Thin-film superconductors of TlBaCaCuO (TBCCO) and YBaCuO (YBCO) were fabricated via an electrodeposition process. The precursors of the superconducting TBCCO films were codeposited at a constant potential of −4 V onto a silver-coated SrTiO3 substrate. The YBCO precursors also were codeposited but under pulsed-potential conditions (in order to improve the film morphology) and onto a silver-coated MgO substrate. The pulsed-potential cycle consisted of 1 s at −4 V followed by 1 s at −1 V. The post-annealed TBCCO film showed zero resistance at about 102 K and critical current density at 76 K of 20 000 A/cm2 in zero magnetic field and 5000 A/cm2 in a 10 kOe field parallel to the film plane. The post-annealed YBCO film showed zero resistance at approximately 80 K and critical current density of 5160 A/cm2 at 4 K in zero magnetic field.

In situ electrical conductivity measurements were employed to study the kinetics of decomposition of YBa2Cu3O7−x in flowing 5% CO2/95% O2 atmosphere at 815 °C. Three regimes could be observed in the decay of the conductivity with time, interpreted as corresponding to nucleation over the initial 5–10 min, rapid formation of Y2Cu2O5, BaCO3, and CuO between 10 min and 1 h, and finally transition to the formation of Y2BaCuO5, BaCO3, and CuO at longer times. The absence of dispersion in impedance measurements as a function of frequency together with the gradual decay of conductivity (roughly corresponding to the remaining volume fraction of YBa2Cu3O7−x) indicates that not all grain boundaries are involved in the decomposition process.

Oxygenation characteristics in high-density YBa2Cu3Ox ceramics with a relative sintered density ≥97%, which were produced by hot-pressing to have various oxygen contents as-hot-pressed, have been investigated. The results indicate that the oxygenation characteristic in the materials was strongly affected by their oxygen content before oxygenation; that is, the attainable oxygen content (directly connected with the superconducting temperature Tc) of the materials after oxygenation increases with a decrease in their oxygen content before oxygenation. Oxygen annealing at 500 °C for 24 h dramatically increased the oxygen content of an YBa2Cu3Ox with x = 6.08 before the oxygen annealing up to 6.90, while the oxygen content of an YBa2Cu3Ox ceramic with x = 6.32 before oxygenation rose only to a value of 6.61 after the same oxygen annealing. This newly observed phenomenon on the oxygenation characteristic in the present materials may provide an idea for improving the superconducting properties in high-density YBa2Cu3Ox ceramics.

Microstructures of two MPMG processed YBaCuO materials with and without Y2BaCuO5 (211) inclusions were investigated by transmission electron microscopy. Using the MPMG process, it is possible to change the quantity of the 211 inclusions in the YBa2Cu3O7 (123) matrix. We prepared two YBaCuO samples with 0 and 30 vol. % 211 and with respective critical current density values of 2000 and 30 000 A/cm2 at 77 K and 1 T (magnetic field parallel to the c-axis). As possible pinning centers, we found stacking faults in the 123 matrix. However, we observed no appreciable change in their number and structure by introducing the 211 inclusions. Therefore, the difference in Jc values can be attributed to the 211 inclusion itself.

Thin films of YBCO and thallium-based superconductor compounds have been deposited with very similar polycrystalline structures. The critical current densities carried by the YBCO films are much lower than measured in the thallium films (>103, as opposed to >104 A/cm2). Grain boundaries in these films have been studied to correlate microstructure with the measured electrical properties. High defect densities and frequent microcracking have been observed at and around the boundaries in the YBCO films, but these defects are not seen in the thallium-based films. We suppose that this difference is because of the higher differential thermal expansion stresses set up in YBCO during cooling. Our observations imply that eventual application of polycrystalline superconducting films prepared by an ex situ process is more likely for the thallium-based materials than for YBCO.

