Overview of optical properties of Al2O3 films prepared by various techniques

We study optical properties of Al₂O₃ films prepared by various techniques using spectroscopic ellipsometry. The film preparation techniques include conventional pulsed magnetron sputtering in various gas mixtures, high power impulse magnetron sputtering, annealing of as-deposited Al₂O₃ in an inert atmosphere and annealing of as-deposited Al in air. We focus on the effect of the preparation technique, deposition parameters and annealing temperature on the refractive index, n, and extinction coefficient, k, of stoichiometric Al₂O₃. At a wavelength of 550 nm we find n of 1.50-1.67 for amorphous deposited Al₂O₃, 1.65-1.67 for amorphous Al₂O₃ obtained by Al annealing, 1.46-1.69 for γ-Al₂O₃ and decreasing n for Al₂O₃ annealing temperature increasing up to 890 °C. The results facilitate correct interpretation of optical characterization of Al₂O₃, as well as selection of a preparation technique corresponding to a required Al₂O₃ structure and properties.     

Nanocrystalline SnO2 and Au:SnO2 thin films prepared by direct current magnetron reactive sputtering

Nanocrystalline pure and gold doped SnO₂(Au:SnO₂) films were prepared on unheated glass substrates by dc magnetron reactive sputtering and, subsequently, the as deposited films were annealed in air. The films structure, surface morphology, photoluminescence, electrical and optical properties were investigated. After annealing the as deposited SnO₂ films, crystallinity increased and the surface roughness decreased. The intensity of PL peaks increases sharply with the annealing temperature. The optical transmittance of the films was around 89% after annealing the as deposited SnO₂ films at 450 °C. The as deposited Au:SnO₂ films show better crystallinity than the as deposited SnO₂ films, the average grain size was around 4.4 nm. The emission peaks of Au:SnO₂ films are slightly blue shifted as compare to undoped SnO₂ films. The Au:SnO₂ films show the lowest electrical resistivity of 0.001 Ωcm with optical transmittance of 76%, after annealing at 450 °C.     

Formation process of Al2O3 thin film by reactive sputtering

Al and Al₂O₃ films were deposited by RF magnetron sputtering using a mixed gas of Ar and O₂. The surface of the Al target was changed from the metallic mode to the oxide mode at a critical O₂ flow ratio of 8%. The atomic ratio of sputtered Al atoms to supplied oxygen atoms was found to be approximately 2:3 at the critical O₂ flow ratio. The oxide layer thickness formed on the Al target was estimated to be 5-7 nm at an O₂ flow ratio of 100% by ellipsometry.     

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.     

Characterizations of SnO2 and SnO2:Sb thin films prepared by PECVD

Structural characterizations of tin oxide (SnO₂) thin films, deposited by plasma-enhanced chemical vapor deposition (PECVD), were investigated with scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The results show that the films are porous, the crystalline structure transforms from crystalline to amorphous phase as deposition temperature changes from 500°C to 200°C, and the chemical component is non-stoichiometric (Sn:O is 1.0716 prepared at 450°C with a value of O₂ flow 3.5 l/min). Sheet resistance of the thin films decreases with increasing of deposition temperature. Whereas, sheet resistance increases with increasing of oxygen flow. Tin oxide doped with antimony (SnO₂:Sb) thin films prepared by same method have a better selectivity to alcohol than to carbon monoxide; the maximum sensitivity is about 220%. The gas-sensing mechanism of SnO₂ thin films is commentated.     

Influence of oxidant source on the property of atomic layer deposited Al2O3 on hydrogen-terminated Si substrate

