Structural and electrical properties of Na1/2La1/2TiO3 ceramics

Na_1/2La_1/2TiO₃ (NLT) ceramic was prepared by a high-temperature solid-state reaction technique. A preliminary structural analysis (XRD) suggested the formation of a single-phase orthorhombic structure. SEM micrograph of the material showed uniform grain distribution on the surface of the sample. The dielectric permittivity and the loss tangent of the sample were measured in a frequency range from 1 kHz to 1 MHz and a temperature range 28 °C to 525 °C. Electrical properties of the material were studied using an ac impedance spectroscopic technique. Detailed analysis of the impedance spectrum suggested that the electrical properties of the material are strongly temperature dependant. The Nyquist plots clearly showed the presence of both bulk and grain boundary effect in the compound. The activation energy was estimated to be 1.1 eV from the temperature variation of dc conductivity. The a.c. conductivity spectrum suggests a typical signature of ion conducting system. PACS 77.22.Ch; 77.22.Gm; 77.80.Bh; 77.22.Ej     

Studies on structural and dielectric properties of Na1/2Dy1/2TiO3 ceramic

The polycrystalline sample of Na_1/2Dy_1/2TiO₃ ceramic was prepared by a standard high-temperature solid-state reaction technique. X-ray structural analysis confirmed the formation of single-phase (with minor secondary phase) compound in the orthorhombic (distorted tetragonal) crystal system at room temperature. Study of surface morphology by scanning electron microscope exhibits uniform distribution of rectangular/cubical grains with less voids. The elemental composition of the prepared compound was confirmed by energy dispersive X-ray spectroscopy microanalysis. Detailed studies of dielectric properties exhibit a dielectric anomaly at 94 °C suggesting a possible ferroelectric–paraelectric phase transition in the compound. The activation energy (E_a), calculated from the temperature dependence of ac conductivity plot, was found to be small (∼0.1 eV) in low temperature and large (∼0.5 eV) in high temperature region.     

Electromechanical and ferroelectric properties of (Bi1/2Na1/2)TiO3-(Bi1/2K1/2)TiO3- (Bi1/2Li1/2)TiO3-BaTiO3 lead-free piezoelectric ceramics for accelerometer application

Lead-free (0.90-x)(Bi_1/2Na_1/2)TiO₃-0.05(Bi_1/2K_1/2)TiO₃-x(Bi_1/2Li_1/2)TiO₃-0.05BaTiO₃ piezoelectric ceramics (abbreviated as BNKLBT-100x, with x ranged from 0 to 2.5 mol %) were prepared by a conventional mixed oxide method. Effects of the amount of (Bi_1/2Li_1/2)TiO₃ (BLT) on the electrical properties and crystal structure of the BNKLBT ceramics were examined. BNKLBT-1.5 ceramics have good properties with piezoelectric constant d₃₃=163 pC/N, electromechanical coupling factor k_p=0.33, k_t=0.53, relative permittivity ε_r=785 and dissipation factor cosδ=2.2% at 1 kHz. The sample has larger remnant polarization than BNKLBT-0 ceramics and the same coercive field as BNKLBT-0 ceramics. X-ray diffraction analysis shows that the incorporated BLT diffuses into the BNT–BKT–BT lattice to form a solid solution during sintering, but changes the crystal structure from rhombohedral to tetragonal symmetry at higher BLT amounts. Depolarization temperature (T_d) of the BNKLBT-100x ceramics increases from 102 °C to ∼136 °C for BNKLBT-0 to BNKLBT-2.5. BNKLBT-1.5 is used as the transduction element in compressive type accelerometer and its sensitivity is calibrated by the back-to back method. Within the ±2.5% tolerance, the lead-free accelerometer has a mean value of 2.97 pC/ms^-2 within 50 Hz–12.45 kHz and the lead-based accelerometer has a mean value of 4.34 pC/ms^-2 within 50 Hz to 8.24 kHz. PACS 77.22.Ej; 77.84.-s; 85.50.-n     

Acoustic anomalies and relaxation dynamics of relaxor ferroelectric Na1/2Bi1/2TiO3 single crystals studied by using Brillouin spectroscopy

Acoustic anomalies of relaxor ferroelectric Na_1/2Bi_1/2TiO₃ single crystals were investigated over a wide temperature range from −196 °C to 900 °C by using Brillouin spectroscopy. The longitudinal sound velocity, the acoustic absorption coefficient and the elastic constant C₁₁ were determined for the acoustic phonon mode propagating in the [100] direction. Two acoustic anomalies, weaker ones at the cubic-tetragonal phase transition temperature of ~540 °C and more pronounced ones at temperatures near 315 °C near the dielectric maximum temperature, were investigated and discussed in relation with the relevant order parameters coupled to the acoustic waves. The relaxation dynamics in the cubic phase were studied based on the flattening of the mode frequency and the half width, which was observed for the first time, and a modified Arrhenius law.     

