Low temperature metal oxide film deposition and reaction kinetics in supercritical carbon dioxide

An effective method is developed for low temperature metal oxide deposition through thermal decomposition of metal diketonates in supercritical carbon dioxide (scCO₂) solvent. The rates of Al(acac)₃ (Aluminum acetyl acetonate) and Ga(acac)₃ (Gallium acetyl acetonate) thermal decomposition in scCO₂ to form conformal Al₂O₃ and Ga₂O₃ thin films on planar surfaces were investigated. The thermal decomposition reaction of Al(acac)₃ and Ga(acac)₃ was found to be initialized at  150 °C and 160 °C respectively in scCO₂ solvent, compared to  250 °C and 360 °C in analogous vacuum-based processes. By measuring the temperature dependence of the growth rates of metal oxide thin films, the apparent activation energy for the thermal decomposition of Al(acac)₃ in scCO₂ is found to be 68 ± 6 kJ/mol, in comparison with 80–100 kJ/mol observed for the corresponding vacuum-based thermal decomposition reaction. The enhanced thermal decomposition rate in scCO₂ is ascribed to the high density solvent which effectively reduces the energy of the polar transition states in the reaction pathway. Preliminary results of thin film deposition of other metal oxides including ZrO_x, FeO_x, Co₂O₃, Cr₂O₃, HfO_x from thermal decomposition of metal diketonates or fluorinated diketonates in scCO₂ are also presented.     

Electrical characterization of Ta2O5 films deposited by laser reactive ablation of metallic Ta

Tantalum oxide films have been deposited by 355 nm pulsed laser ablation of metallic Ta target in O₃/O₂ ambient. The structure and the composition of as-deposited and annealed films were examined by X-ray diffraction and Fourier transform infrared spectroscopy. The measurements of the current–voltage and capacitance–voltage characteristics of the Al/Ta₂O₅/Si capacitors were performed to reveal the electrical properties of the Ta₂O₅ films. The effects of annealing temperature on the characteristics of thin films have been studied. The results suggest that the films annealed above 700°C have the structure of orthorhombic β-Ta₂O₅, thc annealing treatment at high temperature decreases the bulk trap charge, the border trap, and the interface trap densities of as-deposited films, and improves significantly the dielectric and electrical properties of Ta₂O₅ film.     

Thickness-dependent properties of sprayed iridium oxide thin films

Iridium oxide thin films with variable thickness were deposited by spray pyrolysis technique (SPT), onto the amorphous glass substrates kept at 350 °C. The volume of iridium chloride solution was varied to obtain iridium oxide thin films with thickness ranging from 700 to 2250 Å. The effect of film thickness on structural and electrical properties was studied. The X-ray diffraction (XRD) studies revealed that the as-deposited samples were amorphous and those annealed at 600 °C for 3 h in milieu of air were polycrystalline IrO₂. The crystallinity of Ir-oxide films ameliorate with film thickness thereby preferred orientation along (1 1 0) remains unchanged. The infrared spectroscopic results show Ir–O and Ir–O₂ bands. The room temperature electrical resistivity (ρ_RT) of these films decreases with increase in film thickness. The p-type semiconductor to metallic transition was observed at 600 °C.     

Synthesis and characterization of p-type transparent conducting CuAlO2 thin film by DC sputtering

P-type transparent conducting thin films of copper aluminium oxide were prepared by DC sputtering of polycrystalline CuAlO₂ target, which was fabricated by heating a stoichiometric mixture of Cu₂O and Al₂O₃ at 1375 K for 24 h. Thin films of CuAlO₂ were deposited on Si (4 0 0) and glass substrates. The sputtering was performed in Ar+O₂ (40 vol.%) atmosphere and the substrate temperature was 453 K. X-ray diffraction spectra of the films showed the peaks that could be assigned with those of the crystalline CuAlO₂. Fourier transform infrared spectra showed Cu---O, Al---O, O---Cu---O bonding. UV–Vis–NIR spectrophotometric measurement showed high transparency of the films in the visible region. Both direct and indirect band gaps were found to exist and their corresponding estimated values were 3.66 and 2.1 eV, respectively. The room temperature conductivity of the film was fairly high and was of the order of 0.08 S cm⁻¹, while the activation energy was 0.26 eV. Thermoelectric power measurement indicated positive value of Seebeck coefficient and its room temperature value was +128 μV K⁻¹. Positive value of Hall coefficient (R_H=+16.7 cm³ C⁻¹) also confirmed p-type conductivity of the films.     

