Optical properties of plasma-deposited amorphous hydrogenated carbon films were studied by spectroscopic ellipsometry. From the ellipsometry data, the real and imaginary parts, n and k, of the complex index of refraction of the film have been deduced for photon energies between 2.0 and 4.0 eV for as-grown as well as for thermally annealed films. Here n and k showed considerable variation with subsequent annealing, even under 400°C. A tentative explanation of the results is proposed.

Materials derived by precipitation or polymerization chemistry (e.g., “sol-gel” methods) are usually obtained in noncrystalline or otherwise metastable phases, and transformation to more thermodynamically stable phases generally occurs by a nucleation and growth process. In a fully reconstructive transformation, such as occurs in the alumina system, the activation energy for nucleation may be higher than that for simple short-range diffusion. Hence nucleation frequency can be a controlling factor in the development of microstructurc. The efficacy of seeding as a method of microstructural and phase control in solution-derived or so-called sol-gel materials has been clearly demonstrated for the alumina system. The epitaxial nature of this phenomenon is explored, using the polarizing microscope to follow the crystallographic orientation of the transformed material as the transformation proceeds, showing that this is epitaxial in nature, and that the nucleation frequency in unseeded material is relatively low (∼ 1010 cm−3). The microscope was then used to demonstrate the effect on nucleation frequency of seeding with materials selected to be isostructural, isotypic, and having little or no similarity to the corundum structure. Using these and other methods, the seeding phenomenon in alumina gels is shown to result from epitaxial growth of the stable corundum phase on isostructural or isotypic nuclei in the solid state. This approach is applied to formulate hypotheses for the mechanisms by which some of the previously reported effects of seeding, e.g., enhanced densification and microstructural refinement, can be understood and to formulate a set of generalizations for its potential application to other systems.

For liquid phase epitaxial (LPE) growth of BiYIG films, MoO3 is shown to be a flux modifier that increases Bi content xBi, and growth-induced anisotropy Ku8, for MoO3 flux concentrations up to 12 mol %. The addition of MoO3 to PbO–Bi2O3 fluxed garnet melts caused the saturation temperature to increase at a rate of 7 deg/mol % while growth rates decreased. For a given amount of supercooling, ΔTs, xBi increased with MoO3 flux content up to 12 mol %. A linear dependence of xBi on ΔTs, was observed for all MoO3 concentration levels. The anisotropy increased both with supercooling and with MoO3 flux concentration. The Kgu can be represented by a two-variable model, Kgu = A +BxBi + C4IIMs, where B increases from 143–213 kerg/cm3 per Bi atom per formula unit as the MoO3 content of the flux increases from 0–12 mol %. The density of the melt decreases with increased MoO3 content. A melt based on a 15 mol % MoO3 flux is less dense than gadolinium gallium garnet.

The visible-laser sublimation of CdTe, HgCdTe, CdS, and GaAs has been studied. A dynamic light guiding has been identified with an active feedback mechanism and is connected to the observation of 0.4 μm wide single-mode guiding structures during deep etching. The incipient stages of sublimation have been studied by mass spectrometry and are discussed in relation to diffusion mechanisms in the solid state.

Mechanical properties of GaAs crystals grown by the liquid encapsulated Czochralski technique and the boat technique are investigated by means of compression tests. Stressstrain characteristics of a GaAs crystal in the temperature range 400°–500°C are very similar to those of a Si crystal in the temperature range 800°–900°C. This seems to reflect the fact that the dislocation mobility in a GaAs crystal in the former temperature range is comparable to that in a Si crystal in the latter temperature range. Dislocations in GaAs crystals are found to be easily immobilized at an intermediate temperature due to gettering of impurities and/or impurity-point defect complexes. In comparison to a Si crystal, the surface of a GaAs crystal seems to involve irregularities that act easily as effective generation centers for dislocations. Thus the magnitude of the yield stress of an aged GaAs crystal is controlled by the surface condition and is not influenced by the density of dislocations involved in the crystal. The socalled steady state of deformation is realized in a GaAs crystal in the deformation stage after the lower yield point as in Si and Ge crystals. Dislocation distributions in a deformed GaAs crystal observed by transmission electron microscopy is very similar to those in deformed Si and Ge crystals.

Nanosecond resolution time-resolved visible (632.8 nm) and infrared (1152 nm) reflectivity measurements, together with structural and Z-contrast transmission electron microscope (TEM) imaging, have been used to study pulsed laser melting and subsequent solidification of thick (190–410 nm) amorphous (a) Si layers produced by ion implantation. Melting was initiated using a KrF (248 nm) excimer laser of relatively long [45 ns full width half maximum (FWHM)] pulse duration; the microstructural and time-resolved measurements cover the entire energy density (E1) range from the onset of melting (at ∼ 0.12J/cm2) up to the onset of epitaxial regrowth (at ∼ 1.1 J/cm2). At low E1 the infrared reflectivity measurements were used to determine the time of formation, the velocity, and the final depth of “explosively” propagating buried liquid layers in 410 nm thick a-Si specimens that had been uniformly implanted with Si, Ge, or Cu over their upper ∼ 300 nm. Measured velocities lie in the 8–14 m/s range, with generally higher velocities obtained for the Ge- and Cu-implanted “a-Si alloys.” The velocity measurements result in an upper limit of 17 (± 3) K on the undercooling versus velocity relationship for an undercooled solidfying liquid-crystalline Si interface. The Z-contrast scanning TEM measurements of the final buried layer depth were in excellent agreement with the optical measurements. The TEM study also shows that the “fine-grained polycrystalline Si” region produced by explosive crystallization of a-Si actually contains large numbers of disk-shaped Si flakes that can be seen only in plan view. These Si flakes have highly amorphous centers and laterally increasing crystallinity; they apparently grow primarily in the lateral direction. Flakes having this structure were found both at the surface, at low laser E1, and also deep beneath the surface, throughout the “fine-grained poly-Si” region formed by explosive crystallization, at higher E1. Our conclusion that this region is partially amorphous (the centers of flakes) differs from earlier results. The combined structural and optical measurements suggest that Si flakes nucleate at the undercooled liquid-amorphous interface and are the crystallization events that initiate explosive crystallization. Time-resolved reflectivity measurements reveal that the surface melt duration of the 410 nm thick a-Si specimens increases rapidly for 0.3E1 <0.6 J/cm2, but then remains nearly constant for E1 up to ∼ 1.0 J/cm2. For 0.3 < E1 < 0.6 J/cm2 the reflectivity exhibits a slowly decaying behavior as the near-surface pool of liquid Si fills up with growing large grains of Si. For higher E1, a flat-topped reflectivity signal is obtained and the microstructural and optical studies together show that the principal process occurring is increasingly deep melting followed by more uniform regrowth of large grains back to the surface. However, cross-section TEM shows that a thin layer of fine-grained poly-Si still is formed deep beneath the surface for E1<0.9 J/cm2, implying that explosive crystallization occurs (probably early in the laser pulse) even at these high E1 values. The onset of epitaxial regrowth at E1 = 1.1 J/cm2 is marked by a slight decrease in surface melt duration.

A previous bulk thermodynamic model, which used enthalpies of compound and alloy formation to predict metal/compound–semiconductor interface reactivity, is extended to include entropy. It is shown that, for most metals on CdTe, GaAs, GaSe, InP, and MoS2, solid-state reactions are energetically favored up to semiconductor dissociation temperatures and, consequently, entropy effects are minimal. Gold and silver, with their small enthalpies of metal–semiconductor anion compound formation, can be exceptions. Even here, the results for gold/III–V systems favor solid-state reaction at room temperature, but at higher temperatures entropy drives the reaction via vapor-phase production of the group V element. The binary phase bulk thermodynamic model is not sufficient to predict absolute reactivity, but can rank the reactivity of the various metal–semiconductor combinations successfully, as long as possible alloy formation is included. It is suggested that the limitations of the model are due to the specific effects of the interface.

