Tungsten trioxide thin films prepared by electrostatic spray deposition technique

Tungsten trioxide (WO₃) thin films deposited on a Pt-coated alumina substrate using the electrostatic spray deposition (ESD) technique is reported in this paper. As precursor solution, tungsten (VI) ethoxide in ethanol was used. The morphology and the microstructure of the films were studied using scanning electron microscopy coupled with energy dispersive X-ray analysis, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy. Dense to porous morphologies were obtained by tuning the deposition temperature. Impedance spectroscopy and current-voltage measurements were used to study the electrical behaviour of the films in air, in temperature range 300-500 °C. The activation energy was estimated from Arrhenius plots. Considering the obtained results, the ESD technique proved to be an effective technique for the fabrication of porous tungsten trioxide thin films.     

Synthesis of carbon nanofiber films and nanofiber composite coatings by laser-assisted catalytic chemical vapor deposition

Uniform carbon nanofiber films and nanofiber composite coatings were synthesized from ethylene on nickel coated alumina substrates by laser-assisted catalytic chemical vapor deposition. Laser annealing of a 50 nm thick nickel film produced the catalytic nanoparticles. Thermal decomposition of ethylene over nickel nanoparticles was initiated and maintained by an argon ion laser operated at 488 nm. The films were examined by scanning electron microscopy and by transmission electron microscopy. Overall film uniformity and structure were assessed using micro-Raman spectroscopy. Film quality was related to the experimental parameters such as incident laser power density and irradiation time. For long irradiation times, carbon can be deposited by a thermal process rather than by a catalytic reaction directly over the nanofiber films to form carbon nanocomposite coatings. The process parameters leading to high quality nanofiber films free of amorphous carbon by-products as well as those leading to nanofiber composite coatings are presented.     

磷酸处理对多孔SiO2薄膜质子导电特性和双电层薄膜晶体管性能的影响

采用等离子体增强化学气相沉积法(PECVD)制备了多孔SiO₂薄膜, 系统地研究了不同浓度磷酸处理对多孔SiO₂薄膜的质子导电特性、双电层电容和以此多孔SiO₂薄膜为栅介质的铟锌氧(IZO)双电层薄膜晶体管性能的影响。结果表明: 多孔SiO₂薄膜的质子电导率和双电层电容随磷酸浓度升高而增大, 60%浓度磷酸处理后多孔SiO₂薄膜质子电导率和双电层电容分别达到1.51×10^-4 S/cm和6.33 μF/cm²。随磷酸浓度升高, 双电层薄膜晶体管的工作电压降低, 并且, 电流开关比也变大。其中60%浓度磷酸处理后器件工作电压为1.2 V, 迁移率为20 cm²/(V·s), 电流开关比为4×10⁶。这种双电层薄膜晶体管有望应用在化学和生物传感等领域。     

Preparation of (Ti1−xAlx)N films from mixed alkoxide solutions by plasma CVD

(Ti_1−xAl_x)N films were prepared on a Si wafer at 700°C from toluene solution of alkoxides (titanium tetraetoxide and aluminum tri-butoxide) in an Ar/N₂/H₂ plasma by the thermal plasma chemical vapor deposition (CVD) method. The films were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, electrical resistivity, and Vickers micro-hardness. Single phase TiN formed at an Al atomic fraction of 0–0.2, with a mixed TiN and AlN phase occurring up to 0.6 and single phase AlN forming above 0.8. The films had relatively sooth surfaces, 0.4 μm thick at an Al atomic fraction of 0.2, and thickened with increasing Al fraction. The atomic concentration of Ti, Al, N, O, and C determined from their respective XPS areas showed that the Ti and Al contents of the films changes with the solution composition in a complementary way. The impurities were about 10 at.% oxygen and carbon. The electrical resistivity was almost unchanged from the value of 10³ μΩ cm at 0–0.6 Al but then suddenly increased to 10⁴ μΩ cm at higher Al contents. The hardness showed a synergic maximum of about 20 GPa at an Al fraction of 0.6–0.8.     

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.     

