Electrophysical properties of the multicomponent PBZT-type ceramics doped by Sn 4+

In the work, the multicomponent Pb0.75Ba0.25(Zr0.65Ti0.35)1-aSnaO3 (PBZT/Sn) ceramics were obtained with various tin amounts (a from the range of 0.0 to 0.1). The densification of the PBZT/Sn ceramic samples was performed using pressureless sintering method. The effect of SnO2 content on the crystal structure of PBZT/Sn ceramics, microstructure, DC electrical conductivity and electrophysical properties (including dielectric and ferroelectric testes), were investigated. The PBZT/Sn ceramic samples exhibit high values of dielectric permittivity at the temperature of ferro-paraelectric phase transition and show the relaxor character of phase transition. Excessive SnO2 contents doping of the PBZT/Sn materials (already for a = 0.1) might lead to lattice stress and structure defects, which successively leads to the deterioration of ferroelectric and dielectric properties of the ceramic samples. The presented research shows that the addition of SnO2 to the base PBZT compound (in the proper proportion) gives an additional possibility of influencing the parameters essential for practical applications, from the areas of micromechatronics and microelectronics.     

Relaxor Behavior of (Sr0.8Ba0.2)TiO3 Ceramic Solid Solution Doped with Bismuth

The dielectric properties of (Sr_0.8Ba_0.2)_1-1.5xBi_xTiO₃ ceramics in the range 0 x 0.18 are investigated. A ferroelectric relaxor behavior is observed. The degree of the diffuseness and the relaxation of the phase transition increases as the Bi content increases. A random electric field is suggested to be responsible for the relaxor behavior observations. The dependence of the diffuseness on the grain size is presented.     

Temperature-Stable High-ε Dielectrics Ceramics Based on (1 − x) Ba5NdTi3Ta7O30/xBi4Ti3O12

Modification of Ba₅NdTi₃Ta₇O₃₀ dielectric ceramics was investigated through introducing Bi₄Ti₃O₁₂. With increasing of Bi₄Ti₃O₁₂ content, the dielectric constant increased, and the temperature coefficient of the dielectric constant changed from negative to positive. The small temperature coefficient ( < 50 ppm/°C) combined with high dielectric constant ( = 178) and low dielectric loss (tan = 0.007 at 1 MHz) was achieved in the composition x = 0.6.     

Dielectric Properties of Homoepitaxial SrTiO3SrTiO3SrTiO3 Thin Films Grown in the Step-Flow Mode

We have deposited SrTiO₃ thin films on Nb-doped SrTiO₃ substrates by pulsed laser deposition at temperatures of up to 1400°C. Reflection high energy electron diffraction was used to monitor the film growth mode at various temperatures and it was shown that growth proceeded in the step-flow mode at above 900°C. Capacitors were formed by evaporating platinum pads on the film surface and gold pads on the substrate. Films grown in the step-flow mode showed consistently higher dielectric constants below 200 K than films grown in the layer-by-layer mode. Films with the highest dielectric constant () were obtained using a stoichiometric ablation target at an oxygen pressure of 10SrTiO₃ ^–6SrTiO₃ Torr.     

Synthesis of Sr0.5Ba0.5Nb2O6 by Coprecipitation Method—Dielectric and Microstructural Characteristics

Sr_0.5Ba_0.5Nb₂O₆ (SBN50) has been synthesized by coprecipitation method using Sr(NO₃)₂, Ba(NO₃)₂ and Nb-oxalate as precursors and ammonium hydroxide as precipitant. Calcination at 1150C resulted in pure SBN50 phase (XRD) and nano powder with size varying between 100–250 nm (TEM). The average grain size (SEM) in the sintered pellets ranged from 2.5 to 5 m as the sintering temperature varied from 1250 to 1350C. The maximum sintered density was observed to be 93% of _th. The plot of dielectric constant vs. temperature clearly showed a shift of dielectric maxima (_max) with frequency, indicating the relaxor nature of SBN50. The room temperature dielectric constant (_RT > 2300) observed for all these samples is higher compared to the earlier reported values (_RT 1500). The T_c (for 1 KHz) varied from 47–60C depending on the sintering conditions. The hystersis loops were recorded at various temperatures. The maximum saturation polarization for the unpoled pellets was found to be 2.3 C/cm² when sintered at 1350C. The improvement in dielectric and ferroelectric behavior is attributed to the enhanced homogeneity attained by the coprecipitation synthesis route used in the present study. Correlations between microstructure (sintering conditions) and dielectric behavior is explored.     

