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)     

Effective electro‐optic coefficient of (1–x)Pb(Zn1/3Nb2/3)O3–xPbTiO3 single crystals

Refractive indices and effective electro‐optic coefficient γ_c of (1–x)Pb(Zn_1/3Nb_2/3)O₃–xPbTiO₃ (PZN‐xPT, x = 0.05, 0.09 and 0.12) single crystals were measured at 532 nm wavelength. Orientation and temperature dependences of the electro‐optic coefficient were investigated. Large electro‐optic coefficient (γ_c = 470 pm/V) was observed in [001]‐poled PZN‐0.09PT crystal. More importantly, γ_c of tetragonal PZN‐0.12PT is almost unchanged in a temperature range −20 ∼ 80 °C. The γ_c of PZN‐xPT single crystals are much higher than that of widely used electro‐optic crystal LiNbO₃ (γ_c = 20 pm/V). These results show that PZN‐xPT single crystals are very promising materials for electro‐optic modulators in optical communications.     

Crystal growth,dielectric and FIR reflectivity studies on PZN(0.91)‐PT(0.09) single crystals

Crystal growth of PZN‐PT single crystals using slow cooling flux technique with PbO flux is reported in this communication. Optimum growth conditions to maximize the amount of perovskite are also suggested. The grown crystals are characterized by dielectric and FIR spectroscopy. Temperature dependence of ε′ very close to the transition temperature shows a first order phase transition. Diffused phase transition and strong frequency dependence of ε′ around transition temperature are also observed. The real part of ε′ was found to obey the relation ε′ – ε_∞ = χ′(T‐T_o)². Dispersion in the ferroelectric phase is suggested to originate from ordering of domains. Competition in the B‐site occupancy by Zn, Nb and Ti ions is suggested to be the origin for the additional modes in the FIR reflectivity at room temperature. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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)     

Impedance analysis and high temperature conduction mechanism of flux grown Pb(Zn1/3Nb2/3)0.91Ti0.09O3 single crystal

The electrical properties of Pb(Zn_1/3 Nb_2/3)_0.91Ti_0.09O₃ single crystals over a wide range of frequencies (20 Hz to 2 MHz) and temperature (30 to 490 °C) were studied using impedance spectroscopic technique. A strongly frequency dependant Debye type relaxation process in crystals was observed. The activation energy for relaxation was found to be 1.72 eV. The nature of Cole‐Cole plot reveals the contribution of only grain (bulk) effect in the sample. The temperature dependant conductivity was found to different in different temperature regions, which shows the presence of different carrier for conduction. The activation energy for conduction in the order of 1.69 eV suggested that the conduction process in higher temperature region is governed by the presence of lead vacancy defect in the sample. Further, the negative temperature thermistor behaviour of the system was explored and various associated parameters were calculated. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and single crystal X‐ray structure of the tetragonal tungsten bronze Pb0.91K1.72Li1.46Nb5O15

Crystals of Pb_0.91K_1.72Li_1.46Nb₅O₁₅, belonging to tetragonal tungsten bronze materials, were grown by the slow cooling technique, and characterized by means of single crystal X‐ray diffraction: the structure was solved in the P4bm tetragonal space group, with the following unit cell parameters: a = 12.548(5), c = 4.042(5) Å, V = 636.4(9) ų. The three‐dimensional framework can be described as a layered structure down crystallographic axis c, with arrays of NbO₆ octahedra, whose corner sharing makes up the formation of tunnels filled up by Li, Pb and K displaying complex cation‐oxygen coordinations. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Role of oxygen vacancies in the coloration of 0.65Pb(Mg1/3Nb2/3)O3‐0.35PbTiO3 single crystals

The coloration and oxygen vacancies in 0.65Pb(Mg_1/3Nb_2/3)O₃‐0.35PbTiO₃ (PMN‐PT(65/35)) (starting composition) single crystals grown by a so‐called modified Bridgman technique were investigated in this paper. Light yellow and dark brown colored crystals were generally observed for the typical as‐grown PMN‐PT(65/35) single crystals. X‐ray diffraction results demonstrated that they were both of pure perovskite structure, but good electric properties were only obtained for the light yellow crystal. X‐ray photoelectron spectroscopy (XPS) was used to investigate the electronic structure of its components. The O 1s photoelectron spectra of the dark brown colored crystals located at the higher binding energy side, which meant the existence of the more oxygen vacancies. It accordingly led to the formation of the low valence cations associated with the coloration of the crystals, which is also testified by the obtained X‐ray photoelectron spectra of Ti and Nb. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

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(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.     

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.     

Preparation and Characterization of (1 — x) Pb(Mg1/3Nb2/3) O3 — x PbTiO3 Electrocaloric Ceramics

Lead magnesium niobate Pb(Mg_1/3Nb_2/3)O₃ — lead titanate PbTiO₃ [abbr. as (1 — x) PMN — x PT] ferroelectric ceramics with different excesses of MgO and PbO were systematically studied under different processing conditions for ferroelectric refrigeration application. It was found that the excess amount of MgO and PbO, and the sintering temperature have great effect on the crystallographic properties of the ceramics. In our experiments, (1 — x) PMN —x PT (x = 0.08, x = 0.10, and x = 0.25 respectively) with the excesses of 2 mol% MgO and 2 mol% PbO ceramics sintered at 1250 °C/1 hour possess the desired perovskite structures and large electrocaloric temperature change (ΔT = 1 K and more) in the vicinity of room temperature under a dc electric field of 1.5 kV/mm. It is expected that (1 — x) PMN — x PT electrocaloric ceramics could be applied for cascade refrigeration near room temperature.     

Investigation on birefringence property in uniaxial crystal (Ca0.28Ba0.72)0.75(Sr0.60Ba0.40)Nb2O6

The birefringence of (Ca_0.28Ba_0.72)_0.75(Sr_0.60Ba_0.40)Nb₂O₆ crystal is measured basing on polarization‐ extinction method and conoscopic interference method. Experimental results show that the birefringence in this crystal is up to 10^‐5, the natural birefringence in this crystal is (n_o ‐n_e) = 5.89 x 10^‐5 with the He‐Ne laser wavelength at 632.8nm and the birefringence grads with wavelength at 532nm is 5.68 x 10^‐5, which indicate the good optical homogeneity of this crystal. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Theoretical and experimental study on the conoscopic interference in uniaxial crystal (Ca0.28Ba0.72)x(Sr0.60Ba0.40)1‐xNb2O6

Conoscopic interference of polarized light for the white‐light and LPS‐7,5Volts direct current semiconductor laser (Green light) with wavelength at 532 nm in (Ca_0.28Ba_0.72)_x(Sr_0.60Ba_0.40)_1‐xNb₂O₆ crystals were observed with the beams transmitting along optical‐axes and deflection optical‐axes from 0 to 140°. Endo‐exo variation from looseness to tightness of conoscopic interference patterns were analyzed in theory. A hyperbolic black cross of interference patterns were observed as well as its formation process was proposed in this paper. Also, the inferences of the birefringence with different Ca²⁺‐doped were obtained in this investigation. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal and molecular structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione

The crystal structure of 1‐allyl‐5‐(4‐methylbenzoyl)‐4‐(4‐methylphenyl)pyrimidine‐2(1H)‐thione (C₂₂H₂₀N₂OS) has been determined from three dimensional single crystal X‐ray diffraction data. The title compound crystallizes in the monoclinic space group P 2₁/c, with a = 10.6674(13), b = 10.1077(7), c = 17.9467(19) Å, β = 98.460(9)°, V = 1914.0(3) ų, D_calc = 1.251 g cm^–3, Z = 4. In the title compound, the allyl group shows positional disorder. Molecules are linked by C‐H···O, C‐H···N and C‐H···S intermolecular interactions forming two‐dimensional network. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and crystal growth of sillenite phases in the Bi2O3 ‐ TiO2 ‐ Nb2O5 system

The synthesis of Bi₂O₃‐Nb₂O₅ sillenite phase (BNbO) and the solubility of this phase with Bi₁₂TiO₂₀ was investigated by solid‐state reaction synthesis and niobium doped Bi₁₂TiO₂₀ (BTO:Nb) crystals were grown by the Top Seeded Solution Growth (TSSG) technique. The structures of polycrystalline compounds were checked by X‐ray powder diffraction method at room temperature. The correct composition of the sillenite phase stabilized with niobium was determined as Bi₁₂[Nb_0.17Bi_0.83]O_19.7 (BNbO) with unit cell parameter a = 10.261(2) Å. The system BTO‐BNbO is poorly soluble, but niobium doped BTO crystals were grown from the liquid composition 10Bi₂O₃ : xTiO₂ : (1‐x)/2 Nb₂O₅, with x = 0.95 and 0.90. A niobium concentration limit in the liquid phase is established in order to grow BTO:Nb with good crystalline quality. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Synthesis and crystal structure determination of 6,7‐dihydro‐2‐methoxy‐4‐(substituted)‐5H ‐benzo[6,7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile

The compounds 6,7‐dihydro‐2‐methoxy‐4‐(4‐methylphenyl)‐5H ‐benzo[6.7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile (compound IIIa) and 4‐(4‐chlorophenyl)‐6,7‐dihydro‐2‐methoxy‐5H ‐benzo[6,7]cyclohepta[1,2‐b ]pyridine‐3‐carbonitrile (compound IIIb) were synthesized and their structures have been determined from three dimensional X‐ray data using direct method and refined by full matrix least squares with anisotropic thermal parameters for non‐hydrogen atoms to conventional R(gt) of 0.036 and 0.038 for the two compounds respectively. For compound (IIIa) the crystals are monoclinic, space group C_c, with a=11.2909 (5) Å, b=17.7755(8) Å, c=9.1437(4) Å and β=95.428(3)°, while the crystals of the second compound (IIIb) are triclinic, space group P1, with a=8.7465(3)Å, b=10.3958(3)Å, c=10.9011(4)Å, α= 108.3870(10)°, β=101.3741(12)°, γ=97.9594(12)°. The molecular structure of the two compounds have nearly the same configuration, where the cyclohepta ring takes the boat shape and the methoxy and the carbonitrile groups are attached at the same position C₂ and C₈. The difference occurs only at the position C₄, where the substituent is methylphenyl for compound (IIIa) and chlorophenyl for the other. The bond lengths, valency angles and the hydrogen bonding were calculated and fully discussed. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)