Co-precipitation synthesis in the presence of surfactant and characterization of nanosized CaRuO3 powders and its application in fired thick film resistors in nanoelectronics

In this paper, we are presenting the co-precipitation synthesis of CaRuO₃ from the solutions of CaCl₂·2H₂O and RuCl₃·xH₂O in the presence of CTAB as the surfactant at pH 9.41 and dried at 100 °C in air and at 250 °C in vacuum. The resultant powders were characterized by TGA/DTA, SEM-EDX, XRD, and TEM-SAED techniques. The transmission electron micro-structural studies of powders revealed that the average particle size is around 12 nm. The particle size of CaRuO₃ powder prepared by this solution route without CTAB is around 150–250 nm and solid-state route is 300–400 nm. The resistor paste was formulated by using nano-powders of CaRuO₃ and lead borosilicate glass admixtures pre-heated at 600 °C and peak firing at 850 °C. The electrical studies (sheet resistance and hot/cold temperature coefficient of resistance) of fired thick film resistors prepared from these powders are presented in this paper. We are also presenting the investigation of cross sectional microstructures of above fired thick film resistors. The hot and cold TCR values are higher than the expected values due to the processing of the paste in less than 1 g and non-exchange reactions between Ca²⁺ and Pb²⁺ of functional material and glass respectively due to ionic radii difference of these two metal ions.     

Investigation on electrical and microstructural properties of Thick Film Lead-Free resistor series under various firing conditions

The paper presents investigation of four lead free thick film resistor pastes, developed at ITME, denoted R-100, R-1k, R-10k and R-100k with sheet resistivities of 0.1, 1, 10 and 100 kΩ/□, respectively. The resistors were based on RuO₂ as the conductive phase. The aim of the work was to evaluate the influence of firing conditions of the resistive pastes on a sintering process. The pastes were screen printed onto alumina substrate with prefired AgPd lead-free terminations. They were fired at several temperatures from 750 to 950 °C for 10 min at peak temperature, as well as fired at the highest temperature for 6 h, in order to bring the sintering process into the equilibrium. The properties of the resistors, i.e , sheet resistivity and temperature coefficient of resistance (TCR), microstructure changes, glass crystallization upon firing, etc., were examined. Dried and fired resistor samples were evaluated by X-Ray diffraction analysis and by the scanning electron microscopy. The RuO₂ conductive phase maintained the same crystal structure regardless of the firing conditions. No devitrification was observed in lead-free resistors glasses. The lattice constants of RuO₂ were uniform after firing at temperatures over 800 °C. The resistors matched the desired resistivity and the TCR was the least temperature dependent at the firing temperatures around 850 °C.     

Thermal stability of magnetron sputtered Si–B–C–N materials at temperatures up to 1700 °C

Thermal stability of deposited Si–B–C–N materials (film fragments or powders without a substrate) in inert gases (He and Ar) up to 1700 °C was investigated using differential scanning calorimetry, high-resolution thermogravimetry and X-ray diffraction measurements. Amorphous Si–B–C–N films were fabricated by dc magnetron co-sputtering of a single B₄C–Si target in two nitrogen–argon gas mixtures (50% N₂ + 50% Ar or 25% N₂ + 75% Ar). It was found that the deposited Si–B–C–N materials can be more stable at high temperatures in the inert atmosphere than the usually used substrates (e.g. SiC or BN). The materials with the compositions (in at.%) Si_32–33B₁₀C₂N_50–51, for which N/(Si + B + C) = 1.1–1.2, retained their amorphous structure up to 1600 °C without any structural transformations and detectable mass changes.     

