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Title: Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores

Abstract

Graphene nanoribbons (GNRs) attract a great attention from researchers due to their tunable physical properties and potential for becoming nanoscale building blocks of electronic devices. GNRs can be synthesized with atomic precision by on-surface approaches from specially designed molecular precursors. While a considerable number of ribbons with very diverse structures and properties have been demonstrated in recent years, there have been only limited examples of on-surface synthesized GNRs modified with functional groups. In this study, we designed a nanoribbon, in which the chevron GNR backbone is decorated with phenyl functionalities, and demonstrate the on-surface synthesis of these GNRs on Au(111). We show that the phenyl modification affects the assembly of the GNR polymer precursors through π-π interactions. Scanning tunneling spectroscopy of the modified GNRs on Au(111) revealed that they have a band gap of 2.50±0.02 eV, which is comparable to that of the parent chevron GNR. The phenyl functionalization leads to a shift of the band edges to lower energies, suggesting that it could be a useful tool for the GNR band structure engineering. We also investigated lateral fusion of the phenyl-modified GNRs and demonstrate that it could be used to engineer different kinds of atomically precise graphene nanopores. Amore » similar functionalization approach could be potentially applied to other GNRs to affect their on-surface assembly, modify their electronic properties, and realize graphene nanopores with a variety of structures.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Univ. of Nebraska, Lincoln, NE (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1466610
Report Number(s):
BNL-207943-2018-JAAM
Journal ID: ISSN 1936-0851
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 12; Journal Issue: 8; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
47 OTHER INSTRUMENTATION

Citation Formats

Shekhirev, Mikhail, Zahl, Percy, and Sinitskii, Alexander. Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores. United States: N. p., 2018. Web. https://doi.org/10.1021/acsnano.8b04489.
Shekhirev, Mikhail, Zahl, Percy, & Sinitskii, Alexander. Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores. United States. https://doi.org/10.1021/acsnano.8b04489
Shekhirev, Mikhail, Zahl, Percy, and Sinitskii, Alexander. Tue . "Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores". United States. https://doi.org/10.1021/acsnano.8b04489. https://www.osti.gov/servlets/purl/1466610.
@article{osti_1466610,
title = {Phenyl Functionalization of Atomically Precise Graphene Nanoribbons for Engineering Inter-ribbon Interactions and Graphene Nanopores},
author = {Shekhirev, Mikhail and Zahl, Percy and Sinitskii, Alexander},
abstractNote = {Graphene nanoribbons (GNRs) attract a great attention from researchers due to their tunable physical properties and potential for becoming nanoscale building blocks of electronic devices. GNRs can be synthesized with atomic precision by on-surface approaches from specially designed molecular precursors. While a considerable number of ribbons with very diverse structures and properties have been demonstrated in recent years, there have been only limited examples of on-surface synthesized GNRs modified with functional groups. In this study, we designed a nanoribbon, in which the chevron GNR backbone is decorated with phenyl functionalities, and demonstrate the on-surface synthesis of these GNRs on Au(111). We show that the phenyl modification affects the assembly of the GNR polymer precursors through π-π interactions. Scanning tunneling spectroscopy of the modified GNRs on Au(111) revealed that they have a band gap of 2.50±0.02 eV, which is comparable to that of the parent chevron GNR. The phenyl functionalization leads to a shift of the band edges to lower energies, suggesting that it could be a useful tool for the GNR band structure engineering. We also investigated lateral fusion of the phenyl-modified GNRs and demonstrate that it could be used to engineer different kinds of atomically precise graphene nanopores. A similar functionalization approach could be potentially applied to other GNRs to affect their on-surface assembly, modify their electronic properties, and realize graphene nanopores with a variety of structures.},
doi = {10.1021/acsnano.8b04489},
journal = {ACS Nano},
number = 8,
volume = 12,
place = {United States},
year = {2018},
month = {8}
}

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Works referenced in this record:

