Microhardness and structure of thick silica films prepared by vacuum deposition

The relationships are investigated between the microhardness, density and composition of silica films 7 to 10m thick prepared by resistance heating and electron beam evaporation. The Vickers hardness of the film prepared by electron beam evaporation gives 180 to 620 kg mm^–2 for varying pressures and is higher than that of film prepared by resistance heating evaporation. The silica films of higher density show higher hardness irrespective of the kinds of evaporation. The porosity of the films, which is 0 to 30% and decreases with lowering pressure, is estimated from the ratio of measured density of the film to assumed bulk density.     

Electrochemical characteristics of Ba0.5Sr0.5Co0.8Fe0.2O3−δ–Sm0.2Ce0.8O1.9 composite materials for low-temperature solid oxide fuel cell cathodes

In this paper, Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ–xSm_0.2Ce_0.8O_1.9 (BSCF–xSDC, x = 0–60 wt.%) composite cathodes were prepared by soft chemical methods, and then examined for potential applications in lower temperature solid oxide fuel cells. Both DC polarization and AC impedance spectroscopy measurements indicated that the addition of SDC electrolyte into BSCF remarkably improved the electrochemical properties. The optimum composition was found to be BSCF–30SDC, which exhibited 5.5 times higher polarization current density and 15.1% polarization resistance, compared with the pure-phase BSCF cathode at 550 °C.     

Comparisons of immersion and electrochemical properties of highly biocompatible Ti–15Zr–4Nb–4Ta alloy and other implantable metals for orthopedic implants

Metal release from implantable metals and the properties of oxide films formed on alloy surfaces were analyzed, focusing on the highly biocompatible Ti–15Zr–4Nb–4Ta alloy. The thickness and electrical resistance (R_p) of the oxide film on such an alloy were compared with those of other implantable metals. The quantity of metal released during a 1-week immersion test was considerably smaller for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy. The potential (E₁₀) indicating a current density of 10 μA cm⁻² estimated from the anodic polarization curve was significantly higher for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy and other metals. Moreover, the oxide film (4–7 nm thickness) formed on the Ti–15Zr–4Nb–4Ta surface is electrochemically robust. The oxide film mainly consisted of TiO₂ with small amounts of ZrO₂, Nb₂O₅ and Ta₂O₅ that made the film electrochemically stable. The R_p of Ti–15Zr–4Nb–4Ta was higher than that of Ti–6Al–4V, i.e. 0.9 Ω cm² in 0.9% NaCl and 1.3 Ω cm² in Eagle''s medium. This R_p was approximately five-fold higher than that of stainless steel, which has a history of more than 40 years of clinical use in the human body. Ti–15Zr–4Nb–4Ta is a potential implant material for long-term clinical use. Moreover, E₁₀ and R_p were found to be useful parameters for assessing biological safety.     

Preparation and properties of ferroelectric Pb1 − xCaxTiO3 thin films produced by the polymeric precursor method

Pb_{1 – x} Ca _x TiO₃ thin films with x = 0.24 composition were prepared by the polymeric precursor method on Pt/Ti/SiO₂/Si substrates. The surface morphology and crystal structure, and the ferroelectric and dielectric properties of the films were investigated. X-ray diffraction patterns of the films revealed their polycrystalline nature. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) analyses showed the surface of these thin films to be smooth, dense and crack-free with low surface roughness. The multilayer Pb_{1 – x} Ca _x TO₃ thin films were granular in structure with a grain size of approximately 60–70 nm. The dielectric constant and dissipation factor were, respectively, 174 and 0.04 at a 1 kHz frequency. The 600-nm thick film showed a current density leakage in the order of 10^–7 A/cm² in an electric field of about 51 kV/cm. The C-V characteristics of perovskite thin films showed normal ferroelectric behavior. The remanent polarization and coercive field for the deposited films were 15 C/cm² and 150 kV/cm, respectively.     

