Preparation of porous (Ba,Sr)TiO3 by adding corn-starch

A new method of preparing porous (Ba,Sr)TiO₃ ceramics has been introduced, using an ordinary ceramics processing technique. The effect of corn-starch on the positive temperature coefficient of resistivity characteristics and microstructure of the porous (Ba,Sr)TiO₃ ceramics has been investigated. When the corn-starch addition was 1-20 wt%, the PTCR jump was over 10⁶ and 1-2 orders higher than that of samples without corn-starch. Also, it was found that the (Ba,Sr)TiO₃ ceramics had porous microstructure by the addition of corn-starch. The porosity of the ceramics with 20 wt% corn-starch was 44%. The electrical properties of the (Ba,Sr)TiO₃ ceramics have been discussed, based on the microstructure, resistivity of grain boundaries, donor concentration of grains and the electrical potential barrier of grain boundaries.     

Electronic structure of BaTiO3 using resonant X-ray emission spectroscopy at the Ba-L3 and Ti-K absorption edges

We have studied the electronic properties of the ferroelectric barium titanate BaTiO₃ using two complementary bulk-sensitive spectroscopic probes, resonant X-ray emission spectroscopy (RXES) and X-ray absorption spectroscopy in the partial fluorescence mode (PFY-XAS) at the Ba-L₃ and Ti-K absorption edges. Contrary to a previous study, we found no fine structure in the pre-edge area of the PFY-XAS spectrum at the Ba-L₃ edge, and no temperature-induced spectral change was observed between room temperature and 150 °C. This result is not supportive of the possible presence of the displacement around Ba²⁺ at the Curie temperature. RXES spectra were measured at the Ti-K edge for BaTiO₃, along with SrTiO₃ and La-doped metallic SrTiO₃. The photon energy of the emission peak is found to be nearly constant throughout the absorption edge for all three compounds. We deduce the Ti 3d states to have a delocalized character, in contrast with the Ba 5d states, a property which is consistent with the proposed scenario of the formation of electric dipoles in BaTiO₃.     

Atomic force microscopy studies of twins in yttrium-doped barium titanate

Barium titanate is the main constituent of PTC materials and their electric properties are sensitive to microstructure and defects, in atomic scale, that are significantly affected by processing parameters. The microstructure of barium titanate doped with yttrium was investigated using topographic images obtained by AFM in contact mode. The AFM images of barium titanate doped with yttrium showed the effect of large grains with double twins at different (1 1 1) planes.     

Synthesis and characterisation of Gd-doped BaTiO3 thin films prepared by laser ablation for optoelectronic applications

The results of gadolinium (Gd)-doped barium titanate (BaTiO₃) thin films prepared by laser ablation on glass and silicon substrates are reported. Rutherford backscattering (RBS) analyses carried out on glass samples indicated the substitution of barium (Ba) by gadolinium (Gd) after annealing, leading to a film with composition Ba_0.76TiGd_0.01O_2.5. There is a reduction in the thickness from 2.21 to 2.02 microns for as-deposited and annealed films. The films on silicon showed a higher degree of crystallinity compared to that of glass substrates due to increased annealing temperature. The average grain size calculated using the X-ray diffraction (XRD) pattern from silicon substrates was 30 nm. The film has a tetragonal structure with a “c/a” ratio of 1.03 signifying that the incorporation of Gd in BaTiO₃ led to the elongation of the c-axis. The percentage transmittance reduced from 80 to 50% due to annealing and this is probably due to structural changes in the film. Swanepoel envelope method employed on the interference fringes of the transmittance pattern led to the determination of the variation of the refractive index with wavelength. Sellmier single oscillator model was applied to determine the optical constants of the films on glass substrates. Bandgap analyses carried out showed the reduction in bandgap with annealing and also the possibility that Gd incorporation has modified the film chemistry leading to the existence of direct (4.35 eV) and indirect (3.88 eV) allowed transitions in the annealed films. Dielectric property measurement carried out under ambient conditions gave a relaxation time τ of 1.6×10⁻⁴ s and conduction by small polaron with the onset of polaron conduction set at about 7 kHz. It is conjectured that these properties, especially the high refractive index and the high bandgaps, can make Gd-doped BaTiO₃ a good candidate for optoelectronic applications.     