Edge state in graphene ribbons: Nanometer size effect and edge shape dependence
journal, December 1996


Half-metallic graphene nanoribbons
journal, November 2006

  • Son, Young-Woo; Cohen, Marvin L.; Louie, Steven G.
  • Nature, Vol. 444, Issue 7117
  • DOI: 10.1038/nature05180

Quasiparticle Energies and Band Gaps in Graphene Nanoribbons
journal, November 2007


Atomically precise bottom-up fabrication of graphene nanoribbons
journal, July 2010

  • Cai, Jinming; Ruffieux, Pascal; Jaafar, Rached
  • Nature, Vol. 466, Issue 7305
  • DOI: 10.1038/nature09211

Spatially Resolved Electronic Structures of Atomically Precise Armchair Graphene Nanoribbons
journal, December 2012

  • Huang, Han; Wei, Dacheng; Sun, Jiatao
  • Scientific Reports, Vol. 2, Issue 1
  • DOI: 10.1038/srep00983

Tuning the Band Gap of Graphene Nanoribbons Synthesized from Molecular Precursors
journal, June 2013

  • Chen, Yen-Chia; de Oteyza, Dimas G.; Pedramrazi, Zahra
  • ACS Nano, Vol. 7, Issue 7
  • DOI: 10.1021/nn401948e

Ultra-narrow metallic armchair graphene nanoribbons
journal, December 2015

  • Kimouche, Amina; Ervasti, Mikko M.; Drost, Robert
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms10177

On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons
journal, February 2017


Seamless Staircase Electrical Contact to Semiconducting Graphene Nanoribbons
journal, September 2017


Revealing the Electronic Structure of Silicon Intercalated Armchair Graphene Nanoribbons by Scanning Tunneling Spectroscopy
journal, March 2017


Synthesis of armchair graphene nanoribbons from the 10,10′-dibromo-9,9′-bianthracene molecules on Ag(111): the role of organometallic intermediates
journal, February 2018


Molecules–Oligomers–Nanowires–Graphene Nanoribbons: A Bottom-Up Stepwise On-Surface Covalent Synthesis Preserving Long-Range Order
journal, January 2015

  • Basagni, Andrea; Sedona, Francesco; Pignedoli, Carlo A.
  • Journal of the American Chemical Society, Vol. 137, Issue 5
  • DOI: 10.1021/ja510292b

Doping of Graphene Nanoribbons via Functional Group Edge Modification
journal, July 2017

  • Carbonell-Sanromà, Eduard; Hieulle, Jeremy; Vilas-Varela, Manuel
  • ACS Nano, Vol. 11, Issue 7
  • DOI: 10.1021/acsnano.7b03522

On-surface synthesis of graphene nanoribbons with zigzag edge topology
journal, March 2016

  • Ruffieux, Pascal; Wang, Shiyong; Yang, Bo
  • Nature, Vol. 531, Issue 7595
  • DOI: 10.1038/nature17151

Toward Cove-Edged Low Band Gap Graphene Nanoribbons
journal, May 2015

  • Liu, Junzhi; Li, Bo-Wei; Tan, Yuan-Zhi
  • Journal of the American Chemical Society, Vol. 137, Issue 18
  • DOI: 10.1021/jacs.5b03017

Self-Assembly Strategy for Fabricating Connected Graphene Nanoribbons
journal, October 2015


Precursor Geometry Determines the Growth Mechanism in Graphene Nanoribbons
journal, January 2017

  • Schulz, Fabian; Jacobse, Peter H.; Canova, Filippo Federici
  • The Journal of Physical Chemistry C, Vol. 121, Issue 5
  • DOI: 10.1021/acs.jpcc.6b12428

Substrate-Independent Growth of Atomically Precise Chiral Graphene Nanoribbons
journal, August 2016

