We report experience in our laboratory with the growth of epitaxial compounds using molecular beam epitaxy. These include the L12 structures, Laves phases, perovskite, bixbyite and spinels, with complicated structures and up to 80 atoms per cell. In many cases the growth takes place with surprising ease, even though the complexity of the process verges on self assembly. The paper describes diffusion measurements in epitaxial MgO directed towards the determination of impurity content and the level of structural defects. The synthesis of ‘ultrapure’ epitaxial MgO, and the resulting properties is described.

MgO is used as an optical isolation layer for waveguides epitaxially grown on silicon. The crystalline perfection of MgO is a critical issue because it serves as a substrate for the single crystal, perovskite guiding layer. Imperfections in the MgO will result in imperfections in the guiding layer and lead to large optical losses for the planar waveguide structure. We show that the most common defect to form in thin films of MgO are twin boundaries between {111}-type planes. The highest density of twins is observed when (001) MgO is grown directly on silicon/MgO interlayers containing barium. Twinning is shown to accommodate the large size of barium impurities incorporated in the MgO films through the formation of internal grain boundaries and open surfaces other than the growing (001) of MgO.

Advanced thin film technology based on laser MBE has enabled us to control the molecular layer-by-layer epitaxial growth and interface structure of oxide thin films in an atomic scale. Molecular layer epitaxy of oxide thin film growth was verified from in situ monitoring of intensity oscillation in reflection high energy electron diffraction (RHEED). Advanced oxide thin film technology was applied to form oxide superlattices for quantum functional oxides and to achieve lattice-matched heteroepitaxy in oxide films on silicon substrate for all epitaxial oxide/silicon hybrid devices. The key factors to develop oxide lattice engineering are discussed with respect to not only in situ monitoring of growth process using RHEED but also atomic regulation of the substrate surface by atomic force microscopy and ion scattering spectroscopy.

Using tabulated thermodynamic data, a comprehensive investigation of the thermodynamic stability of binary oxides in contact with silicon at 1000 K was conducted. Reactions between silicon and each binary oxide at 1000 K, including those involving ternary phases, were considered. Sufficient thermodynamic data exists to conclude that all binary oxides except the following are unstable in contact with silicon at 1000 K: Li20, the alkaline earth oxides (BeO, MgO, CaO, SrO, and BaO), the column IIIB oxides (Sc2O3, Y2O3, and Re2O3 where Re is a rare earth), ThO2, UO2, ZrO2, HfO2, and Al2O3. Of these remaining oxides, sufficient thermodynamic data exists to conclude that BeO, MgO, CaO, and ZrO2 are thermodynamically stable in contact with silicon at 1000 K. Our results are consistent with reported investigations of silicon/binary oxide interfaces and identify candidate materials for future investigations.

High quality crystalline γ -Al2O3 films were epitaxially grown on Si(111) substrates at growth temperatures from 750 to 900°C by molecular beam epitaxy using an Al solid source and N2O gas. Very thin γ -Al2O3 films grown at a growth temperature of 850°C showed streaky reflection high-energy electron diffraction patterns. By in situ x-ray photoelectron spectroscopy measurements, carbon contamination, as is seen in the films grown with a Al(CH3)3 source, was not detected within the measurement sensitivity. The stoichiometry of the grown film was found to be similar to that of Al2O3. Growth rates of epitaxial γ -Al2O3 layers decreased with increasing growth temperatures. The predominant growth of the γ -Al2O3(111) crystal orientation was confirmed on Si(110) and Si(100) substrates.

We have grown epitaxial thin films of a new family of copper-oxide-based isotropic metallic oxides such as La6.4Sr1.6Cu8O20, La5BaCu6O13 and La6BaYCu8O20in situ by 900° off-axis sputtering. These metallic oxides are pseudo-cubic perovskites with essentially isotropic properties, which could be ideal normal metals for SNS junctions in superconducting devices. We have also grown epitaxial SNS superconducting heterostructures (c-axis YBa2Cu3O7 / La6.4Sr1.6Cu8O20 / c-axis YBa2Cu3O7) with a copper-oxide-based isotropic metallic oxide (La6.4Sr1.6Cu8O20) normal metal barrier. X-ray diffraction and cross-sectional transmission electron microscopy reveal these heterostructures to have high crystalline quality and clean interfaces. This material will facilitate fabrication of ideal SNS Josephson junctions with low boundary resistance due to its excellent chemical compatibility and lattice match with cuprate superconductors and will be useful for determining the source of interface resistance in such heterostructures.

