Characterization of Mo-Al-N nanocrystalline films synthesized by reactive magnetron sputtering

Mo-Al-N films were deposited by a dc reactive magnetron sputtering technique. The effects of N₂ partial pressure, substrate temperature, and aluminum content on the phase composition, microstructure, hardness and oxidation resistance of the films were studied. The MoAlN films as prepared are fcc Mo₂N structure where partial Mo sites were substituted by Al, and the grain size of the crystallites increased from 8 to 30 nm when the Al concentration was increased from 6% to 33%. In the Mo_0.94Al_0.06N film, the hardness can reach 29 GPa, which is much higher than that in binary Mo-N systems. The oxidation resistance temperature of Mo-Al-N film with an Al content of 6% was higher than that of Mo-N films, and with further addition of Al content, the oxidation resistance temperature increased slightly.     

Oxidation behavior of copper nanoparticles at low temperature

A mass gain for copper nanoparticles with a mean diameter of 20 nm in a 20% oxygen-nitrogen atmosphere was measured at 150-300 °C using thermogravimetry (TG). The mass gain equilibrium of the copper particles differed at each temperature, and a threshold temperature was recorded. Oxide products, consisting mainly of Cu₂O, formed on the copper nanoparticles below the threshold temperature. Above the threshold temperature, there was an initial, and drastic, formation of Cu₂O, which then changed to CuO. The activation energy for the oxidation of the copper nanoparticles that could be calculated from the rate of the mass gain was an indication of the nano-effect of the copper nanoparticles.     

Rietveld refinement study of nanocrystalline copper doped zirconia

Structural studies of Cu-doped zirconia samples with varying Cu content have been carried out. Copper-zirconia samples containing 2-20 mol% Cu were prepared by the co-precipitation technique using tetramethylammonium hydroxide as the precipitating agent and calcined at 773 K in air. The powder XRD data following Rietveld refinement revealed stabilization of zirconia in both tetragonal and cubic phases for all the samples with some monoclinic impurity phase. A decrease in the unit cell parameters of the cubic and tetragonal phase indicates incorporation of copper in the zirconia lattice of both the phases. An increase in the copper concentration (up to 20 mol%) stabilizes zirconia into the cubic phase at the expense of the tetragonal phase, with a decrease in the crystallite size (6-8 nm). Rietveld refinement of the high temperature XRD data reveals that both cubic and tetragonal phases exist up to 723 K with the cubic phase dominating (80% at 723 K). At temperature higher than 723 K, cubic phase gets transformed into the tetragonal phase, which further transforms into the monoclinic phase at 1173 K. At 1173 K, copper comes out of the cubic zirconia lattice forming a separate copper oxide phase and only the tetragonal and monoclinic polymorphs of zirconia exist.     

Synthesis and characterization of boron-oxygen-hydrogen thin films at low temperatures

We have studied the influence of synthesis temperature on chemical composition and mechanical properties of X-ray amorphous boron-oxygen-hydrogen (B-O-H) films. These B-O-H films have been synthesized by RF sputtering of a B-target in an Ar atmosphere. Upon increasing the synthesis temperature from room temperature to 550 °C, the O/B and H/B ratios decrease from 0.73 to 0.15 and 0.28 to 0.07, respectively, as determined by elastic recoil detection analysis. It is reasonable to assume that potential sources of O and H are residual gas and laboratory atmosphere. The elastic modulus, as measured by nanoindentation, increases from 93 to 214 GPa, as the O/B and H/B ratios decreases within the range probed. Hence, we have shown that the effect of impurity incorporation on the elastic properties is extensive and that the magnitude of the incorporation is a strong function of the substrate temperature.     

Preparation and characterization of Ag-doped BaTiO3 based X7R ceramics

Ag-doped BaTiO₃ based X7R (temperature coefficient of capacitance within the range of ±15% between −55 and +125 °C) ceramics with different amounts of silver (0.0-20.0 mol%) were prepared in this paper. The X-ray diffraction analysis indicated that no phases other than BaTiO₃ and silver were observed in the ceramics. The energy dispersive X-ray spectroscopy analysis showed that the silver particles presented homogeneous distribution in the BaTiO₃ ceramics. The dielectric properties of Ag-doped ceramics were investigated. A small amount of silver (<0.5 mol%) and a large amount of silver (>2.0 mol%) could both improve the sintered density and permittivity, but more content of silver (0.5-2.0 mol%) would decrease the relative density and permittivity. Specially, the temperature coefficient of capacitors of the ceramics doped with 20 mol% silver still met the X7R characteristics, and the room temperature permittivity of the ceramics was 6823, which was the highest dielectric constant in the BaTiO₃ based X7R ceramics.     