Optical properties of rare earth ion (Nd, Er and Tb)-doped alumina films prepared by the sol–gel method

Rare earth ion (Nd³⁺, Er³⁺ and Tb³⁺)-doped alumina films were prepared by the sol–gel method using aqueous alumina sol. The effects of dopant concentration and treatment temperature on the optical properties, absorption and emission were examined for the doped films. Alumina films prepared by this method gave a high dopant concentration (0–15 mol% per alumina). Significant concentration quenching did not occur in this concentration range. The emissions from ⁵D₃ and ⁵D₄ of Tb³⁺-doped film reflected sensitively a matrix environment around Tb³⁺ ions. Er³⁺- and Nd³⁺-doped alumina films resonantly excited by cw Ti–sapphire laser (800 nm) showed upconversion emission at room temperature. The former gave 548 nm (⁴S_3/2→⁴I_15/2) and 640 nm (⁴F_9/2→⁴I_11/2) signals, and the latter 640 nm (⁴G_7/2→⁴I_11/2), which were dependent on alumina.     

AC impedance spectroscopy of porous silicon thin films containing metallic cations

Thin porous silicon (PS) films were prepared by HF/HNO₃ vapor etching on silicon wafers. The infiltration of metallic cations inside the porous silicon matrix followed by slow heating in air leads to an interesting electrical and optical physical phenomena. Al³⁺, Cu⁺, K⁺, Li⁺ metallic cations as chloride or as nitrate solutions are infiltrated inside the silicon porous matrix. After annealing in air at 500 °C during 2 h a structure was achieved in order to measure the Nyquist diagram corresponding to the cations embedded in PS/silicon. The real and imaginary parts of the whole structure depend on the voltage bias and on the frequency. Those signify that the junction is a Schotky-barrier junction.

From the variation of Ln(σT) versus absolute temperature T, where σ is the conductivity, we have deduced the activation energy of the metallic impurities in the [100 °C–400 °C] temperature range. We have found that the activation energies are of about 0.19 eV, 0.25 eV, 0.49 eV and 0.71 eV for Cu⁺, K⁺, Al³⁺ and Li⁺ cations respectively. These kinds of structures are suitable for gas sensing, optical sensing or for the fabrication of fuel cell membranes.     

Fibrous monoliths of mullite-AlPO4 and alumina/YAG-alumina platelets

Two-layer, fibrous monolithic composites consisting of mullite-aluminum phosphate (AlPO₄) and 50 vol.% alumina:50 vol.% YAG in situ composite matrix–alumina platelet interphase components, were fabricated by a co-extrusion technique. The four powders were characterized for particle size, specific surface area, and SEM analysis. The mixing formulations for extruding the powders were developed using ethylene vinylacetate copolymer as a binder. The variation in the mixing torque, in a Brabender mixer, as a function of temperature was measured. The binder removal behavior of the mullite-AlPO₄ fibrous monolithic composite was studied by thermogravimetric analysis (TGA). The AlPO₄ and alumina platelet interphase layers formed a porous and less porous interphase region, respectively, after sintering. The sintered mullite-AlPO₄ two-layer fibrous monolithic showed non-brittle fracture behavior. Its 3-point bend strength and work of fracture were 76 ± 5 MPa and 0.45 ± 0.02 kJ/m², respectively.     

Reactions in Au/Nb bilayer thin films

The interdiffusion and intermetallic compound formation of Au/Nb bilayer thin films annealed at 200–400 °C have been investigated. The bilayer thin films were prepared by electron beam deposition. The Nb film was 50 nm thick and the Au film was 50–200 nm thick. The interdiffusion of annealed specimens was examined by measuring the electrical resistance and depth-composition profile and by transmission electron microscopy. Interdiffusion between the thin films was detected at temperatures above 325 °C in a vacuum of 10^-4 Pa. The intermetallic compound Au₂Nb₃ and other unknown phases form during annealing at over 400 °C. The apparent diffusion constants, determined from the penetration depth for annealing at 350 °C, are 3.5 × 10⁻¹⁵ m² s⁻¹ for Nb in Au and 8.6 × 110^7minus;15 m² s⁻¹ for Au in Nb. The Au surface of the bilayer films becomes uneven after annealing at over 400 °C due to the reaction.     

