Preparation of new ferroelectric glycine phosphite single crystals

An experimental procedure adopted to prepare the recent ferroelectric glycine phosphite single crystals is presented. As the crystal solubility in water depends on temperature, single crystals were grown from fine seed crystals in a saturated solution by employing the slow cooling technique. Transparent, colourless crystals with habit morphology weighing about 8 g were obtained within a month. The same procedure was used to grow single crystals with urea (UGPI). Powder X-ray diffraction studies as well as FTIR studies were carried out on both the crystals. The thermal properties of glycine phosphite (GPI) and UGPI across the ferroelectric phase transition temperature has been carried out. The results will be discussed in detail.     

Growth and physico chemical characterization of lanthanum neodymium oxalate single crystals

Single crystals of lanthanum neodymium oxalate (LNO) are grown in sodium meta silicate gels, by the diffusion of a mixture of aqueous solutions of lanthanum nitrate and neodymium nitrate into the test tube having the set gel containing oxalic acid. The bluish pink coloured tabular crystals of LNO having well defined hexagonal basal planes appear either as ‘foggy’ or ‘clear’, the latter at the greater depths inside the gel. The colouration of LNO visually observed is evidenced in UV-visible spectrum, by the revelation of well pronounced characteristic peaks in the visible region (500–900 nm). X-ray diffraction (XRD) of powdered LNO is ordered, meaning crystalline in nature, besides its ‘isostructurality’ with similarly grown lanthanum samarium oxalate crystals. The single crystallinity of LNO is established by its oscillation XRD pattern. Thermogravimetric analysis (TGA) and differential scanning colorimetry (DSC) support that LNO loses water of crystallization around 120°C and CO and CO₂ around 350–450°C, while the infrared absorption (IR) spectrum of LNO establishes the presence of oxalate (C₂O₄)²⁻ ions. Energy dispersive X-ray analysis (EDAX) confirms the presence of La and Nd in the sample. X-ray photoelectron spectroscopic (XPS) studies of LNO establish the presence of La and Nd in their respective oxide states. An empirical structure for LNO has been proposed on the basis of these findings. The ‘smokiness’ in the foggy LNO crystal has been attributed due to the ‘gel inclusion’ during the growth process.     

碲铟汞晶体制备及其热稳定性研究

以高纯Hg、In、Te单质为原料,通过元素直接化合反应合成了碲铟汞(MIT)多晶料,并利用合成的高纯多晶料,在特殊设计的坩埚中,采用垂直Bridgman法通过自发成核方式成功地生长了尺寸为Φ15mm×175mm的MIT单晶体.利用X射线粉末衍射技术对MIT晶体结构及物相进行的分析表明,所获得的晶体是单相的MIT晶体,为缺陷闪锌矿结构,空间群为F43m.采用高分辨X射线衍射仪测量了所生长MIT晶体的摇摆曲线,结果表明所得晶体完整性较好,为高质量的单晶体.对所生长的MIT晶体进行了热分析,发现在MIT晶体中有Hg溢出现象.     

Growth and characterization of new oxide and fluoride crystals for optical applications

High quality oxide and fluoride single crystals for optical applications have been grown by the Czochralski technique. Lattice parameter investigation of grown Gd₃Yb _x Ga_5−x O₁₂ suggested that this crystal will be a superior material as substrate for optical isolators with large Faraday effect. Growth conditions of (La,Sr)(Al,Ta)O₃ single crystals are discussed. These crystals have excellent lattice matching with GaN, a promising material for optoelectronic devices. Ce-doped fluoride single crystals—LiCaAIF₆, LiYF₄ and BaLiF₃—have been grown for solid state UV laser applications. Growth results and optical characterization are discussed.     

Preparation and characterization of some single,mixed and doped crystals and instrumentation aspects

The preparation and characterization (salient ones) of KAl (SO₄)₂. 12H₂O, KCr (SO₄)₂·12H₂O, mixed crystals of both with 10 to 90% of each component, mixed crystals of CsCl with CuCl₂, doped crystals of KBr with K₃FeCN₆, mixed crystals (NH₄)₂SO₄ with CuSO₄ or NiSO₄, NaCl with growth improver Pb⁺², Mn⁺², metallic crystals of Zn, Bi, ionic crystals of alkali halides with Pb⁺², or Cd⁺², etc. are presented. Instrumentation aspects of a rotary crystallizer, a homogeniser, an ingot release mechanism and a zone refiner are shown.     

