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.

Thin Film Materials: Stress, Defect Formation and Surface Evolution

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.

Electrical and optical properties of TiO2 anatase thin films

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.

Ultrafine metal particles

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.

https://iopscience.iop.org/article/10.1088/0953-8984/4/5/001/pdf

Surface-enhanced Raman scattering

Metasurfaces: From microwaves to visible

Internal stress and young's modulus of TiC coatings

Interface structures and adhesion to silicon after different surface pretreatments have been investigated for Ni(500–1000 nm)/Ti(250 nm) films prepared in a dc planar magnetron sputtering apparatus. In order to obtain high adhesion, a chemical pretreatment (with buffered HF) has been found to be favorable in comparison with a conventional Ar ion bombardment pretreatment (with cathodic voltage: 400 V). High resolution transmission electron microscopy (HRTEM) showed that there were two layers between Ti and Si in the case of Ar ion bombardment pretreatment. Energy dispersive x‐ray spectroscopy (EDS) and electron diffraction (ED) showed that they were amorphous Ti–Si alloy and amorphous Si containing Ar. Moreover, a peeling pattern, after the test with adhesive tape, could be found at the boundary between the amorphous Ti–Si alloy layer and the amorphous Si layer containing Ar by using x‐ray photoelectron spectroscopy (XPS). In the case of chemical pretreatment, only an amorphous Ti–Si alloy layer was observ...

Effects of different pretreatments on the surface structure of silicon and the adhesion of metal films

Scratch, peel, and pull methods for adhesion measurement were applied to deposited thin film/solid substrate combinations. Scatter in the experimental data was observed and its origin is discussed. The interface between the thin film and the substrate was investigated by transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and Auger electron spectroscopy (AES), and the correlation of the interface structure with the adhesion strength was investigated. Ion bombardment and heat treatment were carried out to enhance the adhesion. Accumulation of bombarding gas ions at the interface was observed and the role of ion bombardment in improving adhesion is considered.

Adhesion measurement of thin metal films by scratch, peel, and pull methods

The crystallization of amorphous indium tin oxide (ITO) films was achieved by rf (13.56MHz) plasma treatment. Although the films were crystallized after 2min, the sample temperature was lower than 90°C without compulsory cooling even after 10min of treatment and polyethylene terephthalate (PET) substrates had no damage. Plasma-crystallized sputtered ITO films have a bixbite structure and the resistivity reached to 1.6×10−4Ω∙cm. ITO thin films have almost the same resistivity in both cases of PET and glass substrates used and plasma-treated PET ITO films have a bit higher resistivity than that of glass ITO films, while mass spectroscopy measurements indicated that ITO films deposited on PET substrates are expected to include no apparent gas species ejected from PET substrate. It was found that the plasma gas pressure is the key parameter for the effective crystallization and the appropriate gas pressure depends on the plasma gas species.

Room temperature crystallization of indium tin oxide films on glass and polyethylene terephthalate substrates using rf plasma

Ni(100–1000 nm)/Ti(250 nm) films were prepared by dc planar magnetron sputtering on Si(100) surfaces. Interface structures between Ti and Si and adhesion of the Ti films to Si after different surface pretreatments have been investigated. Before the film deposition, the Si substrate received an Ar ion bombardment or a chemical etching treatment. In the case of the Ar ion bombardment, we have investigated the effect of the cathodic voltage. A low cathodic voltage (50 V) resulted in high adhesion. The results by Rutherford backscattering spectroscopy showed that the amount of Ar incorporated in the Si surface during the Ar ion bombardment is increased with the cathodic voltage. The existence of Ar at the interface between the Si substrate and the Ti–Si mixed layer seems to lower the adhesion. In the case of the chemical pretreatment, we have investigated the effect of the exposure time in the atmosphere after the chemical etching treatment. A shorter exposure time (within 1 h) has been found to be preferred ...

Akira Kinbara

Papers

Internal stress and young's modulus of TiC coatings

Effects of different pretreatments on the surface structure of silicon and the adhesion of metal films

Adhesion measurement of thin metal films by scratch, peel, and pull methods

Room temperature crystallization of indium tin oxide films on glass and polyethylene terephthalate substrates using rf plasma

Interface structure and adhesion of sputtered metal films on silicon: The influence of Si surface condition