Nobuya Hiroshiba

Sub-10 nm Nanofabrication via Nanoimprint Directed Self-Assembly of Block Copolymers

Directed self-assembly (DSA) of block copolymers (BCPs), either by selective wetting of surface chemical prepatterns or by graphoepitaxial alignment with surface topography, has ushered in a new era for high-resolution nanopatterning. These pioneering approaches, while effective, require expensive and time-consuming lithographic patterning of each substrate to direct the assembly. To overcome this shortcoming, nanoimprint molds--attainable via low-cost optical lithography--were investigated for their potential to be reusable and efficiently template the assembly of block copolymers (BCPs) while under complete confinement. Nanoimprint directed self-assembly conveniently avoids repetitive and expensive chemical or topographical prepatterning of substrates. To demonstrate this technique for high-resolution nanofabrication, we aligned sub-10 nm resolution nanopatterns using a cylinder-forming, organic-inorganic hybrid block copolymer, polystyrene-block-polydimethylsiloxane (PS-b-PDMS). Nanopatterns derived from oxidized PDMS microdomains were successfully transferred into the underlying substrate using plasma etching. In the development phase of this procedure, we investigated the role of mold treatments and pattern geometries as DSA of BCPs are driven by interfacial chemistry and physics. In the optimized route, silicon molds treated with PDMS surface brushes promoted rapid BCP alignment and reliable mold release while appropriate mold geometries provided a single layer of cylinders and negligible residual layers as required for pattern transfer. Molds thus produced were reusable to the same efficacy between nanoimprints. We also demonstrated that shear flow during the nanoimprint process enhanced the alignment of the BCP near open edges, which may be engineered in future schemes to control the BCP microdomain alignment kinetics during DSA.

Selection of di(meth)acrylate monomers for low pollution of fluorinated mold surfaces in ultraviolet nanoimprint lithography.

We used fluorescence microscopy to show that low adsorption of resin components by a mold surface was necessary for continuous ultraviolet (UV) nanoimprinting, as well as generation of a low release energy on detachment of a cured resin from a template mold. This is because with low mold pollution, fracture on demolding occurred at the interface between the mold and cured resin surfaces rather than at the outermost part of the cured resin. To achieve low mold pollution, we investigated the radical photopolymerization behaviors of fluorescent UV-curable resins and the mechanical properties (fracture toughness, surface hardness, and release energy) of the cured resin films for six types of di(meth)acrylate-based monomers with similar chemical structures, in which polar hydroxy and aromatic bulky bisphenol moieties and methacryloyl or acryloyl reactive groups were present or absent. As a result, we selected bisphenol A glycerolate dimethacrylate (BPAGDM), which contains hydroxy, bisphenol, and methacryloyl moieties, which give good mechanical properties, monomer bulkiness, and mild reactivity, respectively, as a suitable base monomer for UV nanoimprinting under an easily condensable alternative chlorofluorocarbon (HFC-245fa) atmosphere. The fluorescent UV-curable BPAGDM resin was used for UV nanoimprinting and lithographic reactive ion etching of a silicon surface with 32 nm line-and-space patterns without a hard metal layer.

Rubrene single crystal field-effect transistor with epitaxial BaTiO3 high-k gate insulator

High quality BaTiO3 thin-film epitaxially grown on a Nb-doped SrTiO3 (BTO/Nb-STO) substrate by a laser ablation technique is employed as a high-k gate insulator for a field-effect transistor of a rubrene single crystal in order to search for the possibility of high carrier accumulation. The high dielectric constant ϵ of 280esu for the prepared BaTiO3 thin-film accumulates 0.1holes∕rubrene-molecule, which is 2.5 times as high as the maximum carrier number of 0.04holes∕rubrene-molecule attained in the case of SiO2. This is the highest carrier number so far obtained in organic field-effect transistors (FETs). Other important parameters of rubrene single crystal FETs on BTO/Nb-STO are described in comparison with those on SiO2/doped-Si.

Strain-effect for controlled growth mode and well-ordered structure of quaterrylene thin films.

We investigated the evolution of quaterrylene thin films on SiO(2) and on an octadecyltrichlorosilane self-assembled monolayer (OTS-SAM) to examine the impact of film strains on the growth processes and evolving structure. Surface modification by SAMs allowed tailoring of the growth process from a Stranski-Krastanov (SK) mode (layer-plus-island) on the SiO(2) surface to a Frank-van der Merwe mode (layer-by-layer) on the OTS surface. Detailed structural analysis by x-ray diffraction techniques confirmed that the SK mode was driven by lattice strain in the initial wetting layers on the SiO(2) surface. On the other hand, strain-free wetting layers were already formed at the beginning of growth on the OTS surface, thereby suppressing three-dimensional island formation. Moreover, the films on the SiO(2) surface were found to incorporate high microstrain induced by crystal defects such as dislocations and a mosaic structure. In contrast, few crystal defects were present in the films on OTS surface, demonstrating that OTS treatment enables marked improvement of the molecular alignment. These results clearly indicate that the lattice strain induced by the molecular-substrate interaction is essential for controlling the overall growth process.