Impedance spectroscopy study of Na<Subscript>1/2</Subscript>Sm<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript> ceramic

Complex impedance analysis of a valence-compensated perovskite ceramic oxide Na_1/2Sm_1/2TiO₃, prepared by a mixed oxide (solid-state reaction) method, has been carried out. The formation of single-phase material was confirmed by X-ray diffraction studies, and it was found to be an orthorhombic phase at room temperature. In a scanning electron microscope, grains separated by well-defined boundaries are visible, which is in good agreement with that of impedance analysis. Alternating current impedance measurements were made over a wide temperature range (31–400 °C) in an air atmosphere. Complex impedance and modulus plots helped to separate out the contributions of grain and grain boundaries to the overall polarization or electrical behavior. The physical structure of the samples was visualized most prominently at higher temperatures (275 °C) from the Nyquist plots showing inter- and intragranular impedance present in the material. The frequency dependence of electrical data is also analyzed in the framework of the conductivity and modulus formalisms. The bulk resistance, evaluated from the impedance spectrum, was observed to decrease with rise in temperature, showing a typical negative temperature coefficient of resistance-type behavior like that of semiconductors. The modulus mechanism indicates the non-Debye type of conductivity relaxation in the materials, which is supported by the impedance data. PACS 77.22.Ch; 77.22.Ej; 77.22.Gm; 77.22.Jp; 77.84.Bw     

Preparation and characterisation of compositionally graded BaxSr1-xTiO3 thin films

Ba_xSr_1-xTiO₃ thin films with a compositional gradient of x=0.3 to 1 (in 0.1 mole fraction increments) were fabricated on Pt/Ti/SiO₂/Si substrates using a modified sol–gel technique. The graded film crystallised in a perovskite structure and consists of a uniform microstructure with comparatively larger grains. The room-temperature relative dielectric constant (ε_r) and dielectric loss (cosδ) at 100 kHz were found to be 305 and 0.03 respectively. Dielectric peaks were not observed in the temperature range from -20 °C to 120 °C. The dielectric constant and dielectric loss were almost independent of temperature. Polarisation–electric field measurements at room temperature revealed a saturated but slim hysteresis loop with a remanent polarisation (P_r) of 0.6 μC/cm² and a coercive field (E_c) of 2.4 kV/mm. The graded film behaves as a stack of Ba_xSr_1-xTiO₃ capacitors connected in series and hence the dielectric Curie peaks are removed. Received: 4 October 2001 / Accepted: 17 October 2001 / Published online: 23 January 2002     

Grain size effect on the giant dielectric and nonlinear electrical behaviors of Bi1/2Na1/2Cu3Ti4O12 ceramics

Single phase Bi_1/2Na_1/2Cu₃Ti₄O₁₂ (BNCTO) ceramics with different grain sizes (1.4–4.3 μm) are prepared by a modified Pechini method to investigate their giant dielectric and nonlinear electrical behaviors. The results show that the giant dielectric and nonlinear electrical behaviors are strongly dependent on grain size. With the increment of grain size, the dielectric constant increases monotonically from 14110 (for 1.4 μm sample) to 36183 (for 4.3 μm sample) at 1 kHz, in accompaniment with the breakdown voltage reducing from 112.5 to 43.2 V/mm and the nonlinear coefficient reducing from 4.9 to 3.4. On the basis of the internal barrier layer capacitor (IBLC) model and the IBLC model of Schottky-type potential barrier, an interpretation of the grain size effect on the giant dielectric and nonlinear electrical behaviors is presented.     

Space-charge relaxation and electrical conduction in?K0.5Na0.5NbO3 at high temperatures

Sodium potassium niobate K_0.5Na_0.5NbO₃(KNN) ceramic was synthesized by a solid-state technique. The X-ray diffraction of the sample at room temperature showed a monoclinic phase. The real part (ε′) and imaginary part (ε″) of dielectric permittivity of the sample were measured in a frequency range from 40 Hz to 1 MHz and in a temperature range from 350 to 850 K. The ε′ deviated from Curie–Weiss law above 702 K, due to additional dielectric contributions resulting from universal dielectric response and thermally activated space charges at high temperatures. This anomaly arose from a Debye dielectric dispersion that slowed down following an Arrhenius law. We have established a link between the dielectric relaxation and the conductivity.     