Preparation and super-hydrophilic properties of TiO2/SnO2 composite thin films

SnO₂-TiO₂ composite thin films were fabricated on soda-lime glass with sol-gel technology. By measuring the contact angle of the film surface and the degradation of methyl orange, we studied the influence of SnO₂ doping concentration, heat-treatment temperature and film thickness on the super-hydrophilicity and photocatalytic activity of the composite films. The results indicate that the doping of SnO₂ into TiO₂ can improve their hydrophilicity and photocatalytic activity, and the composite film with 1-5 mol% SnO₂ and heat-treated at 450°C is of super-hydrophilicity. The optimal SnO₂ concentration for the photocatalytic activity is 10 mol% and larger film thickness is helpful to reduce the contact angle of the composite films.     

Nitrogen-doped titanium dioxide—Characterization of structural and optical properties

We have chosen oxidation of titanium nitride, TiN, in air atmosphere as a preparation method of nitrogen-doped titanium dioxide for photocatalytic application. Powders and thin films were selected for systematic studies. Self-propagating high-temperature synthesis (SHS) and dc reactive magnetron sputtering were used for elaboration of stoichiometric TiN powder and thin films, respectively. Samples microstructure was studied by means of AFM and SEM. The phase and chemical composition were investigated by means of XRD and XPS. The optical spectra were measured over the visible and UV ranges of light spectrum. SEM images of powders revealed a change in grain shape from sharp-edged TiN grains with well-defined facets to regular and oval TiO₂. XRD studies set out the temperature limit of TiN existence at 400 °C. XPS investigations confirmed nitrogen presence in TiO₂ lattice even at 500 °C. Optical analysis revealed an additional absorption over the visible range - powders, and a shift of the fundamental absorption edge towards visible range of the light spectrum - thin films.     

Electrical and gas sensing properties of self-aligned copper-doped zinc oxide nanoparticles

Electrical and gas sensing properties of nanocrystalline ZnO:Cu, having Cu X wt% (X = 0.0, 0.5, 1.0, and 1.5) in ZnO, in the form of pellet were investigated. Copper chloride and zinc acetate were used as precursors along with oxalic acid as a precipitating reagent in methanol. Material characterization was done by X-ray diffraction (XRD), scanning electron microscopy (SEM), field emission scanning electron microscopy (FE-SEM) and inductive coupled plasma with optical emission spectrometry (ICP-OES). FE-SEM showed the self-aligned Cu-doped ZnO nano-clusters with particles in the range of 40-45 nm. The doping of 0.5% of copper changes the electrical conductivity by an order of magnitude whereas the temperature coefficient of resistance (TCR) reduces with increase in copper wt% in ZnO. The material has shown an excellent sensitivity for the H₂, LPG and CO gases with limited temperature selectivity through the optimized operating temperature of 130, 190 and 220 °C for H₂, LPG and CO gases, respectively at 625 ppm gas concentration. The %SF was observed to be 1460 for H₂ at 1% Cu doping whereas the 0.5% Cu doping offered %SF of 950 and 520 for CO and LPG, respectively. The response and recovery time was found to be 6 to 8 s and 16 s, respectively.     

Structural, electrical and optical studies of SILAR deposited cadmium oxide thin films: Annealing effect

Successive ionic layer adsorption and reaction (SILAR) method has been successfully employed for the deposition of cadmium oxide (CdO) thin films. The films were annealed at 623 K for 2 h in an air and changes in the structural, electrical and optical properties were studied. From the X-ray diffraction patterns, it was found that after annealing, H₂O vapors from as-deposited Cd(O₂)_0.88(OH)_0.24 were removed and pure cubic cadmium oxide was obtained. The as-deposited film consists of nanocrystalline grains of average diameter about 20-30 nm with uniform coverage of the substrate surface, whereas for the annealed film randomly oriented morphology with slight increase in the crystallite size has been observed. The electrical resistivity showed the semiconducting nature with room temperature electrical resistivity decreased from 10⁻² to 10⁻³ Ω cm after annealing. The decrease in the band gap energy from 3.3 to 2.7 eV was observed after the annealing.     

Electrical conductivity of yttrium-doped SrTiO3: influence of transition metal additives

The electrical conductivity of yttrium-doped SrTiO₃ with transition metals added as acceptor dopants (V, Mn, Fe, Co, Ni, Cu, Zn, Mo, Mg, Zr, Al, or Ga) was measured by the dc four-probe method at 600-900°C in reducing atmospheres. The replacement of 5 mol% titanium by acceptors leads to a decrease of conductivity of Sr_1−1.5xY_xTiO_3−δ. The degree of the decrease depends strongly on the type of dopant. Of the 5 mol% acceptor-doped compositions, the system Sr_0.85Y_0.10Ti_0.95Co_0.05O_3−δ had the highest conductivity of 45 S/cm at 800°C and oxygen partial pressure of 10⁻¹⁹ atm. The oxidation kinetics of yttrium-doped SrTiO₃ was significantly retarded by the addition of cobalt or manganese dopants. The ionic conductivity of SrTiO₃ doped with 5 mol% acceptors at Ti-sites was estimated from the total conductivity to lie in the vicinity of 10⁻⁴ S/cm, depending on oxygen partial pressure and temperature.     