We describe a chemical vapour deposition technique for the controlled growth of ZnO films, containing grain boundaries which are suitable for detailed atomic resolution studies. Using this technique, we have grown; (1) random polycrystalline, (2) highly textured polycrystalline and (3) nominally single crystal films Also, a technique for doping the grain boundaries in these specimens with Bi by an “in-diffusion” method is demonstrated. The grain boundary atomic level structure and chemistry is studied by means of High Resolution Electron Microscopy (HREM) and STEM/EDX microanalysis. Some results obtained from boundaries in textured polycrystalline films which have the c-axes in neighboring grains lined-up to ˜1 ° are described.

Thin films of V2O3 with thickness from 20 to 450 nm were deposited on (0001) oriented sapphire substrates by reactive e-beam evaporation. LEED, x-ray diffraction and AFM studies show highly oriented grains with a lateral size of 50 to 800 nm, dependent on substrate temperature and deposition rate. The films were characterized by optical and infrared transmission, electrical resistance and Hall effect measurements. Films grown directly on the Al2O3-substrate show a very broad metal-insulator (MI) transition as a function of temperature. The width of the transition decreases with increasing film thickness. The insertion of Cr2O3 buffer layers decreases the transition width by a further factor of three. The electronic properties of the films can be drastically influenced by the growth conditions.

Sb doped SnO2 has been deposited on polished ceramic Al2O3 substrates by Pulsed Laser Deposition. Conductivity, charge carrier density and mobility of these thin films have been measured as a function of temperature. A model for the electrical properties of the films is proposed. Since Sb doped SnO2 is a transparent, high mobility material, it is shown that it can be used as channel material for an all-oxide thin film transparent field-effect transistor with a linear dielectric.

Bismuth based artificial superlattices have been formed by a layer-by-layer laser deposition with in-situ monitoring of RHEED. The Bi2O2/WO6, Bi2O2/SrTa2O9, Bi2O2/SrTa2O9 /SrTiO3 and Bi2O2/SrTa2O9/BaTiO3 are constructed epitaxially by a single, double and triple perovskite layers sandwiched by Bi2O2 layers, respectively. The dielectric constant increases with increasing the number of perovskite layers. And the D-E hysteresis loop (ferroelectric properties) appears along the c-axis direction in odd perovskite layers (n=l and 3). We have also formed the SrTiO3/BiWO6/SrTiO3 multi layers. With this combination, the STO layers are isolated by the BWO layers. The dimensionality of STO layer can be controlled by changing the thickness of BWO layers. Below the BWO thickness of 500 Å, the εr increases monotonously with decreasing the BWO thickness. Therefore, the the coulomb force, which is in proportion to inverse of the distance, plays an essential role for the dielectric constant. The formation of “artificially constructed ferroelectric films” by a layer-by-layer deposition method will be discussed ad an essential approach to elucidate the mechanism of ferroelectricity.

Epitaxial films of NbxTi1−xO2 rutile were grown on TiO2 (110) and (100) at 600 °C by oxygen-plasma-assisted molecular beam epitaxy using elemental Ti and Nb sources. The epitaxial films were characterized by means of reflection high-energy and low-energy electron diffraction (RHEED/LEED), x-ray photoelectron spectroscopy and diffraction (XPS/XPD), ultraviolet photoemission spectroscopy (UPS) and atomic force microscopy (AFM). The epitaxial films grow in a layer-by-layer fashion and have excellent short- and long-range structure order at x≤0.3 on TiO2(110) and at x≤0.15 on TiO2(100). However, the epitaxial films become rough and disorder at higher doping levels. Nb substitutionally incorporates at cation lattice sites, leading to NbxTi1−xO2 solid solutions. In addition, the oxidation state of Nb in the NbxTi1−xO2 films has been determined to be +4.

