Study of the dielectric properties in the NaNbO3 -KNbO3-In2O3 system using AC impedance spectroscopy

We report a comparative study of the dielectric properties of solid-state (ceramic method) synthesized NaNbO₃ (NN), Na_0.75K_0.25NbO₃ (K25NN), K_0.5Na_0.5NbO₃ (KNN) and some composite materials containing In₂O₃ and NN or KNN using an AC impedance method. Powder X-ray diffraction (PXRD) was employed to investigate the phase purity. No significant amount of impurity phase was observed for NN, K25NN, and KNN. Substitutions of 10, 15 and 25 mol% In³⁺ for Nb⁵⁺ in KNN and NN using solid-state reactions at 1150 °C resulted in composite materials. AC impedance studies of NN, KNN and K25NN in the temperature range of 500-800 °C showed a single semicircle (attributed to the bulk property) in the high-frequency range of 10³ to 10⁶ Hz. The individual contributions from the bulk and grain boundary on the dielectric properties were resolved and quantified from the impedance data. The calculated dielectric values for NN were consistent with previously reported in the literature. 10% Indium based KNN composite materials had the lowest dielectric loss 0.585 and the dielectric constant of 233 at 100 kHz at the temperature of 650 °C.     

Synthesis and photoluminescence of In2O3 nanocrystals and submicron crystals from InCl3•4H2O and thiourea

Two routes have been proposed for the synthesis of In₂O₃ powders from InCl₃•4H₂O and thiourea. One route involved a two-step procedure (that is, firstly, In₂S₃ clusters constructed with mainly nanoflakes were synthesized by heating the mixture of InCl₃•4H₂O and thiourea in air from room temperature to 200 °C, coupled with a subsequent washing treatment; secondly, In₂O₃ was obtained by calcining the In₂S₃ clusters in air at 600 °C for 6 h), and the other route was a one-step procedure (that is, In₂O₃ was synthesized directly by calcining the mixture of InCl₃•4H₂O and thiourea in air at 600 °C for 6 h). The resultant products were characterized by X-ray diffraction, energy dispersive X-ray spectroscopy, scanning electronic microscope and room temperature photoluminescence (RT-PL) spectra. It was observed that the In₂O₃ nanocrystals obtained via the two-step procedure exhibited PL peaks at about 453 and 471 nm, corresponding to the defeat-related emission; while the In₂O₃ submicron polyhedral crystals obtained via the one-step procedure and In₂O₃ pyramids obtained by calcining the only InCl₃•4H₂O in air at 600 °C for 6 h displayed a PL band centered at around 338 nm, corresponding to the band edge emission.     

In2O3 microcrystals obtained from rapid calcination in domestic microwave oven

The simple way to prepare In₂O₃ microcrystals is reported in this paper. The precursor, In(OH)₃ microstructures, were obtained using the Microwave-Assisted Hydrothermal (MAH) Method. By annealing as-prepared In(OH)₃ precursor at 500 °C for 5 min in a domestic microwave oven (MO), In₂O₃ microcrystals were prepared, inheriting the morphology of their precursor while still slightly distorted and collapsed due to the In(OH)₃ dehydration process which was studied by thermal analysis. The In(OH)₃ and In₂O₃ were characterized using powder X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and Raman spectroscopy. These techniques confirm the chemical dehydration of In(OH)₃ and the formation of In₂O₃ powders. The domestic MO promotes a rapid structural organization as compared with a CF (conventional furnace). The MAH method and the subsequent annealing in a domestic MO were shown to be a low cost route for the production of In₂O₃, with the advantages of lower temperature and smaller time.     

Thermal expansion studies of Gd2Mo3O12 and Gd2W3O12

Simultaneous thermogravimetric/differential thermal analysis of Gd₂Mo₃O₁₂ showed an irreversible phase transition at 1178 K where as Gd₂W₃O₁₂ showed reversible phase transition at 1433 K, which were confirmed by powder X-ray diffraction. The thermal expansion behavior of α-Gd₂Mo₃O₁₂ (room temperature phase), β-Gd₂Mo₃O₁₂ (phase obtained by heating Gd₂Mo₃O₁₂ at 1223 K) and Gd₂W₃O₁₂ have been investigated using high temperature X-ray diffractometer. The cell volume of α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂, fit into polynomial expression with respect to temperature, showed positive thermal expansion up to 1073, 1173 and 1173 K, respectively. The average volume expansion coefficients for α-Gd₂Mo₃O₁₂, β-Gd₂Mo₃O₁₂ and Gd₂W₃O₁₂ are 39.52 × 10⁻⁶, 21.23 × 10⁻⁶ and 37.96 × 10⁻⁶ K⁻¹, respectively.     