  • de Oteyza, Dimas G.; García-Lekue, Aran; Vilas-Varela, Manuel
  • ACS Nano, Vol. 10, Issue 9
  • DOI: 10.1021/acsnano.6b05269

Atomically controlled substitutional boron-doping of graphene nanoribbons
journal, August 2015

  • Kawai, Shigeki; Saito, Shohei; Osumi, Shinichiro
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9098

Site-Specific Substitutional Boron Doping of Semiconducting Armchair Graphene Nanoribbons
journal, July 2015

  • Cloke, Ryan R.; Marangoni, Tomas; Nguyen, Giang D.
  • Journal of the American Chemical Society, Vol. 137, Issue 28
  • DOI: 10.1021/jacs.5b02523

Nitrogen-Doping Induced Self-Assembly of Graphene Nanoribbon-Based Two-Dimensional and Three-Dimensional Metamaterials
journal, August 2015


Bottom-Up Synthesis of N = 13 Sulfur-Doped Graphene Nanoribbons
journal, January 2016

  • Nguyen, Giang D.; Toma, Francesca M.; Cao, Ting
  • The Journal of Physical Chemistry C, Vol. 120, Issue 5
  • DOI: 10.1021/acs.jpcc.5b09986

Graphene nanoribbon heterojunctions
journal, September 2014

  • Cai, Jinming; Pignedoli, Carlo A.; Talirz, Leopold
  • Nature Nanotechnology, Vol. 9, Issue 11
  • DOI: 10.1038/nnano.2014.184

Intraribbon Heterojunction Formation in Ultranarrow Graphene Nanoribbons
journal, February 2012

  • Blankenburg, Stephan; Cai, Jinming; Ruffieux, Pascal
  • ACS Nano, Vol. 6, Issue 3
  • DOI: 10.1021/nn203129a

Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions
journal, January 2015


Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor
journal, September 2017

  • Nguyen, Giang D.; Tsai, Hsin-Zon; Omrani, Arash A.
  • Nature Nanotechnology, Vol. 12, Issue 11
  • DOI: 10.1038/nnano.2017.155

Hierarchical On-Surface Synthesis of Graphene Nanoribbon Heterojunctions
journal, January 2018


Electronic Structure of Spatially Aligned Graphene Nanoribbons on Au(788)
journal, May 2012


Electronic Structure of Atomically Precise Graphene Nanoribbons
journal, July 2012

  • Ruffieux, Pascal; Cai, Jinming; Plumb, Nicholas C.
  • ACS Nano, Vol. 6, Issue 8
  • DOI: 10.1021/nn3021376

Epitaxial growth of aligned atomically precise chevron graphene nanoribbons on Cu(111)
journal, January 2017

  • Teeter, Jacob D.; Costa, Paulo S.; Mehdi Pour, Mohammad
  • Chemical Communications, Vol. 53, Issue 60
  • DOI: 10.1039/C6CC08006E

Aligning the Band Gap of Graphene Nanoribbons by Monomer Doping
journal, March 2013

  • Bronner, Christopher; Stremlau, Stephan; Gille, Marie
  • Angewandte Chemie International Edition, Vol. 52, Issue 16
  • DOI: 10.1002/anie.201209735

Synthesis of Graphene Nanoribbons by Ambient-Pressure Chemical Vapor Deposition and Device Integration
journal, November 2016

  • Chen, Zongping; Zhang, Wen; Palma, Carlos-Andres
  • Journal of the American Chemical Society, Vol. 138, Issue 47
  • DOI: 10.1021/jacs.6b10374

Large-scale solution synthesis of narrow graphene nanoribbons
journal, February 2014

  • Vo, Timothy H.; Shekhirev, Mikhail; Kunkel, Donna A.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4189

Charge-Transport Tuning of Solution-Processable Graphene Nanoribbons by Substitutional Nitrogen Doping
journal, September 2013

  • Kim, Kyung Tae; Lee, Jong Won; Jo, Won Ho
  • Macromolecular Chemistry and Physics, Vol. 214, Issue 23
  • DOI: 10.1002/macp.201300529

