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

Senkovskiy, Boris V.; Usachov, Dmitry Yu; Fedorov, Alexander V.; Haberer, Danny; Ehlen, Niels; Fischer, Felix R.; Gruneis, Alexander

doi:10.1088/2053-1583/aabb70

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

Journal Article · 16 April 2018 · 2D Materials

DOI: https://doi.org/10.1088/2053-1583/aabb70 · OSTI ID:1460343

^[1];

^[2];

^[3]; Haberer, Danny ^[4]; Ehlen, Niels ^[5]; Fischer, Felix R. ^[6];

^[5]

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)

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 (m_e), 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 m_e, 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.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1460343

Journal Information:: 2D Materials, Vol. 5, Issue 3; ISSN 2053-1583

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 20 works

Citation information provided by
Web of Science

References (74)

Atomically precise bottom-up fabrication of graphene nanoribbons Cai, Jinming; Ruffieux, Pascal; Jaafar, Rached Nature, Vol. 466, Issue 7305 https://doi.org/10.1038/nature09211	journal	July 2010
Tuning the Band Gap of Graphene Nanoribbons Synthesized from Molecular Precursors Chen, Yen-Chia; de Oteyza, Dimas G.; Pedramrazi, Zahra ACS Nano, Vol. 7, Issue 7 https://doi.org/10.1021/nn401948e	journal	June 2013
Exciton-dominated optical response of ultra-narrow graphene nanoribbons Denk, Richard; Hohage, Michael; Zeppenfeld, Peter Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5253	journal	July 2014
Graphene nanoribbon heterojunctions Cai, Jinming; Pignedoli, Carlo A.; Talirz, Leopold Nature Nanotechnology, Vol. 9, Issue 11 https://doi.org/10.1038/nnano.2014.184	journal	September 2014
Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions Chen, Yen-Chia; Cao, Ting; Chen, Chen Nature Nanotechnology, Vol. 10, Issue 2 https://doi.org/10.1038/nnano.2014.307	journal	January 2015
Atomically controlled substitutional boron-doping of graphene nanoribbons Kawai, Shigeki; Saito, Shohei; Osumi, Shinichiro Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9098	journal	August 2015
Site-Specific Substitutional Boron Doping of Semiconducting Armchair Graphene Nanoribbons Cloke, Ryan R.; Marangoni, Tomas; Nguyen, Giang D. Journal of the American Chemical Society, Vol. 137, Issue 28 https://doi.org/10.1021/jacs.5b02523	journal	July 2015
Nitrogen-Doping Induced Self-Assembly of Graphene Nanoribbon-Based Two-Dimensional and Three-Dimensional Metamaterials Vo, Timothy H.; Perera, U. Gayani E.; Shekhirev, Mikhail Nano Letters, Vol. 15, Issue 9 https://doi.org/10.1021/acs.nanolett.5b01723	journal	August 2015
On-Surface Synthesis of Rylene-Type Graphene Nanoribbons Zhang, Haiming; Lin, Haiping; Sun, Kewei Journal of the American Chemical Society, Vol. 137, Issue 12 https://doi.org/10.1021/ja511995r	journal	March 2015
Ultra-narrow metallic armchair graphene nanoribbons Kimouche, Amina; Ervasti, Mikko M.; Drost, Robert Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms10177	journal	December 2015
On-surface synthesis of graphene nanoribbons with zigzag edge topology Ruffieux, Pascal; Wang, Shiyong; Yang, Bo Nature, Vol. 531, Issue 7595 https://doi.org/10.1038/nature17151	journal	March 2016
Substrate-Independent Growth of Atomically Precise Chiral Graphene Nanoribbons de Oteyza, Dimas G.; García-Lekue, Aran; Vilas-Varela, Manuel ACS Nano, Vol. 10, Issue 9 https://doi.org/10.1021/acsnano.6b05269	journal	August 2016