Superconducting Tl–Ca–Ba–Cu–oxide films have been prepared on yttria stabilized zirconia substrates via the reaction of Tl2O vapor with precursor Ca–Ba–Cu–oxide films prepared by the spray pyrolysis of a solution of the metal nitrates. The vapor reaction process, evaluated in both air and oxygen ambients, was carried out in a two-zone reactor which permitted the independent control of the temperatures of the sample and of a boat containing thallium oxide. Sample temperatures of 865–905 °C and boat temperatures of 775–870 °C were investigated. X-ray diffraction analysis of the best samples, which were prepared in an oxygen ambient at sample temperatures of 895–900 °C and boat temperatures of 805–810 °C, revealed the presence of a highly oriented Tl2Ca2Ba2Cu3O10+y phase with a trace of the Tl2CaBa2Cu2O8+y phase. FWHM's of ∼2°θ were obtained in x-ray rocking curve analyses of the oriented 2223 phase. Tc (0) values of 95–105 K were measured for the better samples, and a zero field critical current density of 28 800 amps/cm2 was measured at 77 K for the best sample. SEM micrographs taken of the highest Jc samples reveal a highly textured structure consisting of platelike crystals.

Superconducting Bi1.84Pb0.34Sr2.03Ca1.9Cu3.06Oy thick films were prepared on MgO substrates by screen printing with the powder consisting almost entirely of the 110 K phase. The thick film sandwiched between the two MgO substrates was then hot-pressed in air under various conditions. The thickness of the film was 20–40 μm. The degree of grain orientation was quantitatively evaluated through the image analysis on the SEM micrographs for the chemically etched cross sections of the samples. The degree of grain orientation and the critical current density (Jc) increased with increasing hot-pressing temperature. When hot-pressed at 855 °C under a constant pressure of 500 kg/cm2 for 270 min, the Jc had a maximum value of 9500 A/cm2 (77 K, 0 Oe), and the critical temperature was 110 K. When the hot-pressing pressure was higher than 200 kg/cm2, the degree of grain orientation was almost independent of hot-pressing pressure. Nevertheless, the Jc increased with increasing hot-pressing pressure. The relationship between the magnetic field dependence of Jc and hot-pressing conditions was examined.

Gas-atomized spray deposition involves the creation of a spray of droplets by a gas atomizer and the consolidation and solidification of these droplets on a substrate. The present paper describes an investigation of the fundamental characteristics of heat transfer and solidification during spray deposition. Spray deposition was used to manufacture Sn-15 and 38 wt. % Pb preforms using atomizer-substrate distances of 180 and 360 mm, gas flow rates of 2.5 and 3.4 g/s, and melt flow rates of 61 and 35 g/s. Analytical and numerical models were developed to predict the thermal history of the spray deposit for a range of deposit-substrate heat transfer coefficients. A deposit-substrate heat transfer coefficient of ∼104 W m−2 K−1 was determined by comparing measured and calculated spray-deposit thermal histories both during and after spray deposition. Microstructural analysis of transverse sections of the spray deposits revealed maximum values of spray-deposit density and cell/grain size at specific distances from the deposit-substrate interface. The distance between the density and cell/grain-size maxima and the deposit-substrate interface increased from 0.9 to 10 mm for Sn–15 wt. % Pb and from 2.6 to 11.3 mm for Sn–38 wt. % Pb as the atomizer-substrate distance was increased from 180 to 360 mm and the melt to gas mass flow rate ratio was decreased from 24 to 10. The origin of these microstructural features is described in terms of heat transfer during spray deposition.

A theory of vacancy formation in Cu3Au-type ordered fcc alloys is presented. The present theory, which is based on the pairwise bonding model, is found to be in good agreement with the experimentally observed vacancy properties in ordered Cu3Au and Ni3Al. Various shortcomings in the previous theoretical calculations have also been identified.

This paper presents a geometrical description of aperiodic grain boundaries within the framework of a quasiperiodic lattice. Experimental evidence is given in support of a structural unit model of quasiperiodic [100]45°twist and [100]45°twist plus tilt grain boundaries in aluminum.