Ionic conductivity of a gel polymer electrolyte based on Mg(ClO4)2 and polyacrylonitrile (PAN)

Magnesium ion containing gel polymer electrolytes based on polyacrylonitrile (PAN) have been synthesized and characterized using ac impedance measurements. The electrolyte composition having the highest room temperature conductivity was found by varying the ratios propylene carbonate/ethylene carbonate (PC/EC) and PAN/Mg(ClO₄)₂. The corresponding composition was 18 mol% PAN:64 mol% EC:14 mol% PC:4 mol% Mg(ClO₄)₂. The ac conductivity measurements were carried out from room temperature upto 70 °C with blocking (stainless steel) electrodes. The room temperature conductivity is 3.2×10⁻³ S cm⁻¹ and the activation energy is 0.24 eV over the temperature range used. The high conductivity and the low activation energy of the material could possibly be due to the liquid electrolyte, Mg(ClO₄)₂ in EC/PC trapped in a matrix of PAN, as suggested by previous workers. According to dc polarization measurements, the gel electrolyte appears to be predominantly an anionic conductor.     

Dielectric and microstructural properties of barium titanate hafnate thin films

Barium titanate hafnate (BaTi_1−xHf_xO₃, 0 ≤ x ≤ 0.25) thin films have been deposited by a chemical solution method on copper foil substrates. The films were crystallized at 900 °C and in a reducing atmosphere to prevent substrate oxidation. Perovskite phase formation was identified for each composition, accompanied by an increased pseudocubic lattice parameter. Temperature dependent dielectric measurements revealed a decreasing phase transition temperature and peak permittivity with increasing hafnium level. The decrease in permittivity resulted from grain size reduction with increasing hafnium content. Compositions containing 25 mol% barium hafnate display a deviation from Curie-Weiss behavior indicating the onset of relaxor behavior.     

Effect of temperature on nonlinear electrical behavior and dielectric properties of (Ca, Ta)-doped TiO2 ceramics

TiO₂ ceramics doped with 0.75 mol% Ca and 2.5 mol% Ta were sintered at different temperatures ranging from 1300 to 1450°C. The effects of sintering temperature on the microstructure, nonlinear electrical behavior, and dielectric properties of the ceramics were studied. The sample sintered at 1300°C exhibits the highest nonlinear coefficient (5.5) and a comparatively lower relative dielectric constant.     

Optimization of reaction conditions in selective oxidation of styrene over fine crystallite spinel-type CaFe2O4 complex oxide catalyst

The CaFe₂O₄ spinel-type catalyst was synthesized by citrate gel method and well characterized by thermogravimetric analysis, atomic absorption spectroscopy, Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. The crystallization temperature of the spinel particle prepared by citrate gel method was 600 °C which was lower than that of ferrite prepared by other methods. CaFe₂O₄ catalysts prepared by citrate gel method show better activity for styrene oxidation in the presence of dilute H₂O₂ (30%) as an oxidizing agent. In this reaction the oxidative cleavage of carbon-carbon double bond of styrene takes place selectively with 38 ± 2 mol% conversion. The major product of the reaction is benzaldehyde up to 91 ± 2 mol% and minor product phenyl acetaldehyde up to 9 ± 2 mol%, respectively. The products obtained in the styrene oxidation reaction were analyzed by gas chromatography and mass spectroscopy. The influence of the catalyst, reaction time, temperature, amount of catalyst, styrene/H₂O₂ molar ratio and solvents on the conversion and product distribution were studied.     

Facile synthesis of antimony-doped tin oxide nanoparticles by a polymer-pyrolysis method

In this article, antimony-doped tin oxide (ATO) nanoparticles was synthesized by a facile polymer-pyrolysis method. The pyrolysis behaviors of the polymer precursors prepared via in situ polymerization of metal salts and acrylic acid were analyzed by simultaneous thermogravimetric and differential scanning calorimetry (TG-DSC). The structural and morphological characteristics of the products were studied by powder X-ray diffraction (XRD) and transmission electron microscope (TEM). The results reveal that the ATO nanoparticles calcined at 600 °C show good crystallinity with the cassiterite structure and cubic-spherical like morphology. The average particle size of ATO decreases from 200 to 15 nm as the Sb doping content increases from 5 mol% to 15 mol%. Electrical resistivity measurement shows that the resistivity for the 10-13 mol% Sb-doped SnO₂ nanoparticles is reduced by more than three orders compared with the pure SnO₂ nanoparticles. In addition, due to its versatility this polymer-pyrolysis method can be extended to facile synthesis of other doped n-type semiconductor, such as In, Ga, Al doped ZnO, Sn doped In₂O₃.     