Microwave dielectric properties of BaO–TeO2 binary compounds

A series of BaO–TeO₂ binary ceramic compounds were explored for microwave dielectric applications with ultra-low processing temperatures. During the calcination of mixed BaCO₃ and TeO₂ raw powders, BaTe₄O₉, BaTe₂O₆, BaTeO₃, and Ba₂TeO₅ phases were obtained through the sequential phase formations from Te-rich to Ba-rich phases at temperatures ranging from 500 to 850 °C. Sintering temperatures were as low as only 550 °C for the Te-rich phases. Barium tellurate ceramics exhibited excellent microwave dielectric properties with intermediate dielectric permittivities and high quality factors (Q). The dielectric properties at microwave frequencies were ε_r = 10–21, Q × f = 34,000–55,000 GHz, and TCf = − 51 to − 124 ppm/°C, depending on compositions.     

Stacking faults in an epitaxially grown PbTiO3 thick film and their size distribution

The microstructure of an epitaxial PbTiO₃ thick film, grown on a SrRuO₃/SrTiO₃ substrate at 600 °C by pulsed-MOCVD method, was investigated by using transmission electron microscopy. A number of extrinsic or intrinsic stacking faults were observed in the epitaxial PbTiO₃ thick film and they were parallel to the (0 0 1) plane of the PbTiO₃. We also investigated the size distribution of these stacking faults. The width of these stacking faults along the [1 0 0] axis of the PbTiO₃ was very small, ranging from 2 to 13 nm. It was also revealed that the size distribution of stacking faults depends on the position in the film: near the surface, near the substrate, near threading dislocations, and near 90° domain boundaries.     

Application of carbonated apatite coating on a Ti substrate by aqueous spray method

The fabrication and characterization of a carbonate-containing apatite film deposited on a Ti plate via an aqueous spray method is described. The mist of the spray solution emitted from a perpendicularly oriented airbrush was made to strike a warmed Ti substrate. The thicknesses of the sprayed film and those heat-treated at 400 °C–700 °C under Ar gas flow were in the range 1.21–1.40 μm. The results of elemental analyses and Fourier transform infrared spectroscopy of the powders that were mechanically collected from the surface of the sprayed film suggest that the film was Ca₁₀(PO₄)6(CO₃) · 2CO₂ · 3H₂O. The presence of the carbonate ion and the lattice CO₂ molecule was confirmed via the aforementioned analyses; the finding was also consistent with the X-ray diffraction patterns of the films and the chemical identity of the sprayed and heat-treated films that were measured using X-ray photoelectron spectroscopy. The sprayed film comprises a characteristic network structure, which contains round particles within the networks, as was observed by field-emission scanning electron microscopy. A scratch test indicated that the shear stress of the sprayed film (21 MPa) significantly improved to 40 and > 133 MPa after heat-treatment at 600 °C and 700 °C, respectively, under Ar gas flow for 10 min.     

Microstructure and mechanical properties of MoSi2–MoSi2 joints brazed by Ag–Cu–Zr interlayer

The present work investigates joining of two MoSi₂ parts through Cusil/Zr/Cusil interlayer with Cusil being a commercial eutectic of Cu–Ag alloy. The joining operation was implemented in an inert gas tube furnace by brazing. The brazing temperature ranged from 800 to 930 °C while the operation lasted for 60 min. Evaluation of joints strength through shear loading identified the maximum strength 60.31 MPa for the brazed sample at 830 °C. Interfacial microstructure was studied by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS) and X-ray Diffraction (XRD) techniques. Applying the temperature of 830 °C was led to a uniform dense joint consisting of various phases with excellent bonding within the interfaces. XRD and EDS results revealed different phases such as Mo₅Si₃, Ag-rich solid solution and Cu₁₀Zr₇ at the interface. At higher brazing temperatures the amount of intemetallic compounds and residual stresses increased and therefore, mechanical properties of the joint degraded. The fracture analysis by SEM revealed various fracture path and morphology for different brazing temperatures.     

