Ryota Shimizu

Ca intercalated bilayer graphene as a thinnest limit of superconducting C6Ca

Success in isolating a 2D graphene sheet from bulky graphite has triggered intensive studies of its physical properties as well as its application in devices. Graphite intercalation compounds (GICs) have provided a platform of exotic quantum phenomena such as superconductivity, but it is unclear whether such intercalation is feasible in the thinnest 2D limit (i.e., bilayer graphene). Here we report a unique experimental realization of 2D GIC, by fabricating calcium-intercalated bilayer graphene C6CaC6 on silicon carbide. We have investigated the structure and electronic states by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. We observed a free-electron–like interlayer band at the Brillouin-zone center, which is thought to be responsible for the superconductivity in 3D GICs, in addition to a large π* Fermi surface at the zone boundary. The present success in fabricating Ca-intercalated bilayer graphene would open a promising route to search for other 2D superconductors as well as to explore its application in devices.

Systematic analyses of vibration noise of a vibration isolation system for high-resolution scanning tunneling microscopes

We designed and constructed an effective vibration isolation system for stable scanning tunneling microscopy measurements using a separate foundation and two vibration isolation stages (i.e., a combination of passive and active vibration isolation dampers). Systematic analyses of vibration data along the horizontal and vertical directions are present, including the vibration transfer functions of each stage and the overall vibration isolation system. To demonstrate the performance of the system, tunneling current noise measurements are conducted with and without the vibration isolation. Combining passive and active vibration isolation dampers successfully removes most of the vibration noise in the tunneling current up to 100 Hz. These comprehensive vibration noise data, along with details of the entire system, can be used to establish a clear guideline for building an effective vibration isolation system for various scanning probe microscopes and electron microscopes.

Self-Assembly Strategy for Fabricating Connected Graphene Nanoribbons

We use self-assembly to fabricate and to connect precise graphene nanoribbons end to end. Combining scanning tunneling microscopy, Raman spectroscopy, and density functional theory, we characterize the chemical and electronic aspects of the interconnections between ribbons. We demonstrate how the substrate effects of our self-assembly can be exploited to fabricate graphene structures connected to desired electrodes.

Negligible “Negative Space-Charge Layer Effects” at Oxide-Electrolyte/Electrode Interfaces of Thin-Film Batteries

In this paper, we report the surprisingly low electrolyte/electrode interface resistance of 8.6 Ω cm(2) observed in thin-film batteries. This value is an order of magnitude smaller than that presented in previous reports on all-solid-state lithium batteries. The value is also smaller than that found in a liquid electrolyte-based batteries. The low interface resistance indicates that the negative space-charge layer effects at the Li3PO(4-x)N(x)/LiCoO2 interface are negligible and demonstrates that it is possible to fabricate all-solid state batteries with faster charging/discharging properties.

Unconventional Charge-Density-Wave Transition in Monolayer 1T-TiSe2.

Reducing the dimension in materials sometimes leads to unexpected discovery of exotic and/or pronounced physical properties such as quantum Hall effect in graphene and high-temperature superconductivity in iron-chalcogenide atomically thin films. Transition-metal dichalcogenides (TMDs) provide a fertile ground for studying the interplay between dimensionality and electronic properties, since they exhibit a variety of electronic phases like semiconducting, superconducting, and charge-density-wave (CDW) states. Among TMDs, bulk 1T-TiSe2 has been a target of intensive studies due to its unusual CDW properties with the periodic lattice distortions characterized by the three-dimensional (3D) commensurate wave vector. Clarifying the ground states of its two-dimensional (2D) counterpart is of great importance not only to pin down the origin of CDW, but also to find unconventional physical properties characteristic of atomic-layer materials. Here, we show the first experimental evidence for the realization of 2D CDW phase without Fermi-surface nesting in monolayer 1T-TiSe2. Our angle-resolved photoemission spectroscopy (ARPES) signifies an electron pocket at the Brillouin-zone corner above the CDW-transition temperature (TCDW ∼ 200 K), while, below TCDW, an additional electron pocket and replica bands appear at the Brillouin-zone center and corner, respectively, due to the back-folding of bands by the 2 × 2 superstructure potential. Similarity in the spectral signatures to bulk 1T-TiSe2 implies a common driving force of CDW, i.e., exciton condensation, whereas the larger energy gap below TCDW in monolayer 1T-TiSe2 suggests enhancement of electron-hole coupling upon reducing dimensionality. The present result lays the foundation for the electronic-structure engineering based with atomic-layer TMDs.

