Separation of Neighboring Terraces on a Flattened Si(111) Surface by Selective Etching along Step Edges Using Total Wet Chemical Processing.

We propose a bottom-up technique using total wet chemical treatments to separate neighboring terraces on Si(111). First, Ag cations were reduced at the step edges of a vicinal Si(111) surface composed of biatomic steps and flat terraces, resulting in self-assembled Ag rows consisting of nanodots and nanowires. By immersing this sample into a mixed solution of HF and H2O2, almost continuous nanotrenches with depths and widths of nanometer scales were fabricated along the edges. The potential electrochemical processes in the solution/Ag/Si system that lead to the formation of nanotrenches are discussed. Additionally, we present how we plan to use our approach to create atomic-thickness Si ribbons.

Center of excellence for atomically controlled fabrication technology.

This short review aims to show the introduction of the educational and research program of "Center of excellence of atomically controlled fabrication technology" supported ministry of education, culture, sports, science and technology--Japan. We would like to introduce research activity and a unique trait of educational system.

Selective adsorption of organosilane molecules along step edges of atomically flattened Si(111) surfaces.

We investigate the selective adsorption of organosilane molecules (3-aminopropyltriethoxysilane (APTES) and octadecyltrichlorosilane (OTS)) at the step edges of a flattened Si(111) surface by atomic force microscopy. The flattened Si(111) surface is formed by dipping a vicinal Si(111) wafer into ultralow-dissolved-oxygen water after treatment with HF. The selective adsorption of these organosilanes is achieved only when the Si(111) sample is pretreated with a Cu-containing solution to form Cu wires along the step edges of the Si(111) surface. This is probably due to the simultaneous formation of one-dimensional Si oxide covered with hydroxyl (OH) groups underneath Cu wires during the electroless reduction of Cu ions in water. At the step edges, APTES and OTS molecules are adsorbed as disperse clusters and as rows of bumps, respectively. The reason for this difference is still unclear, but a key factor is probably the control of the moisture content in the environment. The step edges, which are functionalized by organosilane molecules with various terminations such as -NH2 and -CH3, are expected to be utilized in novel nanoscale devices and processes.

Characterization of terraces and steps on Cl-terminated Ge(111) surfaces after HCl treatment in N2 ambient.

Germanium (Ge) is a promising substrate for semiconductor devices in the near future. However, wet-chemical preparations that enable the control of the structure of the Ge surface have not yet been developed. In this study, the surface structure of Ge(111) after HCl treatment is characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and scanning tunneling microscopy (STM). XPS spectra revealed that purging with inert gas, such as nitrogen, is necessary to obtain a Ge surface free of oxide, probably because dissolved oxygen from air rapidly oxidizes the surface. Cl-terminated Ge surfaces are microscopically rough, but are composed of terraces and steps, as revealed by magnified STM images. Step edges run not along specific directions reflecting the crystallographic nature of the (111) surface but randomly. Many atomic-scale protrusions with the height of around 0.1 nm are dispersed on terraces. They are likely to be impurities such as carbon contaminants and water on Cl-terminated terraces attracted by Cl atoms with high electronegativity.

Improved optical and electrical characteristics of free-standing GaN substrates by chemical polishing utilizing photo-electrochemical method.

The optical and electrical properties of GaN(0001) surfaces treated by a novel chemical polishing method are described. Scanning microscopic photoluminescence images reveal that the polished GaN surface shows improved luminescence properties compared to the untreated surface. Current-voltage measurements of Schottky barriers formed using the GaN substrates show that the polished GaN surface has a lower reverse leakage current, and that the barrier height and ideality factor are improved after the polishing treatment.

Dependence of process characteristics on atomic-step density in catalyst-referred etching of 4H-SiC(0001) surface.

Catalyst-referred etching (CARE) is a novel abrasive-free planarization method. CARE-processed 4H-SiC(0001) surfaces are extremely flat and undamaged over the whole wafer. They consist of single-bilayer-height atomic steps and atomically flat terraces. This suggests that the etching properties depend principally on the atomic-step density of the substrate surface. We used on-axis and 8 degrees off-axis substrates to investigate the processing characteristics that affect the atomic-step density of these substrates. We found a strong correlation between the removal rate and the atomic-step density of the two substrates. For the on-axis substrate, the removal rate increased with increasing surface roughness, which increases with an increasing atomic-step density. The removal rate ratio is approximately the same as the atomic-step density ratio of the two substrates.

Structure and magnetic properties of mono- and bi-layer graphene films on ultraprecision figured 4H-SiC(0001) surfaces.

