Real-time observation of epitaxial graphene domain reorientation.
ABSTRACT: Graphene films grown by vapour deposition tend to be polycrystalline due to the nucleation and growth of islands with different in-plane orientations. Here, using low-energy electron microscopy, we find that micron-sized graphene islands on Ir(111) rotate to a preferred orientation during thermal annealing. We observe three alignment mechanisms: the simultaneous growth of aligned domains and dissolution of rotated domains, that is, 'ripening'; domain boundary motion within islands; and continuous lattice rotation of entire domains. By measuring the relative growth velocity of domains during ripening, we estimate that the driving force for alignment is on the order of 0.1?meV per C atom and increases with rotation angle. A simple model of the orientation-dependent energy associated with the moiré corrugation of the graphene sheet due to local variations in the graphene-substrate interaction reproduces the results. This work suggests new strategies for improving the van der Waals epitaxy of 2D materials.
Project description:Graphene grown by high temperature molecular beam epitaxy on hexagonal boron nitride (hBN) forms continuous domains with dimensions of order 20??m, and exhibits moiré patterns with large periodicities, up to ~30?nm, indicating that the layers are highly strained. Topological defects in the moiré patterns are observed and attributed to the relaxation of graphene islands which nucleate at different sites and subsequently coalesce. In addition, cracks are formed leading to strain relaxation, highly anisotropic strain fields, and abrupt boundaries between regions with different moiré periods. These cracks can also be formed by modification of the layers with a local probe resulting in the contraction and physical displacement of graphene layers. The Raman spectra of regions with a large moiré period reveal split and shifted G and 2D peaks confirming the presence of strain. Our work demonstrates a new approach to the growth of epitaxial graphene and a means of generating and modifying strain in graphene.
Project description:The intrinsic atomic mechanisms responsible for electronic doping of epitaxial graphene Moirés on transition metal surfaces is still an open issue. To better understand this process we have carried out a first-principles full characterization of the most representative Moiré superstructures observed on the Gr/Pt(111) system and confronted the results with atomically resolved scanning tunneling microscopy experiments. We find that for all reported Moirés the system relaxes inducing a non-negligible atomic corrugation both, at the graphene and at the outermost platinum layer. Interestingly, a mirror "anti-Moiré" reconstruction appears at the substrate, giving rise to the appearance of pinning-points. We show that these points are responsible for the development of the superstructure, while charge from the Pt substrate is injected into the graphene, inducing a local n-doping, mostly localized at these specific pinning-point positions.
Project description:Microelectromechanical systems, which can be moved or rotated with nanometre precision, already find applications in such fields as radio-frequency electronics, micro-attenuators, sensors and many others. Especially interesting are those which allow fine control over the motion on the atomic scale because of self-alignment mechanisms and forces acting on the atomic level. Such machines can produce well-controlled movements as a reaction to small changes of the external parameters. Here we demonstrate that, for the system of graphene on hexagonal boron nitride, the interplay between the van der Waals and elastic energies results in graphene mechanically self-rotating towards the hexagonal boron nitride crystallographic directions. Such rotation is macroscopic (for graphene flakes of tens of micrometres the tangential movement can be on hundreds of nanometres) and can be used for reproducible manufacturing of aligned van der Waals heterostructures.
Project description:We present strong experimental evidence for the moiré origin of superlattices on graphite by imaging a live transition from one superlattice to another with concurrent and direct measurement of the orientation angle before and after rotation using scanning tunneling microscopy (STM). This has been possible due to a fortuitous observation of a superlattice on a nanometer-sized graphene flake wherein we have induced a further rotation of the flake utilizing the capillary forces at play at a solid-liquid interface using STM tip motion. We propose a more "realistic" tip-surface meniscus relevant to STM at solid-liquid interfaces and show that the capillary force is sufficient to account for the total expenditure of energy involved in the process.
Project description:We present simulations of quantum transport in graphene p-n junctions (pnJs) in which moiré superlattice potentials are incorporated to demonstrate the interplay between pnJs and moiré superlattice potentials. It is shown that the longitudinal and Hall resistivity maps can be strongly modulated by the pnJ profile, junction height, and moiré potentials. Device resistance measurements are subsequently performed on graphene/hexagonal- boron-nitride heterostructure samples with accurate alignment of crystallographic orientations to complement and support the simulation results.
