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.     

23Na NMR in the relaxor ferroelectric Na1/2Bi1/2TiO3

The ²³Na NMR spectra of a Na_1/2Bi_1/2TiO₃ crystal are studied at frequencies of 79.4 and 15.7 MHz in the temperature range 150–720 K. It is revealed that, at all temperatures, the crystal contains regions with a nearly cubic matrix and polar clusters. The temperature dependence of the local distortion of the Na environment in the clusters is determined. The dynamics of the reorientation of the local cluster polarization in the tetragonal and trigonal NBT phases is analyzed.     

Luminescence properties of K1/2Bi1/2TiO3:Pr3+ and Na1/2Bi1/2TiO3:Pr3+

The luminescence properties of K(1/2)Bi(1/2)TiO(3):Pr(3+) and Na(1/2)Bi(1/2)TiO(3):Pr(3+) powders are investigated in the temperature range 10-600 K. The experimental data are interpreted on the basis of metal-to-metal charge transfer processes and by considering Bi(3+)-to-Pr(3+) sensitization effects.     

Na1/2 Bi1/2 TiO3体系的电子结构与极化特性

采用自洽场离散变分X_α计算方法,研究了ABO₃型钙钛矿结构无铅压电陶瓷Na_1/2Bi_1/2TiO₃体系的电子结构,分析了A,B位元素取代对Na_1/2Bi_1/2TiO₃压电陶瓷极化性能的影响.结果表明:NBT体系压电陶瓷材料存在自发极化,B位离子位移使铁电性增强,Ba,Sr与Mn离子A,B位复合取代可降低矫顽场、提高自发极化强度,从而提高材料的铁电性能,并通过实验对此结论进行了验证.     

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.     

Structural and dielectric studies of lead-free ceramics: Na1/2Y1/2TiO3

The polycrystalline samples of Na_1/2Y_1/2TiO₃ were prepared by the mixed-oxide method. A preliminary X-ray structural analysis was shown to exhibit the formation of a single-phase compound with an orthorhombic structure. Microstructural analysis by scanning electron microscopy (SEM) exhibits well defined grains distributed uniformly through out the sample suggesting the compactness and homogeneity of the sample. Detailed studies of dielectric properties of Na_1/2Y_1/2TiO₃ in a wide frequency range (102–106 Hz) at different temperatures (31–500°C) show a dielectric anomaly at 105°C, which may be related to a ferroelectricparaelectric phase transition as suggested by hysteresis loop at room temperature. An ac conductivity (σ _ac) of the material is mainly governed by the polaron hopping mechanism, which is also influenced by both frequency and temperature. The activation energy was obtained from the plot of temperature with a.c. 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     

Study of phase transformation dynamics in Na1/2Bi1/2TiO3 by Mandelstam-Brillouin scattering

The results of the study of Mandelstam-Brillouin light scattering in single-crystal Na_1/2Bi_1/2TiO₃ within a broad temperature interval covering successively the cubic, tetragonal, and rhombohedral phases are reported. Measurements conducted within the range 820–300 K have revealed quasi-elastic scattering and distortion of the phonon spectra in shape, which suggests possible coupling between the low-frequency transverse optical and acoustic modes. These two observed phenomena are believed to be closely interrelated.     

Ferroelectric (Na1/2Bi1/2)TiO3 thin films showing photoluminescence properties

Polycrystalline lead-free (Na_1/2Bi_1/2)TiO₃ (NBT) ferroelectric thin films doped with 1 mol% of rare earth (RE) elements are processed on Pt-terminated silicon substrates using a solution deposition method. The thin films that exhibit single-phase perovskite structure show photoluminescence properties with highest intensities in the wavelength range between 700 and 850 nm, depending on RE element. The ferroelectric properties of the pure NBT film (P _r: 20.5 µC cm^?2, E _c: 150 kV cm^?1) are somewhat decreased for the doped films, which is ascribed to decreasing of the number of Bi lone pairs through the substitution of Bi with RE elements in the perovskite lattice.     

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 and structural relaxation phenomena in Na0.5Bi0.5TiO3 single crystal

Abstract

Dielectric permittivity studies of Na_0.5Bi_0.5TiO₃ single crystals in a broad range of frequency up to 10 MHz and temperature 300—823 K are reported. In this temperature range dielectric dispersion below 1 MHz has been found. The obtained data were fitted to the Cole-Cole relation. The mean relaxation time τ is strongly temperature dependent (0.04 ? 2.6 × 10^?5 s). A remarkable hysteresis effect in the values of τ on cooling and heating took place. The Δε(T) dependence (the maximal value of Δε ～ 400) is similar to the global ε′(T) response at low frequency. An isothermal structural transformation in Na_0.5Bi_0.5TiO₃ was observed by X-ray measurements. The order of the time in which the transformation takes place (～300 minutes) corresponds to the time in which the strongest time evolution of electric permittivity and time changes of dielectric dispersion were detected.     

23Na NMR study of the local order in the Na1/2Bi1/2TiO3 structure in a weak magnetic field

The orientation dependences of the second-order quadrupole shifts of the central component in the ²³Na NMR spectrum were studied in the temperature range 293–760 K. The profile of the spectral distribution is calculated using various models of the Na_1/2Bi_1/2TiO₃ structure. The calculations agree with the experimental data for the monoclinic structure of a polar cluster with two Na displacement components: a displacement along the [111] _p direction and a small displacement statistically or dynamically disordered over six equally probable [100] _p -type directions. Tetragonal-phase nuclei and monoclinic clusters with a very small displacement component along the [111] _p direction are found to coexist and have close energies over the temperature range 580–610 K. The results obtained provide new information concerning the character of the diffuse phase transition at 610 K.     

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     

Effect of Mn doping on the acoustic and vibrational behaviors of lead-free piezoelectric (Na1/2Bi1/2)TiO3-xBaTiO3 single crystals

The acoustic and vibrational properties of Mn-doped (Na_1/2Bi_1/2)TiO₃-xBaTiO₃ with x = 0.05 were investigated by using Brillouin and Raman spectroscopies and compared with those of undoped crystals. The mode frequency and the half width of the Brillouin doublet of the longitudinal acoustic mode showed more drastic changes near the dielectric maximum temperature compared to the broad and diffused changes of the undoped crystals, which indicates that Mn-doping induces polar domains larger than the typical polar nanoregions formed in undoped counterpart. The acoustic anomalies were most pronounced along the <100> direction suggesting that the polarization fluctuations are anisotropic and largest along this direction. Temperature dependence of Raman spectra showed that there are two characteristics temperatures where mode splitting occurs due to local symmetry changes. The high-temperature anomaly was associated with the changes in the acoustic properties, while the low-temperature mode splitting was related to the dielectric anomaly near depolarization temperature.     

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.     

Optical and dielectric anomalies in PbIn1/2Nb1/2O3-xPbTiO3 crystals in an electric field

A study is reported of the effect produced by application of a dc electric field (0 < E < 5 kV/cm) in different regimes on structural phase transformations and behavior of the phase boundary in [001]-oriented PbIn_1/2Nb_1/2O₃-37PbTiO₃ single crystals (starting composition) near the morphotropic phase boundary. The dielectric methods have been complemented for the first time by optical probing. It has been demonstrated that the content of PbTiO₃ in the samples under study is less than that in the starting composition. A suggestion is advanced that, in the samples studied, the stable room-temperature state with no electric field applied is that formed in the mixture of the rhombohedral R and monoclinic M _a phases. It has been found that the number, symmetry, and stability of the phases formed in a field depend on the regime of field application. The E-T phase diagrams have been constructed for different field application regimes. Phase diagrams obtained for the same crystal have been shown to differ for different regimes of field application.     

Properties of (Bi1/9Na2/3)(Mn1/3Nb2/3)O3 analysed within dielectric permittivity,conductivity, electric modulus and derivative techniques approach

