Domain structure studies on Pb(Zn1/3Nb2/3)O3–PbTiO3 mixed crystal system

In this investigation, ferroelectric Pb(Zn_1/3Nb_2/3)O₃–PbTiO₃ single crystals have been grown by modified flux technique with PbO self flux. Well-defined domain patterns were observed through polarized light on the as-grown crystals. Fingerprint like pattern and tweed pattern have also been observed. In PZN–PT system the fingerprint domain area is found to be elongated along one direction for increasing PT content.     

Structure and electrical properties of (100)-oriented Pb(Zn1/3Nb2/3)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films on La0.7Sr0.3MnO3 electrode by chemical solution deposition

(100)-oriented 0.462Pb(Zn_1/3Nb_2/3)O₃–0.308Pb(Mg_1/3Nb_2/3)O₃–0.23PbTiO₃ (PZN-PMN-PT) perovskite ferroelectric thin films were prepared on La_0.7Sr_0.3MnO₃/LaAlO₃ (LSMO/LAO) substrate via a chemical solution deposition route. The perovskite LSMO electrode was found to effectively suppress the pyrochlore phase while promote the growth of the perovskite phase in the PZN-PMN-PT film. The film annealed at 700 °C exhibited a high dielectric constant of 2130 at 1 kHz, a remnant polarization, 2P_r, of 29.8 μC/cm², and a low leakage current density of 7.2 × 10^− 7 A/cm² at an applied field of 200 kV/cm. The ferroelectric polarization was fatigue-free at least up to 10¹⁰ cycles. Piezoelectric coefficient, d₃₃, of 48 pm/V was also demonstrated. The results showed that much superior properties could be achieved with the PZN-PMN-PT thin films on the solution derived LSMO electrode than on Pt electrode by sputtering.     

High electrical properties of W-additive Mn-modified PZT–PMS–PZN ceramics for high power piezoelectric transformers

The ceramics were prepared successfully by the addition of WO₃ to the Mn-modified Pb(Zr_0.52Ti_0.48)O₃–Pb(Mn_1/3Sb_2/3)O₃–Pb(Zn_1/3Nb_2/3)O₃ (PZT–PMS–PZN) for high power piezoelectric transformers application. XRD analysis indicated that the ceramics were mainly composed of a tetragonal phase in the range of 0–1.0 wt.% WO₃ addition. The grain size of the ceramics significantly decreased from 10.0 to 2.9 μm by addition of WO₃. Moreover, the addition of WO₃ promoted densification of the ceramics and increased mechanical quality factor (Q_m), planar coupling factor (K_p) and piezoelectric constant (d₃₃) kept high values, whereas, dielectric loss (tan δ) was low. Δf (=f_a − f_r) slightly changed when WO₃ addition was above 0.5 wt.%. The ceramics with 0.6 wt.% WO₃ addition, sintered at 1150 °C showed the optimized piezoelectric and dielectric properties with Q_m of 1852, K_p of 0.58, d₃₃ of 243 pC/N and tan δ of 0.0050. The ceramics are promising candidates for high power piezoelectric transformers application.     

Piezoelectric and dielectric properties of PZT–PZN–PMS ceramics prepared by molten salt synthesis method

Piezoelectric powders and ceramics with the composition of Pb_0.95Sr_0.05(Zr_0.52Ti_0.48)O₃–Pb(Zn_1/3Nb_2/3)O₃–Pb(Mn_1/3Sb_2/3)O₃ (PZT–PZN–PMS) were prepared by molten salt synthesis (MSS) and conventional mixed-oxide (CMO) methods, respectively. The influence of synthesis process on the properties of powders and ceramics were investigated in detail. The results show that the MSS method significantly improved the sinterability of PZT–PZN–PMS ceramics, resulting in an improvement of dielectric and piezoelectric properties compared to the CMO method. The optimum values of MSS samples are as follows: _r = 1773; tan δ = 0.0040; T_c = 280 °C; d₃₃ = 455 pC/N; k_p = 0.70; Q_m = 888; E_c = 10.3 kV/cm; and P_r = 28.2 μC/cm², at calcination of 800 °C and sintering of 1120 °C temperature.     

