Microwave dielectric properties of low-temperature sinterable α-MoO3

The α-MoO₃ ceramics were prepared by uniaxial pressing and sintering of MoO₃ powder at 650 °C and their structure, microstructure, densification and sintering and microwave dielectric properties were investigated. The sintering temperature of α-MoO₃ was optimized based on the best densification and microwave dielectric properties. After sintering at 650 °C the relative permittivity was found to be 6.6 and the quality factor was 41,000 GHz at 11.3 GHz. The full-width half-maximum of the A_1g Raman mode of bulk α-MoO₃ at different sintering temperatures correlated well with the Qf values. Moreover, the sintered samples showed a temperature coefficient of the resonant frequency of ?25 ppm/°C in the temperature range from ?40 to 85 °C and they exhibited a very low coefficient of thermal expansion of ±4 ppm/°C. These microwave dielectric properties of α-MoO₃ will be of great benefit in future MoO₃ based materials and their applications.     

The molybdenum species of MoO3/SiO2 and their catalytic activities for the epoxidation of propylene with cumene hydroperoxide

The MoO₃/SiO₂ catalysts containing different surface molybdenum species were prepared by a sol–gel method, and the effects of the preparation condition and MoO₃ loading on the surface molybdenum species and property of MoO₃/SiO₂ were studied. The XRD, FT-IR, UV–vis and Raman spectroscopies were used to characterize the surface molybdenum species, and temperature-programmed desorption of NH₃ adsorbed on a catalyst was used to detect the surface acidic properties. The results show that, there were the dispersed polymolybdate, α-MoO₃, β-MoO₃, monomeric molybdenum species and silicomolybdic acid on the MoO₃/SiO₂ catalyst, and their distributions and subsistence states were affected by the preparation condition and MoO₃ loading. Different molybdenum species exhibit different catalytic activities for the epoxidation of propylene with cumene hydroperoxide. In the 15 wt% MoO₃/SiO₂ catalyst synthesized at pH 9.1 and dried appropriately, there are the small size β-MoO₃ and monomeric molybdenum species that they are mainly effective catalyst components for the epoxidation of propylene. Using this catalyst, the ～100% conversion of cumene hydroperoxide and ～100% selectivity to propylene oxide can be obtained in the tert-butyl alcohol solvent at 2.6 MPa and 80 °C for 4 h.     

Study on SO42−/ZrO2-MoO3 in the integrative transformation of cottonseed oil deodorizing distillate

With the integrative transformation of non α-tocopherols, glycerides, free fatty acids, and methyl alcohol in cottonseed oil deodorizing distillate as the target reaction, we prepared highly catalytic SO₄^2?/ZrO₂-MoO₃ solid acid catalyst by precipitation–wet impregnation. The optimal conditions for catalyst preparation were then determined by varying sulfuric acid concentration, MoO₃ loading factor, calcination temperature, and calcination time. The structure of SO₄^2?/ZrO₂-MoO₃ solid acid catalyst was then examined by X-ray diffraction (XRD), Brunauer–Emmett–Teller measurements, scanning electron microscopy, and other methods. Results show that the MoO₃ loading factor (percentage weight ratio of MoO₃ to ZrO₂), impregnation concentration of sulfuric acid, and calcination temperature were the most important factors that influenced catalytic activity. The optimal conditions for catalyst preparation were an MoO₃ loading factor of 20%, a sulfuric acid impregnation concentration of 0.75 mol/L, a calcination temperature of 550 °C, and a calcination time of 6 h. The obtained catalyst exhibited the highest catalytic activity under these conditions.     

Electrochemical presodiation promoting lithium storage performance of Mo-based anode materials

Stabilizing the layer structures of Mo-based anode materials is still a challenge for Li ion batteries. Herein, we proposed an electrochemical presodiation strategy for MoS₂ and MoO₃ to improve their cycling stability. It is interesting to note that the cycling stability of as-treated MoS₂ and MoO₃ was significantly improved. Although the reversible discharge capacity was slightly decreased, the capacity of the pretreated MoS₂ at 300 mA g⁻¹ was retained at 345 mA h g⁻¹ after 100 cycles while that of the pristine one decreased to 151 mA h g⁻¹. The capacity of the pretreated MoO₃ after 60 cycles was also improved from 275 mA h g⁻¹ (the pristine one) to 460 mA h g⁻¹. The stabilizing effect was further verified by scanning electron microscope (SEM) analysis. Electrochemical presodiation here could be a promising modification strategy for Mo-based anode materials.     