In situ optical microspectroscopy of the growth and oxidation of silver nanoparticles in silica thin films on soda-lime glass

An in situ optical microspectroscopy investigation of the growth and oxidation of silver nanoparticles (NPs) embedded in SiO₂ thin films deposited on soda-lime glass has been conducted in real time during thermal processing in air. Variation of Ag NP size is followed by fitting of surface plasmon resonance (SPR) with spectra calculated by Mie theory, and analysed concurrently with the time evolution of SPR peak intensity. The NP transformations appeared to be temperature and time dependent. Silver NPs were indicated to grow at relatively high temperatures (e.g. 600 °C) due to Ostwald ripening, followed by a plateau and a gradual decrease in size resulting in SPR vanishing due to oxidation. The three phases were well separated in time. Oxidation appeared dominant at lower temperatures (e.g. 400 °C) as indicated by a continuous decrease in Ag particle size. The product of Ag NP oxidation was revealed by photoluminescence spectroscopy as single Ag⁺ ions. Furthermore, the data indicated that: (i) Ag⁺ ions are formed during heat treatment under an Ag/Ag⁺ redox equilibrium; (ii) the ions diffuse from the SiO₂ matrix towards the soda-lime substrate where they stabilize; and (iii) the continuous removal of these ions from the matrix is necessary in order for the equilibrium to be displaced towards oxidation.     

Microstructure and mechanical properties of titanium carbonitride whisker reinforced β-sialon matrix composites

The microstructure, hardness, fracture toughness and thermal shock resistance were investigated for 15 vol.% TiC_0.3N_0.7 whisker reinforced β-sialon (Si_6−zAl_zO₂N_8−z with z=0.6) composites with additions of three different volume fractions 2, 5 and 20 vol.%, of an yttrium-containing glass oxynitride phase. The composites were prepared by hot pressing at 1750°C for 90 min under a uniaxial pressure of 30 MPa in nitrogen atmosphere. The TiC_0.3N_0.7 whiskers were found to survive without deteriorating in morphology or reacting with the β-sialon matrix and/or the glass phase. The TiC_0.3N_0.7 whiskers had no obvious influence on the matrix microstructure, but their presence improved both the hardness and the fracture toughness of the composites. The highest hardness was obtained for the whisker composite with 2 vol.% glass phase (H_v=18.6 GPa). The fracture toughness and thermal shock resistance improved with increasing glass content. The whisker reinforced composite containing 20 vol.% glass showed the highest fracture toughness (K_1C=6.8 MPa m^1/2). No unstable crack extension occurred during the thermal shock test of the obtained composites in the temperature interval 90-700°C, but above 700°C severe oxidation of the whiskers precludes further evaluation of thermal shock properties by the indentation-quench method applied.     

Optical properties of nanocrystalline SnS2 thin films

Thin films of nanocrystalline SnS₂ on glass substrates were prepared from solution by dip coating and then sulfurized in H₂S (H₂S:Ar = 1:10) atmosphere. The films had an average thickness of 60 nm and were characterized by X-ray diffraction studies, scanning electron microscopy, EDAX, transmission electron microscopy, UV-vis spectroscopy, and Raman spectroscopy. The influence of annealing temperature (150-300 °C) on the crystallinity and particle size was studied. The effect of CTAB as a capping agent has been tested. X-ray diffraction analysis revealed the polycrystalline nature of the films with a preferential orientation along the c-axis. Optical transmission spectra indicated a marked blue shift of the absorption edge due to quantum confinement and optical band gap was found to vary from 3.5 to 3.0 eV with annealing temperature. Raman studies indicated a prominent broad peak at ∼314 cm⁻¹, which confirmed the presence of nanocrystalline SnS₂ phase.     

Structure and dielectric performance of K-doped (Pb0.5Ba0.5)ZrO3 thin films

In the present investigation (Pb_0.5Ba_0.5)ZrO₃ (PBZ) thin films doped by K (KPBZ) from 0 to 5 mol% were successfully deposited on Pt-buffered silicon substrates by a sol-gel method. The K content dependence of microstructure and electrical properties of KPBZ thin films were studied in detail. It was found that, although all the films displayed a pure perovskite structure without obvious difference, the surface roughness of KPBZ films was decreased with increasing K content. Dielectric measurements showed that the figure of merit (FOM) values of KPBZ thin films were greatly increased by K-doping, and at the same time that the temperature-dependent stability was also improved. Thus, K doping is a promising way to optimize the overall electrical properties of PBZ thin films for potential application in tunable devices.