0.90(Bi1/2Na1/2)TiO3–0.05(Bi1/2K1/2)TiO3– 0.05BaTiO3 transducer for ultrasonic wirebonding applications

Lead-free piezoelectric ceramic 0.90(Bi_1/2Na_1/2)TiO₃–0.05(Bi_1/2K_1/2)TiO₃–0.05BaTiO₃ (BNKBT-5) rings (OD=12.7 mm, ID=5.1 mm and 2.3-mm thick) were fabricated and characterized. Four ceramic rings were used as the driving element in an ultrasonic wirebonding transducer and the performance of the transducer was characterized. The lead-free transducer was found to have comparable voltage rise and fall times as a lead-based PZT transducer and has a relatively large vibration amplitude, thus showing that BNKBT-5 has the potential to be used in fabricating lead-free ultrasonic wirebonding transducers. PACS 77.22.Ej; 77.84.-s; 85.50.-n     

Orientation dependence of electrical properties of 0.96Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-0.04BaTiO<Subscript>3</Subscript> lead-free piezoelectric single crystal

In this paper, a single crystal of 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ with dimensions of Φ 30×10 mm was grown by the top-seeded-solution growth method. X-ray powder diffraction results show that the as-grown crystal possesses the rhombohedral perovskite-type structure. The dielectric, piezoelectric and electrical conductivity properties were systematically investigated with 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples. The room-temperature dielectric constants for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal samples are found to be 650, 740 and 400 at 1 kHz. The (T _m, ε _m) values of the dielectric temperature spectra are almost independent of the crystal orientations; they are (306°C, 3718), (305°C, 3613) and (307°C, 3600) at 1 kHz for the 〈001〉, 〈110〉 and 〈111〉 oriented crystal. The optimum poling conditions were obtained by investigating the piezoelectric constants d ₃₃ as a function of poling temperature and poling electric field. For the 〈001〉 and 〈110〉 crystal samples, the maximum d ₃₃ values of 146 and 117 pC/N are obtained when a poling electric field of 3.5 kV/mm and a poling temperature of 80°C were applied during the poling process. The as-grown 0.96Na_0.5Bi_0.5TiO₃-0.04BaTiO₃ crystal possesses a relatively large dc electrical conductivity, especially at higher temperature, having a value of 1.98×10⁻¹¹ Ω⁻¹⋅m⁻¹ and 3.95×10⁻⁹ Ω⁻¹⋅m⁻¹ at 25°C and 150°C for the 〈001〉 oriented crystal sample.     

Preparation of TiO<Subscript>2</Subscript>-coated LiCo<Subscript>1/3</Subscript>Ni<Subscript>1/3</Subscript>Mn<Subscript>1/3</Subscript>O<Subscript>2</Subscript> by electrostatic self-assembly method and its properties

A precursor of TiO₂–LiCo_1/3Ni_1/3Mn_1/3O₂ was prepared by electrostatic self-assembly method. The final product was obtained by heating the precursor at 400–450 °C for 4–6 h in air. X-ray diffraction (XRD), scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS), and electrochemical tests were used to examine the structural, morphology, elementary valence, and electrochemical characteristics. XRD indicated that the TiO₂-coated material can be indexed by α-NaFeO₂ layered structure, which belongs to hexagonal-type space group R3m. XPS results confirmed the existence of TiO₂ compound on the surface of the coated sample. The SEM image showed that the material had spherically porous morphology with the uniform size about 6 μm. The initial charge–discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ material was 168.8/160.0 mAh/g. After 60 cycles, the discharge capacity of the TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ sample was 147.0 mAh/g, and the coulombic efficiency was 94.0%. Compared with the uncoated sample, the electrochemical performance of TiO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ was improved.     

Ac-conductivity and dielectric relaxations above glass transition temperature for parylene-C thin films

45% semi-crystalline parylene-C (–H₂C–C₆H₃Cl–CH₂–) _n thin films (5.8 μm) polymers have been investigated by broadband dielectric spectroscopy for temperatures above the glass transition (T _g =90°C). Good insulating properties of parylene-C were obtained until operating temperatures as high as 200°C. Thus, low-frequency conductivities from 10⁻¹⁵ to 10⁻¹² S/cm were obtained for temperatures varying from 90 to 185°C, respectively. This conductivity is at the origin of a significant increase in the dielectric constant at low frequency and at high temperature. As a consequence, Maxwell–Wagner–Sillars (MWS) polarization at the amorphous/crystalline interfaces is put in evidence with activation energy of 1.5 eV. Coupled TGA (Thermogravimetric analysis) and DTA (differential thermal analysis) revealed that the material is stable up to 400°C. This is particularly interesting to integrate this material for new applications as organic field effect transistors (OFETs). Electric conductivity measured at temperatures up to 200°C obeys to the well-known Jonscher law. The plateau observed in the low frequency part of this conductivity is temperature-dependent and follows Arrhenius behavior with activation energy of 0.97 eV (deep traps).     