Flame-made MoO3/SiO2–Al2O3 metathesis catalysts with highly dispersed and highly active molybdate species

MoO₃/SiO₂–Al₂O₃ catalysts are prepared via flame spray pyrolysis and evaluated in the self-metathesis of propene to ethene and butene. Their specific surface area ranges between 100 and 170 m² g^?1 depending on the MoO₃ loading (1–15 wt.%, corresponding to Mo surface density between 0.3 and 6.1 Mo atoms per nm²). The catalysts were characterized by N₂-physisorption, X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectroscopy (ToF-SIMS). The silica–alumina matrix condenses first in the flame and forms non-porous spherical particles of 5–20 nm, followed by the dispersion of Mo oxide at their surface. Depending on the MoO₃ loading, different MoO_x species are stabilized: dispersed and amorphous molybdates (mono- and oligomeric) at low loadings (<5 wt.%, <1.5 Mo nm^?2) and crystalline MoO₃ species at higher loadings. Raman spectroscopy suggests the presence of monomeric species for surface densities of 0.3, 0.5 and 0.8 Mo nm^?2. The formation of MoOMo bonds is, however, clearly established by ToF-SIMS from surface densities as low as 0.5 Mo nm^?2. At 1.5 Mo nm^?2, crystallites of β-MoO₃ (2–3 nm) are detected and further increasing the loading induces the formation of bigger α- and β-MoO₃ crystals (around 20 nm). The speciation of Mo proves to have a marked impact on the metathesis activity of the catalysts. Catalysts with high Mo loading and exhibiting MoO₃ crystals are poorly active, whereas catalysts with low Mo loading (<5 wt.%) perform well in the reaction. The catalyst loaded with only 1 wt.% of MoO₃ (0.3 Mo nm^?2) is the most active, reaching turn over frequencies seven times higher than reference catalysts reported in the literature. Moreover, the specific metathesis activity is clearly inversely correlated to the degree of condensation of the molybdenum oxide phase (as evaluated by ToF-SIMS). The latter finding indicates that monomeric MoO_x species are the main active centres in the olefin metathesis.     

Structural,optical and methanol sensing properties of sprayed In2O3 nanoparticle thin films

Indium oxide (In₂O₃) nanoparticle thin films were grown on cleaned glass substrates by the chemical spray pyrolysis technique using the precursor solution of indium nitrate (In (NO₃)₃). The XRD studies confirm that the films are polycrystalline In₂O₃, possessing cubic structure with lattice parameters, a = b = c = 10.17 Å. The optical studies show a direct optical band gap of 3.32 eV and an indirect band gap of 2.6 eV in the prepared films. The films exhibit high optical transparency >80% in the visible region, reaching a maximum of 85% at 684 nm wavelength. Further, the gas sensing properties of the films have been investigated for various concentrations of methanol in air at different operating temperatures. At 300 °C the film exhibits a very high response 99% to methanol vapor at a concentration of 40 ppm in air, which is ideal to be used as a methanol sensor. The film shows fast response and recovery to methanol vapor at higher operating temperatures. A possible methanol sensing mechanism has been proposed.     

H2 response characteristics for sol–gel-derived WO3-SnO2 dual-layer thin films

This paper describes the deposition of SnO₂ and WO₃ thin films and WO₃-SnO₂ dual-layer thin films using the sol-gel process. The microstructure and morphology of these three thin films were analyzed with FE-SEM and X-ray diffraction. The H₂ response characteristics, including response magnitude, time and transients of the three samples, were investigated at different operation temperatures and H₂ gas concentrations. Although the maximum response magnitude of 29.31 towards 1000 ppm H₂ gas appeared at 225 °C,the WO₃-SnO₂ dual-layer films still had a response magnitude of 24.23 at 175 °C, which is much higher than those of the SnO₂ (4.19) and WO₃ (6.73) thin films. The linear response magnitude profile of the WO₃-SnO₂ dual-layer thin films toward H₂ gas concentration was obtained. The mechanism of the enhanced gas response characteristics was explained by the band bending theory.     