Successive deposition of layered titanium oxide/indium tin oxide films on unheated substrates by twin direct current magnetron sputtering

Layered titanium oxide/indium tin oxide (TiO₂/ITO) films were successively deposited on unheated glass substrates in situ using a twin direct current magnetron sputtering system. The layered TiO₂/ITO films exhibited a strongly polycrystalline structure that comprises anatase and rutile phases, as revealed by X-ray diffraction and Raman spectra. The X-ray photoelectron spectrum of Ti2p also verified the stoichiometric state of titanium oxide near the surface. The photo-induced hydrophilic properties of the films were determined from changes in the water contact angles under ultra-violet (UV) irradiation. The results revealed that the layered TiO₂/ITO films possessed a dissipated rate of 30% when they were stored in the dark for 12 h. This result shows that the layered TiO₂/ITO films acted as “electron pools” with an inherent energy storage capability. This unique property is attributable to the rougher surface and nearly porosity-free columnar structure, which is responsible for increased UV energy absorption and loss-free hole or electron transportation.     

Effects of substrate temperature on structural, electrical and optical properties of As-doped ZnO films

As-doped ZnO films were prepared by co-sputtering ZnO and Zn₃As₂ targets on glass substrates at various temperatures from 250 to 500 °C. The effects of substrate temperature on structural, electrical and optical properties of the films were investigated. The films grown at temperatures from 250 to 400 °C were c-axis oriented and those deposited above 400 °C exhibited poor crystallinity. Hall measurement showed that p-type ZnO:As films were prepared at different temperatures. With increasing the substrate temperature from 250 to 500 °C, the optical band gap (E_g) first decreased, and then increased. The E_g changes upon the substrate temperature were due to the effect of substrate temperature on the crystallinity of ZnO films.     

Electrical properties of Ta2O5 thin films deposited on Cu

The electrical and dielectric properties of reactively sputtered Ta₂O₅ thin films with Cu as the top and bottom electrodes forming a simple metal insulator metal (MIM) structure, Cu/Ta₂O₅/Cu/n-Si, were studied. Ta₂O₅ films subjected to rapid thermal annealing (RTA) at 800°C for 30 s in N₂ ambient crystallized the film, decreased the leakage current density and resulted in reliable time-dependent dielectric breakdown characteristics. The conduction mechanism at low electric fields (<100 kV/cm) is due to Ohmic conduction; however, the Schottky mechanism becomes predominant at high fields (>100 kV/cm). Present studies demonstrate the use of Cu as a potential electrode material to replace the conventional precious metal electrodes for Ta₂O₅ storage capacitors.     

Influence of Mn doping on microstructure and DC-accelerated aging behaviors of ZnO–V2O5-based varistors

The microstructure, electrical properties, dielectric characteristics, and DC-accelerated aging behavior of the ZnO–V₂O₅–MnO₂ system sintered were investigated for MnO₂ content of 0.0–2.0 mol% by sintering at 900 °C. For all samples, the microstructure of the ZnO–V₂O₅–MnO₂ system consisted of mainly ZnO grain and secondary phase Zn₃(VO₄)₂. The incorporation of MnO₂ to the ZnO–V₂O₅ system was found to restrict the abnormal grain growth of ZnO. The nonlinear properties and stability against DC-accelerated aging stress improved with the increase of MnO₂ content. The ZnO–V₂O₅–MnO₂ system added with MnO₂ content of 2.0 mol% exhibited not only a high nonlinearity, in which the nonlinear coefficient is 27.2 and the leakage current density is 0.17 mA/cm², but also a good stability, in which %ΔE_1 mA = −0.6%, %Δ = −26.1%, and %Δtan δ = +22% for DC-accelerated aging stress of 0.85E_1 mA/85 °C/24 h.     

