DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Finding the hidden valence band of N = 7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy

Abstract

To understand the optical and transport properties of graphene nanoribbons, an unambiguous determination of their electronic band structure is needed. In this work we demonstrate that the photoemission intensity of each valence sub-band, formed due to the quantum confinement in quasi-one-dimensional (1D) graphene nanoribbons, is a peaked function of the two-dimensional (2D) momentum. We resolve the long-standing discrepancy regarding the valence band effective mass (m*VB) of armchair graphene nanoribbons with a width of N = 7 carbon atoms (7-AGNRs). In particular, angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy report m*VB ≈0.2 and ≈0.4 of the free electron mass (me), respectively. ARPES mapping in the full 2D momentum space identifies the experimental conditions for obtaining a large intensity for each of the three highest valence 1D sub-bands. Our detail map reveals that previous ARPES experiments have incorrectly assigned the second sub-band as the frontier one. The correct frontier valence sub-band for 7-AGNRs is only visible in a narrow range of emission angles. For this band we obtain an ARPES derived effective mass of 0.4 me, a charge carrier velocity in the linear part of the band of 0.63 x 106 m s-1 and an energy separation of only ≈60 meVmore » to the second sub-band. Lastly, our results are of importance not only for the growing research field of graphene nanoribbons but also for the community, which studies quantum confined systems.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4];  [5];  [6]; ORCiD logo [5]
  1. Univ. zu Koln, Koln (Germany); St. Petersburg State Univ., St. Petersburg (Russia)
  2. St. Petersburg State Univ., St. Petersburg (Russia)
  3. St. Petersburg State Univ., St. Petersburg (Russia); IFW-Dresden, HelmholtzstraBe (Germany)
  4. Univ. of California, Berkeley, CA (United States)
  5. Univ. zu Koln, Koln (Germany)
  6. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1460343
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
2D Materials
Additional Journal Information:
Journal Volume: 5; Journal Issue: 3; Journal ID: ISSN 2053-1583
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; graphene; nanoribbons; ARPES; electronic structure

Citation Formats

Senkovskiy, Boris V., Usachov, Dmitry Yu, Fedorov, Alexander V., Haberer, Danny, Ehlen, Niels, Fischer, Felix R., and Gruneis, Alexander. Finding the hidden valence band of N = 7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy. United States: N. p., 2018. Web. doi:10.1088/2053-1583/aabb70.
Senkovskiy, Boris V., Usachov, Dmitry Yu, Fedorov, Alexander V., Haberer, Danny, Ehlen, Niels, Fischer, Felix R., & Gruneis, Alexander. Finding the hidden valence band of N = 7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy. United States. https://doi.org/10.1088/2053-1583/aabb70
Senkovskiy, Boris V., Usachov, Dmitry Yu, Fedorov, Alexander V., Haberer, Danny, Ehlen, Niels, Fischer, Felix R., and Gruneis, Alexander. Mon . "Finding the hidden valence band of N = 7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy". United States. https://doi.org/10.1088/2053-1583/aabb70. https://www.osti.gov/servlets/purl/1460343.
@article{osti_1460343,
title = {Finding the hidden valence band of N = 7 armchair graphene nanoribbons with angle-resolved photoemission spectroscopy},
author = {Senkovskiy, Boris V. and Usachov, Dmitry Yu and Fedorov, Alexander V. and Haberer, Danny and Ehlen, Niels and Fischer, Felix R. and Gruneis, Alexander},
abstractNote = {To understand the optical and transport properties of graphene nanoribbons, an unambiguous determination of their electronic band structure is needed. In this work we demonstrate that the photoemission intensity of each valence sub-band, formed due to the quantum confinement in quasi-one-dimensional (1D) graphene nanoribbons, is a peaked function of the two-dimensional (2D) momentum. We resolve the long-standing discrepancy regarding the valence band effective mass (m*VB) of armchair graphene nanoribbons with a width of N = 7 carbon atoms (7-AGNRs). In particular, angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling spectroscopy report m*VB ≈0.2 and ≈0.4 of the free electron mass (me), respectively. ARPES mapping in the full 2D momentum space identifies the experimental conditions for obtaining a large intensity for each of the three highest valence 1D sub-bands. Our detail map reveals that previous ARPES experiments have incorrectly assigned the second sub-band as the frontier one. The correct frontier valence sub-band for 7-AGNRs is only visible in a narrow range of emission angles. For this band we obtain an ARPES derived effective mass of 0.4 me, a charge carrier velocity in the linear part of the band of 0.63 x 106 m s-1 and an energy separation of only ≈60 meV to the second sub-band. Lastly, our results are of importance not only for the growing research field of graphene nanoribbons but also for the community, which studies quantum confined systems.},
doi = {10.1088/2053-1583/aabb70},
journal = {2D Materials},
number = 3,
volume = 5,
place = {United States},
year = {Mon Apr 16 00:00:00 EDT 2018},
month = {Mon Apr 16 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: Sketch of the ARPES experiment and the structure of hydrogen-terminated 7-AGNR with a = 2.46 Å. The cutting lines of 7-AGNR inside the unfolded 1D BZ with band indices n = 1, . . . 7 and the 2D BZ of graphene are shown. The measurements plane ismore » aligned vertically along the ribbons. The center of the scan is adjusted along k|| by the tilt angle, while k is changed by the polar angle. The horizontally polarized light with a photon energy of 45 eV is utilized.« less