Characterization of ZnO-In2O3 transparent conducting films by pulsed laser deposition

Transparent conducting oxide (TCO) films in the ZnO-In₂O₃ system were prepared by a pulsed laser deposition method. A target that consists of the mixture of ZnO and In₂O₃ powders was used. Influences of the target composition x (x = [Zn]/([Zn] + [In])) and heater temperature on structural, electrical and optical properties of the TCO films were examined. Introduction of oxygen gas into the chamber during the deposition was necessary for improvement in the transparency of the deposited films. The amorphous phase was observed for a wide range of x = 0.20-0.60 at 110 °C. Minimum resistivity was 2.65 × 10⁻⁴ Ω cm at x = 0.20. The films that showed the minimum resistivity had an amorphous structure and the composition shifted toward larger x, as the substrate temperature increased. The films were enriched in indium compared to the target composition and the cationic In/Zn ratio increased as the substrate temperature was increased.     

Highly selective ethanol In2O3-based gas sensor

The sensitive composite material was prepared by loading Pt and La₂O₃ into ultrafine In₂O₃ matric material (8 nm) synthesized by microemulsion method. A highly selective ethanol gas sensor was developed based on hot-wire type gas sensor, which was sintered in a bead (0.8 mm in diameter) to cover a platinum wire coil (0.4 mm in diameter). The gas sensor was operated by a bridge electric circuit. The influences of La₂O₃ and Pt additives on C₂H₅OH sensing properties of In₂O₃-based gas sensor were discussed. The addition of La₂O₃ resulted in a prominent selectivity for C₂H₅OH, and the addition of Pt improved the response rate to C₂H₅OH without affecting the sensitivity. The temperature and humidity characteristics of the sensor output were also investigated. The selective sensor had low power consumption, significantly minor humidity and temperature dependence, high selectivity and prominent long-term stability.     

Controlled synthesis of Mn3O4 and MnCO3 in a solvothermal system

Controlled synthesis of Mn₃O₄ nanocrystals and MnCO₃ aggregates was achieved by a facile solvothermal method using different divalent manganese source in the solvent of N,N-dimethylformamide (DMF) with/without the introduction of poly(vinylpyrrolidone) (PVP). PVP was used as a co-reducing reagent in the controlled formation of MnCO₃ crystal. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED), Fourier transform infrared (FTIR) spectra, Raman spectrum and magnetic measurement. Higher process temperature and longer solvothermal time were favorable for the formation of MnCO₃ single phase using MnCl₂ as the manganese source. Mn₃O₄ nanocrystals were prepared at a relatively lower temperature. MnCO₃ aggregates consisted by small nanoparticles have a certain orientation, showing that the nanocrystals formed earlier through oriented aggregation. The size of Mn₃O₄ nanocrystals was 22.5 ± 7.3 nm and 7.3 ± 1.4 nm prepared using MnCl₂ and Mn(CH₃COO)₂, respectively, at 160 °C for 24 h. Raman spectra showed size-dependent characteristics. Smaller Mn₃O₄ nanoparticle resulted in a red-shift in Raman spectra. Magnetic property of the prepared Mn₃O₄ nanoparticle was influenced by the size distribution and crystallinity.     