Results from the x-ray photoelectron spectroscopy (XPS or ESCA), ion scattering spectroscopy (ISS or LEIS), and Fourier transform infrared spectrometry (FTIR) analyses are presented for unmodified and modified poly (methylmethacrylate)/poly (methacrylic acid) (PMMA/PMAA) copolymer films. Analyses of the unmodified PMMA/PMAA copolymer series, via ESCA, ISS, and FTIR, established the surface composition and functionality of the PMMA/PMAA copolymers before the H2O/Ar rf-plasma treatment was employed. The ESCA, ISS, and FTIR analysis of these modified PMMA/PMAA copolymers show that surface modification over a limited depth (50–200 Å) has occurred. The composition, bonding, and functionality changes of the surfaces are discussed. A two-step modification mechanism (surface reduction of the PMMA/PMAA copolymer followed by H2O adsorption) is proposed to interpret the spectroscopic results.

The ultrasonic transverse-wave velocity in the high-Tc metal-oxide superconductor YBa2Cu3O7−x between 275 and 4 K was measured. Above Tc the velocity shows normal behavior: during cooling, it displays a monotonic increase with decreasing slope. During cooling below Tc the shear modulus departs from normal behavior, increasing as ΔG /G = b [1 − (T/Tc)n, where n = 3. These results depart dramatically from those expected for a simple second-order normal-superconducting phase transition.

Log wavelength optical photons in a quanternary In1−x Gax AsyP1−y alloy are investigated based on the Green's function technique utilizing the concentration-dependent modified rigid ion model (MRIM). In order to obtain four-mode behavior in an A1−xBxCyD1−y quaternary alloy, formation of two cells AB and CD has been considered. In addition to the interactions betwen A, B, C, and D in their concentration ratios with a nonrandom ness parameter, the intercell and the intracell interactions are also taken into account. The results for the In1−xGaxAsyP1−y quaternary alloy are found to be in satisfactory agreement with the available experimental results.

The reactions between (100) GaAs and the near-noble metals Ni, Pd, and Pt have been investigated by application of high-resolution transmission electron microscopy (TEM), energy-dispersive analysis of x-rays in the scanning TEM and Rutherford backscattering spectrometry. Emphasis is placed on the evolution of the phase distributions, film compositions, and interface morphologies during annealing at temperatures up to 480°C. The first phase in the Ni/GaAs reaction is shown to have the nominal composition Ni3GaAs. Ternary phases of the type PdxGaAs are also found to be the dominant products of the Pd/GaAs reaction. Conversely, only binary phases result from the Pt/GaAs reaction. These observations are used to construct isothermal sections of the M-Ga-As thin-film phase diagrams. The behavior of a thin (1–2 nm) native oxide-hydrocarbon layer during the Ni/GaAs, Pd/GaAs, and Pt/GaAs reactions is also investigated. Only the Ni/GaAs reaction is noticeably impeded in some regions by this intervening layer. In contrast, the Pd/GaAs and Pt/GaAs reactions tend to mechanically disperse the native oxide layers.

An atomistic model for the dependence on interface orientation and velocity v of the solute partition coefficient k during rapid solidification is developed in detail. Starting with a simple stepwise growth model, the simple continuous growth model result is obtained for k(v) when the growth steps are assumed to pass at random intervals rather than periodically. The model is applied to rapid solidification of silicon. Crystal growth at all orientations is assumed to occur by the rapid lateral passage of (111) steps at speeds determined by the interface velocity and orientation. Solute escape is parametrized by a diffusion coefficient at the edge of the moving step and a diffusion coefficient at the terrace, far from the step edge. The model results in an excellent fit to data for the velocity and orientation dependence of k of Bi in Si.

High-Tc superconductivity is due to the action of two mechanisms: (1) plasmon mechanism, i.e., exchange of two-dimensional (2-D) plasmons and (2) strong electron-phonon coupling. The low dimensionality and the small value of the carrier concentration make the plasmon mechanism favorable. The small value of the coherence length leads to a unique opportunity to observe a multigap structure. The proximity effect can be used in order to increase Tc of A-15 compounds.

A compilation is made of the crystallographic mechanisms whereby (simulated) radwaste species are incorporated in the “synroc” phases zirconolite, perovskite, hibonite, and “hollandite.” From these data and consideration of the crystal chemical criteria of valence and effective ionic radii, the most probable host phases for transuranic isotopes are identified. The distinction is drawn between incorporation of radwaste species as dilute homogeneous, continuous solid solutions and as heterogeneous, noncontinuous solid solutions. It is shown that compositional variations at the nanometer level are frequently accompanied by the generation of new interstices within extended defects, which are suitable for the location of radwaste. Nuclides that are unstable towards beta and gamma decay lead to transmutation-induced changes in stoichiometry. Crystallochemical mechanisms that minimize structural disruption during the formation of radiogenic species are discussed. Thermally promoted recovery of metamict phases, which were rendered aperiodic by direct atomic displacements of alpha-recoil nuclei, are examined in terms of recrystallization via the hierarchial arrangement of space groups. An evaluation is made of the hydrothermal durability of synroc phases under conditions likely to be experienced by the wasteform should the repository be breached by groundwaters shortly after disposal.