Dielectric and Mechanical Losses in (Ba,Sr)TiO3 Systems

In the application of tuneable microwave devices of ferroelectric (BaSr)TiO₃ systems the two critical parameters needed for optimal device performance are high tunability and low dielectric loss. The dielectric loss of the materials is strongly dependent on microstructure. This paper is concerned with an investigation of the variation in the dielectric and mechanical losses in Ba _x Sr_{1 – x} TiO₃ systems (x = 0.5, 0.6, 0.7 and 1.0) with microstructure (grain sizes from 1 m to 50 m). The magnitude of the loss peak and sharpness of the anomaly in the dielectric constant/elastic modulus observed for the phase transitions in Ba _x Sr_{1 – x} TiO₃, depend not only on the composition and but also on the grain size. A relaxation peak has been observed in large grain material, which is indication of interactions between different configurations of domain walls and the diffusion of oxygen vacancies in the domains.     

Tunable Dielectric Characteristics of 0.9Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>/0.1CaTiO<Subscript>3</Subscript>

Tunable dielectric characteristics of 0.9Pb(Fe_1/2Nb_1/2)O₃/0.1CaTiO₃ relaxor ferroelectric ceramics were investigated as the function of DC bias field and temperature. High tunability (more than 20%) was obtained in the present ceramics under a relatively weak DC bias field (1.4 kV/cm). The value of tunability changed from negative to positive with increasing DC field. For the simulation of the dielectric constant under DC bias field, modified model needs to be constructed for the relaxor ferroelectrics. The dielectric constant curve as a function of temperature without and under DC field was well fitted using the equation of diffuse phase transition. The lower ε_max, higher T_max and higher diffuseness parameter under DC field were observed and only the lower ε_max contributed to positive tunability.     

Effects of Processing Conditions on the Dielectric Properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

There have been a number of recent reports of anomalously large permittivities (ε _r ≈ 10⁴) in the material CaCu₃Ti₄O₁₂. The dielectric spectra is characterized by a large, relatively temperature independent permittivity near room temperature which exhibits a dielectric relaxation above 100 K. The crystal structure of CaCu₃Ti₄O₁₂ can be described as pseudo-perovskite with a cubic unit cell with a lattice constant of 7.391 Å. The ubiquitous occurrence of this dielectric behavior in ceramics, single crystals, and thin films suggests that the polarization is not related to a simple conducting grain/insulating grain boundary-type system. While the precise origin of the dielectric response is not entirely clear, in this work it is shown that processing conditions have a significant influence on the room temperature dielectric properties. Specifically, the permittivity and loss exhibit a strong dependence on the oxygen partial pressure and sintering time. In fact, studies of the effects of sintering time and supporting evidence from capacitance-voltage measurements conclusively show that there is no direct relationship between the permittivity and grain size, as is the case in classical boundary layer systems. Lastly, with aliovalent doping the room temperature dielectric properties can be optimized to provide a high permittivity (ε _r ～ 8,000) dielectric with relatively low loss (tan δ < 0.05 at 1 kHz).     

Synthesis and Dielectric Characterization of Pyrochlore-Free Pb1−x Ba x (Zn1/3Nb2/3)O3 Ceramics

The dielectric properties and synthesis of pyrochlore-free lead zinc niobate ceramics with Ba substituting for Pb were investigated. Ba partial substitution for Pb was effective in stabilizing the perovskite structure in PZN ceramics, where the minimum amount of Ba substitution needed was about 20 mol%. The dielectric loss and the temperature coefficient of dielectric constant of PZN were reduced markedly with Ba substitution, while the dielectric constant was greater than 110. Good dielectric properties were obtained for the composition of Pb_0.3Ba_0.7(Zn_1/3Nb_2/3)O₃: = 133.5, tan = 0.0009, = –811 ppm/°C.     

Niobium doping effects and ferroelectric relaxor behavior of bismuth lantanium titanate

Ferroelectrics Bi_3.25La_0.75(Ti_3−x Nb_x)O₁₂ (BLTN, x = 0∼ 0.1) solid solution systems were prepared, and Nb doping effects and relaxor behaviors were investigated. The BLTN single phases were confirmed by XRD. The phase transition temperature decreased as the Nb content increased, and the corresponding dielectric constant maximum broadened. The temperature T _m of the dielectric maximum depended on frequency and increased, which indicate that the relaxor behavior was caused by Nb substitution. The substitution of Nb for Ti ions affected the degree of disorder and modified the dielectric properties from those of normal ferroelectrics to relaxor ferroelectrics.     

(Gd,Co, Ta)-Doped SnO<Subscript>2</Subscript> Varistor Ceramics

The effect on the microstructure and electrical properties of (Co, Ta)-doped SnO₂ varistors upon the addition of Gd₂O₃ was investigated. The threshold electric field of the SnO₂ based varistors increased significantly from 720 V/mm to 1455 V/mm, the relative dielectric constants of the SnO₂ based varistors decreased greatly from 833 to 330 as Gd₂O₃ concentration was increased up to 1.2 mol%. The significant decrease of the SnO₂ mean grain size, from 3.8 to 1.6 m with increasing Gd₂O₃ concentration over the range of 0 to 1.2 mol%, is the origin for increase in the threshold voltage and decrease of the dielectric constants. The mean grain size reduction is attributed to the segregation of Gd₂O₃ at grain boundaries hindering the SnO₂ grains from conglomerating into large particles. Varistors were found to have superhigh threshold voltage and comparatively large nonlinear coefficient . For 0.8 mol% Gd₂O₃-doped sample, threshold electrical field E and nonlinear coefficient were measured to be 1125 V/mm and 24.0, for 1.2 mol% Gd₂O₃-doped sample, E and were 1355 V/mm and 23.0. Superhigh threshold voltage and large nonlinear coefficient qualify the Gd-doped SnO₂ varistor as an excellent candidate in use for high voltage protection system.     

Planar and Parallel Dielectric Properties of Compositionally Graded (Ba,Sr)TiO3 Thin Films for Tunable Microwave Applications

Compositionally graded (Ba_x,Sr_{1 ? x})TiO₃ [BST] ferroelectric thin films have been received much attention in graded ferroelectric devices due to their unique properties, such as large pyroelectric coefficients, large polarization offset and small temperature coefficient of dielectric constant for microwave tunable devices. Compositionally graded BST thin films were deposited epitaxially on LaAlO₃ [LAO] and Nb-doped SrTiO₃ [STO:Nb] substrates by pulsed laser deposition. The planar and parallel dielectric properties of compositionally graded BST epitaxial thin films ware investigated in the frequency ranges of 100 Hz ～ 1 MHz as a function of the direction of the composition gradient with respect to the substrate at room temperature. The dielectric properties of the graded BST films depended strongly on the direction of the composition gradient with respect to the substrate. The graded ST → BT films grown on LAO and STO:Nb substrates exhibited a excellent dielectric properties than the graded BT → ST films.     

Low Temperature Sintering of BaTi<Subscript>4</Subscript>O<Subscript>9</Subscript>-Based Middle-<Emphasis Type="Italic">k</Emphasis> Dielectric Composition for LTCC Applications

Effect of glass addition on the low-temperature sintering and microwave dielectric properties of BaTi₄O₉-based ceramics were studied to develop the middle-k dielectric composition for the functional substrate of low-temperature co-fired ceramics. When 10 wt% of glass was added, sufficient densification was obtained and the relative density more than 98% was reached at the sintering temperature of 875C. The microwave dielectric properties were k = 32, Q × f = 9000 GHz, and t_cf = 10 ppm/C. As the added amount of glass frit with base dielectric composition, phase changes from BaTi₄O₉ to BaTi₅O₁₁ and Ba₄Ti₁₃O₃₀ was observed, which result in the modification of microwave dielectric properties.     

