Preparation of Ba2YCu3O7-δ Thin Films with Preferred Orientation through an Organometallic Route

Superconducting Ba₂YCu₃O_7-δ thin films were prepared through an organometallic route. Single-phase Ba₂YCu₃O_7-δ thin films with preferred orientation were successfully prepared on SrTiO₃ (100) single-crystal substrates at 800°C by a dip coating method using partially hydrolyzed Ba-Y-Cu organometallic solutions. Preferentially oriented Ba₂YCu₃-O_7-δ thin films were also prepared on MgO (100) substrates. By controlling the partial hydrolysis conditions, a coating solution for precursor thin films was kept accurately at the stoichiometric composition. The use of ozone gas during the pyrolysis of the precursor thin films was found to suppress the formation of BaCO₃. Ba₂YCu₃O_7-δ thin films with c -axis orientation perpendicular to a SrTiO₃ (100) substrate, which were heat-treated at 900°C for 15 min, exhibited a superconductivity transition with an onset of 90 K and an end of 75 K.     

Synthesis and Electrical Properties of Stabilized Manganese Dioxide (α-MnO2) Thin-Film Electrodes

Manganese dioxide (α-MnO₂) thin films have been explored as a cathode material for reliable glass capacitors. Conducting α-MnO₂ thin films were deposited on a borosilicate glass substrate by a chemical solution deposition technique. High carbon activities originated from manganese acetate precursor, (Mn(C₂H₃O₂)₂·4H₂O) and acetic acid solvent (C₂H₄O₂), which substantially reduced MnO₂ phase stability, and resulted in Mn₂O₃ formation at pyrolysis temperature in air. The α-MnO₂ structure was stabilized by Ba²⁺ insertion into a (2 × 2) oxygen tunnel frame to form a hollandite structure. With 15–20 mol% Ba addition, a conducting α-MnO₂ thin film was obtained after annealing at 600–650°C, exhibiting low electrical resistivity (∼1 Ω·cm), which enables application as a cathode material for capacitors. The hollandite α-MnO₂ phase was stable at 850°C, and thermally reduced to the insulating bixbyte (Mn₂O₃) phase after annealing at 900°C. The phase transition temperature of Ba containing α-MnO₂ was substantially higher than the reported transition temperature for pure MnO₂ (∼500°C).     

Flexible Dielectric Bi1.5Zn1.0Nb1.5O7 Thin Films on a Cu-Polyimide Foil

Flexible thin films of Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) were deposited on a Cu/polyimide (PI) foil by aerosol deposition at room temperature. The BZN film thickness was in the range of 1.2–17.9 μm. Highly dense and nanocrystalline films were obtained without any heat treatment. The dielectric constant and loss of the film at 100 kHz were over 150 and 0.04, respectively. Furthermore, the as-deposited film showed markedly low leakage current densities of <10⁻⁹ A/cm² at 3.0 V. These reasonably high dielectric properties were due to the nanocrystallinity of the films. The results confirm the significant potential of the BZN films as passive components in flexible printed circuit board applications.     

Characterization of Photoluminescent (Y1–xEux)2O3 Thin Films Prepared by Metallorganic Chemical Vapor Deposition

The purpose of this study was to identify and correlate the microstructural and luminescence properties of europium-doped Y₂O₃ (Y_{1– x} Eu _x )₂O₃ thin films deposited by metallorganic chemical vapor deposition (MOCVD), as a function of deposition time and temperature. The influence of deposition parameters on the crystallite size and microstructural morphology were examined, as well as the influence of these parameters on the photoluminescence emission spectra. (Y_{1– x} Eu _x )₂O₃ thin films were deposited onto (111) silicon and (001) sapphire substrates by MOCVD. The films were grown by reacting yttrium and europium tris(2,2,6,6-tetramethyl–3,5-heptanedionate) precursors with an oxygen atmosphere at low pressures (5 torr (1.7 × 10³ Pa)) and low substrate temperatures (500°–700°C). The films deposited at 500°C were smooth and composed of nanocrystalline regions of cubic Y₂O₃, grown in a textured [100] or [110] orientation to the substrate surface. Films deposited at 600°C developed, with increasing deposition time, from a flat, nanocrystalline morphology into a platelike growth morphology with [111] orientation. Monoclinic (Y_{1– x} Eu _x )₂O₃ was observed in the photoluminescence emission spectra for all deposition temperatures. The increase in photoluminescence emission intensity with increasing postdeposition annealing temperature was attributed to the surface/grain boundary area-reduction effect.     

