An effective growth method to improve the homogeneity of relaxor ferroelectric single crystal Pb(In1/2Nb1/2)O3‐ Pb(Mg1/3Nb2/3)O3‐PbTiO3

Compositional segregation usually has negative effects on the growth of solid solution ferroelectric single crystals of Pb(In_1/2Nb_1/2)O₃‐Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (abbr. PIN‐PMN‐PT or PIMNT). A modified Bridgman method was adopted in this work to control the segregation and improve the compositional homogeneity significantly. The characteristic of this work is to use multiround growths and gradient composition raw materials in order to keep the PbTiO₃ concentration constant during the crystal growth. As an example, the two‐round growth of ternary PIN‐PMN‐PT single crystal is conducted in the same Pt crucible with gradient raw materials, where the first‐round boule was used as the seed crystal for the second‐round growth. Our results show that the as‐grown (Ф80 mm × 270 mm) PIN‐PMN‐PT crystals exhibit higher phase transition temperatures (T_c∼180 °C, T_r/t∼110 °C) and larger coercive field (E_c∼5–5.5 kV/cm), which are much better than the performances of Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ crystals, and similar dielectric and piezoelectric performances (ε∼5000, tanδ∼1.25%, d₃₃∼1500 pC/N, k_t∼60%). And about 85 percent of the crystal boule grown by the two‐round growth technique could maintain its compositions around the morphotropic phase boundary.     

Refractive index dispersion of relaxor ferroelectric 0.9Pb(Zn1/3Nb2/3)O3‐0.1PbTiO3 single crystal

The refractive indices of 0.9Pb(Zn_1/3Nb_2/3)O₃‐0.1PbTiO₃ single crystal at different wavelengths have been measured by the minimum deviation method at room temperature, and their dispersion equations are obtained. The parameters connected to the energy band structure are obtained by fitting single‐oscillator dispersion equation. Despersion energies are found to take on covalent crystal values. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

On the effect of ordering on vibrational spectrum of relaxor ferroelectric PbSc1/2Ta1/2O3 in paraphase

The effect of the ordering of Sc³⁺ and Ta⁵⁺ ions on the behavior of the phonon subsystem in the relaxor ferroelectric PbSc_1/2Ta_1/2O₃ from the numerous AB′ _x B″ _x?1O₃ family has been studied. The nature of an additional contribution to the light-scattering spectra has been analyzed on the experimental data on Raman scattering in PbSc_1/2Ta_1/2O₃, SrAl_1/2Ta_1/2O₃, SrAl_1/2Nb_1/2O₃, and BaMg_1/3Ta_2/3O₃ compounds and inelastic neutron scattering in PbSc_1/2Ta_1/2O₃. It is shown that broadening of the lines in the Raman spectra of PbSc_1/2Ta_1/2O₃ crystals is caused by additional scattering by phonons from various points of the Brillouin zone.     

Compositional variation in 0.65 PbMg2/3Nb1/3O3 ‐0.35 PbTiO3 single crystals grown by high temperature solution growth technique

Single crystals of lead magnesium niobate titanate, 0.65 PbMg_2/3Nb_1/3O₃ (PMN) ‐0.35PbTiO₃ (PT) were grown using flux method near morphotropic phase boundary (MPB) composition. The crystals grown at the centre of the platinum crucible were found to PT deficient compared to those grown near the walls of the crucibles. A variation of ∼3.8 mol% in PT concentration was found in the crystals grown at the wall and at the centre of the crucible. The difference in the chemical composition of crystals grown at the centre and the near the wall of the crucible was observed by X‐ray diffraction, EDXRF, dielectric and thermal measurements. The presence of PT rich and deficient crystals is explained in terms of the segregation coefficient of PT in PMN. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Pb(In1/2Nb1/2)O3-Pb(Ni1/3Nb2/3)O3-PbTiO3压电陶瓷的介电、铁电和压电性能

