The optical absorption and photoluminescence of Eu2+ : Sm3+-doped CaS films have been investigated in this paper. The energy dependence of the refractive index and absorption coefficient of the film were obtained by analyzing transmission and reflection spectra of the thin film. The refractive index at low energies is very close to the bulk value for CaS (n = 2.03) and decreases with increasing energy in the range of 1.2 to 2.5 eV. The energy gap of CaS: Eu2+ : Sm3+ thin films is found to be a direct gap with value Eg = 4.48 eV. Photoluminescence studies on annealed CaS: Eu2+ : Sm3+ thin films showed a broad band at ∼1.92 eV identified with emission from Eu2+ ions, and a set of sharp lines corresponding to emission from Sm3+ ions. Most of the strong features presented in the room temperature spectra are found in good agreement with previous bulk studies of CaS: Eu2+ and CaS: Sm3+. The abnormal increase of the Sm3+ photoluminescence with increasing temperature is explained by the phonon-assisted energy transfer from Eu2+ ions to Sm3+ ions.

The structural evolution of amorphous and microcrystalline SiC prepared from polycarbosilane was studied using various spectroscopic methods, 13C CPMAS NMR (cross-polarization, magic angle spinning nuclear magnetic resonance), ESR (electron spin resonance), FTIR (Fourier transformation infrared spectroscopy), and Raman. These studies indicate that the carbon-rich a-SiC has two major structural defects, C==C double bonds and C-dangling bonds. Both defect concentrations vary with firing conditions. The effect of hydrogen on the defect concentrations was also investigated by heat-treating the sample under hydrogen atmosphere. The mechanisms of the conversion process were discussed and the structural models for both amorphous and microcrystalline SiC were also proposed.

A stochastic model for the MBE growth kinetic study of compound semiconductors is developed based on the master equation approach, the solid-on-solid restriction, and the quasi-chemical approximation. The developed model is suitable for the zinc blende crystals with 001 as the growth direction. In the modeling, the diamond cubic structure and the two sublattice nature of the zinc blende crystal are taken into account. The stochastic model is extended to compound semiconductor alloys such as GaAlAsSb to make it suitable for the MBE kinetic studies of alloys. Up to four elements with two in each sublattice can be accommodated. The presence of two elements in the same sublattice was taken into account. A procedure for the evaluation of the model parameters based on the available thermodynamic and experimental data is discussed. Advantages and limitations of the stochastic model over the available theoretical models are discussed.

A fine-grained ($\overline \iota$m) laminate containing 91.0 wt.% magnesium and 9.0 wt. % lithium was prepared by a foil metallurgy technique involving rolling and pressing at low homologous temperature (0.39–0.49 Tm). The processed material exhibits superplastic characteristics above 70 °C (0.40 Tm). The strain-rate-sensitivity exponent is about 0.5 and an elongation-to-failure of 450% was obtained at 100 °C (0.43 Tm). The activation energy for plastic flow in the superplastic region is 65 kJ/mole. This value of the activation energy is related to the expected activation energy for grain boundary diffusion.

We performed diamond deposition experiments from a gas phase containing H2, CH4, and sometimes CO, using a microwave plasma ball reactor operating at 400 mbar pressure. The molybdenum substrates were stamped with a suitable tool to form a number of flattened cones on its surface. A strong preference for crystal growth on top of the cones was observed. Numerical calculations were used to solve the underlying thermal conduction and diffusion problems. At the substrate, the flow of the active species entering by diffusion from the bulk of the gas phase was balanced by those leaving the system due to incorporation in the crystals. Comparison with the experiments showed that at least 10% of the active species striking the surface are incorporated. Thus, the limitation of diamond growth in our investigation lies in gas phase transport and not in incorporation difficulties at the growing surface.

The evolution of hardness and transmittance of irradiated LiF single crystals at elevated temperatures has been investigated. The Vickers hardness is proportional to φ1/3 where φ is the dosage of γ-rays. The thermal annealing of hardness which is analyzed according to a first-order kinetic process has one stage for φ = 100 KGy and two stages for φ ≥ 250 KGy. For a given dosage, the activation energy of stage I is larger than that of stage II. The transmittance of irradiated LiF crystals is attributed to F, M, R1, and R2 centers. The transmittance decreases with increasing time at the brief durations, then oscillates, and finally increases monotonically. The region in which the transmittance increases monotonically with time is simulated by a second-order kinetic process of the color center. The activation energy of optical absorption was determined. Comparing both activation energies of hardness and optical absorption, we find that the mechanism of the kinetic process for hardness differs from that for optical absorption.

