Rational synthesis of atomically precise graphene nanoribbons directly on metal oxide surfaces

Kolmer, Marek; Steiner, Ann-Kristin; Izydorczyk, Irena; Ko, Wonhee; Engelund, Mads; Szymonski, Marek; Li, An-Ping; Amsharov, Konstantin

doi:10.1126/science.abb8880

Title: Rational synthesis of atomically precise graphene nanoribbons directly on metal oxide surfaces

Journal Article · Thu Jun 25 00:00:00 EDT 2020 · Science

DOI:https://doi.org/10.1126/science.abb8880· OSTI ID:1767838

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Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Friedrich Alexander Univ., Erlangen (Germany)
Jagiellonian Univ., Krakow (Poland)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
Espeem S.A.R.L., Esch-sur-Alzette (Luxembourg)
Friedrich Alexander Univ. Erlangen-Nuremberg, Erlangen (Germany); Martin-Luther-Univ. Halle-Wittenberg, Halle (Germany)

Atomically precise graphene nanoribbons (GNRs) attract great interest because of their highly tunable electronic, optical, and transport properties. However, on-surface synthesis of GNRs is typically based on metal surface–assisted chemical reactions, where metallic substrates strongly screen their designer electronic properties and limit further applications. In this work, we present an on-surface synthesis approach to forming atomically precise GNRs directly on semiconducting metal oxide surfaces. The thermally triggered multistep transformations preprogrammed in our precursors’ design rely on highly selective and sequential activations of carbon-bromine (C-Br) and carbon-fluorine (C-F) bonds and cyclodehydrogenation. The formation of planar armchair GNRs terminated by well-defined zigzag ends is confirmed by scanning tunneling microscopy and spectroscopy, which also reveal weak interaction between GNRs and the rutile titanium dioxide substrate.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); US Department of the Navy, Office of Naval Research (ONR); Polish Ministry of Science and Higher Education; German Research Foundation (DFG)

Grant/Contract Number:: AC05-00OR22725; N00014-16-1-3213; N00014-20-1-2302; 0341/IP3/2016/74; 182849149−SFB 953

