Fabricating TiO2 Photocatalysts by rf Reactive Magnetron Sputtering at Varied Oxygen Partial Pressures

Titanium dioxide (TiO₂) thin films were fabricated onto non-alkali glass substrates by rf reactive magnetron sputtering at room temperature using Ti-metal target at varied oxygen partial pressure [O₂/(Ar + O₂)]. The sputtering deposition was performed under an rf power of 200 W. The target to substrate distance was kept at 80 mm, and the total gas pressure was 10 mTorr after 2 h of deposition. It was found that the crystalline structure, surface morphology, and photocatalytic activities of the TiO₂ thin films were affected by the oxygen partial pressure during deposition. The XRD patterns exhibited a broad-hump shape indicating the amorphous structure of TiO₂ thin films. The thin films deposited at a relatively high value of oxygen partial pressure (70%) had a good photo-induced decomposition of methylene blue (MB), photo-induced hydrophilicity, and had a small grain size.     

Reactive sputtering of TiOxNy coatings by the reactive gas pulsing process: Part II: The role of the duty cycle

The reactive gas pulsing process (RGPP) was used to deposit titanium oxynitride thin films by dc reactive magnetron sputtering. A titanium target was sputtered in a reactive atmosphere composed of Ar + O₂ + N₂. Argon and nitrogen gases were continuously introduced into the sputtering chamber whereas oxygen was injected with a well-controlled pulsing flow rate following a rectangular and periodic signal. A constant pulsing period T = 45 s was used for every deposition and the duty cycle α = t_ON/T was systematically changed from 0 to 100%. The operating conditions were investigated taking into account the poisoning phenomena of the target surface by oxygen and nitrogen. Kinetics of poisoning were followed from measurements of the total sputtering pressure and titanium target potential during the depositions. Deposition rate and optical transmittance of titanium oxynitride coatings were also analysed and correlated with the process parameters. Pulsing the oxygen flow rate with rectangular patterns and using suitable duty cycles, RGPP method allows working according to reversible nitrided-oxidised target conditions and leads to the deposition of a wide range of TiO_xN_y thin films, from metallic TiN to insulating TiO₂ compounds.     

Fabrication and characterization of ceramic thin films by RF magnetron sputtering using Zn-enriched (Ba0.3Sr0.7)(Zn1/3Nb2/3)O3 as target

Dielectric ceramic thin film was fabricated on SiO₂ (1 1 0) substrates by radio frequency (RF) magnetron sputtering method using a Zn-enriched (Ba_0.3Sr_0.7)(Zn_1/3Nb_2/3)O₃ target. The microstructure, components, and morphological properties of the thin films were characterized thoroughly. The results reveal that the main phases of the thin films are Ba_xSr_1−xNb₂O₆, which are of different compositions from that of the ceramic target due to Zn loss. The thin films are polycrystalline and of dense structure with uniform grain sizes and well-defined grain boundaries.     

Filtered vacuum arc deposition of undoped and doped ZnO thin films: Electrical, optical, and structural properties

