Dielectric and pyroelectric anisotropy in melt-quenched BaBi2(Nb1 − xVx)2O9 ceramics

The (0 0 l) textured BaBi₂(Nb_1 − xV_x)₂O₉ (where x = 0, 0.03, 0.07, 0.1 and 0.13) ceramics were fabricated via the conventional melt-quenching technique followed by high temperature heat-treatment (800-1000 °C range). The influence of vanadium content and sintering temperature on the texture development and relative density were investigated. The samples corresponding to the composition x = 0.1 sintered at 1000 °C for 10 h exhibited the maximum orientation of about 67%. The Scanning electron microscopic studies revealed the presence of platy grains having the a-b planes perpendicular the pressing axis. The dielectric constant and the pyroelectric co-efficient values in the direction perpendicular to the pressing axis were higher. The anisotropy in the dielectric constant is about 100 (at 100 kHz) at the dielectric maximum temperature and anisotropy in the pyroelectric co-efficient is about 50 μC cm⁻² °C⁻¹ in the vicinity of pyroelectric anomaly for the sample corresponding to the composition x = 0.1 sintered at 1000 °C. Higher values of the dielectric loss and electrical conductivity were observed in the direction perpendicular to the pressing axis which is attributed to the high oxygen ion conduction in the a-b planes.     

Detection of various self-assembled monolayers by AlN-based film bulk acoustic resonator

Various self-assembled monolayers such as carcinoembryonic antigen (CEA), beta actin, and bovine serum albumin (BSA) were detected using an AlN-based film bulk acoustic resonator (FBAR). AlN thin film was deposited by reactive RF magnetron sputtering, on a substrate of Mo (100 nm)/Ti (34 nm)/SiO₂ (480 nm)/Si (300 μm)/Si₃N₄ (300 nm). The film showed a strongly c-axis preferred orientation with a main (0 0 2) peak, as well as a good full width at half maximum (FWHM) of 2.50° in XRD and rocking curve results. The AlN-based FBAR was confirmed to have a resonant frequency of 2.477 GHz and a sensitivity of 3514 Hz cm²/ng. In beta actin, BSA, and CEA, the frequency properties showed variation values of 472.142, 932.573, and 685.421 kHz and mass sensitivities of 3530, 3506, and 3514 Hz-cm²/ng, respectively. The FBAR sensor was confirmed to be very useful for detecting target antigens through the binding of an antigen and an anti-body.     

Chemical stability and dielectric properties of RO-La2O3-B2O3 (R = Ca, Mg, Zn)-based ceramics

New lanthanum borate (La₂O₃-B₂O₃) glasses modified with divalent oxides, such as CaO, MgO and ZnO were investigated as potential low temperature dielectrics by understanding compositional dependence of dielectric properties and chemical leaching resistance. Firing behavior, such as densification and crystallization, depended strongly on the glass composition and is found to influence the resultant dielectric performance. Specifically, the dielectric composition of 20ZnO-20La₂O₃-60B₂O₃ glass with 40 wt% Al₂O₃ as a filler showed distinct enhancements of dielectric properties, i.e., k ∼ 8.3 and Q ∼ 1091 at the resonant frequency of 17.1 GHz, as a result of 850 °C firing. The result was believed related to earlier densification and unexpected evolvements of ZnAl₂O₄ and La(BO₂)₃ phases during firing. The Mg-containing glass sample was most stable in strong acid solutions and did not show any significant changes in microstructure even after 300 min exposure. The Ca-containing glass sample was not regarded as a promising candidate for low temperature dielectrics from the observed low quality factor and weak chemical durability.     

