successfully applied to the growth of AGNRs 11-13 and related structures [14][15][16] . Here, we describe the successful bottom-up synthesis of ZGNRs, which are fabricated by the surface-assisted colligation and cyclodehydrogenation of specifically designed precursor monomers including carbon groups that yield atomically precise zigzag edges. Using scanning tunnelling spectroscopy we prove the existence of edge-localized states with large energy splittings. We expect that the availability of ZGNRs will finally allow the characterization of their predicted spin-related properties such as spin confinement 17 and filtering 18,19 , and ultimately add the spin degree of freedom to graphene-based circuitry.To explore the fundamental electronic and magnetic properties related to zigzag edges and to realize specific carbon nanostructures for the controlled manipulation of their spin states,ZGNRs with atomically precise edges are required. For GNRs with armchair edges, it was demonstrated that atomic precision can indeed be achieved by a bottom-up approach based on the surface-assisted polymerization and subsequent cyclodehydrogenation of specifically designed oligophenylene precursor monomers 11 . The on-surface synthesis has been applied by many groups to fabricate a number of different AGNR structures [11][12][13] , N-doped AGNRs 14,15 as well as AGNR heterostructures 15,16 . It is, however, not directly suited forZGNRs since polymerization of monomers via aryl-aryl coupling does not take place along the zigzag but along the armchair direction (Fig. 1a). In addition, dehydrogenative cyclization of phenyl subgroups is not sufficient to form pure zigzag edges, thus calling for a totally new chemical design. Thereby, additional carbon functions must be placed at the edges of the monomers to complete the tiling toolbox needed for the bottom-up fabrication of arbitrary GNR structures.Here, we report a bottom-up fabrication approach to ZGNRs. In our unique protocol, surfaceassisted polymerization and subsequent cyclization of suitably designed molecular precursors carrying the full structural information of the final ZGNR afford atomic precision with respect to ribbon width and edge morphology. The groundbreaking idea depends upon the choice of a unique U-shaped monomer as 1 shown in Fig. 1b. With two halogen functions for thermally induced aryl-aryl-coupling at the R 1 positions, it allows the polymerization toward a snake-like polymer. It is the beauty of this design that additional phenyl groups at the R 2 position fill the holes in the interior of the undulating polymer. The crucial precursor is monomer 1a which carries two additional methyl groups. In such a case, apart from the 3 polymerization and planarization, an oxidative ring closure including the methyl groups is expected which would then establish two new six-membered rings together with the zigzag edge structure. To our delight, this concept could indeed be synthetically realized under reaction monitoring and structure proof by scanning tunneling microscopy (S...

The bottom-up approach to synthesize graphene nanoribbons strives not only to introduce a band gap into the electronic structure of graphene but also to accurately tune its value by designing both the width and edge structure of the ribbons with atomic precision. We report the synthesis of an armchair graphene nanoribbon with a width of nine carbon atoms on Au(111) through surface-assisted aryl-aryl coupling and subsequent cyclodehydrogenation of a properly chosen molecular precursor. By combining high-resolution atomic force microscopy, scanning tunneling microscopy, and Raman spectroscopy, we demonstrate that the atomic structure of the fabricated ribbons is exactly as designed. Angle-resolved photoemission spectroscopy and Fourier-transformed scanning tunneling spectroscopy reveal an electronic band gap of 1.4 eV and effective masses of ≈0.1 m for both electrons and holes, constituting a substantial improvement over previous efforts toward the development of transistor applications. We use ab initio calculations to gain insight into the dependence of the Raman spectra on excitation wavelength as well as to rationalize the symmetry-dependent contribution of the ribbons' electronic states to the tunneling current. We propose a simple rule for the visibility of frontier electronic bands of armchair graphene nanoribbons in scanning tunneling spectroscopy.

Ab-initio calculations on graphene doped with boron nitride (BN) nanoribbons and patches show opening of a band gap in all cases. The smallest width of graphene in these hybrid layers controls the band gap that varies slowly around ∼0.75 eV when the width of graphene region is in the range of 2 to 5 zigzag chains. Most interestingly the band gap is direct in all the cases we have studied and nearly the same for different doping if the smallest graphene width is the same. These results show the possibility of ultrathin hybrid semiconductor graphene with band gap similar to silicon and an additional attractive feature that it is direct.

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