Filtered vacuum (cathodic) arc deposition (FVAD, FCVD) of metallic and ceramic thin films at low substrate temperature (50-400 °C) is realized by magnetically directing vacuum arc produced, highly ionized, and energetic plasma beam onto substrates, obtaining high quality coatings at high deposition rates. The plasma beam is magnetically filtered to remove macroparticles that are also produced by the arc. The deposited films are usually characterized by their good optical quality and high adhesion to the substrate. Transparent and electrically conducting (TCO) thin films of ZnO, SnO₂, In₂O₃:Sn (ITO), ZnO:Al (AZO), ZnO:Ga, ZnO:Sb, ZnO:Mg and several types of zinc-stannate oxides (ZnSnO₃, Zn₂SnO₄), which could be used in solar cells, optoelectronic devices, and as gas sensors, have been successfully deposited by FVAD using pure or alloyed zinc cathodes. The oxides are obtained by operating the system with oxygen background at low pressure. Post-deposition treatment has also been applied to improve the properties of TCO films.The deposition rate of FVAD ZnO and ZnO:M thin films, where M is a doping or alloying metal, is in the range of 0.2-15 nm/s. The films are generally nonstoichiometric, polycrystalline n-type semiconductors. In most cases, ZnO films have a wurtzite structure. FVAD of p-type ZnO has also been achieved by Sb doping. The electrical conductivity of as-deposited n-type thin ZnO film is in the range 0.2-6 × 10^− 5 Ω m, carrier electron density is 10²³-2 × 10²⁶ m^− 3, and electron mobility is in the range 10-40 cm²/V s, depending on the deposition parameters: arc current, oxygen pressure, substrate bias, and substrate temperature. As the energy band gap of FVAD ZnO films is ∼ 3.3 eV and its extinction coefficient (k) in the visible and near-IR range is smaller than 0.02, the optical transmission of 500 nm thick ZnO film is ∼ 0.90.     

Structural and optical properties of electrodeposited ZnO thin films on conductive RuO2 oxides

ZnO thin films were grown on the 150 nm-thick RuO₂-coated SiO₂/Si substrates by electrochemical deposition in zinc nitrate aqueous solution with various electrolyte concentrations and deposition currents. Crystal orientation and surface structure of the electrodeposited ZnO thin films were characterized by X-ray diffraction (XRD) and scanning electron microscopy, respectively. The XRD results show the as-electrodeposited ZnO thin films on the RuO₂/SiO₂/Si substrates have mixed crystallographic orientations. The higher electrolyte concentration results in the ZnO thin films with a higher degree of c-axis orientation. Moreover, the use of an ultra-thin 5 nm-thick ZnO buffer layer on the RuO₂/SiO₂/Si substrate markedly improves the degree of preferential c-axis orientation of the electrodeposited ZnO crystalline. The subsequent annealing in vacuum at a low temperature of 300 °C reduces the possible hydrate species in the electrodeposited films. The electrodeposited ZnO thin films on the 5 nm-thick ZnO buffered RuO₂/SiO₂/Si substrates grown in 0.02 M electrolyte at −1.5 mA with a subsequent annealing in vacuum at 300 °C had the best structural and optical properties. The UV to visible emission intensity ratio of the film can reach 7.62.     

A giant polarization value in bismuth ferrite thin films

An approach is used to improve the remanent polarization of BiFeO₃ thin films, where the BiFe_0.96Zn_0.04O₃ thin film with (1 1 1) orientation was grown on the SrRuO₃/SrTiO₃(1 1 1) substrate by rf sputtering. A higher dielectric constant and a lower dielectric loss are demonstrated for the BiFe_0.96Zn_0.04O₃ thin film as compared with those of pure BiFeO₃ thin film. The introduction of Zn deteriorates the magnetic properties of BFO thin films. A giant polarization value of 2P_r ∼ 268.5 μC/cm² is induced for the BiFe_0.96Zn_0.04O₃ thin film as confirmed by PUND, owing to the (1 1 1) orientation, the introduction of Zn, and a low leakage current density.     

Lanthanum silicate thin films for SOFC electrolytes synthesized by magnetron sputtering and subsequent annealing

Thin films of La and Si with Si/(La + Si) atomic ratios ranging from 0.36 to 0.44 were produced by magnetron sputtering in pure Ar. For all compositions, the apatite-like La_9.33Si₆O₂₆ phase was formed during annealing in air at 900 °C. A preferential orientation was developed during annealing of the films with higher silicon content while formation of oxide impurities was detected for the films with less silicon. Silicon segregation to the thin film/substrate interface was observed after annealing for thin films with higher Si/(La + Si) atomic ratios. The higher ionic conductivity values were obtained with the films with lower silicon content (2.81 × 10^− 3 Scm^− 1 at 800 °C for the film with Si/(La + Si) atomic ratio of 0.36). This film presented the lower activation energy E_a (0.94 eV).     

Oxidation resistance and mechanical property of cosputtered quasi-amorphous Ta-Si-N films under vacuum rapid thermal annealing

The oxidation resistance and mechanical properties of Ta-Si-N films at high temperature are important issues for application. In this paper, quasi-amorphous Ta-Si-N thin films were fabricated by using reactive magnetron co-sputtering at different Si/Ta power ratios and nitrogen flow ratios (FN₂% = FN₂/(FAr + FN₂) × 100%). Vacuum rapid thermal annealing at 600-900 °C at 2.6 Pa was performed to investigate the oxidation resistance of films. At the higher Si/Ta power ratio and increased FN₂%, there is low oxygen fraction (O/(O + N) ≤ 0.2) of films at high annealing temperature which corresponds to benefit oxidation resistance. The crystalline δ-Ta₂O₅ phase was formed at 900 °C for all films. The islands of oxide were formed on the surface of films at low-Si-content (≤ 20 at.%) after 900 °C annealing. The hardness of all as-deposited Ta-Si-N films was between 16 and 24 GPa. The low-Si-content Ta-Si-N films has higher hardness than high-Si-content (≥ 20 at.%) ones due to lower fraction of soft amorphous SiN_x. The effect of annealing temperature on the correlation among process parameters, microstructure, phase transformation and hardness is discussed. The Ta-Si-N formed at 6 FN₂% and Si/Ta power ratio of 2/1 can be the best candidate for good oxidation resistance with appropriate mechanical property.     

Oxidation of single crystal PWA 1483 at 950 °C in flowing air

The oxidation behaviour of single crystal PWA 1483 at 950 °C was investigated by means of XRD, SEM and EDS. The parabolic oxidation behaviour, as defined by mass gain and the respective oxide layer thicknesses, is characterized by a parabolic rate constant of about 4 × 10⁻⁶ mg²/(cm⁴ × s) and the formation of a multi-layered oxide scale. An outer scale contains a Ti-bearing thin film composed of TiO₂ and NiTiO₃ but mostly Cr in Cr₂O₃ and (Ni/Co)Cr₂O₄ besides NiTaO₄. This outer scale is connected to a discontinuous layer of Al₂O₃ and an area of γ′-depletion within the base material.     

Compositionally graded bismuth ferrite thin films

The compositionally graded (Bi_0.92La_0.08)(Fe_1−xZn_x)O₃ (x = 0.03, 0.07, and 0.13) thin film was layer-by-layer grown on Pt/Ti/SiO₂/Si(1 0 0) substrates without any buffer layers by radio frequency sputtering. This thin film has a pure polycrystalline perovskite structure with random orientation, a dense microstructure, and a low leakage current density. A large remanent polarization of 2P_r ∼ 142.00 μC/cm² and a good magnetic behavior of 2 M_s ∼ 27.52 emu/cm³ are demonstrated in such a thin film. The applied electric fields and measurement frequencies strongly affect its fatigue endurance, that is, its fatigue endurance was degraded with decreasing frequencies and electric fields.     

Proposal of self-healing coatings for nuclear fusion applications

Avoiding cracks in ceramic coatings is one of the most important problems to be solved for the thermally sprayed tritium permeation barriers in fusion reactor. In this paper, a self-healing composite coating composed of TiC + mixture (TiC/Al₂O₃) + Al₂O₃ was developed to address this problem. The coating was deposited on certain martensitic steel by plasma spraying. The morphology and phase of the coating were investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD) while the porosity was analyzed by using Image Pro software. The thermal shock resistance test and residual stress measurement of the coating were also performed. In the experiment, NiAl + TiC + mixture (TiC/Al₂O₃) + Al₂O₃ and mixture (TiC/Al₂O₃) + Al₂O₃ films were also fabricated and studied respectively. The results showed that the TiC + mixture (TiC/Al₂O₃) + Al₂O₃ coating exhibited the best mechanical integrity and self-healing ability among the three samples with the porosity decreased by 90% after heat-treatment under normal atmosphere. The oxidation/expansion of TiC in the coating played an important role in the sealing of pores. This self-healing coating made by thermal spraying is proposed as a good candidate for tritium permeation barrier in fusion reactors.     

Effects of deposition parameters on characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition

The effects of deposition parameters on characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition are investigated. The deposition parameters are selected as follows. The CH₄/(CH₄ + N₂) ratio is in the range between 20% and 100%; the temperature is set from 1173 to 1248 K; the working pressure is arranged between 50 and 100 kPa, and the residence time is ranging from 1.47 to 7.37 s. The deposition rate, microstructure, and electrical resistivity of carbon coatings are measured. The low-temperature surface morphology of carbon-coated optical fibers is elucidated. Experimental results indicate that the deposition rate increases with increasing the CH₄/(CH₄ + N₂) ratio, deposition temperature, working pressure, and residence time. The activation energy (= 456 kJ/mol) of carbon deposition from methane was shown to correlate to the activation energy of methane dissociation. The deposition rate is proportional to about first-order of partial pressure of methane, and thus, the deposition process is mainly controlled by the process to create mono-carbon species in the carbon film. As the deposition rate increases, the size and number of particles on the carbon coating surface and electrical resistivity of carbon coatings increase, while the ordered degree, nano-crystallite size, and sp² carbon atoms of the carbon coatings decrease. Additionally, the low-temperature surface morphology of carbon coatings shows that as the carbon coating thickness is large enough to sustain the thermal loading, decreasing the deposition rate is good for producing hermetic optical fiber coatings.     

Solution processing of V2O5-WO3 composite films for enhanced Li-ion intercalation properties

We have employed a simple and novel solution processing method to prepare V₂O₅-WO₃ composite films which demonstrate enhanced Li-ion intercalation properties for applications in lithium-ion batteries or electrochromic displays. This solution processing method employs precursors that only contain the elements of V, W, O and H, which avoids impurity elements such as Na that has been commonly used in other solution methods (e.g. using precursors of sodium metavanadate and sodium tungstate solution). The V₂O₅-WO₃ composite films show enhanced Li-ion intercalation properties compared to pure V₂O₅ and WO₃ films. For example, at a high current density of 1.33 A/g, V₂O₅-WO₃ film with a V₂O₅/WO₃ molar ratio of 10/1 exhibits the highest capacities of 200 mA h/g at the first cycle and 132 mA h/g after 50 cycles, while pure V₂O₅ film delivers discharge capacities of 108 mA h/g at the first cycle and 122 mA h/g after 50 cycles. The enhanced Li-ion intercalation properties of the composite films are ascribed to the reduced crystallinity, the increased porosity and thus the enhanced surface area. Both the cyclic voltammogram and chronopotentiometric curves of the V₂O₅-WO₃ film with a molar ratio of 10:1 are distinctively different from those of pure oxide films, suggesting a different Li-ion intercalation process in the V₂O₅-WO₃ film with the molar ratio of 10:1.     

Magnetic Properties,Microwave Characteristics,and Thermal Stability of the FeCoAlN Films

FeCoAlN films were prepared by reactive radio frequency magnetron co-sputtering technique in an argon and nitrogen mixture atmosphere. The soft magnetic properties, GHz dynamic properties, and magnetic thermal stability of the FeCoAlN films were investigated. The FeCoAlN films deposited at N₂/(Ar + N₂) gas flux percentages larger than 8% have amorphous structure. The (Fe_64.8Co_35.2)_96.3Al_3.7N film as-deposited at the N₂/(Ar + N₂) gas flux percentage of 9% has good magnetic softness and uniaxial in-plane anisotropy, as demonstrated by the typical hysteresis loops along easy and hard axis. The magnetic thermal stability of the FeCoN films can be obviously improved by introduction of a high Al content. The (Fe_64.8Co_35.2)_86.5Al_13.5N films annealed at 400 °C for 1 h exhibit good magnetic softness and GHz dynamic properties with a saturation magnetization (μ₀ M _s) of 1.21 T, an easy axis coercive field (H _ce) of 8.5 Oe, an anisotropy field (H _k) of 35 Oe, a ferromagnetic resonance frequency (f _r) of 1.89 GHz, and a real part of permeability (μ′) of 380. The dynamic characteristics can be described by the theoretical model based on Landau-Lifshitz-Gilbert (L-L-G) equation and eddy current dynamics.     

