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.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

高性能铌镁酸铅-钛酸铅定向压电陶瓷的研究

用定向凝固技术制备了择优方向为[112]的0．70Pb(Mg1／3Nb2／3)O3—0．30PbTiO3高性能定向压电陶瓷．该陶瓷[112]方向的取向度约为35％，准静态压电常数d33约为1500～1600pC／N，耦合系数κt～0．51，κ33～0．82，22kV／cm时的场致应变约为0．23％。     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Pb(Mg1/3Nb2/3)O3-PbTiO3晶体组分对结构与性能的影响

用熔体Modified Brdgman法生长出尺寸直径40 mm长度80 mm的弛豫铁电单晶PMNT90/10,表明该方法不仅适合在准同型相界(MPB)附近生长PMNT单晶,也适合生长PT含量很低的PMNT单晶.在生长出的PMNT90/10晶体中,铁电相与顺电相两相共存,并呈现亚微畴结构特征.随着晶体组分由PMN组元变化到MPB组分附近,PMNT的电畴结构呈现微畴-亚微畴-不规则宏畴-规则宏畴演化系列,而介电弛豫特性则逐步弱化.PMNT固熔体的电学性能依赖于晶体组分,(001)切型PMNT90/10晶体的压电常数d33约80 pC/N,显著低于MPB附近组分,但其介电常数ε达到12600,明显高于后者.     

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.     

67 Pb(Mg1/3Nb2/3)O3-33PbTiO3单晶90铁电畴光学研究

采用偏光显微镜观察了67Pb(Mg1/3Nb2/3)O3-33PbTiO3固溶体铁电单晶在室温时90铁电畴结构.铁电畴结构与晶体质量有关,在正交偏光显微镜下光学透明晶体中存在着尺寸为23mm的均匀大畴,不同极化方向的大畴重叠形成雾状区,使晶体表现出光学质量宏观不均匀.在光学质量差的雾状晶体中则存在着0.1mm宽的110型带状孪生畴,使晶体形成表面浮凸,带状畴内还存在着90°亚畴.并对这些畴的形成作了讨论     

Nanoscale study by piezoresponse force microscopy of relaxor 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 and 0.9Pb(Mg1/3Nb2/3)O3-0.1PbTiO3 thin films grown on platinum and LaNiO3 electrodes

Relaxor 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (70/30 PMN-PT) and 0.9Pb(Mg_1/3Nb_2/3)O₃-0.1PbTiO₃ (90/10 PMN-PT) thin films have been grown by RF-sputtering on platinum (Pt) and lanthanum nickelate (LaNiO₃) bottom electrodes. For both electrodes, macroscopic measurements evidence lower coercive fields, remnant polarizations and piezoelectric coefficients d₃₃ for 90/10 PMN-PT films compared to 70/30 PMN-PT films. For both compositions, coercive fields and remnant polarizations are lower for films grown on LaNiO₃ compared to on Pt while piezoelectric coefficients d₃₃ are higher. For each electrode and composition, a similar behavior is revealed for electromechanical activity at the nanoscale when measuring local piezoelectric hysteresis loops; on the other hand, the voltages required for switching the domains are the highest for 90/10 PMN-PT films grown on LaNiO₃. The existence of large grain boundaries in the films grown on Pt and the presence of local random fields with polar nano-domains for the 90/10 composition could explain the differences measured in domains switching properties at the macroscale and nanoscale levels.     

Phase developments in the Pb(Zn1/2W1/2)O3-Pb(Zn1/3Ta2/3)O3-Pb(Zn1/3Nb2/3)O3 pseudo-ternary system

The phase stability ranges in the B-site precursor (Zn_1/2W_1/2)O₂-(Zn_1/3Ta_2/3)O₂-(Zn_1/3Nb_2/3)O₂ were determined by X-ray diffraction (XRD), where wolframite, tri-αPbO₂, and columbite phases were identified. Next attempts were carried out (with the addition of PbO) for the system Pb(Zn_1/2W_1/2)O₃-Pb(Zn_1/3Ta_2/3)O₃-Pb(Zn_1/3Nb_2/3)O₃, where the perovskite phase did not develop in the entire compositions investigated. Instead, only the Pb₂WO₅ and pyrochlore phases (along with ZnO) resulted.     

