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 »
- Authors:
-
- Univ. zu Koln, Koln (Germany); St. Petersburg State Univ., St. Petersburg (Russia)
- St. Petersburg State Univ., St. Petersburg (Russia)
- St. Petersburg State Univ., St. Petersburg (Russia); IFW-Dresden, HelmholtzstraBe (Germany)
- Univ. of California, Berkeley, CA (United States)
- Univ. zu Koln, Koln (Germany)
- 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}
}
Web of Science
Figures / Tables:
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
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
Exciton-dominated optical response of ultra-narrow graphene nanoribbons
journal, July 2014
- Denk, Richard; Hohage, Michael; Zeppenfeld, Peter
- Nature Communications, Vol. 5, Issue 1
Graphene nanoribbon heterojunctions
journal, September 2014
- Cai, Jinming; Pignedoli, Carlo A.; Talirz, Leopold
- Nature Nanotechnology, Vol. 9, Issue 11
Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions
journal, January 2015
- Chen, Yen-Chia; Cao, Ting; Chen, Chen
- Nature Nanotechnology, Vol. 10, Issue 2
Atomically controlled substitutional boron-doping of graphene nanoribbons
journal, August 2015
- Kawai, Shigeki; Saito, Shohei; Osumi, Shinichiro
- Nature Communications, Vol. 6, Issue 1
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
Nitrogen-Doping Induced Self-Assembly of Graphene Nanoribbon-Based Two-Dimensional and Three-Dimensional Metamaterials
journal, August 2015
- Vo, Timothy H.; Perera, U. Gayani E.; Shekhirev, Mikhail
- Nano Letters, Vol. 15, Issue 9
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
Ultra-narrow metallic armchair graphene nanoribbons
journal, December 2015
- Kimouche, Amina; Ervasti, Mikko M.; Drost, Robert
- Nature Communications, Vol. 6, Issue 1
On-surface synthesis of graphene nanoribbons with zigzag edge topology
journal, March 2016
- Ruffieux, Pascal; Wang, Shiyong; Yang, Bo
- Nature, Vol. 531, Issue 7595
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
On-Surface Synthesis of Atomically Precise Graphene Nanoribbons
journal, February 2016
- Talirz, Leopold; Ruffieux, Pascal; Fasel, Roman
- Advanced Materials, Vol. 28, Issue 29
Raman Fingerprints of Atomically Precise Graphene Nanoribbons
journal, May 2016
- Verzhbitskiy, Ivan A.; Corato, Marzio De; Ruini, Alice
- Nano Letters, Vol. 16, Issue 6
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
Making Graphene Nanoribbons Photoluminescent
journal, April 2017
- Senkovskiy, B. V.; Pfeiffer, M.; Alavi, S. K.
- Nano Letters, Vol. 17, Issue 7
Experimental and Theoretical Investigations of Surface-Assisted Graphene Nanoribbon Synthesis Featuring Carbon–Fluorine Bond Cleavage
journal, May 2017
- Hayashi, Hironobu; Yamaguchi, Junichi; Jippo, Hideyuki
- ACS Nano, Vol. 11, Issue 6
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
Quantum Dots in Graphene Nanoribbons
journal, June 2017
- Wang, Shiyong; Kharche, Neerav; Costa Girão, Eduardo
- Nano Letters, Vol. 17, Issue 7
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
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
Voltage-dependent conductance of a single graphene nanoribbon
journal, October 2012
- Koch, Matthias; Ample, Francisco; Joachim, Christian
- Nature Nanotechnology, Vol. 7, Issue 11
Bottom-up graphene nanoribbon field-effect transistors
journal, December 2013
- Bennett, Patrick B.; Pedramrazi, Zahra; Madani, Ali
- Applied Physics Letters, Vol. 103, Issue 25
Revealing the Electronic Structure of Silicon Intercalated Armchair Graphene Nanoribbons by Scanning Tunneling Spectroscopy
journal, March 2017
- Deniz, Okan; Sánchez-Sánchez, Carlos; Dumslaff, Tim
- Nano Letters, Vol. 17, Issue 4
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
Seamless Staircase Electrical Contact to Semiconducting Graphene Nanoribbons
journal, September 2017
- Ma, Chuanxu; Liang, Liangbo; Xiao, Zhongcan
- Nano Letters, Vol. 17, Issue 10
Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution
journal, December 2016
- Carbonell-Sanromà, Eduard; Brandimarte, Pedro; Balog, Richard
- Nano Letters, Vol. 17, Issue 1
Electronic Structure of Atomically Precise Graphene Nanoribbons
journal, July 2012
- Ruffieux, Pascal; Cai, Jinming; Plumb, Nicholas C.