Microstructure and mechanical properties of small amounts of In2O3 reinforced Pb(ZrxTi1−x)O3 ceramics

Piezoelectric Pb(Zr_xTi_1−x)O₃ (PZT) ceramics with small amount (0.5-2.0 wt.%) of In₂O₃ are prepared by conventional sintering method. Based on X-ray diffraction analysis, the tetragonality of PZT matrix decreases with In₂O₃ content, indicating that In₂O₃ diffuses into PZT matrix. The microstructure of PZT matrix is significantly refined by doping small amounts of In₂O₃. The grain size reduction and the matrix grain boundary reinforcement are the probable mechanism responsible for the high strength and hardness in the PZT/In₂O₃ materials. The enhancement in Young’s modulus is attributed to In³⁺ substitution. The decreased tetragonality with In₂O₃ addition results in less crack energy absorption by domain switching and, hence, causes the small reduction in fracture toughness.     

(ZnO)3In2O3 fine powder prepared by combustion reaction of nitrates-glycine mixture

Conducting fine powder was obtained in the ZnInO system by combustion of the gel prepared from an aqueous solution of mixed zinc and indium nitrates in the presence of glycine. Glycine worked as a fuel as well as a gelling agent in the combustion under the strong oxidizing power of the nitrates. In spite of the low furnace temperature of 350 °C, the product was (ZnO)₃In₂O₃ which has been obtained above 1260 °C in a solid state reaction of a mixture of ZnO and In₂O₃. The combustion synthesis led to an aggregated fine powder of hexagonal platelets of about 40 nm in diameter. Its compacted mass showed an electrical resistivity of about 700 Ω cm. The agglomeration was improved by dispersing the fine powder in an acetic acid aqueous solution.     

Self-flux synthesis and photoluminescent properties of LiAl5O8

Pure-phase LiAl₅O₈ was selected as an oxide ceramic red phosphor material without dopants (color centers) and was synthesized using a self-flux method. The LiAl₅O₈ was formed by heating a powder mixture consisting of γ-Al₂O₃:Li₂SO₄ = 1:2 (molar ratio) at over 1100 °C for 1 h. Photoluminescence (PL) properties for the synthesized LiAl₅O₈ were investigated. The maximum intensity of the excitation spectrum for the photoluminescent emission of LiAl₅O₈ synthesized was at 274 nm. The peak intensity of the emission spectrum was at a wavelength of 667 nm (red color). The intensity of the peak emission spectrum increased with the heating temperature, i.e., the maximum peak intensity of the red emission spectrum was detected for the LiAl₅O₈ synthesized by heating at 1500 °C for 1 h.     

Improved microwave dielectric properties of B2O3-doped Nd(Co1/2Ti1/2)O3 ceramics with near zero temperature coefficient of resonant frequency

The microwave dielectric properties and the microstructures of Nd(Co_1/2Ti_1/2)O₃ ceramics prepared by conventional solid-state route have been studied. The prepared Nd(Co_1/2Ti_1/2)O₃ exhibited a mixture of Co and Ti showing 1:1 order in the B-site. It is found that low-level doping of B₂O₃ (up to 0.75 wt.%) can significantly improve the density and dielectric properties of Nd(Co_1/2Ti_1/2)O₃ ceramics. Nd(Co_1/2Ti_1/2)O₃ ceramics with additives could be sintered to a theoretical density higher than 98.5% at 1320 °C. Second phases were not observed at the level of 0.25-0.75 wt.% B₂O₃ addition. The temperature coefficient of resonant frequency (τ_f) was not significantly affected, while the dielectric constants (?_r) and the unloaded quality factors Q were effectively promoted by B₂O₃ addition. At 1320 °C/4 h, Nd(Co_1/2Ti_1/2)O₃ ceramics with 0.75 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 27.2, a Q × f value of 153,000 GHz (at 9 GHz) and a temperature coefficient of resonant frequency (τ_f) of 0 ppm/°C. The B₂O₃-doped Nd(Co_1/2Ti_1/2)O₃ ceramics can find applications in microwave devices requiring low sintering temperature.     

Preparation and characterization of porous ultrafine Fe2O3 particles

Porous ultrafine Fe₂O₃ particles were prepared by homogeneous precipitation method. Fe³⁺ and urea were chosen as starting materials and anionic surfactant as the template. It is shown that the reaction results in the precipitation of a gelatinous hydrous iron oxide/surfactant mixture, which gives ultrafine Fe₂O₃ particles after drying and calcinations. The products were characterized by XRD, TEM, TG/DTA and BET. Conventional XRD patterns show that the products are mixture of γ-Fe₂O₃ and α-Fe₂O₃ phase after being sintered at 350 °C, and γ-Fe₂O₃ transforms entirely to α-Fe₂O₃ when sintered at 650 °C. The low-angle XRD patterns indicate that the mesostructure can only exist between 350 and 400 °C. TEM results show that the Fe₂O₃ particles have diameters of about 30 nm and lengths ranging from 100 to 120 nm; in each particle, there are several vermiculate-like mesopores with diameter of about 20-25 nm. The BET surface areas in excess of 50 m²/g are obtained after calcinations at 350 °C. The BJH desorption average pore width is around 22 nm, which is in agreement with the TEM results. The results show that anionic surfactant and sintering temperature are important to obtain this special morphology.     

Microwave dielectric properties and microstructures of the 11Li2O-3Nb2O5-12TiO2 ceramics with B2O3 addition

The effects of B₂O₃ addition, as a sintering agent, on the sintering behavior, microstructure and microwave dielectric properties of the 11Li₂O-3Nb₂O₅-12TiO₂ (LNT) ceramics have been investigated. With the low-level doping of B₂O₃ (≤2 wt.%), the sintering temperature of the LNT ceramic could be effectively reduced to 900 °C. The B₂O₃-doped LNT ceramics are also composed of Li₂TiO₃ss and “M-phase” phases. No other phase could be observed in the 0.5-2 wt.% B₂O₃-doped ceramics sintered at 840-920 °C. The addition of B₂O₃ induced no obvious degradation in the microwave dielectric properties but increased the τ_f values. Typically, the 0.5 wt.% B₂O₃-doped ceramics sintered at 900 °C have better microwave dielectric properties of ?_r = 49.2, Q × f = 8839 GHz, τ_f = 57.6 ppm/°C, which suggest that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

Influence of Bi2O3 and CuO addition on low-temperature sintering and dielectric properties of Ba0.6Sr0.4TiO3 ceramics

In this study, we tried to lower the sintering temperature of Ba_0.6Sr_0.4TiO₃ (BST) ceramics by several kinds of adding methods of Bi₂O₃, CuO and CuBi₂O₄ additives. The effects of different adding methods on the microstructures and the dielectric properties of BST ceramics have been studied. In the all additive systems, the single addition of CuBi₂O₄ was the most effective way for lowering the sintering temperature of BST. When CuBi₂O₄ of 0.6 mol% was mixed with starting BST powders and sintered at 1100 °C, the derived ceramics demonstrated dense microstructure with a low dielectric constant (? = 4240), low dielectric loss (tan δ = 0.0058), high tunability (Tun = 38.3%) and high Q value (Q = 251). It was noteworthy that the sintering temperature was significantly lowered by 350 °C compared with no-additive system, and the derived ceramics maintained the excellent microwave dielectric properties corresponding to pure BST.     

Varistor properties of ZnO-Pr6O11-CoO-Cr2O3-Y2O3-In2O3 ceramics

The varistor properties of the ZnO-Pr₆O₁₁-CoO-Cr₂O₃-Y₂O₃-In₂O₃ ceramics were investigated for different concentrations of In₂O₃. The increase of In₂O₃ concentration slightly increased the sintered density (5.60-5.63 g/cm³) and slightly decreased the average grain size (3.4-2.9 μm). The breakdown field increased from 6023 to 14822 V/cm with increasing concentration of In₂O₃. The nonlinear coefficient increased from 17.6 to 44.6 for up to 0.005 mol%, whereas the further doping caused it to decrease to 36.8. In₂O₃ acted as an acceptor due to the donor concentration, which decreases in the range of 1.02 × 10¹⁷ to 0.24 × 10¹⁷/cm³ with increasing concentration of In₂O₃.     