67Pb(Mg1/3Nb2/3)O3-33PbTiO3单晶的微结构与铁电畴

用偏光显微镜(PLM)和透射电镜(TEM)观察了67Pb(Mg1/3Nb2/3)O3-33PbTiO3单晶的畴结构.在PLM下,光学质量不同的晶体具有不同的畴结构,透明晶体具有毫米尺度的大畴,透明性差的晶体的带状孪生畴宽约为0.1mm;在TEM下,雾状晶体中存在着复杂的微米尺度的孪生畴,而均匀晶体中存在着不规则的微米尺度的180°畴.原位EDS分析表明,在孪生晶体中存在Nb-Ti-Mg-Pb-O非晶相.透明晶体的介电和压电常数显著地高于雾状晶体.讨论了化学不均性对畴结构的影响.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Microwave dielectric in the Sm(Co1/2Ti1/2)O3-CaTiO3 ceramic system with near-zero temperature coefficient with resonant frequency

The ceramic system prepared by the conventional solid state method was investigated for its microstructures and microwave dielectric properties. To achieve a temperature-stable material, two compounds with negative and positive temperature coefficients were employed to form mixed phases. The microwave dielectric properties are strongly correlated with composition. For practical application, a dielectric constant (ε_r) of 37, a quality factor (Q × f value) of 43,000 GHz and a temperature coefficient of resonant frequency (τ_f) of 1 ppm/°C for 0.6Sm(Co_1/2Ti_1/2)O₃-0.4CaTiO₃ sintered at 1420 °C are proposed.     

Optical band gap studies on xPb3O4–(1−x)P2O5 lead[(II, IV)] phosphate glasses

A series of glasses in the xPb₃O₄–(1−x)P₂O₅ (red lead phosphate) (RLP) system with ‘x' varying from 0.075 to 0.4 were prepared by the single-step melt quenching process from Pb₃O₄ and NH₄H₂PO₄. The optical absorption spectra of these glasses have been recorded in the ultraviolet region from 200 to 400 nm and the fundamental absorption edges have been identified. The optical band gap E_opt values have been determined for all the glasses using the known theories. The (E_opt) values vary from 4.90 to 3.21 eV the highest being 4.57 eV, corresponding to the most stable glass of x=0.225. The absorption edge is attributed to the indirect transitions and the origin of the Urbach energy ΔE is suggested to be thermal vibrations. These glasses promise as potential candidates for application in optical technology compared to simple xPbO–(1−x)P₂O₅ (lead phosphate) (LP) glasses.     

Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer

Thin films of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT) on Pt/Ti/SiO₂/Si (Pt/Si) substrates both with and without a Pb(Zr_0.52Ti_0.48)O₃ (PZT) interfacial layer were investigated. Perovskite and pyrochlore coexistence was observed for PMN-PT thin films without a PZT interfacial layer. Interestingly, most of the pyrochlore phase was observed in single-coated films and in the first layer of multi-coated films. The pyrochlore phase exhibited grains with an average size of about 25 nm, which is smaller than those of the perovskite phase (about 90 nm). In contrast, for PMN-PT thin films grown on a PZT interfacial layer, the formation of a pyrochlore phase at the interface between PMN-PT layers and the substrate is completely suppressed. Moreover, small grains are not observed in the films with a PZT interfacial layer. The measured polarization-electric field (P-E) hysteresis loops of PMN-PT films with and without PZT layers indicate that enhanced electrical properties can be obtained when a PZT interfacial layer is used. These enhanced properties include an increase in the value of remanent polarization P_r from 2.7 to 5.8 μC/cm² and a decrease in the coercive field E_c from 60.5 to 28.0 kV/cm.     

Growth and characterization of Ba(Cd1/3Ta2/3)O3 thin films

We have synthesized stoichiometric Ba(Cd_1/3Ta_2/3)O₃ [BCT] (100) dielectric thin films on MgO (100) substrates using Pulsed Laser Deposition. Over 99% of the BCT film was found to be epitaxial [BCT (100) || MgO (100) and BCT (010) || MgO (010)] when grown with an elevated substrate temperature of 635 °C, an enhanced oxygen pressure of 53 Pa and a Cd-enriched BCT target with a 1 mol BCT: 1.5 mol CdO composition. A dielectric constant of 32 was inferred from low-frequency capacitance measurements of a planar interdigital metal pattern. Analysis of ultra violet optical absorption results indicates that BCT has a bandgap of 4.9 eV; while the interference pattern in the visible range is consistent with a refractive index of 2.1. Temperature-dependent electrical measurements indicate that the BCT films have a room temperature conductivity of 3 × 10^− 12 Ω^− 1 cm^− 1 with a thermal activation energy of 0.7 eV. A mean particle size of ~ 100 nm and a root mean square surface roughness of 5 to 6 nm were measured using Atomic Force Microscopy.     

