Title: Fermi-Level Engineering of Nitrogen Core-Doped Armchair Graphene Nanoribbons

Abstract

Substitutional heteroatom doping of bottom-up engineered 1D graphene nanoribbons (GNRs) is a versatile tool for realizing low-dimensional functional materials for nanoelectronics and sensing. Previous efforts have largely relied on replacing C–H groups lining the edges of GNRs with trigonal planar N atoms. This type of atomically precise doping, however, only results in a modest realignment of the valence band (VB) and conduction band (CB) energies. Here, we report the design, bottom-up synthesis, and spectroscopic characterization of nitrogen core-doped 5-atom-wide armchair GNRs (N_2-5-AGNRs) that yield much greater energy-level shifting of the GNR electronic structure. Here, the substitution of C atoms with N atoms along the backbone of the GNR introduces a single surplus π-electron per dopant that populates the electronic states associated with previously unoccupied bands. First-principles DFT-LDA calculations confirm that a sizable shift in Fermi energy (∼1.0 eV) is accompanied by a broad reconfiguration of the band structure, including the opening of a new band gap and the transition from a direct to an indirect semiconducting band gap. Scanning tunneling spectroscopy (STS) lift-off charge transport experiments corroborate the theoretical results and reveal the relationship among substitutional heteroatom doping, Fermi-level shifting, electronic band structure, and topological engineering for this new N-dopedmore » GNR.« less

Authors:

Wen, Ethan Chi Ho  ^[1];

• Search DOE PAGES for author "Wen, Ethan Chi Ho"
• Search DOE PAGES for ORCID "0000-0002-8656-5285"

Jacobse, Peter H. ^[2]; Jiang, Jingwei  ^[3];

• Search DOE PAGES for author "Jiang, Jingwei"
• Search DOE PAGES for ORCID "0000-0002-0949-4401"

Wang, Ziyi  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-1049-5038"

Louie, Steven G.  ^[3];

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• Search DOE PAGES for ORCID "0000-0003-0622-0170"

Crommie, Michael F.  ^[4];

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• Search DOE PAGES for ORCID "0000-0001-8246-3444"

Fischer, Felix R.  ^[5]

• Search DOE PAGES for author "Fischer, Felix R."
• Search DOE PAGES for ORCID "0000-0003-4723-3111"

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+ Show Author Affiliations

1. Department of Chemistry, University of California, Berkeley, California 94720, United States
2. Department of Physics, University of California, Berkeley, California 94720, United States
3. Department of Physics, University of California, Berkeley, California 94720, United States, Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
4. Department of Physics, University of California, Berkeley, California 94720, United States, Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
5. Department of Chemistry, University of California, Berkeley, California 94720, United States, Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Kavli Energy NanoSciences Institute at the University of California Berkeley and the Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States, Bakar Institute of Digital Materials for the Planet, Division of Computing, Data Science, and Society, University of California, Berkeley, California 94720, United States

Publication Date:

Wed Aug 23 00:00:00 EDT 2023

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); US Department of the Navy, Office of Naval Research (ONR); National Science Foundation (NSF); Croucher Foundation; National Institutes of Health (NIH)

OSTI Identifier:

1996463

Alternate Identifier(s):

OSTI ID: 2281669

Grant/Contract Number:  

AC02-05-CH11231; SC0023105; AC02-05CH11231; N00014-19-1-2503; N00014-19-1-2596; DMR-1926004; CHE-2203911; CHE-2204252; N00014-20-1-2824; S10OD024998

Resource Type:

Published Article

Journal Name:

Journal of the American Chemical Society

Additional Journal Information:

Journal Name: Journal of the American Chemical Society Journal Volume: 145 Journal Issue: 35; Journal ID: ISSN 0002-7863

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY