Fabrication of NiO bicrystals having Σ5 (310) and Σ13 (510) coincidence-site tilt boundaries was successfully carried out by a CVT (Chemical Vapor Transport) method. The CVT method was a very advantageous way to grow ultra pure crystals since it preferentially transported NiO from the source pellet to the substrate by reaction with a HCl carrying gas. Single crystal MgO was used as a substrate for epitaxial growth of NiO as the readily available MgO crystals have only a 1% lattice mismatch with NiO. Moreover, MgO is soluble in acids while NiO is not. This permitted removal of the substrate crystal after growth to provide a free-standing NiO crystal. Using two single crystals of MgO with the desired tilt orientation as a substrate, NiO bicrystals were fabricated at growth rates greater than 100 μm/hour at 1,400K using 250 torr of HCI(g) as a carrying agent. The purity of the epitaxial NiO crystals was determined by mass spectrometry and neutron activation analysis. The grain boundary in the bicrystals is exactly perpendicular to the (100) growth surface. Highly-reflective facets along the growth direction suggest high mechanical quality. High-resolution transmission electron microscopy of the Σ13 boundary revealed structure at the atomic scale that provided no evidence for segregated phases.

Interphase boundaries and orientation relationships for yttria - yttrium-aluminum monoclinic and yttrium-aluminum monoclinic - yttrium-aluminum perovskite eutectics were observed by standard and high resolution TEM techniques. Three and five orientation relationships were found for each system, respectively. These eutectics all had a monoclinic phase and therefore had little potential for high symmetry overlap. In many cases low index planes with similer spacings or spacing multiples were parallel. However, presence of a monoclinic phase made definition of a three-dimensional low index near-CSL very difficult, so a combination of planes corresponding to reciprocal-space directions and zones corresponding to real-space directions were often needed for a geometric description of the orientation relationship. In general, two planes and the real-space direction corresponding to the zone for these planes described the orientation relationships. The disregistry between reciprocal-space coincidence sites was not localized by dislocations large enough to be visible.

The specimens of Yttria Stabilized Zirconia(3Y-TZP) were bonded by a diffusion process. The microstructural evolution at the bonded interfaces was examined for the bonding conditions. We confirmed that above general sintering temperature(1500 °C), grain coarsening, which enhances the size fluctuation at the bonding interface, not only eliminates free surfaces but also is the main mechanism of bonding. In order to enhance the diffusion rate at the bonding interface, Ceria was added as a dopant, and grain boundary undulation was examined. We found that the bonding characteristics were improved by the Ceria doping. Specimens with an undulating bonded interface exhibited transgranular fracture, while specimens with a straight interface showed intergranular fracture. The undulation at the bonded interface is suggested to improve ceramic to ceramic bonding.

When a 6H-SiC single crystal is deformed under indentation or uniaxial compression in orientations not favorable for the activation of the 1/3[1120](0001) easy glide system, the secondary slip system is activated. Additionally, for low- temperature deformations, “kinks” and/or micro-cracks form in the crystal. In this paper, experimental results on relatively lowtemperature compression and indentation tests of single crystal 6H-SiC, and the microstructure of the deformed crystals, are presented. Based on the results, the secondary slip system in 6HSiC has been determined to be 1/3[1120](1100), which may actually be a combination of alternate glide of 1/3[1120] dislocations on the (1102) and (1102) planes. Further, dislocation mechanisms for the nucleation of prism-plane and basal-plane cracks, and for the process of kinking, in deformed 6H-SiC are proposed.

Using facing target sputtering, crystalline magnetoplumbite-type barium ferrite (BaFe12O19 or BaM) thin films have been prepared in-situ at a substrate temperature of 640°C without postdeposition annealing. BaM thin films grow randomly if they are directly deposited onto Si or thermally oxidized Si substrates. However, deposited onto a sputtered ZnO layer (∼230Å) on Si substrates, BaM thin films show excellent c-axis out-of-plane texture with a 0.2° c-axis dispersion angle, as indicated by X-ray diffraction (XRD) study. Cross section transmission electron microscopy (TEM) reveals that the textured films epitaxially grow on a transition layer, which is formed between BaM and ZnO. No direct epitaxial relation between BaM and ZnO was observed. This transition layer is identified by TEM and XRD as ZnFe2O4, which, from a structure point of view, reduces the lattice mismatch between BaM and ZnO, and also enhances the c-axis out-of-plane epitaxial growth.

Fabrication of ultra smooth films, free of micro-shorts, is essential to the development of High Temperature Superconducting (HTS) thin film devices. One such example is a SNS junction consisting of two HTS layers separated by a uniformly smooth continuous barrier material. Other schemes under consideration require multilayer structures of up to 5 - 7 epitaxially grown layers of complex oxide material. Successful fabrication of such devices necessitates understanding the epitaxial growth of polycrystalline oxide films on polycrystalline film templates. Toward this end we have developed a set of deposition parameters that produce high quality epitaxial insulating layers suitable for HTS device applications. All films in this study were grown by off-axis RF magnetron sputter deposition. LaAlO3 films were deposited over MgO grown YBa2Cu3O7 (YBCO) c-axis thin films at temperatures ranging from 200 to 700C and on virgin substrates at 600C. Atomic Force Microscopy, eddy current measurements, and x-ray diffraction techniques were used to monitor the effect of growth conditions on the resulting film crystallinity, nanostructure, and electrical properties.

Ex-situ interrupted growth characterization of these materials has yielded new insight into the processes that control the growth mechanism and resulting microstructure. All films were polycrystalline. Below 600C, LaAlO3 films were not epitaxial while films grown at 650C showed some <200> orientation. The shape of the underlying YBCO film is most clearly evident for the film grown at 400C. Surface roughness depended on the appearance of crystals on the film surface. The superconducting properties of the underlying YBCO film required O2 annealing prior to deposition of the LaAlO3 layer.

Epitaxial MgO layers were grown on cleaved NiO(100) single crystal surfaces. The less than 1% lattice mismatch between MgO and NiO allows almost ideal epitaxy of MgO at 100°C. The epitaxial films were created by dosing Mg onto stoichiometric NiO(100) both in ultra-high vacuum (UHV) and in an O2 atmosphere (5×10−7 Torr). Chemical interactions at the resulting interfaces were studied using XPS. When Mg is dosed onto NiO(100) in UHV, MgO forms by interacting with oxygen anions in the NiO substrate thereby reducing the nickel cations. Metallic Mg layers begin to form upon subsequent dosing. When Mg is deposited in O2, epitaxial MgO(100) layers grow to a thickness of at least 50Å as confirmed by in situ RHEED and LEED observations. Negligible intermixing between the MgO and NiO is observed during growth at 100°C and on subsequent annealing in UHV up to 600°C.

We have grown by molecular beam epitaxy (MBE) structurally coherent layers of MgO and a random bcc alloy of 70% Cr and 30% Mo to which MgO is lattice matched. Specimens werecharacterized by means of reflection high-energy electron diffraction (RHEED), x-ray photoelectron spectroscopy and diffraction (XPS/XPD), transmission electron microscopy (TEM), and atomic force microscopy (AFM). These systems exhibit excellent long- and shortrange crystallographic order, as well as nearly perfect structural coherence across the interface.

The deposition of MgO on the Fe(001) surface has been carried out using electron beam evaporation. MgO is observed to grow epitaxially with a 45° rotation between the Fe(001) and MgO(001) unit cell axes. Oscillations in the intensity of the RHEED specular beam are observed at room temperature showing that growth is two-dimensional. The relaxation of the in-plane lattice parameter during the growth at room temperature has been investigated in-situ by measuring the position of the RHEED streaks and ex-situ with GIXD experiments. Pseudomorphic growth is observed up to about five monolayers. Then the in-plane lattice parameter starts to evolve towards the MgO bulk parameter. HREM shows that the relaxation of MgO occurs via the generation of 1/2<011> misfit dislocations which are non-uniformly spaced at the Fe/MgO interface.

The microstructure of Ta2N thin films deposited by d.c. magnetron sputtering on (1120) surface of Al2O3 is investigated using transmission electron microscopy. The effects of exposing the thin film structure to a 600°C air environment are also explored. It will be shown that under the standard deposition conditions, stresses exist in the thin film structure which leads to the formation of a textured structure in the as-deposited Ta2N. Exposure of the thin film structure to an air environment transforms the Ta2N to Ta2O5 in the orthorhombic structure. In addition, evidence for a epitaxial relationship between the Ta2O5 and Al2O3 will be presented.

Time resolved optical reflectivity (TRR) and Rutherford backscattering spectrometry (RBS) and ion channelling methods have been applied to determine the crystallization kinetics of Fe-doped A1203 in the temperature range of 900-1050°C. Amorphous A1203 films, approximately 250 nm thick and with Fe cation concentrations of 0, 1.85, 2.2 and 4.5%, were formed by e-beam deposition on single crystal, [0001] oriented, A1203 substrates. Annealing was performed under an oxygen ambient in a conventional tube furnace, and the optical changes which accompany crystallization were monitored, in situ, by TRR with a 633nm wavelength laser.

Crystallization is observed to proceed via solid phase epitaxy. An intermediate, epitaxial phase of -γ-Al203 is formed before the samples reach the ultimate annealing temperature. The 5% Fe-doped film transforms from γ to α-A1203 at a rate approximately 10 times that of the pure A1203 film and the 1.85% and 2.2% Fe-doped films transform at rates between these two extremes. The Fe-dopants occupy substitional lattice sites in the epilayer. Each of the four sets of specimens displays an activation energy in the range 5.0±0.2eV for the γ,α phase transition.

The stability of MoSi2, films with respect to mass loss at high temperature has been investigated in vacuum and dry air environments at temperatures up to 1300° C. Samples were sputter deposited films of approximate composition MoSi3, on sapphire substrates. Post heat treatment analysis by X-ray diffraction, scanning electron microscopy, and electron microprobe analysis indicated that the films recrystallized, and that phase separation of the excess silicon from the MoSi2, occurred early in the heating process. With continued heating, silicon was lost from the films by evaporation, leading to the conversion of the films to Mo5Si3. The rate of mass loss was much less in the air environment due to the formation of a SiO2, layer which served as a diffusion barrier to silicon. Evidence of a reaction along the MoSi2,/A12O3 interface was observed visually, but could not be detected chemically.

Single crystal films of n-type 3C-SiC were hydrothermally processed at pressures ranging from 10 to 70 MPa at 550°C. To study the effects of initial thin film microstructure on hydrothermal processing, two different samples of CVD-grown SiC were studied: one, 200 nm thick, contained low angle boundaries and a high density of planar defects; the other, 3500 nm thick, was planar and contained relatively few defects. Raman Spectroscopy, X-Ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) were used to study the chemistry and microstructure of the SiC material both before and after hydrothermal treatment. This study reveals that low temperature (T=550°C) oxidation of single crystal epitaxial SiC is possible but that the resulting oxide film microstructure is strongly dependent on the initial film microstructure and oxidation is greatly enhanced along low angle grain boundaries and on planar defects.

Oxides grown on Zr-20Nb were characterized by Raman Spectroscopy (RS), X-Ray Diffraction (XRD) and Transmission Electron Microscopy (TEM). These oxides were steamformed at 400°C, water-formed at 360 °C and at 300 °C, and air-grown at 400°C. For the oxides grown after relatively short exposures at 360°C and at 400°C, Raman spectra revealed broad peaks at 260 and 660 cm− indicating a crystal structure with high symmetry. Comparison with reference Raman spectra of cubic (c), tetragonal (t), and monoclinic (m) ZrO2 suggested that the oxide was predominantly nearly-cubic (tetragonal with c/a ratio ≈ 1), with minor amounts of moxide. The tetragonality is found to be consistent with TEM analyses and XRD results which showed the presence of a doublet near 2θ ° 74°. The crystal structure in the short-term exposed oxides is interpreted in terms of a tetragonal distortion arising from the displacement of oxygen atoms within the cubic ZrO2 crystal structure. For oxides grown after longer periods of exposure at 300°C and at 400°C, RS and XRD indicate increased amounts of m-oxide.