Fabrication and properties of Ba(Zr1−xCex)0.9Y0.1O2.95/NaCl composite electrolyte materials

Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95/NaCl (x = 0.1, 0.2 and 0.3) composite electrolyte materials were fabricated with ZnO as sintering aid. The effect of ZnO on the properties of Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 matrix were investigated. The phase composition and microstructure of samples were characterized by XRD and SEM, respectively. The electrochemical performances were studied by three-probe conductivity measurement and AC impedance spectroscopy. XRD results showed that Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 with 2 mol% of ZnO was perovskite structure. The relative density of this sample was above 95% when sintered at 1450 °C for 6 h. By adding 10 mol% of NaCl to Ba(Zr_1−xCe_x)_0.9Y_0.1O_2.95 with 2 mol% of ZnO that was sintered at 1400 °C for 6 h, the conductivity was increased. The electrical conductivity of 1.26 × 10⁻² S/cm and activation energy of 0.23 eV were obtained when tested at 800 °C in wet hydrogen.     

Constitution, microstructure, and battery performance of magnetron sputtered Li-Co-O thin film cathodes for lithium-ion batteries as a function of the working gas pressure

Li-Co-O thin film cathodes have been deposited onto Si and stainless steel substrates by RF magnetron sputtering from a ceramic LiCoO₂ target at various working gas pressures from 0.15 to 25 Pa. Composition, crystal structure and thin film morphology were examined and properties such as intrinsic stress, conductivity and film density were determined. As-deposited films at 0.15 Pa as well as in the range between 5 Pa and 10 Pa working gas pressure showed a nanocrystalline metastable rocksalt structure with disordered cation arrangement and were nearly stoichiometric. To induce a cation ordering the films were annealed in a furnace at temperatures between 100 and 600 °C for 3 h in argon/oxygen atmosphere (Ar:O₂ = 4.5:5) of 10 Pa. This cation ordering process was observed by XRD and Raman spectroscopy. For the films deposited at 10 Pa gas pressure an annealing temperature of 600 °C leads to the formation of the high temperature phase HT-LiCoO₂ with a layered structure. The Raman spectrum of the films deposited at 0.15 Pa and annealed at 400 °C indicates the formation of the low temperature phase LT-LiCoO₂ with a cubic spinel-related structure, which is assumed to be stabilized due to high compressive stress in the film. The electrochemical characterisation of annealed thin film cathodes revealed that the discharge capacity strongly depends on the crystal structure. Thin Li-Co-O films with a perfect layered HT-LiCoO₂ structure showed the highest discharge capacities.     

Investigation of novel low temperature atmospheric pressure plasma system for deposition photo-catalytic TiO2 thin film

The purpose of this study was to develop a novel low-temperature atmospheric pressure (AP) plasma system and to use the system to deposit photo-catalytic titanium dioxide (TiO₂) thin film. In this study, titanium tetraisopropoxide (TTIP) was used as a precursor for TiO₂ thin film deposition. The precursor was vaporized by ultrasonic oscillator and introduced into an atmospheric plasma system by argon (Ar) carrier gas. The main plasma working gas was Ar mixed with O₂. Microstructure evolutions of TiO₂ thin film were investigated by low-angle grazing-incidence x-ray diffraction (GID), x-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM), and transmission electron microscope (TEM). The photo-catalytic properties were determined by contact angle and methylene orange de-coloration testing. In this study, the substrate temperature, the precursor flow rate and the O₂ flow rate were varied. TiO₂ thin film grown at a temperature of 350 °C, with precursor and O₂ flow rates of 20 sccm and 200 sccm, respectively, revealed the optimum photo-catalytic properties. It was also found that titanium dioxide thin films synthesized by the AP plasma method possess reasonable photo-catalytic characteristics like other deposition techniques.     

