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.

Bottom-up synthesized graphene nanoribbons and graphene nanoribbon heterostructures have promising electronic properties for high-performance field-effect transistors and ultra-low power devices such as tunneling field-effect transistors. However, the short length and wide band gap of these graphene nanoribbons have prevented the fabrication of devices with the desired performance and switching behavior. Here, by fabricating short channel (L ch ~ 20 nm) devices with a thin, high-κ gate dielectric and a 9-atom wide (0.95 nm) armchair graphene nanoribbon as the channel material, we demonstrate field-effect transistors with high on-current (I on > 1 μA at V d = −1 V) and high I on /I off ~ 105 at room temperature. We find that the performance of these devices is limited by tunneling through the Schottky barrier at the contacts and we observe an increase in the transparency of the barrier by increasing the gate field near the contacts. Our results thus demonstrate successful fabrication of high-performance short-channel field-effect transistors with bottom-up synthesized armchair graphene nanoribbons.

On-surface synthesis is a powerful route toward the fabrication of specific graphene-like nanostructures confined in two dimensions. This strategy has been successfully applied to the growth of graphene nanoribbons of diverse width and edge morphology. Here, we investigate the mechanisms driving the growth of 9-atom wide armchair graphene nanoribbons by using scanning tunneling microscopy, fast X-ray photoelectron spectroscopy, and temperature-programmed desorption techniques. Particular attention is given to the role of halogen functionalization (Br or I) of the molecular precursors. We show that the use of iodine-containing monomers fosters the growth of longer graphene nanoribbons (average length of 45 nm) due to a larger separation of the polymerization and cyclodehydrogenation temperatures. Detailed insight into the growth process is obtained by analysis of kinetic curves extracted from the fast X-ray photoelectron spectroscopy data. Our study provides fundamental details of relevance to the production of future electronic devices and highlights the importance of not only the rational design of molecular precursors but also the most suitable reaction pathways to achieve the desired final structures.

Recent advances in bottom-up synthesis of atomically defined graphene nanoribbons (GNRs) with various microstructures and properties have demonstrated their promise in electronic and optoelectronic devices. Here we synthesized N = 9 armchair graphene nanoribbons (9-AGNRs) with a low optical band gap of ∼1.0 eV and extended absorption into the infrared range by an efficient chemical vapor deposition process. Time-resolved terahertz spectroscopy was employed to characterize the photoconductivity in 9-AGNRs and revealed their high intrinsic charge-carrier mobility of approximately 350 cm·V·s.

The electronic properties of graphene nanoribbons grown on metal substrates are significantly masked by the ones of the supporting metal surface. Here, we introduce a novel approach to access the frontier states of armchair graphene nanoribbons (AGNRs). The in situ intercalation of Si at the AGNR/Au(111) interface through surface alloying suppresses the strong contribution of the Au(111) surface state and allows for an unambiguous determination of the frontier electronic states of both wide and narrow band gap AGNRs. First-principles calculations provide insight into substrate induced screening effects, which result in a width-dependent band gap reduction for substrate-supported AGNRs. The strategy reported here provides a unique opportunity to elucidate the electronic properties of various kinds of graphene nanomaterials supported on metal substrates.

Recent progress in the on-surface synthesis of graphene nanoribbons (GNRs) has given access to atomically precise narrow GNRs with tunable electronic band gaps which makes them excellent candidates for room temperature switching devices such as field-effect transistors (FET). However, in spite of their exceptional properties, significant challenges remain for GNR processing and characterization. This contribution addresses some of the most important challenges, including GNR fabrication scalability, substrate transfer, long-term stability under ambient conditions, and ex situ characterization. We focus on 7- and 9-atom-wide armchair graphene nanoribbons (i.e., 7-AGNR and 9-AGNR) grown on 200 nm Au(111)/mica substrates using a high throughput system. Transfer of both 7- and 9-AGNRs from their Au growth substrate onto various target substrates for additional characterization is accomplished utilizing a polymer-free method that avoids residual contamination. This results in a homogeneous GNR film morphology with very few tears and wrinkles, as examined by atomic force microscopy. Raman spectroscopy indicates no significant degradation of GNR quality upon substrate transfer and reveals that GNRs have remarkable stability under ambient conditions over a 24 month period. The transferred GNRs are analyzed using multiwavelength Raman spectroscopy, which provides detailed insight into the wavelength dependence of the width-specific vibrational modes. Finally, we characterize the optical properties of 7- and 9-AGNRs via ultraviolet–visible (UV–vis) spectroscopy.

The on‐surface synthesis of graphene nanoribbons (GNRs) allows for the fabrication of atomically precise narrow GNRs. Despite their exceptional properties which can be tuned by ribbon width and edge structure, significant challenges remain for GNR processing and characterization. Herein, Raman spectroscopy is used to characterize different types of GNRs on their growth substrate and track their quality upon substrate transfer. A Raman‐optimized (RO) device substrate and an optimized mapping approach are presented that allow for the acquisition of high‐resolution Raman spectra, achieving enhancement factors as high as 120 with respect to signals measured on standard SiO2/Si substrates. This approach is well suited to routinely monitor the geometry‐dependent low‐frequency modes of GNRs. In particular, the radial breathing‐like mode (RBLM) and the shear‐like mode (SLM) for 5‐, 7‐, and 9‐atom‐wide armchair GNRs (AGNRs) are tracked and their frequencies are compared with first‐principles calculations.