Determining the Number of Graphene Nanoribbons in Dual-Gate Field-Effect Transistors.

Bottom-up synthesized graphene nanoribbons (GNRs) are increasingly attracting interest due to their atomically controlled structure and customizable physical properties. In recent years, a range of GNR-based field-effect transistors (FETs) has been fabricated, with several demonstrating quantum-dot (QD) behavior at cryogenic temperatures. However, understanding the relationship between the cryogenic charge-transport characteristics and the number of the GNRs in the device is challenging, as the length and location of the GNRs in the junction are not precisely controlled. Here, we present a methodology based on a dual-gate FET that allows us to identify different scenarios, such as single GNRs, double or multiple GNRs in parallel, and a single GNR interacting with charge traps. Our dual-gate FET architecture therefore offers a quantitative approach for comprehending charge transport in atomically precise GNRs.

Contacting individual graphene nanoribbons using carbon nanotube electrodes.

Graphene nanoribbons synthesized using bottom-up approaches can be structured with atomic precision, allowing their physical properties to be precisely controlled. For applications in quantum technology, the manipulation of single charges, spins or photons is required. However, achieving this at the level of single graphene nanoribbons is experimentally challenging due to the difficulty of contacting individual nanoribbons, particularly on-surface synthesized ones. Here we report the contacting and electrical characterization of on-surface synthesized graphene nanoribbons in a multigate device architecture using single-walled carbon nanotubes as the electrodes. The approach relies on the self-aligned nature of both nanotubes, which have diameters as small as 1 nm, and the nanoribbon growth on their respective growth substrates. The resulting nanoribbon-nanotube devices exhibit quantum transport phenomena-including Coulomb blockade, excited states of vibrational origin and Franck-Condon blockade-that indicate the contacting of individual graphene nanoribbons.

Edge Contacts to Atomically Precise Graphene Nanoribbons.

Bottom-up-synthesized graphene nanoribbons (GNRs) are an emerging class of designer quantum materials that possess superior properties, including atomically controlled uniformity and chemically tunable electronic properties. GNR-based devices are promising candidates for next-generation electronic, spintronic, and thermoelectric applications. However, due to their extremely small size, making electrical contact with GNRs remains a major challenge. Currently, the most commonly used methods are top metallic electrodes and bottom graphene electrodes, but for both, the contact resistance is expected to scale with overlap area. Here, we develop metallic edge contacts to contact nine-atom-wide armchair GNRs (9-AGNRs) after encapsulation in hexagonal boron-nitride (h-BN), resulting in ultrashort contact lengths. We find that charge transport in our devices occurs via two different mechanisms: at low temperatures (9 K), charges flow through single GNRs, resulting in quantum dot (QD) behavior with well-defined Coulomb diamonds (CDs), with addition energies in the range of 16 to 400 meV. For temperatures above 100 K, a combination of temperature-activated hopping and polaron-assisted tunneling takes over, with charges being able to flow through a network of 9-AGNRs across distances significantly exceeding the length of individual GNRs. At room temperature, our short-channel field-effect transistor devices exhibit on/off ratios as high as 3 × 105 with on-state current up to 50 nA at 0.2 V. Moreover, we find that the contact performance of our edge-contact devices is comparable to that of top/bottom contact geometries but with a significantly reduced footprint. Overall, our work demonstrates that 9-AGNRs can be contacted at their ends in ultra-short-channel FET devices while being encapsulated in h-BN.

Edge Disorder in Bottom-Up Zigzag Graphene Nanoribbons: Implications for Magnetism and Quantum Electronic Transport.

We unveil the nature of the structural disorder in bottom-up zigzag graphene nanoribbons along with its effect on the magnetism and electronic transport on the basis of scanning probe microscopies and first-principles calculations. We find that edge-missing m-xylene units emerging during the cyclodehydrogenation step of the on-surface synthesis are the most common point defects. These "bite" defects act as spin-1 paramagnetic centers, severely disrupt the conductance spectrum around the band extrema, and give rise to spin-polarized charge transport. We further show that the electronic conductance across graphene nanoribbons is more sensitive to "bite" defects forming at the zigzag edges than at the armchair ones. Our work establishes a comprehensive understanding of the low-energy electronic properties of disordered bottom-up graphene nanoribbons.

Controlled Quantum Dot Formation in Atomically Engineered Graphene Nanoribbon Field-Effect Transistors.