On-Surface Synthesis of Atomically Precise Graphene Nanoribbons Talirz, Leopold; Ruffieux, Pascal; Fasel, Roman Advanced Materials, Vol. 28, Issue 29 https://doi.org/10.1002/adma.201505738	journal	February 2016
Raman Fingerprints of Atomically Precise Graphene Nanoribbons Verzhbitskiy, Ivan A.; Corato, Marzio De; Ruini, Alice Nano Letters, Vol. 16, Issue 6 https://doi.org/10.1021/acs.nanolett.5b04183	journal	May 2016
Giant edge state splitting at atomically precise graphene zigzag edges Wang, Shiyong; Talirz, Leopold; Pignedoli, Carlo A. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11507	journal	May 2016
Making Graphene Nanoribbons Photoluminescent Senkovskiy, B. V.; Pfeiffer, M.; Alavi, S. K. Nano Letters, Vol. 17, Issue 7 https://doi.org/10.1021/acs.nanolett.7b00147	journal	April 2017
Experimental and Theoretical Investigations of Surface-Assisted Graphene Nanoribbon Synthesis Featuring Carbon–Fluorine Bond Cleavage Hayashi, Hironobu; Yamaguchi, Junichi; Jippo, Hideyuki ACS Nano, Vol. 11, Issue 6 https://doi.org/10.1021/acsnano.7b02316	journal	May 2017
Graphene-like nanoribbons periodically embedded with four- and eight-membered rings Liu, Meizhuang; Liu, Mengxi; She, Limin Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14924	journal	March 2017
Quantum Dots in Graphene Nanoribbons Wang, Shiyong; Kharche, Neerav; Costa Girão, Eduardo Nano Letters, Vol. 17, Issue 7 https://doi.org/10.1021/acs.nanolett.7b01244	journal	June 2017
Doping of Graphene Nanoribbons via Functional Group Edge Modification Carbonell-Sanromà, Eduard; Hieulle, Jeremy; Vilas-Varela, Manuel ACS Nano, Vol. 11, Issue 7 https://doi.org/10.1021/acsnano.7b03522	journal	July 2017
Atomically precise graphene nanoribbon heterojunctions from a single molecular precursor Nguyen, Giang D.; Tsai, Hsin-Zon; Omrani, Arash A. Nature Nanotechnology, Vol. 12, Issue 11 https://doi.org/10.1038/nnano.2017.155	journal	September 2017
Voltage-dependent conductance of a single graphene nanoribbon Koch, Matthias; Ample, Francisco; Joachim, Christian Nature Nanotechnology, Vol. 7, Issue 11 https://doi.org/10.1038/nnano.2012.169	journal	October 2012
Bottom-up graphene nanoribbon field-effect transistors Bennett, Patrick B.; Pedramrazi, Zahra; Madani, Ali Applied Physics Letters, Vol. 103, Issue 25 https://doi.org/10.1063/1.4855116	journal	December 2013
Revealing the Electronic Structure of Silicon Intercalated Armchair Graphene Nanoribbons by Scanning Tunneling Spectroscopy Deniz, Okan; Sánchez-Sánchez, Carlos; Dumslaff, Tim Nano Letters, Vol. 17, Issue 4 https://doi.org/10.1021/acs.nanolett.6b04727	journal	March 2017
Semiconductor-to-Metal Transition and Quasiparticle Renormalization in Doped Graphene Nanoribbons Senkovskiy, Boris V.; Fedorov, Alexander V.; Haberer, Danny Advanced Electronic Materials, Vol. 3, Issue 4 https://doi.org/10.1002/aelm.201600490	journal	March 2017
Seamless Staircase Electrical Contact to Semiconducting Graphene Nanoribbons Ma, Chuanxu; Liang, Liangbo; Xiao, Zhongcan Nano Letters, Vol. 17, Issue 10 https://doi.org/10.1021/acs.nanolett.7b02938	journal	September 2017
Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution Carbonell-Sanromà, Eduard; Brandimarte, Pedro; Balog, Richard Nano Letters, Vol. 17, Issue 1 https://doi.org/10.1021/acs.nanolett.6b03148	journal	December 2016
