Microstructural, photocatalysis and electrochemical investigations on CeTi2O6 thin films

The properties of sol–gel derived CeTi₂O₆ thin films deposited using a solution of cerium chloride heptahydrate and titanium propoxide in ethanol are discussed. The effect of annealing temperature on structural, optical, photoluminescence, photocatalysis and electrochemical characteristics has been examined. Lowest annealing temperature for the formation of crystalline CeTi₂O₆ phase in these samples is identified as 580 °C. The optical transmittance of the films is observed to be independent of the annealing temperature. The optical energy bandgap of the 600 °C annealed film for indirect transition is influenced by the presence of anatase phase of TiO₂ in its structure. Fourier transform infrared spectroscopy investigations have evidenced increased bond strength of the Ti–O–Ti network in the films as a function of annealing temperature. The photoluminescence intensity of the films has shown dependence on the annealing temperature with the films fired at 450 °C exhibiting the maximum photoluminescence activity. The decomposition of methyl orange and eosin (yellow) under UV–visible light irradiation in the presence of crystalline CeTi₂O₆ films shows the presence of photoactivity in these films. The photocatalytic response of CeTi₂O₆ films is found to be superior to the TiO₂ films. In comparison to crystalline films, the amorphous films have shown superior electrochemical characteristics. The 500 °C annealed amorphous films have exhibited the most appropriate properties for incorporation in electrochromic devices comprising tungsten oxide as the primary electrochromic electrode.     

Atmospheric plasma discharge chemical vapor deposition of SnOx thin films using various tin precursors

A series of 0.2–0.6 μm thick SnO_x films were deposited onto borosilicate and sodalime silica glass substrates by atmospheric plasma discharge chemical vapor deposition at 80 °C. SnO_x films deposited from monobutyltin trichloride contained a large percentage of SnCl₂:2H₂O, and therefore were partially soluble in water. SnO_x coatings deposited from tetrabutyltin were not soluble in water or organic solvents, had good adhesion even at growth rates as high as 2.3 nm/s, had high transparency of  90% and electrical resistivity of 10⁷ Ω cm. As-grown tin oxide coatings were amorphous with a small concentration of SnO₂, SnO and Sn crystalline phases as determined by grazing angle X-ray diffraction and X-ray photoelectron spectroscopy measurements. Upon annealing in air at 600 °C the resistivity of SnO_x films decreased to 5–7 Ω cm. Furthermore, optical and X-ray measurements indicated that SnO_x was converted into SnO₂ (cassiterite) with a direct band gap of 3.66 eV. Annealing of as-grown SnO_x films in vacuum at 340 °C led to formation of the p-type conductor SnO/SnO_x. The indirect band gap of SnO was calculated from the optical spectra to be 0.3 eV.     

Surface Preparation of Aluminum Nitride for Metallization: Effect of Temperature on Surface Reactivity

The current aqueous cleaning step in the surface preparation of aluminum nitride (AlN) prior to metallization causes performance and reliability issues for the substrates used for microelectronic packaging due to surface reactions. These issues limit the use of AlN and its replacing of BeO, an environmentally hazardous material currently used. The aim of this investigation was to determine the effects of different solutions on the surface of AlN substrates under varying conditions at times up to 2419.2 ks (28 days). Concentration of the solutions, temperature, and immersion time were varied for the AlN samples in the solutions. Both elevated temperatures (50°C and 90°C) and low temperatures (5°C) were investigated.

Four general types of behavior were observed: minor changes in average surface roughness and microstructure, linear change in average surface roughness and pitted grains, nonlinear change in average surface roughness and product formation on AlN surface, and miscellaneous change in average surface roughness with surface product formation.

The surface roughening kinetics were very complex due to changes in both the reaction product morphology and reaction mechanism with temperature, solvent, and pH for a specific solvent. Minor changes in average surface roughness and microstructure were observed for HCl pH = 5, H₂ SO₄ pH = 5, NaOH pH = 8, NaOH pH = 10, NaOH pH = 12, deionized water and Alfred tap water at 5°C, HCl pH = 3 and oleic acid at 50°C and citric acid and oleic acid at 90°C. Linear changes in average surface roughness and pitted grains were observed for HCl pH = 2 and H₂SO₄ pH = 3 at 50°C and HCl pH = 2, H₂SO₄ pH = 3, and deionized water at 90°C. Non-linear change in average surface roughness and product formation on AlN surface was observed for HCl pH = 5, NaOH pH = 8 and Alfred tap water at 50°C and HCl pH = 5 and H₂SO₄ pH = 2 at 90°C. Miscellaneous changes in average surface roughness with surface product formation were observed for H₂SO₄ pH = 2, H₂SO₄ pH = 5, NaOH pH = 10, NaOH pH = 12, citric acid, Micro-90 and deionized water at 50°C and HCl pH = 3, H₂SO₄ pH = 5, NaOH pH = 8, NaOH pH = 10, NaOH pH = 12, Micro-90 and Alfred tap water at 90°C.     

DC magnetron reactive sputtered InN thin film electrodes as photoanodes in aqueous solution. A study of as prepared and nitrogen annealed electrodes

Thin films of indium nitride, InN, were produced by reactive magnetron DC sputtering. By post treatment in dinitrogen, N₂, in the temperature range 350–500 °C a set of films gradually going from InN to indium oxide, In₂O₃ was obtained (due to dioxygen impurities in the annealing gas). Those films were characterized by X-ray diffraction, optical-, resistivity- and photoelectrochemical measurements for the aim of direct watersplitting in a photoelectrochemical cell.

Surprisingly, the caused change in the film composition by annealing gave no significant change in the room temperature resistivity, but the free electron density and the optical properties were affected. In 0.1 M NaOH annealing improved the photoresponse of the thin films. A pronounced optimum was observed for films annealed at 425 °C. Even for those films the quantum efficiency was low; at most 2% of the photons at 350 nm were transformed into readable photoelectrons. The onset wavelength for photocurrent was located around 600 nm (2.1 eV), which is far off from the onset of absorption 900 nm (1.4 eV).     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

Effect of high temperature annealing on texture and microstructure on an AISI-444 ferritic stainless steel

AISI 444 is a Mo-alloyed ferritic stainless steel which presents good naphthenic corrosion resistance, making it attractive for applications in petroleum refining plants; however, good formability is also important. To achieve good formability with this alloy the annealing process is crucial. The annealing temperature in ferritic stainless steel is usually around 850 °C, which falls in the range of sigma phase precipitation. A means to avoid this precipitation is to anneal at temperatures around 1000 °C followed by rapid cooling. Annealing at high temperatures can cause grain growth and carbide or nitride precipitation which can result in a reduction of room temperature toughness. In this paper, the rolling and recrystallization textures of AISI 444 steel were studied in samples cold rolled with different thickness reductions (30%, 60%, 80% and 90%) followed by annealing at 955, 980 and 1010 °C. Aspects of grain size and carbide precipitation after annealing were characterized using EBSD and AFM. The material drawability was analyzed through strain rate or Lankford (r) coefficients calculated from texture results.     

Effect of negatively charged species on the growth behavior of silicon films in hot wire chemical vapor deposition

The deposition behavior of silicon in hot wire chemical vapor deposition was investigated, focusing on the generation of negatively charged species in the gas phase using a gas mixture of 20% SiH₄ and 80% H₂ at a 450 °C substrate temperature under a working pressure of 66.7 Pa. A negative current of 6–21 µA/cm² was measured on the substrate at all processing conditions, and its absolute value increased with increasing wire temperature in the range of 1400 °C–1900 °C. The surface roughness of the films deposited on the silicon wafers increased with increasing wire temperature in the range of 1510 °C–1800 °C. The film growth rate on the positively biased substrates (+ 100 V, + 200 V) was higher than that on the neutral (0 V) and negatively biased substrates (− 100 V, − 200 V, − 300 V). These results indicate that the negatively charged species are generated in the gas phase and contribute to deposition. The surface roughness evolved during deposition was attributed to the electrostatic interaction between these negatively charged species and the negatively charged growing surface.     

