mechanism. These experimental results are corroborated by first principles simulations. Such spin-selective photochemistry diversifies SWCNT emission tunability by controlling the morphology of the emitting sites.
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This content will become publicly available on December 1, 2023
Formation of organic color centers in air-suspended carbon nanotubes using vapor-phase reaction
Abstract Organic color centers in single-walled carbon nanotubes have demonstrated exceptional ability to generate single photons at room temperature in the telecom range. Combining the color centers with pristine air-suspended nanotubes would be desirable for improved performance, but all current synthetic methods occur in solution which makes them incompatible. Here we demonstrate the formation of color centers in air-suspended nanotubes using a vapor-phase reaction. Functionalization is directly verified by photoluminescence spectroscopy, with unambiguous statistics from more than a few thousand individual nanotubes. The color centers show strong diameter-dependent emission, which can be explained with a model for chemical reactivity considering strain along the tube curvature. We also estimate the defect density by comparing the experiments with simulations based on a one-dimensional exciton diffusion equation. Our results highlight the influence of the nanotube structure on vapor-phase reactivity and emission properties, providing guidelines for the development of high-performance near-infrared quantum light sources.
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- Award ID(s):
- 1839165
- NSF-PAR ID:
- 10352759
- Date Published:
- Journal Name:
- Nature Communications
- Volume:
- 13
- Issue:
- 1
- ISSN:
- 2041-1723
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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