OSTI ID:: 1767838

Journal Information:: Science, Vol. 369, Issue 6503; ISSN 0036-8075

Publisher:: AAASCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Towards Nonalternant Nanographenes through Self‐Promoted Intramolecular Indenoannulation Cascade by C−F Bond Activation Akhmetov, Vladimir; Feofanov, Mikhail; Papaianina, Olena Chemistry – A European Journal, Vol. 25, Issue 50 https://doi.org/10.1002/chem.201902586	journal	August 2019
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
Electronic transport in planar atomic-scale structures measured by two-probe scanning tunneling spectroscopy Kolmer, Marek; Brandimarte, Pedro; Lis, Jakub Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-09315-6	journal	April 2019
Fluorine-programmed nanozipping to tailored nanographenes on rutile TiO ₂ surfaces Kolmer, M.; Zuzak, R.; Steiner, A. K. Science, Vol. 363, Issue 6422 https://doi.org/10.1126/science.aav4954	journal	January 2019
Tailoring Diindenochrysene through Intramolecular Multi‐Assemblies by C−F Bond Activation on Aluminum Oxide Akhmetov, Vladimir; Feofanov, Mikhail; Troyanov, Sergey Chemistry – A European Journal, Vol. 25, Issue 32 https://doi.org/10.1002/chem.201901450	journal	May 2019
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
Synthesis and Characterization of Teranthene: A Singlet Biradical Polycyclic Aromatic Hydrocarbon Having Kekulé Structures Konishi, Akihito; Hirao, Yasukazu; Nakano, Masayoshi Journal of the American Chemical Society, Vol. 132, Issue 32 https://doi.org/10.1021/ja1049737	journal	August 2010
Efficient and reliable method for the simulation of scanning tunneling images and spectra with local basis sets Paz, Óscar; Soler, José M. physica status solidi (b), Vol. 243, Issue 5 https://doi.org/10.1002/pssb.200541453	journal	April 2006
Surface-assisted cyclodehydrogenation provides a synthetic route towards easily processable and chemically tailored nanographenes Treier, Matthias; Pignedoli, Carlo Antonio; Laino, Teodoro Nature Chemistry, Vol. 3, Issue 1 https://doi.org/10.1038/nchem.891	journal	November 2010
Dimethylcethrene: A Chiroptical Diradicaloid Photoswitch Ravat, Prince; Šolomek, Tomáš; Häussinger, Daniel Journal of the American Chemical Society, Vol. 140, Issue 34 https://doi.org/10.1021/jacs.8b05465	journal	July 2018
Single spin localization and manipulation in graphene open-shell nanostructures Li, Jingcheng; Sanz, Sofia; Corso, Martina Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-08060-6	journal	January 2019
A chemical path to quantum information von Kugelgen, Stephen; Freedman, Danna E. Science, Vol. 366, Issue 6469 https://doi.org/10.1126/science.aaz4044	journal	November 2019
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
The Rolling-Up of Oligophenylenes to Nanographenes by a HF-Zipping Approach Steiner, Ann-Kristin; Amsharov, Konstantin Y. Angewandte Chemie International Edition, Vol. 56, Issue 46 https://doi.org/10.1002/anie.201707272	journal	October 2017
On-surface polymerization on a semiconducting oxide: aryl halide coupling controlled by surface hydroxyl groups on rutile TiO ₂ (011) Kolmer, Marek; Zuzak, Rafal; Ahmad Zebari, Amir A. Chemical Communications, Vol. 51, Issue 56 https://doi.org/10.1039/C5CC02989A	journal	January 2015
Cyclodehydrofluorination of fluoroarenes on metal oxides: Toward bottom-up synthesis of carbon nanostructures on insulating surfaces: Cyclodehydrofluorination of fluoroarenes on metal oxides Amsharov, Konstantin physica status solidi (b), Vol. 253, Issue 12 https://doi.org/10.1002/pssb.201600211	journal	September 2016
Coherent spin manipulation of individual atoms on a surface Yang, Kai; Paul, William; Phark, Soo-Hyon Science, Vol. 366, Issue 6464 https://doi.org/10.1126/science.aay6779	journal	October 2019
Surface-Synthesized Graphene Nanoribbons for Room Temperature Switching Devices: Substrate Transfer and ex Situ Characterization Borin Barin, Gabriela; Fairbrother, Andrew; Rotach, Lukas ACS Applied Nano Materials, Vol. 2, Issue 4 https://doi.org/10.1021/acsanm.9b00151	journal	March 2019
Mapping the Conductance of Electronically Decoupled Graphene Nanoribbons Jacobse, Peter H.; Mangnus, Mark J. J.; Zevenhuizen, Stephan J. M. ACS Nano, Vol. 12, Issue 7 https://doi.org/10.1021/acsnano.8b02770	journal	June 2018
Cethrene: The Chameleon of Woodward–Hoffmann Rules Šolomek, Tomáš; Ravat, Prince; Mou, Zhongyu The Journal of Organic Chemistry, Vol. 83, Issue 8 https://doi.org/10.1021/acs.joc.8b00656	journal	March 2018
Solution-Synthesized Chevron Graphene Nanoribbons Exfoliated onto H:Si(100) Radocea, Adrian; Sun, Tao; Vo, Timothy H. Nano Letters, Vol. 17, Issue 1 https://doi.org/10.1021/acs.nanolett.6b03709	journal	December 2016
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
Topological band engineering of graphene nanoribbons Rizzo, Daniel J.; Veber, Gregory; Cao, Ting Nature, Vol. 560, Issue 7717 https://doi.org/10.1038/s41586-018-0376-8	journal	August 2018
Polymerization of Polyanthrylene on a Titanium Dioxide (011)-(2×1) Surface Kolmer, Marek; Ahmad Zebari, Amir A.; Prauzner-Bechcicki, Jakub S. Angewandte Chemie International Edition, Vol. 52, Issue 39 https://doi.org/10.1002/anie.201303657	journal	August 2013
