Graphene shows promise as a future material for nanoelectronics owing to its compatibility with industry-standard lithographic processing, electron mobilities up to 150 times greater than Si and a ...thermal conductivity twice that of diamond. The electronic structure of graphene nanoribbons (GNRs) and quantum dots (GQDs) has been predicted to depend sensitively on the crystallographic orientation of their edges; however, the influence of edge structure has not been verified experimentally. Here, we use tunnelling spectroscopy to show that the electronic structure of GNRs and GQDs with 2-20 nm lateral dimensions varies on the basis of the graphene edge lattice symmetry. Predominantly zigzag-edge GQDs with 7-8 nm average dimensions are metallic owing to the presence of zigzag edge states. GNRs with a higher fraction of zigzag edges exhibit a smaller energy gap than a predominantly armchair-edge ribbon of similar width, and the magnitudes of the measured GNR energy gaps agree with recent theoretical calculations.
Chemical vapor deposition of graphene on Cu often employs polycrystalline Cu substrates with diverse facets, grain boundaries (GBs), annealing twins, and rough sites. Using scanning electron ...microscopy (SEM), electron-backscatter diffraction (EBSD), and Raman spectroscopy on graphene and Cu, we find that Cu substrate crystallography affects graphene growth more than facet roughness. We determine that (111) containing facets produce pristine monolayer graphene with higher growth rate than (100) containing facets, especially Cu(100). The number of graphene defects and nucleation sites appears Cu facet invariant at growth temperatures above 900 °C. Engineering Cu to have (111) surfaces will cause monolayer, uniform graphene growth.
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Narrow atomically precise graphene nanoribbons hold great promise for electronic and optoelectronic applications, but the previously demonstrated nanoribbon-based devices typically suffer from low ...currents and mobilities. In this study, we explored the idea of lateral extension of graphene nanoribbons for improving their electrical conductivity. We started with a conventional chevron graphene nanoribbon, and designed its laterally extended variant. We synthesized these new graphene nanoribbons in solution and found that the lateral extension results in decrease of their electronic bandgap and improvement in the electrical conductivity of nanoribbon-based thin films. These films were employed in gas sensors and an electronic nose system, which showed improved responsivities to low molecular weight alcohols compared to similar sensors based on benchmark graphitic materials, such as graphene and reduced graphene oxide, and a reliable analyte recognition. This study shows the methodology for designing new atomically precise graphene nanoribbons with improved properties, their bottom-up synthesis, characterization, processing and implementation in electronic devices.Atomically precise graphene nanoribbons are a promising platform for tailored electron transport, yet they suffer from low conductivity. Here, the authors devise a strategy to laterally extend conventional chevron nanoribbons, thus achieving increased electrical conductivity and improved chemical sensing capabilities.
Spatially nonuniform strain is important for engineering the pseudomagnetic field and band structure of graphene. Despite the wide interest in strain engineering, there is still a lack of control on ...device-compatible strain patterns due to the limited understanding of the structure–strain relationship. Here, we study the effect of substrate corrugation and curvature on the strain profiles of graphene via combined experimental and theoretical studies of a model system: graphene on closely packed SiO2 nanospheres with different diameters (20–200 nm). Experimentally, via quantitative Raman analysis, we observe partial adhesion and wrinkle features and find that smaller nanospheres induce larger tensile strain in graphene; theoretically, molecular dynamics simulations confirm the same microscopic structure and size dependence of strain and reveal that a larger strain is caused by a stronger, inhomogeneous interaction force between smaller nanospheres and graphene. This molecular-level understanding of the strain mechanism is important for strain engineering of graphene and other two-dimensional materials.
