Anomalous Strength Characteristics of Tilt Grain Boundaries in Graphene

Using molecular dynamics simulations and first principles calculations, we have studied the structure and mechanical strength of tilt grain boundaries in graphene sheets that arise during CVD growth of graphene on metal substrates. Surprisingly, we find that for tilt boundaries in the vicinity of both the zig-zag and arm-chair orientations, large angle boundaries with a higher density of 5-7 defect pairs are stronger than the low-angle boundaries which are comprised of fewer defects per unit length. Interestingly, the trends in our results cannot be explained by a continuum Griffith-type fracture mechanics criterion, which predicts the opposite trend due to that fact that it does not account for the critical bonds that are responsible for the failure mechanism. We have identified the highly-strained bonds in the 7-member rings that lead to the failure of the sheets, and we have found that large angle boundaries are able to better accommodate the strained 7-rings. Our results provide guidelines for designing growth methods to obtain grain boundary structures that can have strengths close to that of pristine graphene

Parallel Stitching of Two-Dimensional Materials

Diverse parallel stitched two-dimensional heterostructures are synthesized, including metal-semiconductor (graphene-MoS2), semiconductor-semiconductor (WS2-MoS2), and insulator-semiconductor (hBN-MoS2), directly through selective sowing of aromatic molecules as the seeds in chemical vapor deposition (CVD) method. Our methodology enables the large-scale fabrication of lateral heterostructures with arbitrary patterns, and clean and precisely aligned interfaces, which offers tremendous potential for its application in integrated circuits.Comment: 30 pages, 4 figures, Accepted by Advanced Material

The effect of fluorination on the surface structure of truxenones

LAR, AJR and TSJ acknowledge support from the Engineering and Physical Sciences Research Council [Grant Number EP/H021388/1]. SH and CBN acknowledge support from the following funding bodies: EPSRC Project EP/G037515/1, EC FP7 Project SC2 (610115), EC FP7 Project ArtESun (604397), and EC FP7 POLYMED (612538). The raw data associated with this article can be accessed at the following DOI: 10.17632/mmp65j8jgs.

Semiconducting Monolayer Materials as a Tunable Platform for Excitonic Solar Cells

The recent advent of two-dimensional monolayer materials with tunable optoelectronic properties and high carrier mobility offers renewed opportunities for efficient, ultra-thin excitonic solar cells alternative to those based on conjugated polymer and small molecule donors. Using first-principles density functional theory and many-body calculations, we demonstrate that monolayers of hexagonal BN and graphene (CBN) combined with commonly used acceptors such as PCBM fullerene or semiconducting carbon nanotubes can provide excitonic solar cells with tunable absorber gap, donor-acceptor interface band alignment, and power conversion efficiency, as well as novel device architectures. For the case of CBN-PCBM devices, we predict the limit of power conversion efficiencies to be in the 10 - 20% range depending on the CBN monolayer structure. Our results demonstrate the possibility of using monolayer materials in tunable, efficient, polymer-free thin-film solar cells in which unexplored exciton and carrier transport regimes are at play.Comment: 7 pages, 5 figure

Oxidation resistance of graphene-coated Cu and Cu/Ni alloy

The ability to protect refined metals from reactive environments is vital to many industrial and academic applications. Current solutions, however, typically introduce several negative effects, including increased thickness and changes in the metal physical properties. In this paper, we demonstrate for the first time the ability of graphene films grown by chemical vapor deposition to protect the surface of the metallic growth substrates of Cu and Cu/Ni alloy from air oxidation. SEM, Raman spectroscopy, and XPS studies show that the metal surface is well protected from oxidation even after heating at 200 \degree C in air for up to 4 hours. Our work further shows that graphene provides effective resistance against hydrogen peroxide. This protection method offers significant advantages and can be used on any metal that catalyzes graphene growth

Transfer-free growth of graphene on SiO2 insulator substrate from sputtered carbon and nickel films

AbstractHere we demonstrate the growth of transfer-free graphene on SiO2 insulator substrates from sputtered carbon and metal layers with rapid thermal processing in the same evacuation. It was found that graphene always grows atop the stack and in close contact with the Ni. Raman spectra typical of high quality exfoliated monolayer graphene were obtained for samples under optimised conditions with monolayer surface coverage of up to 40% and overall graphene surface coverage of over 90%. Transfer-free graphene is produced on SiO2 substrates with the removal of Ni in acid when Ni thickness is below 100nm, which effectively eliminates the need to transfer graphene from metal to insulator substrates and paves the way to mass production of graphene directly on insulator substrates. The characteristics of Raman spectrum depend on the size of Ni grains, which in turn depend on the thickness of Ni, layer deposition sequence of the stack and RTP temperature. The mechanism of the transfer-free growth process was studied by AFM in combination with Raman. A model is proposed to depict the graphene growth process. Results also suggest a monolayer self-limiting growth for graphene on individual Ni grains