Project description:The specific rotational alignment of two-dimensional lattices results in a moiré superlattice with a larger period than the original lattices and allows one to engineer the electronic band structure of such materials. So far, transport signatures of such superlattices have been reported for graphene/hBN and graphene/graphene systems. Here we report moiré superlattices in fully hBN encapsulated graphene with both the top and the bottom hBN aligned to the graphene. In the graphene, two different moiré superlattices form with the top and the bottom hBN, respectively. The overlay of the two superlattices can result in a third superlattice with a period larger than the maximum period (14 nm) in the graphene/hBN system, which we explain in a simple model. This new type of band structure engineering allows one to artificially create an even wider spectrum of electronic properties in two-dimensional materials.
Project description:The emerging field of twistronics, which harnesses the twist angle between two-dimensional materials, represents a promising route for the design of quantum materials, as the twist-angle-induced superlattices offer means to control topology and strong correlations. At the small twist limit, and particularly under strain, as atomic relaxation prevails, the emergent moiré superlattice encodes elusive insights into the local interlayer interaction. Here we introduce moiré metrology as a combined experiment-theory framework to probe the stacking energy landscape of bilayer structures at the 0.1?meV/atom scale, outperforming the gold-standard of quantum chemistry. Through studying the shapes of moiré domains with numerous nano-imaging techniques, and correlating with multi-scale modelling, we assess and refine first-principle models for the interlayer interaction. We document the prowess of moiré metrology for three representative twisted systems: bilayer graphene, double bilayer graphene and H-stacked MoSe<sub>2</sub>/WSe<sub>2</sub>. Moiré metrology establishes sought after experimental benchmarks for interlayer interaction, thus enabling accurate modelling of twisted multilayers.
Project description:Revealing the graphene growth mechanism at the atomic-scale is of great importance for achieving high quality graphene. However, the lack of direct experimental observation and density functional theory (DFT) verification hinders a comprehensive understanding of the structure of the carbon clusters and evolution of the graphene growth on surface. Here, we report an in-situ low-temperature scanning tunneling microscopy (LT-STM) study of the elementary process of chemical vapor deposition (CVD) graphene growth via thermal decomposition of methane on Cu(110), including the formation of monodispersed carbon clusters at the initial stage, the graphene nucleation and the ripening of graphene islands to form continuous graphene film. STM measurement, supported by DFT calculations, suggests that the carbon clusters on the surface are C2H5. It is found that graphene layers can be joined by different domains, with a relative misorientation of 30°. These graphene layers can be decoupled from Cu(110) through low temperature thermal cycling.
Project description:Bloch electrons lacking inversion symmetry exhibit orbital magnetic moments owing to the rotation around their center of mass; this moment induces a valley splitting in a magnetic field. For the graphene/h-BN moiré superlattice, inversion symmetry is broken by the h-BN. The superlattice potential generates a series of Dirac points (DPs) and van Hove singularities (vHSs) within an experimentally accessible low energy state, providing a platform to study orbital moments with respect to band structure. In this work, theoretical calculations and magnetothermoelectric measurements are combined to reveal the emergence of an orbital magnetic moment at vHSs in graphene/h-BN moiré superlattices. The thermoelectric signal for the vHS at the low energy side of the hole-side secondary DP exhibited significant magnetic field-induced valley splitting with an effective g-factor of approximately 130; splitting for other vHSs was negligible. This was attributed to the emergence of an orbital magnetic moment at the second vHS at the hole-side.
Project description:Moiré superlattices were generated in two-dimensional (2D) van der Waals heterostructures and have revealed intriguing electronic structures. The appearance of mini-Dirac cones within the conduction and valence bands of graphene is one of the most striking among the new quantum features. A Moiré superstructure emerges when at least two periodic sub-structures superimpose. 2D Moiré patterns have been particularly investigated in stacked hexagonal 2D atomic lattices like twisted graphene layers and graphene deposited on hexagonal boron-nitride. In this letter, we report both experimentally and theoretically evidence of superlattices physics in transport properties of one-dimensional (1D) Moiré crystals. Rolling-up few layers of graphene to form a multiwall carbon nanotube adds boundaries conditions that can be translated into interference fringes-like Moiré patterns along the circumference of the cylinder. Such a 1D Moiré crystal exhibits a complex 1D multiple bands structure with clear and robust interband quantum transitions due to the presence of mini-Dirac points and pseudo-gaps. Our devices consist in a very large diameter (>80 nm) multiwall carbon nanotubes of high quality, electrically connected by metallic electrodes acting as charge reservoirs. Conductance measurements reveal the presence of van Hove singularities assigned to 1D Moiré superlattice effect and illustrated by electronic structure calculations.