Effect of reaction temperature on crystallite size and sensing response of chromium oxide nanoparticles

Nanoparticles of chromium oxide have been synthesized following a precipitation technique at reaction temperatures 5, 27 and 65 °C. Synthesized powders were characterized using X-ray diffraction, transmission electron microscope and Brunauer–Emmett–Teller techniques to carry out structural and morphological analysis. The reaction temperature has been found to be playing a crucial role in controlling particle size. It has been observed that Cr₂O₃ nanoparticles synthesized at 27 °C were smaller as compared to those synthesized at 5 and 65 °C. Chromium oxide samples thus prepared were deposited as thick films on alumina substrates to act as gas sensors and their sensing response to ethanol vapour was investigated at different operable temperatures. It has been observed that all the sensors exhibited optimum response at 250 °C. The investigations revealed that sensing response of Cr₂O₃ nanoparticles synthesized at 27 °C was exceptionally higher than that of Cr₂O₃ nanoparticles synthesized at 5 and 65 °C.     

Photoluminescence properties of the Yb:Er co-doped Al2O3 thin film fabricated by microwave ECR plasma source enhanced RF magnetron sputtering

The Yb:Er co-doped Al₂O₃ thin film was deposited on oxidized silicon wafers by microwave ECR plasma source enhanced RF magnetron sputtering, and annealed from 800 °C to 1000 °C. The photoluminescence at 1.53 μm of thin film was obtained under room temperature. The mixture phase structure of γ and θ is observed by XRD, and the compositions of the thin film are investigated by EPMA. The maximum PL intensity was achieved with O₂:Ar at 1:1, annealing temperature at 900 °C, and experimental ratio of Yb:Er at 1:3.6. The energy transfer mechanism between Er and Yb ions is supported by theoretical analysis and experiment results.     

Synthesis of TiO2 thin films using single molecular precursors by MOCVD method for dye-sensitized solar cells application and study on film growth mechanism

For dye-sensitized solar cells application, in this study, we have synthesized TiO₂ thin films at deposition temperature in the range of 300–750 °C by metalorganic chemical vapor deposition (MOCVD) method. Titanium(IV) isopropoxide, {TIP, Ti(OⁱPr)₄} and Bis(dimethylamido)titanium diisopropoxide, {BTDIP, (Me₂N)₂Ti(OⁱPr)₂} were used as single source precursors that contain Ti and O atoms in the same molecule, respectively. Crack-free, highly oriented TiO₂ polycrystalline thin films with anatase phase were deposited on Si(1 0 0) with TIP at temperature as low as 450 °C. XRD and TED data showed that below 500 °C, the TiO₂ thin films were dominantly grown in the [2 1 1] direction on Si(1 0 0), whereas with increasing the deposition temperature to 700 °C, the main film growth direction was changed to [2 0 0]. Above 700 °C, however, rutile phase TiO₂ thin films have only been obtained. In the case of BTDIP, on the other hand, only amorphous film was grown on Si(1 0 0) below 450 °C while a highly oriented anatase TiO₂ film in the [2 0 0] direction was obtained at 500 °C. With further increasing deposition temperatures over 600 °C, the main film growth direction shows a sequential change from rutile [1 0 1] to rutile [4 0 0], indicating a possibility of getting single crystalline TiO₂ film with rutile phase. This means that the precursor together with deposition temperature can be one of important parameters to influence film growth direction, crystallinity as well as crystal structure. To investigate the CVD mechanism of both precursors in detail, temperature dependence of growth rate was also carried out, and we then obtained different activation energy of deposition to be 77.9 and 55.4 kJ/mol for TIP and BTDIP, respectively. Also, we are tested some TiO₂ film synthesized with BTDIP precursor to apply dye-sensitized solar cell.     

Influence of thermal treatment on the structure,humidity sensitivity,electrical and magnetic properties of barium–tungsten ferrite

The purpose of this study was to analyze the methods and effects of introducing tungsten ions in a hexagonal barium ferrite structure by partial substitute of barium with tungsten. For this investigation we prepared a tungsten substitution on the barium hexaferrite Ba_0.5W_0.5Fe₁₂O₁₉ using sol–gel self-combustion technology. The powder was treated for 30 min, without atmosphere precautions, at 850 °C, 900 °C, 950 °C, 1000 °C and 1050 °C. Scanning electron microscopy has revealed the crystallite size and shape, and the X-ray diffraction was provided information related to the phase compositions. The investigation was focused on the variation of permittivity and electrical resistivity, in relation to the treatment temperature, frequency and humidity. We have also investigated the influence of thermal treatment on to Curie temperature and frequency characteristics of the relative permeability. Because barium–tungsten ferrite shows a porous structure, the measurements are strongly influenced by humidity conditions, and in this respect we analyzed the variations with humidity of permittivity and electrical resistivity.     

The tribological behavior of W–S–C films in pin-on-disk testing at elevated temperature

W–S–C films were deposited by magnetron sputtering in an Ar atmosphere with a Ti interlayer. A carbon target with several pellets of WS₂ incrusted in the zone of the preferential erosion was used. The number of pellets was changed to modify the carbon content in the films, which varied from 29 up to 70 at%. Doping W–S films with carbon led to a substantial increase of the hardness in the range 4–10 GPa; the maximum of hardness was obtained for coatings with the carbon content of 40 at%. X-ray diffraction (XRD) patterns showed that there was a loss of crystallinity with the increase of the carbon content in the film.The coatings were tested by pin-on-disk from room temperature (RT) up to 400 °C. At RT, the friction coefficient was in the range 0.2–0.30. At temperatures higher than 100 °C, the friction is below 0.05 for all compositions. The tribological behavior of the coatings with increasing temperatures depended on the films carbon content. For low-carbon content up to 40%, the wear rate was almost independent of the temperature up to 300 °C, while it increased dramatically in the case of the coatings with high-carbon content. In general, the limiting temperature for W–S–C coatings is 400 °C.     

Studies on optical,chemical, and electrical properties of rapid SiO2 atomic layer deposition using tris(tert-butoxy)silanol and trimethyl-aluminum

Rapid SiO₂ atomic layer deposition (ALD) was used to deposit amorphous, transparent, and conformal SiO₂ films using tris(tert-butoxy)silanol (TBS) and trimethyl-aluminum (TMA) as silicon oxide source and catalytic agent, respectively. The growth rate of the SiO₂ films drastically increased to a maximum value (2.3 nm/cycle) at 200 °C and slightly decreased to 1.6 nm/cycle at 275 °C. The SiO₂ thin films have C–H species and hydrogen content (～8 at%) at 150 °C because the cross-linking rates of SiO₂ polymerization may reduce below 200 °C. There were no significant changes in the ratio of O/Si (～2.1) according to the growth temperatures. On the other hand, the film density slightly increased from 2.0 to 2.2 although the growth rate slightly decreased after 200 °C. The breakdown strength of SiO₂ also increases from 6.20 ± 0.82 to 7.42 ± 0.81 MV/cm. These values suggest that high cross-linking rate and film density may enhance the electrical property of rapid SiO₂ ALD films at higher growth temperature.     

Isothermal oxidation behavior of the TZAV-20 alloy

Oxidation behavior is important for secure and long-life service of metals and alloys. The isothermal oxidation behavior of the Ti–20Zr–6.5Al–4V alloy at 470 to 670 °C was investigated. The kinetics analysis shows that the oxidation of TZAV-20 alloy below 570 °C accords with the parabolic law. While the alloy oxidized at 670 °C, obeys the linear law. As oxidation temperature increases from 470 to 670 °C, the oxidation products change as: TiO₂ → TiO₂ + ZrO₂ → TiO₂ + ZrO₂ + Al₂O₃. Relation between weight gain and thickness of oxidation film shows that the weight will increase 0.171 mg/cm² for every 1 μm increasing in thickness. The surface hardness increases from approximately 380 HV for base material to 689 HV for 670 °C oxidized specimen. In short, the TZAV-20 alloy has favorable inoxidizability below 570 °C. The findings will not only promote practical applications of the new TiZrAlV series alloys but also supplement the oxidation theory.     