- ACS Nano, Vol. 6, Issue 8
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
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
Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy
journal, January 2015
- Söde, Hajo; Talirz, Leopold; Gröning, Oliver
- Physical Review B, Vol. 91, Issue 4
On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons
journal, February 2017
- Talirz, Leopold; Söde, Hajo; Dumslaff, Tim
- ACS Nano, Vol. 11, Issue 2
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
Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires
journal, January 2016
- Basagni, Andrea; Vasseur, Guillaume; Pignedoli, Carlo A.
- ACS Nano, Vol. 10, Issue 2
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
Analytical study of electronic structure in armchair graphene nanoribbons
journal, April 2007
- Zheng, Huaixiu; Wang, Z. F.; Luo, Tao
- Physical Review B, Vol. 75, Issue 16
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
Intra- and Intermolecular Band Dispersion in an Organic Crystal
journal, July 2007
- Koller, G.; Berkebile, S.; Oehzelt, M.
- Science, Vol. 317, Issue 5836
Reconstruction of Molecular Orbital Densities from Photoemission Data
journal, September 2009
- Puschnig, P.; Berkebile, S.; Fleming, A. J.
- Science, Vol. 326, Issue 5953
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
- Puschnig, Peter; Lüftner, Daniel
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 200
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
Measurement of electron wave functions and confining potentials via photoemission
journal, February 2003
- Mugarza, A.; Ortega, J. E.; Himpsel, F. J.
- Physical Review B, Vol. 67, Issue 8
Brillouin-zone-selection effects in graphite photoelectron angular distributions
journal, May 1995
- Shirley, Eric L.; Terminello, L. J.; Santoni, A.
- Physical Review B, Vol. 51, Issue 19
Quasiparticle dynamics in graphene
journal, December 2006
- Bostwick, Aaron; Ohta, Taisuke; Seyller, Thomas
- Nature Physics, Vol. 3, Issue 1
Characterization of graphene through anisotropy of constant-energy maps in angle-resolved photoemission
journal, May 2008
- Mucha-Kruczyński, M.; Tsyplyatyev, O.; Grishin, A.
- Physical Review B, Vol. 77, Issue 19
Illuminating the dark corridor in graphene: Polarization dependence of angle-resolved photoemission spectroscopy on graphene
journal, March 2011
- Gierz, Isabella; Henk, Jürgen; Höchst, Hartmut
- Physical Review B, Vol. 83, Issue 12
Visualizing Electronic Chirality and Berry Phases in Graphene Systems Using Photoemission with Circularly Polarized Light
journal, October 2011
- Liu, Y.; Bian, G.; Miller, T.
- Physical Review Letters, Vol. 107, Issue 16
Direct measurement of quantum phases in graphene via photoemission spectroscopy
journal, September 2011
- Hwang, Choongyu; Park, Cheol-Hwan; Siegel, David A.