Annealing Effects on Structural and Dielectric Properties of Tunable BZT Thin Films

Ba(Zr, Ti)O₃ thin films have attracted great attention in recent years for their potential use in DRAMs and MCMs due to their high dielectric constant and relatively low leakage current. However, their tunable dielectric properties were rarely investigated and the corresponding potential for tunable microwave applications was seldom reported. In this paper, we present the tunable dielectric behavior of BZT thin films deposited by RF magnetron sputtering from a Ba(Zr_0.3Ti_0.7)O₃ ceramic target on MgO single crystal substrates. The composition, thickness and crystallinity of the thin films were analyzed by Rutherford backscattering (RBS), scanning electron microscopy (SEM) and X-ray diffraction (XRD), respectively. The dielectric constant and loss tangent were measured as a function of electric field (0–7 kV/mm) and temperature (–140 to +160°C) at frequencies up to 1 MHz, using interdigital capacitors (IDC) with Au electrodes on thin films. By optimizing the preparation process, a tunability {defined as = [ (0) – (E_max)]/ (0)} of 76% at E_max = 7 kV/mm and a low loss tangent of 0.0078 can be achieved. In addition, the influence of annealing temperature on the dielectric properties of the thin films is also discussed.     

Development of Ferroelectric Ceramics with High Dielectric Constant and Low Dissipation Factor for High-Voltage Capacitors

Both ferroelectric BaTiO₃-based and SrTiO₃-based dielectric ceramics with high dielectric constant and low dissipation factor have been successfully developed, and applied into mass production for high-voltage ceramic capacitors. Crystalline phases of the ceramics were identified by XRD. STEM study of the ceramics was also conducted. Based on the computer simulation of a shell-core and two-phase mixed structural model proposed, a novel processing method was employed to produce SrTiO₃-based ceramics with the following satisfactory dielectric properties: dielectric constant at room temperature _20C=2000, dissipation factor at room temperature D _20C=0.003, temperature coefficient of dielectric constant = –8% (–25°C to 85°C), and, breakdown electric field E _b=10kV/mm(dc). Optional composition of BaTiO₃-based ceramics has been obtained through the orthogonal design experimentation: BaTiO₃-xBaZrO₃-yBaSnO₃, where x = 8wt% and y = 6wt%, with minor additions of MnSiO₃, WO₃, CeO₂, Bi₂(SnO₃)₃ and ZnO. Its major properties are as follows: Curie temperature T _c = 21°C, _20C=18,000, D _20'C = 0.008, =–80% (–25°C+85°C) and E _b = 8kV/mm (dc).     

Grain-Boundary Effect on the Curie-Weiss Law of Ferroelectric Ceramics and Polycrystalline Thin Films: Calculation by the Method of Effective Medium

The influence of grain boundaries on the dielectric properties of ferroelectric ceramics and polycrystalline thin films is described theoretically by the method of effective medium. Grain boundaries are modeled by low-permittivity (dead) layers, which do not exhibit ferroelectric instability. The effective permittivity of a polycrystalline material is calculated in the paraelectric regime above the transition temperature. The calculations are based on the solution of electrostatic problem for a spherical dielectric inclusion separated from the surrounding dissimilar matrix by a low-permittivity interface layer. For isotropic bulk ceramics, an analytic expression is derived for the effective permittivity as a function of the grain size, dead-layer thickness, and its permittivity. Temperature dependence of the aggregate dielectric response is calculated for BaTiO₃ (BT) ceramics of different grain sizes and found to be in good agreement with measurements. It is shown that grain boundaries not only renormalize the Curie-Weiss temperature and constant, but may also cause deviations from the Curie-Weiss law. For BT polycrystalline thin films grown on dissimilar substrates, numerical calculations of the effective dielectric constants are performed, taking into account both the grain-boundary and substrate effects on the film anisotropic dielectric response. Theoretical predictions are compared with the grain size dependence of the permittivity of BT films grown on Pt-coated Si.     