Highly conducting doped poly-Si deposited by hot wire CVD and its applicability as gate material for CMOS devices

Highly conducting p- and n-type poly-Si:H films were deposited by hot wire chemical vapor deposition (HWCVD) using SiH₄+H₂+B₂H₆ and SiH₄+H₂+PH₃ gas mixtures, respectively. Conductivity of 1.2×10² (Ω cm)⁻¹ for the p-type films and 2.25×10² (Ω cm)⁻¹ for the n-type films was obtained. These are the highest values obtained so far by this technique. The increase in conductivity with substrate temperature (T_s) is attributed to the increase in grain size as reflected in the atomic force microscopy results. Interestingly conductivity of n-type films is higher than the p-type films deposited at the same T_s. To test the applicability of these films as gate contact Al/poly-Si/SiO₂/Si capacitor structures with oxide thickness of 4 nm were fabricated on n-type c-Si wafers. Sputter etching of the poly-Si was optimized in order to fabricate the devices. The performance of the HWCVD poly-Si as gate material was monitored using C–V measurements on a MOS test device at different frequencies. The results reveal that as deposited poly-Si without annealing shows low series resistance.     

The optical and electrical properties of copper indium di-selenide thin films

Thin films of copper indium di-selenide (CIS) with a wide range of compositions near stoichiometry have been formed on glass substrates in vacuum by the stacked elemental layer (SEL) deposition technique. The compositional and optical properties of the films have been measured by proton-induced X-ray emission (PIXE) and spectrophotometry (photon wavelength range of 300–2500 nm), respectively. Electrical conductivity (σ), charge-carrier concentration (n), and Hall mobility (μ_H) were measured at temperatures ranging from 143 to 400 K. It was found that more indium-rich films have higher energy gaps than less indium-rich ones while more Cu-rich films have lower energy gaps than less Cu-rich films. The sub-bandgap absorption of photons is minimum in the samples having Cu/In ≈ 1 and it again decreases, as Cu/In ratio becomes less than 0.60. Indium-rich films show n-type conductivities while near-stoichiometric and copper-rich films have p-type conductivities. At 300 K σ, n and μ_H of the films vary from 2.15 × 10⁻³ to 1.60 × 10⁻¹ (Ω cm)⁻¹, 2.28 × 10¹⁵ to 5.74 × 10¹⁷ cm⁻³ and 1.74 to 5.88 cm² (V s)⁻¹, respectively, and are dependent on the composition of the films. All the films were found to be non-degenerate. The ionization energies for acceptors and donors vary between 12 and 24, and 3 and 8 meV, respectively, and they are correlated well with the Cu/In ratios. The crystallites of the films were found to be partially depleted in charge carriers.     

Solid polymer electrolytes based on poly(vinylchloride)–lithium sulfate

Ionic conductivity studies in the temperature range 304–373 K for PVC---Li₂SO₄---dibutylphthalate polymer electrolyte systems are reported and discussed. Poly(vinylchloride) (PVC) has an electrical conductivity 10⁻⁸ S cm⁻¹. The prepared films were studies by X-ray diffraction, Fourier transformation infrared, scanning electron microscopy and thermal analysis. The temperature dependence of the conductivity of the polymer films obeys the Vogel–Tammann–Fulcher relation.     

VACUUM VAPOR DEPOSITION PROCESS FOR CERAMICS DEVELOPMENT OF THE VACUUM VAPOR DEPOSITION PROCESS FOR CERAMICS BY CO2 LASER

The vacuum vapor deposition process using a CO₂lase; has been studied (or producing high adhesion ceramic films on various materials. Deposition of aluminum oxide and silicon oxide films with adhesion strengths above 50 MPa on stainless steel was achieved at high deposition rates with substrate heating, For silicon oxide films, addition of a moderate oxygen supply allowed deposition of highly adherent films at lower substrate temperatures. Adhesion strengths above 50 MPa were estimated at a substrate temperature of 470°K and an oxygen flow rate of 1.9 x 10^-7 m₃/s, in spitof the high deposition rate of 30 nm/s     

Processing of alumina and zirconia nano-powders and compacts

Magnesia–doped alumina and yttria–doped zirconia nano-powders were synthesized using sucrose as a chelating agent and template material from the aqueous solutions of aluminium nitrate, magnesium nitrate, ytrrium nitrate and zirconyl nitrate, respectively. Synthesis parameters were optimized with varying sucrose to metal ion ratio, calcinations time, and temperature to produce these nano-powders. As-synthesized powders were characterized by room temperature X-ray diffraction, BET surface area analyzer and transmission electron microscopy. Y₂O₃–ZrO₂ nano-powders had particle size in the range of 80–200 nm with specific average surface area of 119 m²/g and for MgO–Al₂O₃ powders, particle sizes were 30–200 nm with the specific average surface area of 250 m²/g. Our results indicate that this synthesis method is a versatile one and can be applied to a variety of oxide-based materials to form nano-powders. Nano-powders were compacted uniaxially and densified in a muffle furnace. Sintered discs were used for hardness testing and density measurements, as well as for microstructural characterization.     

Growth and properties of silicon nitride films prepared by low pressure chemical vapor deposition using trichlorosilane and ammonia

Amorphous silicon nitride (a-SiN_x) films were prepared by low pressure chemical vapor deposition from SiHCl₃(Trichlorosilane, TCS)---NH₃---N₂ system to obtain stoichiometric film with low hydrogen content. The growth kinetics was investigated as a function of total pressure, NH₃/TCS flow ratio and deposition temperature. The film compositions and topography were characterized by X-ray photoelectron spectroscopy, Auger depth profile, Fourier transform infrared spectroscopy, elastic recoil detection and atomic force microscopy, respectively. The growth rate of the films follows an Arrhenius behavior with apparent activation energy of 171 kJ mol⁻¹ between 730 and 830 °C. At lower NH₃/TCS flow rate ratios, silicon-rich a-SiN_x films were obtained while all deposits were stoichiometric with a N/Si atomic ratio of approximately 1.30–1.33 as the ratios is higher. The hydrogen content of the prepared a-SiN_x films is 1.2 at.% that is approximately 15 times lower than those of traditional PECVD films and approximately three times lower than those of previous LPCVD films using silane or dichlorosilane and ammonia. The surface topography of the prepared film is smooth and uniform with a root mean square roughness value of 0.47 nm.     

Granular nanocrystalline zirconia electrolyte layers deposited on porous SOFC cathode substrates

Thin granular yttria-stabilized zirconia (YSZ) electrolyte layers were prepared by chemical vapor synthesis and deposition (CVD/CVS) on a porous substoichiometric lanthanum–strontium–manganite (ULSM) solid oxide fuel cell cathode substrate. The substrate porosity was optimized with a screen printed fine porous buffer layer. Structural analysis by scanning electron microscopy showed a homogeneous, granular nanocrystalline layer with a microstructure that was controlled via reactor settings. The CVD/CVS gas-phase process enabled the deposition of crack-free granular YSZ films on porous ULSM substrates. The electrolyte layers characterized with impedance spectroscopy exhibited enhanced grain boundary conductivity.     

CVD of hard DLC films in a radio frequency inductively coupled plasma source

Chemical vapor deposition (CVD) of hard diamond-like carbon (DLC) films on silicon (100) substrates from methane was successfully carried out using a radio frequency (r.f.) inductively coupled plasma source (ICPS). Different deposition parameters such as bias voltage, r.f. power, gas flow and pressure were involved. The structures of the films were characterized by Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy. The hardness of the DLC films was measured by a Knoop microhardness tester. The surface morphology of the films was characterized by atomic force microscope (AFM) and the surface roughness (R_a) was derived from the AFM data. The films are smooth with roughness less than 1.007 nm. Raman spectra shows that the films have typical diamond-like characteristics with a D line peak at 1331 cm⁻¹ and a G line peak at 1544 cm⁻¹, and the low intensity ratio of I_D/I_G indicate that the DLC films have a high ratio of sp³ to sp² bonding, which is also in accordance with the results of FTIR spectra. The films hardness can reach approximately 42 GPa at a comparatively low substrate bias voltage, which is much greater than that of DLC films deposited in a conventional r.f. capacitively coupled parallel-plate system. It is suggested that the high plasma density and the suitable deposition environment (such as the amount and ratio of hydrocarbon radicals to atomic or ionic hydrogen) obtained in the ICPS are important for depositing hard and high quality DLC films.     