Save / Share:

Works referenced in this record:

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

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

Exciton-dominated optical response of ultra-narrow graphene nanoribbons
journal, July 2014

  • Denk, Richard; Hohage, Michael; Zeppenfeld, Peter
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5253

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

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


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


On-Surface Synthesis of Rylene-Type Graphene Nanoribbons
journal, March 2015

  • Zhang, Haiming; Lin, Haiping; Sun, Kewei
  • Journal of the American Chemical Society, Vol. 137, Issue 12
  • DOI: 10.1021/ja511995r

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 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

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

On-Surface Synthesis of Atomically Precise Graphene Nanoribbons
journal, February 2016

  • Talirz, Leopold; Ruffieux, Pascal; Fasel, Roman
  • Advanced Materials, Vol. 28, Issue 29
  • DOI: 10.1002/adma.201505738

Raman Fingerprints of Atomically Precise Graphene Nanoribbons
journal, May 2016


Giant edge state splitting at atomically precise graphene zigzag edges
journal, May 2016

  • Wang, Shiyong; Talirz, Leopold; Pignedoli, Carlo A.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11507

Making Graphene Nanoribbons Photoluminescent
journal, April 2017


Experimental and Theoretical Investigations of Surface-Assisted Graphene Nanoribbon Synthesis Featuring Carbon–Fluorine Bond Cleavage
journal, May 2017


Graphene-like nanoribbons periodically embedded with four- and eight-membered rings
journal, March 2017

  • Liu, Meizhuang; Liu, Mengxi; She, Limin
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14924

Quantum Dots in Graphene Nanoribbons
journal, June 2017


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

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

Voltage-dependent conductance of a single graphene nanoribbon
journal, October 2012

  • Koch, Matthias; Ample, Francisco; Joachim, Christian
  • Nature Nanotechnology, Vol. 7, Issue 11
  • DOI: 10.1038/nnano.2012.169

Bottom-up graphene nanoribbon field-effect transistors
journal, December 2013

  • Bennett, Patrick B.; Pedramrazi, Zahra; Madani, Ali
  • Applied Physics Letters, Vol. 103, Issue 25
  • DOI: 10.1063/1.4855116

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


Semiconductor-to-Metal Transition and Quasiparticle Renormalization in Doped Graphene Nanoribbons
journal, March 2017

  • Senkovskiy, Boris V.; Fedorov, Alexander V.; Haberer, Danny
  • Advanced Electronic Materials, Vol. 3, Issue 4
  • DOI: 10.1002/aelm.201600490

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


Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution
journal, December 2016


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

Effect of electron injection in copper-contacted graphene nanoribbons
journal, July 2016

  • Simonov, Konstantin A.; Vinogradov, Nikolay A.; Vinogradov, Alexander S.
  • Nano Research, Vol. 9, Issue 9
  • DOI: 10.1007/s12274-016-1162-2

Spectroscopic characterization of N  = 9 armchair graphene nanoribbons : Spectroscopic characterization of
journal, July 2017

  • Senkovskiy, B. V.; Haberer, D.; Usachov, D. Yu.
  • physica status solidi (RRL) - Rapid Research Letters, Vol. 11, Issue 8
  • DOI: 10.1002/pssr.201700157

Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy
journal, January 2015


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


Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires
journal, January 2016

  • Vasseur, Guillaume; Fagot-Revurat, Yannick; Sicot, Muriel
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10235

Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires
journal, January 2016


Π Band Dispersion along Conjugated Organic Nanowires Synthesized on a Metal Oxide Semiconductor
journal, April 2016

  • Vasseur, Guillaume; Abadia, Mikel; Miccio, Luis A.
  • Journal of the American Chemical Society, Vol. 138, Issue 17
  • DOI: 10.1021/jacs.6b02151

Analytical study of electronic structure in armchair graphene nanoribbons
journal, April 2007


Electron Wave Function in Armchair Graphene Nanoribbons
journal, April 2011

  • Sasaki, Ken-ichi; Wakabayashi, Katsunori; Enoki, Toshiaki
  • Journal of the Physical Society of Japan, Vol. 80, Issue 4
  • DOI: 10.1143/JPSJ.80.044710

Intra- and Intermolecular Band Dispersion in an Organic Crystal
journal, July 2007


Reconstruction of Molecular Orbital Densities from Photoemission Data
journal, September 2009


Simulation of angle-resolved photoemission spectra by approximating the final state by a plane wave: From graphene to polycyclic aromatic hydrocarbon molecules
journal, April 2015


Lateral quantum wells at vicinal Au(111) studied with angle-resolved photoemission
journal, December 2002