Growth of oxide microcrystals at the edge of nickel grains could be observed using highresolution microscopy. Three types of samples were examined: a nickel-cermet material, and pure annealed nickel, both ion-beam milled; and a standard electropolished nickel foil. Microstructural features, such as crystallite size, facets, orientation relationship and lattice parameter are described.

Diamond films with high preferential orientation (111) on silicon (100) crystalline orientation substrates had been obtained by hot-filament chemical vapor deposition (HFCVD) method. X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and high-resolution cross-sectional transmission electron microscopy (HREM) are used to characterizate the structure and morphology of the synthesised diamond films. Diamond (111) plans had been local grown epitaxially on the Si(100) substrate observed by HREM. SEM photographes show that plane diamond crystals have been obtained.

Electron Spectroscopic Imaging (ESI) in an energy filtering TEM is a new analytical technique which allows one to obtain two-dimensional elemental distribution images. In the present paper the detection limits of the new technique will be discussed. Si3N4 ceramics with different thicknesses of the amorphous oxide grain boundary layers have been chosen as a model system. Quantitative results have been obtained on three different energy filtering instruments and will be compared with the results of theoretical calculations. The application of ESI for the mapping of near edge fine structure will be discussed.

The interfacial electronic structure, presented as the interband transition strength Jcv(ω) of the interatomic bonds, can be determined by Kramers Kronig (KK) analysis of vacuum ultraviolet (VUV) reflectance or spatially resolved valence electron energy loss (SR-VEEL) spectra. For the wetted interfaces in Si3N4, equilibrium thin glass films are formed whose thickness is determined by a force balance between attractive and repulsive force terms. KK analysis of Jcv(ω) to yield ξ(ξ) for the phases present, permits the direct calculation of the configuration-dependent Hamaker constants for the attractive vdW forces from the interfacial electronic structure.

Interband transition strengths and full spectral Hamaker constants for Si3N4 samples containing a SiYA1ON glass have been determined using SR-VEELS from grains and grain boundaries and compared with results from bulk VUV spectroscopy on separate samples of glass and nitride. The At2, Hamaker constant for Si3N4 with glass of the bulk composition is 8 zJ (zJ = 10−21 J) from the more established optical method. The EELS method permits the determination of vdW forces based upon actual local compositions and structure, which may differ noticeably from bulk standards. Current results show that full spectral Hamaker constants determined from VUV and SR-VEEL measurements of uniform bulk samples agree, but care must be taken in the single scattering and zero loss subtraction corrections, and more work is ongoing in this area. Still the results show that for the grain boundary films present in these polycrystalline Si3N4 samples the glass composition is of lower index of refraction. This can arise from increased oxygen content in the intergranular glass and leads to an increased value of the Hamaker constant (24 zJ) determined in situ from the SR-VEELS of a particular grain boundary film.

Images of the YBa2Cu3OT7−x (YBCO) / BaF2 interface obtained with a scanning transmission electron microscope (STEM) show a relatively wide (∼40 Å) band of contrast at the interface, despite attempts to orient the interface plane parallel to the beam. Simulation of STEM annular dark field (ADF) images of several different interface geometries suggests that strain is the dominant cause of this wide band of contrast at the interface. In particular, it is the dislocations which run normal to the beam direction which make a significant contribution to the width of the contrast band in the case of this YBCO / BaF2 interface. A line scan taken across the interface using energy dispersive X-ray spectrometry (EDX) suggests that there is no significant Ba concentration at the interface, indicating that Z-contrast is not the primary contrast mechanism in these ADF images of the YBCO / BaF2 interface.

Spatially resolved electron energy loss spectroscopy analysis has been conducted on planar inversion domain boundaries in aluminum nitride. The defects were found to contain 1.5 monolayers of oxygen, in agreement with the most recent structural model of Westwood. From variations in near-edge structure, the local atomic environments of both oxygen and aluminum are compared with α-A1203, γ-A1203 and γ-AION standards. Based upon this study the stnrcture of the inversion domain boundary is found to resemble that of the cubic γ-AION spinel, and eliminates from consideration those structural models based upon ai-Al203. Furthermore, quantification of the shape resonances provided Al-O bond-length data from the inversion domain boundary interface. These distances closely agree with the Youngman Model that has recently been further refined by Westwood et al.