Electrolytic capacitors produced from deformation-processed two-phase alloys

Arc cast Cu-Ta and powder processed Al-Ta and Al-Nb composite alloys have been examined as potential materials for making electrolytic capacitors. These two phase alloys can be severely cold-worked, deformation-processed, to produce Ta surface areas considerably larger than those possible with the powder processing used in current Ta capacitors. The three alloys were deformation-processed into sheet and rod form and then processed through anodization, electrolyte formation and cathode fabrication steps to make prototype capacitors. The capacitors were tested for capacitance, effective series resistance and leakage. The figure of merit,CVg^–1, (capacitance × voltage per gram) values obtained closely approached those of currently manufactured capacitors but d.c. leakage values were unacceptably high using a solid electrolyte. To realize the full potential of this new method for fabricating Al-Ta capacitors further research is required to improve the deformation of the Ta powders and to find methods of anodization and solid-state electrolyte formation capable of maintaining oxide film integrity.     

Effect of Ta2O5/TiO2 thin film on mechanical properties,corrosion and cell behavior of the NiTi alloy implanted with tantalum

The NiTi shape memory alloy has been modified by plasma immersion ion implantation (PIII) with Ta at different incident currents to improve the corrosion resistance and other surface and biological properties. The surface topography, chemical components, mechanical properties, corrosion resistance and cytocompatibility are investigated. Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) revealed that Ta implantation led to the formation of compact Ta₂O₅/TiO₂ nano-film on the surface of the NiTi alloy. The results of Auger electron spectroscopy (AES) showed that Ni was suppressed in the superficial surface layer of the modified NiTi alloy samples. The results of nano-indentation illustrated a lower level of nano-hardness and Young's modulus after Ta implantation. Potentiodynamic anodic polarization curves showed that the corrosion resistance of NiTi alloys was enhanced by Ta implantation. Cells reached confluency and a double-layered structure had developed after cultured for three days. The NiTi alloy modified by a moderate incident current possesses a uniform and slippery surface morphology and the largest surface roughness, leading to the best corrosion resistance and the highest cell proliferation rate, respectively.     

Morphology and composition of layered anodic films on InP

The composition and morphology of the double-layered anodic film formed at 5 mA cm^–2 on InP in aqueous sodium tungstate electrolyte is examined by transmission electron microscopy (TEM), atomic force microscopy (AFM), Rutherford backscattering spectroscopy and nuclear reaction analysis. The outer layer is composed mainly of In₂O₃ of relatively low atomic density, about 50% that of crystalline In₂O₃. The low density is probably due partly to the presence of numerous cavities in the layer, revealed by TEM and AFM. The inner layer is enriched in phosphorus relative to the composition of the substrate, with a P : In atomic ratio of about 2.17. From the measured ratio of phosphorus to indium, the composition of the inner layer can be expressed as either In₂O₃.2.17P₂O₅ or In(PO₃)_2.17. The average nm V^–1 ratio is 1.99 ± 0.07. However, there are wide variations of the local film thickness, associated with roughness at the substrate/film and film/electrolyte interfaces and local variability in the ionic current density due to cavities in the film. The film forms with a small loss of indium species to the electrolyte. The outer layer represents about 32% of the total thickness of a film formed at 100% efficiency.     

Comparisons of immersion and electrochemical properties of highly biocompatible Ti–15Zr–4Nb–4Ta alloy and other implantable metals for orthopedic implants

Abstract

Metal release from implantable metals and the properties of oxide films formed on alloy surfaces were analyzed, focusing on the highly biocompatible Ti–15Zr–4Nb–4Ta alloy. The thickness and electrical resistance (R_p) of the oxide film on such an alloy were compared with those of other implantable metals. The quantity of metal released during a 1-week immersion test was considerably smaller for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy. The potential (E₁₀) indicating a current density of 10 μA cm^?2 estimated from the anodic polarization curve was significantly higher for the Ti–15Zr–4Nb–4Ta than the Ti–6Al–4V alloy and other metals. Moreover, the oxide film (4–7 nm thickness) formed on the Ti–15Zr–4Nb–4Ta surface is electrochemically robust. The oxide film mainly consisted of TiO₂ with small amounts of ZrO₂, Nb₂O₅ and Ta₂O₅ that made the film electrochemically stable. The R_p of Ti–15Zr–4Nb–4Ta was higher than that of Ti–6Al–4V, i.e. 0.9 Ω cm² in 0.9% NaCl and 1.3 Ω cm² in Eagle's medium. This R_p was approximately five-fold higher than that of stainless steel, which has a history of more than 40 years of clinical use in the human body. Ti–15Zr–4Nb–4Ta is a potential implant material for long-term clinical use. Moreover, E₁₀ and R_p were found to be useful parameters for assessing biological safety.     

