Tomohiro Shimizu

Extended Arrays of Vertically Aligned Sub-10 nm Diameter [100] Si Nanowires by Metal-Assisted Chemical Etching

Large-area high density silicon nanowire (SiNW) arrays were fabricated by metal-assisted chemical etching of silicon, utilizing anodic aluminum oxide (AAO) as a patterning mask of a thin metallic film on a Si (100) substrate. Both the diameter of the pores in the AAO mask and the thickness of the metal film affected the diameter of SiNWs. The diameter of the SiNWs decreased with an increase of thickness of the metal film. Large-area SiNWs with average diameters of 20 nm down to 8 nm and wire densities as high as 10 (10) wires/cm (2) were accomplished. These SiNWs were single crystalline and vertically aligned to the (100) substrate. It was revealed by transmission electron microscopy that the SiNWs were of high crystalline quality and showed a smooth surface.

Ordered arrays of vertically aligned [110] silicon nanowires by suppressing the crystallographically preferred etching directions.

The metal-assisted etching direction of Si(110) substrates was found to be dependent upon the morphology of the deposited metal catalyst. The etching direction of a Si(110) substrate was found to be one of the two crystallographically preferred 100 directions in the case of isolated metal particles or a small area metal mesh with nanoholes. In contrast, the etching proceeded in the vertical [110] direction, when the lateral size of the catalytic metal mesh was sufficiently large. Therefore, the direction of etching and the resulting nanostructures obtained by metal-assisted etching can be easily controlled by an appropriate choice of the morphology of the deposited metal catalyst. On the basis of this finding, a generic method was developed for the fabrication of wafer-scale vertically aligned arrays of epitaxial [110] Si nanowires on a Si(110) substrate. The method utilized a thin metal film with an extended array of pores as an etching catalyst based on an ultrathin porous anodic alumina mask, while a prepatterning of the substrate prior to the metal depostion is not necessary. The diameter of Si nanowires can be easily controlled by a combination of the pore diameter of the porous alumina film and varying the thickness of the deposited metal film.

Electro-functional octupolar π-conjugated columnar liquid crystals.

A series of propeller-shaped π-conjugated molecules based on 2,4,6-tris(thiophene-2-yl)-1,3,5-triazines has been designed and synthesized to obtain ambipolar charge-transporting liquid-crystalline materials. The 3-fold electron-donating aromatic units are attached to the electron-accepting triazine core, which forms electro-functional octupolar π-conjugated structures. These octupolar molecules self-organize into one-dimensional columnar nanostructures and exhibit ambipolar carrier transport behavior, which has been revealed by time-of-flight measurements. In this approach, electron-donor and acceptor electro-active segments are assembled individually in each column to give one-dimensional nanostructured materials with precisely tuned electronic properties. Their desirable electronic structures responsible for both hole and electron conductions have also been examined by cyclic voltammetry and theoretical calculations. The present results provide a new guideline and versatile approach to the design of ambipolar conductive nanostructured liquid-crystalline materials.

Electrical resistivity and photoluminescence spectrum of layered oxysulfide (LaO)CuS

Abstract On growth conditions the dependence of the electrical resistivity and the photoluminescence (PL) spectrum of a layered oxysulfide (LaO)CuS have been investigated. The electrical resistivity shows semiconducting behavior and its magnitude decreases with the increase in the sintering temperature and time, which is considered to introduce structural defects such as Cu or La vacancies. The PL spectrum consists of six emission bands which are assigned to a direct interband transition and the transitions originating in two kinds of donor and acceptor levels corresponding to defect centers in the band gap. The PL spectra depend on the growth conditions. The introduction of lattice imperfection increases the intensity of the wide emission bands, and the (LaO)CuS sample visually appears to be ‘white’ under UV excitation. The white luminescence is an important property for the application to display back-light.

Vertical epitaxial wire-on-wire growth of Ge/Si on Si(100) substrate.

Vertically aligned epitaxial Ge/Si heterostructure nanowire arrays on Si(100) substrates were prepared by a two-step chemical vapor deposition method in anodic aluminum oxide templates. n-Butylgermane vapor was employed as new safer precursor for Ge nanowire growth instead of germane. First a Si nanowire was grown by the vapor liquid solid growth mechanism using Au as catalyst and silane. The second step was the growth of Ge nanowires on top of the Si nanowires. The method presented will allow preparing epitaxially grown vertical heterostructure nanowires consisting of multiple materials on an arbitrary substrate avoiding undesired lateral growth.