Novel Deposition of Columnar Y3Al5O12 Coatings by Electrostatic Spray-Assisted Vapor Deposition

A novel and cost-effective electrostatic spray-assisted vapor deposition (ESAVD) was used to deposit Y₃Al₅O₁₂ (YAG) coatings. Polycrystalline single-phase Y₃Al₅O₁₂ coatings were synthesized using the ESAVD method in an open atmosphere at 650°C, and then annealed at 700°–900°C for 1 h. The ESAVD process involves the decomposition and chemical reactions of charged aerosol in vapor phase. The low-temperature coating deposition characteristics of the ESAVD process using a suitable sol precursor decreases the reaction and crystallization temperatures for forming Y₃Al₅O₁₂ coatings. The microstructure of the Y₃Al₅O₁₂ coating prepared using the ESAVD method is columnar and such strain-resistance microstructure could be useful for thermal barrier coating applications.     

Imaging and Diffraction Study of Continuous α-Fe2O3 Films on (0001)Al2O3

Continuous α-Fe₂O₃ films grown on bulk (0001)Al₂O₂ substrates by low-pressure chemical vapor deposition have been studied by transmission electron microscopy and the observations compared to those obtained from discontinuous films at an earlier stage of the growth process. Plan-view specimens revealed significant thermal stress in the continuous films, while cross-sectional specimens showed that cracking occurs in thicker films. The free surface of the film and the film/substrate interface appeared sharp and flat, apart from growth ledges and steps. Weak-beam imaging revealed a hexagonal misfit dislocation network consisting of perfect edge dislocations. Fine structure in the selected-area diffraction patterns which corroborates these observations is also discussed. The misfit network of partial dislocations previously observed in the discontinuous films was not observed for the continuous films, indicating an effect of film thickness, growth rate, or surface preparation on the Fe₂O₃/(0001)Al₂O₃ interface structure.     

Indentation of Silicate-Glass Films on Al2O3 Substrates

The deformation of thin layers of glass on crystalline materials has been examined using newly developed experimental methods for nanomechanical testing. Continuous films of anorthite (CaAl₂Si₂O₈) were deposited onto Al₂O₃ surfaces by pulsed-laser deposition. Mechanical properties such as Young's modulus and hardness were probed with a high-resolution depth-sensing indentation instrument. Nanomechanical testing, combined with AFM in situ imaging of the deformed regions, allowed force-displacement measurements and imaging of the same regions of the specimen before and immediately after indentation. This new technique eliminates any uncertainty in locating the indentation after unloading. Emphasis has been placed on examining how the Al₂O₃ substrate crystallographic orientation will affect mechanical composite response of silicate-glass film/Al₂O₃ system.     

Growth of Single-Crystal and Polycrystalline Thin Films of MgAl2O4 and MgFe2O4

Single-crystal and polycrystalline films of Mg-Al₂O₄ and MgFe₂O₄ were formed by two methods on cleavage surfaces of MgO single crystals. In one procedure, aluminum was deposited on MgO by vacuum evaporation. Subsequent heating in air at about 510°C formed a polycrystalline γ-Al₂O₈ film. Above 540°C, the γ-Al₂O, and MgO reacted to form a single-crystal MgAl₂O₄ film with {001} MgAl₂O₄‖{001} MgO. Above 590°C, an additional layer of MgAl₂O₄, which is polycrystalline, formed between the γ-Al₂O₃ and the single-crystal spinel. Polycrystalline Mg-Al₂O₄ formed only when diffusion of Mg²⁺ ions proceeded into the polycrystalline γ-Al₂O₃ region. Corresponding results were obtained for Mg-Fe₂O₄. MgAl₂O₄ films were also formed on cleaved MgO single-crystal substrates by direct evaporation, using an Al₂O₃ crucible as a source. Very slow deposition rates were used with source temperatures of ∼1350°C and substrate temperatures of ∼800°C. Departures from single-crystal character in the films may arise through temperature gradients in the substrate.     

Structural Variation of the BaTi4O9 Thin Films Grown by RF Magnetron Sputtering

BaTi₄O₉ thin films were grown on a Pt/Ti/SiO₂/Si substrate using rf magnetron sputtering and the structure of the thin films were then investigated. For the films grown at low temperature (≤350°C), an amorphous phase was formed during the deposition, which then changed to the BaTi₅O₁₁ phase when the annealing was conducted below 950°C. However, when the annealing temperature was higher than 950°C, a BaTi₄O₉ phase was formed. On the contrary, for the films grown at high temperature (>450°C), small BaTi₄O₉ grains were formed during the deposition, which grew during the annealing. The homogeneous BaTi₄O₉ thin films were successfully grown on Pt/Ti/SiO₂/Si substrate when they were deposited at 550°C and subsequently rapid thermal annealed at 900°C for 3 min.     

