Growth of beta barium borate (β-BaB2O4) thin films by injection metal organic chemical vapour deposition

Thin films containing beta barium borate (β-BaB₂O₄ so called β-BBO) were grown on silicon (100) substrates by injection metal organic chemical vapour deposition for different deposition temperatures. The films were characterized by optical microscopy, micro-Raman spectroscopy and X-ray photoelectron Spectroscopy (XPS). The micro-Raman spectra show an intense peak at 637 cm^− 1 that is the fingerprint of β-BBO. Our XPS analysis permits the measurement of the Ba, B and O core levels, which are reported here for the first time for β-BBO thin films. The formation of a new spectral component appearing with lower growth temperatures has been observed as well.     

Al2O3 formation on Si by catalytic chemical vapor deposition

Catalytic chemical vapor deposition (Cat-CVD) has been developed to deposit alumina (Al₂O₃) thin films on silicon (Si) crystals using N₂ bubbled tri-methyl aluminum [Al(CH₃)₃, TMA] and molecular oxygen (O₂) as source species and tungsten wires as a catalyzer. The catalyzer dissociated TMA at approximately 600 °C. The maximum deposition rate was 18 nm min⁻¹ at a catalyzer temperature of 1000 °C and substrate temperature of 800 °C. Metal oxide semiconductor (MOS) diodes were fabricated using gates composed of 32.5-nm-thick alumina film deposited at a substrate temperature of 400 °C. The capacitance measurements resulted in a relative dielectric constant of 7.4, fixed charge density of 1.74×10¹² cm⁻², small hysteresis voltage of 0.12 V, and very few interface trapping charges. The leakage current was 5.01×10⁻⁷ A cm⁻² at a gate bias of 1 V.     

Protection of polymer from atomic-oxygen erosion using Al2O3 atomic layer deposition coatings

Thin films of Al₂O₃ grown using atomic layer deposition (ALD) techniques can protect polymers from erosion by oxygen atoms. To quantify this protection, polyimide substrates with the same chemical repeat unit as Kapton^® were applied to quartz crystal microbalance (QCM) sensors. Al₂O₃ ALD films with varying thicknesses were grown on the polyimide substrates. The ALD-coated polyimide materials were then exposed to a hyperthermal atomic-oxygen beam. The mass loss versus oxygen-atom exposure time was measured in situ by the QCM. Al₂O₃ ALD film thicknesses of ∼ 35 Å were found to protect the polymer from erosion.     

Microstructure of Al2O3 nanocrystalline/cobalt-based alloy composite coatings by laser deposition

Composite coatings, made of nano-Al₂O₃/cobalt-based alloy, produced by a 5-kW CO₂ laser on Ni-based superalloy were investigated. The coatings were examined to reveal their microstructure using optical microscope, scanning electron microscope, transmission electron microscope and X-ray diffraction instrument. The results showed that some equilibrium or non-equilibrium phases, such as γ-Co, Cr₂₃C₆, CoAl₂O₄, Al₂O₃ and ε-Co existed in the coatings. Fine and short dendritic microstructure and columnar to equiaxed transition occurred by adding nano-Al₂O₃ particle. With the increase of nano-materials (1%, mass fraction), fully equiaxed crystallization appeared. These were contributed to that nano-Al₂O₃ particles acted as new nucleation site and rapid solidification of the melted pool. The results also showed inhomogeneous dispersion of nano-Al₂O₃ that resulted in the formation of ε-Co phase in the coatings. The sub-microstructure of the clad was stacking fault. The mechanism of formation of equiaxed grains was also analyzed.     

Effect of partial pressure of the reactant gas on the chemical vapour deposition of Al2O3

Films of Al₂O₃ were deposited onto TiN-coated cemented carbide substrates by a chemical vapour deposition technique using AlCl₃, CO₂ and H₂ gases. The effects of the deposition temperature and the partial pressures of the reactants on the final structure of the Al₂O₃ film were investigated, especially the effect of the supersaturations of the reactants (H₂O and AlCl₃) on the final structure of the Al₂O₃ film. The supersaturations of the reactants are calculated assuming chemical equilibria. It is found that the deposition rate of Al₂O₃ is limited by both the AlCl₃ concentration and the [H₂]/[CO₂] ratio, but the crystal size of Al₂O₃ film decreases with increasing H₂O supersaturation. The supersaturation of AlCl₃, however, seems not to affect the crystal size of Al₂O₃ film under our experimental conditions. It is also found that the crystallographic structure of the Al₂O₃ film changes from random orientation to (10$\text{1}$4)-preferred orientation with increasing deposition temperature.     

Pulsed plasma-enhanced chemical vapor deposition of Al2O3-TiO2 nanolaminates

Self-limiting synthesis of alumina-titania nanolaminates (ATO, Al₂O₃/TiO₂) was accomplished via pulsed plasma-enhanced chemical vapor deposition. At the synthesis temperature of 150 °C the alumina layers were amorphous, while TiO₂ layers displayed a polycrystalline anatase structure. Digital control over nanolaminate structure was demonstrated through elemental analysis and transmission electron microscopy imaging. The dielectric performance of the ATO structures was examined as a function of composition and bilayer thickness. Capacitance-voltage measurements showed that the effective dielectric constant was consistent with treating the nanolaminates as individual capacitors in series. Current-voltage measurements showed that leakage current deteriorated with TiO₂ content, though low leakage was restored through interfacial engineering.     

Single-source chemical vapor deposition of clean oriented Al2O3 thin films

Clean oriented Al₂O₃ thin film with a dominant Al₂O₃ <1 1 3> plane was deposited on Si <1 0 0> substrate at 550 °C, by single-source chemical vapor deposition (CVD) using aluminium(III) diisopropylcarbamate, Al₂(O₂CNⁱPr₂)₆. This process represents a substantial reduction in typical CVD film growth temperatures which are typically > 1000 °C. Through the studies of thermal stability of this precursor, we propose a specific β-elimination decomposition pathway to account for the low temperature of the precursor decomposition at the substrate, and for the lack of carbon impurity byproducts in the resulting alumina films that are characterized using X-ray photoelectron spectroscopy and depth profiling.     

Nanostructured ZnO network films deposited on Al2O3 substrates by chemical bath deposition

Nanostructured ZnO network films have been fabricated on Al₂O₃ substrates by the combination of chemical bath deposition and thermal decomposition process. Layered basic zinc nitrate (LBZN) network films were deposited on the Al₂O₃ substrates with LBZN crystal seeds in methanol solution of zinc nitrate hexahydrate and hexamethylenetetramine. The LBZN precursor films were then transformed into nanostructured ZnO films by heating at 260 °C in air. During the thermal decomposition process abnormal exothermic heat effect was observed at 200-210 °C and CH₃ groups were found in the as-deposited films. We propose that methanol molecules are integrated in the LBZN films forming LBZN-CH₃OH complex and that the heat effect comes from the exothermic release of the methanol.     

Improvement of adhesion of plasma-sprayed Al2O3 coatings by using dry-ice blasting

Dry-ice blasting, as an environment-friendly method, was introduced for the first time into atmospheric plasma spraying for improving properties of Al₂O₃ coatings. The tensile adhesion of the coating was examined. The microstructure of the coating was characterized using scanning electron microscopy. The temperature evolutions during the spraying were measured using an infrared pyrometer measurement system. The adhesive strength of Al₂O₃ coating deposited with dry-ice blasting exceeded 60 MPa, which was nearly increased by 30% compared with that of the coating deposited with conventional air cooling. The comparison of adhesions and microstructures of Al₂O₃ coatings plasma-sprayed with dry-ice blasting and with air cooling revealed that dry-ice blasting can optimize the coated substrate besides a cooling effect, and consequently resulted in the improved adhesion of plasma-sprayed Al₂O₃ coatings.     

Ni包覆Al2O3粉体的RCVD法制备及机理研究

金属Ni包覆于陶瓷粉体的表面,可以促进其烧结、提高导电性或赋予新的功能性质.本文采用旋转化学气相沉积法(RCVD),利用二茂镍(NiCp_2)前驱体的热分解,借助载体氢气对反应的催化促进作用,在Al_2O_3粉体表面包覆了均匀分散的Ni纳米粒子,并研究了包覆温度和原料供应速率对反应产物物相、粒度和形貌的影响规律.研究表明,在包覆温度为450~550℃、前驱体二茂镍(NiCp_2)供给速率为(0.6~2.0)×10~(-6)kg/s条件下,通过对反应过程中镍纳米粒子的包覆温度和前驱体二茂镍(NiCp_2)供给速率调控可对镍纳米粒子的粒径大小和包覆层数进行调控.结合实验结果,分析了载体氢气对二茂镍反应的催化促进作用,阐述了旋转化学气相沉积条件下Ni纳米粒子在Al_2O_3粉体表面均匀包覆的过程与机制.通过调控包覆温度和原料供应速率,可以影响前驱体二茂镍的分解行为,从而调控镍纳米粒子在Al_2O_3粉体表面的包覆状态.     

Preparation of nanocrystalline SnO2 thin film coated Al2O3 ultrafine particles by fluidized chemical vapor deposition

Fluidized chemical vapor deposition (FCVD) technology was developed for coating SnO₂ thin film on Al₂O₃ ultrafine particles. TEM and HREM analysis found that SnO₂ films with different structures were deposited by controlling the coating temperature, reactant concentration, etc. Nanocrystalline SnO₂ film was coated at 573.15 K by gas phase reaction of SnCl₄ with H₂O. EPMA and EDS studies indicated that the distribution of SnO₂ inner and outer of the agglomerates was uniform. Nucleation and film deposition were coexisted mechanism during the FCVD coating process. The fraction of SnO₂ in the composite particles increased with increasing coating temperature, SnCl₄ concentration, and coating time. The mass fraction of SnO₂ in the composite particles increased strongly with the ratio of P_H2O and P_SnCl4 at low mole ratio of H₂O with SnCl₄, but increased little under the conditions of excess H₂O with respect to SnCl₄.     

Corrosion resistance of the Al2O3+ZrO2 thermal barrier coatings on stainless steel substrates

Al₂O₃ + ZrO₂ composite thermal barrier coatings (TBCs) were deposited on SUS304 substrates using the gas tunnel type plasma spraying method. Groups of coating samples with different mixing ratios of Al₂O₃ and different thicknesses were respectively obtained. The graded microstructure of the coatings was examined using optical microscopy (OM) and a scanning electron microscope (SEM). It is well known that the thermal oxidation of interfaces is the main reason for the spallation of TBC coatings, because sprayed TBCs contain micropores and microcracks. The anodic polarization characterization of sprayed TBCs provides a way, to some extent, to investigate the mechanism of the interface oxidation. In this research, anodic polarization was performed to investigate the effect of coatings on the corrosion resistance. The results showed that a higher alumina mixing ratio and thicker coatings lead to higher corrosion resistance. The corrosion potential and deactivated corrosion current of the samples were correlated and analyzed according to the coating porosity, because the through pores in the coatings provided the way for the oxidants of the ambient solution to access the interface. The analysis indicated that lowering the porosity and increasing the gradient of coating porosity help lowering the oxidation.     

Cr2O3 thin films grown at room temperature by low pressure laser chemical vapour deposition

Chromia (Cr₂O₃) has been extensively explored for the purpose of developing widespread industrial applications, owing to the convergence of a variety of mechanical, physical and chemical properties in one single oxide material. Various methods have been used for large area synthesis of Cr₂O₃ films. However, for selective area growth and growth on thermally sensitive materials, laser-assisted chemical vapour deposition (LCVD) can be applied advantageously.Here we report on the growth of single layers of pure Cr₂O₃ onto sapphire substrates at room temperature by low pressure photolytic LCVD, using UV laser radiation and Cr(CO)₆ as chromium precursor. The feasibility of the LCVD technique to access selective area deposition of chromia thin films is demonstrated. Best results were obtained for a laser fluence of 120 mJ cm⁻² and a partial pressure ratio of O₂ to Cr(CO)₆ of 1.0. Samples grown with these experimental parameters are polycrystalline and their microstructure is characterised by a high density of particles whose size follows a lognormal distribution. Deposition rates of 0.1 nm s⁻¹ and mean particle sizes of 1.85 μm were measured for these films.     

Er2O3阻氚涂层的化学溶液法制备研究

由于具有高的绝缘性和热力学稳定性,近年来氧化铒( Er2O3)作为一种新型的阻氚渗透涂层材料受到极大的研究重视.本文采用化学溶液法在316L不锈钢基体上制备了Er2O3阻氚涂层,研究了前躯体液pH值、浓度和晶化处理气氛对涂层结构和性能的影响.结果表明,前躯体液在pH值为7.6～7.8、浓度为0.4 mol/L进行涂覆并在空气气氛中进行晶化处理,可获得表面连续、致密的Er2O3阻氚涂层,涂层与基体的结合力达到7.8 N,涂层绝缘电阻率为106 Ω·m～109Ω·m,绝缘性能、抗热冲击性能良好.     

原位气相生长法制备碳纳米管/Al2O3陶瓷复合材料

以Al₂O₃陶瓷成型体为基体,通过化学气相反应在陶瓷体内原位生长碳纳米管（CNTs）,制备出CNTs/Al₂O₃陶瓷复合材料。结果表明,Al₂O₃陶瓷体中均匀分布有可观量的多壁CNTs,碳管根部嵌于Al₂O₃晶粒间并从晶粒表面生长出。在Al₂O₃陶瓷成型体中原位生长CNTs需严格控制生长条件,尤其是生长温度（850℃）,温度过高和过低都难以长出CNTs,此外造孔剂、碳源和催化剂也影响CNTs的原位生长。对原位生长的CNTs/Al₂O₃复合体进一步高温烧结获得致密化的复合材料,其导电率达3.7 S/m,较纯Al₂O₃提高13个数量级。在陶瓷成型体中原位生长CNTs是一步法制备CNTs/陶瓷复合材料的新方法,可用于发展高性能的结构陶瓷和具有导电导热等多功能特性的新型陶瓷复合材料。     