Fabrication and dielectric property of ferroelectric PLZT films grown on metal foils

We have grown ferroelectric Pb_0.92La_0.08Zr_0.52Ti_0.48O₃ (PLZT) films on platinized silicon and LaNiO₃-buffered nickel substrates by chemical solution deposition using a sol-gel process based on acetic acid chemistry. The following measurements were obtained under zero-bias field: relative permittivity of ≈960 and dielectric loss of ≈0.04 on the PLZT film grown on Pt/Si substrates, and relative permittivity of ≈820 and dielectric loss of ≈0.06 on the PLZT film grown on LNO-buffered Ni substrates. In addition, a relative permittivity of 125 and dielectric loss of 0.02 were measured at room temperature under a high bias field of 1 × 10⁶ V/cm on PLZT deposited on LNO-buffered nickel substrate. Furthermore, a steady-state leakage current density of ≈8.1 × 10⁻⁹ A/cm² and mean breakdown field strength of 1.7 × 10⁶ V/cm were measured at room temperature. Finally, remanent polarization (P_r) of ≈2.0 × 10⁻⁵ C/cm², coercive electric field (E_c) of ≈3.4 × 10⁴ V/cm, and energy density of ≈45 J/cm³ were determined from room-temperature hysteresis loop measurements on PLZT/LNO/Ni film-on-foil capacitors with 250-μm-diameter platinum top electrodes.     

Modified tunable dielectric properties by addition of MgO on BaZr0.25Ti0.75O3 ceramics

Phase composition, microstructure and tunable dielectric properties of (1 − x)BaZr_0.25Ti_0.75O₃-xMgO (BZTM) composite ceramics fabricated by solid-state reaction were investigated. It was found Mg not only existed in the matrix as MgO, there was also trace amount of Mg²⁺ ions dissolved in the BZT grains, which led to Curie temperature of the BZTM composites ceramics shifting to below −100 °C. Dielectric permittivity of the BZTM composite ceramics was reduced from thousands to hundreds by manipulating the content of MgO. Johnson's phenomenological equation based on Devonshire's theory was used to describe the nonlinear dielectric permittivity of the ceramics with increasing applied DC field. With increasing content of MgO, anharmonic constant α_(T) increased monotonously. Dielectric permittivity was 672, while dielectric tunability was as high as 30.0% at 30 kV/cm and dielectric loss was around 0.0016 for the 0.6BaZr_0.25Ti_0.75O₃-0.4MgO sample at 10 kHz and room temperature.     

Synthesis, low-temperature sintering and the dielectric properties of the ZnO-(1 − x)TiO2-xSnO2 (x = 0.04-0.2)

ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) ceramics were prepared by conventional mixed-oxide method combined with a chemical processing. Fine particle powders were prepared by chemical processing to activate the formation of compound and to improve the sinterability. One wt.% of V₂O₅ and B₂O₃ with the mole ratios of 3:1 were used to lower the sintering temperature of ceramics. The effect of Sn content on phase structure and dielectric properties were investigated. The results show that the substituting Sn for Ti accelerates the hexagonal phase transition to cubic phase, and an inverse spinel structure Zn₂(Ti_1−xSn_x)O₄ solid solution forms. The best dielectric properties obtained at x = 0.12. The ZnO-0.88TiO₂-0.12SnO₂ ceramics sintered at 900 °C exhibit a good dielectric property: ?_r = 29 and tan δ = 9.86 × 10⁻⁵. Due to their good dielectric properties, low firing characteristics, ZnO-(1 − x)TiO₂-xSnO₂ (x = 0.04-0.2) can serve as the promising microwave dielectric capacitor.     

Preparation and dielectric properties of B-doped SiC powders by combustion synthesis

The SiC(B) solid solution powders were synthesized via combustion reaction of Si/C system in Ar atmosphere, using boron powder as the dopant and polytetrafluoroethylene as the chemical activator, which were investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and Raman spectra. Results show that the prepared powders are C-enriched SiC with C antisites and sp² carbon defects in which the sp² carbon is transformed to the sp³ carbon due to boron doping. The electric permittivities of the prepared powders were determined in the frequency range of 8.2-12.4 GHz. The dielectric real part ?′ and dielectric loss tan δ of undoped powder have maximum values (?′ = 5.5-5.3, tan δ = 0.23-0.20), and decrease with increasing boron content. The mechanism of dielectric loss by doping has been discussed.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Different microstructure and dielectric properties of Ba1−xCaxTiO3 ceramics and pulsed-laser-ablated films