Structure and electrical behavior in air of TiO2-doped stabilized tetragonal zirconia ceramics

2 -doped YTZP ([%mol]3 Y₂O₃) compositions sintered in the temperature range of 1300 to 1450 °C, the tetragonal zirconia solid solutions field for the ZrO₂-Y₂O₃-TiO₂ system was established. The solubility of TiO₂ in YTZP was found to be about 12–[%mol]14 at 1450 °C. Structural characterization of the Ti-YTZP tetragonal zirconia solid solutions was carried out using X-ray absorption spectroscopy (EXAFS and XANES) to provide information on the environment of Ti atoms. The electrical behavior in air of the TiO₂-doped tetragonal zirconia solid solutions was studied by impedance spectroscopy in the temperature range of 300 to 800 °C, and it was found that the ionic conductivity decreases with increasing titania content. EXAFS and XANES results show that as the Ti⁴⁺ ions dissolve into the tetragonal zirconia YTZP matrix, a displacement of Ti ions from the center of symmetry takes place, leading to a non-random substitution of Ti⁴⁺ ions on Zr⁴⁺ lattice sites. Ti-O bond distances derived from EXAFS indicate that the Ti ion can be in a square-pyramidal arrangement, i.e., fivefold oxygen-coordinated. As a consequence two kinds of cation–oxygen vacancy associations are created; the high-mobility oxygen-vacancy–eightfold-coordinated cation (Zr⁴⁺) and the low-mobility oxygen-vacancy–fivefold-coordinated cation (Ti⁴⁺). This results in a decrease in the global concentration of moving oxygen vacancies and, therefore, in a decrease of the electrical conductivity. Received: 1 April 1998/Accepted: 28 September 1998     

Dielectric relaxation in complex perovskite oxide BaCo1/2W1/2O3

Polycrystalline BaCo_1/2W_1/2O₃ (BCW) is prepared by the solid-state reaction technique. The X-ray diffraction study of the compound at room temperature reveals the monoclinic phase. The field dependence of the dielectric constant and the conductivity are measured in the frequency range from 50 Hz to1 MHz and in the temperature range from 300 to 413 K. An analysis of the real and imaginary parts of the dielectric permittivity with frequency is performed. The frequency-dependent maxima in the imaginary impedance are found to obey an Arrhenius law with an activation energy=0.86 eV. The frequency-dependent electrical data are also analysed in the framework of the conductivity and modulus formalisms.     

Dielectric properties of BiMg1/2Ti1/2O3 and BiMg1/2Zr1/2O3 perovskite ceramics with elimination of the contribution for direct current conductivity

A technique for analysis of the electric modulus spectrum of dielectric ceramics based on the elimination of the direct current conductivity (σ _dc ) contribution has been developed. Expressions are given for the real (M′ _ac ) and imaginary (M′′ _ac ) parts of the complex electrical modulus related only to the dielectric polarization and not containing the contribution of σ _dc . The frequency dependence of M′′ _ac and the M′′ _ac – M′ _ac diagram for BiMg_1/2Ti_1/2O₃ and BiMg_1/2Zr_1/2O₃ perovskite ceramics are analyzed.     

Structural and electrical properties of KCa<Subscript>2</Subscript>Nb<Subscript>5</Subscript>O<Subscript>15</Subscript> ceramics

A polycrystalline sample of KCa₂Nb₅O₁₅ with tungsten bronze structure was prepared by a mixed oxide method at high temperature. A preliminary structural analysis of the compound showed an orthorhombic crystal structure at room temperature. Surface morphology of the compound shows a uniform grain distribution throughout the surface of the sample. Studies of temperature variation on dielectric response at various frequencies show that the compound has a transition temperature well above the room temperature (i.e., 105°C), which was confirmed by the polarization measurement. Electrical properties of the material have been studied using a complex impedance spectroscopy (CIS) technique in a wide temperature (31–500°C) and frequency (10²–10⁶ Hz) range that showed only bulk contribution and non-Debye type relaxation processes in the material. The activation energy of the compound (calculated from both the loss and modulus spectrum) is same, and hence the relaxation process may be attributed to the same type of charge carriers. A possible ‘hopping’ mechanism for electrical transport processes in the system is evident from the modulus analysis. A plot of dc conductivity (bulk) with temperature variation demonstrates that the compound exhibits Arrhenius type of electrical conductivity.      