Origin of visible photoluminescence from arrays of vertically arranged Si-nanopillars decorated with Si-nanocrystals

Arrays of vertically aligned Si-nanopillars, with average diameters of 100 nm and 5 μm length, have been prepared by wet chemical etching of crystalline silicon in a special manner. Samples with smooth- and porous-walled nanopillars have been studied. In the case of the latter, Si-nanocrystals, passivated with SiO(x), decorating the surface of the nanopillars are identified by the means of TEM and FTIR. When excited by UV-blue light, the porous-walled Si-nanopillars are found to have a strong broad visible emission band around 1.8 eV with a nearly perfect Gaussian shape, μs luminescence lifetimes, minor emission polarization and a non-monotonic temperature dependence of luminescence. The Si-nanocrystal surface is found to be responsible for the luminescence. The red-shift of the emission maximum and the luminescence quenching induced by oxidation in UV-ozone confirm this assumption. A model of luminescence involving UV photon absorption by Si-nanocrystals with subsequent exciton radiative recombination on defect sites in SiO(x) covering Si-nanocrystals has been proposed. Possible applications of the nanopillar arrays are discussed.

Epitaxial Growth of Cu Nanodot Arrays Using an AAO Template on a Si Substrate

We established a method to clean the Si surface that exists at the bottom of anodic aluminum oxide (AAO) nanoholes after removal of the amorphous barrier layer, and we succeeded in the preparation of epitaxial Cu dot arrays on the Si surface in the nanoholes. The Si surfaces at the AAO nanohole bottoms were cleaned with dilute hydrofluoric acid after annealing at 900°C in Ar ambient, and we sputtered Cu on the AAO template to form Cu dot arrays. This method for preparing nanohole arrays on a single crystalline substrate enables growth of a variety of highly regular epitaxial nanodot/wire arrays.

Synthesis of silicon nanotubes with cobalt silicide ends using anodized aluminum oxide template

Silicon nanotubes (SiNTs) are compatible with Si-based semiconductor technology. In particular, the small diameters and controllable structure of such nanotubes are remaining challenges. Here we describe a method to fabricate SiNTs intrinsically connected with cobalt silicide ends based on highly ordered anodic aluminum oxide (AAO) templates. Size and growth direction of the SiNTs can be well controlled via the templates. The growth of SiNTs is catalyzed by the Co nanoparticles reduced on the pore walls of the AAO after annealing, with a controllable thickness at a given growth temperature and time. Simultaneously, cobalt silicide forms on the bottom side of the SiNTs.

Oxide thickness dependence of resistive switching characteristics for Ni/HfOx/Pt resistive random access memory device

The switching process of the conductive filament formed in Ni/HfOx/Pt resistive random access memory (ReRAM) devices were studied. We evaluated the oxide thickness dependence and temperature dependence of voltage for the Forming, Set and Reset operations for HfOx layers whose thickness are between 3.3 and 6.5 nm. The resistance of conductive filaments showed typical metallic behavior, which suggests Ni filament formation in the HfOx layer. There is a clear dependence of switching voltages for the Set and Reset processes on oxide thickness, which implies that the formation and rupture of conductive filaments occur in the entire thickness range of the HfOx layer. This finding differs from that of a previous study by Yang, which suggests the existence of a constant-thickness switching region. It is suggested that the thickness of the switching region in HfOx may be larger than 6.5 nm.

Magnetoresistance of conductive filament in Ni/HfO2/Pt resistive switching memory

Ferromagnetic conductive filaments (CFs) were formed in a conductive-bridge random access memory (CBRAM) with a Ni electrode using high current compliances during a set process. We investigated CFs in a Ni/HfO2/Pt CBRAM using the current compliance dependences of the set process, low-temperature characteristics, and anisotropic magnetoresistance (AMR). Set processes occurred when a positive bias was applied to the Ni electrode only; therefore, the switching phenomena showed polarity. The resistance of the ON state (low resistance state) was dependent on the current compliance between 2 and 5 mA. The ON state of the device showed a metallic conduction property, suggested by the temperature dependence of resistance. When a high current compliance (5 mA) was used for programming, the ON state showed AMR, which was direct evidence of ferromagnetic CF formation. This suggests that the formation of a ferromagnetic CF is associated with the accumulation of Ni ions that diffused from the Ni electrode. The OFF-state (high resistance state) resistance slightly increased with decreasing temperature and AMR was not observed.