- Physical Review B, Vol. 84, Issue 12
Sublattice Interference as the Origin of Band Kinks in Graphene
journal, May 2016
- Jung, Sung Won; Shin, Woo Jong; Kim, Jimin
- Physical Review Letters, Vol. 116, Issue 18
Interlayer Interaction and Electronic Screening in Multilayer Graphene Investigated with Angle-Resolved Photoemission Spectroscopy
journal, May 2007
- Ohta, Taisuke; Bostwick, Aaron; McChesney, J. L.
- Physical Review Letters, Vol. 98, Issue 20
Energy-momentum mapping of -derived Au(111) states in a thin film
journal, January 2016
- Sheverdyaeva, P. M.; Requist, R.; Moras, P.
- Physical Review B, Vol. 93, Issue 3
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
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
Full-potential nonorthogonal local-orbital minimum-basis band-structure scheme
journal, January 1999
- Koepernik, Klaus; Eschrig, Helmut
- Physical Review B, Vol. 59, Issue 3
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
Dirac fermions and flat bands in the ideal kagome metal FeSn
journal, December 2019
- Kang, Mingu; Ye, Linda; Fang, Shiang
- Nature Materials, Vol. 19, Issue 2
Atomically controlled substitutional boron-doping of graphene nanoribbons
text, January 2015
- Shigeki, Kawai,; Shohei, Saito,; Shinichiro, Osumi,
- Nature Publishing Group
Quantum Dots in Graphene Nanoribbons
text, January 2017
- Wang, Shiyong; Kharche, Neerav; Costa Girão, Eduardo
- American Chemical Society
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
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
Exciton-dominated optical response of ultra-narrow graphene nanoribbons
text, January 2014
- Söde, Hajo; Zeppenfeld, Peter; Molinari, Elisa
- Nature Publishing Group
On-Surface Synthesis of Atomically Precise Graphene Nanoribbons
text, January 2016
- Ruffieux, Pascal; Fasel, Roman; Talirz, Leopold
- Wiley-VCH
Giant edge state splitting at atomically precise graphene zigzag edges
text, January 2016
- Pignedoli, Carlo A.; Ruffieux, Pascal; Feng, Xinliang
- Nature Publishing Group
Atomically precise bottom-up fabrication of graphene nanoribbons
text, January 2010
- Cai, J. M.; Ruffieux, P.; Jaafar, R.
- Nature Publishing Group
Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy
text, January 2015
- Ruffieux, Pascal; Söde, Hajo; Müllen, Klaus
- American Physical Society
Illuminating the dark corridor in graphene: polarization dependence of angle-resolved photoemission spectroscopy on graphene
text, January 2010
- Gierz, Isabella; Henk, Juergen; Hoechst, Hartmut
- arXiv
Dirac cones reshaped by interaction effects in suspended graphene
text, January 2011
- Elias, D. C.; Gorbachev, R. V.; Mayorov, A. S.
- arXiv
Direct measurement of quantum phases in graphene via photoemission spectroscopy
text, January 2011
- Hwang, Choongyu; Park, Cheol-Hwan; Siegel, David A.
- arXiv
Electronic Band Dispersion of Graphene Nanoribbons via Fourier-Transformed Scanning Tunneling Spectroscopy
text, January 2014
- Söde, Hajo; Talirz, Leopold; Gröning, Oliver
- arXiv
Energy-momentum mapping of d-derived Au(111) states in a thin film
text, January 2016
- Sheverdyaeva, P. M.; Requist, R.; Moras, P.
- arXiv
Measurement of electron wave functions and confining potentials via photoemission
text, January 2002
- Mugarza, A.; Ortega, J. E.; Himpsel, F. J.
- arXiv
Analytical Study of Electronic Structure in Armchair Graphene Nanoribbons
text, January 2006
- Zheng, Huaixiu; Wang, Zhengfei; Luo, Tao
- arXiv
On-surface synthesis of graphene nanoribbons with zigzag edge topology
text, January 2016
- Fasel, Roman; Talirz, Leopold; Passerone, Daniele
- Macmillan Journals Ltd.
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
Figures / Tables found in this record: