Preparation of Octadecylamine-Graphene/MgCl2-Supported Ziegler-Natta Catalyst and Its Application in Ethylene Polymerization.

A facile coagglomeration method for preparing a long alkyl chain modified graphene oxide (MGO)/MgCl2-supported Ti-based Ziegler-Natta catalyst was reported. The effects of MGO on the catalyst morphology and activity for ethylene polymerization were examined. The resultant polyethylene (PE)/MGO nanocomposites exhibited a layered morphology, with the MGO fillers being well dispersed and exhibiting strong interfacial adhesion to the PE matrix. The thermal stability and mechanical properties of the PE were significantly enhanced with the introduction of a small amount of the MGO filler. Thus, this work provides a facile approach to the production of high-performance PE.

Direct momentum-resolved observation of one-dimensional confinement of externally doped electrons within a single subnanometer-scale wire.

Cutting-edge research in the band engineering of nanowires at the ultimate fine scale is related to the minimum scale of nanowire-based devices. The fundamental issue at the subnanometer scale is whether angle-resolved photoemission spectroscopy (ARPES) can be used to directly measure the momentum-resolved electronic structure of a single wire because of the difficulty associated with assembling single wire into an ordered array for such measurements. Here, we demonstrated that the one-dimensional (1D) confinement of electrons, which are transferred from external dopants, within a single subnanometer-scale wire (subnanowire) could be directly measured using ARPES. Convincing evidence of 1D electron confinement was obtained using two different gold subnanowires with characteristic single metallic bands that were alternately and spontaneously ordered on a stepped silicon template, Si(553). Noble metal atoms were adsorbed at room temperature onto the gold subnanowires while the overall structure of the wires was maintained. Only one type of gold subnanowire could be controlled using external noble metal dopants without transforming the metallic band of the other type of gold subnanowires. This result was confirmed by scanning tunnelling microscopy experiments and first-principles calculations. The selective control clearly showed that externally doped electrons could be confined within a single gold subnanowire. This experimental evidence was used to further investigate the effects of the disorder induced by external dopants on a single subnanowire using ARPES.

Epitaxial growth of a single-crystal hybridized boron nitride and graphene layer on a wide-band gap semiconductor.

Vertical and lateral heterogeneous structures of two-dimensional (2D) materials have paved the way for pioneering studies on the physics and applications of 2D materials. A hybridized hexagonal boron nitride (h-BN) and graphene lateral structure, a heterogeneous 2D structure, has been fabricated on single-crystal metals or metal foils by chemical vapor deposition (CVD). However, once fabricated on metals, the h-BN/graphene lateral structures require an additional transfer process for device applications, as reported for CVD graphene grown on metal foils. Here, we demonstrate that a single-crystal h-BN/graphene lateral structure can be epitaxially grown on a wide-gap semiconductor, SiC(0001). First, a single-crystal h-BN layer with the same orientation as bulk SiC was grown on a Si-terminated SiC substrate at 850 °C using borazine molecules. Second, when heated above 1150 °C in vacuum, the h-BN layer was partially removed and, subsequently, replaced with graphene domains. Interestingly, these graphene domains possess the same orientation as the h-BN layer, resulting in a single-crystal h-BN/graphene lateral structure on a whole sample area. For temperatures above 1600 °C, the single-crystal h-BN layer was completely replaced by the single-crystal graphene layer. The crystalline structure, electronic band structure, and atomic structure of the h-BN/graphene lateral structure were studied by using low energy electron diffraction, angle-resolved photoemission spectroscopy, and scanning tunneling microscopy, respectively. The h-BN/graphene lateral structure fabricated on a wide-gap semiconductor substrate can be directly applied to devices without a further transfer process, as reported for epitaxial graphene on a SiC substrate.

Seamless lamination of a concave-convex architecture with single-layer graphene.

Graphene has been used as an electrode and channel material in electronic devices because of its superior physical properties. Recently, electronic devices have changed from a planar to a complicated three-dimensional (3D) geometry to overcome the limitations of planar devices. The evolution of electronic devices requires that graphene be adaptable to a 3D substrate. Here, we demonstrate that chemical-vapor-deposited single-layer graphene can be transferred onto a silicon dioxide substrate with a 3D geometry, such as a concave-convex architecture. A variety of silicon dioxide concave-convex architectures were uniformly and seamlessly laminated with graphene using a thermal treatment. The planar graphene was stretched to cover the concave-convex architecture, and the resulting strain on the curved graphene was spatially resolved by confocal Raman spectroscopy; molecular dynamic simulations were also conducted and supported the observations. Changes in electrical resistivity caused by the spatially varying strain induced as the graphene-silicon dioxide laminate varies dimensionally from 2D to 3D were measured by using a four-point probe. The resistivity measurements suggest that the electrical resistivity can be systematically controlled by the 3D geometry of the graphene-silicon dioxide laminate. This 3D graphene-insulator laminate will broaden the range of graphene applications beyond planar structures to 3D materials.

Designed three-dimensional freestanding single-crystal carbon architectures.

Single-crystal carbon nanomaterials have led to great advances in nanotechnology. The first single-crystal carbon nanomaterial, fullerene, was fabricated in a zero-dimensional form. One-dimensional carbon nanotubes and two-dimensional graphene have since followed and continue to provide further impetus to this field. In this study, we fabricated designed three-dimensional (3D) single-crystal carbon architectures by using silicon carbide templates. For this method, a designed 3D SiC structure was transformed into a 3D freestanding single-crystal carbon structure that retained the original SiC structure by performing a simple single-step thermal process. The SiC structure inside the 3D carbon structure is self-etched, which results in a 3D freestanding carbon structure. The 3D carbon structure is a single crystal with the same hexagonal close-packed structure as graphene. The size of the carbon structures can be controlled from the nanoscale to the microscale, and arrays of these structures can be scaled up to the wafer scale. The 3D freestanding carbon structures were found to be mechanically stable even after repeated loading. The relationship between the reversible mechanical deformation of a carbon structure and its electrical conductance was also investigated. Our method of fabricating designed 3D freestanding single-crystal graphene architectures opens up prospects in the field of single-crystal carbon nanomaterials and paves the way for the development of 3D single-crystal carbon devices.