采用两步法制备了0.30Pb(In1/2 Nb1/2)O3-(0.70-x)Pb(Ni1/3Nb2/3)O3-xPbTiO3(PIN-PNN-PT,x=0.33,0.35,0.37,0.39)压电陶瓷.研究了PIN-PNN-PT压电陶瓷的相结构、介电、铁电和压电性能.研究表明位于准同型相界(MPB)的组分0.30PIN-0.33PNN-0.37PT具有最佳电学性能,其居里温度TC、压电系数d33、平面机电耦合系数kp、自由介电常数ε二介电损耗tanδ、剩余极化Pr、矫顽场EC分别为200℃、386 pC/N、50;、2692、0.045、34 μC/cm2、18 kV/cm.结果 显示PIN-PNN-PT三元系相比于PNN-PT有更高的居里温度,同时保持了优异的压电性能.     

Pb(Sc1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3-PbZrO3弛豫铁电晶体的生长及表征

采用高温溶液法生长了准同型相界(MPB)四元弛豫铁电单晶Pb(Sc1/2Nb1/2) O3-Pb(Mg1/3 Nb2/3)O3-PbTiO3-PbZrO3,得到较大尺寸且具有规则外形的立方单晶.研究结果表明所生长的晶体为钙钛矿结构,立方晶粒平整的暴露面均为(001)面;晶体以层状方式生长,生长机制为搭桥生长;所生长晶体的矫顽场Ec～3.52kV/cm,三方四方相变温度Tr-t～104℃,居里温度Tc～149.5℃,压电常数d33～1089 pC/N,剩余极化强度Pr～25.4 μC/cm2;随着频率增加,晶体的相变弥散度减小.     

三元铁电单晶Pb(Yb1/2Nb1/2)O3-Pb(Zn1/3Nb2/3)O3-PbTiO3生长及性能表征

采用高温助熔剂法首次成功生长出了Pb(Yb1/2Nb1/2) O3-Pb(Zn1/3Nb2/3) O3-PbTiO3 (PYZNT)三元铁电单晶,并对晶体组分、介电、铁电和压电性能进行了研究.结果表明,晶体为纯三方钙钛矿相,实际组分为0.68PYN-0.22PZN-0.1PT.分别对晶体的介电,铁电和压电性能进行研究.介电常数ε'和介电损耗tanδ对温度和频率表现出典型的弛豫行为.晶体的居里温度TC为80℃.由于反铁电体PYN含量较高,晶体具有非常大的矫顽场,在100kV/cm的外电场条件下极化还不能反转,因而无法得到饱和的电滞回线.在未极化条件下,测得晶体的压电常数d33为78 pC/N.     

Nb2O5掺杂对Pb(Mg1/3Nb2/3)O3-PbZrO3-PbTiO3陶瓷组织与性能的影响

采用固相烧结法制备Nb2O5掺杂的Pb(Mg1/3Nb2/3) O3-PbZrO3-PbTiO3+ 0.5mol; ZnO(PMN-PZT)压电陶瓷,研究了不同Nb2O5掺杂量对材料结构及压电介电性能的影响.实验结果表明,随着Nb2O5掺杂量的增加(0～1 mol;),PMN-PZT陶瓷的晶界强度提高,断裂模式由沿晶断裂逐渐转变为穿晶断裂,而且陶瓷的压电介电性能升高.当Nb2O5掺杂量为1mol;时,1250℃烧结的陶瓷样品性能参数为:d33=430 pC/N,Qm=60,kp=0.52,kt=0.38,εr=3620,tanδ=0.017.     

Formation of α-Al2O3 by thermal decomposition of basic aluminium chlorides at low temperatures

Basic aluminium chloride gels and the crystalline salt AlCl₃ · 2 Al(OH)₃ · 6 H₂O are thermally decomposed to an amorphous product in a first step at low temperatures. If the reaction gas is rapidly removed the amorphous decomposition product directly transforms to corundum at increased temperature. Starting from gels the α-Al₂O₃ formation begins at 420 °C, transformation of the crystalline salt at 530 °C. Structural similarities of precursor compounds and corundum are discussed as a reason for this behaviour. High contents of HCl and H₂O in the atmosphere surrounding the specimen result in decomposition to transition aluminas at increasing temperature, which are transformed into α-Al₂O₃ above 1000 °C.     