Growth and electrical performance of Pb(Mg1/3Nb2/3)O3-PbTiO3-Pb(Fe1/2Nb1/2)O3 single crystals

For the first time, we have grown ferroelectric single crystals Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-Pb(Fe_1/2Nb_1/2)O₃ (PMN-PT-PFN) from the melt by the simple slow cooling process. The chemical composition of the single crystals PMN-PT-PFN (0.59/0.31/0.10) is near the morphotropic phase boundary (MPB). X-ray diffraction (XRD) was used to study phase structure of the as-grown crystals, energy dispersive X-ray spectrometer (EDS) and electron probe micro-analyzer (EPMA) were employed to confirm the chemical composition and element distribution of the as-grown crystals, respectively. The ferroelectric, dielectric and piezoelectric properties of the as-grown PMN-PT-PFN (0.59/0.31/0.10) single crystal oriented along the (0 0 1) axis were measured, which showed that the remnant polarization (P_r), coercive electric fields (E_c), the Curie temperature (T_c) and the piezoelectric coefficient (d₃₃) were 50.2 μC/cm², 13.9 kV/cm, 158 °C and about 1800 pC/N, respectively. All the results indicated that the PMN-PT-PFN (0.59/0.31/0.10) single crystals are promising for applying to field of high frequency.     

Stoichiometric Pb(Mg1/3Nb2/3)O3 perovskite ceramics produced by reaction-sintering process

Stoichiometric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), perovskite ceramics produced by reaction-sintering process were investigated. Without calcination, a mixture of PbO, Nb₂O₅, and Mg(NO₃)₂ was pressed and sintered directly. Stoichiometric PMN ceramics of 100% perovskite phase were obtained for 1, 2, and 4 h sintering at 1250 and 1270 °C. PMN ceramics with density 8.09 g/cm³ (99.5% of theoretical density 8.13 g/cm³) and K_max 19,900 under 1 kHz were obtained.     

Effect of Pb(Fe1/2Nb1/2)O3 modification on dielectric and piezoelectric properties of Pb(Mg1/3Nb2/3)O3-PbZr0.52Ti0.48O3 ceramics

10 mol% Pb(Fe_1/2Nb_1/2)O₃ (PFN) modified Pb(Mg_1/3Nb_2/3)O₃-PbZr_0.52Ti_0.48O₃ (PMN-PZT) relaxor ferroelectric ceramics with compositions of (0.9 − x)PMN-0.1PFN-xPZT (x = 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 and 0.9) were prepared. X-ray diffraction investigations indicated that as-prepared ceramics were of pure perovskite phase and the sample with composition of x = 0.8 was close to morphotropic phase boundary (MPB) between rhombohedral and tetragonal phase. Dielectric properties of the as-prepared ceramics were measured, and the Curie temperature (T_c) increased sharply with increasing PZT content and could be higher than 300 °C around morphotropic phase boundary (MPB) area. At 1 kHz, the sample with composition of x = 0.1 had the largest room temperature dielectric constant ?_r = 3519 and maximum dielectric constant ?_m = 20,475 at T_m, while the sample with composition of x = 0.3 possessed the maximum dielectric relaxor factor of γ = 1.94. The largest d₃₃ = 318 pC/N could be obtained from as-prepared ceramics at x = 0.9. The maximum remnant polarization (P_r = 28.3 μC/cm²) was obtained from as-prepared ceramics at x = 0.4.     

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.     

Comparative investigation of structure and dielectric properties of Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) and 10% PbZrO3-doped Pb(Mg1/3Nb2/3)O3-PbTiO3 (65/35) ceramics prepared by a modified precursor method

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) and 10% PbZrO₃-doped Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics were both prepared by a modified precursor method, which was based on the high-temperature synthesis of an oxide precursor that contained all the B-site cations for the consideration of B-site homogeneity. The dielectric properties of Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramic was more of normal ferroelectric behavior, but the high dielectric constant (?_m = 34,200 at 1 kHz) and piezoelectric constant (d₃₃ = 709 pC/N) were observed for this composition close to the morphotropic phase boundary. Comparatively, introduction of 10% PbZrO₃ into Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (65/35) ceramics enhanced the diffuse phase transition as well as the rhombohedral to tetragonal phase transition temperature, while it also kept the high dielectric constant (?_m = 29,600 at 1 kHz) and piezoelectric constant (d₃₃ = 511 pC/N).