La1−xSrxCoO3 (LSCO) and La1−xCaxMnO3 (LCMO) are a class of magnetic oxides exhibiting the colossal magnetoresistance (CMR) effect. However, the CMR ratio of LSCO is much lower than that of LCMO. Microstructure studies were carried out to understand this difference. In La0.5Sr0.5CoO3 (LSCO), an ordered, anisotropic perovskite-type structure n-LSCO was observed. The ordered structure has a tetragonal cell with a La-Co-Sr-Co- [001] layered atom distribution along the c-axis. This new structure is intrinsic for the LSCO system and is a direct result of the lattice substitution between La and Sr. The entire film is composed of [001], [010] and [100] anisotropic domains with sizes on the order of 30–200 nm. The La0 7Ca0.3MnO3 (LCMO) film, however, does not exhibit a domain structure. It is concluded that the domain structure may have negative effect on the CMR ratio.

(Zr, Sn)TiO4 is considered as a promising dielectric material for microwave devices owing to the temperature stability of capacitance and excellent microwave properties. Preferential (111)-oriented (ZrSn)TiO4 thin film was obtained by an ArF laser ablation. Properties of the crystallized film were as follows; the temperature coefficient of capacitance TCC was 17.6ppm/°C at 3MHz and the dielectric constant εr, 38 in the microwave range of 1GHz˜10GHz. It has turned out that the crystallization of this material is quite effective for improving dielectrical properties. Surface morphologies were observed by atomic force microscope(AFM). Grains grew on the crystallized film at 1 μm × 1 μm size.

Micromechanical properties of the interfaces between alumina and calcium-aluminosilicate (CAS) glasses were tested using various micro/nanoindentation techniques. The interfaces were produced by depositing continuous films of anorhtite (CaAl2Si2O8) onto single-crstal α-Al2O3 of two crystallographic orientations by pulsed-laser deposition (PLD).

The mechanical behavior of the interfaces was examined using two different depthsensing indentation instruments. Three types of tests, namely indentation, microscratch, and in-situ indentation combined with atomic force microscopy (AFM) imaging were conducted using different operating modes. The deformation behavior observed for the indentations and microscratches has been correlated with irregularities observed in the load-displacement curves. In the first two cases, scanning electron microscopy (SEM) has been used to characterize the deformation structures associated with the deformed regions. The in-situ experiments allow force-displacement measurements and AFM imaging immediately before and after indentation. The preindent and postindent morphology of the surface could then be characterized.

Cubic and pseudocubic perovskite films on perovskite substrates are used to study the influence of the lattice mismatch on the epitaxial growth of thin films on substrates of the same structure. For the growth of the films, a metalorganic decomposition route (MOD) using 2-ethylhexanoates and neodecanoates as precursors, was developed. The decomposition of the precursors was investigated with thermogravimetric analysis (TGA) and x-ray diffraction (XRD). The films were spin-coated on (001)-oriented SrTiO3- and LaAlO3-substrates, pyrolyzed and afterwards annealed between 600°C and 1200°C. XRD-nvestigations and conventional transmission electron microscopy (CTEM) show, that epitaxial films with the orientation relationship [100](001) film ║ [100](001) substrate can be grown. With XRD, it could be shown, that not only ternary oxide films (SrZrO3, BaZrO3 and BaCeO3), but also perovskite solid solution films (SrTi0.5Zr0.5O3and BaCe0.5Zr0.5O3) can be prepared. Strong interdiffusion, detected by a shift of the film lattice parameter towards the substrate lattice parameter was found in SrZrO3- and BaZrO3-films on SrTiO3, annealed at temperatures above 1050°C. High resolution electron microscopy (HREM) studies of SrZrO3 on SrTiO3 show that a crystalline semicoherent interface with a periodical array of misfit dislocations is present.