Electronic Structure of Spatially Aligned Graphene Nanoribbons on Au(788) Linden, S.; Zhong, D.; Timmer, A. Physical Review Letters, Vol. 108, Issue 21 https://doi.org/10.1103/PhysRevLett.108.216801	journal	May 2012
Electronic Structure of Atomically Precise Graphene Nanoribbons Ruffieux, Pascal; Cai, Jinming; Plumb, Nicholas C. ACS Nano, Vol. 6, Issue 8 https://doi.org/10.1021/nn3021376	journal	July 2012
Effect of electron injection in copper-contacted graphene nanoribbons Simonov, Konstantin A.; Vinogradov, Nikolay A.; Vinogradov, Alexander S. Nano Research, Vol. 9, Issue 9 https://doi.org/10.1007/s12274-016-1162-2	journal	July 2016
Spectroscopic characterization of N = 9 armchair graphene nanoribbons : Spectroscopic characterization of Senkovskiy, B. V.; Haberer, D.; Usachov, D. Yu. physica status solidi (RRL) - Rapid Research Letters, Vol. 11, Issue 8 https://doi.org/10.1002/pssr.201700157	journal	July 2017
Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy Söde, Hajo; Talirz, Leopold; Gröning, Oliver Physical Review B, Vol. 91, Issue 4 https://doi.org/10.1103/PhysRevB.91.045429	journal	January 2015
On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons Talirz, Leopold; Söde, Hajo; Dumslaff, Tim ACS Nano, Vol. 11, Issue 2 https://doi.org/10.1021/acsnano.6b06405	journal	February 2017
Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires Vasseur, Guillaume; Fagot-Revurat, Yannick; Sicot, Muriel Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10235	journal	January 2016
Tunable Band Alignment with Unperturbed Carrier Mobility of On-Surface Synthesized Organic Semiconducting Wires Basagni, Andrea; Vasseur, Guillaume; Pignedoli, Carlo A. ACS Nano, Vol. 10, Issue 2 https://doi.org/10.1021/acsnano.5b07683	journal	January 2016
Π Band Dispersion along Conjugated Organic Nanowires Synthesized on a Metal Oxide Semiconductor Vasseur, Guillaume; Abadia, Mikel; Miccio, Luis A. Journal of the American Chemical Society, Vol. 138, Issue 17 https://doi.org/10.1021/jacs.6b02151	journal	April 2016
Analytical study of electronic structure in armchair graphene nanoribbons Zheng, Huaixiu; Wang, Z. F.; Luo, Tao Physical Review B, Vol. 75, Issue 16 https://doi.org/10.1103/PhysRevB.75.165414	journal	April 2007
Electron Wave Function in Armchair Graphene Nanoribbons Sasaki, Ken-ichi; Wakabayashi, Katsunori; Enoki, Toshiaki Journal of the Physical Society of Japan, Vol. 80, Issue 4 https://doi.org/10.1143/JPSJ.80.044710	journal	April 2011
Intra- and Intermolecular Band Dispersion in an Organic Crystal Koller, G.; Berkebile, S.; Oehzelt, M. Science, Vol. 317, Issue 5836 https://doi.org/10.1126/science.1143239	journal	July 2007
Reconstruction of Molecular Orbital Densities from Photoemission Data Puschnig, P.; Berkebile, S.; Fleming, A. J. Science, Vol. 326, Issue 5953 https://doi.org/10.1126/science.1176105	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 Puschnig, Peter; Lüftner, Daniel Journal of Electron Spectroscopy and Related Phenomena, Vol. 200 https://doi.org/10.1016/j.elspec.2015.06.003	journal	April 2015
Lateral quantum wells at vicinal Au(111) studied with angle-resolved photoemission Mugarza, A.; Mascaraque, A.; Repain, V. Physical Review B, Vol. 66, Issue 24, Article No. 245419 https://doi.org/10.1103/PhysRevB.66.245419	journal	December 2002
Measurement of electron wave functions and confining potentials via photoemission Mugarza, A.; Ortega, J. E.; Himpsel, F. J. Physical Review B, Vol. 67, Issue 8 https://doi.org/10.1103/PhysRevB.67.081404	journal	February 2003