A strong correlation of crystal structure and Curie point of barium titanate ceramics with Ba/Ti ratio of precursor composition

A series of barium titanate powders were synthesized from precursors BaCO₃ and TiO₂ with Ba/Ti ratio ranged from 0.96 to 1.04. For the ceramics sintered at 1300 °C for 2 h, with increasing Ba/Ti ratio from 0.96 to 1.04, the tetragonal distortion of perovskite barium titanate phase was decreased continuously and the Curie point was decreased monotonously from 122.9 to 98.0 °C. At the same time, the content of secondary phases was very low. This correlation of crystal structure and Curie point of barium titanate ceramics was explained by composition variation of the perovskite phase itself rather than by the influence from secondary phases. Due to very controversial results reported by different groups, it was proposed that BaTiO₃ has some different states with different solubilities for BaO and TiO₂. Further investigations should be conducted on the preparation and the properties of BaTiO₃ with much BaO or TiO₂ dissolved.     

高温无铅BaTiO_3-(Bi_(1/2)Na_(1/2))TiO_3正温度系数电阻陶瓷阻抗和介电谱分析

采用固相反应法制备了Y2O3施主掺杂的92 mol%BaTiO3-8 mol%(Bi1/2Na1/2)TiO3(BBNT8)高温无铅正温度系数电阻(positive temperature coe?cient resistivity,PTCR)陶瓷.利用透射电镜观察材料的显微结构,发现陶瓷的显微结构主要包括晶粒和晶界两部分,观察不到明显的壳层结构.进一步利用交流阻抗谱研究了陶瓷的宏观电学性能,发现陶瓷的总电阻是晶粒和晶界两部分的贡献,而晶粒电阻很小,在居里温度以上变化不大,材料的PTCR效应主要是晶界部分的贡献.当温度高于居里温度时,随着温度的升高,晶界介电常数逐渐减小,导致势垒增加,晶界电阻增大,从而产生正温度系数效应.最后,通过测试材料的介电频谱特性,研究计算了陶瓷的室温电阻率.     

The phase transitions and ferroelectric behavior of dense nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering

Dense nanocrystalline BaTiO₃ ceramics with uniform grain sizes of 30 nm was obtained by pressure assisted sintering. The phase transitions were investigated by Raman scattering at temperatures ranging from −190 to 200 °C. With increasing temperature, similar to 3 μm BaTiO₃ normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, tetragonal to cubic were also observed in 30 nm BaTiO₃ ceramics. Especially, the coexistence of ferroelectric tetragonal and orthorhombic phases was found at room temperature. The ferroelectric behavior was further characterized by P-E hysteresis loop. The experimental results indicate that the critical grain size of the disappearance of ferroelectricity in nanocrystalline BaTiO₃ ceramics fabricated by pressure assisted sintering is below 30 nm.     

Dielectric and leakage current properties of Li doped (Ba,Sr)TiO3 thick film interdigital capacitors on the alumina substrates

Li doped (Ba,Sr)TiO₃ thick films were fabricated by employing the screen printing method on the alumina (Al₂O₃) substrates. Interdigital capacitor patterns with seven fingers of 200 μm gap, 250 μm length were designed and screen printed on the alumina substrates. Ba_0.5Sr_0.5TiO₃ materials, paraelectric state at the room temperature, have been chosen for the microwave devices due to high dielectric permittivity and low loss tangent, however, the sintering temperature of (Ba,Sr)TiO₃ is over 1350 °C. In order to lower the sintering temperature, Li (3 wt%) was added to the (Ba,Sr)TiO₃ materials. Li doped (Ba,Sr)TiO₃ thick films screen printed on the alumina (Al₂O₃) substrates were sintered at 900 °C for 1.5 h. The structural feature was analyzed with X-ray diffraction method. Temperature dependent dielectric properties were characterized from 303 to 403 K at 1 MHz. Within the ±100 V of bias voltage, current-voltage characteristics of Li doped (Ba,Sr)TiO₃ films were investigated from 303 to 403 K. Through the current-voltage characteristics, the resistivity of Li doped (Ba,Sr)TiO₃ films were calculated.In this paper, the significant negative temperature coefficient of resistance (NTCR) of Li doped (Ba,Sr)TiO₃ films will be presented through the activation energy fitting. Measured activation energy is approximately 0.366 eV.     

NTCR behavior of Sm-substituted barium zirconium titanate nanocrystalline solid solution

Ceramic solid solution of nanocrystalline barium zirconium titanate in the form of Ba(Zr_0.52Ti_0.48)O₃ substituted by samarium (Sm³⁺) was prepared using the conventional solid state reaction method. The phase assemblage analyzed by the X-ray diffraction technique was fitted for cubic-crystal-symmetry. The change in the grain size depicted the influence of Sm³⁺ ions on the microstructure. The electrical behavior was studied in the temperature range from 323 to 773 K. The sintered samples exhibited a negative temperature coefficient of resistance (NTCR) and superior semiconducting behavior above 513 K. Addition of Sm³⁺ increased the room temperature resistivity of Ba(Zr_0.52Ti_0.48)O₃ solid solution. The results obtained from the thermoelectric power measurement confirm electrons as the majority charge carriers.     

The room-temperature ferromagnetism of defect-rich ZnMgO semiconductor thin films

The positive temperature coefficient of resistance (PTCR) characteristics of Na₂Ti₆O₁₃ (NT)-doped 0.94BaTiO₃–0.06(Bi_0.5Na_0.5)TiO₃ (BBNT) ceramics were investigated in order to evaluate the effect of NT as a new additive for lead-free PTCR thermistor application. The BBNT ceramic sintered at 1325°C exhibited a relatively high Curie temperature (T _C ) of 158°C while its PTCR characteristic was not satisfactory for thermistor application. However, doping with NT significantly influenced the PTCR behavior of BBNT ceramic. It is considered that NT was responsible for grain growth of the BBNT by forming a liquid phase during sintering due to its low melting temperature of 1300°C. The grain growth resulted in the enhanced PTCR characteristics of BBNT ceramic. In particular, 0.1 mol% NT doped BBNT ceramic exhibited excellent PTCR performance of low resistivity at room temperature (1.6×10² Ω cm), resistivity increase near T _C (1.28×10⁴) and high T _C of 158°C, suitable for lead-free PTCR thermistor application.     

The Electronic Structure of Pristine and Doped (100) Tilt Grain Boundaries in SrTiO3

To understand the electronic properties of doped grain boundaries, we reviewed the atomic scale techniques currently available to study the electronic structure at pristine SrTiO₃ grain boundaries. The knowledge gained from the pristine boundaries is used to interpret experimental and theoretical results from a Mn doped 5 SrTiO₃ grain boundaries. Mn atoms are shown to preferentially substitute at specific Ti sites at the grain boundary core. Furthermore, the formal oxidation state of the Mn atoms at the grain boundary core was found to be reduced compared to the Mn atoms substituting for Ti in the bulk. This change of valence did not, however, significantly affect the atomic structure of the grain boundary, as determined by Z-contrast imaging and electron energy-loss spectroscopy, which revealed similar fine-structure features at both the doped and pristine grain boundary. We conclude, therefore, that composition and atomic structure have different effects on the local electronic structure and should be treated separately in any segregation and electrical conductivity models for grain boundaries.     

Improved properties & fatigue resistant behaviour OF Ba(Zr0.15Ti0.85)O3 ferroelectric ceramics

The microstructure, dielectric and piezoelectric properties of Zr doped BaTiO₃ ceramics sintered at optimum temperature, are investigated. High energy ball milling technique is adopted to realize nano-sized powders of Ba(Zr_0.15Ti_0.85)O₃ ceramics. Increased boundary mobility of fine powders aided to obtain a relative density of >98.8% of theoretical density corresponding to ceramics under study. Internal stresses in these ceramics are found to be relieved by grain-boundary sliding. The Ba(Zr_0.15Ti_0.85)O₃ ceramics synthesized at relatively low sintering temperatures exhibit remarkable, enhanced dielectric properties viz. improved polarization, high unipolar strain values comparable to Zr doped BaTiO₃ single crystals of same composition, at relatively lower electric fields and also exhibit better fatigue tolerant properties. The underlying mechanisms responsible for superior dielectric, ferroelectric and piezoelectric properties are discussed.     

Dielectric properties and ac-conductivity analysis of Bi3.25La0.75Ti3O12 ceramic using impedance spectroscopy

Investigations have been performed on lanthanum-modified layered ferroelectric bismuth titanate for composition Bi_3.25La_0.75Ti₃O₁₂ (BLT) using impedance spectroscopy to understand the role of microstructure on the dielectric properties of this important material. A wide range of frequency and a wide range of temperature passing through the Curie point were chosen for the measurement. The frequency dependence suggested an interfacial polarization controlled Maxwell–Wagner type relaxation at low frequencies, and the impedance spectrum correlated with the mathematical fitting indicated the presence of two types of interfaces, which were attributed to the metallurgical boundaries and the twinned planes parallel to the bismuth oxide layers inherent to the crystal structure within the metallurgical grains. A careful analysis of the dielectric properties, particularly the ac-conductivity analysis revealed that the grain boundaries did also follow their own Jonscher-like relaxation, and the overall relaxation of the sample changed to a purely grain boundary-limited response at low frequency to a pure grain-limited response at higher frequencies. And overall admittance of the ceramic sample neither follow unmodified nor modified Jonscher's law rather its behaviour can be well described by series addition of Jonscher's admittance corresponding to grain boundary and grain. It was demonstrated that the frequency response of the ac conductivity was related to the microstructure exactly in the same way as any other dielectric function, like the impedance or dielectric constant, a fact, which is not much emphasized in the open literature.     

Structure-related infrared optical properties of BaTiO3 thin films grown on Pt/Ti/SiO2/Si substrates

BaTiO₃ thin films with different thickness have been grown on Pt/Ti/SiO₂/Si substrates by a modified sol-gel method. X-ray diffraction analyses show that the BaTiO₃ thin films are polycrystalline. The crystalline quality of the films is improved with increasing thickness. The infrared optical properties of the BaTiO₃ thin films have been investigated using an infrared spectroscopic ellipsometry in the wave number range of 800-4000 cm⁻¹ (2.5-12.5 μm). By fitting the measured pseudodielectric functions with a three-phase model (Air/BaTiO₃/Pt), and a derived classical dispersion relation for the thin films, the optical constants and thicknesses of the thin films have been simultaneously obtained. The refractive index of the BaTiO₃ thin films increases and on the other hand, the extinction coefficient does not change with increasing thickness in the entirely measured wave number range. The dependence of the refractive index on the film thickness has been discussed in detail and was mainly due to both the crystalline quality of the films and packing density. Finally, the absorption coefficient was calculated in the infrared region for applications in the pyroelectric IR detectors.     

Electronic conductivity and chemical diffusion in n-conducting barium titanate ceramics at high temperatures

The electronic conductivity as well as the chemical diffusion coefficient of barium titanate ceramics doped with Y and Mn (donor-doped and acceptor co-doped) have been determined by application of conductivity relaxation experiments. The equilibrium values of the electronic conductivity of n-conducting BaTiO₃ have been analyzed by application of a defect chemical model involving electrons and cation vacancies as the predominant defect species at oxidizing conditions (fairly high oxygen partial pressures). The relaxation curves of the electronic conductivity yield the chemical diffusion coefficient of the bulk by employing a spherical grain model where the appropriate diffusion length is the radius of grains (average grain size). The conductivity relaxation experiments have been performed as a function of temperature ranging from 1100 to 1250 °C at oxygen partial pressures between 0.01 and 1 bar. The kinetics of the oxygen exchange process can be interpreted in terms of extremely fast diffusion of oxygen via oxygen vacancies along the grain boundaries and slow diffusion of Ti (cation)-vacancies from the grain boundaries into the grains. The Ti-vacancy diffusion coefficients were extracted from the chemical diffusion coefficients as a function of temperature. Typical values for the Ti-vacancy diffusivity are around 10^− 15 cm² s^− 1 with an activation energy of 3.9 ± 0.7 eV.     

Effective diffusivity of solute in multiphase materials with segregation

The effective diffusion coefficient D_eff for solute in a multiphase microstructure in which solute segregation can occur is related to D_eff for an isomorphic microstructure in which no segregation occurs. This permits analytical expressions (approximations, bounds, etc.) and methods of numerical calculation for D_eff that neglect solute segregation to be applied to systems that exhibit segregation. As an example, exact results are obtained for solute diffusion and segregation to grain boundaries in an idealized polycrystalline microstructure.     

Electrical conductivity of Sb-doped BaTiO3

Electrical conductivity of undoped and Sb-doped BaTiO₃ are measured under P_O2 between 2×10^-14 and 10⁵ Pa in the temperature range 1123–1273 K. Both powers of the oxygen pressure dependence and activation energies of electrical conductivity are determined. It has been concluded that the mechanism of Sb incorporation into BaTiO₃ depends on composition. At lower concentrations (below 0.15 mo1% Sb₂O₅) Sb incorporates into both Ba and Ti sublattices froming donor centers. Above this concentration Sb incorporates preferentially into Ti sites forming acceptor centers.     

Low temperature thermoelectric properties of Pb- or Sn-doped Bi-Sb alloys

Pb- or Sn-doped Bi₈₈Sb₁₂ alloys were prepared by direct melting, quenching, and annealing. The Bi-Sb alloy phase was predominant in all samples. Pb or Sn atoms were distributed almost uniformly in Bi₈₈Sb_12, while some segregation was confirmed at the grain boundaries when Pb or Sn was involved heavily. The thermoelectric properties of these doped materials were investigated by measuring the Hall coefficient, electrical resistivity, and Seebeck coefficient between 20 K and 300 K. The Hall and Seebeck coefficients of Pb- or Sn-doped samples were positive at low temperatures, indicating that the doping element acted as an acceptor. Temperatures resulting in positive Hall and Seebeck coefficients further increased with increasing doping amount and with respect to the annealing process. As a result, a large power factor of 1.2 W/mK² could be obtained in the 3-at% Sn-doped sample at 220 K, with a large positive Seebeck coefficient.     

The effect of Zr content on electrical properties of Ba(Ti<Subscript>1-x</Subscript>Zr<Subscript>x</Subscript>)O<Subscript>3</Subscript> ceramics

The effect of Zr content on the crystal structure and electrical properties of barium zirconate titanate (Ba(Zr,Ti)O₃) was studied by X-ray diffraction and dielectric, ferroelectric and impedance spectroscopy. An increase of Zr content into BaTiO₃ leads to a reduction in its c-parameter and an increase in its a-parameter, resulting in a change from tetragonal to cubic symmetry of the BaTiO₃ unit cell. The Curie temperatures are lowered and the relative permittivity values are decreased with increasing Zr content. The presence of BaZrO₃ secondary phases has the affect of decreasing tanδ. A higher applied electric field is required during the polarization process because of the effect of domain-wall pinning caused by oxygen vacancies. Impedance spectroscopy studies of Ba(Ti_0.95Zr_0.05)O₃ ceramics show a decrease in the bulk resistance with increasing temperature, indicating a typical negative temperature coefficient of resistance. PACS 74.62.Bf; 74.62.Yb; 77.22.Ch; 77.80.Bh; 77.84.Dy     

Structural characterization of dense reduced BaTiO3 and Ba0.95La0.05TiO3 nanoceramics showing colossal dielectric values

BaTiO_3−x and Ba_0.95La_0.05TiO_3−x nanoceramics showing colossal permittivity values have been characterized. While starting powders are of cubic symmetry, X-ray and Neutron Diffraction techniques and Raman Spectroscopy measurements show that the one-step processed ceramics obtained by Spark Plasma Sintering (SPS) contain cubic and tetragonal phases. Rather large oxygen deficiency determined in such ceramics by Electron Micro Probe analysis and Electron Energy Loss Spectroscopy analyzes is explained by the presence of Ti³⁺, as evidenced by X-ray Photoelectron Spectroscopy measurements. Transmission Electron Microscopy and High Resolution Transmission Electron Microscopy show that these ceramics contain 50-300 nm grains, which have single-domains, while grain boundaries are of nanometer scale. Colossal permittivity values measured in our dense nanoceramics are explained by a charge hopping mechanism and an interfacial polarization of a large number of polarons generated after sample reduction in SPS apparatus.