We have utilized white x-ray beam and a Ge solid state detector, in energy dispersive mode, to study the diffraction from the surface layers of ceria deposited on (001) surface of Y stabilized cubic zirconia with grazing incident beam. We found that ceria forms islands, oriented epitaxially with respect to the zirconia substrate, with a lateral coherence of the order of 60 Å.

Epitaxial CeO2 films were grown on Si(111) substrates by laser ablation of CeO2 targets under UHV conditions. The as-grown films were found to have poor electrical properties due to the presence of a large amount of defects near the oxide-silicon interface. Improved MOS electrical characteristics were obtained by annealing in an O2 environment. This however resulted in the growth of a SiO2 layer that can be 10 nm thick at the silicon interface which will thus reduce the capacitance of the grown structure. Annealing in argon and argon followed by oxygen environments were investigated as means to reduce the defects while minimizing the intermediate SiO2 layer thickness. The annealed films were compared based on their RBS yields, breakdown voltages and capacitance-voltage characteristics. Growth and annealing conditions were optimized to achieve device quality MOS structures.

Using the MOCVD process to produce Pb(Zr, Ti)O3 (PZT) thin films, control of the film stoichiometry and crystalline phase was achieved. The PZT films obtained showed good step coverage, 67%. Uniform PZT and PLZT thin films with a variation of film thickness of less than ±1.5% were successfully obtained on a 6–8 inch silicon wafer. For the evaluation of the crystallinity and epitaxial relationship of the PZT thin films, the total reflection X-ray diffraction (TRXD) method was used for the first time. Using TRXD, the in-plane orientations of PZT and Pt in PZT/Pt/MgO were evaluated. The growth mechanism of PbTiO3 and PZT thin films at the initial growth stage was also investigated using an atomic force microscope (AFM). The switching characteristics of PZT capacitors using Ir and IrO2 electrodes for memory device applications were also investigated and a PZT capacitor with no fatigue up to a switching cycle of 1011 was obtained.

Single-crystal thin films covering the full compositional range of Pb(ZrxTi1−x)O3(PZT) 0≤x≤1 have been deposited by metal-organic chemical vapor deposition (MOCVD). The films were grown on epitaxial, RF-sputter-deposited SrRuO3 thin film electrodes on (001) SrTiO3 substrates. X-ray diffraction (XRD), energy-dispersive electron spectroscopy (EDS) and optical waveguiding were used to characterize the crystalline structure, composition, refractive index, and film thickness of the deposited films. We found that the PZT films were single-crystalline for all compositions exhibiting cube-on-cube epitaxy with the substrate with very high degrees of crystallinity and orientation. We report the systematic variations in the optical, dielectric, polarization, and transport properties as a function of composition and the epitaxy-induced modifications in the solid-solution phase diagram of this system. These films exhibited electronic properties which showed clear systematic variations with composition. High values of remnant polarization (30–55 μC/cm2) were observed at all ferroelectric compositions. Unlike previous studies, the dielectric constant exhibited a clear dependence on composition with values ranging from 225–650. The coercive fields decreased with increasing Zr concentration to a minimum of 20 kV/cm at the (70/30) composition. In addition, these films exhibited both high resistivity and dielectric-breakdown strength (˜1013 Ω-cm at 100 kV/cm and >300 kV/cm, respectively) without any compensative doping.

Thin films of perovskite Pb–Ti–O3 families were heteroepitaxially grown by sputtering on (0001)sapphire and/or (001)SrTiO (ST). These epitaxial films contained microstructures, although X–ray diffraction analysis suggested formation of single crystal phase with three dimentional crystal orientation. Their microstructures were studied by the electron microscopy, atomic force microscopy, and spectroscopic ellipsometry so as to find factors which influence the formation of the microstructure. It was found that the orientation of the substrate surface and the chemical composition of adatoms during initial film growth strongly affected the formation of the microstructures. Sputtered PbTiO3 (PT) thin films under a stoichiometric condition on a miscut(001) ST(miscut 1.7 degree) realized the growth of continuous single crystal thin films of 10–100nm thick with extremely smooth surface with surface roughness less than 3nm. Deposition on a miscut substrate under a stoichiometric condition is essential to make continuous thin films of perovskite of single crystal phase.