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      Large Bandgap Shrinkage from Doping and Dielectric Interface in Semiconducting Carbon Nanotubes

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      1 , a , 1
      Scientific Reports
      Nature Publishing Group

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          Abstract

          The bandgap of a semiconductor is one of its most important electronic properties. It is often considered to be a fixed property of the semiconductor. As the dimensions of semiconductors reduce, however, many-body effects become dominant. Here, we show that doping and dielectric, two critical features of semiconductor device manufacturing, can dramatically shrink (renormalize) the bandgap. We demonstrate this in quasi-one-dimensional semiconducting carbon nanotubes. Specifically, we use a four-gated device, configured as a p-n diode, to investigate the fundamental electronic structure of individual, partially supported nanotubes of varying diameter. The four-gated construction allows us to combine both electrical and optical spectroscopic techniques to measure the bandgap over a wide doping range.

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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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            Optoelectronic devices based on electrically tunable p-n diodes in a monolayer dichalcogenide.

            The p-n junction is the functional element of many electronic and optoelectronic devices, including diodes, bipolar transistors, photodetectors, light-emitting diodes and solar cells. In conventional p-n junctions, the adjacent p- and n-type regions of a semiconductor are formed by chemical doping. Ambipolar semiconductors, such as carbon nanotubes, nanowires and organic molecules, allow for p-n junctions to be configured and modified by electrostatic gating. This electrical control enables a single device to have multiple functionalities. Here, we report ambipolar monolayer WSe2 devices in which two local gates are used to define a p-n junction within the WSe2 sheet. With these electrically tunable p-n junctions, we demonstrate both p-n and n-p diodes with ideality factors better than 2. Under optical excitation, the diodes demonstrate a photodetection responsivity of 210 mA W(-1) and photovoltaic power generation with a peak external quantum efficiency of 0.2%, promising values for a nearly transparent monolayer material in a lateral device geometry. Finally, we demonstrate a light-emitting diode based on monolayer WSe2. These devices provide a building block for ultrathin, flexible and nearly transparent optoelectronic and electronic applications based on ambipolar dichalcogenide materials.
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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 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 ~ 1 eV in the semiconducting (8,0) tube and by ~ 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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                Author and article information

                Journal
                Sci Rep
                Sci Rep
                Scientific Reports
                Nature Publishing Group
                2045-2322
                24 June 2016
                2016
                : 6
                : 28520
                Affiliations
                [1 ]Colleges of Nanoscale Science and Engineering, SUNY-Polytechnic Institute , Albany, NY 12203, USA.
                Author notes
                Article
                srep28520
                10.1038/srep28520
                4919786
                27339272
                6b8672b0-ab16-4dcd-b06d-17670e253413
                Copyright © 2016, Macmillan Publishers Limited

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 06 April 2016
                : 02 June 2016
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