Al₂O₃ thin films were deposited on hydrogen-terminated Si substrate using atomic layer deposition (ALD) technique with tri-methylaluminum (TMA) and an oxidant source of H₂O vapor, O₂ plasma, or O₃. Substrate temperature was maintained at 350 °C when the Al₂O₃ films were grown with the oxidant sources of H₂O vapor and O₃, and with the oxidant source of O₂ plasma, Al₂O₃ films were deposited at the substrate temperature of 200 °C. Growth rates of Al₂O₃ films on HF-cleaned Si surface were saturated at 0.08, 0.14, and 0.06 nm/cycle for H₂O vapor, O₂ plasma, and O₃, respectively. Equivalent oxide thickness (EOT) and leakage current vs. physical thickness of atomic layer deposited Al₂O₃ films grown with various oxidant sources were also measured in this study. To investigate the main cause of different EOT with oxidant sources, interfacial properties were examined by using transmission electron microscopy (TEM) and X-ray photoelectron microscopy (XPS). In the TEM analysis, interfacial layers with the thickness of about 1.7 and 1.3 nm were observed in as-deposited Al₂O₃ films grown using O₂ plasma and O₃. We confirmed that the interfacial layers were mainly composed of SiO_x in the XPS depth analysis. Using angle resolved X-ray photoelectron spectroscopy, effect of annealing on the interfacial structure of Al₂O₃ films grown with O₃ and O₂ plasma was also studied, and we found that after annealing, the peak corresponding to silicon suboxide and Al-silicate disappeared and fully oxidized Si⁴⁺ increased.     

Influence of TiO2 incorporation in HfO2 and Al2O3 based capacitor dielectrics

Atomic layer deposition was applied to fabricate metal oxide films on planar substrates and also in deep trenches with appreciable step coverage. Atomic layer deposition of Ru electrodes was realized on planar substrates. Electrical and structural behaviour of HfO₂-TiO₂ and Al₂O₃-TiO₂ nanolaminates and mixtures as well as Al₂O₃ films were evaluated. The lowest leakage current densities with the lowest equivalent oxide thickness were achieved in mixed Al₂O₃-TiO₂ films annealed at 700 °C, compared to all other films in as-deposited state as well as annealed at 900 °C. The highest permittivities in this study were measured on HfO₂-TiO₂ nanolaminates.     

Bond strength and microstructure investigation of Al2O3/Al/Al2O3 joints with surface modification of alumina by titanium

Joints of Al₂O₃/Al/Al₂O₃ are formed by liquid-state bonding of alumina substrates covered with thin titanium film of 800 nm thickness using an Al interlayer of 30 or 300 μm at 973 K under a vacuum of 0.2 mPa for 5 min and an applied pressure of 0.01 MPa. The bond strength of the joints is examined by a four-point bend testing at room temperature coupled with optical, scanning and transmission electron microscopy. Results show that: (i) bonding occurs due to the formation of a reactive interface on the metal side of the joint with the presence of Al₃Ti precipitates (ii) a decrease in Al layer thickness leads to stronger Al₂O₃/Al/Al₂O₃ bonds accompanied by a change of both the distribution of reaction products (Al₃Ti) in the region of the interface and the failure surface characteristics.     

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.     

Microstructure and electrical properties of Al2O3-ZrO2 composite films for gate dielectric applications

Al₂O₃-ZrO₂ composite films were fabricated on Si by ultrahigh vacuum electron-beam coevaporation. The crystallization temperature, surface morphology, structural characteristics and electrical properties of the annealed films are investigated. Our results indicate that the amorphous and mixed structure is maintained up to an annealing temperature of 900 °C, which is much higher than that of pure ZrO₂ film, and the interfacial oxide layer thickness does not increase after annealing at 900 °C. However, a portion of the Al₂O₃-ZrO₂ film becomes polycrystalline after 1000 °C annealing and interfacial broadening is observed. Possible explanations are given to explain our observations. A dielectric constant of 20.1 is calculated from the 900 °C-annealed ZrO₂-Al₂O₃ film based on high-frequency capacitance-voltage measurements. This dielectric characteristic shows an equivalent oxide thickness (EOT) as low as 1.94 nm. An extremely low leakage current density of ∼2×10⁻⁷ A/cm² at a gate voltage of 1 V and low interface state density are also observed in the dielectric film.     