Monolayer and bilayer graphene films with a few hundred nm domain size were grown on ultraprecision figured 4H-SiC(0001) on-axis and 8 degrees -off surfaces by annealing in ultra-high vacuum. Using X-ray photoelectron spectroscopy (XPS), atomic force microscopy, reflection high-energy electron diffraction, low-energy electron diffraction (LEED), Raman spectroscopy, and scanning tunneling microscopy, we investigated the structure, number of graphene layers, and chemical bonding of the graphene surfaces. Moreover, the magnetic property of the monolayer graphene was studied using in-situ surface magneto-optic Kerr effect at 40 K. LEED spots intensity distribution and XPS spectra for monolayer and bilayer graphene films could become an obvious and accurate fingerprint for the determination of graphene film thickness on SiC surface.

Damage-free highly efficient plasma-assisted polishing of a 20-mm square large mosaic single crystal diamond substrate.

Plasma-assisted polishing (PAP) as a damage-free and highly efficient polishing technique has been widely applied to difficult-to-machine wide-gap semiconductor materials such as 4H-SiC (0001) and GaN (0001). In this study, a 20-mm square large mosaic single crystal diamond (SCD) substrate synthesized by microwave plasma chemical vapor deposition (CVD) was polished by PAP. Argon-based plasma containing oxygen was used in PAP to modify the surface of quartz glass polishing plate, and a high material removal rate (MRR) of 13.3 µm/h was obtained. The flatness of SCD polished by PAP measured by an interferometer was 0.5 µm. The surface roughness measured by both scanning white light interferometer (SWLI) (84-µm square) and atomic force microscope (AFM) (5-µm square) was less than 0.5 nm Sq. The micro-Raman spectroscopy measurement results of mosaic SCD substrate processed by PAP showed that residual stress and non-diamond components on the surface after PAP processing were below the detection limit.

Ion segregation and deliquescence of alkali halide nanocrystals on SiO2.

The adsorption of water on alkali halide (KBr, KCl, KF, NaCl) nanocrystals on SiO2 and their deliquescence was investigated as a function of relative humidity (RH) from 8% to near saturation by scanning polarization force microscopy. At low humidity, water adsorption solvates ions at the surface of the crystals and increases their mobility. This results in a large increase in the dielectric constant, which is manifested in an increase in the electrostatic force and in an increase in the apparent height of the nanocrystals. Above 58% RH, the diffusion of ions leads to Ostwald ripening, where larger nanocrystals grow at the expense of the smaller ones. At the deliquescence point, droplets were formed. For KBr, KCl, and NaCl, the droplets exhibit a negative surface potential relative to the surrounding region, which is indicative of the preferential segregation of anions to the air/solution interface.

Surface Modification and Microstructuring of 4H-SiC(0001) by Anodic Oxidation with Sodium Chloride Aqueous Solution.

Anodic oxidation is a promising surface modification technique for the manufacture of SiC wafers owing to its high oxidation rate. It is also possible to fabricate porous SiC by anodic oxidation and etching owing to the material properties of SiC. In this study, the anodic oxidation of a 4H-SiC(0001) surface was investigated by performing repeated anodic oxidation and hydrofluoric acid etching on a 4H-SiC(0001) surface, during which the formation of porous SiC was observed and studied. Anodic oxidation is very effective for removing the surface damage formed by mechanical polishing, and the surface after removing the surface damage can be oxidized uniformly and has a higher oxidation rate than a surface newly finished by chemical mechanical polishing (CMP). We proposed a model based on the electrochemical impedance method to explain the difference in the oxidation between an as-CMP-finished surface and an oxidized/etched surface. Porous SiC was obtained in this study, which was due to the anisotropy of the SiC crystal. The structure of the porous SiC was significantly dependent on the etch pits generated at the beginning of anodic oxidation and can be controlled via anodic oxidation parameters. Anodic oxidation and hydrofluoric acid etching cannot remove porous SiC owing to the anisotropic oxidation of the SiC surface and the difficulty of anodizing SiC fibers. This study shows that anodic oxidation is a promising technique for the modification of SiC surfaces and the fabrication of porous SiC.

FTIR-ATR evaluation of organic contaminant cleaning methods for SiO2 surfaces.