A new diffraction imaging technique for the characterization of polycrystalline materials is proposed and applied to obtain direct information about individual grains and their size and shape distributions and, in turn, strains in these materials. Unlike traditional powder diffractometry, where divergent and focusing x-ray optics are essential to collect information from an ensemble of grains, the nearly parallel and monochromatic beam available from a synchrotron x-ray source is employed to observe and measure diffraction images from individual grains and component particles in consolidated materials prepared by various processes. Images can be recorded by traditional methods, such as film and pulse counting detectors, but modern image detectors, such as charge coupled device (CCD) detectors and image analyzers, make the proposed imaging technique more practical. Unlike traditional diffractometry, this new technique provides the ability to measure shape, size, and strain without model based analyses. The spatial distribution of strain within individual grains, displayed as a diffraction image (topograph), indicates the presence of defects, such as dislocations, subgrain boundaries, and precipitates, and sheds new light on the origins of residual strains (stresses) in industrial materials. The resolution of the imaging system used is limited to grains ∼10 μm or larger due to diffraction broadening (∼20” from the size effect) and the resolution of the recording medium.

Amorphous iron and titanium-based alloys containing various amounts of chromium, phosphorus, and boron exhibit high corrosion resistance. We report some physical properties of Fe and Ti-based metallic alloy films deposited on a glass substrate by a dc-magnetron sputtering technique. The films were characterized using differential scanning calorimetry (DSC), stress analysis, scanning electron microscopy (SEM), x-ray diffraction (XRD), secondary ion mass spectrometry (SIMS), electron microprobe, and potentiodynamic polarization technique.

The nature and rates of erosion of diamond, graphite, and diamond-like carbon (DLC) films exposed to oxygen plasmas were evaluated by comparison of surface morphological changes and weight losses. The RF plasma oxidation at ambient temperature caused severe etching of graphite and DLC specimens, while causing only minor damage to diamond film surfaces. The results suggest that erosion by low energy ions is very selective to the sp2 and sp states compared to the sp3 state of carbon. The selectivity of etching by oxygen plasma is significant, as compared to what has been reported for hydrogen in atomic and ionic states, or for oxidation at elevated temperatures in molecular oxygen. These observations have significant implications to the synthesis of diamond films by chemical vapor deposition (CVD) as well as to the application of diamond film coatings on graphite or other substrates for protection against energetic atomic oxygen prevailing in the low earth orbits (LEO).

An early stage of diamond growth in hot-filament chemical vapor deposition on silicon substrates was examined by the high resolution electron microscope. “Pretreatment” of the substrate surfaces by diamond powder abrading was found to plant diamond seed crystals with a density of as high as 1011/cm2. These crystals provide sites for subsequent growth of diamond films. The CVD grown diamond particles tend to be cuboctahedra. Smaller particles in nanometer size are faultless, but larger ones of several tens of nanometers develop crystal faults. Some of them may originate from the seed crystals. Degradation of the diamond seed crystals due to the electron beam irradiation is discussed in terms of fabrication of diamond film.

Since copper has some advantages relative to aluminum as an interconnection material, it is appropriate to investigate its mechanical properties in order to be prepared in advance for possible problems, such as the cracks and voids that have plagued aluminum interconnect systems. A model previously used to interpret the behavior of aluminum films proves to be, with minor modification, also applicable to copper. Although the thermal expansion of copper is closer to that of silicon and, consequently, the thermally induced strains are smaller, the much larger elastic modulus of copper results in substantially higher stresses. This has implications for the interaction of copper lines with dielectrics.

The stability of selectively formed TiSi2 films on single crystal and polycrystalline silicon layers at elevated process temperatures is reported. Extensive electrical and analytical studies were performed to understand the high-temperature stability of TiSi2 films as a function of (i) substrate dopant concentration, (ii) titanium silicide thickness, (iii) silicide formation sequence, and (iv) silicide post-processing steps. It is shown that all four process variations have a profound influence on the thermal stability of TiSi2 films. It is observed that titanium silicide films formed on single crystal silicon are stable at higher processing temperatures compared to those formed on polysilicon substrates under similar conditions. The degradation of high-temperature stability of TiSi2 films on polycrystalline silicon can be related to increased number of defects and grain boundaries. It is shown that TiSi2 films can be successfully used in silicon integrated circuit applications where the post-silicide processing temperatures do not exceed 1000 °C.