Deposition of HfO2 thin films on ZnS substrates

HfO₂ thin films with columnar microstructure were deposited directly on ZnS substrates by electron beam evaporation process. SiO₂ thin films, deposited by reactive magnetron sputtering, were used as buffer layers, HfO₂ thin films of granular microstructure were obtained on SiO₂ interlayer by this process. X-ray diffraction patterns demonstrate that the as-deposited HfO₂ films are in an amorphous-like state with small amount of crystalline phase while the HfO₂ films annealed at 450 °C in O₂ for 30 min and in Ar for 150 min underwent a phase transformation from amorphous-like to monoclinic phase. Antireflection effect in certain infrared wave band, such as 3–6 μm, 4–12 μm, 4–8 μm and 3–10 μm, can be observed, which was dependent on the thickness of thin films. The cross-sectional images of HfO₂ films, obtained by field emission scanning electron microscopy, revealed that there was no distinct morphological change upon annealing.     

Microstructure modification of amorphous titanium oxide thin films during annealing treatment

Thin films of titanium oxide have been deposited on (100) silicon wafers and on quartz substrates by reactive r.f. magnetron sputtering from a 99.6% pure Titanium target. Amorphous and overoxidised coatings (TiO_2.2) have been obtained from this technique. The influence of the post-deposition annealing between 300 °C and 1100 °C on the structural and optical properties and on the surface morphology has been investigated. The results of X-ray diffraction showed that films annealed from 300 to 500 °C have an anatase crystalline structure whereas those annealed at 1100 °C have a rutile crystalline structure. Optical analyses showed that UV-Vis transmission spectra are strongly modified by the annealing temperature and refractive index of TiO_x layers also changes. Atomic force microscopy measurements corroborate optical and structural analyses and showed that the surface of the coatings can have various appearances and morphologies for the annealing temperatures investigated.     

Electrochromic properties of nanocrystalline MoO3 thin films

Electrochromic MoO₃ thin films were prepared by a sol–gel spin-coating technique. The spin-coated films were initially amorphous; they were calcined, producing nanocrystalline MoO₃ thin films. The effects of annealing temperatures ranging from 100 °C to 500 °C were investigated. The electrochemical and electrochromic properties of the films were measured by cyclic voltammetry and by in-situ optical transmittance techniques in 1 M LiClO₄/propylene carbonate electrolyte. Experimental results showed that the transmittance of MoO₃ thin films heat-treated at 350 °C varied from 80% to 35% at λ = 550 nm (ΔT =  45%) and from 86% to 21% at λ ≥ 700 nm (ΔT =  65%) after coloration. Films heat-treated at 350 °C exhibited the best electrochromic properties in the present study.     

Influence of conventional furnace and rapid thermal annealing on the quality of polycrystalline β-FeSi2 thin films grown from vapor-deposited Fe/Si multilayers

Thin films of polycrystalline β-FeSi₂ were grown on (100) Si substrates of high resistivity by electron beam evaporation of Si/Fe ultrathin multilayers and subsequent annealing by conventional vacuum furnace (CVF) and rapid thermal annealing (RTA) for 1 h and 30 s, respectively, in the temperature range from 600 to 900°C. X-ray diffraction, Raman spectroscopy, spectroscopic ellipsometry, resistivity and Hall measurements were employed for characterization of the silicide layers quality in terms of the annealing conditions. For the silicide layers prepared by CVF annealing, although the grain size increase with increasing the annealing temperature, the optimum temperature to obtain the higher material quality (carrier mobility of the order of 100 cm² Vs⁻¹ and carrier concentration of about 1 × 10¹⁷ cm⁻³) is about 700°C. At higher annealing temperatures, the quality of the material is degraded due to the presence of the oxide Fe₂O₃. In the case of the silicides prepared by RTA, the quality of the material is improved progressively with increasing the annealing temperature up to 900°C.     