Nanostructured SnO2 thin films for NO2 gas sensing applications

We report the synthesis of nanostructured SnO₂ by a simple inexpensive sol–gel spin coating method using m-cresol as a solvent. This method facilitates rapid synthesis at comparatively lower temperature enabling formation of nanostructures suitable for gas-sensing applications. Various physicochemical techniques have been used for the characterization of SnO₂ thin films. X-ray diffraction analysis confirmed the single-phase formation of tetragonal SnO₂ having crystallite size 5–10 nm. SnO₂ showed highest response (19%) with 77.90% stability toward 100 ppm nitrogen dioxide (NO₂) at 200 °C. The response time of 7 s and recovery time of 20 min were also observed with the same operating parameters. The probable mechanism is proposed to explain the selective response toward nitrogen dioxide. Impedance spectroscopy studies showed that the response to nitrogen dioxide is mainly contributed by grain boundaries. The reproducibility and stability study of SnO₂ sensor confirmed its candidature for detection of NO₂ gas at low concentration (10–100 ppm) and lower operating temperature.     

ZnO thin film nanostructures for hydrogen gas sensing applications

A ZnO thin film-based gas sensor was fabricated using a SiO₂/Si substrate with a platinum comb-like integrated electrode and heating element. The structural characteristics, morphology, and surface roughness of the as-grown ZnO nanostructure were investigated. The film revealed the presence of a c-axis oriented (002) phase with a grain size of 20.8 nm. The sensor response was tested for hydrogen concentrations of 50, 70, 100, 200, 400, and 500 ppm at the optimum operating temperature of 350 °C. The sensitivities towards 50 and 200 ppm of hydrogen gas at 350 °C were approximately 78% and 98%, respectively. A linear response was observed for hydrogen concentrations within the range of 50 ppm–200 ppm. These results demonstrated the potential application of the ZnO nanostructure for the fabrication of cost-effective and high-performance gas sensors.     

Influence of Pd-loading on gas sensing characteristics of SnO2 thick films

Nanocrystalline pristine and 0.5, 1.5 and 3.0 wt% Pd loaded SnO₂ were synthesized by a facile co-precipitation route. These powders were screen-printed on alumina substrates to form thick films to investigate their gas sensing properties. The crystal structure and morphology of different samples were characterized by using X-ray diffraction, scanning electron microscopy and transmission electron microscopy techniques. The 3.0 wt% Pd:SnO₂ showed response of 85% toward 100 ppm of LPG at operating temperature of 250 °C with fast response (8 s) and quick recovery time (24 s). The high response toward LPG on Pd loading can be attributed to lowering of crystallite size (9 nm) as well as the role of Pd particles in exhibiting spill-over mechanism on the SnO₂ surface. Also selectivity of 3.0 wt% Pd:SnO₂ toward LPG was confirmed by measuring its response to other reducing gases like acetone (CH₃COCH₃), ethanol (C₂H₅OH) and ammonia (NH₃) at optimum operating temperature.     

Dielectric properties and bright red emission of Y3+/Eu3+-codoped ZrO2 thin films prepared by chemical solution deposition

We report on an effective combination of good dielectric properties with bright red emission in Y³⁺/Eu³⁺-codoped ZrO₂ thin films. The thin films were deposited on fused silica and Pt/TiO₂/SiO₂/Si substrates using a chemical solution deposition method. The crystal structure, surface morphology, electrical and optical properties of the thin films were investigated in terms of annealing temperature, and Y³⁺/Eu³⁺ doping content. The 5%Eu₂O₃–3%Y₂O₃–92%ZrO₂ thin film with 400 nm thickness annealed at 700 °C exhibits optimal photoluminescent properties and excellent electrical properties. Under excitation by 396 nm light, the thin film on fused silica substrate shows bright red emission bands centered at 593 nm and 609 nm, which can be attributed to the transitions of Eu³⁺ ions. Dielectric constant and dissipation factor of the thin films at 1 kHz are 30 and 0.01, respectively, and the capacitance density is about 65.5 nf/cm² when the bias electric field is less than 500 kV/cm. The thin films also exhibit a low leakage current density and a high optical transmittance with a large band gap.     