Heteroepitaxial growth of tungsten oxide films on sapphire for chemical gas sensors

The performance of chemiresistive gas sensors made from semiconducting metal oxide films is influenced by film stoichiometry, crystallographic structure, surface morphology and defect structure. To obtain well-defined microstructures, heteroepitaxial WO₃ films were grown on r-cut and c-cut single crystal sapphire substrates using rf magnetron Ar/O₂ reactive sputtering of a W target. On r-cut sapphire, an epitaxial tetragonal WO₃ phase is produced at a 450°C deposition temperature whereas 650°C growth stabilizes an epitaxial monoclinic WO₃ phase. On c-cut sapphire, a metastable hexagonal WO₃ phase is formed. RHEED and X-ray diffraction indicate that the films have a ‘polycrystalline epitaxial structure’ in which several grains are present, each having the same crystallographic orientation. STM analysis of the film surfaces reveals morphological features that appear to be derived from the substrate symmetries. The monoclinic phase has a step/terrace growth structure, has the smallest mosaic spread in XRD rocking curves and exhibits the highest degree of reproducibility suggesting that it is the best suited for sensor applications. Measurements of film conductivity versus temperature indicate that the charge transport mechanisms are also dependent on the crystallographic phase and microstructure of the WO₃ films.     

Preparation of SiO2 thin films using the Cat-CVD method

Using the catalytic chemical vapor deposition (Cat-CVD) method, a-Si and SiN_x films have been the main focus of studies. SiO₂ films have not been studied because of the limited life of catalysts such as tungsten or molybdenum in an oxidative atmosphere. In this report, we describe oxide film preparation using an iridium catalyst. We determined the most appropriate catalyst material for the oxide film process by exposing heated materials in tetraethoxysilane (TEOS) or O₂ gas. As the result, it was confirmed that the Ir catalyst works in a slow oxidative atmosphere. Using the Ir catalyst, SiO₂ films were deposited in two gas combinations: TEOS and N₂O, and SiH₄ and N₂O. Although the SiO₂ film processed with the combination of TEOS and N₂O was stoichiometric, its breakdown voltage is not sufficient. The SiO₂ film processed with the combination of SiH₄ and N₂O showed good electrical property.     

Structure and electrical properties of boron-added (Ba,Sr)TiO3 thin films fabricated by the sol-gel method

Thin films of Ba_xSr_1−xTiO₃ (BST, with x=0.5) were fabricated on a RuO₂/Ru/SiO₂/Si substrate by the spin coating of the multicomponent sol prepared using metal alkoxides. Boron alkoxide was intentionally introduced to establish a better microstructure and to reduce the leakage current. AFM indicated that a crack-free uniform microstructure having a smooth surface was gradually developed with increasing boron content. The relative dielectric permittivity of the 250-nm thick BST thin films fired at 700°C decreased with increasing content of boron, from 420 for the undoped film to 190 for the 10 mol% boron-added film at 1 MHz. This observation was interpreted in terms of a serial capacitance composed of the perovskite BST grain and the interfacial B₂O₃ glassy phase having a low dielectric permittivity. The leakage current density (J) also decreased with the amount of boron added. The leakage current for the applied voltage greater than 1 V showed a linear variation of logJ with E^1/2 at room temperature, suggesting that the interface-controlled Schottky emission was the dominant conduction process for the BST thin films fabricated on the RuO₂ electrode.     

Studies of the electrical properties of bismuth oxide films

A detailed study has been made of the resistivity , activation energy ΔE, Hall coefficient R_H, mobility μ, thermoelectric power and TCR of vacuum-deposited films of bismuth oxide evaporated from silica and molybdenum boats in the temperature range 78°–525°K. The electrical parameters of these films differed considerably from those of oxidized films and this difference has been attributed to the dissociation of the bismuth oxide and the formation of intermediate products.     

