Diffuse Phase Transition of the Sr0.3−3y/2LayBa0.7Nb2O6 Ceramic System

The effect of Lanthanum cation doping in the diffuse phase transition of the Sr_0.3–3y/2La_yBa_0.7Nb₂O₆ ceramic system is studied for y=0.01, 0.03 and 0.05. For these compositions, the transition temperature T _c shifts towards higher values with increasing frequency and the temperature dependence of the electrical permittivity presents strongly broadened curves which suggest a non Curie-Weiss behavior near the transition temperature for temperatures far from T _c. The diffuse phase transition coefficient () was also determined and its values lead us to conclude that the degree of disorder in the system increases with the presence of the Lanthanum cation. This result is corroborated by calorimetric measurements, where an increase in entropy with the Lanthanum concentration is also found.     

Dielectric Properties of La3+ Doped Sr0.3–3y/2Lay Ba0.7Nb2O6 Ceramics Prepared under Different Sintering Conditions*

A study of the dielectric properties of the Lanthanum doped Sr_0.3Ba_0.7Nb₂O₆ (SBN30) ceramic according to the stoichiometric formulation Sr_0.3–3y/2La_yBa_0.7Nb₂O₆ with y = 0.01, 0.03 and 0.05, and the influence of the sintering conditions is reported. The XRD shows single phase compounds for Sr_0.285La_0.01Ba_0.7Nb₂O₆ (LSBN1) and Sr_0.225La_0.03Ba_0.7Nb₂O₆ (LSBN3) ceramics, both samples having similar microstructure, densification and dielectric properties. The density increases linearly with ln t, where t is the sintering time, and the values of the maximum ferroelectric peaks of the permittivity increase steadily with t. Using the Bruggeman model to estimate the theoretical permittivity, it is concluded that the magnitude of the experimental permittivity peaks are mainly affected by the volume fraction of porosity of the samples. In this study we also establish that pore diffusion mechanisms behave according to the Ginstling-Brownshtein equation. For the Sr_0.225La_0.05Ba_0.7Nb₂O₆ (LSBN5) sample, XRD analysis reveals the presence of isostructural compounds of the intermediate phases BaNb₂O₆ and SrNb₂O₆, and the dielectric properties start to deteriorate. This fact indicates the existence of a solubility limit of Lanthanum ions in the SBN solid solution.     

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.     

Ferroelectric properties of Ba1−x Sr x TiO3 thin films synthesized by using novel sol–gel technique through carbonates

Ba_1?x Sr _x TiO₃ (BST) thin films were prepared on the substrate of Pt/Ti/SiO₂/Si by using novel sol–gel process through carbonates. The surface morphology and domain contrast of the films were investigated by atomic force microscopy (AFM), and the domain structures of the BST film were observed when AFM were operated in piezoelectric force microscopic (PFM) analysis and in the friction mode (FFM). The ferroelectric properties of the films were also investigated. It is shown that BST films obtained by the new sol–gel process through carbonates exhibit good properties.     

Effect of Ba2+ – Sr2+ co-substitution on the structural and dielectric properties of Lead Titanate

Growing interest in developing new materials for device applications led to study of ferroelectric oxides in a wide range and variety of compositions. In the present work, polycrystalline samples of lead barium strontium titanate (Pb_1-xBa_0.5xSr_0.5xTiO₃) solid solution system have been synthesized. Phase formation studies and crystal structure analysis were carried out by X ray diffractometry at room temperature, which suggested formation of single phase compound with tetragonal structure up to x?=?0.8 and cubic structure for x?=?1.0. The XRD pattern has been analyzed by employing Rietveld method. The phase transition in the system was confirmed by Differential Scanning Calorimetry (DSC). Samples with 0.0????x????0.8 are in ferroelectric state whereas with x?=?1.0 is found to be in paraelectric state at room temperature. Co-substitution of Ba²⁺ and Sr²⁺ into lead titanate shows reduction in anisotropy as well as porosity. The dielectric studies of the system as a function of temperature and frequency were carried out in the range 323?K to 773?K and 100?Hz to 1?MHz respectively. Variation of dielectric constant and loss tangent with temperature shows peaking effect near Curie temperature. Frequency dependant dielectric studies clearly show that the dielectric constant and loss tangent decrease exponentially with increased frequency.     

A/B-Ratio and Transport Properties of (La0.85Sr0.15)sCoO3−δ Perovskites

The perovskites (La_0.85Sr_0.15)_0.98CoO_{3 –} and (La_0.85Sr_0.15)_1.00CoO_{3 –} have been investigated using x-ray diffraction (XRD), scanning electron microscopy (SEM) and electrical conductivity relaxation (ECR). This system was chosen in order to investigate the influence of cation vacancies on the transport properties in the materials. From ECR-measurements it is concluded that no difference in the chemical diffusion coefficient for oxide ions between the two samples can be found. The activation energy for the chemical diffusion coefficient has been found to be 107 ± 5 kJ mol^{– 1}. However, the surface exchange coefficient differs between the two samples. The Co-rich sample has a significantly higher surface exchange coefficient than the A/B-stoichiometric sample. For both samples the surface exchange coefficient was almost independent of the temperature. At all temperatures the Co-rich sample had a significantly higher electrical conductivity. The difference in electrical conductivity between the two samples diminished when going to higher temperatures. Both materials can be assigned to a single phase hexagonal perovskite. An annealed sample of (La_0.85Sr_0.15)_0.98CoO_{3 –} did however contain an unidentified secondary phase on the surface.     

Structure and dielectric properties of Ca-doped (Ba0.7Sr0.3) TiO3 thin films fabricated by sol–gel method

A wide range of Ca-doped (Ba_0.7Sr_0.3)TiO₃ (BST) thin films (from 0 to 20 mol%) have been prepared on Pt/Ti/SiO₂/Si (100) substrates by sol–gel technique. The structural and dielectric properties of BST thin films were investigated as a function of Ca dopant concentration. The results showed that the microstructure and dielectric properties of the BST films were strongly dependent on the Ca contents. With the Ca dopant concentration increasing, the grain size, dielectric constant and dielectric loss of the BST thin films decreased. As the content of Ca dopant reaches 10 mol%, the dielectric constant, dielectric loss, tunability, the value of FOM and the leakage current density are 281, 0.0136, 16.7%, 12.3 and 5.5?×?10^?6 A/cm², respectively.     

Properties of (001)-textured Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) thin films with [001] preferential orientation were deposited on platinized silicon wafers by a sol–gel method, in which a PbO seeding layer was involved. The influences of annealing temperature on the crystal phase, microstructure, and electrical properties of the PMN–PT films were investigated. Pyrochlore-free perovskite PMN–PT films could be formed on PbO-seeded Pt(111)/Ti/SiO₂/Si wafers at 800 °C, which was also the optimal annealing temperature for endowing the film with the best ferroelectric and dielectric properties. The enhanced properties were attributed to the improved crystallinity and microstructure. The leakage behaviors of the PMN–PT films annealed at different temperatures were also measured and discussed.     

Investigation of microwave dielectric properties in the BaO–Nb2O5–P2O5 system

BaNb₂P₂O₁₁ and Ba₃Nb₂P₄O₁₈ compounds with corner-sharing NbO₆ octahedra and PO₄ tetrahedra were prepared by a conventional solid-state reaction method. The crystal structure and microstructure were investigated by X-ray powder diffraction and field emission scanning electron microscope, respectively. The microwave dielectric properties were measured using a network analyzer. Both ceramics were sintered at a relatively low temperature of 1150 °C and had a relative density of ～96%. Compared to Ba₃Nb₂P₄O₁₈, BaNb₂P₂O₁₁ had a higher permittivity of 31.7. However, the quality factor of BaNb₂P₂O₁₁, was smaller than Ba₃Nb₂P₄O₁₈. Furthermore, the effect of the crystal structure on the microwave dielectric properties was investigated.     

Effect of additive SrWO4 on microwave dielectric properties of SrTiO3–Sr(Mg1/3Nb2/3)O3 ceramics

The crystal structure and the properties of a new microwave dielectric ceramics x SrTiO₃–(1???x)Sr(Mg_1/3Nb_2/3)O₃ have been investigated. With x?=?0.025, The new microwave dielectric ceramic achieves the dielectric properties of a dielectric constant ? _r ～27.8, a Q?×?f value ～26,800, and a τ _f value ～7.4 ppm/°C. When the SrWO₄ is added, the sintering temperature of x SrTiO₃–(1???x)Sr(Mg_1/3Nb_2/3)O₃ ceramics will fall to 1350 °C, and its Q?×?f value can be improved further and the τ _f value becomes smaller. When the SrWO₄ is added by 0.07 mol, the specimen acquires the following microwave properties: a dielectric constant ? _r ～30.3, a Q?×?f value ～29,500, and a τ _f value of approximately ?0.4 ppm/°C.     

Synthesis and dielectric properties of Ba2TiSi2O8 glass-ceramics from the sol–gel process

The Ba₂TiSi₂O₈ glass-ceramics were prepared by sol–gel process using barium acetate, titanium butoxide, tetraethoxyorthosilicate and boric acid as raw materials. Because of the existence of glass and sintering additive, the Ba₂TiSi₂O₈ glass-ceramics can be sintered at 880 °C in air. The structure of sintered sample was characterized by means of XRD and SEM. XRD patterns showed that fresnoite Ba₂TiSi₂O₈ is the dominant crystalline phase in the sintered samples. SEM images indicated that the shape of Ba₂TiSi₂O₈ grains varied with the molar ratio of ([Ba(Ac)₂/Ti(OBuⁿ)₄/Si(OEt)₄]). With an increase of Si(OEt)₄ content, the length/diameter ratio of Ba₂TiSi₂O₈ grains decreases. The Ba₂TiSi₂O₈ glass-ceramics studied in this work have ?_r in the range of 6–12 (100 MHz) and demonstrate very low dielectric losses (tanδ <2?×?10^?3, 100 MHz). The experimental results suggested that the Ba₂TiSi₂O₈ glass-ceramics could be used as dielectric materials for low temperature co-fired ceramics (LTCC) process.     

Microstructural and Electrical Properties of (Ba x Sr 1 − x )Ti 1 + y O 3 + z Thin Films Prepared by RF Magnetron Sputtering

The electrical and microstructural properties of (Ba x Sr 1 m x )Ti 1+y O 3+z (BST) thin films prepared by RF magnetron sputtering were investigated as a function of deposition temperature over the range of 100 C to 650 C. Films deposited above approximately 350 C on Pt/TiO 2 /SiO 2 /Si substrates were polycrystalline with relative permittivites of 100 nm thick BST thin films varying from 100 at 350 C to 600 at 650 C. For deposition temperatures below approximately 350 C, the electrical properties were strongly influenced by the presence of a less crystalline BST layer. Films deposited at 250 C were comprised of a multilayer polycrystalline/less crystalline BST structure. The less crystalline BST layer strongly affected both measured dielectric permittivity and leakage properties. Leakage characteristics of Pt/BST(250C)/Pt capacitors exhibited a power law dependence on voltage or an exponential dependence on square root of the applied voltage depending on whether the top Pt electrode adjacent ot the polycrystalline BST layer was biased at a high or low electric potential, respectively. Mechanisms for the observed leakage behavior are discussed.     

Study of the electrical properties of Pb(Zn,Ni)1/3Nb2/3O3–PbTiO3 ceramics across the morphotropic phase boundary

Structure and electrical properties of (1???x)Pb(Zn_0.2Ni_0.8)_1/3Nb_2/3O₃–xPbTiO₃ ceramics with x?=?0.24–0.38 were examined in detail. X-ray diffraction measurements reveal that all samples are in pure perovskite phase, and most of them lie within the morphotropic phase boundary (MPB) region. The dielectric behaviors of all compositions are characterized with diffuse phase transition and frequency dispersion. The variable power law and the Vogel–Fulcher relation have been used to describe such dielectric behaviors. The highest dielectric constant and the largest piezoelectric coefficient are simultaneously observed when x?=?0.30. The variation of the ferroelectric property with PT content is also discussed.     

Microstructural Design and Properties of LaCoO3/La2(Zr,Y)2O7−δ Composites

LaCoO_3–/La₂(Zr,Y)₂O₇-based composites were designed in view of three main properties: electrical conductivity, thermal expansion and resistance to thermal cycling. Composition and processing conditions were investigated on the basis of an experimental plan according to the Taguchi method. The phase distribution was estimated from image analysis and related to electrical and thermo-mechanical behavior. Results indicate that an homogeneous and fine grained phase distribution is essential in order to obtain materials with the desired thermal expansion, electrical properties and thermomechanical properties.     

Investigation of the BaTiO3–BaMg1/3Nb2/3O3 system: Structural, dielectric, ferroelectric and electromechanical studies

Lead-free (1?x) BaTiO₃ –x BaMg_1/3Nb_2/3O₃ ceramics with x?=?0.03, 0.04, 0.05 and 0.06 were prepared by solid-state synthesis. The effects of the Ba(Mg_1/3Nb_2/3)O₃ addition on the phase composition, dielectric and ferroelectric properties, as well as the electromechanical response of the classic ferroelectric BaTiO₃ were investigated. The room-temperature X-ray diffraction analyses of all the ceramics revealed a perovskite phase after sintering at 1300 °C with a composition-dependent symmetry. The samples with a lower concentration of Ba(Mg_1/3Nb_2/3)O₃, i.e., x?=?0.03 and 0.04, were tetragonal, while the samples with x?=?0.05 and 0.06 were found to be cubic. The result is in agreement with the dielectric, ferroelectric and electromechanical properties. With x increasing from 0.03 to 0.06 the temperature of the diffused maximum of the dielectric permittivity decreased from 348 K to 265 K. All the ceramics showed a large electromechanical response: the calculated room-temperature electrostrictive coefficient M ₃₃ of the sample with x?=?0.06 was 1.4 · 10^?16?m²/V², which is comparable to the value measured for Pb(Mg_1/3Nb_2/3)O₃ ceramics.     

Synthesis and characterizations of the (1 − x)Pb(Sc1/2Nb1/2)O3–xPbTiO3 solid solution ceramics

We report a systematic study of the (1???x)Pb(Sc_1/2Nb_1/2)O₃–xPbTiO₃ (PSN–PT) solid solution in the form of ceramics with compositions at or near the morphotropic phase boundary (MPB) region (0.35?≤?x?≤?0.50). The PSN–PT ceramics have been synthesized by an improved two-step wolframite precursor method. The synthetic process has been optimized in terms of calcining and sintering conditions. Both dielectric permittivity measurements and differential scanning calorimetry (DSC) show a clear peak at T _C, at which the transition from the paraelectric to ferroelectric phase takes place. Interestingly, the solid solution of the MPB compositions displays a T _C?>?200 °C, i.e. higher than the T _C of the Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ and Pb(Zn_1/3Nb_2/3)O₃–PbTiO₃ solid solutions, making the PSN–PT system very promising piezoelectric and ferroelectric materials for high-temperature applications. A dielectric maximum as high as 50,000 is obtained for the 0.65PSN–0.35PT ceramic with losses smaller than 0.05. The values of the remnant polarization and the strain level of the PSN–PT ceramics are comparable to those of the PZT ceramics.     

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.     

Effect of B2O3 Nano-Coating on the Sintering Behaviors and Electrical Microwave Properties of Ba(Nd2 − x Sm x )Ti4O12 Ceramics

Ba(Nd_0.8Sm_0.2)₂Ti₄O₁₂ ceramics prepared by conventional solid-state sintering have a dielectric constant of about 80 and a nearly zero temperature coefficient of resonant frequency; however, the sintering temperature is above 1350_C. Doping with B₂O₃ (up to 5 wt%) promotes the densification and dielectric properties of BNST ceramics. It is found that coating BNST powder with thin B₂O₃ layer of about 180 nm reduces the sintering temperature to below 1020_C. The effects of B₂O₃ nano-coating on the dielectric microwave properties and the microstructures of BNST ceramics are investigated. Ninety-six percent of theoretical densities is obtained for specimens coated with 2 wt% B₂O₃ sintered at 960_C and the samples exhibit significant (002) preferred orientation and columnar structure.     

Effects of ZnO–xV2O5 substitution on the microstructure and microwave dielectric properties of ZnNb2O6 ceramics

The ZnO–xV₂O₅ substituted ZnNb₂O₆ ceramics with chemical formula Zn(Nb_0.9V _x )₂O_5.5+5x (0?<?x?≤?0.10) were prepared by solid-state reaction route. The densities, microstructures and microwave dielectric properties were investigated according to the different substitution amount of V₂O₅ and sintering temperature. A small amount of substitution of ZnO–xV₂O₅ was effective to lower sintering temperature of ZnNb₂O₆ ceramics from 1,150 °C to 900 °C. The V₂O₅ substitution led to growth of rod-like grains with the help of liquid phase formed from ZnO and V₂O₅. The dielectric properties depended largely on the amount of V₂O₅ substitution and sintering temperature. The dense ceramics with x?=?0.05 were obtained at 950 °C, which had excellent dielectric properties: ?_r?=?24, Q?×?f?=?72,800 GHz and τ_f?=??63.5 ppm/°C. The interface analysis for cofired multilayer composites composed of the present LTCC and metal Ag demonstrated good co-firing chemical compatibility at co-sintering temperature.     

Piezoelectric properties of MnO2 doped low temperature sintering Pb(Mn1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr0.50Ti0.50)O3 ceramics

In this study, in order to develop the composition ceramics for low loss and low temperature sintering multilayer piezoelectric actuator, Pb(Mn_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr_0.50Ti_0.50)O₃ (abbreviated as PMN-PNN-PZT) ceramics were fabricated using Li₂CO₃ and Na₂CO₃ as sintering aids, and their piezoelectric and dielectric characteristics were investigated according to the amount of MnO₂ addition. At the 0.2 wt% MnO₂ doped specimen sintered at 900 °C, density and mechanical quality factor (Q _m) showed the maximum values of 7.81[g/cm³]and 1186, respectively. And also, at 0.1 wt% MnO₂ doped specimen, electromechanical coupling factor (k _p), piezoelectric constant (d ₃₃) of specimen showed the maximum values of 0.608 and 377[pC/N], respectively. Dielectric constant (? _r) slightly decreased with increasing MnO₂. Taking into consideration the density of 7.81[g/cm³], electromechanical coupling factor (k _p)of 0.597 the mechanical quality factor (Q _m) of 1,186, and piezoelectric constant (d ₃₃) of 356[pC/N], it could be concluded that 0.2 wt% MnO₂ doped composition ceramics sintered at 900 °C was best for low loss and low temperature sintering multilayer piezoelectric actuator application.