Growth processes of lithium titanate thin films deposited by using pulsed laser deposition

We have investigated the pulsed laser deposition(PLD)growth processes of spinel lithiumtitanates based on the preparation of Li4Ti5O12 and LiTi2O4 from a Li4Ti5O12 target. The Li/Ti atomic ratio of the species arriving at substrate during the deposition was only ∼0.5. The LiTi2O4epitaxialthin films fabricated on MgAl2O4 (111) substrate exhibited high conductivity at room temperature (∼3.0 × 103 Ω−1 cm−1) and a superconducting transition temperature of ∼12 K. These values are the highest reported for epitaxialthin films. Our results demonstrate the importance of the target composition, providing further insights into the Li-containing metal oxide deposition processes using PLD.

Atomic-Scale Visualization of Initial Growth of Homoepitaxial SrTiO3 Thin Film on an Atomically Ordered Substrate

The initial homoepitaxial growth of SrTiO(3) on a (√13 × √13)-R33.7° SrTiO(3)(001) substrate surface, which can be prepared under oxide growth conditions, is atomically resolved by scanning tunneling microscopy. The identical (√13 × √13) atomic structure is clearly visualized on the deposited SrTiO(3) film surface as well as on the substrate. This result indicates the transfer of the topmost Ti-rich (√13 × √13) structure to the film surface and atomic-scale coherent epitaxy at the film/substrate interface. Such atomically ordered SrTiO(3) substrates can be applied to the fabrication of atom-by-atom controlled oxide epitaxial films and heterostructures.

Thickness-dependent local surface electronic structures of homoepitaxial SrTiO3 thin films

We have investigated the atomically-resolved substrate and homoepitaxial thin film surfaces of SrTiO3(001) using low-temperature scanning tunneling microscopy/scanning tunneling spectroscopy (STS) combined with pulsed laser deposition. It was found that a typical annealing treatment for preparation of SrTiO3 substrates, unexpectedly, resulted in a disordered surface on an atomic scale. In contrast, homoepitaxial SrTiO3 thin films grown on this disordered substrate exhibited a (2×2) surface reconstruction. The STS measurements revealed a number of surface defects in a 10 unit cell thick SrTiO3 film but much fewer in a 50 unit cell thick film, indicating nonuniform stoichiometry along the growth direction. These results suggest the possibility of using homoepitaxial SrTiO3 film surfaces as idealized substrates, opening a way to extract novel functionalities in complex oxides heterostructures.

Effect of oxygen deficiency on SrTiO3(001) surface reconstructions

The contribution of oxygen deficiencies to SrTiO3(001) surface reconstructions is studied using low-energy electron diffraction and scanning tunneling microscopy. We have prepared a SrTiO3 sample with spatially graded oxygen deficiencies, in which R33.7°-(13×13), (2×1), and R26.6°-(5×5) surface reconstructions are observed while increasing the amount of oxygen deficiencies. This indicates that oxygen nonstoichiometry has an influence on the formation of various surface reconstructions as one of the important factors. This concept is also applicable to other transition metal oxides to prepare atomically ordered surfaces in a reproducible manner.

Atomically Resolved Surface Structure of SrTiO3(001) Thin Films Grown in Step-Flow Mode by Pulsed Laser Deposition

The surface structure of SrTiO3(001) thin films homoepitaxially grown in step-flow mode by pulsed laser deposition was characterized using scanning tunneling microscopy. One-dimensional (1D) TiOx-based nanostructures were formed on the surface, and their density increased with increasing film thickness. Most of the 1D nanostructures disappeared after post-deposition annealing, and the resulting surface exhibited a domain structure with (2×1) and (1×2) reconstructions and fewer oxygen vacancies. These results imply that the step-flow growth is likely to produce a TiOx-rich surface and Ti deficiencies in the film, and that annealing can effectively reduce the density of atomic defects.