Electric-field-induced strain and piezoelectric properties of a high Curie temperature Pb(In1/2Nb1/2)O3-PbTiO3 single crystal

The temperature dependence of dielectric and piezoelectric properties, electric-field-induced strains of 0.66 Pb(In_1/2Nb_1/2)O₃-0.34 PbTiO₃ single crystals, which were grown directly from melt by using the modified Bridgman technique with the allomeric Pb(Mg_2/3Nb_1/3)O₃-PbTiO₃ seed crystals, were determined as a function of crystallographic orientation with respect to the prototypic (cubic) axes. Ultrahigh piezoelectric response (d₃₃∼2000 pC/N, k₃₃∼94%) and strain levels up to 0.8%, comparable to rhombohedral (1−x)Pb(Mg_2/3Nb_1/3)O₃-xPbTiO₃ and (1−x)Pb(Zn_2/3Nb_1/3)O₃-xPbTiO₃ single crystals, were observed for the 〈0 0 1〉-oriented crystals. Strain levels up to 0.47% and piezoelectric constant d₃₃∼1600 pC/N could be achieved being related to an electric-field-induced rhombohedral-orthorhombic phase transition for the 〈1 1 0〉-oriented crystals. In addition, high electromechanical coefficients k₃₃ (∼88%) can be achieved even heating to 110 °C. High T_C (∼200 °C), large electromechanical coefficients k₃₃ (∼94%) and low dielectric loss factor (∼1%), along with large strain make the crystals promising candidates for a wide range of electromechanical transducers.     

A SO2 gas sensor based upon composite Nasicon/Sr-β-Al2O3 bielectrolyte

A new SO₂ gas sensor based upon interfacing two composite solid electrolytes-NASICON containing up to 40 wt.% Na₂O·Al₂O₃·4SiO₂ glass and Sr-β-Al₂O₃ containing 3 mol % Y₂O₃-ZrO₂ with a Na₂SO₄ electrode and a Pt/O₂ reference electrode has been designed and tested. In this design, both the electrodes are exposed to the same test gas thus eliminating the need for a separate reference compartment. The experimental results have shown that the measured emf of the sensor varied linearly as a function of logarithm of partial pressure of SO₂ over a concentration range of 1-1000 ppm in the temperature range of 873-1073 K. The emfs were stable and reproducible and the response time was approximately 1 min.     

Electrical properties of Pb0.97La0.02(Zr0.95Ti0.05)O3 antiferroelectric thin films on TiO2 buffer layer

Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ antiferroelectric thin films with thickness of 500 nm were successfully deposited on TiO₂ buffered Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) and Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates via sol-gel process. Microstructure of Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was studied by X-ray diffraction analyses. The antiferroelectric nature of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ thin films was confirmed by the double hysteresis behaviors of polarization and double buffer fly response of dielectric constant versus applied voltage at room temperature. The capacitance-voltage behaviors of the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films with and without TiO₂ buffer layer were studied, as a function of temperature. The temperature dependence of dielectric constant displayed a similar behavior and the Curie temperature (T_c) was 193 °C for films on both substrates. The current caused by the polarization and depolarization of polar in the Pb_0.97La_0.02(Zr_0.95Ti_0.05)O₃ films was detected by current density-electric field measurement.     

Effect of phosphorus addition on the sintering and dielectric properties of Pb(Zr0.52Ti0.48)O3

It has been found that the sintering temperature of piezoelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT) can be reduced by phosphorus addition without compromising the dielectric properties. A sintered density of 98.6% of the theoretical density was obtained for 2 wt.% P₂O₅ addition after sintering at 1050 °C for 4 h. The P₂O₅ addition, either above or below 2 wt.%, showed an inferior densification. Coincidentally, the P₂O₅ addition gave rise to a lower lead loss, and the dielectric constant showed a peak at 1 wt.% P₂O₅ addition.     

Photoluminescence properties of the In2O3 octahedrons synthesized by carbothermal reduction method

In₂O₃ octahedrons were synthesized by carbothermal reduction method. The products were characterized by X-ray diffraction (XRD), energy dispersive X-ray (EDX), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected-area electron diffraction analysis (SAED) and room-temperature photoluminescence (PL) spectra. The results show that the products are single-crystalline In₂O₃ octahedrons with the arrises length in the range of 400-3000 nm. The PL spectra displays blue and green emission peaks which can be indexed to default and oxygen vacancies; blue-shift and intensity decrease was observed when excitation wavelength decreases from 380 nm to 325 nm. The growth mechanism of the In₂O₃ octahedrons is discussed.