A comparative study of the microstructure and dielectric properties between Ba_1−xCa_xTiO₃ (BCT) ceramics and films were performed in the whole Ca concentration range of x = 0-1. The ceramics were prepared by conventional solid-state reaction technique and the films by the method of pulsed-laser deposition. X-ray diffraction (XRD) study of the BCT ceramics exhibited a pure tetragonal phase for x = 0-0.25, a tetragonal-orthorhombic diphase for x = 0.25-0.85 and a pure orthorhombic phase for x = 0.90-1.00. And the dielectric phase transition temperature from tetragonal to cubic was marginally affected by the Ca doping into BaTiO₃. However, BCT films deposited on Pt/Si/SiO₂/Si substrates showed a different microstructure and dielectric properties. Tetragonal-orthorhombic diphase was not found in the BCT films for x = 0.25-0.85, and a large decrease of the Curie point and diffuse phase transition were observed in the BCT films. Based on the compositional analysis, such phenomena were ascribed to the occupancy of some Ca²⁺ to the Ti⁴⁺ sites in the BCT films.     

Dielectric properties of Ba3−xKxCaNb2O9−δ (0.5 < x < 1.25) (KBCN) double perovskites

We report synthesis, structure and dielectric properties of double perovskite-type Ba_3−xK_xCaNb₂O_9−δ (x = 0.5, 0.75, 1, 1.25) (KBCN). Powder X-ray diffraction (XRD) confirmed the formation of double perovskite-type structure and lattice constant decreases with increasing K in KBCN. AC impedance study showed a single semicircle over the investigated temperatures and frequencies in dry H₂, H₂ + 3% H₂O, 3% H₂O + N₂, while two semicircles were observed at low temperatures in air, which could be attributed to bulk and grain-boundary contributions. Unlike un-doped BCN, KBCN exhibits negligible grain-boundary and electrode effects to the total electrical properties and is consistent with perovskite-type K-doped BaZrO₃. The bulk dielectric constant and dielectric loss were found to increase with increasing K content in KBCN and also found to change with sintering temperature. Among the samples investigated, Ba_1.75K_1.25CaNb₂O_9−δ sintered at 1100 °C showed the highest dielectric constant of 65 at 10⁶ Hz and dielectric loss of 0.14 at 400 °C in air. Isothermal dielectric constant and electrical conductivity at 1 MHz were found to be independent at elevated temperatures, while vary at low-frequency and low temperatures. Below 700 °C, dielectric constant and dielectric loss decreases with increasing frequency, whereas an opposite trend was observed for the electrical conductivity.     

Electrical properties of MgAl2-2xZrxMxO4 (M = Co, Ni and x = 0.00-0.20) synthesized by coprecipitation technique using urea

This paper presents the results of a study concerning the structural and electrical properties of MgAl_2-2xZr_xM_xO₄ (x = 0.00-0.20 and M = Co²⁺ and Ni²⁺) prepared by a coprecipitation technique using urea as a precipitating agent. The X-ray diffraction data for the pure and its doped samples are consistent with the single-phase spinel and their crystallite sizes are in the range 7-20 ± 4 nm. The DC resistivity increases from 3.09 × 10⁹ Ω cm to 6.73 × 10⁹ and 8.06 × 10⁹ Ω cm whereas dielectric constant decreases from 5.80 to 5.11 and 4.95 on doping with Zr-Co and Zr-Ni, respectively. The electrical resistivity variations with increase in the dopant contents indicate two types of conduction mechanisms in operation. Several parameters such as, hopping energy (W), metal-semiconductor transition temperature (T_MS) and Debye temperature (θ_D) have also been determined. The increase in DC resistivity and decrease in dielectric constant suggest that the synthesized materials can be considered for application as an insulating and structural material in fusion reactors.     

Study on properties of CaO-SiO2-B2O3 system glass-ceramic

Low temperature co-fired ceramic (LTCC) is prepared by sintering a glass selected from CaO-SiO₂-B₂O₃ system, and its sintered bodies are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). It is found that the optimal sintering temperature for this glass-ceramic is 820 °C for 15 min, and the major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. The glass-ceramic possesses excellent dielectric properties: ?_r = 6.5, tan δ < 2 × 10⁻³ at 10 MHz, temperature coefficient of dielectric constant about −51 × 10⁻⁶ °C⁻¹ and coefficient of thermal expansion about 8 × 10⁻⁶ °C⁻¹ at 20-400 °C. Thus, this material is supposed to be suitable for the tape casting process and be compatible with Ag electrode, which could be used as the LTCC materials for the application in wireless communications.     

Preparation, structure and dielectric properties of Ba4LaMNb3O15 (M = Ti, Sn ) ceramics

Two new cation-deficient hexagonal perovskites Ba₄LaMNb₃O₁₅ (M = Ti, Sn) ceramics were prepared by high temperature solid-state reaction route. The phase and structure of the ceramics were characterized by X-ray diffraction, scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The Ba₄LaTiNb₃O₁₅ has high dielectric constant of 52, high quality factors (Q) 3500 (at 4.472 GHz), and temperature variation of resonant frequency (τ_f) +93 ppm °C⁻¹ at room temperature; Ba₄LaSnNb₃O₁₅ has dielectric constant of 39 with high Q value of 2510 (at 5.924 GHz), and τ_f −29 ppm °C⁻¹.     

Investigations on structural evolution and dielectric characteristics of high performance Bi-based dielectrics

A new system of (Bi_1.5Zn_1−x/3Ti_xNb_1.5−2x/3)O₇ (0 ≤x ≤ 1.5) ceramics have been successfully developed and the dielectric properties have been systematically studied. The results showed the formation of temperature compensation dielectrics over the wide range of Ti concentrations. The incorporation of Ti⁴⁺ into the bismuth zinc niobate ceramics induce the decrease of lattice constant linear while remaining cubic pyrochlore phase. The IR spectra confirm the formation of pyrochlore structure and give information about the distribution of ions between the A and B sites. It has been found that the effect of Ti substitution on dielectric properties of sintered ceramics intensifies with a higher x. The system exhibits the novel high permittivity and low dielectric loss: the permittivity values (?_r) saturate at 160-210, and loss values remain at low values (∼1 × 10⁻⁴). The temperature dependence of permittivity is strongly dependent with the compositions. Dielectric relaxation phenomena have been observed during low temperature. New high frequency and MW materials, differed by Ti content, with temperature compensation and controllable dielectric constant of 150-210 have been developed.     

Microstructural evolution and dielectric properties of Cu-deficient and Cu-excess CaCu3Ti4O12 ceramics

The microstructural evolution and dielectric properties of CaCu_3−xTi₄O_12−x (3 − x = 2.8-3.05) ceramics were investigated. Normal grain growth behavior was observed at Cu/Ca ≤ 2.9, while abnormal grain growth was observed at Cu/Ca ≥ 2.95. A CuO-rich intergranular liquid phase at Cu/Ca ≥ 2.95 and angular grain morphology were the main reasons for abnormal grain growth. However, the abundant intergranular liquid at Cu/Ca = 3.05 significantly affected the relative dielectric permittivity and dielectric loss. The CuO composition is the key parameter that determines the microstructure and dielectric properties of CCTO ceramics.     

A quaternary lead based perovskite structured materials with diffuse phase transition behavior

A lead based quaternary compound composed of 0.25(PbZr_0.52Ti_0.48O₃) + 0.25(PbFe_0.5Ta_0.5O₃) + 0.25 (PbF_0.67W_0.33O₃) + 0.25(PbFe_0.5Nb_0.5O₃) - (PZT-PFT-PFW-PFN) was synthesized by conventional solid-state reaction techniques. It showed moderate high dielectric constant, low dielectric loss, and two diffuse phase transitions, one below the room temperature ∼261 K and other above ∼410 K. X-ray diffraction (XRD) patterns revealed a tetragonal crystal structure at room temperature where as scanning electron micrograph (SEM) indicates inhomogeneous surface with an average grain size of 500 nm-3 μm. Well saturated ferroelectric hysteresis loops with good saturation polarization (spontaneous polarization, P_s ∼ 30.68 μC/cm²) were observed. Temperature-dependent ac conductivity displayed low conductivity with kink in spectra near the phase transition. In continuing search for developing new ferroelectric materials, in the present study we report stoichiometric compositions of complex perovskite ceramic materials: (PZT-PFT-PFW-PFN) with diffuse phase transition behavior. The crystal structure, dielectric properties, and ferroelectric properties were characterized by XRD, SEM, dielectric spectroscopy, and polarization. 1/? versus (T) plots revealed diffuse relaxor phase transition (DPT) behavior. The compositional variation on the phase transition temperature, dielectric constant, and ferroelectric to paraelectric phase transitions are discussed.     