The effectiveness of cleaning organic contaminants from silicon dioxide (SiO2) surfaces was studied by conducting highly sensitive measurements using Fourier Transform Infrared Attenuated Total reflectance (FTIR-ATR) with a Si prism as the waveguide. To serve as an example, the surface of the prism was oxidized to an order of a few nanometers. The oxidized Si surface film was allowed to stand in the atmosphere and then wet-cleaned in a repeated manner; subsequently its thickness was measured by ellipsometry. Although, various wet-cleaning methods were tested, they only showed values of 0.1-0.2 nm larger than, but not equal to, the original thickness immediately after oxidation. FTIR-ATR measurements of the spectral change after exposure to air revealed that organic species, such as C-CH3 and -(CH2)n-, increased with time. Wet-cleaning the sample failed to remove the C-CH3 species, which indicates that they corresponded to the film thickness increment from the original.

Absolute flatness measurements of silicon mirrors by a three-intersection method by near-infrared interferometry.

Absolute flatness of three silicon plane mirrors have been measured by a three-intersection method based on the three-flat method using a near-infrared interferometer. The interferometer was constructed using a near-infrared laser diode with a 1,310-nm wavelength light where the silicon plane mirror is transparent. The height differences at the coordinate values between the absolute line profiles by the three-intersection method have been evaluated. The height differences of the three flats were 4.5 nm or less. The three-intersection method using the near-infrared interferometer was useful for measuring the absolute flatness of the silicon plane mirrors.

Metal-assisted chemical etching of Ge(100) surfaces in water toward nanoscale patterning.

We propose the metal-assisted chemical etching of Ge surfaces in water mediated by dissolved oxygen molecules (O2). First, we demonstrate that Ge surfaces around deposited metallic particles (Ag and Pt) are preferentially etched in water. When a Ge(100) surface is used, most etch pits are in the shape of inverted pyramids. The mechanism of this anisotropic etching is proposed to be the enhanced formation of soluble oxide (GeO2) around metals by the catalytic activity of metallic particles, reducing dissolved O2 in water to H2O molecules. Secondly, we apply this metal-assisted chemical etching to the nanoscale patterning of Ge in water using a cantilever probe in an atomic force microscopy setup. We investigate the dependences of probe material, dissolved oxygen concentration, and pressing force in water on the etched depth of Ge(100) surfaces. We find that the enhanced etching of Ge surfaces occurs only when both a metal-coated probe and saturated-dissolved-oxygen water are used. In this study, we present the possibility of a novel lithography method for Ge in which neither chemical solutions nor resist resins are needed.

Mechanism of atomic-scale passivation and flattening of semiconductor surfaces by wet-chemical preparations.

Atomic arrangements of Si(001), Si(110) and 4H-SiC(0001) surfaces after wet-chemical preparations are investigated with scanning tunneling microscopy. Their passivated structures as well as the surface formation mechanisms in aqueous solutions are discussed. On both Si(001) and Si(110) surfaces, simple 1 × 1 phases terminated by H atoms are clearly resolved after dilute HF dipping. Subsequent etching with water produces the surfaces with 'near-atomic' smoothness. The mechanisms of atomic-scale preferential etching in water are described in detail together with first-principles calculations. Furthermore, 4H-SiC(0001), which is a hard material and where it is difficult to control the surface structure by solutions, is flattened on the atomic scale with Pt as a catalyst in HF solution. After a mechanism is proposed based on electroless oxidation, the flattened surface mainly composed of a 1 × 1 phase is analyzed. The obtained results will be helpful from various scientific and technological viewpoints.

Single-nanometer focusing of hard x-rays by Kirkpatrick-Baez mirrors.

We have constructed an extremely precise optical system for hard-x-ray nanofocusing in a synchrotron radiation beamline. Precision multilayer mirrors were fabricated, tested, and employed as Kirkpatrick-Baez mirrors with a novel phase error compensator. In the phase compensator, an at-wavelength wavefront error sensing method based on x-ray interferometry and an in situ phase compensator mirror, which adaptively deforms with nanometer precision, were developed to satisfy the Rayleigh criterion to achieve diffraction-limited focusing in a single-nanometer range. The performance of the optics was tested at BL29XUL of SPring-8 and was confirmed to realize a spot size of approximately 7 nm.

Metal-insulator-gap-insulator-semiconductor structure for sensing devices.

We report on the use of sensing devices that have a metal-insulator-gap-insulator-semiconductor structure. We have used capacitance-voltage measurements from a metal-insulator-gap-insulator-semiconductor sensing device to characterize different pH solutions and deoxyribonucleic acid (DNA) solutions. Hysteresis in the capacitance-voltage curves results from mobile ionic charges in the solutions and the influence of changes on the sensing surface condition. As the pH decreases in the pH range of 2.7 to 7.0, the flatband voltage shift toward the negative voltage increases. The differences in the flatband voltage shift in capacitance-voltage curves are related to the mobile ionic charge density in solutions with different pH values or DNA molecules.