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)     

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)     

Growth and characterization of large La1‐xPbxMnO3+δ (x=0.32–0.35) crystals

Large crystals of La_0.63Pb_0.37Mn O_3+δ with small La(Pb)‐ deficiency of about 0.005‐0.01 at.% were grown by high temperature solution growth method. The structure of the grown crystals was determined as rhombohedral with R‐3 space group by single‐crystal X‐ray diffractometry. The surface morphology of the crystals and the exact chemical composition was examined by scanning electron microscopy and energy dispersive X‐ray analysis methods, respectively. The IR‐transmission spectrum reveals the presence of Mn³⁺O₆‐ and Mn⁴⁺O₆‐ octahedra in the lattice of La_0.63Pb_0.37Mn O_3+δ crystals. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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)     

Domain structure and birefringence studies on a 0.91Pb(Zn1/3Nb2/3)O3 ‐0.09PbTiO3 single crystal

Domain structure and phase transition sequence of 0.91PZN‐0.09PT single crystal, grown from high temperature solution, have been analysed using polarised light microscopy. The domain structure of (001)_cub cut single crystal exhibit co‐existence of rhombohedral and tetragonal phases. The sequence and phase transition temperatures have been determined from temperature dependence of birefringence. Birefringence measurements during heating and cooling reveal a first order nature of phase transition between rhombohedral (R3m) and tetragonal (P4mm). The birefringence was measured with accuracy of 10^‐3. However, dielectric measurement does not provide any evidence of R3m ‐ P4mm phase transition. It is shown that in‐situ analysis of domain structure and phase transition can be used as non‐destructive analytical tool for determination of local composition and phase transition sequence. (© 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.     

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.     

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)     

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 of PZN‐PT single crystals and critical issues for higher piezoelectric coefficient

Single crystals of lead zinc niobate‐lead titanate (1‐x)Pb(Zn_1/3Nb_2/3)O₃–xPbTiO₃ for x = 8% and 9% have been grown by flux method using Lead Oxide (PbO) as flux. Low scan rate XRD has been carried out to investigate on the structural influence of the compositional variations in the grown crystals. Transmission spectra in the range of UV‐Vis‐Near IR and mid IR regions have been carried out to understand the distortions caused in the BO₆ octahedral lattice. Morphological aspects of as‐grown PZN‐PT crystals have also been investigated. Dielectric measurements clearly explained the dependence of T_c and diffusiveness with PT content. The values of P_r and E_cobtained from P‐E loops suggest the presence of ordered domain state in these PZN‐PT single crystals. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Preparation,single crystal growth and characterization of bis(tetrabutylammonium)bis(4,5‐dithiolato‐1,3‐dithiole‐2‐thione)copper

The preparation and single crystal growth of bis(tetrabutylammonium)bis(4,5‐dithiolato‐1,3‐dithiole‐2‐thione)copper, (I), are described. The energy gap Eg of (I) is about 2.38 eV. The nonlinear optical susceptibility χ⁽³⁾ is about 1.3×10^‐3 esu at 1064 nm. The characterization of (I) has been performed by electronic absorption, infrared and X‐ray powder diffraction spectroscopy. The thermal behavior of (I) has been investigated by means of thermogravimetric analysis (TGA) and differential thermal analysis (DTA) measurements in air. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of N‐[(1Z)‐1‐(3‐methyl‐3‐phenylcyclobutyl)‐2‐thiomorpholin‐4‐ylethylidene] thiourea

The crystal structure of N‐[(1Z)‐1‐(3‐methyl‐3‐phenylcyclobutyl)‐2‐thiomorpholin‐4‐ylethylidene] thiourea (C₁₈H₂₆N₄S₂) has been determined by X‐ray crystallographic techniques. The compound crystallizes in the orthorhombic space group Pbca, with unit cell parameters: a = 15.692(3), b = 20.803(8), c = 11.979(6)Å, Z = 8, V = 3911(7)ų. The crystal structure was solved by direct methods and refined by full‐matrix least squares to a final R‐value of 0.084 for 1447 observed reflections [I > 2σ ( I ) ]. In the thiosemicarbazide moiety, the S = C bond length is 1.656(6), N‐C‐N angle is 115.6(5)°. The crystal structure is stabilized by the intermolecular N‐H...S hydrogen bonds. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of 4‐(1‐methyl‐1‐mesitylcyclobutane‐3‐yl)‐2‐aminothiazole

The crystal structure of 4‐(1‐methyl‐1‐mesitylcyclobutane‐3‐yl)‐2‐aminothiazole (C₁₇H₂₂N₂S₁) has been determined by X‐ray crystallographic techniques. The compound crystallizes in the triclinic space group P‐1 with Z = 6. The crystal structure was solved by direct methods and refined by full‐matrix least squares to a final R‐value of 0.052 for 2298 observed reflections [I > 2σ ( I ) ]. There are three crystallographically independent molecules, I, II and III. These molecules are held together by intermolecular N‐H...N hydrogen bonds. © 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

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.     

Crystallographic Analysis of Acetyl β ‐boswellic acid

The crystal structure of the title compound (3 α ‐acetoxy‐urs‐12‐en‐24‐oic acid, C₃₂H₅₀O₄) has been determined by X‐ray crystallographic techniques. The compound crystallizes into orthorhombic space group P2₁2₁2₁ with unit cell parameters : a = 12.773(2), b=16.381(4), c=27.929(7)Å. The structure has been solved by direct methods and refined to R = 0.054 for 4930 observed reflections. The structure contains two crystallographically independent molecules in the asymmetric unit which are almost identical in geometry. Rings A, B, D and E have chair conformations while ring C assumes a sofa conformation in both the molecules. The molecules in the structure are linked together by intra‐ and intermolecular O‐H…= and C‐H…O hydrogen bonds.     

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.     

Crystal growth and structure of KBi(WO4)2 single crystals

Potassium bismuth tungstate [KBi(WO₄)₂] single crystals have been grown by the top‐seeded solution growth technique. Bulk crystal with dimensions up to several centimeters is obtained for the first time. Several self‐flux systems have been used for the growth from the solution and the experiments using K₂W₂O₇ as a solvent are detailed. Powder and single crystal X‐ray diffraction of this crystal are reported. The structure refinement shows that KBi(WO₄)₂ crystallizes in the monoclinic space group C2/c, with a=10.837(3), b=10.586(3), c=7.622(2)Å, β=130.860(3)°, V=661.4(3)ų, and Z=4. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Role of oxygen vacancies in the origin of ferromagnetism in Mn‐doped ZnO

The relationship between the oxygen vacancy and ferromagnetism in Mn‐doped ZnO has been studied based on the first‐principles calculations. Three possible charge states of oxygen vacancies, i.e., neutral (V_O⁰), 1+ (V_O¹⁺) and 2+ (V_O²⁺) are considered. Results show that the lattice relaxations around oxygen vacancies are large difference under different charge states. It is found that V_O¹⁺ and V_O²⁺ oxygen vacancies induce ferromagnetism. However, Mn‐doped ZnO system shows ferromagnetism with V_O⁰ oxygen vacancies in hydrogenated environment, the ferromagnetism is attributed to the interstitial H, which forms a bridge bond and mediates d ‐d coupling and stabilizes the ferromagnetic state. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)