Phase transition characteristics in PbZrO(3) based PZT-PZN solid solution ceramics

The ternary oxide solution of lead zirconate titanate (PZT) with a complex perovskite oxide Pb(Zn_1/3Nb_2/3)O₃ , (PZN), a composition that is near that of PbZrO₃, was prepared, and its phase transition behavior was investigated. An extension of the ferroelectric phase by the addition of PZN and a change of the transition between two ferroelectric phases from a first-order to a second-order nature are described     

Investigation of the Effect of the Annealing Process on the Domain Structure of 0.65Pb(Mg1/3Nb2/3)O3–0.35 PbTiO3 Single Crystal Using Scanning Electron Acoustic Microscopy

Scanning electron acoustic microscopy has been used to reveal the ferroelectric and ferroelastic domain structures in a 0.65 Pb(Mg_1/3Nb_2/3)O₃–0.35 PbTiO₃ single crystal without any sample pretreatment. The investigation revealed the presence of the ferroelectric tetragonal 90° domain structure in the original material. The formation of twofold symmetrical butterfly-shaped ferroelastic domains was observed after the sample had been annealed at 300°C for 3 h and then slowly cooled. The origin of the butterfly-shaped domains is discussed.     

Present and future of piezoelectric single crystals and the importance of B-site cations for high piezoelectric response

High quality piezoelectric single crystals, such as Pb(Zn_1/3 Nb_2/3)O₃-PbTiO₃ (PZNT) and Pb(Mg _1/3Nb_2/3)O₃-PbTiO₃ (PMNT), have been investigated, and, because their piezoelectric properties are greatly superior to those of Pb(Zr_1-xTi_x)O₃ (PZT) ceramics, they have been used for certain transducer applications since the late 1990s. The present situation for these relaxor-PT (lead titanate) single crystals is summarized. In this review, some possible high Tc > 200°C single crystals are also introduced. Single crystals of Pb(In_1/2Nb_1/2)O₃-PbTiO₃ (PINT) binary system and Pb(Mg_1/3Nb_2/3)O₃ -Pb(Sc_1/2Nb_1/2)O₃-PbTiO₃ (PSMNT) tertiary system have been synthesized, and their electrical properties are reported. In addition, a novel guiding principle for discovering excellent piezoelectric materials, namely the presence of low molecular mass B-site ions that can enter the lead-perovskite Pb(B'B")O₃ structure, is introduced     

Conduction analysis of Li2O doped 0.2[Pb(Mg1/3Nb2/3)]–0.8[PbTiO3–PbZrO3] ceramics fabricated by columbite precursor method

We have fabricated 0.2Pb(Mg_1/3Nb_2/3)O₃–0.8Pb(Zr_0.475Ti_0.525)O₃ [PMN–PZT] ceramics doped with various amounts of Li₂O (0, 0.05, 0.1, 0.2, 0.3 wt.%) using the columbite precursor method. The effects of Li-doping on the conduction behavior of PMN–PZT ceramics are discussed in relation to the low frequency dielectric dispersion and frequency domain measurement. The Li-doped PMN–PZT ceramics sintered at 950 °C showed a sufficient densification with large dielectric constant and low dielectric loss. The incorporation of Li⁺ ion in PMN–PZT ceramics led to an appreciable reduction in electrical conductivity and further enhanced the ferroelectric and piezoelectric properties. The activation energies of PMN–PZT + xLi₂O (x = 0, 0.05, 0.1, 0.2, 0.3 wt.%) ceramics calculated from ac conductivity measurement using the Arrhenius relation were 1.05, 1.25, 1.27, 1.38 and 1.41 eV, respectively. The conduction behavior is examined in the low frequency and high temperature region and the results are discussed in detail through crystal defect mechanism.     

Characteristics of relaxor-based piezoelectric single crystals forultrasonic transducers

For ultrasonic transducers, piezoelectric ceramics offer a range of dielectric constants (K~1000-5000), large piezoelectric coefficients (d_ij~200-700 pC/N), and high electromechanical coupling (k _t≃50%, k₃₃≃75%). For several decades, the material of choice has been polycrystalline ceramics based on the solid solution Pb(Zr_1-xB_2x)O₃ (PZT), compositionally engineered near the morphotropic phase boundary (MPB). The search for alternative MPB systems has led researchers to revisit relaxor-based materials with the general formula, Pb(B₁,B₂)O₃ (B₁:Zn²⁺ , Mg²⁺, Sc³⁺, Ni²⁺..., B₂ :Nb⁵⁺ Ta⁵⁺...). There are some claims of superior dielectric and piezoelectric performance compared to that of PZT materials. However, when the properties are examined relative to transition temperature (T₃), these differences are not significant. In the single crystal form, however, Relaxor-PT materials, represented by Pb(Zn_1/3Nb_2/3)O₃-PbTiO ₃ (PZN-PT), Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) have been found to exhibit longitudinal coupling coefficients (k₃₃)>90%, thickness coupling (k_t)>83%, dielectric constants ranging from 1000 to 5000 with low dielectric loss <1%, and exceptional piezoelectric coefficients d₃₃>2000 pC/N, the later promising for high energy density actuators. For single crystal piezoelectrics to become the next generation material of ultrasonic transducers, further investigation in crystal growth, device fabrication and testing are required     