Spray deposition of CuInS2 on electrodeposited ZnO for low-cost solar cells

CuInS₂ (CIS) thin films are deposited using chemical spray pyrolysis on top of a single (compact) and a double (compact + porous) ZnO film obtained by electrodeposition by changing the composition, pH and temperature of the bath. Conductive glass has been used as primary substrate. CIS films are deposited at 300 °C and using N₂ as carrier. A buffer layer of TiO₂ is incorporated by spray to protect the ZnO layer against dissolution during the subsequent spraying of CIS. Relevant properties, such as morphology, composition and thickness are evaluated using SEM, EDX and XRD. Also, UV-Vis analyses are carried out to assess the band gap value of CIS, resulting in 1.42 eV. Carrier densities and flat band potentials (V_fb) are calculated from Mott-Schottky plots. The values of V_fb are 0.70, 1.10 and 0.42 V for TiO₂, ZnO and CIS respectively. I-V curves in the dark and under illumination prove that the materials can be combined to obtain solar cells. The dark response for the two devices built with single and double layers of ZnO is very similar, showing diode behavior with good rectification ratios. Under illumination, the presence of the porous ZnO improves the performance of the cell, as reflected by the higher values of photocurrent and open circuit potential.     

Self-healing mechanism of a protective film prepared on a Ce(NO3)3-pretreated zinc electrode by modification with Zn(NO3)2 and Na3PO4

Self-healing mechanism of a protective film against corrosion of zinc at scratches in an aerated 0.5 M NaCl solution was investigated by polarization measurements, X-ray photoelectron spectroscopy (XPS) and electron-probe microanalysis (EPMA). The film was prepared on a zinc electrode by treatment in a Ce(NO₃)₃ solution and addition of aqueous solutions containing 9.98 or 19.9 μg/cm² of Zn(NO₃)₂ · 6H₂O and 55.2 μg/cm² of Na₃PO₄ · 12H₂O. After the coated electrode was scratched with a knife-edge crosswise and immersed in the NaCl solution for many hours, polarization measurements, observation of pit formation at the scratches, XPS and EPMA were carried out. This film was remarkably protective and self-healing against zinc corrosion on the scratched electrode. The cathodic and anodic processes of zinc corrosion were markedly suppressed by coverage of the surface except for scratches with a thin Ce₂O₃ layer containing a small amount of Ce⁴⁺ and the surface of scratches with a layer composed of Zn₃(PO₄)₂ · 4H₂O, Zn(OH)₂ and ZnO mostly.     

Electrical and optical properties of tantalum oxide thin films prepared by reactive magnetron sputtering

Tantalum oxide thin films were prepared by using reactive dc magnetron sputtering in the mixed atmosphere of Ar and O₂ with various flow ratios. The structure and O/Ta atom ratio of the thin films were analyzed by X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The optical and dielectric properties of the Ta₂O₅ thin films were investigated by using ultraviolet-visible spectra, spectral ellipsometry and dielectric spectra. The results reveal that the structure of the samples changes from the amorphous phase to the β-Ta₂O₅ phase after annealing at 900 °C. The XPS analysis showed that the atomic ratio of O and Ta atom is a stoichiometric ratio of 2.50 for the sample deposited at Ar:O₂ = 4:1. The refractive index of the thin films is 2.11 within the wavelength range 300-1000 nm. The dielectric constants and loss tangents of the Ta₂O₅ thin films decrease with the increase of measurement frequency. The leakage current density of the Ta₂O₅ thin films decreases and the breakdown strength increases with the increase of Ar:O₂ flow ratios during deposition.