On-surface Synthesis of Graphene Nanoribbons with Zigzag Edge Topology References and Notes

Graphene-based nanostructures exhibit electronic properties that are not present in extended graphene. For example, quantum confinement in carbon nanotubes and armchair graphene nanoribbons leads to the opening of substantial electronic bandgaps that are directly linked to their structural boundary conditions. Nanostructures with zigzag edges are expected to host spin-polarized electronic edge states and can thus serve as key elements for graphene-based spintronics. The edge states of zigzag graphene nanoribbons (ZGNRs) are predicted to couple ferromagnetically along the edge and antiferromagnetically between the edges, but direct observation of spin-polarized edge states for zigzag edge topologies—including ZGNRs—has not yet been achieved owing to the limited precision of current top-down approaches. Here we describe the bottom-up synthesis of ZGNRs through surface-assisted polymerization and cyclodehydrogenation of specifically designed precursor monomers to yield atomically precise zigzag edges. Using scanning tunnelling spectroscopy we show the existence of edge-localized states with large energy splittings. We expect that the availability of ZGNRs will enable the characterization of their predicted spin-related properties, such as spin confinement and filtering, and will ultimately add the spin degree of freedom to graphene-based circuitry.

[1]  G. Kabalka,et al.  The Conversion of Phenols to the Corresponding Aryl Halides Under Mild Conditions , 2005 .

[2]  Reinhard Berger,et al.  Graphene nanoribbon heterojunctions. , 2014, Nature nanotechnology.

[3]  V. Krongauz,et al.  Searching for photochromic liquid crystals Spironaphthoxazine substituted with a mesogenic group , 1990 .

[4]  K. Sun,et al.  On-surface synthesis of rylene-type graphene nanoribbons. , 2015, Journal of the American Chemical Society.

[5]  Wei Han,et al.  Graphene spintronics. , 2014, Nature nanotechnology.

[6]  J. Pei,et al.  Fusion at the non-K-region of pyrene: an alternative strategy to extend the π-conjugated plane of pyrene. , 2013, Organic letters.

[7]  M. Sigrist,et al.  Electronic and magnetic properties of nanographite ribbons , 1998, cond-mat/9809260.

[8]  S. Hecht,et al.  Aligning the band gap of graphene nanoribbons by monomer doping. , 2013, Angewandte Chemie.

[9]  Teter,et al.  Separable dual-space Gaussian pseudopotentials. , 1996, Physical review. B, Condensed matter.

[10]  Fujita,et al.  Electronic structure of graphene tubules based on C60. , 1992, Physical review. B, Condensed matter.

[11]  Joost VandeVondele,et al.  Gaussian basis sets for accurate calculations on molecular systems in gas and condensed phases. , 2007, The Journal of chemical physics.

[12]  G. Ertl,et al.  Dynamics of Electron-Induced Manipulation of Individual CO Molecules on Cu(111) , 1998 .

[13]  K. Schanze,et al.  Synthesis of Monodisperse Platinum Acetylide Oligomers End-Capped with Naphthalene Diimide Units , 2009 .

[14]  N. Miyaura,et al.  Palladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters , 1995 .

[15]  Fawzi Mohamed,et al.  Simulating fluid-phase equilibria of water from first principles. , 2006, The journal of physical chemistry. A.

[16]  V. Mamane,et al.  Flexible Synthesis of Phenanthrenes by a PtCl2-Catalyzed Cycloisomerization Reaction. , 2003 .

[17]  William R. Gemmill,et al.  Facile Synthesis of a Highly Crystalline, Covalently Linked Porous Boronate Network , 2006 .

[18]  Andrea Marini,et al.  yambo: An ab initio tool for excited state calculations , 2008, Comput. Phys. Commun..

[19]  Chen Li,et al.  Efficient tuning of LUMO levels of 2,5,8,11-substituted perylenediimides via copper catalyzed reactions. , 2011, Organic letters.

[20]  M. Weinert,et al.  Direct experimental determination of onset of electron–electron interactions in gap opening of zigzag graphene nanoribbons , 2014, Nature Communications.

[21]  J. Bhattacharjee Half-metallicity in graphene nanoribbons with topological defects at edge. , 2012, The Journal of chemical physics.

[22]  Yafei Li,et al.  Preserving the Edge Magnetism of Zigzag Graphene Nanoribbons by Ethylene Termination: Insight by Clar's Rule , 2013, Scientific Reports.