La(1−x)SrxCoO3 for thin film thermocouple applications

In this study, the LSCO (lanthanum strontium cobalt oxide) family has been investigated for thin film thermocouple applications. Thin films of La_(1−x)Sr_xCoO₃ (x=0.3,0.5,0.7) were prepared on sapphire substrates by pulsed laser deposition. The films were annealed at different temperatures in air and characterized for phase, composition and microstructure to determine their thermal stability. From the phase and composition analyses, it is clear that as the Sr content in LSCO increases, the thermal stability decreases. Among the three compositions studied, x=0.3 had the best phase and chemical stability, and microstructural properties. It was observed that La_0.7Sr_0.3CoO₃ possesses excellent phase, composition and microstructural stability up to 1273 K. Above 1273 K, however, LSCO decomposes resulting in the loss of cobalt and formation of individual oxide phases. Electrical resistivity and Seebeck coefficients were measured in situ as a function of temperature in air up to 1023 K. The electrical and Seebeck coefficient properties were found to be stable for all the three compositions up to 1023 K and studies indicated that electrical conduction occurs through a small polaron hopping mechanism. In conclusion, LSCO possessed good thermal stability in air up to 1273 K and exhibits excellent potential in thin film thermocouple applications.     

Synthesis, structural and mechanical characterization of sputtered tungsten oxide coatings

Tungsten oxide coatings were deposited without substrate bias by DC reactive magnetron sputtering of a tungsten target using oxygen as reactive gas. By tuning the partial pressure of oxygen (p_O2/p_Ar) between 0 and 4, the oxygen content of the films was changed from 0 to 75 at.%. The structure of the films (investigated by X-ray diffraction) depends on their oxygen content. For low oxygen contents, the -W and β-W₃O phases were observed (< 30 at.%), and with the increase of oxygen content (30 at.% < O < 67 at.%) the structure became amorphous. A transition region was obtained for oxygen content between 67 at.% and 75 at.%, and when O > 75 at.%, a nanocrystalline (WO₃) structure was reached.

The hardness and Young's modulus were evaluated by depth sensing indentation. The decrease in hardness followed the four different ranges of chemical compositions accordingly, from ≈ 23 GPa for pure W down to ≈ 7 GPa for WO₃ films. A similar behaviour was observed for the Young's modulus, which ranged from 450 GPa to 150 GPa. The cohesion/adhesion of the films were investigated using a scratch-test apparatus. These coatings displayed a low adhesion (critical load, L_c < 15 N) to the steel substrate because the depositions were carried out intentionally without an adhesion interfacial layer.     

Transparent conducting F-doped SnO2 thin films grown by pulsed laser deposition

Transparent conducting fluorine-doped tin oxide (SnO₂:F) films have been deposited on glass substrates by pulsed laser deposition. The structural, electrical and optical properties of the SnO₂:F films have been investigated as a function of F-doping level and substrate deposition temperature. The optimum target composition for high conductivity was found to be 10 wt.% SnF₂ + 90 wt.% SnO₂. Under optimized deposition conditions (T_s = 300 °C, and 7.33 Pa of O₂), electrical resistivity of 5 × 10^− 4 Ω-cm, sheet resistance of 12.5 Ω/□, average optical transmittance of 87% in the visible range, and optical band-gap of 4.25 eV were obtained for 400 nm thick SnO₂:F films. Atomic force microscopy measurements for these SnO₂:F films indicated that their root-mean-square surface roughness ( 6 Å) was superior to that of commercially available chemical vapor deposited SnO₂:F films ( 85 Å).     