Brillouin-zone-selection effects in graphite photoelectron angular distributions Shirley, Eric L.; Terminello, L. J.; Santoni, A. Physical Review B, Vol. 51, Issue 19 https://doi.org/10.1103/PhysRevB.51.13614	journal	May 1995
Quasiparticle dynamics in graphene Bostwick, Aaron; Ohta, Taisuke; Seyller, Thomas Nature Physics, Vol. 3, Issue 1 https://doi.org/10.1038/nphys477	journal	December 2006
Characterization of graphene through anisotropy of constant-energy maps in angle-resolved photoemission Mucha-Kruczyński, M.; Tsyplyatyev, O.; Grishin, A. Physical Review B, Vol. 77, Issue 19 https://doi.org/10.1103/PhysRevB.77.195403	journal	May 2008
Illuminating the dark corridor in graphene: Polarization dependence of angle-resolved photoemission spectroscopy on graphene Gierz, Isabella; Henk, Jürgen; Höchst, Hartmut Physical Review B, Vol. 83, Issue 12 https://doi.org/10.1103/PhysRevB.83.121408	journal	March 2011
Visualizing Electronic Chirality and Berry Phases in Graphene Systems Using Photoemission with Circularly Polarized Light Liu, Y.; Bian, G.; Miller, T. Physical Review Letters, Vol. 107, Issue 16 https://doi.org/10.1103/PhysRevLett.107.166803	journal	October 2011
Direct measurement of quantum phases in graphene via photoemission spectroscopy Hwang, Choongyu; Park, Cheol-Hwan; Siegel, David A. Physical Review B, Vol. 84, Issue 12 https://doi.org/10.1103/PhysRevB.84.125422	journal	September 2011
Sublattice Interference as the Origin of σ Band Kinks in Graphene Jung, Sung Won; Shin, Woo Jong; Kim, Jimin Physical Review Letters, Vol. 116, Issue 18 https://doi.org/10.1103/PhysRevLett.116.186802	journal	May 2016
Interlayer Interaction and Electronic Screening in Multilayer Graphene Investigated with Angle-Resolved Photoemission Spectroscopy Ohta, Taisuke; Bostwick, Aaron; McChesney, J. L. Physical Review Letters, Vol. 98, Issue 20 https://doi.org/10.1103/PhysRevLett.98.206802	journal	May 2007
Energy-momentum mapping of d -derived Au(111) states in a thin film Sheverdyaeva, P. M.; Requist, R.; Moras, P. Physical Review B, Vol. 93, Issue 3 https://doi.org/10.1103/PhysRevB.93.035113	journal	January 2016
Dirac cones reshaped by interaction effects in suspended graphene Elias, D. C.; Gorbachev, R. V.; Mayorov, A. S. Nature Physics, Vol. 7, Issue 9 https://doi.org/10.1038/nphys2049	journal	July 2011
Structural and electronic properties of graphene nanoflakes on Au(111) and Ag(111) Tesch, Julia; Leicht, Philipp; Blumenschein, Felix Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep23439	journal	March 2016
Full-potential nonorthogonal local-orbital minimum-basis band-structure scheme Koepernik, Klaus; Eschrig, Helmut Physical Review B, Vol. 59, Issue 3 https://doi.org/10.1103/PhysRevB.59.1743	journal	January 1999
Electronic states of graphene nanoribbons and analytical solutions Wakabayashi, Katsunori; Sasaki, Ken-ichi; Nakanishi, Takeshi Science and Technology of Advanced Materials, Vol. 11, Issue 5 https://doi.org/10.1088/1468-6996/11/5/054504	journal	October 2010
Dirac fermions and flat bands in the ideal kagome metal FeSn Kang, Mingu; Ye, Linda; Fang, Shiang Nature Materials, Vol. 19, Issue 2 https://doi.org/10.1038/s41563-019-0531-0	journal	December 2019
Atomically controlled substitutional boron-doping of graphene nanoribbons Shigeki, Kawai,; Shohei, Saito,; Shinichiro, Osumi, Nature Publishing Group https://doi.org/10.5451/unibas-ep40346	text	January 2015