Dielectric and optical properties of electroceramic PBZNZT thin films prepared by pulsed laser deposition process

The 0.6[0.94Pb(Zn_1/3Nb_2/3)O₃ + 0.06BaTiO₃] + 0.4[0.48(PbZrO₃) + 0.52(PbTiO₃)], PBZNZT, thin films were synthesized by pulsed laser deposition (PLD) process. The PBZNZT films possess higher insulating characteristics than the PZT (or PLZT) series materials due to the suppressed formation of defects, therefore, thin-film forms of these materials are expected to exhibit superior ferroelectric properties as compared with the PZT (or PLZT)-series thin films. Moreover, the Ba(Mg_1/3Ta_2/3)O₃ thin film of perovskite structure was used as buffer layer to reduce the substrate temperature necessary for growing the perovskite phase PBZNZT thin films. The PBZNZT thin films of good ferroelectric and dielectric properties (remanent polarization P_r = 26.0 μC/cm², coercive field E_c = 399 kV/cm, dielectric constant K = 737) were achieved by PLD at 400 °C. Such a low substrate temperature technique makes this process compatible with silicon device process. Moreover, thus obtained PBZNZT thin films also possess good optical properties (about 75% transmittance at 800 nm). These results imply that PBZNZT thin films have potential in photonic device applications.     

Anode-supported SOFCs based on Sm0.2Ce0.8O2−δ electrolyte thin-films fabricated by co-pressing using microwave combustion synthesized powders

Decreasing the electrolyte thickness is an effective approach to improve solid oxide fuel cells (SOFCs) performance for intermediate-temperature applications. Sm_0.2Ce_0.8O_2−δ (SDC) powders with low apparent density of 32±0.3 mg cm⁻³ are synthesized by microwave combustion method, and SDC electrolyte films as thin as ~10 μm are fabricated by co-pressing the powders onto a porous NiO–SDC anode substrate. Dense SDC electrolyte thin films with grain size of 300–800 nm are achieved at a low co-firing temperature of 1200 °C. Single cells based on SDC thin films show peak power densities of 0.86 W cm⁻² at 650 °C using 3 vol% humidified H₂ as fuel and ambient air as oxidant. Both the thin thickness of electrolyte films and ultra-fine grained anode structure make contributions to the improved cell performance.     

Thickness effects on microwave properties of (Ba,Sr)TiO3 films for frequency agile technologies

We fabricated (Ba_0.6Sr_0.4)TiO₃ (BST) thin films of various thicknesses on sapphire (−1 1 2 0) substrates using metal-organic decomposition method. These films showed grain growth from 160 to 650 nm with an increase in the thickness from 90 to 1050 nm. At microwave frequencies, the measured capacitances of the planar capacitors decreased with the film thickness because the electro-magnetic field propagates across high permittivity BST films to the low permittivity sapphire substrate. However, we found that the BST-thin film permittivity remained large up to 90 nm thick, based on electro-magnetic field analysis using the finite element method. On the other hand, the BST thin film tunability decreased with the film thickness.     

Structural and electrical properties of sol–gel-derived Al-doped bismuth ferrite thin films

Al-doped BiFeO₃ (BiFe_(1?x)Al_xO₃) thin films with small doping content (x=0, 0.05, and 0.1) were grown on Pt(111)/TiO₂/SiO₂/Si substrates at the annealing temperature of 550 °C for 5 min in air by the sol–gel method. The crystalline structure, as well as surface and cross section morphology were studied by X-ray diffraction and scanning electron microscope, respectively. The dielectric constant of BiFeO₃ film was approximately 71 at 100 kHz, and it increased to 91 and 96 in the 5% and 10% Al-doped BiFeO₃ films, respectively. The substitution of Al atoms in BiFeO₃ thin films reduced the leakage current obviously. At an applied electric field of 260 kV/cm, the leakage current density of the undoped BiFeO₃ films was 3.97×10^?4 A/cm², while in the 10% Al-substitution BiFeO₃ thin films it was reduced to 8.4×10^?7 A/cm². The obtained values of 2P_r were 63 μC/cm² and 54 μC/cm² in the 5% and 10% Al-doped BiFeO₃ films at 2 kHz, respectively.     

Ferroelectric and dielectric properties of manganese-doped Na0.5Bi0.5TiO3 nanocrystalline thin films prepared by metal organic decomposition: A single-layer thickness-dependent study

2 at% Manganese-doped Na_0.5Bi_0.5TiO₃ (NBTMn) thin films with single-layer thicknesses ranging from 15 to 45 nm/l were deposited on the indium tin oxide/glass substrates by a metal organic decomposition process and spin coating technique. The influence of single-layer thickness on the crystal structure, surface morphology, insulating ability, ferroelectric and dielectric properties was mainly investigated. Compared with the other films, NBTMn film with a single-layer thickness of 30 nm/l exhibits the (110)-preferred orientation and dense structure. Also, it shows the enhanced ferroelectricity with a large remanent polarization (P_r) of 38 μC/cm² due to the preferred orientation and low leakage current density. Meanwhile, a high dielectric tunability of 39% for NBTMn with 30 nm/l can be observed by varying the measuring applied voltage and frequency. These results indicate that the suitable layer thickness is beneficial to improve the electrical performances of NBTMn thin film.     