Preparation of fatigue-free SrBi2Ta2O9 thin films by r.f. magnetron sputtering and their ferroelectric properties

Fatigue-free bismuth-layered SrBi₂Ta₂O₉ (SBT) films were deposited on Pt/Ti/SiO₂/Si substrates by r.f. magnetron sputtering at room temperature. The variation of structure and electrical properties were studied as a function of annealing temperatures from 750–850 °C. The films annealed at 800 °C had a composition ratio of Sr:Br:Ta = 0.7:2.0:2.0. X-ray photoelectron spectroscopy signals of bismuth show an oxygen-deficient state within the SBT films. The films annealed at 800 °C have a thickness of 200 nm and a relatively dense microstructure. The remanent polarization (2P _r), and the coercive field (2E _c), obtained for the SIBT films, were 9.1 C cm^–2 and 85 kV cm^–1 at an applied voltage of 3 V, respectively. The films showed fatigue-free characteristics up to 10¹⁰ cycles under 5 V bipolar square pulses. The leakage current density was about 7 × 10^–7 A cm^–2 at 150 kV cm^–1. The SBT films prepared by r.f. magnetron sputtering were attractive for application to non-volatile memories.     

Tantalum Thin-Film Superconducting Transition Edge Thermometers

Sputter deposited Ta thin films make excellent superconducting transition edge temperature sensors. Depending on film thickness, their transition temperature, T_c, ranges from 4.4K to as least as low as 0.5K. A figure of merit of 50K^–1 is easily achieved. The films are mechanically extremely strong, and at room temperature show minimal aging. Using a simple heat treatment technique, T_c can be tuned to the desired operating range.     

Structural and electrical properties of the Y-Ba-Cu-O superconducting films prepared by spray pyrolysis

High-T _c , superconducting YBa₂Cu₃O_7– thin films have been grown on (100) MgO substrates by a chemical spray pyrolysis method. The crystal structure and surface morphology have been studied by X-ray diffraction and scanning electron microscopy, respectively. The assprayed films were amorphous and insulating, but upon annealing the films became superconducting and show a textured surface morphology with an average grain size of the order of 5–15m. The films were highly oriented with thec-axis being perpendicular to the substrate surface. Three different microstructures were recorded: long rod-shaped grains, platelet or rounded-shape grains, and a melting-like growth. Electrical measurements were carried out in a low-temperature cryostat using a standard d.c. four-probe technique. The onset transition temperature was around 83–86 K, and the completion of the transition to zero resistance was in the range 73–78 K. The magnitude of the measured critical current density was in the range 750–3750 A/cm² at 30 K. A correlation between the resistance of the tunnelling junctions and the critical current density was found from the theoretical models.     

反应射频磁控溅射法制备HfTaO薄膜的热稳定性和光学性能

采用反应射频磁控溅射技术制备HfTaO薄膜,利用X射线衍射(XRD)分析了薄膜的微结构,通过紫外-可见光分光光度计测量了薄膜的透过谱,计算了薄膜的折射率和禁带宽度,利用原子力显微镜观察了薄膜的表面形貌。结果表明,随着Ta掺入量(10%,26%,50%)的增加,HfTaO薄膜的结晶化温度分别为800、900、950℃,Ta掺入量继续增加到72%,经过950℃退火处理的HfTaO薄膜仍然保持非晶态,具有优良的热稳定性。AFM形貌分析显示非晶HfTaO薄膜表面非常平整。在550nm处薄膜折射率n随着Ta掺入量的增大而增大,n的变化区间为1.90～2.15。同时HfTaO薄膜的光学带隙Eg随着Ta掺入量的增大而逐渐减小,Eg的变化区间为4.15～5.29eV。     