The (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ ceramics with perovskite structure were sintered. The XRD test proved that the samples are cubic (a?=?3.920?±?0.001?Å). Microstructure and atomic composition were determined with a SEM (JSM-5410) equipped with energy dispersion X-ray analyser (ISIS-300). The fluctuation in the chemical composition was found indicating on local disorder. Broadband dielectric spectroscopy in the range 10^?1–3?·?10⁷?Hz was applied within the range of 100–650?K. The real, ?′(f,?T), and imaginary, ?″(f,?T), parts of complex dielectric permitivity characteristics, both in the temperature and frequency domain, show relaxation processes partially covered by electric conductivity. At high temperatures the electric conductivity exhibits a thermally activated behaviour σ(f,?T)?∝?exp(?E _a/kT) but the variable range hopping (VRH) dependence σ?∝?exp[?(T ₀/T)^1/4] is manifested at low temperatures. The derivatives technique in the frequency (??log??/??log?ω) and temperature (??log??/?T) domain enabled various relaxation processes to be distinguished. The data converted to electric modulus representation, M*(f,?T)?=?1/?*, exhibited clearly resolved relaxation peaks. The relaxation times obtained from the peaks position show a slightly non-Arrhenius temperature behaviour with the activation energy varying in 0.4–0.6?eV range and characteristic time of the electric conductivity relaxation of the order of 10^?12?s. The relaxation times can be fitted at better accuracy with the VRH dependence where T ₀ are of the order of 10⁸?K. It is shown that the low frequency ac-conductivity converges to dc-conductivity and the relation σ(0)?～?ω_m?～?τ_m ^?1 typical for the disordered solids applies. The conduction current relaxation relationship behaves in accord with the VRH system: σ_dc?∝?(T/T ₀)^q (e ²/kT) ω_c, where ω_c?=?ν_ph exp[?(T ₀/T)^1/4] is valid for the locally disordered (Bi_1/9Na_2/3)(Mn_1/3Nb_2/3)O₃ compound.     

Bi0．5Na0．5TiO3纳米晶的制备及其性能研究

采用凝胶自燃烧法合成Bi0.5Na0.5TiO3纳米粉体,并表征了粉体的晶相结构.测试表明应用凝胶自燃工艺合成的Bi0.5Na0.5TiO3粉体材料的粒子大小均匀,晶相单一,不需要经高温处理便能直接形成钙钛矿结构超细粉末.用所合成的粉末压片,1 125 ℃烧结2 h即可获得致密的烧结体,其相对密度为98.08%.用SEM观察烧结样品的平均粒径为2 μm.     

Ionic conduction and dielectric relaxation in polycrystalline Na2SO4

In the present paper, the ionic conductivity and the dielectric relaxation properties of Na₂SO₄ have been investigated by means of impedance spectroscopy measurements over wide ranges of frequencies and temperatures. The frequency dependent impedance data has been modeled by appropriate equivalent circuit representing the bulk and grain boundary properties of the sample. Phase transition temperatures and the activation energies of conduction in different phases have been determined from the temperature dependence of the dc conductivity. Dielectric relaxation has been studied using the complex electric modulus and permittivity formalisms. From the electric modulus formalism it is concluded that the relaxation mechanism is independent of temperature. The dielectric permittivity spectra were analyzed by the Cole–Cole formula where different parameters are determined.     

The effect of CuO and NiO doping on dielectric and ferroelectric properties of Na0.5Bi0.5TiO3 lead-free ceramics

In the present work, lead-free piezoelectric ceramics (Na_0.5Bi_0.5)TiO₃ –xCuO–yNiO (for x = 0.0, 0.02, 0.04 and 0.06) have been prepared by a conventional solid-state reaction method. An investigation of CuO and NiO doping in bismuth sodium titanate (BNT) and a study of the structure, morphology, and dielectric and ferroelectric properties of the NBT–CuNi system have been conducted. Phase and microstructural analysis of the (Na_0.5Bi_0.5)TiO₃ (NBT) based ceramics has been carried out using X-ray diffraction and scanning electron microscopy (SEM) techniques. Field emission scanning electron microscopy (FE-SEM) images showed that inhibition of grain growth takes place with increasing Cu and Ni concentration. The results indicate that the co-doping of NiO and CuO is effective in improving the dielectric and ferroelectric properties of NBT ceramics. Temperature-dependent dielectric studies have also been carried out at room temperature to 400 °C at different frequencies. The NBT ceramics co-doped with x = 0.06 and y = 0.06 exhibited an excellent dielectric constant ?_r = 1514. The study suggests that there is enormous scope of application of such materials in the future for actuators, ultrasonic transducers and high-frequency piezoelectric devices.