Flux crystallization of Pb(Mg1/3Nb2/3)O3 single crystals by the Czochralski method

Single crystals of lead magnesium niobate have been grown by flux crystallization using a modified Czochralski method. The crystals grown are free of pyrochlore impurity and have sizes of (15–28) × (20–30) × 20 mm³. The region of congruent melting of solution is determined. The PbO-B₂O₃ and PbO-B₂O₃-KBO₂ systems are chosen to be solvents.     

Electrical properties of Al2O3 film deposited at low temperatures

Amorphous Al₂O₃ films were deposited on p-Si by rf magnetron sputtering to investigate their potential as a gate dielectric in organic thin film transistors (OTFTs). The deposition was performed at room temperature, 200 and 300 °C using Al₂O₃ and Al targets. Achieved Al₂O₃ films have higher capacitance values than thermally grown SiO₂ as characterized by capacitance-voltage measurements. It is also found from current-voltage and roughness measurements that the leakage current and the surface roughness can be least when the films are deposited at room temperature. The capacitance of the film obtained from the Al₂O₃ target appears higher than that of the Al₂O₃ film from the Al target while the results of electrical breakdown are opposite. These room temperature processes are promising for applications to the gate dielectrics of organic TFTs.     

Flux growth and low temperature dielectric relaxation in piezoelectric Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals

Single crystals of Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT 91/9) have been grown by flux method after modifications in temperature profile, flux ratio and addition of excess ZnO/B₂O₃ which resulted in enhanced perovskite yield (more than 95%). Only a few crystals showed the presence of pyrochlore phase/variation in composition. A comparative characterization of these crystals were carried out in respect of piezoelectric charge coefficient d₃₃, dielectric constant, ac conductivity and hysteresis loop after cutting and poling the crystals along [001] direction. The total activation energy for conduction has been found to increase with Ti‐content in the sample. The effect of ZnO on growth behavior has been analyzed. A detailed analysis of PZNT (91:9) has been carried out at low temperature in respect of the various thermodynamic parameters related to the dielectric relaxation mechanism, like optical dielectric constant, static dielectric constant, free energy of activation for dipole relaxation, enthalpy of activation and relaxation time, have been calculated in the vicinity of transition temperature in the lower temperature region. The activation energy for relaxation at ‐10 and ‐49 °C have been found to be 0.09 and 0.02 eV respectively. The results were analyzed and a detailed dielectric analysis and low temperature relaxation behavior of PZNT crystals were interpreted. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

(Na1/2Bi1/2)TiO3-(Na1/2Bi1/2)(Zn1/3Nb2/3)O3无铅压电陶瓷的介电特性研究

采用固相合成法制备了(1-x)(Na1/2Bi1/2)TiO3-x(Na1/2Bi1/2)(Zn/23Nb2/3)O3(简写为(1-x)NBT-xNBZN)无铅压电陶瓷.研究了该体系陶瓷晶体结构、弥散相变特征与介电弛豫行为.X射线衍射分析表明,所研究的组成均能够形成纯钙钛矿(ABO3)型固溶体.当x≥0.5%摩尔分数时,该体系陶瓷具有三方、四方共存的晶体结构.材料的介电常数-温度曲线显示陶瓷具有两个介电反常峰Tf和Tm.修正的居里-外斯公式较好的描述了陶瓷弥散相变特征,弥散指数随x的增加而增加.x≤0.5%摩尔分数的陶瓷仅在低温介电反常峰Tf附近表现出明显的频率依赖性,随x的增加,陶瓷材料在室温和低温介电反常峰Tf之间都表现出明显的频率依赖性.根据有序-无序转变和宏畴.微畴转变理论探讨了该体系陶瓷介电弛豫特性的机理.     

液相外延生长Pb(Zn1/3Nb2/3)O3-PbTiO3膜及生长机理研究

采用PbO作助溶剂,我们在钛酸锶(STO)衬底上用液相外延方法生长了一层具有特定取向的PZNT岛状外延膜,并通过引入c轴取向的PZT过渡层后,使原来的岛状三维生长转变为二维生长,显著改善了外延膜的质量,获得了几个微米厚、较完整的PZNT膜.实验证明:在氧化镁和铝酸镧(001)基片以及STO(110)/(111)衬底上,PZNT晶粒以自发形核为主,外延生长膜主要呈现岛状形貌;取STO(001)衬底,膜颗粒取向一致性好,并可获得完整的PZNT膜.     

稀土掺杂Pb(Mg1/3Nb2/3)O3-PbTiO3压电陶瓷的烧结特性研究

在传统的固相反应制备工艺中,固相反应的烧结温度直接影响着陶瓷的物相结构、陶瓷致密度以及介电性能等.本文采用固相反应法制备x; Sm3掺杂PMN-PT压电陶瓷,通过控制不同的烧结温度,制备了一系列Sm-PMNPT陶瓷样品.利用X射线衍射仪、介电温谱以及准静态d33测量仪对陶瓷结构、介电性能、压电系数等性能进行表征.研究结果表明:烧结温度在1250℃,x=1.875mol;～2.5mol;,陶瓷样品的钙钛矿含量最大,压电系数最高可达1254 pC/N,kp=0.58,相对介电常数高达30000左右,密度达到8.48 g/cm3.     

Pb(Mg1/3Nb2/3)O3-0.33PbTiO3晶体三方相的压电性能研究

以坐标系二次旋转为理论基础研究了PMN-0.33PT晶体三方相的常用压电模量d15、d24、d31、d33、d36和机电耦合系数k15、k24、k31、k33、k36在三维空间的变化规律.通过MATLAB编程求得以上各系数关于坐标系旋转角度的函数表达式,绘制出了它们的三维空间分布图,并一一求得这些系数的最大值,以及与最大值相对应的旋转角.发现除d33和k33外,d31、d36、k31和k36也在空间变化显著.d31和k31旋转后的最大值比原坐标系下的数值分别扩大了15倍和6倍,对应的旋转角分别为(-4.5°/90°)、(22.5°/270°).d36 和k36在原坐标系下不存在,经旋转后的最大值可分别达到1340 pC/N 和0.73.该研究结果对PMN-0.33PT晶体在压电传感器、换能器中的应用具有重要的理论价值.     

La3+掺杂对Pb(Lu1/2Nb1/2)O3反铁电单晶储能性能的影响

采用顶部籽晶法生长了La3+掺杂Pb(Lu1/2Nb1/2)O3(PLN)反铁电单晶,晶体组分简写为xLa-PLN(x=1;、3;、5;),并详细研究了La3+掺杂对PLN晶体储能性能的影响.通过ICP测试了不同配比晶体的实际掺杂比例,分别为0.3;、1.1;、2.9;.XRD显示该晶体体系为正交相钙钛矿结构,且存在两套超晶格衍射点阵,分别由A位铅离子反平行排列和B位离子有序排列导致.介电温谱给出了晶体的介电常数、介电损耗随温度和频率的变化规律,不存在弥散相变.变温电滞回线显示,该体系均表现出典型的双电滞回线特性,且随着La3+含量的增加,有效储能密度逐渐增大,最高储能密度达到5.1 J/cm3.这主要是由于La3+掺杂导致体系的容忍因子下降,从而增强了反铁电稳定性,最终提高了PLN体系的能量存储密度.     

Investigation on growth defects in Pb(Zn1/3Nb2/3)O3‐PbTiO3 crystals

Relaxor ferroelectric crystal (1‐x)Pb(Zn_1/3Nb_2/3)O₃‐xPbTiO₃ (PZNT) with x=0.07 (PZNT93/7) has been grown by the vertical Bridgman method from the high temperature solution of PZNT‐PbO system. The growth defects, such as nucleation core, inclusions, boundaries and particles, were investigated by optical microscope and scanning electron microscope. Sub‐structures were found in the flux inclusions and the lack of ZnO component in PZNT crystals was attributed to the existence of ZnO particles in the inclusions. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)