Graphene nanoribbons (GNRs) have attracted strong interest from researchers worldwide, as they constitute an emerging class of quantum-designed materials. The major challenges toward their exploitation in electronic applications include reliable contacting, complicated by their small size (<50 nm), and the preservation of their physical properties upon device integration. In this combined experimental and theoretical study, we report on the quantum dot behavior of atomically precise GNRs integrated in a device geometry. The devices consist of a film of aligned five-atom-wide GNRs (5-AGNRs) transferred onto graphene electrodes with a sub 5 nm nanogap. We demonstrate that these narrow-bandgap 5-AGNRs exhibit metal-like behavior at room temperature and single-electron transistor behavior for temperatures below 150 K. By performing spectroscopy of the molecular levels at 13 K, we obtain addition energies in the range of 200-300 meV. DFT calculations predict comparable addition energies and reveal the presence of two electronic states within the bandgap of infinite ribbons when the finite length of the 5-AGNR is accounted for. By demonstrating the preservation of the 5-AGNRs' molecular levels upon device integration, as demonstrated by transport spectroscopy, our study provides a critical step forward in the realization of more exotic GNR-based nanoelectronic devices.

Optical Imaging and Spectroscopy of Atomically Precise Armchair Graphene Nanoribbons.

We report the optical imaging and absorption spectroscopy on atomically precise armchair graphene nanoribbons (GNRs) on insulating fused silica substrates. This is achieved by controlling light polarization on macroscopically aligned GNRs which greatly enhances the optical contrast of the submonolayer GNRs on the insulating substrates. We measure the linear absorption spectra of 7-armchair and 9-armchair GNRs in this study, and the experimental data agree qualitatively with ab inito calculation results. The polarization spectroscopy technique enables an unambiguous optical identification of GNRs and provides a rapid tool to characterize the transferred film over a large area.

A Universal Length-Dependent Vibrational Mode in Graphene Nanoribbons.

Graphene nanoribbons (GNRs) have attracted considerable interest, as their atomically tunable structure makes them promising candidates for future electronic devices. However, obtaining detailed information about the length of GNRs has been challenging and typically relies on low-temperature scanning tunneling microscopy. Such methods are ill-suited for practical device application and characterization. In contrast, Raman spectroscopy is a sensitive method for the characterization of GNRs, in particular for investigating their width and structure. Here, we report on a length-dependent, Raman-active low-energy vibrational mode that is present in atomically precise, bottom-up-synthesized armchair graphene nanoribbons (AGNRs). Our Raman study demonstrates that this mode is present in all families of AGNRs and provides information on their length. Our spectroscopic findings are corroborated by scanning tunneling microscopy images and supported by first-principles calculations that allow us to attribute this mode to a longitudinal acoustic phonon. Finally, we show that this mode is a sensitive probe for the overall structural integrity of the ribbons and their interaction with technologically relevant substrates.

Bottom-Up Synthesis of Heteroatom-Doped Chiral Graphene Nanoribbons.

Bottom-up synthesis of graphene nanoribbons (GNRs) has significantly advanced during the past decade, providing various GNR structures with tunable properties. The synthesis of chiral GNRs, however, has been underexplored and only limited to (3,1)-GNRs. We report herein the surface-assisted synthesis of the first heteroatom-doped chiral (4,1)-GNRs from the rationally designed precursor 6,16-dibromo-9,10,19,20-tetraoxa-9a,19a-diboratetrabenzo[ a, f, j, o]perylene. The structure of the chiral GNRs has been verified by scanning tunneling microscopy, noncontact atomic force microscopy, and Raman spectroscopy in combination with theoretical modeling. Due to the presence of oxygen-boron-oxygen (OBO) segments on the edges, lateral self-assembly of the GNRs has been observed, realizing well-aligned GNR arrays with different modes of homochiral and heterochiral inter-ribbon assemblies.

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.

Heteroatom-Doped Perihexacene from a Double Helicene Precursor: On-Surface Synthesis and Properties.

We report on the surface-assisted synthesis and spectroscopic characterization of the hitherto longest periacene analogue with oxygen-boron-oxygen (OBO) segments along the zigzag edges, that is, a heteroatom-doped perihexacene 1. Surface-catalyzed cyclodehydrogenation successfully transformed the double helicene precursor 2, i.e., 12a,26a-dibora-12,13,26,27-tetraoxa-benzo[1,2,3-hi:4,5,6-h'i']dihexacene, into the planar perihexacene analogue 1, which was visualized by scanning tunneling microscopy and noncontact atomic force microscopy. X-ray photoelectron spectroscopy, Raman spectroscopy, together with theoretical modeling, on both precursor 2 and product 1, provided further insights into the cyclodehydrogenation process. Moreover, the nonplanar precursor 2 underwent a conformational change upon adsorption on surfaces, and one-dimensional self-assembled superstructures were observed for both 2 and 1 due to the presence of OBO units along the zigzag edges.