The relative energies of the related C11b, C40, and C54 crystal structures of group IV–VII transition-metal disilicides are obtained by ab initio self-consistent band-structure calculations using the augmented-spherical-wave (ASW) method. The structural energy differences among these three structures correlate strongly with d-band filling, with C40 being stabilized relative to C54 and C11b relative to C40 as the transition-metal d-electron count increases. The C40/C11b energy difference is <0.05 eV/atom only for CrSi2 and MoSi2. Relative C11b/C40/C54 energies are similar in magnitude to those obtained in previous studies of L12/D022/D023 competition in transition-metal aluminides.1,2 Calculations of the C49/C54 energetic competition are inaccurate; the differences in atomic coordination in these two structures are probably too large for the computational method to handle accurately. The total-energy results are interpreted by a detailed analysis of the electronic density-of-states (DOS) distributions. The stable structures do not correlate as strongly with DOS effects in the vicinity of the Fermi level as in the aluminides.

Reactions between manganese thin films and silicon substrates, annealed at relatively low temperatures (<430 °C), have been systematically investigated. Three phases, i.e., Mn3Si, Mn5Si3, and MnSi, were formed through a layered growth process. The formation sequence for these silicides was Mn3Si, MnSi, and then Mn5Si3. The unusual phenomena of coexistence of these three phases and simultaneous growth of two phases (MnSi and Mn5Si3) were also observed. A model has been proposed to explain the growth behavior. The formation sequence of Mn3Si, MnSi, and then Mn5Si3, and simultaneous growth of MnSi and Mn5Si3, can be explained by considering both thermodynamic and kinetic effects. Only those reactions that are thermodynamically allowed and kinetically preferred can take place. Kinetic preference is determined by the composition in the reaction region, which is controlled by the diffusion flux of the moving reactant. The proposed model is also compared with existing models.

Solid-state amorphization reaction (SSAR) between GaAs and Co thin films was investigated by transmission electron microscopy and Auger electron spectroscopy. Upon annealing of GaAs/Co thin-film couples at 260–300 °C, an amorphous phase was observed to form. Annealing at higher temperatures or for longer times led to the crystallization of the amorphous phase into a supersaturated CoAs solid solution phase with the B31 structure. Amorphization is attributed to the rapid diffusion of Co in the rather open GaAs structure. In order to consider the thermodynamic driving force for amorphization and subsequent crystallization, the phase diagram of CoGa–CoAs was investigated using DTA and metallography. The pseudobinary system was modeled thermodynamically to yield relative stability data for the various phases between GaAs and Co. These data were used to rationalize the amorphization process.

Point-defect-mediated atomic diffusion in GaAs and AlxGa1−xAs–GaAs superlattices is examined thermodynamically by focusing on activation enthalpy of diffusion. Through a review of available experimental results of impurity diffusion of Si, Zn, and Be, their diffusion phenomena are discussed by taking the characteristics of column-III-site-related point defect, such as Ga vacancy and arsenic-antisite, into consideration. It is suggested that Zn and Be diffusion should be mediated by As-antisite defects. On the other hand, Si diffusion is mediated by either Ga vacancy or As-antisite, depending on the growth method of materials and diffusion conditions. It is argued that As-antisite should be a mediator of diffusion in As-antisite-rich materials and with using As-rich diffusion source under p-type conditions. Cation self-diffusion or interdiffusion is also discussed in the same manner. Impurity-enhanced layer-disordering phenomena are examined by considering the reduction of defect energy of Ga vacancy and As antisite under n-type and p-type conditions, respectively. Beryllium enhanced and suppressed interdiffusion (cation self-diffusion) in MBE-grown AlxGa1−xAs–GaAs superlattices are interpreted in view of point-defect-mediated cation diffusion on the basis of the Fermi-energy dependence of point defect. In order to explain the phenomena, crystal-growth methods and surface-localized point defects which is responsible for Fermi-level stabilization are taken into consideration.