Electrically Conductive Composite Powders and Compounds Produced with Solid State Synthesis

Electrically conductive composite powders and compounds were produced using a mechanical alloying method. As starting materials, copper powder and a mixture of butadiene-acrylonitrile-copolymer and polyvinylchloride were used. After alloying, the powderlike material consisted of a mixture of fine copper powder embedded in the polymer matrix. Milling resulted in a copper powder of particle size 300 nm to 2 μm. The alloyed powders were compacted at a pressure of 0.37 GPa at 90°C with a holding time of 1 minute. The resistivity of the compound was measured to be 8.6 × 10^-4 ohm-cm. The unusual reduction in particle size to the nanometer level and formation of spherically formed copper polymer composite particles is explained by the reactions of the copper atoms with cyano and other functional groups of the polar polymers. The structurally modified polymer forms a tight encapsulation coating on the surface of the copper, and the flat-formed metal particles are recovered in spherical form due to strong interfacial forces, resulting in increased electrical conductivity.     

Study on EB-PVD Zirconia Thermal Barrier Coatings for Gas Turbine Blade Protection

Thermal barrier coatings on hollow turbine blades of DD3 were studied. The DD3 single crystal alloy has excellent mechanical properties, equivalent to that of PWA 1480. The results show that ZrO₂ coatings consist of oriented columnar grains. The coating is composed of t' cubic and tetragonal phases and there is an alumina layer at the ZrO₂-NiCrAlY alloy interface after aging for 30 min. at 1050°C. No degradation occurred to the EBPVD ceramic coatings after 200 thermal cycles at 1100°C for 10 min., air cooling and 100 hours high temperature oxidation at 1100°C.     

Thermal-induced intermixing effects on the optical properties of long wavelength low density InAs/GaAs quantum dots

The effect of post-growth rapid thermal annealing on the photoluminescence properties of long wavelength low density InAs/GaAs (001) quantum dots (QDs) with well defined electronic shells has been investigated. For an annealing temperature of 650 °C for 30 s, the emission wavelength and the intersublevel spacing energies remain unchanged while the integrated PL intensity increases. For higher annealing temperature, blue shift of the emission energy together with a decrease in the intersublevel spacing energies are shown to occur due to the thermal activated In–Ga interdiffusion. While, this behaviour is commonly explained as a consequence of the enrichment in Ga of the QDs, the appearance of an additional exited state for annealing temperatures higher than 650 °C suggests a variation of the intermixed QDs's volume/diameter ratio toward QDs's enlargement.     

Wear and oxidation behaviour of high-chromium white cast irons

High-chromium white cast irons can attain very hard microstructures composed of intergranular chromium carbides dispersed in a tempered martensitic matrix. Two heat-treated high-chromium white cast irons with different carbon contents were studied in this research work using compression at 500 °C, and wear and oxidation tests at 500 and 600 °C. The hot compression behaviour of these products is excellent, with high strengths and significant ductility. They also exhibited good wear and oxidation properties. Fracture micromechanisms are discussed in relation to the chemical composition and microstructure of the two alloys.     

Thermomechanical processing and transport current density of Ag-sheathed (Tl,Cr)Sr2(Ca0.9,Pr0.1)Cu2O7 superconductor tapes

Powders with nominal composition (Tl,Cr_0.15)Sr₂(Ca_0.9,Pr_0.1)Cu₂O₇ (Tl-1212) and T_c90 K were used to fabricate Ag-sheathed superconducting tapes employing the powder-in-tube (PIT) method. The tapes were subjected to intermediate mechanical rolling or pressing. Conditions that enhance the transport critical current density (J_c) of the tapes were investigated. Optimum annealing temperature and period together with uniaxial pressing are necessary to increase J_c of the Tl-1212/Ag tapes. Annealing at 910 °C for 0.5–1 h enhanced the 1212 phase formation and improved intergranular connectivity between grains, as well as to provide healing for the fractured structure caused by deformation process. A relatively longer annealing time at higher temperature gave rise to secondary phases and resulted in the decrease of J_c. Mechanical uniaxial pressing greatly densified the tapes core and thus led to closer contact between grains. At liquid nitrogen temperature and zero field, J_c of the pressed tapes annealed at 910 °C for 1 h is 3060±127 A cm⁻². The initial drastic drop of J_c in low fields (<0.06 T) indicates the performance of the tapes is limited by weak links. No significant anisotropic transport properties were observed in applied magnetic field. This is due to the absence of texturing in the tapes as the grains are randomly oriented revealed through SEM micrographs.     