Intramolecular Aryl–Aryl Coupling of Fluoroarenes through Al ₂ O ₃ -Mediated HF Elimination Amsharov, K. Yu.; Merz, P. The Journal of Organic Chemistry, Vol. 77, Issue 12 https://doi.org/10.1021/jo300783y	journal	May 2012
Reading and writing single-atom magnets Natterer, Fabian D.; Yang, Kai; Paul, William Nature, Vol. 543, Issue 7644 https://doi.org/10.1038/nature21371	journal	March 2017
Topological frustration induces unconventional magnetism in a nanographene Mishra, Shantanu; Beyer, Doreen; Eimre, Kristjan Nature Nanotechnology, Vol. 15, Issue 1 https://doi.org/10.1038/s41565-019-0577-9	journal	December 2019
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
Topological Defect-Induced Magnetism in a Nanographene Mishra, Shantanu; Beyer, Doreen; Berger, Reinhard Journal of the American Chemical Society, Vol. 142, Issue 3 https://doi.org/10.1021/jacs.9b09212	journal	January 2020
Theory and Application for the Scanning Tunneling Microscope Tersoff, J.; Hamann, D. R. Physical Review Letters, Vol. 50, Issue 25 https://doi.org/10.1103/PhysRevLett.50.1998	journal	June 1983
Facile Bucky-Bowl Synthesis by Regiospecific Cove-Region Closure by HF Elimination Amsharov, K. Yu.; Kabdulov, M. A.; Jansen, Martin Angewandte Chemie International Edition, Vol. 51, Issue 19 https://doi.org/10.1002/anie.201200516	journal	April 2012
Edge states and ballistic transport in zigzag graphene ribbons: The role of SiC polytypes Miettinen, A. L.; Nevius, M. S.; Ko, W. Physical Review B, Vol. 100, Issue 4 https://doi.org/10.1103/PhysRevB.100.045425	journal	July 2019
Magnetic Correlations in Short and Narrow Graphene Armchair Nanoribbons Golor, Michael; Koop, Cornelie; Lang, Thomas C. Physical Review Letters, Vol. 111, Issue 8 https://doi.org/10.1103/PhysRevLett.111.085504	journal	August 2013
Short-channel field-effect transistors with 9-atom and 13-atom wide graphene nanoribbons Llinas, Juan Pablo; Fairbrother, Andrew; Borin Barin, Gabriela Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-00734-x	journal	September 2017
The SIESTA method for ab initio order- N materials simulation Soler, José M.; Artacho, Emilio; Gale, Julian D. Journal of Physics: Condensed Matter, Vol. 14, Issue 11 https://doi.org/10.1088/0953-8984/14/11/302	journal	March 2002
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
Magnetic resonance imaging of single atoms on a surface Willke, Philip; Yang, Kai; Bae, Yujeong Nature Physics, Vol. 15, Issue 10 https://doi.org/10.1038/s41567-019-0573-x	journal	July 2019
‘Forbidden’ Electrocyclizations of Diradicaloids Šolomek, Tomáš; Ravat, Prince; Juríček, Michal Trends in Chemistry, Vol. 1, Issue 7 https://doi.org/10.1016/j.trechm.2019.08.005	journal	October 2019
Electronic and Magnetic Properties of Zigzag Graphene Nanoribbons on the (111) Surface of Cu, Ag, and Au Li, Yan; Zhang, Wei; Morgenstern, Markus Physical Review Letters, Vol. 110, Issue 21 https://doi.org/10.1103/PhysRevLett.110.216804	journal	May 2013
Termini of Bottom-Up Fabricated Graphene Nanoribbons Talirz, Leopold; Söde, Hajo; Cai, Jinming Journal of the American Chemical Society, Vol. 135, Issue 6 https://doi.org/10.1021/ja311099k	journal	January 2013
Topological Phases in Graphene Nanoribbons: Junction States, Spin Centers, and Quantum Spin Chains Cao, Ting; Zhao, Fangzhou; Louie, Steven G. Physical Review Letters, Vol. 119, Issue 7 https://doi.org/10.1103/PhysRevLett.119.076401	journal	August 2017
Quantum units from the topological engineering of molecular graphenoids Lombardi, Federico; Lodi, Alessandro; Ma, Ji Science, Vol. 366, Issue 6469 https://doi.org/10.1126/science.aay7203	journal	November 2019
Convenient Synthetic Routes to 1,4-Difluoroanthracene-9,10-Dione Krapcho, A. Paul; Getahun, Zelleka Synthetic Communications, Vol. 15, Issue 10 https://doi.org/10.1080/00397918508063889	journal	August 1985
The Mechanism of Cyclodehydrofluorination on γ‐Alumina Sharapa, Dmitry; Steiner, Ann‐Kristin; Amsharov, Konstantin physica status solidi (b), Vol. 255, Issue 12 https://doi.org/10.1002/pssb.201800189	journal	June 2018
Engineering of robust topological quantum phases in graphene nanoribbons Gröning, Oliver; Wang, Shiyong; Yao, Xuelin Nature, Vol. 560, Issue 7717 https://doi.org/10.1038/s41586-018-0375-9	journal	August 2018
Controlling a Chemical Coupling Reaction on a Surface: Tools and Strategies for On-Surface Synthesis Clair, Sylvain; de Oteyza, Dimas G. Chemical Reviews, Vol. 119, Issue 7 https://doi.org/10.1021/acs.chemrev.8b00601	journal	March 2019
Atomic‐Scale Manipulation and In Situ Characterization with Scanning Tunneling Microscopy Ko, Wonhee; Ma, Chuanxu; Nguyen, Giang D. Advanced Functional Materials, Vol. 29, Issue 52 https://doi.org/10.1002/adfm.201903770	journal	October 2019
McMurry Chemistry on TiO ₂ (110): Reductive C═C Coupling of Benzaldehyde Driven by Titanium Interstitials Benz, Lauren; Haubrich, Jan; Quiller, Ryan G. Journal of the American Chemical Society, Vol. 131, Issue 41 https://doi.org/10.1021/ja905522c	journal	October 2009
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
Modified Engineering of Graphene Nanoribbons Prepared via On‐Surface Synthesis Zhou, Xiahong; Yu, Gui Advanced Materials, Vol. 32, Issue 6 https://doi.org/10.1002/adma.201905957	journal	December 2019

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