Angular distribution and sputtering yield of Al and Al2O3 during 40 key argon ion bombardment

The angular distribution and sputtering yield of Al and Al₂O₃ during 40 keV argon ion bombardment have been measured by collecting the sputtered particles on a semi-cylindrical collector and analysing them by Rutherford backscattering spectrometry (RBS). It was found that due to the relatively high residual pressures (1–4 · 1O^?4Pa) in the sputtering chamber not only aluminium but also oxygen atoms are deposited on the collector through the mechanism of reactive sputtering both when sputtering the oxide and the metal target. The angular distribution of the collected aluminium and oxygen atoms in the case of pure aluminium sputtering follows a cosine law while in the case of Al₂O₃ sputtering a considerable deviation from the cosine law is observed. This deviation is explained by a preferred orientation (texture) of the crystallites in the polycrystalline oxide targets. It was found that the very thin films deposited on the collector when sputtering both types of targets have a composition close to AlO₂. The sputtering yield of Al and Al₂O₃ by 40 keV argon ions has been determined. On the basis of the obtained values an estimation of the productivity of the reactive sputter deposition of Al₂O₃ films from oxidized and non-oxidized targets is made.     

On the existence of a nanometric multilayered structure in Al2O3/Al thin films

Al₂O₃/Al films (period thickness Λ=20, 40 nm) were deposited onto (1 0 0) silicon substrate by reactive r.f. sputtering for substrate temperatures (T_s) ranging from −90 to 600 °C. Secondary ion mass spectrometry demonstrated the deposition of Al₂O₃/Al stratified thin films with the generation of periodic signals. X-ray reflectometry confirmed the periodicity with the presence of Bragg peaks in the experimental patterns. Nevertheless, the multilayered character of Al₂O₃/Al films is less and less pronounced as T_s increases. At low T_s, the relevant parameter to account for the absence of abrupt interfaces is the roughness of layers due to the aluminium layers, while at high T_s, the chemical interdiffusion clearly dominates.     

Microwave-assisted synthesis and investigation of SnO2 nanoparticles

Microwave technique was adopted for preparation of tin dioxide nanoparticles with particles size ranging from 10 to 11 nm within 10 min. The formation of monocrystalline SnO₂ nanoparticles was confirmed by the XRD (X-Ray Diffraction) and TEM (Transmission Electron Microscopy) as well as with SAED (Selected Area Electron Diffraction) analysis. The structure of the SnO₂ crystal was found to be Cassiterite type tetragonal structure. The FT-IR results further supported the formation of tin dioxide from tin hydroxyl group without any post annealing. The samples were further characterized by thermo gravimetric analysis (TGA), electrical resistance measurements and photoluminescence spectrum.     

Evaluating strength of thermally sprayed Al2O3 on aluminum

We evaluated the strength of thermally sprayed Al₂O₃ on aluminum. The thermally sprayed Al₂O₃ films were processed using low-pressure plasma spraying. The thickness of the thermally sprayed Al₂O₃ was 0.3 mm and 0.7 mm. We arranged a 4-point bending test and a heating test to evaluate the strength of the thermally sprayed Al₂O₃. We also investigated the effect of residual stress on the strength by measuring deformation of the thermally sprayed Al₂O₃ after removing the aluminum substrates. The bending strength was 120 MPa, regardless of thickness. We assumed that the bending strength would be equal to the tensile strength because the thermally sprayed Al₂O₃ films were very thin. A crack was generated at 433 K, regardless of thickness. The thermal stress was 160 MPa when the crack was generated. It was 40 MPa higher than we estimated. We found that the residual stress was compression stress that measured 40 MPa, which contributed to the prevention of the crack generation. We presume that the tensile strength was lower than the thermal stress because the residual stress was reduced by stress-relaxing of the aluminum near the interface in the bending test. The influence of heat-resisting strength is dominant over residual stress. Therefore, strength design should take into account residual stress.     

Preparation and properties of Ti/SnO2-Sb2O5 electrodes by electrodeposition

Sb and Sn coatings were deposited on Ti substrate by the method of cathode deposition, and the Ti/SnO₂-Sb₂O₅ electrodes were obtained by annealing at different temperatures for 3 h. Ti/SnO₂-Sb₂O₅ coating was characterized using technique such as X-ray diffraction (XRD), and scanning electron microscopy (SEM). Ti/SnO₂-Sb₂O₅ electrode calcined at 550 °C exhibits the best catalytic capacity. Ti/SnO₂-Sb₂O₅ electrode obtained by electrodeposition had longer service life and faster degradation capacity compared with that obtained by dip-coating. Accelerated service life tests were carried out in 0.5 mol L^− 1 H₂SO₄ solution with the current density of 100 mA cm^− 2. Service life of Ti/SnO₂-Sb₂O₅ electrode prepared in present study was 15 h, and it was only 0.14 h for Ti/SnO₂-Sb₂O₅ electrode obtained by dip-coating.     

