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      Impact of Dielectric Environment on Trion Emission from Single-Walled Carbon Nanotube Networks

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          Abstract

          Trions are charged excitons that form upon optical or electrical excitation of low-dimensional semiconductors in the presence of charge carriers (holes or electrons). Trion emission from semiconducting single-walled carbon nanotubes (SWCNTs) occurs in the near-infrared and at lower energies compared to the respective exciton. It can be used as an indicator for the presence of excess charge carriers in SWCNT samples and devices. Both excitons and trions are highly sensitive to the surrounding dielectric medium of the nanotubes, having an impact on their application in optoelectronic devices. Here, the influence of different dielectric materials on exciton and trion emission from electrostatically doped networks of polymer-sorted (6,5) SWCNTs in top-gate field-effect transistors is investigated. The observed differences of trion and exciton emission energies and intensities for hole and electron accumulation cannot be explained with the polarizability or screening characteristics of the different dielectric materials, but they show a clear dependence on the charge trapping properties of the dielectrics. Charge localization (trapping of holes or electrons by the dielectric) reduces exciton quenching, emission blue-shift and trion formation. Based on the observed carrier type and dielectric material dependent variations, the ratio of trion to exciton emission and the exciton blue-shift are not suitable as quantitative metrics for doping levels of carbon nanotubes.

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          Band gap fluorescence from individual single-walled carbon nanotubes.

          Fluorescence has been observed directly across the band gap of semiconducting carbon nanotubes. We obtained individual nanotubes, each encased in a cylindrical micelle, by ultrasonically agitating an aqueous dispersion of raw single-walled carbon nanotubes in sodium dodecyl sulfate and then centrifuging to remove tube bundles, ropes, and residual catalyst. Aggregation of nanotubes into bundles otherwise quenches the fluorescence through interactions with metallic tubes and substantially broadens the absorption spectra. At pH less than 5, the absorption and emission spectra of individual nanotubes show evidence of band gap-selective protonation of the side walls of the tube. This protonation is readily reversed by treatment with base or ultraviolet light.
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            Excitonic effects and optical spectra of single-walled carbon nanotubes.

            Many-electron effects often dramatically modify the properties of reduced dimensional systems. We report calculations, based on an ab initio many-electron Green's function approach, of electron-hole interaction effects on the optical spectra of small-diameter single-walled carbon nanotubes. Excitonic effects qualitatively alter the optical spectra of both semiconducting and metallic tubes. Excitons are bound by approximately 1 eV in the semiconducting (8,0) tube and by approximately 100 meV in the metallic (3,3) tube. These large many-electron effects explain the discrepancies between previous theories and experiments.
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              Chirality Pure Carbon Nanotubes: Growth, Sorting, and Characterization

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                Author and article information

                Journal
                J Phys Chem C Nanomater Interfaces
                J Phys Chem C Nanomater Interfaces
                jy
                jpccck
                The Journal of Physical Chemistry. C, Nanomaterials and Interfaces
                American Chemical Society
                1932-7447
                1932-7455
                02 February 2023
                16 February 2023
                : 127
                : 6
                : 3112-3122
                Affiliations
                [1]Institute for Physical Chemistry, Universität Heidelberg , D-69120Heidelberg, Germany
                Author notes
                Author information
                https://orcid.org/0000-0002-2048-217X
                Article
                10.1021/acs.jpcc.2c08338
                9940213
                79a05cb9-cafd-4adf-a798-60f01583a747
                © 2023 The Authors. Published by American Chemical Society

                Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works ( https://creativecommons.org/licenses/by-nc-nd/4.0/).

                History
                : 28 November 2022
                : 10 January 2023
                Funding
                Funded by: H2020 European Research Council, doi 10.13039/100010663;
                Award ID: 817494
                Categories
                Article
                Custom metadata
                jp2c08338
                jp2c08338

                Thin films & surfaces
                Thin films & surfaces

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