[23]  Franz J. Giessibl,et al.  Atomic resolution on Si(111)-(7×7) by noncontact atomic force microscopy with a force sensor based on a quartz tuning fork , 2000 .

[24]  J. Lyding,et al.  The influence of edge structure on the electronic properties of graphene quantum dots and nanoribbons. , 2009, Nature materials.

[25]  S. Louie,et al.  Magnetic edge-state excitons in zigzag graphene nanoribbons. , 2008, Physical review letters.

[26]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[27]  O. Yazyev A guide to the design of electronic properties of graphene nanoribbons. , 2013, Accounts of chemical research.

[28]  F. Colobert,et al.  A Practical Transition Metal-Free Aryl-Aryl Coupling Method: Arynes as Key Intermediates , 2007 .

[29]  C. Joachim,et al.  Molecules on insulating films: scanning-tunneling microscopy imaging of individual molecular orbitals. , 2005, Physical review letters.

[30]  Wei Zhang,et al.  Electronic and magnetic properties of zigzag graphene nanoribbons on the (111) surface of Cu, Ag, and Au. , 2012, Physical review letters.

[31]  J. Tour,et al.  Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons , 2009, Nature.

[32]  R. Needs,et al.  Metal-insulator transition in Kohn-Sham theory and quasiparticle theory. , 1989, Physical review letters.

[33]  S. Louie,et al.  Spatially resolving edge states of chiral graphene nanoribbons , 2011, 1101.1141.

[34]  Ting Cao,et al.  Molecular bandgap engineering of bottom-up synthesized graphene nanoribbon heterojunctions. , 2015, Nature nanotechnology.

[35]  E. Gross,et al.  Exact coulomb cutoff technique for supercell calculations , 2006, cond-mat/0601031.

[36]  H. Dai,et al.  Chemically Derived, Ultrasmooth Graphene Nanoribbon Semiconductors , 2008, Science.

[37]  F. Fischer,et al.  Tuning the band gap of graphene nanoribbons synthesized from molecular precursors. , 2013, ACS nano.

[38]  A. Seitsonen,et al.  Atomically precise bottom-up fabrication of graphene nanoribbons , 2010, Nature.

[39]  Jinlan Wang,et al.  Recent progress and challenges in graphene nanoribbon synthesis. , 2013, Chemphyschem : a European journal of chemical physics and physical chemistry.

[40]  P. Kim,et al.  Energy band-gap engineering of graphene nanoribbons. , 2007, Physical review letters.

[41]  Yanli Wang,et al.  Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials , 2009 .

[42]  H. Sevinçli,et al.  Spin confinement in the superlattices of graphene ribbons , 2008 .

[43]  Cheol-Hwan Park,et al.  Self-interaction in Green ’ s-function theory of the hydrogen atom , 2007 .

[44]  J. Bignon,et al.  Regioselective hydrostannation of diarylalkynes directed by a labile ortho bromine atom: an easy access to stereodefined triarylolefins, hybrids of combretastatin A-4 and isocombretastatin A-4. , 2010, European journal of medicinal chemistry.

[45]  Xinran Wang,et al.  Etching and narrowing of graphene from the edges. , 2010, Nature chemistry.

[46]  P. Liljeroth,et al.  Suppression of electron–vibron coupling in graphene nanoribbons contacted via a single atom , 2013, Nature Communications.

[47]  References , 1971 .

[48]  K. Wakabayashi,et al.  Tuning Charge and Spin Excitations in Zigzag Edge Nanographene Ribbons , 2012, Scientific Reports.

[49]  Chanyong Hwang,et al.  Room-temperature magnetic order on zigzag edges of narrow graphene nanoribbons , 2014, Nature.

[50]  Fujita,et al.  Edge state in graphene ribbons: Nanometer size effect and edge shape dependence. , 1996, Physical review. B, Condensed matter.

[51]  A. Fürstner,et al.  Flexible synthesis of phenanthrenes by a PtCl(2)-catalyzed cycloisomerization reaction. , 2002, The Journal of organic chemistry.

[52]  Klaus Richter,et al.  Spin currents in rough graphene nanoribbons: universal fluctuations and spin injection. , 2007, Physical review letters.

[53]  Peter Liljeroth,et al.  Amplifying the Pacific Climate System Response to a Small 11-Year Solar Cycle Forcing , 2009, Science.