A phenomenological model is developed to treat defect properties and defect chemistry in melt-grown GaAs. Defects are characterized by their charge and their stoichiometric signature (local deviation from stoichiometry); no specific atomic structure is assumed for them. Good fits to existing data are obtained for the room-temperature concentrations of the midgap donor (EL2), an unknown double acceptor, electrons, and holes as functions of melt composition. In obtaining these fits the role and importance of the (unknown) GaAs solidus is emphasized and it is demonstrated that many popular models of EL2 are consistent with the data analyzed. The model is extended to account for the observed decrease of EL2 concentration with increasing boron or silicon doping concentration, and here again attention is clearly focused on certain unknown information concerning the crystal formation process. Fundamental parameters in the model whose values are estimated through fits to the data include (1) the equilibrium constant in the defect reaction between EL2 and the double acceptor, (2) the equilibrium constant in the defect reaction between EL2, BAs and BGa, (3) the fractions of boron and silicon taken up on Ga sites during the crystal formation process, and (4) the proportionality factor between the melt composition and the crystal composition.

Spark erosion is a method for producing fine powders of metals, alloys, semiconductors, and compounds. The technique involves maintaining repetitive spark discharges among chunks of material immersed in a dielectric liquid. As a result of the spark discharge there is highly localized melting or vaporization of the material. The powders are produced by the freezing of the molten droplets or the condensation and freezing of the vapor in the dielectric liquid. Since the powders are quenched in situ, they may be extremely rapidly cooled. Particles can be produced in sizes ranging from 5 nm to 75 μm. The average powder size and production rate depend on the power parameters, material used, and the dielectric liquid.

Thin-film interactions have been increasingly important to various aspects of electronic technologies, including devices and packaging. Extensive outdiffusion and alloy formation, for example, can be detrimental to the yield and reliability of the parts fabricated. Understanding such interactions, and their dependence on various factors, continues to be a challenge to thin-film scientists. Several aspects related to thin-film interactions are described in this paper: a review of the ambient effects that provides an understanding of the basic reaction mechanisms at the interface; an illustration of concerns upon choosing a diffusion barrier layer, and reaction across such a layer; and the effect of undesired outdiffusion on the solder spread related to joining.

The utilization of transformation toughening has hitherto been restricted to increasing the fracture resistance of polycrystalline ceramic materials. Although a number of investigators have attempted to extend the concept to toughening glasses and glass ceramics with tetragonal zirconia, no successful reports have been published. It is argued that the approaches employed are inevitably limited primarily because they do not take into account the necessity of nucleating the tetragonal-to-monoclinic transformation away from the crack tip itself. By concentrating on the nucleation event and using standard ceramic processing techniques, it has been demonstated that transformation toughening can be used to increase the toughness of glass-ceramic materials, and this approach is illustrated by increasing the fracture toughness of a cordierite glass ceramic.

The optoelectronic properties of the II-IV-V2 semiconductor ZnSnP2 are studied as a function of the cooling rate of the crystal growth melt. The structure of the material, as studied by x-ray diffraction, is seen to change from chalcopyrite to sphalerite as the cooling rate is increased. Photoelectrochemical measurements show that the bandgap of the material decreases from 1.64 eV for the chalcopyrite to 1.25 eV as the structure approaches sphalerite. The 119Sn Mössbauer spectroscopy shows both an isomer shift and a broadening of the 119Sn resonance as a result of new tin environments produced by disordering of zinc and tin sites at the faster cooling rates. The 31P solid-state nuclear magnetic resonance spectroscopy clearly shows new resonances associated with the additional phosphorus environments produced by metal site disordering. A model based on zinc and tin site exchange with the introduction of compensating donor and acceptor states is proposed and discussed.