Bottom-up solution synthesis of narrow nitrogen-doped graphene nanoribbons
journal, January 2014

  • Vo, Timothy H.; Shekhirev, Mikhail; Kunkel, Donna A.
  • Chem. Commun., Vol. 50, Issue 32
  • DOI: 10.1039/C4CC00885E

Bottom-up synthesis of multifunctional nanoporous graphene
journal, April 2018


Triphenylene-Based Polymers for Blue Polymeric Light Emitting Diodes
journal, January 2010

  • Saleh, Moussa; Baumgarten, Martin; Mavrinskiy, Alexey
  • Macromolecules, Vol. 43, Issue 1
  • DOI: 10.1021/ma901912t

Conjugated Triphenylene Polymers for Blue OLED Devices: Conjugated Triphenylene Polymers for Blue OLED Devices
journal, July 2009

  • Saleh, Moussa; Park, Young-Seo; Baumgarten, Martin
  • Macromolecular Rapid Communications, Vol. 30, Issue 14
  • DOI: 10.1002/marc.200900332

Laterally extended atomically precise graphene nanoribbons with improved electrical conductivity for efficient gas sensing
journal, October 2017


Heterostructures through Divergent Edge Reconstruction in Nitrogen-Doped Segmented Graphene Nanoribbons
journal, August 2016

  • Marangoni, Tomas; Haberer, Danny; Rizzo, Daniel J.
  • Chemistry - A European Journal, Vol. 22, Issue 37
  • DOI: 10.1002/chem.201603497

Submolecular Imaging by Noncontact Atomic Force Microscopy with an Oxygen Atom Rigidly Connected to a Metallic Probe
journal, December 2015


Solution-Synthesized Chevron Graphene Nanoribbons Exfoliated onto H:Si(100)
journal, December 2016


Electronic characterization of silicon intercalated chevron graphene nanoribbons on Au(111)
journal, January 2018

  • Deniz, O.; Sánchez-Sánchez, C.; Jaafar, R.
  • Chemical Communications, Vol. 54, Issue 13
  • DOI: 10.1039/C7CC08353J

Lateral Fusion of Chemical Vapor Deposited N = 5 Armchair Graphene Nanoribbons
journal, July 2017

  • Chen, Zongping; Wang, Hai I.; Bilbao, Nerea
  • Journal of the American Chemical Society, Vol. 139, Issue 28
  • DOI: 10.1021/jacs.7b05055

Wide graphene nanoribbons produced by interchain fusion of poly(p-phenylene) via two-zone chemical vapor deposition
journal, January 2017

  • Song, Shaotang; Kojima, Takahiro; Nakae, Takahiro
  • Chemical Communications, Vol. 53, Issue 52
  • DOI: 10.1039/C7CC02849K

    Works referencing / citing this record:

    A stretchable laminated GNRs/BNNSs nanocomposite with high electrical and thermal conductivity
    journal, January 2019

    • Tan, Cenxiao; Zhu, Hongze; Ma, Tiantian
    • Nanoscale, Vol. 11, Issue 43
    • DOI: 10.1039/c9nr06060j

    Modified Engineering of Graphene Nanoribbons Prepared via On‐Surface Synthesis
    journal, December 2019


    On‐Surface Synthesis and Spectroscopic Characterization of Laterally Extended Chevron Graphene Nanoribbons
    journal, June 2019

    • Teeter, Jacob D.; Zahl, Percy; Mehdi Pour, Mohammad
    • ChemPhysChem, Vol. 20, Issue 18
    • DOI: 10.1002/cphc.201900445

    The qPlus sensor, a powerful core for the atomic force microscope
    journal, January 2019

    • Giessibl, Franz J.
    • Review of Scientific Instruments, Vol. 90, Issue 1
    • DOI: 10.1063/1.5052264