Chemical and electrical characteristics of low temperature plasma enhanced CVD silicon oxide films using Si2H6 and N2O

Silicon oxide films have been deposited at low temperatures in the range of 30–250 °C using Si₂H₆ and N₂O by conventional plasma enhanced chemical vapor deposition technique. The dependencies of deposition temperatures on the film properties are studied. The leakage current and the etch rate of these low temperature films compare favorably to films deposited by silane and TEOS at higher temperatures, respectively.     

Electrical properties of sol-gel processed barium titanate films

The sol-gel technique has been used to prepare ferroelectric barium titanate (BaTiO₃) films. The electrical properties of the films have been investigated systematically. The room temperature dielectric constant (ε) and loss tangent (tanδ) at 1 kHz were respectively found to be 370 and 0.012. Both ε and tanδ showed anomaly peaks at 125°C. The room temperature remanant polarization (P_r) and coercive field (E_c) were found to be 3.2 μC/cm² and 30 kV/cm, respectively. The capacitance–voltage (C–V) and conductance–voltage (G–V) characteristics also showed hysteresis effect. The temperature variation of C–V and G–V characteristics also confirms the ferroelectric to paraelectric phase transition at 125°C.     

Reactive magnetron sputtering of indium tin oxide films on acrylics – morphology and bonding state

Indium tin oxide (ITO) films were deposited on acrylics by low temperature reactive magnetron sputtering. The effects of oxygen flow and bias voltage on the microstructure, surface morphology and bonding state of films were evaluated. In this investigation, X-ray photoelectron spectroscopy, X-ray diffraction, Atomic force microscope were used. It was found that the grain size of ITO films increased and surface roughness decreased with the increase of oxygen flow rate. The XPS spectra of In 3d and Sn 3d indicated that the oxygen flow had little effect on the binding energy of ITO films. The relative strength of O²⁻_II increased, while that of O²⁻_I decreased with increasing oxygen flow rate. The grain size increased with the bias voltage. However, at a maximum voltage of −90 V fine grains were detected due to the formation of numerous nuclei resulting from bombardment of high energy particles. The bias voltage had little effect on the bonding state of In, Sn and O ions.     

Electrochromic behavior of CVD molybdenum oxide and Mo-W mixed-oxide thin films

Thin films of molybdenum oxide, tungsten oxide, and mixed Mo-W oxide were prepared by atmospheric-pressure chemical vapor deposition. For all films, the technological conditions were kept constant. Mixed oxides are expected to exhibit superior electrochromic properties compared to the pure components, because of more intensive electron transfers between W and Mo states of different valence, or between one and the same metal state but with different structural disordering. The electrochromic characteristics were studied with the help of the cyclic-voltammetric technique. All films showed stabilized current–voltage (C–V) responses and good durability. The electrolyte used was LiClO₄+propylene carbonate. All films showed an electrochromic effect. Coloration as a result of Li intercalation was observed. For the as-deposited as well as the annealed mixed-oxide films, the current density was considerably larger than for pure metal oxide films. The electrochromic behavior was studied as a function of the annealing temperature.     

Nitrogen dilution effects on structural and electrical properties of hot-wire-deposited a-SiN:H films for deep-sub-micron CMOS technologies

Hot-wire chemical vapor-deposited silicon nitride is a potential dielectric material compared to glow-discharge-deposited material due to its lower hydrogen content. In several earlier publications we have demonstrated these aspects of the HWCVD nitride. However, to replace SiO₂ with a-SiN:H as the gate dielectric, this material needs further improvement. In this paper we report the results of our efforts to achieve this through nitrogen dilution of the SiH₄+NH₃ gas mixture used for deposition. To understand the electrical behavior of these nitride films, we characterized the films by high-frequency capacitance–voltage (HFCV) and DC J–E measurements. We attempted to evolve a correlation between the breakdown strength, as determined from the J–E curves, and aspects such as the bond density, etching rate, deposition rate and refractive index. From these correlations, we infer that nitrogen dilution of the source gas mixture has a beneficial effect on the physical and electrical properties of the hot-wire a-SiN:H films. For the highest dilution, we obtained a breakdown voltage of 12 MV cm⁻¹.