Evolution of Structure and Dielectric Properties on Bismuth-Based Pyrochlore with TiO2 Incorporation

The lattice constant and thermal expansion of the pyrochlore oxides (Bi_1.5Zn_0.5)(Zn_0.5–x/3Ti_x Sb_1.5–2x/3)O₇ (0 x 1.5) were studied by X-ray powder diffraction, SEM and IR spectra, respectively. The average grain size is enhanced as the Ti-doping level is increased. The XRD results indicate that all samples have a cubic structure (Fd3m space group) with the lattice parameter decreasing with rising Ti content. The variation of lattice parameters with composition was found to obey Vegard's law. The assignments for the absorption bands in the IR spectra of the series of samples have also been given. The results of diffraction patterns and IR spectra demonstrated that these compounds have the cubic pyrochlore structure. The dielectric properties of the samples were systematically studied. Dielectric constant and temperature coefficient of dielectric constant exhibit strong dependence on the Ti concentration. Dielectric constant varies sharply from 30 when x = 0 to 115 when x = 1.5.     

EFFECT OF ADDITION OF BT ON RELAXOR BEHAVIOR OF PIN-PT CERAMICS

ABSTRACT

Ferroelectric ceramics with chemical formula (1-x)Pb(In_0.5Nb_0.5)O₃-(x)PbTiO₃ and (1-x)Pb(In_0.5Nb_0.5)O₃-(x)PbTiO₃ with 20%mol of BT (x = 0.0, 0.1, 0.2 and 0.3) were prepared via the wolframite method. The relaxor behavior was analyzed from the dielectric properties and thermal expansion measurements. The dielectric properties were measured at frequencies between 100 Hz and 100 kHz whereas the thermal expansion was measured in the temperature range between ?145°C and 500°C. It is found that the addition of BT effects the relaxor behavior of PIN-PT system. The broad and diffused dielectric constant maxima and essentially no change in Burns temperature were measured and thus suggesting the glassy polarization and relaxor behavior in the PIN-PT-BT compositions.     

Low temperature sintering of lead–free (Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript>-SrTiO<Subscript>3</Subscript>-BiFeO<Subscript>3</Subscript> piezoelectric ceramics by adding excess CuO

This study examined the microstructures, crystal structures, and electrical properties of 0.01 mol CuO–added (1–x)(Bi_1/2Na_1/2)TiO₃–xSrTiO₃–2BiFeO₃ (BNST100x–2BF, x?=?0.20 ~ 0.28) ceramics synthesized at two different sintering temperatures. The sintering temperature of the BNST100x–2BF ceramics could be decreased from 1175 °C to 1000 °C by adding a 0.01 mol CuO excess. Low–temperature sintering led to a decrease in average grain size. The dielectrics, polarization hysteresis (P–E), switching current, and electric–field induced strain (S–E) curves changed with increasing SrTiO₃ content and decreasing sintering temperature. Interestingly, the highest reduction ratio of d₃₃^* was calculated to be somewhere in between the high–temperature sintered and low–temperature sintered BNST26–2BF ceramics. These results were attributed to the difference in the stabilized relaxor state and closely related to the electric field–induced reversible phase transition from the relaxor and ferroelectrics.     

Dielectric Behavior and Magnetoelectric Effect in Ni0.75Co0.25Fe2O4 + Ba0.8Pb0.2TiO3 ME Composites

Magnetoelectric composites with ferrite + ferroelectric compositions xBa_0.8Pb_0.2TiO₃ + (1 – x) Ni_0.75Co_0.25Fe₂O₄ in which x varies as 0, 0.55, 0.70, 0.85 and 1.0 were prepared by ceramic method. X-ray analysis confirms single-phase formation in x = 0 and x = 1 compositions, whereas the presence of both phases is shown in x = 0.55, 0.70 and 0.85 compositions. Variation of dielectric constant () with temperature and frequency has been studied. All the samples have show linear magnetoelectric conversion in the presence of static magnetic field. Static magnetoelectric conversion factor, (dE/dH), was measured as a function of magnetic field in the samples with x = 0.55, 0.70 and 0.85 compositions. The maximum value of dE/dH was found to be 140 V/cm/Oe for x = 0.85 composition.