三元陶瓷Pb(In1/2Nb1/2)O3-Pb(Ni1/3Nb2/3)O3-PbTiO3准同型相界附近组分的介电、铁电和压电性能

铅基复合钙钛矿铁电材料广泛应用于机电传感器、致动器和换能器。二元铁电固溶体Pb(Ni_1/3Nb_2/3)O₃- PbTiO₃(PNN-PT)由于其在准同型相界(MPB)区域具有优异的压电、介电性能而备受关注。然而较大的介电损耗和较低的居里温度限制了其在高温高功率器件方面的应用。本研究通过引入Pb(In_1/2Nb_1/2)O₃ (PIN)作为第三组元改善PNN-PT的电学性能, 提高其居里温度; 通过两步法合成了MPB区域的三元铁电陶瓷Pb(In_1/2Nb_1/2)O₃- Pb(Ni_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PNN-PT), 研究了其结构、介电、铁电和压电性能。制备的所有组分陶瓷具有纯的钙钛矿结构。随着PT含量的增加, 陶瓷结构从三方相转变为四方相。通过XRD分析得到了室温下PIN-PNN-PT体系的MPB相图。体系的居里温度由于PIN的加入得到了很大的提高, 更重要的是PIN的引入降低了PNN-PT体系的介电损耗和电导。MPB处的组分展现出了优异的电学性能, 室温下, 性能最优组分为0.30PIN-0.33PNN-0.37PT: d₃₃=417 pC/N, T_C=200 ℃, ε′= 3206, tanδ=0.033, P_r=33.5 μC/cm², E_C=14.1 kV/cm。引入PNN-PT的PIN第三组元使得体系的居里温度和压电性得到提高的同时降低了的介电损耗和电导率, 因此, PIN-PNN-PT三元铁电陶瓷在高温高功率换能器等方面具备一定的应用潜力。     

Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Effects of growth conditions on the domain structure and dielectric properties of (1 − x)Pb(Sc1/2Nb1/2)O3–xPbTiO3 single crystals

The studies of the (1 − x)Pb(Sc_1/2Nb_1/2)O₃–xPbTiO₃ (PSN–PT) single crystals reveal that the chemical and physical properties of the materials are affected by the growth conditions. By the measurements of the dielectric constant as a function of temperature upon cooling, it is found that crystals grown from the same charged stoichiometric composition (x = 0.425), but under different flux environments (i.e. the composition of flux and the flux to PSN–PT ratios are varied), show anomalies (i.e. phase transitions) at different temperatures. This phenomenon is attributed to the complex local chemical structure of the PSN–PT solid solution single crystals with B-site random occupancy of three different cations (Sc³⁺, Nb⁵⁺ and Ti⁴⁺). The dielectric and domain structure of the PSN–PT crystals with composition near the morphotropic phase boundary (MPB) are investigated, showing much more complex situations compared with Pb(Sc_1/2Nb_1/2)O₃.     

Er3+掺杂弛豫铁电材料PMNT的单晶生长与性能表征

按照0.71Pb(Mg_1/3Nb_2/3)O₃-0.26PbTiO₃-0.03Pb(Er_1/2Nb_1/2)O₃化学式所示组分比例, 采用分步高温固相反应合成出Er³⁺掺杂PMNT多晶, 通过熔体坩埚下降法生长出尺寸φ25 mm×100 mm的Er³⁺掺杂PMNT晶体, Er³⁺离子以三元固溶体组元方式被掺杂进入钙钛矿相铁电体晶格; 测试了Er³⁺掺杂PMNT晶片的介电、压电与铁电性能以及上转换发光性能。结果表明, Er³⁺掺杂PMNT晶体呈现跟三方相纯PMNT晶体相近的介电、压电与铁电性能; 在980 nm激发光作用下, 该掺杂晶体呈现出Er³⁺离子特有的较强上转换荧光发射, 并且极化后掺杂晶体的上转换发光强度得到增强。     

Nonlinear pyroelectric energy harvesting from relaxor single crystals

Energy harvesting from temperature variations in a Pb(Zn_1/3Nb_2/3)_0.955Ti_0.045O₃ single crystal was studied and evaluated using the Ericsson thermodynamic cycle. The efficiency of this cycle related to Carnot cycle is 100 times higher than direct pyroelectric energy harvesting, and it can be as high as 5.5% for a 10degC temperature variation and 2 kV/mm electric field. The amount of harvested energy for a 60degC temperature variation and 2 kV/mm electric field is 242.7 mJmiddotcm^-3. The influence of ferroelectric phase transitions on the energy harvesting performance is discussed and illustrated with experimental results.     

