Graphene nanoribbons

Graphene nanoribbons (GNRs, also called nano-graphene ribbons or nano-graphite ribbons) are strips of graphene with width less than 50 nm. Graphene ribbons were introduced as a theoretical model by Mitsutaka Fujita and coauthors to examine the edge and nanoscale size effect in graphene. Large quantities of width-controlled GNRs can be produced via graphite nanotomy, where applying a sharp diamond knife on graphite produces graphite nanoblocks, which can then be exfoliated to produce GNRs. GNRs can also be produced by 'unzipping' or axially cutting nanotubes. In one such method multi-walled carbon nanotubes were unzipped in solution by action of potassium permanganate and sulfuric acid. In another method GNRs were produced by plasma etching of nanotubes partly embedded in a polymer film. More recently, graphene nanoribbons were grown onto silicon carbide (SiC) substrates using ion implantation followed by vacuum or laser annealing. The latter technique allows any pattern to be written on SiC substrates with 5 nm precision. GNRs were grown on the edges of three-dimensional structures etched into silicon carbide wafers. When the wafers are heated to approximately 1,000 °C (1,270 K; 1,830 °F), silicon is preferentially driven off along the edges, forming nanoribbons whose structure is determined by the pattern of the three-dimensional surface. The ribbons had perfectly smooth edges, annealed by the fabrication process. Electron mobility measurements surpassing one million correspond to a sheet resistance of one ohm per square— two orders of magnitude lower than in two-dimensional graphene. Nanoribbons narrower than 10 nm grown on a germanium wafer act like semiconductors, exhibiting a band gap. Inside a reaction chamber, using chemical vapor deposition, methane is used to deposit hydrocarbons on the wafer surface, where they react with each other to produce long, smooth-edged ribbons. The ribbons were used to create prototype transistors. At a very slow growth rate, the graphene crystals naturally grow into long nanoribbons on a specific germanium crystal facet. By controlling the growth rate and growth time, the researchers achieved control over the nanoribbon width. Recently, researchers from SIMIT(Shanghai Institute of Microsystem and Information Technology,Chinese Academy of Sciences) reported on a strategy to grow graphene nanoribbons with controlled widths and smooth edges directly onto dielectric hexagonal boron nitride (h-BN) substrates. The team use nickel nanoparticles to etch monolayer-deep, nanometre-wide trenches into h-BN, and subsequently fill them with graphene using chemical vapour deposition. Modifying the etching parameters allows the width of the trench to be tuned to less than 10 nm, and the resulting sub-10-nm ribbons display bandgaps of almost 0.5 eV. Integrating these nanoribbons into field effect transistor devices reveals on–off ratios of greater than 104 at room temperature, as well as high carrier mobilities of ~750 cm2 V−1 s−1. A bottom-up approach was investigated. In 2017 dry contact transfer was used to press a fiberglass applicator coated with a powder of atomically precise graphene nanoribbons on a hydrogen-passivated Si(100) surface under vacuum. 80 of 115 GNRs visibly obscured the substrate lattice with an average apparent height of 0.30 nm. The GNRs do not align to the Si lattice, indicating a weak coupling. The average bandgap over 21 GNRs was 2.85 eV with a standard deviation of 0.13 eV. The method unintentionally overlapped some nanoribbons, allowing the study of multilayer GNRs. Such overlaps could be formed deliberately by manipulation with a scanning tunneling microscope. Hydrogen depassivation left no band-gap. Covalent bonds between the Si surface and the GNR leads to metallic behavior. The Si surface atoms move outward, and the GNR changes from flat to distorted, with some C atoms moving in toward the Si surface. The electronic states of GNRs largely depend on the edge structures (armchair or zigzag). In zigzag edges each successive edge segment is at the opposite angle to the previous. In armchair edges, each pair of segments is a 120/-120 degree rotation of the prior pair. Zigzag edges provide the edge localized state with non-bonding molecular orbitals near the Fermi energy. They are expected to have large changes in optical and electronic properties from quantization.