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There has been tremendous progress in designing and synthesizing graphene nanoribbons (GNRs). The ability to control the width, edge structure, and dopant level with atomic precision has created a ...large class of accessible electronic landscapes for use in logic applications. One of the major limitations preventing the realization of GNR devices is the difficulty of transferring GNRs onto nonmetallic substrates. In this work, we developed a new approach for clean deposition of solution-synthesized atomically precise chevron GNRs onto H:Si(100) under ultrahigh vacuum. A clean transfer allowed ultrahigh-vacuum scanning tunneling microscopy (STM) to provide high-resolution imaging and spectroscopy and reveal details of the electronic structure of chevron nanoribbons that have not been previously reported. We also demonstrate STM nanomanipulation of GNRs, characterization of multilayer GNR cross-junctions, and STM nanolithography for local depassivation of H:Si(100), which allowed us to probe GNR–Si interactions and revealed a semiconducting-to-metallic transition. The results of STM measurements were shown to be in good agreement with first-principles computational modeling.
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We use scanning tunneling microscopy and spectroscopy to examine the electronic nature of grain boundaries (GBs) in polycrystalline graphene grown by chemical vapor deposition (CVD) on Cu foil and ...transferred to SiO2 substrates. We find no preferential orientation angle between grains, and the GBs are continuous across graphene wrinkles and SiO2 topography. Scanning tunneling spectroscopy shows enhanced empty states tunneling conductance for most of the GBs and a shift toward more n-type behavior compared to the bulk of the graphene. We also observe standing wave patterns adjacent to GBs propagating in a zigzag direction with a decay length of ∼1 nm. Fourier analysis of these patterns indicates that backscattering and intervalley scattering are the dominant mechanisms responsible for the mobility reduction in the presence of GBs in CVD-grown graphene.
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We study interfacial water trapped between a sheet of graphene and a muscovite (mica) surface using Raman spectroscopy and ultrahigh vacuum scanning tunneling microscopy (UHV-STM) at room ...temperature. We are able to image the graphene–water interface with atomic resolution, revealing a layered network of water trapped underneath the graphene. We identify water layer numbers with a carbon nanotube height reference. Under normal scanning conditions, the water structures remain stable. However, at greater electron energies, we are able to locally manipulate the water using the STM tip.
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We analyze the optical, chemical, and electrical properties of chemical vapor deposition (CVD) grown hexagonal boron nitride (h-BN) using the precursor ammonia-borane (H3N–BH3) as a function of Ar/H2 ...background pressure (P TOT). Films grown at P TOT ≤ 2.0 Torr are uniform in thickness, highly crystalline, and consist solely of h-BN. At larger P TOT, with constant precursor flow, the growth rate increases, but the resulting h-BN is more amorphous, disordered, and sp3-bonded. We attribute these changes in h-BN grown at high pressure to incomplete thermolysis of the H3N–BH3 precursor from a passivated Cu catalyst. A similar increase in h-BN growth rate and amorphization is observed even at low P TOT if the H3N–BH3 partial pressure is initially greater than the background pressure P TOT at the beginning of growth. h-BN growth using the H3N–BH3 precursor reproducibly can give large-area, crystalline h-BN thin films, provided that the total pressure is under 2.0 Torr and the precursor flux is well-controlled.
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We examine the transfer of graphene grown by chemical vapor deposition (CVD) with polymer scaffolds of poly(methyl methacrylate) (PMMA), poly(lactic acid) (PLA), poly(phthalaldehyde) (PPA), and ...poly(bisphenol A carbonate) (PC). We find that optimally reactive PC scaffolds provide the cleanest graphene transfers without any annealing, after extensive comparison with optical microscopy, x-ray photoelectron spectroscopy, atomic force microscopy, and scanning tunneling microscopy. Comparatively, films transferred with PLA, PPA, PMMA PC, and PMMA have a two-fold higher roughness and a five-fold higher chemical doping. Using PC scaffolds, we demonstrate the clean transfer of CVD multilayer graphene, fluorinated graphene, and hexagonal boron nitride. Our annealing free, PC transfers enable the use of atomically-clean nanomaterials in biomolecule encapsulation and flexible electronic applications.