Contribution to the comprehension of dissipation phenomena in lead zirconate titanate: aliovalent doping effect

By the solid reaction method, undoped, potassium doped and niobium doped lead zirconate titanate (PZT) are elaborated. The mechanical losses measured in the range of the Hz as a function of temperature shows two peaks R₁ and R₂, and a ferroelectric transition peak P₁ between ferroelectric and para-electric states on the undoped PZT—Pb(Zr_0.54Ti_0.46)O₃—noted PZT54/46. Potassium doped PZT—Pb_1−xK_x(Zr_0.54Ti_0.46)O₃—shortly called PKZT 100x/54/46 shows an increase in the height of both the peaks at a doping content, x, less than 0.5 at.% but an opposite effect is observed above this value. Niobium doped PZT—Pb[(Zr_0.54Ti_0.46)_1−yNb_y]O₃—shortly called PNZT 100y/54/46, shows the vanish of the R₂ peak and the decrease of the height of the R₁ peak when the doping content increases.     

Deposition and photoluminescence of sol–gel derived Tb:Zn2SiO4 films on SiO2/Si

Tb³⁺ doped Zn₂SiO₄ films have been deposited on SiO₂ buffered Si wafers by sol–gel method. The structures of these films have been investigated with X-ray diffraction (XRD), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The results revealed that these films were composed of nanometer-size grains with a Willemite structure and had smooth surfaces. Photoluminescence measurements of the films showed a strong emission from ⁵D₄ to ⁷F₅ at 544 nm. The blue emission from ⁵D₃–⁷F_j was depressed because of cross-relaxation effect. The decay kinetics of the ⁵D₄–⁷F₅ green emission was studied and a best fitting was obtained by a double exponential function. The lifetime of the excited ⁵D₄ state is estimated to be 5.2 ms.     

Effects of ZnO on piezoelectric properties of 0.01PMW–0.41PNN–0.35PT–0.23PZ ceramics

The microstructure and piezoelectric properties of the 0.01Pb(Mg_1/2W_1/2)O₃–0.41Pb(Ni_1/3Nb_2/3)O₃–0.35PbTiO₃–0.23PbZrO₃ + 0.1 and 0.3 wt.% Y₂O₃ + x ZnO ceramics were investigated. The crystal structure changed from psudocubic to tetragonal when ZnO added. The average grain size increased from 4 μm to 8 μm with the addition of ZnO by oxygen diffusion, even if the growth rate was low. When ZnO added until 0.5 wt.%, the , k_p and d₃₃ values of specimens were slightly increased regardless Y₂O₃ contents. The curie point of PMW–PNN–PT–PZ ceramics were increased from 162 °C to 232 °C, as increasing the ZnO contents. When ZnO added, the k_p of specimens slightly was increased regardless Y₂O₃ contents. The mechanical quality factors were abruptly decreased regardless Y₂O₃ contents, when ZnO added until 0.75 wt.%. The optimized piezoelectric properties were obtained; d₃₃ = 730 (pC/N), k_p = 60, Q_m = 50, and  = 4750, when PMW–PNN–PT–PZ + 0.3 wt.% Y₂O₃ + 0.5 wt.% ZnO sintered at 1200 °C for 1 h.     

Calculation of quasi-static electromechanical coupling coefficientsfor electrostrictive ceramic materials

The quasi-static coupling coefficients, k₁₃ and k₃₃, for electrostrictive ceramics are computed analytically. The calculation is based on a three-dimensional constitutive relation that models both electrostriction and nonlinear dielectric behaviors. The results show that the coupling factors depend on the amplitudes of the applied ac field and the dc bias, as well as the mechanical prestress. For an actuator without bias voltage or prestress, the coupling coefficients approach an asymptotic value with increasing electric field. The primary coefficients, k₁₃ and k₃₃ , for a lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃BaTiO ₃(PMN-PT-BT), based relaxor ferroelectric are computed as an example. The results show that the coupling coefficients for PMN-PT-BT materials are roughly comparable with those of existing piezoelectrics. These coefficients are important parameters for material section and power source design for transducer devices     

Zn2GeO4微米球的一步合成及其光催化制氢活性

采用微波辅助水热法一步合成尺寸约为5 μm的Zn₂GeO₄微米球。实验研究了微波水热的反应温度、反应时间、乙酸锌与氧化锗的摩尔比等因素对合成Zn₂GeO₄微米球的影响。采用FE-SEM、TEM、XRD和UV-Vis对合成的微米球进行表征。结果表明, 当乙酸锌：氧化锗为6:2, 微波辐射温度为170℃, 反应时间10 min, 尿素用量3.604 g, 制备的Zn₂GeO₄微米球具有良好的光催化效果。实验测试Zn₂GeO₄微米球比表面积为13 m²/g, 在紫外光辐射下, 在甲醇体系中的光解水产氢速率可达到3.76 mmol/(h·g)。该方法缩短反应时间, 增强了光催化活性。