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Title: On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons

Abstract

The bottom-up approach to synthesize graphene nanoribbons strives not only to introduce a band gap into the electronic structure of graphene but also to accurately tune its value by designing both the width and edge structure of the ribbons with atomic precision. Within this paper, we report the synthesis of an armchair graphene nanoribbon with a width of nine carbon atoms on Au(111) through surface-assisted aryl–aryl coupling and subsequent cyclodehydrogenation of a properly chosen molecular precursor. By combining high-resolution atomic force microscopy, scanning tunneling microscopy, and Raman spectroscopy, we demonstrate that the atomic structure of the fabricated ribbons is exactly as designed. Angle-resolved photoemission spectroscopy and Fourier-transformed scanning tunneling spectroscopy reveal an electronic band gap of 1.4 eV and effective masses of ≈0.1 m e for both electrons and holes, constituting a substantial improvement over previous efforts toward the development of transistor applications. We use ab initio calculations to gain insight into the dependence of the Raman spectra on excitation wavelength as well as to rationalize the symmetry-dependent contribution of the ribbons’ electronic states to the tunneling current. Lastly, we propose a simple rule for the visibility of frontier electronic bands of armchair graphene nanoribbons in scanning tunneling spectroscopy.

Authors:
ORCiD logo [1];  [1];  [2];  [1];  [1];  [1];  [1];  [3]; ORCiD logo [4];  [5];  [6];  [6];  [7];  [2]; ORCiD logo [2];  [8]; ORCiD logo [1]
  1. Swiss Federal Laboratories for Materials Science and Technology (Empa) (Switzerland). nanotech@surfaces Laboratory
  2. Max Planck Institute for Polymer Research (Germany)
  3. Swiss Federal Laboratories for Materials Science and Technology (Empa) (Switzerland). nanotech@surfaces Laboratory and NCCR MARVEL
  4. Rensselaer Polytechnic Institute, Troy, NY (United States). Department of Physics, Applied Physics, and Astronomy; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science (CNMS)
  5. Rensselaer Polytechnic Institute, Troy, NY (United States). Department of Physics, Applied Physics, and Astronomy
  6. Paul Scherrer Institute (Switzerland). Swiss Light Source
  7. Dresden Univ. of Technology (Germany). Center for Advancing Electronics Dresden and Department of Chemistry and Food Chemistry
  8. Swiss Federal Laboratories for Materials Science and Technology (Empa) (Switzerland). nanotech@surfaces Laboratory; University of Bern (Switzerland). Department of Chemistry and Biochemistry
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1346658
Grant/Contract Number:
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 11; Journal Issue: 2; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 77 NANOSCIENCE AND NANOTECHNOLOGY; bottom-up synthesis; graphene nanoribbons; on-surface chemistry; Raman spectroscopy; scanning tunneling spectroscopy