  • Mugarza, A.; Mascaraque, A.; Repain, V.
  • Physical Review B, Vol. 66, Issue 24, Article No. 245419
  • DOI: 10.1103/PhysRevB.66.245419

Measurement of electron wave functions and confining potentials via photoemission
journal, February 2003


Brillouin-zone-selection effects in graphite photoelectron angular distributions
journal, May 1995


Quasiparticle dynamics in graphene
journal, December 2006

  • Bostwick, Aaron; Ohta, Taisuke; Seyller, Thomas
  • Nature Physics, Vol. 3, Issue 1
  • DOI: 10.1038/nphys477

Characterization of graphene through anisotropy of constant-energy maps in angle-resolved photoemission
journal, May 2008


Illuminating the dark corridor in graphene: Polarization dependence of angle-resolved photoemission spectroscopy on graphene
journal, March 2011


Visualizing Electronic Chirality and Berry Phases in Graphene Systems Using Photoemission with Circularly Polarized Light
journal, October 2011


Direct measurement of quantum phases in graphene via photoemission spectroscopy
journal, September 2011


Sublattice Interference as the Origin of σ Band Kinks in Graphene
journal, May 2016


Interlayer Interaction and Electronic Screening in Multilayer Graphene Investigated with Angle-Resolved Photoemission Spectroscopy
journal, May 2007


Energy-momentum mapping of d -derived Au(111) states in a thin film
journal, January 2016


Dirac cones reshaped by interaction effects in suspended graphene
journal, July 2011

  • Elias, D. C.; Gorbachev, R. V.; Mayorov, A. S.
  • Nature Physics, Vol. 7, Issue 9
  • DOI: 10.1038/nphys2049

Structural and electronic properties of graphene nanoflakes on Au(111) and Ag(111)
journal, March 2016

  • Tesch, Julia; Leicht, Philipp; Blumenschein, Felix
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep23439

Full-potential nonorthogonal local-orbital minimum-basis band-structure scheme
journal, January 1999


Electronic states of graphene nanoribbons and analytical solutions
journal, October 2010

  • Wakabayashi, Katsunori; Sasaki, Ken-ichi; Nakanishi, Takeshi
  • Science and Technology of Advanced Materials, Vol. 11, Issue 5
  • DOI: 10.1088/1468-6996/11/5/054504

Dirac fermions and flat bands in the ideal kagome metal FeSn
journal, December 2019


Atomically controlled substitutional boron-doping of graphene nanoribbons
text, January 2015


Quantum Dots in Graphene Nanoribbons
text, January 2017

  • Wang, Shiyong; Kharche, Neerav; Costa Girão, Eduardo
  • American Chemical Society
  • DOI: 10.7892/boris.101816

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

  • Feng, Xinliang; Ruffieux, Pascal; Meunier, Vincent
  • American Chemical Society
  • DOI: 10.7892/boris.101819

On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons
text, January 2017

  • Sanchez-Valencia, Juan Ramon; Ruffieux, Pascal; Dumslaff, Tim
  • American Chemical Society
  • DOI: 10.7892/boris.101823

Exciton-dominated optical response of ultra-narrow graphene nanoribbons
text, January 2014

  • Söde, Hajo; Zeppenfeld, Peter; Molinari, Elisa
  • Nature Publishing Group
  • DOI: 10.7892/boris.58130

On-Surface Synthesis of Atomically Precise Graphene Nanoribbons
text, January 2016


Giant edge state splitting at atomically precise graphene zigzag edges
text, January 2016

  • Pignedoli, Carlo A.; Ruffieux, Pascal; Feng, Xinliang
  • Nature Publishing Group
  • DOI: 10.7892/boris.90588

Atomically precise bottom-up fabrication of graphene nanoribbons
text, January 2010

  • Cai, J. M.; Ruffieux, P.; Jaafar, R.
  • Nature Publishing Group
  • DOI: 10.5167/uzh-36020

Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy
text, January 2015

  • Ruffieux, Pascal; Söde, Hajo; Müllen, Klaus
  • American Physical Society
  • DOI: 10.7892/boris.64991

Dirac cones reshaped by interaction effects in suspended graphene
text, January 2011


Direct measurement of quantum phases in graphene via photoemission spectroscopy
text, January 2011


Energy-momentum mapping of d-derived Au(111) states in a thin film
text, January 2016


Measurement of electron wave functions and confining potentials via photoemission
text, January 2002


Analytical Study of Electronic Structure in Armchair Graphene Nanoribbons
text, January 2006


On-surface synthesis of graphene nanoribbons with zigzag edge topology
text, January 2016

  • Fasel, Roman; Talirz, Leopold; Passerone, Daniele
  • Macmillan Journals Ltd.
  • DOI: 10.7892/boris.90580

Works referencing / citing this record:

Probing the origin of photoluminescence brightening in graphene nanoribbons
journal, April 2019

  • Alavi, Seyed Khalil; Senkovskiy, Boris V.; Pfeiffer, Markus
  • 2D Materials, Vol. 6, Issue 3
  • DOI: 10.1088/2053-1583/ab1116

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.