High concentration erbium doping of silicon-rich SiO2 thin films on silicon

In this work, high concentration erbium doping in silicon-rich SiO₂ thin films is demonstrated. Si plus Er dual-implanted thermal SiO₂ thin films on Si substrates have been fabricated by using a new method, the metal vapor vacuum arc ion source implantation with relatively low ion energy, strong flux and very high dose. X-Ray photoelectron spectroscopy measurement shows that very high Er concentrations on the surfaces of the samples, corresponding to 10 at.% or the doping level of 10²¹ atoms cm⁻³, are achieved. This value is much higher than that obtained by using other fabrication methods such as the high-energy ion implantation and molecular beam epitaxy. Reflective high-energy electron diffraction, atomic force microscopy and cross-section high-resolution transmission electron microscopy observations show that the excess Si atoms in SiO₂ matrix accumulate to form Si clusters and then crystallize gradually into Si nanoparticles embedded in SiO₂ films during dual-ion implantation followed by rapid thermal annealing. Er segregation and precipitates are not formed. Photoluminescence at the wavelength of 1.54 μm exhibits very weak temperature dependence due to the introduction of Si nanocrystals into the SiO₂ matrix. The 1.54-μm light emission signals from annealed samples decrease by less than a factor of 2 when the measuring temperature increases from 77 K to room temperature.     

Corrosion resistant coatings (Al2O3) produced by metal organic chemical vapour deposition using aluminium-tri-sec-butoxide

The metal organic chemical vapour deposition (MOCVD) of amorphous alumina films on steel was performed in nitrogen at atmospheric pressure. This MOCVD process is based on the thermal decomposition of aluminium-tri-sec-butoxide (ATSB). The effect of the deposition temperature (within the range 290–420 °C), the precursor vapour pressure (5.33×10^-3−2.67×10^-2 kPa), and the gas flow (6.5−12.5 1 min^-1) of the MOCVD process have been studied in relation to corrosion properties at high temperatures. The corrosion experiments were performed at 450 °C in a gas atmosphere containing 1% H₂S, 1% H₂O, 19% H₂, and balanced Ar.

It was found that the amount of corrosion products on an alumina film (0.20±0.05 mg cm^-2)-AISI 304 combination decreased with increasing deposition temperature of the coating. This was more pronounced for the products formed through the coating owing to a certain porosity. The crack density, where products were also formed, was almost unaffected.     

316L不锈钢基体氧化铝涂层的氢渗透性能

在316L不锈钢上采用金属有机化学气相沉积(MOCVD)法沉积了氧化铝涂层。使用XRD、SEM分析氧化铝涂层的物相和微观形貌, 采用气相氢渗透装置对涂层氢渗透行为进行表征。结果表明, 973 K退火处理后涂层为非晶氧化铝, 涂层均匀、完整, 厚度为190 nm。氧化铝涂层的氢渗透压力指数为0.56~0.78, 说明氢渗透过程机制为表面过程和体扩散过程共同控制。氧化铝涂层的表观氢渗透率为P = 1.99×10^-6 exp(-117×10³/RT) mol/(m·s·Pa^1/2)。氧化铝涂层的氢渗透激活能为117 kJ/mol, 远高于316L不锈钢的66.6 kJ/mol, 涂层对氢的渗透具有明显的阻挡作用。此外, 在873~973 K氧化铝涂层对316L不锈钢的氢渗透阻挡因子(PRF)为59~119, 涂层氢渗透阻挡性能优异。