Masaharu Tsuji

Epitaxial Chemical Vapor Deposition Growth of Single-Layer Graphene over Cobalt Film Crystallized on Sapphire

Epitaxial chemical vapor deposition (CVD) growth of uniform single-layer graphene is demonstrated over Co film crystallized on c-plane sapphire. The single crystalline Co film is realized on the sapphire substrate by optimized high-temperature sputtering and successive H(2) annealing. This crystalline Co film enables the formation of uniform single-layer graphene, while a polycrystalline Co film deposited on a SiO(2)/Si substrate gives a number of graphene flakes with various thicknesses. Moreover, an epitaxial relationship between the as-grown graphene and Co lattice is observed when synthesis occurs at 1000 °C; the direction of the hexagonal lattice of the single-layer graphene completely matches with that of the underneath Co/sapphire substrate. The orientation of graphene depends on the growth temperature and, at 900 °C, the graphene lattice is rotated at 22 ± 8° with respect to the Co lattice direction. Our work expands a possibility of synthesizing single-layer graphene over various metal catalysts. Moreover, our CVD growth gives a graphene film with predefined orientation, and thus can be applied to graphene engineering, such as cutting along a specific crystallographic direction, for future electronics applications.

Crystal plane dependent growth of aligned single-walled carbon nanotubes on sapphire.

On single-crystal substrates, such as sapphire (alpha-Al 2O 3) and quartz (SiO 2), single-walled carbon nanotubes (SWNTs) align along specific crystallographic axes of the crystal, indicating that the SWNT growth is influenced by the crystal surface. Here, we show that not only the orientation, but also the diameter and chirality of SWNTs are affected by the crystal plane of the sapphire substrate. The aligned SWNTs grown on the A- and R-planes of sapphire have narrower diameter distributions than randomly oriented tubes produced on the C-plane sapphire and amorphous SiO 2. Photoluminescence measurements reveal a striking difference between the aligned SWNTs: near-zigzag tubes are observed on the A-plane and near-armchair tubes on the R-plane. This study shows the route for the diameter and chirality control of SWNTs by surface atomic arrangements of a single-crystal substrate.

Preparation of metal colloids by a laser ablation technique in solution: influence of laser wavelength on the ablation efficiency (II)

Abstract Laser ablations of silver and copper targets in water were performed to prepare nanosize metal colloids. The influence of the laser wavelength, focusing conditions, and laser fluence on the ablation efficiency was studied. The relation between the ablation efficiency and wavelength varied with laser fluence. The ablation efficiency at shorter wavelengths was higher at low fluence, while the ablation efficiency at longer wavelengths was higher at high fluence. These findings were discussed in terms of the “intra-pulse” and “inter-pulse” self-absorptions of the incident laser light by colloidal particles.

Poly(N-vinyl-2-pyrrolidone) (PVP)-capped dendritic gold nanoparticles by a one-step hydrothermal route and their high SERS effect

Dendritic gold (Au) nanoparticles have been successfully synthesized by the one-step hydrothermal reduction of HAuCl4.4H2O using ammonium formate (AF) as a reducing agent in the presence of PVP. Effects of different reactant concentrations on the morphologies of obtained products have been systematically investigated. On the basis of the morphologies of the products observed by transmission electron microscopy (TEM) and scanning electron microscopy (SEM), it has been found that an excessive number of AF molecules are the origin of the dendritic Au particles besides PVP as a stabilizer. AF molecules serve not only as a reductant but probably also as a capping reagent. The study implies that the use of two or more capping reagents with different adsorption abilities will be beneficial to the formation of hyperbranched Au nanoparticles. The new finding will have the potential to be extended to the construction of other highly branched noble metal nanoparticles only by one-step synthesis. In addition, as an example, application of the dendritic particles as an active material in surface-enhanced Raman scattering has been investigated by employing 4-aminothiophenol molecules as a probe.

Catalytic Growth of Graphene: Toward Large-Area Single-Crystalline Graphene.

For electronic applications, synthesis of large-area, single-layer graphene with high crystallinity is required. One of the most promising and widely employed methods is chemical vapor deposition (CVD) using Cu foil/film as the catalyst. However, the CVD graphene is generally polycrystalline and contains a significant amount of domain boundaries that limit intrinsic physical properties of graphene. In this Perspective, we discuss the growth mechanism of graphene on a Cu catalyst and review recent development in the observation and control of the domain structure of graphene. We emphasize the importance of the growth condition and crystallinity of the Cu catalyst for the realization of large-area, single-crystalline graphene.

Formation of hydrogen-capped polyynes by laser ablation of graphite particles suspended in solution

Laser ablation of graphite particles suspended in benzene, toluene, or hexane solution has been studied using a Nd:YAG laser (355, 532, and 1064 nm). Product analyses using HPLC coupled with UV and visible absorption spectroscopy and GC/MS showed that linear hydrogen-capped polyynes (CnH2: n ¼ 10, 12, 14, and 16) were formed in benzene and toluene, while those of n ¼ 8, 10, 12, and 14 were produced in hexane. The formation rates of polyynes increased with increasing particle concentration from 0.5 to 4 mg/ml, then decreased above that until 10 mg/ml. The formation rates of polyynes decreased with increasing wavelength of the Nd:YAG laser, 355 nm > 532 nm > 1064 nm. 2002 Elsevier Science B.V. All rights reserved.