Viscosity range of UV-curable resins usable in print and imprint method for preparing sub-100-nm-wide resin patterns

The authors demonstrated a “print and imprint” method comprising screen printing and ultraviolet (UV) nanoimprinting for preparing sub-100-nm-wide cured resin patterns. In the screen printing, UV-curable resins with viscosities in the range of 6.26–266 Pa s were deposited as droplet shapes on Si surfaces using a polyimide through-hole membrane mask with a hole diameter of 10 μm and a hole pitch of 45 μm. The low-volatile high-viscosity resin of 12.8 Pa s had an advantage of maintaining the droplet shapes 3 h after deposition. The spherical segment-shaped droplets showed an average diameter of 18.9 μm and height of 1.63 μm. The average volume was approximately 230 μm3 (0.230 pl) which was close to that dispensed by ink-jet printing. The droplet resin on a modified Si surface was filled into recesses of a fluorinated silica mold, and the molded resin was cured by UV nanoimprinting. Although the displacement of resin droplets was periodically uniform on substrate surfaces, the thicknesses of residual layers ...

Discharge of viscous UV-curable resin droplets by screen printing for UV nanoimprint lithography

We demonstrated a coating method of screen printing for discharging droplets of a high-viscosity resin on a substrate for ultraviolet (UV) nanoimprint lithography (NIL). Compared with a spin-coated resin film on a silicon substrate, discharged resin droplets on a silicon substrate were effective in terms of the uniformity of residual layer thickness (RLT) in contact with a mold with various pattern densities. Fluorescence microscope observations with a fluorescent-dye-containing UV-curable resin enabled the evaluation of the shapes of resin droplets discharged on a substrate surface. Widely used screen mesh plates composed of a stainless mesh covered with a patterned emulsion film caused defects of undischarged parts, whereas defects-free resin droplets with a narrow size distribution were discharged by mesh-free plates prepared with laser ablation. The pitch-to-diameter ratio in the configuration of 10-µm-diameter holes needs to be larger than 2.5 times for printing a resin having a viscosity of 12,800 mPa s.

Crystallographic polarity effect of ZnO on thin film growth of pentacene

The spontaneous polarization effect of ZnO on the thin film growth of pentacene, which is a typical π conjunction organic semiconductor, was investigated. Pentacene thin films were grown on polar ZnO surfaces by ultraslow organic film physical vapor deposition to obtain layer-by-layer growth. X-ray diffraction measurements revealed that pentacene molecules stand upright on polar ZnO surfaces, and that the films consist of two polymorphs, namely, the thin-film and bulk phases. The thin-film phases of pentacene were observed regardless of the polarity of the ZnO substrate at a thickness of less than six molecular layers. However, pentacene on a Zn-polar ZnO substrate gradually changed to the bulk phase unlike that on an O-polar ZnO substrate. Kelvin probe force microscopy measurements revealed that the surface potential of pentacene becomes more positive with increasing pentacene thickness at less than two molecular layers. The variation in the potential of pentacene on the Zn-polar ZnO substrate was larger than that of pentacene on the O-polar ZnO substrate. These findings indicate that the polarity of the semiconductor can control the growth and electronic state of the inorganic/organic semiconductor interface.

Potential of Directed- and Self-Assembled Molecular Nanowires for Optoelectronic Functional Devices

A variety of applications of molecular nanowires is reviewed in the first part of this article. First of all, growth techniques of molecular nanowires are discussed in terms of directed- and self-assemblies. Subsequently, various kinds of functional devices, e.g., field-effect transistors, memory devices, data storage, photo-electric conversion devices, are described. These devices have been proposed by taking advantages of one-dimensional structures and a wide range of molecular functions. In the second part of this article, we demonstrate our recent work. The main purposes are to provide a guideline on molecular design for growing of one-dimensional nanowires and to discuss their optical and electronic properties. A specific stress is laid on multi-level transistor operation as an evidence of effective utilization of one-dimensional nanowires. Although these performances are still preliminary, our results demonstrate a strong possibility of molecular nanowires as components in novel molecular devices.

Elemental depth profiles and plasma etching rates of positive-tone electron beam resists after sequential infiltration synthesis of alumina

By scanning transmission electron microscopy and energy dispersive X-ray spectroscopy (STEM–EDS), we investigated the elemental depth profiles of organic electron beam resist films after the sequential infiltration synthesis (SIS) of inorganic alumina. Although a 40-nm-thick poly(methyl methacrylate) (PMMA) film was entirely hybridized with alumina, an uneven distribution was observed near the interface between the substrate and the resist as well as near the resist surface. The uneven distribution was observed around the center of a 100-nm-thick PMMA film. The thicknesses of the PMMA and CSAR62 resist films decreased almost linearly as functions of plasma etching period. The comparison of etching rate among oxygen reactive ion etching, C3F8 reactive ion beam etching (RIBE), and Ar ion beam milling suggested that the SIS treatment enhanced the etching resistance of the electron beam resists to chemical reactions rather than to ion collisions. We proposed oxygen- and Ar-assisted C3F8 RIBE for the fabrication of silica imprint molds by electron beam lithography.

Photoelectron spectroscopic study on monolayer pentacene thin-film/polar ZnO single-crystal hybrid interface

The polarity effects of ZnO on the electronic state of a monolayer pentacene/ZnO interface were investigated by X-ray photoelectron spectroscopy (XPS). XPS revealed that the Zn-polar ZnO (Zn-ZnO) strongly depleted electrons in pentacene at the interface. The O-polar ZnO showed greater electron transfer from ZnO to pentacene than Zn-ZnO. The surface potential of pentacene on ZnO was larger than that of bulk pentacene regardless of the ZnO polarity. These findings indicate that the polarity of ZnO has the potential to control the electronic state of the organic/inorganic semiconductor interface.