Akira Kinbara

Abstract: The optical effect of the substrate on the anomalous absorption of aggregated silver films is taken into account in terms of the dipole interaction between an island particle and its mirror image in the substrate. The previously reported relation 2F|+F⊥<1, which holds for the observed values of the apparent depolarizing factors of island particles for an electric field parallel to (F|) and perpendicular to (F|) the substrate surface, is explained by the effect. The parameters characterizing the film structure are optically evaluated by stretching the substrate, and are compared with those evaluated from electron micrographs.

Abstract: We have been investigating the growth of crystalline titanium dioxide films at deposition temperature between room temperature and about 400 °C. The films were prepared by a dc magnetron reactive sputtering on glass and Si(100) substrates. The structural properties of the films were analyzed by x‐ray diffractometry. The influence of total pressure, oxygen mole fraction in the mixture of Ar–O2, discharge current, and substrate temperature on the structural properties were studied. In addition to higher substrate temperature, low total pressure, high discharge current, and small oxygen mole fraction were shown to be preferable for growing anatase–rutile mixture films. Annealing of the films in air at 850 °C showed that anatase–rutile transformation strongly depends on the deposition temperature; the films deposited at temperature below 400 °C were converted to the anatase–rutile mixture films, and the films deposited at 400 °C to complete rutile films.

Abstract: The mechanical properties of carbon films 500–3000 A thick deposited onto glass substrates were investigated. The average internal stress measured by the cantilever method was 5 x 108N m−2 compression. This large stress often generates wrinkles in the films. Young's modulus of the film and the adhesion energy between the film and the substrate can be estimated from the shape and size of the wrinkles. As a method of estimation, the elastic energy of the wrinkled film is considered. The dependence of the size of the wrinkles on the film thickness is deduced and compared with experimental results.

Abstract: A simple equation for the anisotropic dielectric constant of a metal island film is derived and applied to the ellipsometric measurement for an aggregated silver film. The experimental result can be explained when the inter-island dielectric constant is around unity. It is concluded that, in spite of the theoretical prediction that 2F∥+F⊥ = 1, the relation 2F∥+F⊥<1 holds for the observed values of the apparent depolarizing factors for electric fields parallel (F) and perpendicular (F⊥) to the substrate surface.

Abstract: For interpreting the optical properties of aggregated metal films, a modification of Schopper’s model is proposed, based on the assumption that an aggregated film consists of particles in the shape of rotational ellipsoids. Instead of the distribution of the depolarizing factor f in gaussian fashion, which is assumed in Schopper’s model, the logarithmic normal distribution of the axial ratio γ of the ellipsoidal particles was assumed and the parameter σ (standard deviation of the distribution function) was introduced. Besides, the contributions of the dipole interaction between particles and the size-dependent optical constants of the particles were taken into account. Using this modified model, the observed values of silver films continuously measured by ellipsometry during deposition were analyzed and the two parameters, the mean axial ratio γ¯ and the standard deviation σ, were obtained as functions of film thickness. The results showed that as film grows, both γ¯ and σ increase monotonically. Good coincidence of the observed and the calculated absorption spectra from our model seems to show the validity of our modification.

Abstract: 1. Introduction and overview 2. Film stress and substrate curvature 3. Stress in anisotropic and patterned films 4. Delamination and fracture 5. Film buckling, bulging and peeling 6. Dislocation formation in epitaxial systems 7. Dislocation interactions and strain relaxation 8. Equilibrium and stability of surfaces 9. The role of stress in mass transport.

Abstract: Electrical and optical spectroscopic studies of TiO2 anatase thin filmsdeposited by sputtering show that the metastable phase anatase differs in electronic properties from the well‐known, stable phase rutile. Resistivity and Hall‐effect measurements reveal an insulator–metal transition in a donor band in anatase thin films with high donor concentrations. Such a transition is not observed in rutile thin films with similar donor concentrations. This indicates a larger effective Bohr radius of donor electrons in anatase than in rutile, which in turn suggests a smaller electron effective mass in anatase. The smaller effective mass in anatase is consistent with the high mobility, bandlike conduction observed in anatase crystals. It is also responsible for the very shallow donor energies in anatase. Luminescence of self‐trapped excitons is observed in anatase thin films, which implies a strong lattice relaxation and a small exciton bandwidth in anatase. Optical absorption and photoconductivity spectra show that anatase thin films have a wider optical absorption gap than rutile thin films.

Abstract: In this paper we present a novel and versatile t e c h n i q u e f o r t h e p r o d u c t i o n o f u l t r a f i n e m e t a l p a r t i c l e s by evaporation from a temperature‐regulated oven containing a reduced atmosphere of an inert gas. An extensive investigation of particles of oxidized Al, with diameters of 3 to 6 nm, has been performed. We have also studied ultrafine particles of Mg,Zn, and Sn produced in the same manner. A supplementing investigation has been carried out for particles of Cr, Fe, Co, Ni, Cu, and Ga, as well as larger Al particles, produced by ’’conventional’’ inert‐gas evaporation from a resistive filament. Diameter as a function of evaporation rate, inert‐gas pressure, and the kind of inert gas are reported. Crystalline particles smaller than 20 nm look almost spherical in the electron microscope, while larger ones often display pronounced crystal habit. S i z e d i s t r i b u t i o n s have been investigated in detail, and consistently the logarithm of the particle diameter has a Gaussian distribution to a high precision for the smallest sizes, whereas larger particles deviate from such a simple behavior. A statistical growth model, based on the Central Limit Theorem, has been formulated for liquidlike coalescence of particles; this theory accounts satisfactorily for all our data, as well as for most size distributions published in the literature. Applications of the model to colloids, discontinuous films, and supported catalysts are discussed. By comparing size distributions for particles produced by a variety of techniques we found a number of empirical rules for the width of the distributions, as defined by a (geometric) standard deviation σ. For crystalline inert‐gas‐ evaporated particles we obtained consistently 1.36?σ?1.60; for coalescing islands in discontinuous films we found 1.22?σ?1.34; and similar rules are applicable to colloids, supported catalysts, and to ultrafine droplets.

Abstract: On the basis of different types of experiments, the authors develop implicitly the model of surface-enhanced Raman scattering (SERS) of adsorbates on metal surfaces. The long-range enhancement by resonances of the macroscopic laser and Stokes field is separated quantitatively from the metal electron-mediated resonance Raman effect. The latter mechanism proceeds by increased electron-photon coupling at an atomically rough surface and by temporary charge transfer to orbitals of the adsorbates. This model can account for the chemical specificity and vibrational selectivity of SERS and (partly) for the SERS specificity of the various metals.

Abstract: The nature and properties of surface-enhanced vibrational spectra of molecules adsorbed on surfaces that can enhance the absorption and the emission of electromagnetic radiation are discussed. Examples of surface-enhanced resonant Raman scattering, surface-enhanced Raman scattering in the near-infrared and surface-enhanced infrared are given. The rough surfaces used are metal island films coated with a nanometric organic film using the Langmuir-Blodgett technique or deposited by vacuum evaporation.