Preparation and Properties of Barium Titanate Nanopowder/Epoxy Composites

This article is focused on the preparation of barium titanate nanopowder/epoxy composites and studying the effect of barium titanate nanopowder on improving mechanical and thermal characteristics of the epoxy polymer. Composites are prepared by dispersing barium titanate nanopowder in epoxy resin and, subsequently, cross-linking by using diamino diphenyl methane (DDM) curing agents. Synthesis of barium titanate nanopowder/epoxy composites is carried out for different concentrations (1, 3, and 5 by weight) of barium titanate nanopowder at high temperature. High-temperature curing (HTC) involves mixing the resin-nanopowder solution followed by DDM hardener and curing at 120°C. Tensile, flexure, and impact results showed a maximum value of 72.7 MPa, 2.98 GPa, and 2 J/cm, respectively. DSC analysis revealed that curing occurs at low temperature in the presence of barium titanate nanopowder. Thermogravimetry analysis (TGA) showed the increased thermal stability in the nanoparticle filled epoxy composites as compared with the pure epoxy counterparts. Dynamic mechanical analysis (DMA) revealed, maximum storage modulus of 6400 MPa and glass transition temperature of 154°C for 3 wt% barium titanate nanopowder.     

Preceramic polymer derived cellular ceramics

Ceramic foams were prepared by a self-blowing process of a poly(silsesquioxane) melt at 270 °C. The cell size, the interconnectivity density and the shape of the foam cells were adjusted by a thermal pre-curing procedure of the polymer at 200 °C. Inorganic fillers were used to modify processing behaviour and properties of the pyrolysed ceramic foam. After pyrolysis in inert atmosphere at 1200 °C ceramic composite foams with a total porosity up to 87% were obtained. The open cell ceramic foams had a mean cell diameter of 1.2 mm and a mean strut thickness of 0.2 mm. Interpenetrating phase composites (IPCs) were fabricated by infiltrating the open cellular ceramic preform with Mg alloy melt at 680 °C and a pressure of 86 MPa. The mechanical properties were found to depend on the reactions between the metal and the ceramic forming MgO, Mg₂Si and Al₁₂Mg₁₇ as the major reaction products. The IPCs showed a significantly higher creep resistance at 135 °C, compression strength and elastic modulus compared to the unreinforced magnesium alloys.     

Characteristics of Ti–Ni–Pd shape memory alloy thin films

Ti–Ni–Pd thin films were deposited by RF magnetron sputtering. Microstructure and phase transformation behaviors were studied by X-ray diffraction (XRD), by transmission electron microscopy and by differential scanning calorimeter (DSC). Also tensile tests and the internal friction characteristics were examined. Annealing at 750 °C followed by subsequent annealing at 450 °C resulted in relatively homogeneous microstructure and uniform martensite/austenite transformation. The results from DSC showed clearly the martensitic transformation upon heating and cooling, the transformation temperatures are 112 °C (M* peak) and 91 °C (M peak), respectively. The transformation characteristics are also found in strain–temperature curves and internal friction–temperature curves. The film had shape memory effect. The frequency had no effect on the modulus, but the internal friction decreased with increasing frequency.     

Effects of Annealing on the Conductivity of C60 Thin Films

Films of C₆₀, at different stages of annealing of T_t=200°and 300°C have been electrically characterized over the temperature domain from -130°C to T_t. X-ray diffraction revealed a random polycrystalline fee structure with stacking defects of an intrinsic nature, due to deposition conditions. The value of room-temperature conductivity was found to be in the range (6.3-1.0) *10^-10 (0cm)^-1. In the stable annealed state the conductivity showed an activated temperature dependence above 423 K and a non-activated dependence below 330-280 K. The activation energies E_a = 0.8 eV (film thickness 0.70 μm) and E_a = 1.0 eV (film thickness 2.40 μm) were in good agreement with the energy gap values (1.63 eV and 2.08 eV) which were deduced from the absorption spectral dependence. Annealing decreased the non-activated contribution to conduction, extending the intrinsic conduction temperature range.