Citation Formats

Talirz, Leopold, Söde, Hajo, Dumslaff, Tim, Wang, Shiyong, Sanchez-Valencia, Juan Ramon, Liu, Jia, Shinde, Prashant, Pignedoli, Carlo A., Liang, Liangbo, Meunier, Vincent, Plumb, Nicholas C., Shi, Ming, Feng, Xinliang, Narita, Akimitsu, Müllen, Klaus, Fasel, Roman, and Ruffieux, Pascal. On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons. United States: N. p., 2017. Web. doi:10.1021/acsnano.6b06405.
Talirz, Leopold, Söde, Hajo, Dumslaff, Tim, Wang, Shiyong, Sanchez-Valencia, Juan Ramon, Liu, Jia, Shinde, Prashant, Pignedoli, Carlo A., Liang, Liangbo, Meunier, Vincent, Plumb, Nicholas C., Shi, Ming, Feng, Xinliang, Narita, Akimitsu, Müllen, Klaus, Fasel, Roman, & Ruffieux, Pascal. On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons. United States. doi:10.1021/acsnano.6b06405.
Talirz, Leopold, Söde, Hajo, Dumslaff, Tim, Wang, Shiyong, Sanchez-Valencia, Juan Ramon, Liu, Jia, Shinde, Prashant, Pignedoli, Carlo A., Liang, Liangbo, Meunier, Vincent, Plumb, Nicholas C., Shi, Ming, Feng, Xinliang, Narita, Akimitsu, Müllen, Klaus, Fasel, Roman, and Ruffieux, Pascal. Fri . "On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons". United States. doi:10.1021/acsnano.6b06405. https://www.osti.gov/servlets/purl/1346658.
@article{osti_1346658,
title = {On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons},
author = {Talirz, Leopold and Söde, Hajo and Dumslaff, Tim and Wang, Shiyong and Sanchez-Valencia, Juan Ramon and Liu, Jia and Shinde, Prashant and Pignedoli, Carlo A. and Liang, Liangbo and Meunier, Vincent and Plumb, Nicholas C. and Shi, Ming and Feng, Xinliang and Narita, Akimitsu and Müllen, Klaus and Fasel, Roman and Ruffieux, Pascal},
abstractNote = {The bottom-up approach to synthesize graphene nanoribbons strives not only to introduce a band gap into the electronic structure of graphene but also to accurately tune its value by designing both the width and edge structure of the ribbons with atomic precision. Within this paper, we report the synthesis of an armchair graphene nanoribbon with a width of nine carbon atoms on Au(111) through surface-assisted aryl–aryl coupling and subsequent cyclodehydrogenation of a properly chosen molecular precursor. By combining high-resolution atomic force microscopy, scanning tunneling microscopy, and Raman spectroscopy, we demonstrate that the atomic structure of the fabricated ribbons is exactly as designed. Angle-resolved photoemission spectroscopy and Fourier-transformed scanning tunneling spectroscopy reveal an electronic band gap of 1.4 eV and effective masses of ≈0.1 me for both electrons and holes, constituting a substantial improvement over previous efforts toward the development of transistor applications. We use ab initio calculations to gain insight into the dependence of the Raman spectra on excitation wavelength as well as to rationalize the symmetry-dependent contribution of the ribbons’ electronic states to the tunneling current. Lastly, we propose a simple rule for the visibility of frontier electronic bands of armchair graphene nanoribbons in scanning tunneling spectroscopy.},
doi = {10.1021/acsnano.6b06405},
journal = {ACS Nano},
number = 2,
volume = 11,
place = {United States},
year = {Fri Jan 27 00:00:00 EST 2017},
month = {Fri Jan 27 00:00:00 EST 2017}
}

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Cited by: 30works
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  • Cited by 1
  • In this study, we investigate the N = 9 atoms wide armchair-type graphene nanoribbons (9-AGNRs) by performing a comprehensive spectroscopic and microscopic characterization of this novel material. In particular, we use X-ray photoelectron, near edge X-ray absorption fine structure, scanning tunneling, polarized Raman and angle-resolved photoemission (ARPES) spectroscopies. The ARPES measurements are aided by calculations of the photoemission matrix elements which yield the position in k space having the strongest photoemission cross section. Comparison with well-studied narrow N = 7 AGNRs shows that the effective electron mass in 9-AGNRs is reduced by two times and the valence band maximum ismore » shifted to lower binding energy by ~0.6 eV. In polarized Raman measurements of the aligned 9-AGNR, we reveal anisotropic signal depending upon the phonon symmetry. To conclude, our results indicate the 9-AGNRs are a novel 1D semiconductor with a high potential in nanoelectronic applications.« less
    Cited by 1
  • Bottom-up synthesized graphene nanoribbons and graphene nanoribbon heterostructures have promising electronic properties for high-performance field-effect transistors and ultra-low power devices such as tunneling field-effect transistors. However, the short length and wide band gap of these graphene nanoribbons have prevented the fabrication of devices with the desired performance and switching behavior. Here, by fabricating short channel (L ch ~ 20 nm) devices with a thin, high-κ gate dielectric and a 9-atom wide (0.95 nm) armchair graphene nanoribbon as the channel material, we demonstrate field-effect transistors with high on-current (I on > 1 μA at V d = -1 V) and highmore » I on /I off ~ 10 5 at room temperature. We find that the performance of these devices is limited by tunneling through the Schottky barrier at the contacts and we observe an increase in the transparency of the barrier by increasing the gate field near the contacts. Our results thus demonstrate successful fabrication of high-performance short-channel field-effect transistors with bottom-up synthesized armchair graphene nanoribbons.« less
  • We demonstrate and monitor an efficient edge reconstruction process, at the atomic scale, for graphite nanoribbons by Joule heating inside an integrated transmission electron microscope equipped with a scanning tunneling stage STM (TEM-STM system). During Joule annealing, sharp edges and step-edge arrays are formed, mostly with either zigzag or armchair edge configurations. Their formation is driven by both thermal and electric field related mechanisms. Model calculations show that the dominant annealing mechanisms involve point defect annealing and edge reconstruction. Joule heating is thus shown to provide an effective way to produce clean zigzag and armchair edges, which could be usefulmore » for both fundamental studies of edge reactivity, magnetism, and could provide a route for increasing carrier mobility and for the development of future electronics applications.« less