The L12 CrPt3 underlayer effect on the ordering of L10 FePt films

This study discusses the effects of a CrPt₃ alloy underlayer on the magnetic properties and microstructure of FePt films. The L1₂ CrPt₃ phase was chemical long-range ordered at a temperature above 600 °C, and the 120-nm thick CrPt₃ film annealed at 800 °C, resulting in ferrimagnetic behavior. The long-range ordered CrPt₃ underlayer slightly increased the ordering of the L1₀ FePt film, as evidenced by the individual L1₂ CrPt₃ and L1₀ FePt (0 0 1) superlattice peaks. An X-ray slow scan of the [FePt/CrPt₃(T °C)]_400°C bilayer shows that the integrated intensity of the L1₀ FePt (0 0 1) peaks was higher on the long-range order L1₂-type CrPt₃ (T = 600, 800) underlayer and lower on the partial short-range order L1₂ and A₁-types CrPt₃ (T = 400) underlayer. However, optimal magnetic properties were obtained in the [FePt/CrPt₃(400 °C)]_400°C bilayer. When a FePt film is deposited on a ferrimagnetic CrPt₃(800 °C) underlayer, the resulting bilayer shows isotropic magnetic hysteresis loops and cannot be saturated at 1.8 T. Atomic force microscopy (AFM) and transition electron microscopy (TEM) show that the L1₂ CrPt₃(800 °C) underlayer exhibits coarse surface roughness and plate-like grains, respectively. From TEM images, all the FePt grains were isolated uniformly by CrPt₃ matrix.     

Mechanochemical carboaluminothermic reduction of rutile to produce TiC–Al2O3 nanocomposite

This investigation aims to produce TiC–Al₂O₃ nanocomposite by reducing rutile with aluminum and graphite powder via a mechanochemical process. The effect of milling time on this process was investigated. The characterization of phase formation was carried out by XRD and SEM. Results showed that after a 10 h milling, the combustion reaction between Al, TiO₂ and C was started and promoted by a self-propagation high temperature synthesis. Extending the milling time to 20 h, the reaction was completed. The XRD study illustrated after a 20 h milling, the width of TiC and Al₂O₃ peaks increased while the crystallite sizes of these phases decreased to less than 28 nm. After annealing at 800 °C for 1 h in a tube furnace, TiC and Al₂O₃ crystallite sizes remained constant. However, raising the annealing temperature to 1200 °C caused TiC and Al₂O₃ crystallite size to increase to 49 nm and 63 nm, respectively. No new phase was detected after the heat treatment of the synthesised TiC–Al₂O₃ nanocomposite.     

Hexagonal martensite decomposition and phase precipitation in Ti–Cu alloys

The mechanical behavior of Ti–Cu alloys can be improved by controlling Ti₂Cu precipitation. In eutectoid alloys, such precipitation can be achieved by the decomposition of martensite in response to aging heat treatment. The purpose of this work is to discuss the evolution of precipitates during the decomposition of hexagonal martensite in Ti–Cu alloys. First, samples with near-eutectoid compositions were prepared in an arc furnace equipped with a non-consumable tungsten electrode and water-cooled copper hearth under a high purity argon atmosphere. After chemical homogenization at a temperature in the beta field, the samples were water-quenched and examined by differential scanning calorimetry and high-temperature X-ray diffraction. The results indicate that rapidly quenched near-eutectoid Ti–Cu alloys present Ti₂Cu precipitates. Regardless of the cooling rate applied, such precipitation is unavoidable. No evidence of beta phase stabilization was found in the rapidly quenched samples. Precipitation temperatures of coherent and incoherent phases of 415 °C and 550 °C, respectively, were determined from the differential scanning calorimetry measurements. Ti₂Cu precipitation was examined in situ by high temperature X-ray diffraction experiments. The total decay of martensite was found to occur above 575 °C. Vickers hardness testing of aged samples revealed a correlation between phase precipitation and hardening.     