Ferroelectric and Dielectric Properties of Pb(Mg1/3Ta2/3)0.7Ti0.3O3 Thin Films Derived from RF Magnetron Sputtering

Pb(Mg_1/3Ta_2/3)_0.7Ti_0.3O₃ thin films of single perovskite phase were successfully synthesized by using the RF sputtering deposition technique, followed by post-thermal annealing. While the perovskite structure of Pb(Mg_1/3Ta_2/3)_0.7Ti_0.3O₃ is rather unstable, phase evolution in the thin films was manipulated by controlling both working pressure during the sputtering process and post-thermal annealing temperature. The desirable perovskite phase was promoted by increasing the working pressure in the range of 10–25 mTorr, followed by thermal annealing at 600°C. The ferroelectric, dielectric, and polarization behaviors of Pb(Mg_1/3Ta_2/3)_0.7Ti_0.3O₃ films were characterized over a wide range of frequencies. They are strongly affected by the film thickness, where the relative permittivity and remanent polarization increase, while the coercive field decreases with increasing film thickness in the range of 115–360 nm.     

Thermal Stability of Nanocrystalline Sm2O3 and Sm2O3–MgO

Nanocrystalline Sm₂O₃ and Sm₂O₃–MgO powders have been prepared by spray pyrolysis of aqueous precursor solutions containing citric acid as a complexant. Synthesized powders consist of hollow spheres with thin shells. The two-phase samples exhibit an improved microstructural stability compared with pure Sm₂O₃. The microstructure before and after various heat treatments has been investigated by high-resolution transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, and X-ray diffraction.     

Chemical Vapor Deposition of Polycrystalline Al2O3

Polycrystalline Al₂O₃ was chemically vapor-deposited onto sintered Al₂O₃ substrates by reaction of AlCl₃ with (1) H₂O, (2) CO:H₂, and (3) O₂ at 1000° and 1500°C and 0.5 and 5.0 torr. Although the thermodynamics of all these reactions predict the formation of solid Al₂O₃, the deposition rate of the first reaction was considerably greater than that of the second. The third reaction was so slow that no measurable deposit was formed in 6 h at 1500°C. Formation of dense deposits of α-Al₂O₃ was favored by increasing temperature and decreasing pressure. Microstructural examination of the dense deposits showed long columnar grains, the largest of which extended through the deposit from the substrate to the surface.     

Sintering and Electrical Properties of Titania- and Zirconia-Containing ln2O3-Sno2(ITO) Ceramics

The deposition rate and film quality of In₂O₃-SnO₂ (ITO) transparent electrodes processed by sputtering are improved when using dense sputtering targets. Unfortunately, ITO ceramics do not sinter easily. It is shown that addition of TiO₂ (<1 wt%) to ITO greatly increases densification without degrading electrical properties of sputtered films. The influence of ZrO₂ and SiO₂ was also investigated.     

Film Synthesis of Y3Al5O12 and Y3Fe5O12 by the Spray–Inductively Coupled Plasma Technique

Thin films of yttrium aluminum garnet (YAG, Y₃Al₅O₁₂) and yttrium iron garnet (YIG, Y₃Fe₅O₁₂) were synthesized on single-crystal Al₂O₃ substrates by a modification of spray pyrolysis using a high-temperature inductively coupled plasma at atmospheric pressure (spray–ICP technique). Using this technique, films could be grown at faster rates (0.12 μm/min for YAG and 0.10 μm/min for YIG) than using chemical vapor deposition (0.005–0.008 μm/min for YAG) or sputtering (0.003–0.005 μm/min for YIG). The films were dense and revealed a preferred orientation of (211). The growth of YIG was accompanied by coprecipitation of α-Fe₂O₃. The coprecipitation, however, could be largely suppressed by preliminary formation of a Y₂O₃ layer on the substrate.     

Sol–Gel Route to Porous Lanthanum Cobaltite (LaCoO3) Thin Films

Sol–gel-derived LaCoO₃ thin films were deposited on yttria-stabilized zirconia (YSZ) substrates from a lanthanum isopropoxide–cobalt acetate (with 2-methoxyethanol) precursor solution. A chelating agent (2-ethylacetoacetate) and polyethylene glycol (PEG) were used to modify the above-mentioned precursor solution. The La-Co precursor solution was sufficiently viscous, and transparent LaCoO₃ gel films were prepared successfully using a spin-coating technique. Crystallization behavior and microstructure evolution were investigated using X-ray diffractometry (XRD) and scanning electron microscopy (SEM). A single-phase perovskite thin film with the grain size of ∼50 nm was obtained by heat-treating the spin-coated gel film at a temperature of 600°C. SEM observations revealed that the microstructure of LaCoO₃ thin films that were prepared from the precursor solution with PEG was porous, and the LaCoO₃ thin film maintained its porous microstructure to a temperature of 800°C.     

