Effect of Mn-doping on the structure and electrical properties of (Pb0.325Sr0.675)TiO3 ceramics

Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics (x?=?0, 0.001, 0.005, 0.01, and 0.05) were successfully prepared by traditional solid-state reaction method. It was found that the lattice constant calculated through Rietveld refinement initially increased and then decreased with increasing Mn content, which was attributed to the variation in valence state of Mn and Ti ions. The microstructure gradually varied from the coexistence of large grains and fine grains for x?=?0 to the uniform grain for x?=?0.05 by increasing the doping Mn ions. With increasing Mn content from x?=?0 to x?=?0.05, the Curie temperature (Tc) dramatically decreased from 25?°C to ??40?°C and dielectric maximum decreased from 27,100 to 13,200. Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics with x?=?0.001 showed the lowest dielectric loss of 0.006 with a relatively high dielectric peak value of ~ 21,000. The grain boundaries resistance obtained from the complex impedance decreased with the increase of Mn content. The decrease in resistance was ascribed to oxygen vacancies and electronics produced by the change of ionic valence state. X-ray photoemission spectroscopy revealed that Ti ions were Ti⁴⁺ and the valences of Mn ions were deduced to be mainly in the form of Mn²⁺ and/or Mn³⁺ for ceramics with low content of Mn, while the Ti ions were in the form of Ti³⁺ and Ti⁴⁺ and Mn ions were diverse valence states with the coexistence of Mn²⁺, Mn³⁺, and Mn⁴⁺ for ceramics with x?=?0.01 and 0.05.     

Dielectric,ferroelectric, and photoluminescent properties of Sm-doped Bi4Ti3O12 thin films synthesized by sol-gel method

We report on the structure, dielectric, ferroelectric, and photoluminescent properties of Sm³⁺-doped Bi₄Ti₃O₁₂ thin films which were prepared on fused silica and Pt/Ti/SiO₂/Si substrates by sol-gel method. The X-ray diffraction analysis confirmed that the Bi_4-xSm_xTi₃O₁₂ (BSmT) thin films were well crystallized in layered perovskite structure without any secondary phase. Raman spectra indicated that the structure of BSmT thin films was significantly distorted because of the Sm³⁺ doping. An appropriate doping amount of Sm³⁺ ions leads to obvious enhancement in ferroelectric and dielectric properties of BSmT thin films due to structure distortion and reduction in defects. In addition, the BSmT thin films also show orange-red color emission at 601?nm and long florescence lifetime (> 0.6?ms). This study indicated that lead-free BSmT thin films, which are featuring good electrical and photoluminescent properties, may have potential applications in integrated optoelectronic devices.     

Multiferroic and magnetoelectric properties of lead-free Ba0.8Sr0.2Ti0.9Zr0.1O3-Ni0.8Zn0.2Fe2O4 composite films with different deposition sequence

Ba_0.8Sr_0.2Ti_0.9Zr_0.1O₃/Ni_0.8Zn_0.2Fe₂O₄(BN) and Ni_0.8Zn_0.2Fe₂O₄/Ba_0.8Sr_0.2Ti_0.9Zr_0.1O₃ (NB) composite film were deposited on Pt/Ti/SiO₂/Si substrates by the sol-gel method and spin-coating method. The results show that the deposition sequences of the composite films have significant influence on the ferroelectric, ferromagnetic and magnetoelectric properties of the composite films. Two composite films possess not only good ferroelectric and ferromagnetic properties but good magnetoelectric properties as well. The NB composite film has clear interface between the ferroelectric film and ferromagnetic film and possesses greater magnetoelectric coupling effect than the BN composite film under the same H_bias. The maximum value of α_E is 70.14?mV?cm^?1 Oe^?1 was obtained in the NB composite film when H_bias is 638?Oe.     

Thickness dependence of microstructure,dielectric and leakage properties of BaSn0.15Ti0.85O3 thin films

The BaSn_0.15Ti_0.85O₃ (BTS) thin films are prepared on Pt-Si substrates with thickness ranging from ~ 60?nm to ~ 380?nm by radio frequency magnetron sputtering. The effects of thickness on microstructure, surface morphologies and dielectric properties of thin films are investigated. The thickness dependence of dielectric constant is explained based on the series capacitor model that the BTS thin film is consisted by a BTS bulk layer and an interfacial layer (dead layer) between the BTS and bottom electrode. The thin films with thickness of 260?nm give the largest figure of merit of 76.9@100?kHz, while the tunability and leakage current density are 64.6% and 7.46?×?10^?7 A/cm² at 400?kV/cm, respectively.     

Reduced leakage current,enhanced energy storage and dielectric properties in (Ce,Mn)-codoped Ba0.6Sr0.4TiO3 thin film

Ba_0.6Sr_0.4TiO₃, Ce-doped Ba_0.6Sr_0.4TiO₃, Mn-doped Ba_0.6Sr_0.4TiO₃, (Ce,Mn) co-doped Ba_0.6Sr_0.4TiO₃ (abbreviated as BST, BSTCe, BSTMn, BSTCeMn) thin films were deposited on LaNiO₃(LNO)/Si substrates. The effects of ion doping on the microstructure and electrical properties of BST-based thin film have been researched and discussed. The X-ray diffraction pattern shows that each sample has pure perovskite phase structure with high (l00) peaks. The microstructure of each film is quite dense with uniform size. Compared with pure BST, improved insulating properties can be found in ion-doped BST thin films. For all the films, Ohmic conduction, space charge limited conduction and interface-limited Fowler-Nordheim tunneling should be the main conduction mechanisms within different electric field regions. For the case of BSTCeMn thin film, it possesses enhanced energy storage performance with a recoverable energy storage density (18.01?J/cm³) and a energy storage efficiency (75.1%) under 2000?kV/cm. This can be closely related to the small remanent polarization value (P_r=?1.89 μC/cm²), large maximum polarization value (P_max=?28.08?μC/cm²) as well as big maximum electric field (2000?kV/cm). Also, it exhibits a large dielectric constant of 405 and a small dissipation factor of 0.075 at 500?kHz.     

Effect of sputtering pressure on structural and dielectric tunable properties of BaSn0.15Ti0.85O3 thin films grown by magnetron sputtering

Lead?free ferroelectric BaSn_0.15Ti_0.85O₃ (BTS) thin films are grown on Pt-coated Si substrates by magnetron sputtering at 650?°C, the effect of sputtering pressure on the microstructural, surface morphological, dielectric properties and leakage characteristic is systematically investigated. XRD analysis shows the crystallinity of BTS thin films with perovskite structure can be improved by appropriate control of the sputtering pressure. The surface morphology analyses reveal that grain size and roughness can be affected by sputtering pressure. The BTS thin films prepared at sputtering pressure of 3.0?Pa exhibit a low dispersion parameter of 0.006, a medium dielectric constant of ~357, a high dielectric tunability of 65.7%@?400?kV/cm and a low loss tangent of 0.0084?@?400?kV/cm. Calculation of figure of merit (FOM) displays a high value of 84.1, and the measurement of leak current shows a very low value of 4.39?×?10^–7 A/cm² at 400?kV/cm. The results indicate that BTS thin film deposited sputtering pressure of 3.0?Pa is an excellent candidate for electrically steerable applications     

Dysprosium‐Doped (Ba,Sr)TiO3 Thin Films on Nickel Foilsfor Capacitor Applications

The substitution in (Ba_0.70Sr_0.30)TiO₃ thin films by the rare‐earth element dysprosium prepared at 1000°C by chemical solution deposition on nickel foils was investigated. The relatively large thermal budget applied (via annealing temperature) is shown to enhance the solubility of the Dy³⁺doping ion into the crystal lattice of the perovskite films. Preference for B‐site occupancy of this amphoteric cation was further promoted by the addition of BaO excess (1 mol%), which results in slightly larger grains in the films as observed by scanning electron microscopy. Despite this Ba‐rich composition, the presence of secondary phases in the thin films was not detected by X‐ray diffraction. Transmission electron microscopy revealed no evidence for local segregation of Dy at grain boundaries, neither the formation of NiO at the interface between the film and the metal foil was observed. The substitution of Ti⁴⁺ by Dy³⁺ leads to the formation of strong electron acceptors in the system, which balance the number of ionized oxygen vacancies arisen from the reductive crystallization atmosphere used during processing. As a consequence, the dielectric loss (tan σ) and leakage conduction measured in the resulting thin‐film capacitors were significantly reduced with respect to nominally undoped samples. The improvement of this capacitor feature, combined with the relatively high permittivities obtained in the films (490–530), shows the effectiveness of dysprosium doping within a thin‐film fabrication method for potential application into the multilayer ceramic capacitor technology.     

An investigation on the microstructural and electrical properties of La0.85DxSr0.15–xGa0.8Mg0.2O2.825 (D = Ba and Ca) electrolytes in solid oxide fuel cells

La_0.85D_xSr_0.15–xGa_0.8Mg_0.2O_2.825 (D = Ba and Ca, x?=?0, 0.01, 0.03, 0.05, and 0.07) electrolytes were synthesized using a solid-state reaction method, calcined at 1400?°C for 5?h, and sintered at 1400?°C for 5?h. The microstructures, electrical properties, and cell performances of the electrolytes and fuel cells were analyzed by X-ray diffraction, scanning electron microscopy, impedance analysis, and electrochemical analysis. La_0.85Ba_xSr_0.15–xGa_0.8Mg_0.2O_2.825 (LBSGM) and La_0.85Ca_xSr_0.15–xGa_0.8Mg_0.2O_2.825 (LCSGM) exhibit a dense structure and a cubic perovskite phase. Further, they contain small amounts of a secondary phase. The lattice constants of LBSGM and LCSGM are 0.3913–0.3914?nm and 0.3906–0.3909?nm, respectively. The average grain size of the sample increases with increasing Ba²⁺ or Ca²⁺ content. The conductivity of LCSGM (0.197–0.174?S/cm) is usually higher than that of LBSGM (0.181–0.162?S/cm) at 800?°C. The cells with La_0.85Sr_0.15Ga_0.8Mg_0.2O_2.825 and La_0.85Ca_0.03Sr_0.12Ga_0.8Mg_0.2O_2.825 electrolytes exhibit high open-circuit voltages and maximum power densities of 0.96?V and 542?mW/cm² and 0.94?V and 567?mW/cm², respectively, at 800?°C.     

MgO-modified Sr0.7Ba0.3Nb2O6 ceramics for energy storage applications

We explored the phase structure, microstructure, dielectric and energy storage properties of MgO-modified strontium barium niobate Sr_0.7Ba_0.3Nb₂O₆-xwt%MgO (SBNMx; x?=?0–5) ceramics fabricated via conventional solid-state sintering precess. X-ray diffraction analysis indicates Mg²⁺ incorporates into lattice at x?=?0.5 and secondary phases come into formation for samples at x?≥?1, which results in the decrease of dielectric constant. There is also significant reduction of dielectric loss up to 0.002. Compared with pure SBN ceramics, the grain size of SBNMx ceramics becomes denser and more uniform, moreover, the dielectric breakdown strength shows increasing trend from 137?kV/cm to 226?kV/cm, which is in favor of the energy storage. SBNM0.5 ceramics presents the optimal energy storage performance: energy storage density of 0.93?J/cm³ and energy storage efficiency of 89.4% at 157?kV/cm, indicating that SBNM ceramics are prospective candidates for high voltage capacitor applications.     

Molten-salt synthesis of Ba5−xSrxNb4O15 solid solutions and their enhanced humidity sensing properties

Layered perovskite-type niobates A₅Nb₄O₁₅ (A = Ba, Sr) are thought to be good candidates for microwave dielectric and water-splitting applications, but traditional solid-state syntheses of these compounds usually require high temperatures and complicated procedures. In this work, Ba_5?xSr_xNb₄O₁₅ (x = 0 ? 5) perovskite solid solutions were obtained using a facile molten salt synthetic method. The crystal structure of Ba_5?xSr_xNb₄O₁₅ solid solutions were characterized by X-ray diffraction (XRD). Crystal structure parameters with different Sr²⁺ concentrations show that the lattice parameters and unit cell volumes of Ba_5?xSr_xNb₄O₁₅ decrease with increasing [Sr²⁺]. The humidity sensing behavior of Ba_5?xSr_xNb₄O₁₅ solid solutions was investigated over a wide relative humidity (RH) range, from 11% to 95%. Ba₂Sr₃Nb₄O₁₅ shows the highest sensitivity among the obtained samples with a humidity hysteresis of ca. 4% RH. The response-recovery times of the Ba₂Sr₃Nb₄O₁₅ sensor are only 2 s and 17 s as the humidity alternates between 11% and 95% RH, respectively, showing excellent potential as a humidity sensing material for practical applications.     

Microstructures and dielectric properties of spark plasma sintered Ba0.4Sr0.6TiO3/CaCu3Ti4O12 composite ceramics

(1 − x)Ba_0.4Sr_0.6TiO₃/xCaCu₃Ti₄O₁₂ composite ceramics were prepared by spark plasma sintering. Sintering behavior, microstructures and dielectric properties of the composite ceramics were investigated by XRD, SEM, EDS and dielectric spectrometer. Dense composite ceramics consisting of Ba_0.4Sr_0.6TiO₃ phase and CaCu₃Ti₄O₁₂ phase were prepared at 800 °C for 0 min. The dielectric loss of the composite ceramic decreased with increasing amount of Ba_0.4Sr_0.6TiO₃, and the high dielectric constant were retained. Moreover, the better temperature stability of dielectric constant was obtained. These improvements of dielectric characteristics have great scientific significance for potential application.     

Synthesis,characterisation and dielectric properties of low-loss Zr-doped barium strontium titanate materials

ABSTRACT

A series of materials of the composition Ba_0.7Sr_0.3Zr_xTi_(1???x)O₃ (BSZT), where x?=?0.00, 0.01, 0.02 and 0.03, were synthesised through the sol–gel method whereupon the manifestations of partial substitution of Ti⁴⁺ by Zr⁴⁺ on the structural and dielectric behaviour of Ba_0.7Sr_0.3TiO₃ (BST) were studied. X-ray diffraction patterns of all samples showed the development of a single-phase crystalline perovskite structure. The dielectric behaviour of the ceramic samples has been studied in detail in the frequency range 10 Hz to 1 MHz at room temperature, and as a function of increase in temperature. The sample with 2% Zr recorded the highest dielectric constant. The dielectric loss values for all the BSZT compositions are remarkably low, tan?δ?=?0.021～0.026 at 1 MHz, in contrast to the literature reports. It is observed that small amount of Zr doping on BST, where 0?<?x?≤?0.03 results in the enhancement of dielectric constant while decreasing the bulk density and dielectric loss.     

Dielectric stability in the relaxor: Na0.5Bi0.5TiO3-Ba0.8Ca0.2TiO3-Bi(Mg0.5Ti0.5)O3- NaNbO3 ceramic system

Ceramics with temperature-stable dielectric characteristics have been developed in the system: 0.6[0.85Na_0.5Bi_0.5TiO₃-(0.15-x)Ba_0.8Ca_0.2TiO₃-xBi(Mg_0.5Ti_0.5)O₃]?0.4NaNbO₃, x ≤ 0.15. Dielectric measurements exhibited relaxor ferroelectric characteristics with temperature-stable relative permittivity from ε_r~1330 ± 15% in the temperature range from ?70?°C to 215?°C and tanδ ≤ 0.02 from ?20?°C to 380?°C for x = 0 compositions. For the Bi(Mg_0.5Ti_0.5)O₃ modified compositions the temperature range of stable relative permittivity extended from ?70?°C to 400?°C, with ε_r ~ 950 ± 15% and tanδ ≤ 0.02 from ?70?°C to 260?°C. Values of dc resistivity were ~ 10⁸ Ω?m at a temperature of 300?°C and the corresponding RC constant values were in the range from 0.40 ? 0.78?s at 300?°C. All ceramic samples exhibited a linear polarisation-electric field response at maximum applied electric field of 5?kV/cm (1?kHz).     

Microwave dielectric properties of barium substituted screen printed CaBi2Nb2O9 ceramic thick films

In the present study, Aurivillius-structured Ba²⁺ substituted CaBi₂Nb₂O₉ (CBNO) ceramic powder was synthesized by co-precipitation method. The CBNO thick films were delineated by screen printing method on alumina substrates using co-precipitated ceramic powder. The overlay method was adopted to measure the microwave dielectric properties of prepared thick films. Single phase layered perovskite structure of the prepared thick films was confirmed by X-ray Diffraction. The effects of Ba²⁺ substitution on the surface morphology, bonding, and microwave dielectric properties of thick films were systematically presented. The maximum value of microwave dielectric constant for the CBNO thick films at 11.8 GHz is 15.6 for Ba²⁺=0.8 substitution. The shift in the stretching vibration modes of the Nb-O bond of NbO₆ octahedron in the Raman spectra with a substitution of Ba²⁺ in CBNO was observed. The substitution of Ba²⁺ on A-site of CBNO improves the microwave dielectric properties of prepared thick films. This work may provide a new approach to enhance the microwave dielectric performance of Aurivillius-structured ceramic thick films.     

Enhancing piezoelectric properties of Ba0.88Ca0.12Zr0.12Ti0.88O3 lead-free ceramics by doping Co ions

The piezoelectric properties of lead-free Ba_0.88Ca_0.12Zr_0.12Ti_0.88O₃ (BCZT) ceramics were greatly optimized by doping Co ions using a CoO powder. The role of Co²⁺ and Co³⁺ in enhancing the piezoelectric properties and the relationship between the content ratio Co³⁺/Co²⁺ and piezoelectric performance were studied. The X-ray diffraction patterns of all samples indicated that crystalline phases were a BCZT-based single perovskite structure regardless of the Co ion content. The phase transition temperature and lattice distortion degree were related to the Co ion content and the content ratio Co³⁺/Co²⁺ because Co²⁺ resulted in higher oxygen vacancy generation, whereas Co³⁺ induced larger lattice shrinkage. The ceramic containing 0.10 wt% of Co ion showed the best piezoelectric and dielectric performance with the highest piezoelectric constant d₃₃ ~ 490 p.m./V at room temperature and the highest Curie temperature T_c of 110 °C, which increased by 29% and 16%, respectively. In this case, the content ratio Co³⁺/Co²⁺ reached the maximum value of 0.86. The high piezoelectric properties and phase stability of BCZT ceramics by doping Co ions make these ceramics promising piezoelectric materials for practical applications.     

Photoluminescence and optical temperature sensing in Sm3+-doped Ba0.85Ca0.15Ti0.90Zr0.10O3 lead-free ceramics

A series of orange-red emitting Sm³⁺ activated Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ (BCZT: xSm³⁺, x?=?0.001–0.007) are synthesized by a conventional solid-state reaction method. The Sm³⁺ ions composition dependent photoluminescence properties are systematically investigated. Under the excitation of a 407?nm near-ultraviolet light, the ceramics exhibit strong characteristic emission of Sm³⁺ ions with dominant orange-red emission peak at around 595?nm, which is ascribed to the transition of ⁴G_5/2 → ⁶H_7/2. The BCZT: 0.004Sm³⁺ ceramic displays the optimal emission among these Sm³⁺-doped BCZT solid solutions. Moreover, the photoluminescence intensity exhibits extremely sensitive to temperature, suggesting that BCZT: 0.004Sm³⁺ could be applicable for temperature sensing. A maximum relative sensitivity of 1.89%?K^?1 at 453?K is obtained. Furthermore, the existence of ferroelectricity in the BCZT host combined with Sm³⁺ activated photoluminescence properties could be useful for developing optical-electro multifunctional materials and devices.     

Electronic structure and magnetic properties of Ba1-xSrxCoFe11O19 hexaferrites

We have prepared Ba_1-xSr_xCoFe₁₁O₁₉ hexaferrite nanoparticles (NPs) by using a co-precipitation method. The crystal/electronic structures and magnetic properties were then studied. Results revealed that all Ba_1-xSr_xCoFe₁₁O₁₉ NPs with particle sizes of 100–300?nm crystallized in a hexagonal structure. Both the particle shape and the unit-cell parameters are changed when Sr content (x) increases. The analysis of the electronic structure based on the Fe and Co K-edge XAS spectra proved the oxidation states of Fe and Co to be 3?+?and 2?+?, respectively, which are stable versus an x change in Ba_1-xSr_xCoFe₁₁O₁₉. Local-structural studies also revealed the average bond length between Fe and O of 1.89–1.91?Å less changed by Sr doping. Though the electronic structures of Fe and Co were unchanged, the studies about the magnetic property demonstrated a strong dependence of M_s and H_c on Sr doping. While M_s decreases from 46.1?emu/g for x?=?0–34.2?emu/g for x?=?1, H_c tends to increase from 1630?Oe for x?=?0 to ~ 2200?Oe for x?=?0.5, but slightly decreases to 2040?Oe for x?=?1. We think that the addition of the exchange interaction between Fe³⁺ and Co²⁺ ions and the changes of local-geometric structures and microstructures influenced directly M_s and H_c of NPs.     

Dielectric properties of Bi-doped Ba0.8Sr0.2TiO3 ceramic solid solutions

Bismuth-doped barium–strontium–titanate ceramics of the formula (Ba_0.8Sr_0.2)_(1−1.5y)Bi_yTiO₃ were prepared using a conventional solid-state reaction method. The structure, dielectric properties, and ferroelectric relaxor behaviour of all compositions were thoroughly investigated. The findings revealed a broad dielectric anomaly and a shift in dielectric maxima towards higher temperatures with increasing frequency. The diffuseness degree indicator γ was about 1.68, and dielectric relaxation was noted to follow the Vogel–Fulcher relationship, with T_f=185 K, f₀=1.18×10¹⁰ Hz, and Ea=0.35 eV, which further supported the spin-glass-like properties of BBSTs. The latter were also noted to display significant ferroelectric relaxor behaviour that could be attributed to the presence of Bi³⁺ doping ions. The degree of relaxation behaviour was noted to increase with the increase in bismuth concentration. Raman spectra were investigated as a function of temperature, and the findings confirmed the results from X-ray and dielectric measurements. Among the compositions assayed in this solid solution, 10% Bi-doped Ba_0.8Sr_0.2TiO₃ yielded promising relaxor properties that make it a strong candidate for future industrial application in the production of efficient and eco-friendly relaxor ferroelectric materials.     

Studies of dielectric properties of rare earth (Dy,Tb, Eu) doped barium titanate sintered in pure nitrogen

This paper investigated dielectric properties of rare earth (Dy, Tb, Eu)-doped barium titanate sintered in pure nitrogen. The substituting concentration of rare earth (Dy, Tb, Eu) was 2.0 mol%. The doping behaviors of intermediate rare-earth ions (Dy, Tb, Eu) and their effects on the dielectric property of barium titanate were investigated. Eu³⁺ ion was substituted in the A-site of the perovskite lattice. Dy³⁺ and Tb³⁺ ions substituted partially for Ti⁴⁺ site and partially for Ba²⁺ site. The different rare earth element had a crucial effect on dielectric properties of rare-earth-doped BaTiO₃. Among these doped samples, Tb-doped BaTiO₃ had the largest dielectric constant (70,000–80,000); the smallest dielectric loss (less than 4%), and good capacitance-temperature coefficient, which satisfies the X7R specification of the Electronic Industries Association Standards (TCC within ±15% from ?55 °C to 125 °C).     

Defect chemistry and dielectric behavior of Sr0.99Ce0.01Ti1−xO3 ceramics with high permittivity

Sr_0.99Ce_0.01Ti_1-xO₃ (SCT, x?=?0, ±?0.0025, ±?0.0050, 0.0075) ceramics were prepared by solid state reaction methods and sintered in air atmosphere at different temperatures, with a soaking time of 2?h. The dielectric properties of all samples presented excellent temperature independence over a broad temperature range from 25 to 330?℃ and frequency independence between 10?kHz and 1?MHz. Sr_0.99Ce_0.01Ti_0.9925O₃ (SCT0.9925) ceramics sintered in air atmosphere exhibited a high permittivity (~5400) and a low dielectric loss (~0.01) measured at room temperature and 1?kHz. XPS and complex impedance spectroscopy analysis confirmed that the high permittivity and low dielectric loss were attributed to the fully ionized oxygen vacancies and giant defect-dipoles in Ti-deficient samples. However, a higher dielectric loss of Ti-rich samples is owing to the destruction of giant defect dipoles, in which highly localized electrons were transformed into hopping electrons.