In this part of the work (Part II), two typical applications of the stochastic model to the MBE growth kinetic studies are presented. The applications are the MBE growth kinetics of a hypothetical compound semiconductor, ab, and diamond cubic alloy, ax. In this study, the effect of the surface diffusion process on the MBE growth kinetics is analyzed. In the case of the compound, ab, the results of the present stochastic model are compared with that of a Monte Carlo simulation study in the temperature range of 600–850 K. The results of the two studies agree qualitatively. Higher substrate temperatures result in higher growth rate and growth front smoothness due to higher surface diffusion. Beyond 800 K, the growth rate and the growth front smoothness become independent of temperature because of the saturation of the interlayer diffusion process. In the case of the alloy studies, the kinetics of a hypothetical diamond cubic alloy in which the thermodynamics favors phase separation, is studied in the temperature range of 573–898 K. Below 648 K, due to negligible surface diffusion, there is no clustering of the alloy, but the surface roughness is very large. In the intermediate temperature range of 573–798 K, with increasing temperature, the surface diffusion increases, resulting in more clustering and less surface roughness. Above 798 K, due to very high surface diffusion, complete phase separation of the alloy and a smooth surface result.

The electronic transition from localized to delocalized states of carriers in a disordered carbon material is investigated by photoconductivity measurements. Phenol-derived activated carbon fibers, where the carriers are strongly localized due to disorder, are heat treated in the range 300–2500 °C to give rise to the insulator-metal transition. Dark conductivity, Raman spectra, and x-ray diffraction patterns are also measured to characterize their structural changes. As a result, the transition temperature was determined to be rather low, around 1000 °C, considering the rapid decrease in the photoconductivity above this temperature. This decrease was ascribed to a fast recombination between the photoexcited carriers and the delocalized carriers generated by heat treatment.

A variety of TiO2 materials, including a nanophase TiO2 powder, were evaluated for their ability to dissociatively adsorb H2S in a H2 environment. A temperature programmed desorption technique was used to determine the rate of sulfide accumulation on the surface of the samples as a measurement of initial activity. The initial activity for the gas condensation-produced nanophase TiO2 with its rutile structure was found to be greater than that for other samples of TiO2 tested. When normalized for surface area, the initial specific activities of the rutile samples studied for the dissociative adsorption of H2S were similar in magnitude, but significantly higher than those of the anatase TiO2 samples investigated. Thus, the improvement in the activity is attributed mainly to the ability of the nanophase synthesis method to produce high surface area rutile TiO2. When evaluated using x-ray photoelectron spectroscopy, the nanophase TiO2 was found to be significantly deficient in oxygen. Annealing this material in oxygen decreased the number of anion vacancies and lowered the activity. Thus, we conclude that oxygen vacancies also contribute to the H2S dissociative adsorption activity.

Amorphous silicon carbide films (a–SixC1−x :H) deposited by the argon- or helium-diluted PECVD technique were studied as a function of their composition. Microstructural investigations were mainly achieved by means of FTIR and XPS techniques. Nuclear techniques were used to obtain precise information on the film hydrogen content. The Si–H IR-absorption band was deconvoluted in different monohydride and dihydride silicon environments. The existence of SiH2 bonds in the Si-rich composition was evidenced. From the analysis of the C–H and Si–H absorption bands it is shown that hydrogen atoms are preferentially bonded to carbon atoms. The deconvolution of the Si2p core level peak suggests that above a composition of x ∊ 0.5, the noncarburized (Si, Si, H) local environment contribution increases to the detriment of the hydrocarburized (Si, C, H) environments. From the evolution of the C1s peak, it can be deduced that there is a change in the carbon atom bonding states when the film composition is varied. These results are correlated and discussed in terms of the local bonding environments and their evolution with film composition.

To determine the influence of volume constraint, the crystallization behavior of bulk anorthite glass was compared with that of anorthite glass situated at intergranular pockets in an alumina ceramic. Near-100% crystallization of the glass was obtained in both cases. Examination of the crystallized microstructures using SEM and TEM revealed several interesting features. The resulting microstructures, together with the very high degree of crystallization, are discussed with reference to a thermodynamic model for the constrained crystallization of glass.

Time-resolved reflectivity and Rutherford backscattering spectroscopy were used to investigate the effects of regrowth environments on the thermally induced solid phase epitaxial (SPE) regrowth of amorphous near-surface layers produced by ion implantation of single-crystal SrTiO3. Water vapor in the regrowth atmosphere was found to alter both the apparent rate and activation energy of the SPE regrowth. For relatively dry atmospheres, a single constant regrowth rate is observed at any given temperature, and the activation energy is 1.2 ± 0.1 eV. When the concentration of H2O vapor in the atmosphere is increased, however, the regrowth activation energy effectively decreases to ∼0.95 eV. When regrown in atmospheres containing H2O vapor, the SrTiO3 amorphous layer exhibits two distinct stages of SPE regrowth as compared to the single rate found for dry anneals. This two-stage process apparently results from the diffusion of H/OH from the regrowth atmosphere at the surface of the crystal through the amorphous layer to the regrowing crystalline/amorphous interface.

Diamond deposits of well-separated particles have been obtained by the hot filament CVD technique on Si(100) wafers. Particle counting in SEM images and determination of their linear dimensions require a separate study of growth rates and of nucleation densities as a function of time, substrate temperature (500 °C–950 °C), gas phase composition (0.5–2% CH4 in H2), and total pressure (15–76 Torr). It is shown that recent models proposed for the growth process can successfully be applied if proper consideration is given to the high catalytic activity of the growing diamond surface for the heterogeneous recombination of gaseous H-atoms. This fast reaction controls the H-atom concentration at the surface and couples growth rates and nucleation densities via the gas phase.