Investigation of chlorination process in aluminum production by carbothermic-chlorination reduction of Al2O3 under vacuum

The chlorination process in aluminum production by carbothermic-chlorination reduction of Al₂O₃ under vacuum has been investigated by XRD, SEM and thermodynamic analysis. The results of thermodynamic calculations indicated that the chlorination of Al₄C₃ or Al₄O₄C possibly proceeded at temperature 1300 °C under 5-50 Pa. The experiment results showed that aluminum could be produced by the chlorination of Al₄C₃ or Al₄O₄C and the decomposition of AlCl(g). According to the analysis of experiment results, Al₄C₃ and Al₄O₄C were the main reactants participated in chlorination process in aluminum production by carbothermic-chlorination reduction of Al₂O₃ under vacuum. AlCl(g) generated in chlorination of Al₄C₃ or Al₄O₄C would decompose into Al and AlCl₃(g), and then aluminum product would condense in condensation tower.     

Dielectric and non-Ohmic properties of CaCu3Ti4O12 ceramics modified with NiO, SnO2, SiO2, and Al2O3 additives

In order to conciliate dielectric and non-Ohmic properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics, NiO, SnO₂, SiO₂, and Al₂O₃ were added as sintering aids to promote the grain growth of CCTO ceramics. Microstructure, dielectric properties, and non-Ohmic behavior of the CCTO ceramics were investigated. Among them, NiO-modified CCTO exhibits good dielectric and non-Ohmic properties (ε = 69833, tanδ = 0.073, α = 3.66 and E _B = 296.7 V/cm), due to NiO is also one of giant dielectric materials. Therefore, it is suitable for applying semiconductor circuits. The relationship between electrical current density (J) and electrical field (E) demonstrated that Schottky barrier should exist at grain boundaries. Non-linear coefficient α was directly proportional to the height of barrier. Depressing barrier width would improve significantly dielectric permittivity but decrease breakdown voltage.     

Synthesis and properties of epitaxial SnO2 films deposited on MgO (100) by MOCVD

Epitaxial tin oxide (SnO₂) thin films have been prepared on MgO (100) substrates at 500-600 °C by metalorganic chemical vapor deposition method. Structural and optical properties of the films have been investigated in detail. The obtained films were pure SnO₂ with the tetragonal rutile structure. An in-plane orientation relationship of SnO₂ (110) [010]//MgO (200) [110] between the film and substrate was determined. Two variant structure of SnO₂ were analyzed. The structure of the film deposited at 600 °C was investigated by high-resolution transmission electron microscopy, and an epitaxial structure was observed. The absolute average transmittance of the SnO₂ film at 600 °C in the visible range exceeded 90%. The optical band gap of the film was about 3.93 eV.     

Dielectric properties of DC reactive magnetron sputtered Al2O3 thin films

Alumina (Al₂O₃) thin films were sputter deposited over well-cleaned glass and Si < 100 > substrates by DC reactive magnetron sputtering under various oxygen gas pressures and sputtering powers. The composition of the films was analyzed by X-ray photoelectron spectroscopy and an optimal O/Al atomic ratio of 1.59 was obtained at a reactive gas pressure of 0.03 Pa and sputtering power of 70 W. X-ray diffraction results revealed that the films were amorphous until 550 °C. The surface morphology of the films was studied using scanning electron microscopy and the as-deposited films were found to be smooth. The topography of the as-deposited and annealed films was analyzed by atomic force microscopy and a progressive increase in the rms roughness of the films from 3.2 nm to 4.53 nm was also observed with increase in the annealing temperature. Al-Al₂O₃-Al thin film capacitors were then fabricated on glass substrates to study the effect of temperature and frequency on the dielectric property of the films. Temperature coefficient of capacitance, AC conductivity and activation energy were determined and the results are discussed.     

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.