Heat Capacity of Atomically Layered 3He –4He Mixture Films

We report preliminary results of the first heat capacity measurements on atomically layered ³ He – ⁴ He mixture films adsorbed on the surface of graphite. The ⁴ He film consists of two solid and two superfluid atomic layers. The heat capacity has been investigated over the range 1 – 70mK as a function of the surface density of ³ He atoms added to the film. At coveragesn₃ < 4nm ^–2 , the ³He forms a uniform two dimensional Fermi system. The coverage dependence of the linear coefficient of the heat capacity, , allows a determination of the hydrodynamic effective mass and . At higher coverages a step-like increase in is observed, interpreted as the formation of a second two dimensional Fermi system.     

Phases Resulting from the Reduction of Manganese Metaniobate by Niobium and Tantalum

The sequence of reactions in the reduction of manganese metaniobate with Nb, NbO, and Ta is studied. The reduction of MnNb₂O₆ by Nb or NbO differs in some respects from that by Ta. No Mn(Nb_{2 – x} Ta _x )O_4.33 or Mn(Nb_{2 – x} Ta _x )O_3.67 solid solutions were detected in the reduction products. Tantalum converts directly into manganese metatantalate, without oxidation according to the scheme Ta–TaO–TaO₂–Ta₂O₅. A reaction scheme is suggested for the reduction of MnNb₂O₆ by niobium and tantalum. The unit-cell parameters of the orthorhombic phase MnNb₂O_4.33 resulting from the reduction of MnNb₂O₆ with Nb or Ta are determined.     

Yttrium-substituted bismuth titanate (Bi4−x Y x Ti3O12) thin film for use in non-volatile memories

Fatigue-free Bi_3.2Y_0.8Ti₃O₁₂ (BYT) thin films were grown on Pt/TiO₂/SiO₂/Si substrates using direct liquid injection–metal organic chemical vapor deposition. The BYT film capacitor with top Au electrode showed higher remanent polarization (2P _r) and lower leakage current density compared with Bi_3.2La_0.8Ti₃O₁₂ (BLT) film capacitors. BYT films showed strong (1 1 7) orientation with smaller grain size, while BLT films showed strong c-axis orientation. The 2P _r value of the BYT capacitor was 15 C cm^–2 and remained essentially constant up to 1×10¹⁰ read/write switching cycles at a frequency of 1 MHz. The leakage current of the BYT film was 3.5×10^–7 A cm^–2 at an applied voltage of 2 V, which is about three orders lower than that of the BLT film.     

氧化铈膜制备及其耐腐蚀性能

采用不同的制备溶液及制备参数在X80钢表面制备出不同的氧化铈膜,并对其耐腐蚀性能进行了研究.利用扫描电镜、能谱仪、XRD、拉曼光谱、接触角测试仪对不同的氧化铈膜腐蚀前后的表面形貌、元素、物相及亲水性进行了分析,利用电化学工作站对不同的氧化铈膜在3.5wt.％NaCl溶液中的开路电位、线性极化电阻、交流阻抗、极化曲线进行...     

Ab Initio Study of Magnetism in III-V- and II-VI-Based Diluted Magnetic Semiconductors

Electronic structure and magnetic properties of Ga_1–x Mn _x As, Ga_1–x Mn _x N, Zn_1–x M _x O, and Zn_1–x M _x Te (M=V, Cr, Mn, Fe, and Co) diluted magnetic semiconductors (DMS) are calculated by the tight-binding LMTO method in the 64-atom supercell. Calculations are made at several x with varied spatial distribution of dopant atoms and codoping of DMSs. The results show that stability of the ferro- and antiferromagnetic (FM and AFM) states in DMSs strongly correlates with the occupation and energy position of 3d-dopant bands. Adequacy of the double exchange and superexchange mechanisms for explanation of the FM vs. AFM competition is discussed.     