Epitaxial growth of Au@Pd core–shell nanocrystals prepared using a PVP-assisted polyol reduction method

Au@Cu core-shell nanocrystals were prepared using a two-step polyol reduction method. First, mixtures of ochedral, triangular and hexagonal platelike, decahedral, and icosahedral Au core seeds were prepared by reducing HAuCl 4 ·4H 2 O in ethylene glycol (EG) using microwave (MW) heating in the presence of polyvinylpyrrolidone (PVP) as a polymer surfactant. Then Cu shells were overgrown on Au core seeds by reducing Cu 2 (OAc) 4 in EG with PVP using oil-bath heating. Resultant crystal structures were characterized using TEM, high-resolution (HR)-TEM, TEM-EDS, and selected area electron diffraction (SAED) measurements. A large mismatch exists in lattice constants between Au (0.4079 nm) and Cu (0.3615 nm). No monometallic Cu nanocrystals having well-defined facets were prepared by reducing Cu 2 (OAc) 4 in EG. Therefore, the epitaxial growth ofCu shells over Au cores was expected to be difficult. Nevertheless, flat {111} facets of Cu shells were grown epitaxially on {111} facets of Au cores. The SAED patterns and Moire patterns showed Cu layers parallel to Au layers. The Cu shell growth on sharp Au-core corners was slower than that on flat {111} facets and single twin facets. This report is the first describing epitaxial growth of core—shell nanocrystals despite a large lattice mismatch (11.4%). The Au@Cu nanoparticles were more antioxidative than pure Cu particles prepared under identical conditions.

Enhanced Chemical Reactivity of Graphene Induced by Mechanical Strain

Control over chemical reactivity is essential in the field of nanotechnology. Graphene is a two-dimensional atomic sheet of sp(2) hybridized carbon with exceptional properties that can be altered by chemical functionalization. Here, we transferred single-layer graphene onto a flexible substrate and investigated the functionalization using different aryl diazonium molecules while applying mechanical strain. We found that mechanical strain can alter the structure of graphene, and dramatically increase the reaction rate, by a factor of up to 10, as well as increase the final degree of functionalization. Furthermore, we demonstrate that mechanical strain enables functionalization of graphene for both p- and n-type dopants, where unstrained graphene showed negligible reactivity. Theoretical calculations were also performed to support the experimental findings. Our findings offer a simple approach to control the chemical reactivity of graphene through the application of mechanical strain, allowing for a tuning of the properties of graphene.

Rapid Transformation from Spherical Nanoparticles, Nanorods, Cubes, or Bipyramids to Triangular Prisms of Silver with PVP, Citrate, and H2O2

Rapid sphere-to-prism (STP) transformation of silver was studied in aqueous AgNO(3)/NaBH(4)/polyvinylpyrrolidone (PVP)/trisodium citrate (Na(3)CA)/H(2)O(2) solutions by monitoring time-dependent surface plasmon resonance (SPR) bands in the UV-vis region, by examining transmission electron microscopic (TEM) images, and by analyzing emitted gases during fast reaction. Roles of PVP, Na(3)CA, and H(2)O(2) were studied without addition of a reagent, with different timing of each reagents addition, and with addition of H(2)O(2) to mixtures of spheres and prisms. Results show that prisms can be prepared without addition of PVP, although it is useful to synthesize smaller monodispersed prisms. A new important role of citrate found in this study, besides a known role as a protecting agent of {111} facets of plates, is an assistive agent for shape-selective oxidative etching of Ag nanoparticles by H(2)O(2). The covering of Ag nanoparticles with carboxylate groups is necessary to initiate rapid STP transformation by premixing citrate before H(2)O(2) addition. Based on our data, rapid prism formation starts from the consumption of spherical Ag particles because of shape-selective oxidative etching by H(2)O(2). Oxidative etching of spherical particles by H(2)O(2) is faster than that of prisms. Therefore, spherical particles are selectively etched and dissolved, leaving only seeds of prisms to grow into triangular prisms. When pentagonal Ag nanorods and a mixture of cubes and bipyramids were used as sources of prisms, rod-to-prism (RTP), cube-to-prism (CTP), and bipyramid-to-prism (BTP) transformations were observed in Ag nanocrystals/NaBH(4)/PVP/Na(3)CA/H(2)O(2) solutions. Shape-selective oxidative etching of rods was confirmed using flag-type Ag nanostructures consisting of a triangular plate and a side rod. These data provide useful information for the size-controlled synthesis of triangular Ag prisms, from various Ag nanostructures and using a chemical reduction method, having surface plasmon resonance (SPR) bands at a desired wavelength.

Strain engineering the properties of graphene and other two-dimensional crystals

Graphene has been widely studied for its many extraordinary properties, and other two-dimensional layered materials are now gaining increased interest. These excellent properties make thin layer materials very attractive for integration into a wide variety of technologies, particularly in flexible optoelectronic devices. Therefore, gaining control over these properties will allow for a more focused design and optimisation of these possible technologies. Through the application of mechanical strain it is possible to alter the electronic structures of two-dimensional crystals, such as graphene and transition metal dichalcogenides (e.g. MoS2), and these changes in electronic structure can alter their behaviour. In this perspective we discuss recent advances in the strain engineering of thin layer materials, with a focus on using Raman spectroscopy and electrical transport to investigate the effect of strain as well as the effect of strain on the chemical functionalisation of graphene.