The evolution of the reaction between the binary graphitide KC8 and CoCl2 dissolved in anhydrous tetrahydrofuran (THF) has been investigated by in situ x-ray diffraction (XRD). During the reaction and whatever the host graphite (powder or HOPG), the first stage graphite intercalation compounds K(THF)2.5C24 and K(THF)1.7C24 are first formed and then transformed into higher stages. Finally the matrix is exfoliated and the phases identified are graphite, metallic cobalt, and KCl. Analyses by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) clearly show that the products are mainly located at the edge planes of the graphite, indicating that the electronic exchange occurs at the edge of the graphene layers. It is now clear that graphite-cobalt intercalation compounds cannot be obtained by this method.

A discrete model of springs with bond-bending forces is proposed to simulate the fracture process in a composite of short stiff fibers in a softer matrix. Both components are assumed to be linear elastic up to failure. We find that the critical fiber length of a single fiber composite increases roughly linearly with the ratio of the fiber elastic modulus to matrix modulus. The finite size of the lattice in the direction perpendicular to the fiber orientation considerably alters the behavior of the critical length for large values of the modulus ratio. The simulations of the fracture process reveal different fracture behavior as a function of the fiber content and length. We calculate the Young's modulus, fracture stress, and the strain at maximum stress as a function of the fiber volume fraction and aspect ratio. The results are compared with the predictions of other theoretical studies and experiments.

Molecular species were found to diffuse readily into the octahedral interstitial sites of the fcc lattice of C60. The 13C NMR spectrum of C60 under magic angle spinning (MAS) conditions consisted of a primary resonance at 143.7 ppm and a minor peak shifted 0.7 ppm downfield. The downfield shift obeys Curie's law and is attributed to the Fermi-contact interaction between paramagnetic oxygen molecules and all 60 carbon atoms of rapidly rotating adjacent C60 molecules. Exposure of C60 to 1 kbar oxygen for 1.75 h at room temperature resulted in a spectrum of seven evenly spaced resonances corresponding to the filling of 0 to 6 of the adjacent octahedral interstitial sites with oxygen molecules. The distribution of site occupancies about a C60 molecule provided evidence that the intercalation process is controlled by diffusion kinetics. Exposure to 0.14 kbar hydrogen gas at room temperature for 16 h filled a substantial fraction of the interstitial sites of C60 and C70 with hydrogen molecules.

Ultrafine particles (UFPs) of aluminum oxide were prepared by an arc discharge, sintered in a custom-built ultrahigh vacuum (UHV) furnace system, and characterized in a high resolution electron microscope (HREM) operating under UHV conditions. The UFPs produced range in size from 20 to 50 nm and have highly faceted surfaces. The atomic structure of the UFPs corresponds to the cubic (γ) and orthorhombic (δ) variants of the spinel structure. Sintering in these UFPs demonstrates three major issues. Surface faceting plays a major role in determining the final sintering geometry with sintering occurring predominantly on the close-packed {111} facets. Surface diffusion is the predominant mechanism for sintering, as evidenced by the fact that many sintered particles have their initial adhesion structure ‘locked-in’ during sintering with no reorientation occurring. Furthermore, the necks formed during sintering have well-defined, atomically sharp contact angles which suggests that the neck growth process is controlled by the faceted structures and may be modeled by a mechanism similar to crystal growth due to ledges, grain boundaries, and twins. The driving force for sintering can be considered as a chemical potential difference between facet surfaces and the neck region.

The optical properties of polycrystalline CdSe films prepared using electroless deposition techniques are discussed. Refractive index measurements are reported for the wavelength region 400–2000 nm. Extinction and absorption coefficient measurements are reported for the strong absorption regime (450–750 nm). UV reflectance measurements are also discussed.

The kinetics of disorder → B2 order transformations in ternary alloys were studied in the pair approximation. The predictions of two sets of rate equations were compared, one based on an atom-atom interchange mechanism and the other based on an atom-vacancy interchange mechanism. Examples are presented to show how the evolution of order is affected by differences in interatomic potentials, differences in activation barrier heights, and effects of vacancy ordering. A wide variety of states of order are possible during the disorder → order transformation in ternary alloys, and qualitative features of the sequences of these states are discussed. The sequences of states, or “kinetic paths”, are much less intuitive than for binary alloys.

Indium tin oxide (ITO) films were prepared on a glass substrate by thermal decomposition of ethylene glycol (EG) solutions which were prepared by dissolving indium and tin chlorides into ethylene glycol and then heating the solution at 200 °C. Homogeneous ITO film with a thickness of 1 μm without any cracks was obtained from the EG solution with a viscosity of about 50 cSt by spin coating, with the rotation of the substrate at 2000 rpm. The crystallization of the film thus obtained occurred above 400 °C. A well-crystallized ITO film was obtained by heat-treating at 600 °C. The resistivity of the ITO film obtained on a glass substrate showed a minimum value of 1.1 × 10−4 ohm cm at about 7 at.% Sn.