Quantum Dots in Graphene Nanoribbons Wang, Shiyong; Kharche, Neerav; Costa Girão, Eduardo American Chemical Society https://doi.org/10.7892/boris.101816	text	January 2017
Revealing the Electronic Structure of Silicon Intercalated Armchair Graphene Nanoribbons by Scanning Tunneling Spectroscopy Feng, Xinliang; Ruffieux, Pascal; Meunier, Vincent American Chemical Society https://doi.org/10.7892/boris.101819	text	January 2017
On-Surface Synthesis and Characterization of 9-Atom Wide Armchair Graphene Nanoribbons Sanchez-Valencia, Juan Ramon; Ruffieux, Pascal; Dumslaff, Tim American Chemical Society https://doi.org/10.7892/boris.101823	text	January 2017
Exciton-dominated optical response of ultra-narrow graphene nanoribbons Söde, Hajo; Zeppenfeld, Peter; Molinari, Elisa Nature Publishing Group https://doi.org/10.7892/boris.58130	text	January 2014
On-Surface Synthesis of Atomically Precise Graphene Nanoribbons Ruffieux, Pascal; Fasel, Roman; Talirz, Leopold Wiley-VCH https://doi.org/10.7892/boris.90587	text	January 2016
Giant edge state splitting at atomically precise graphene zigzag edges Pignedoli, Carlo A.; Ruffieux, Pascal; Feng, Xinliang Nature Publishing Group https://doi.org/10.7892/boris.90588	text	January 2016
Atomically precise bottom-up fabrication of graphene nanoribbons Cai, J. M.; Ruffieux, P.; Jaafar, R. Nature Publishing Group https://doi.org/10.5167/uzh-36020	text	January 2010
Electronic band dispersion of graphene nanoribbons via Fourier-transformed scanning tunneling spectroscopy Ruffieux, Pascal; Söde, Hajo; Müllen, Klaus American Physical Society https://doi.org/10.7892/boris.64991	text	January 2015
Illuminating the dark corridor in graphene: polarization dependence of angle-resolved photoemission spectroscopy on graphene Gierz, Isabella; Henk, Juergen; Hoechst, Hartmut arXiv https://doi.org/10.48550/arxiv.1010.1618	text	January 2010
Dirac cones reshaped by interaction effects in suspended graphene Elias, D. C.; Gorbachev, R. V.; Mayorov, A. S. arXiv https://doi.org/10.48550/arxiv.1104.1396	text	January 2011
Direct measurement of quantum phases in graphene via photoemission spectroscopy Hwang, Choongyu; Park, Cheol-Hwan; Siegel, David A. arXiv https://doi.org/10.48550/arxiv.1109.3680	text	January 2011
Electronic Band Dispersion of Graphene Nanoribbons via Fourier-Transformed Scanning Tunneling Spectroscopy Söde, Hajo; Talirz, Leopold; Gröning, Oliver arXiv https://doi.org/10.48550/arxiv.1412.1954	text	January 2014
Energy-momentum mapping of d-derived Au(111) states in a thin film Sheverdyaeva, P. M.; Requist, R.; Moras, P. arXiv https://doi.org/10.48550/arxiv.1603.08879	text	January 2016
Measurement of electron wave functions and confining potentials via photoemission Mugarza, A.; Ortega, J. E.; Himpsel, F. J. arXiv https://doi.org/10.48550/arxiv.cond-mat/0208254	text	January 2002
Analytical Study of Electronic Structure in Armchair Graphene Nanoribbons Zheng, Huaixiu; Wang, Zhengfei; Luo, Tao arXiv https://doi.org/10.48550/arxiv.cond-mat/0612378	text	January 2006
On-surface synthesis of graphene nanoribbons with zigzag edge topology Fasel, Roman; Talirz, Leopold; Passerone, Daniele Macmillan Journals Ltd. https://doi.org/10.7892/boris.90580	text	January 2016

Cited By (1)

Probing the origin of photoluminescence brightening in graphene nanoribbons Alavi, Seyed Khalil; Senkovskiy, Boris V.; Pfeiffer, Markus 2D Materials, Vol. 6, Issue 3 https://doi.org/10.1088/2053-1583/ab1116	journal	April 2019