Analysis of material degradation and life assessment of 25Cr–38Ni–Mo–Ti wrought alloy steel (HPM) for cracking tubes in an ethylene plant

Radiant tubes made of wrought 25Cr–38Ni–Mo–Ti alloy steel (HPM) have been in-service for 76,500 h as cracking tubes in an ethylene plant and they are expected to provide reliable service for 100,000 h (11.4 years) or more. During service, the tube inner surfaces were operated at temperature in the range of 820–835 °C within which thermal cracking process occurred. These aged tubes were assessed to ensure continued safe operation. The assessment of material degradation was carried out using optical microscopy, scanning electron microscopy (SEM) in combination with energy dispersive X-ray (EDX) analysis, X-ray powder diffraction (XRD) analysis, Vickers microhardness measurement and stress rupture test to obtain stress–Larson–Miller parameter (LMP) curves for remaining life prediction. Results showed that microstructural degradation was observed at the inner surface of the radiant tubes marked by the damage of protective oxide film containing Cr₂O₃, Fe₂O₃ and SiO₂. Once this film was removed, carburization occurred and free C atoms involved during cracking of ethylene easily penetrated along austenitic grain boundaries. In addition, carbon diffusion into the tube metal seemed to promote precipitation of Cr₂₃C₆ at grain boundaries and within the grains resulting in a sharp increase in hardness. The outer surface of the radiant tubes, on the other hand, was exposed to higher temperature, typically 1040–1100 °C during operation and creep damage seemed to be the main cause of material degradation. Based on stress rupture test, the remaining life of the radiant tubes is expected to be 21,107 h (2.4 years) consistent with the design life. In the present investigation, factors affecting creep are discussed.     

Effect of V2O5 additive to 0.4SrTiO3–0.6La(Mg0.5Ti0.5)O3 ceramics on sintering behavior and microwave dielectric properties

The effect of V₂O₅ addition on the microwave dielectric properties and the microstructures of 0.4SrTiO₃–0.6La(Mg_0.5Ti_0.5)O₃ ceramics sintered for 5 h at different sintering temperature were investigated systematically. It was found that the sintering temperature was effectively lowered about 200 °C by increasing V₂O₅ addition content. The grain sizes, bulk density as well as microwave dielectric properties were greatly dependent on sintering temperature and V₂O₅ content. The 4ST–6LMT ceramics with 0.25% V₂O₅ sintered at 1400 °C for 5 h in air exhibited optimum microwave dielectric properties of ɛ_r = 50.7, Q × f = 15049.6 GHz, T_f = −1.7 ppm/°C.     

Effects of CaF2 addition on sintering behavior and microwave dielectric properties of ZnTa2O6 ceramics

Microwave dielectric ceramics ZnTa₂O₆ were prepared by conventional mixed oxide route. The effects of CaF₂ addition on the microstructures and microwave dielectric properties of ZnTa₂O₆ ceramics were investigated. Formation of second phase can be detected at the high addition of CaF₂ (0.5–1.0 wt.%). Variation of grain shapes were observed with CaF₂ content increasing. The sintering temperature of CaF₂-doped ZnTa₂O₆ ceramics can be effectively lowered from 1400 °C to 1225 °C due to liquid phase effect. The microwave dielectric properties were affected by the amount of CaF₂ addition. At 1225 °C for 4 h, ZnTa₂O₆ ceramics with 0.25 wt.% CaF₂ possesses excellent microwave dielectric properties: ε_r = 31.32, Q × ? = 73600 GHz(6.8 GHz) and τ_? = ? 6.97 ppm/°C.