Post-deposition annealed MoO3 film based high performance MSM UV photodetector fabricated on Si (100)

Molybdenum oxide (MoO₃) films were prepared on Si (100) at room temperature using radiofrequency (RF) magnetron sputtering technique. The films were annealed in the presence of air at different temperatures from 100 to 550 °C. The as-prepared films were amorphous as revealed by the X-ray diffraction analysis. Post-deposition annealing of MoO₃ film enhanced its crystalline structure, showing β-MoO₃ phase at 100 °C and a mixture of α-MoO₃ and β-MoO₃ phases at 300 °C. The crystallinity of α-MoO₃ improved with increasing the annealing temperature to 500 °C, however, the β-MoO₃ phase became amorphous. The film was dissolved at 550 °C as no diffraction peak of MoO₃ was detected at this temperature. The band gap of MoO₃ was evaluated through ultraviolet–visible spectroscopy. The results showed a decrease in the band gap from 3.70 to 3.39 eV with increasing the annealing temperature to 500 °C. The film with optimum crystalline quality was used to fabricate a metal-semiconductor-metal (MSM) photodetector device. The photo-detection characteristics of the film were studied after the deposition of Nickel contacts on MoO₃ using a metal mask having interdigitated electrodes. The fabricated device exhibited a high current gain and sensitivity under 365 nm UV illumination. The responsivity of the device under UV light was 0.41 A/W at 7 V. The rise and decay time of UV photodetector were 0.32 and 0.23 s respectively. These findings suggested that the MoO₃ film with dominant orthorhombic α-phase can potentially be used for the photodetector application.     

A study on the photoluminescence properties of electrospray deposited amorphous and crystalline nanostructured ZnO thin films

Transparent amorphous and crystalline nanostructured zinc oxide (ZnO) thin films were prepared by electrospray deposition technique on a glass substrate at 250 °C using zinc nitrate and ammonia as the precursors. The structural morphology and optical properties of the thin films were evaluated and also the effect of formation rate of basic generating species on the morphology of the thin films was discussed. Optical studies indicated that all of the thin films have a near band edge emission at 374 nm and a band gap of 3.32 eV. In addition, the films have an emission at 393 nm corresponding to ultra violet (UV) transmittance. However, the amorphous thin films have oxygen trap peak at 430 nm and two green transmittance peaks at 485 nm and 530 nm which are absent in the 0.1 molar nanostructured sample. The crystallite size of the thin films which calculated from XRD patterns via Debye–Scherrer's formula was around 30 nm.     

Effect of substrate temperature on structural and electrical properties of BaZr0.2Ti0.8O3 lead-free thin films by pulsed laser deposition

Barium zirconate titanate (BaZr_0.2Ti_0.8O₃, BZT) 250 nm thick thin films were fabricated by pulsed laser deposition and the influence of the substrate temperature on their preferred orientation, microstructure, morphology and dielectric properties was investigated. Dielectric measurements indicated the (1 1 0)-oriented BZT thin films deposited at 750 °C to show good dielectric properties with high dielectric constant (~500 at 100 kHz), low loss tangent (<0.01 at 100 kHz), and superior tunability (>70% at 400 kV/cm), while the largest figure of merit was 78.8. The possible microstructural background responsible for the high dielectric constant and tenability is discussed. In addition, thin films deposited at 750 °C with device quality factor of 8738 and dielectric nonlinearity coefficient of 1.66×10⁻¹⁰ J/C⁴m⁵ were demonstrated.     

Mo2N nanobelts for dehydrogenation of aromatic alcohols

Mo₂N nanobelts about 60 nm wide and 0.5–7.2 μm long have been synthesized by reacting a belt-shaped α-MoO₃ precursor with ammonia at 850 °C. The Mo₂N nanobelts effectively and selectively catalyzed dehydrogenation of a variety of aromatic alcohols. The coordinatively unsaturated Mo sites on the surface of the Mo₂N nanobelts might be the active species.