ZnO/Al2O3 coatings for the photoprotection of polycarbonate

ZnO and ZnO/Al₂O₃ thin films were deposited by r.f. magnetron sputtering on polycarbonate (PC) films in order to protect this polymer against photodegradation. The composition, structure and optical properties of the ceramic coatings were characterised. CO₂-plasma treatments were applied to PC in order to improve the coating adhesion. The PC surface energy was characterised by wettability measurements and the chemical bonds were analysed by XPS.It was found that ZnO coatings improve the stability of PC to UV radiations and that an intermediate alumina coating inhibits the photocatalytic oxidation of PC at the PC/ZnO interface. Additionally an external alumina coating brings a high hardness to the coating.     

Mechanomaking of Fe/Al2O3 and FeCr/Al2O3 nanocomposites powders fabrication

Nanocomposite powders (Fe or Fe-Cr alloy)/-Al₂O₃ (75 and 85 vol.%) were obtained by room-temperature high-energy milling powder mixtures of hematite (and chromium oxide) with aluminum and alumina in a high-capacity mill for 8-10 h. The composition of iron and iron alloys was followed by Mössbauer spectroscopy, while the appearance of other phases was revealed by X-ray diffraction. The powder particles produced are assemblies of grains (10–20 nm in size) with a wide size distribution (from well below 1 μm up to several hundreds) and low porosity (fully dense particles). Both the metallic and ceramic phases have crystallite sizes below 15 nm for all the compositions investigated. Nano-nano type ceramic nanocomposites were, therefore, obtained.     

Chemical deposition of Al2O3 thin films on Si substrates

Uniform Al₂O₃ films were deposited on silicon substrates by the sol–gel process from stable coating solutions. The technological procedure includes spin coating deposition and investigating the influence of the annealing temperature on the dielectric properties. The layers were studied by Fourier transform infrared spectroscopy and Scanning Electron Spectroscopy. The electrical measurements have been carried out on metal–insulator–semiconductor (MIS) structures. The C–V curves show a negative fixed charge at the interface and density of the interface state, Dit, 3.7 × 10¹¹ eV^− 1cm^− 2 for annealing temperature at 750 °C.     

Atomic layer deposition of palladium films on Al2O3 surfaces

We examined the atomic layer deposition (ALD) of Pd films using sequential exposures of Pd(II) hexafluoroacetylacetonate (Pd(hfac)₂) and formalin and discovered that formalin enables the efficient nucleation of Pd ALD on Al₂O₃. In situ quartz crystal microbalance measurements revealed that the Pd nucleation is hampered by the relatively slow reaction of the adsorbed Pd(hfac)₂ species, but is accelerated using larger initial Pd(hfac)₂ and formalin exposures. Pd nucleation proceeds via coalescence of islands and leaves hfac contamination at the Al₂O₃ interface. Pd films were deposited on the thermal oxide of silicon, glass and mesoporous anodic alumina following the ALD of a thin Al₂O₃ seed layer and analyzed using a variety of techniques. We measured a Pd ALD growth rate of 0.2 Å/cycle following a nucleation period of slower growth. The deposited films are cubic Pd with a roughness of 4.2 nm and a resistivity of 11 μΩ cm at 42 nm thickness. Using this method, Pd deposits conformally on the inside of mesoporous anodic alumina membranes with aspect ratio ∼1500 yielding promising hydrogen sensors.     

机械化学合成Ni2Al3/Al2O3去合金化制备Raney-Ni/Al2O3复合粉体

以NiO粉和Al粉为原料,采用机械球磨诱发化学反应制备了Ni_2Al_3/Al_2O_3复合粉体。利用X射线衍射仪(XRD)和附带能量色散谱仪(EDS)的扫描电子显微镜(SEM)对复合粉体球磨过程中的固态反应过程、表面形貌进行表征。将Ni_2Al_3/Al_2O_3复合粉体用浓度为20%的NaOH溶液腐蚀2h,可得到纳米晶结构的Ni/Al_2O_3复合粉体。利用XRD和TEM对其物相和结构进行了表征。结果表明,球磨1h后混合粉末仍为NiO粉和Al粉,球磨3h后NiO粉和Al粉在机械力的作用下反应形成Ni_2Al_3和Al_2O_3粉体,机械力诱发的NiO和Al之间的反应属于突发型反应,继续球磨10h后形成Ni_2Al_3/Al_2O_3复合粉体。Ni_2Al_3/Al_2O_3复合粉体在70℃、质量比为20%NaOH溶液中刻蚀2h,可获得Ni/Al_2O_3复合粉体。