Amorphous alloys resistant to corrosion in artificial saliva solution

The tailoring of new corrosion-resistant alloys with specific properties has recently been performed mostly by the sputter deposition technique. The aim of this work was to investigate corrosion resistance of aluminum–tungsten (Al–W) amorphous alloys in artificial saliva solution, pH=5.5, based on the electrochemical methods of cyclic voltammetry and linear polarization. Thin alloy films were prepared on a sapphire substrate by magnetron codeposition. Completely amorphous films were obtained in the Al₈₀W₂₀–Al₆₇W₃₃ composition range. Amorphous Al–W alloys exhibit very high corrosion resistance due to their homogeneous single-phase nature. The passive films spontaneously formed at their surface are uniform with characteristics of an insulator film and prevent corrosion progression in the bulk in a very demanding oral environment. The mechanism of increasing resistivity of Al–W alloys to pitting corrosion and generalized corrosion has been discussed in the view of increasing tungsten content in the alloy. Considering these exceptional corrosion properties and microhardness which falls in the range 7.5±1.6 Pa, Al–W alloys represent promising materials for dental applications.     

Tantalum and niobium as a diffusion barrier between copper and silicon

The efficiency of Ta and Nb films as diffusion barriers between thin Cu film and Si substrate has been studied using Auger electron spectroscopy, X-ray diffraction, optical microscopy, scanning electron microscopy and sheet resistance measurements. Two kinds of system were prepared by electron-beam evaporation: Cu/Ta (or Nb)/Si and Cu/Ta (or Mb) SiO₂/Si. The samples were annealed at temperatures from 400 to 800C in a vacuum of 1 × 10^–7 torr (13 Pa) for 30 min. In the Cu/Ta (or Nb)/Si system, the thermal stability was determined by interdiffusion at local sites, forming suicides, whereas the Cu/Ta (or Nb)/SiO₂/Si system degraded by interdiffusion at the interface between Ta (or Nb) and Cu. It appears that Ta is a more effective diffusion barrier than Nb for both kinds of system. This difference in the barrier effect of the transition metals is attributed to differences between oxygen segregation at grain boundaries of barrier layers and differences between diffusion coefficients through barrier layers. It is suggested that the driving force for interdiffusion may play a major role in the reaction that determines the thermal stability of a given contact system; this suggestion is based on the fact that the interdiffusion in Cu/barrier/Si systems is suppressed by interposing an SiO₂ layer in the Si substrate.     

Microstructure and anodic polarization behavior of experimental Ag–18Cu–15Pd–12Au alloy in aqueous sulfide solution

The anodic corrosion behavior of an experimental Ag–15Pd–18Cu–12Au alloy in 0.1% Na₂S solution in relation to its microstructure was investigated using potentiodynamic and potentiostatic polarization techniques with analyses of corrosion products by X-ray diffractometry, Auger electron spectroscopy, and X-ray photoelectron spectroscopy. The role of Pd in improvement of the corrosion resistance was also investigated. In the potential/current density curve, three distinct current peaks, at –520 mV (peak I), –425 mV (peak II) and –175 mV (peak III), were observed. The Ag-rich ₂ matrix with coarse Cu and Pd-rich lamellae was the most corrosion-susceptible region, and this region was preferentially corroded at peak I with the formation of granular deposits of Ag₂S. A small amount of Ag–Cu mixed sulfide deposited on the Cu and Pd-rich coarse particles and dissolution of Ag as AgO^– might have occurred in parallel with Ag₂S formation at peak II. Enrichment of Pd on the alloy surface occurred at peak III due to preferential dissolution of Ag and Cu. A high level of corrosion resistance was attained with the formation of a thin Pd-rich sulfide film, which enhanced the passivity of the alloy in an alkaline sulfide solution. It was found that passivity is an important phenomenon not only for base metal alloys but also for noble metal alloys to maintain high levels of resistance to corrosion and tarnishing in sulfide environments.