Microwave dielectric properties of the 5.5Li<Subscript>2</Subscript>O–Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–7TiO<Subscript>2</Subscript> ceramics

A new Li₂O–Nb₂O₅–TiO₂ (LNT) ceramic with the Li₂O:Nb₂O₅:TiO₂ mole ratio of 5.5:1:7 was prepared by solid state reaction route. The phase and structure of the ceramic were characterized by X-ray diffraction and scanning electron microscopy (SEM). The microwave dielectric properties of the ceramics were studied using a network analyzer. The microwave dielectric ceramic has low sintering temperature (∼1075°C) and good microwave dielectric properties of ε _r=42, Q×f=16900 GHz (5.75 GHz), and τ _f =63.7 ppm/°C. The addition of B₂O₃ can effectively lower the sintering temperature from 1075 to 875°C and does not induce degradation of the microwave dielectric properties. Obviously, the LNT ceramics can be applied to microwave low temperature-cofired ceramics (LTCC) devices.     

H2/Pt/Ce0.9Gd0.1O1.95/Pt/O2 fuel cell operated in the intermediate temperature range 500 – 700°C

Ce_0.9Gd_0.1O_1.95 (GCO), is one of the potential candidate electrolytes for intermediate temperature Solid Oxide Fuel Cells (ITSOFC). GCO has high oxide ion conductivity in the intermediate temperature range (500 – 700 °C) compared to other Ce_1−yGd_yO_2-2/y compositions and the Gd³⁺ ion is the most appropriate dopant material compared to other rare earth materials such as Sm³⁺, Y³⁺, Zr³⁺, etc. Our results show that the fuel cell H₂/Pt/Ce_0.9Gd_0.1O_1.95/Pt/O₂ operated in the temperature range 500 – 700°C gives the maximum power densities 0.0049 W/cm² at 500 °C and 0.0126 W/cm² at 650 °C for cell voltages 0.6275 V and 0.6278 V, respectively, where the electrolyte was kept in 5% H₂ (+ Argon) for 12 hours before use in the fuel cell. Maximum power densities are 0.0038 W/cm² at 500 °C and 0.0270 W/cm² at 650 °C for cell voltages 0.5986 and 0.5913 V, respectively, where the electrolyte was kept in 2 % O₂ (+ Argon) for 12 hours before use in the fuel cell. Paper presented at the 2nd International Conference on Ionic Devices, Anna University, Chennai, India, Nov. 28–30, 2003.     

Effect of excess Bi2O3 on the electrical properties and microstructure of (Bi1/2Na1/2)TiO3 ceramics

(Bi_1/2Na_1/2)TiO₃ ceramics (BNT) with 0–6 mol% of excess Bi₂O₃ are prepared by conventional solid-state sintering. The electrical properties of the samples are examined. The addition of excess Bi₂O₃ reduces the leakage current of BNT ceramics significantly, thus facilitating the poling process, and improves their piezoelectric properties slightly for certain amounts of added Bi₂O₃. BNT ceramics have very high dielectric constants and dissipation factors at low frequency and high temperature due to their high conductivity. Adding excess Bi₂O₃ to BNT ceramics affects their dielectric behavior and phase transition temperatures. Grain growth is suppressed by adding Bi₂O₃ and no second phase is observed for BNT ceramics with up to 6 mol% of excess Bi₂O₃ added.     

Dielectric property of CaCu3Ti4O12 thin film grown on Nb-doped SrTiO3(100) single crystal

Thin film of CaCu₃Ti₄O₁₂ (CCTO) has been deposited on Nb-doped SrTiO₃(100) single crystal using pulsed laser deposition. The dielectric constant and AC conductivity of CCTO film in the metal–insulator–metal capacitor configuration over a wide temperature (80 to 500 K) and frequency (100 Hz to 1 MHz) range have been measured. The small dielectric dispersion with frequency observed in the lower temperature region (<300 K) indicates the presence of small defects in the deposited CCTO thin film. The frequency-dependent AC conductivity at lower temperature indicates the hopping conduction. The dielectric dispersion data has been analyzed in the light of both conductivity relaxation and Debye type relaxation with a distribution of relaxation times. Origin of dielectric dispersion is attributed to the distribution of barrier heights such that some charge carriers are confined between long-range potential wells associated with defects and give rise to dipolar polarization, while those carriers which do not encounter long-range potential well give rise to DC conductivity.