Monitoring the On-Surface Synthesis of Graphene Nanoribbons by Mass Spectrometry

We present a mass spectrometric approach to characterize and monitor the intermediates of graphene nanoribbon (GNR) formation by chemical vapor deposition (CVD) on top of Au(111) surfaces. Information regarding the repeating units, lengths, and termini can be obtained directly from the surface sample by a modified matrix-assisted laser desorption/ionization (MALDI) method. The mass spectrometric results reveal ample oxidative side reactions under CVD conditions that can be drastically diminished by the introduction of protective H₂ gas at ambient pressure. Simultaneously, the addition of hydrogen extends the lengths of the oligophenylenes and thus the final GNRs. Moreover, the prematurely formed cyclodehydrogenation products during the oligomer growth can be assigned by the mass spectrometric technique. The obtained mechanistic insights provide valuable information for optimizing and upscaling the bottom-up fabrication of GNRs. Given the important role of GNRs as semiconductors, the mass spectrometric analysis provides a readily available tool to characterize and improve their structural perfection

Lateral Fusion of Chemical Vapor Deposited <i>N</i> = 5 Armchair Graphene Nanoribbons

Bottom-up synthesis of low-bandgap graphene nanoribbons with various widths is of great importance for their applications in electronic and optoelectronic devices. Here we demonstrate a synthesis of <i>N</i> = 5 armchair graphene nanoribbons (5-AGNRs) and their lateral fusion into wider AGNRs, by a chemical vapor deposition method. The efficient formation of 10- and 15-AGNRs is revealed by a combination of different spectroscopic methods, including Raman and UV–vis-near-infrared spectroscopy as well as by scanning tunneling microscopy. The degree of fusion and thus the optical and electronic properties of the resulting GNRs can be controlled by the annealing temperature, providing GNR films with optical absorptions up to ∼2250 nm

Chemical Vapor Deposition Synthesis and Terahertz Photoconductivity of Low-Band-Gap <i>N</i> = 9 Armchair Graphene Nanoribbons

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 <i>N</i> = 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 cm²·V^–1·s^–1