High quality monolayer graphene synthesized by resistive heating cold wall chemical vapour deposition

Emerging flexible and wearable technologies such as healthcare electronics and energy-harvest devices could be transformed by the unique properties of graphene. The vision for a graphene-driven industrial revolution is motivating intensive research on the synthesis of (1) high quality and (2) low cost graphene. Hot-wall chemical vapour deposition (CVD) is one of the most competitive growth methods, but its long processing times are incompatible with production lines. Here we demonstrate the growth of high quality monolayer graphene using a technique that is 100 times faster than standard hot-wall CVD, resulting in 99% reduction in production costs. A thorough complementary study of Raman spectroscopy, atomic force microscopy, scanning electron microscopy and electrical magneto-transport measurements shows that our cold wall CVD-grown graphene is of comparable quality to that of natural graphene. Finally, we demonstrate the first transparent and flexible graphene capacitive touch-sensor that could enable the development of artificial skin for robots.Comment: Bointon, T. H., Barnes, M. D., Russo, S. and Craciun, M. F. (2015), High Quality Monolayer Graphene Synthesized by Resistive Heating Cold Wall Chemical Vapor Deposition. Adv. Mater.. doi:10.1002/adma.20150160

Engineering the electronic bandgaps and band edge positions in carbon-substituted 2D boron nitride: a first-principles investigation

Modification of graphene to open a robust gap in its electronic spectrum is essential for its use in field effect transistors and photochemistry applications. Inspired by recent experimental success in the preparation of homogeneous alloys of graphene and boron nitride (BN), we consider here engineering the electronic structure and bandgap of C2xB1−xN1−x alloys via both compositional and configurational modification. We start from the BN end-member, which already has a large bandgap, and then show that (a) the bandgap can in principle be reduced to about 2 eV with moderate substitution of C (x < 0.25); and (b) the electronic structure of C2xB1−xN1−x can be further tuned not only with composition x, but also with the configuration adopted by C substituents in the BN matrix. Our analysis, based on accurate screened hybrid functional calculations, provides a clear understanding of the correlation found between the bandgap and the level of aggregation of C atoms: the bandgap decreases most when the C atoms are maximally isolated, and increases with aggregation of C atoms due to the formation of bonding and anti-bonding bands associated with hybridization of occupied and empty defect states. We determine the location of valence and conduction band edges relative to vacuum and discuss the implications on the potential use of 2D C2xB1−xN1−x alloys in photocatalytic applications. Finally, we assess the thermodynamic limitations on the formation of these alloys using a cluster expansion model derived from first-principles

In situ epitaxial engineering of graphene and h-BN lateral heterostructure with a tunable morphology comprising h-BN domains

Graphene and hexagonal boron nitride (h-BN), as typical two-dimensional (2D) materials, have long attracted substantial attention due to their unique properties and promise in a wide range of applications. Although they have a rather large difference in their intrinsic bandgaps, they share a very similar atomic lattice; thus, there is great potential in constructing heterostructures by lateral stitching. Herein, we present the in situ growth of graphene and h-BN lateral heterostructures with tunable morphologies that range from a regular hexagon to highly symmetrical star-like structure on the surface of liquid Cu. The chemical vapor deposition (CVD) method is used, where the growth of the h-BN is demonstrated to be highly templated by the graphene. Furthermore, large-area production of lateral G-h-BN heterostructures at the centimeter scale with uniform orientation is realized by precisely tuning the CVD conditions. We found that the growth of h-BN is determined by the initial graphene and symmetrical features are produced that demonstrate heteroepitaxy. Simulations based on the phase field and density functional theories are carried out to elucidate the growth processes of G-h-BN flakes with various morphologies, and they have a striking consistency with experimental observations. The growth of a lateral G-h-BN heterostructure and an understanding of the growth mechanism can accelerate the construction of various heterostructures based on 2D materials

Planar and van der Waals heterostructures for vertical tunnelling single electron transistors

Despite a rich choice of two-dimensional materials, which exists these days, heterostructures, both vertical (van der Waals) and in-plane, offer an unprecedented control over the properties and functionalities of the resulted structures. Thus, planar heterostructures allow p-n junctions between different two-dimensional semiconductors and graphene nanoribbons with well-defined edges; and vertical heterostructures resulted in the observation of superconductivity in purely carbon-based systems and realisation of vertical tunnelling transistors. Here we demonstrate simultaneous use of in-plane and van der Waals heterostructures to build vertical single electron tunnelling transistors. We grow graphene quantum dots inside the matrix of hexagonal boron nitride, which allows a dramatic reduction of the number of localised states along the perimeter of the quantum dots. The use of hexagonal boron nitride tunnel barriers as contacts to the graphene quantum dots make our transistors reproducible and not dependent on the localised states, opening even larger flexibility when designing future devices