Magnetic and dielectric study of R0.5Sr0.5MnO3 (R = Gd, Tb and Dy)

Magnetic and dielectric properties of perovskite manganites R_0.5Sr_0.5MnO₃ (R = Gd, Tb and Dy) have been investigated. DC and AC magnetic measurements showed short-range glassy magnetic ordering at T_g ∼ 40 K. Such ordering was observed by neutron diffraction and is ascribable to the size mismatch of R³⁺ and Sr³⁺ settled randomly at the same crystallographic site. Dielectric constants for each material were ∼1000-10,000 between ∼50 and ∼300 K and showed broad maximums above T_g. Dielectric dispersion showed poor coherency of the motion of polar regions, plausibly because of the size-mismatch effect; both the magnetic and dielectric properties of this system are governed by the randomness at the R/Sr site. The tan δ and EXAFS data suggest that the dielectric response is rooted in a transfer of the Mn-3d electrons.     

Preparation and characterization of Ba1 − xSrxTiO3 thin films deposited on Pt/SiO2/Si by sol-gel method

BST thin films have been investigated as potential candidates for use in frequency agile microwave circuit devices. Stoichiometric (Ba_1 − xSr_x)TiO₃ (BST) thin films have been prepared on Pt/SiO₂/Si substrates using sol-gel method. The BST films were characterized by X-ray fluorescence (XRF) spectroscopy analysis, X-ray diffraction (XRD), scanning electron microscope (SEM) and electrical measurements. The relationships of processing parameters, microstructures, and dielectric properties are discussed. The results show that the films exhibit pure perovskite phase through rapid thermal anneal at 700 °C and their grain sizes are about 20-40 nm. The dielectric constants of BST5, BST10, BST15 and BST20 are 323, 355, 382 and 405, respectively, at 80 kHz.     

Dielectric properties of barium strontium titanate thick films prepared by electrophoretic deposition

Ba_xSr_1−xTiO₃ (x = 0.5, 0.6, 0.7) thick films were prepared by electrophoretic deposition (EPD) technique on platinum metallic foils using BaTiO₃ and SrTiO₃ nanoparticles with different molar proportion of 1:1, 3:2 and 7:3, respectively. An isostatic pressure method was used to increase density of the thick films before high temperature sintering. Microstructures of the deposited films were examined with XRD and SEM techniques. Porosity of the thick films decreased after the isostatic pressure process. The Ba_0.5Sr_0.5TiO₃ thick films of 10 μm, 15 μm and 20 μm showed a tunability of 28.8%, 33.3% and 33.9%, respectively, at room temperature and at a biasing field of 2 kV/mm. The dielectric constant was from 2138 to 3446 and dielectric loss was from 0.016 to 0.011 at zero bias field at 10 kHz. The temperature dependence of dielectric constant was also measured and the effect of porosity and thickness on the electrical performance of the thick films was discussed.     

Sintering of stacked pellets for controlling the temperature coefficient of dielectrics

Bearing in mind the excellent dielectric properties at high frequency of the oxides Ba₅Nb₄O₁₅, BaNb₂O₆, ZnNb₂O₆ and Zn₃Nb₂O₈ (?_r ∼ 20-45, tan(δ) < 10 × 10⁻⁴, ρ_i > 10¹⁰ Ω cm), “glass composites” of these materials were investigated in order to control their permittivity temperature coefficients for various applications. In a first method, samples constituted of mixed powders with temperature coefficient of opposite sign have been conventionally sintered. The obtained properties are not the expected ones because of the high reactivity between the mixed phases. In a second method, samples constituted of two stacked pellets with temperature coefficient of opposite sign have been co-sintered by the sinter-forging process, i.e. while maintaining a pressure, the two stacked pellets were co-sintered, leading to a good mechanical behaviour. More importantly we show that this technique avoids the delamination at the interface and that the so obtained dielectric properties are globally in good agreement with the mixing rule. Clearly, it is demonstrated that the temperature coefficient of these dielectrics can be tuned using the sinter-forging process, opening a new route for the optimization of multilayer capacitors.