Control of Microstructure and Orientation in Solution-Deposited BaTiO3 and SrTiO3 Thin Films

Columnar and highly oriented (100) BaTiO₃ and SrTiO₃ thin films were prepared by a chelate-type chemical solution deposition (CSD) process by manipulation of film deposition conditions and seeded growth techniques. Randomly oriented columnar films were prepared on platinum-coated Si substrates by a multilayering process in which nucleation of the perovskite phase was restricted to the substrate or underlying layers by control of layer thickness. The columnar films displayed improvements in dielectric constant and dielectric loss compared to the fine-grain equiaxed films that typically result from CSD methods. Highly oriented BaTiO₃ and SrTiO₃ thin films were fabricated on LaAlO₃ by a seeded growth process that appeared to follow a standard "two-step" growth mechanism that has been previously reported. The film transformation process involved the bulk nucleation of BaTiO₃ throughout the film, followed by the consumption of this matrix by an epitaxial overgrowth process originating at the seed layer. Both BaTiO₃ and PbTiO₃ seed layers were effective in promoting the growth of highly oriented (100) BaTiO₃ films. Based on the various processing factors that can influence thin film microstructure, the decomposition pathway involving the formation of BaCO₃ and TiO₂ appeared to dictate thin film microstructural evolution.     

Synthesis of V2O3 Powder by Evaporative Decomposition of Solutions and H2 Reduction

The evaporative decomposition of solutions method was used to form V₂O₅. Spraying above the congruent melting temperature of V₂O₅ (690°C) resulted in dense spherical particles with a smooth surface. Spraying below the V₂O₅ melting temperature yielded porous V₂O₅ powder with a rough surface. Reduction of the V₂O₅ to V₂O₃ was done in a H₂ atmosphere. Spherical V₂O₃ powder was attained when the reduction temperature was low enough to reduce the V₂O₅ surface before partial sintering (necking) between V₂O₅ particles occurred. The resulting V₂O₃ particle size was smaller than the precursor V₂O₅ powder as expected by the differences in densities between V₂O₅ ( p = 3.36 g/cm³) and V₂O₃ ( p = 4.87 g/cm³).     

Fabrication and Characterization of a (100) Three-Axis-Oriented Single-Crystal (Ba0.7Sr0.3)TiO3 Thin Film Prepared by the Chemical Solution Deposition Method

Epitaxially grown single-crystal perovskite (100) three-axis-oriented (Ba_0.7Sr_0.3)TiO₃ thin films were prepared on a (100) platinum-coated (100) magnesium oxide (MgO) single-crystal substrate by the chemical solution deposition method using a solution derived from Ba(CH₃COO)₂, Sr(CH₃COO)₂, and Ti(O- i -C₃H₇)₄.
The growth of the film was found to depend on the annealing condition. A (Ba,Sr)TiO₃ thin film annealed at 1073 K was found to be a single crystal by transmission electron microscope. The single-crystal film exhibited a (100) three-axis orientation that followed the (100) orientation of the Pt substrate, as observed from an X-ray pole figure measurement and selected area electron diffraction patterns.     

Synthesis of ZrO2 and Y2O3-Doped ZrO2 Thin Films Using Self-Assembled Monolayers

Undoped or Y₂O₃-doped ZrO₂ thin films were deposited on self-assembled monolayers (SAMs) with either sulfonate or methyl terminal functionalities on single-crystal silicon substrates. The undoped films were formed by enhanced hydrolysis of zirconium sulfate (Zr(SO₄)·4H₄O) solutions in the presence of HCl at 70°C. Typically, these films were a mixture of two phases: nanocrystalline tetragonal- ( t -) ZrO₂ and an amorphous basic zirconium sulfate. However, films with little or no amorphous material could be produced. The mechanism of film formation and the growth kinetics have been explained through a coagulation model involving homogeneous nucleation, particle adhesion, and aggregation onto the substrate. Annealing of these films at 500°C led to complete crystallization to t -ZrO₂. Amorphous Y₂O₃-containing ZrO₂ films were prepared from a precursor solution containing zirconium sulfate, yttrium sulfate (Y₂(SO₄)₃8·H₂O), and urea (NH₂CONH₂) at pH 2.2–3.0 at 80°C. These films also were fully crystalline after annealing at 500°C.     

Nanocrystalline α-Al2O3 Using Sucrose

Nanocrystalline α-Al₂O₃ ceramic powders have been prepared from an aqueous solution of aluminum nitrate and sucrose. Soluble Al ion-sucrose solution forms the precursor material once it is completely dehydrated. Heat treatment of the dehydrated precursors at low temperature (600°C) results in the formation of porous single-phase α-Al₂O₃. The precursor and heat-treated powders have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and BET surface area analysis. The phase-pure nanocrystalline α-Al₂O₃ particles had an average specific surface area of >190 m²/g, with an average pore size between 18 and 25 nm.