Growth and scintillation properties of Yb doped aluminate, vanadate and silicate single crystals

For the purpose of quick screening for charge transfer (CT) transitions of Yb³⁺ in various hosts, (Lu_1−xYb_x)₃Al₅O₁₂ (Yb:LuAG) with x=0.05, 0.15, 0.30 and (Y_1−xYb_x)AlO₃ (Yb:YAP) with x=0.05, 0.10, 0.30 were grown by the micro-pulling-down method. (Y,Yb)VO₄ with strong wetting was grown by edge defined film-fed growth method and materials, which require moderate temperature gradient, such as Ca₈(La,Yb)₂(PO₄)₆O₂ and (Gd,Yb)₂SiO₅ were grown by Czochralski method. Strong dependence of the CT luminescence decay time and intensity on temperature was observed for Yb-doped LuAG and YAP. Super fast decay with 0.85 ns decay time was observed in Yb(30%) doped YAP at room temperature. Though the emission intensity is weak at room temperature, it exceeds several times that of PbWO₄. In addition, CT luminescence of Yb:YAP occurs at longer wavelength than in BaF₂, which enables the usage of glass-based photomultiplier for the detection. In addition, higher stopping power will be expected due to the higher density host compared with BaF₂.     

Growth by SR method and characterization of hippuric acid single crystals

The potential organic nonlinear optical material of hippuric acid (HA) has been grown by novel unidirectional solution growth method using dimethyl formamide (DMF) as the solvent. The crystal system has been identified and lattice dimensions have been measured from the single crystal X-ray diffraction analysis. The crystalline perfection has been evaluated by high resolution X-ray diffraction (HRXRD) technique and found that the crystal quality is reasonably good. However, it contains a low angle structural grain boundary. The relative second harmonic generation (SHG) has been tested using Kurtz powder technique and found to be 1.54 times higher than that of potassium dihydrogen phosphate (KDP) single crystal. Its optical character has been assessed by UV-Vis. analysis and found that there is no absorption in the entire visible region.     

Growth of lithium doped silver niobate single crystals and their piezoelectric properties

Lithium doped silver niobate (Ag_1−xLi_xNbO₃, 0 < x < 0.1) is one of the candidate materials for lead-free piezoelectric materials. In this study, Ag_1−xLi_xNbO₃ single crystals were successfully grown by a slow cooling method. Crystal structure was assigned to perovskite-type orthorhombic (monoclinic) phase. Dielectric properties were measured as a function of temperature. As a result, with increasing lithium contents, the phase transition at around 60 °C was shifted to lower temperature while the phase transition at around 400 °C was shifted to higher temperature. On the basis of these peak shifts, the lithium contents in Ag_1−xLi_xNbO₃ single crystals were determined. Moreover, P–E hysteresis measurement revealed that pure silver niobate crystal was weak ferroelectrics with P_r of 0.095 μC/cm² while Ag_0.9Li_0.1NbO₃ (ALN10) crystal was normal ferroelectrics with P_r of 10.68 μC/cm². About this ALN10 crystal, polling treatment was performed and finally piezoelectric properties were measured. As a result, high electromechanical coupling coefficient k₃₁ over 70% was observed.     

Melt growth and characterization of Mg2Si bulk crystals

We have grown Mg₂Si bulk crystals by the vertical Bridgman method using a high-purity Mg (6N-up) source. The grown crystals were single-phase Mg₂Si and had well-developed grains (1-5 mm³). Laue observations and SEM-EDX observations confirmed that crystalline quality in the grains was single crystal with stoichiometric composition. Electron concentration of the single crystalline specimens grown from 6N-up-Mg was 4.0 × 10¹⁵ cm^− 3 at room temperature (RT). This value is more than one order of magnitude lower than that of specimens grown from 4N-Mg [(5-7) × 10¹⁶ cm^− 3]. The Hall mobility of 14,500 cm²/Vs was observed at 45 K in the crystals grown from 6N-up-Mg. We also found that Al impurity plays an important role in the crystals grown from a low-purity Mg source. From the optical absorption measurement, we estimated that the indirect energy gap was about 0.66 eV at 300 K and about 0.74 eV at 4 K.     

In situ observation of electric-field-induced domain switching and crack propagation in poled PMNT62/38 single crystals

It is important to in situ observe the crack propagation and the corresponding domain switching in ferroelectrics subjected to electric loading since domain switching has been widely assumed to play a critical role in the electric-field-induced crack growth. In this investigation, we in situ observed the crack propagation and the domain switching in PMNT62/38 single crystals poled along the [001] orientation. An experimental setup was designed and constructed to investigate the crack propagation and the domain switching in thin plate specimens with pre-crack subjected to electric field by using polarized light microscope (PLM). The pre-crack began to propagate forward accompanied by the appearance of domain switching zones near the crack tip and the disappearance of switched zones behind the crack tip at the unipolar electric field of E = 0.8E_C. The results indicate that the structure mismatch of the adjacent switched zones with different polarizations stimulated by the intensive electric field near the crack tip results in the electric-field-induced crack growth.     

Growth and characterization of 4-dimethylamino-N-methyl 4-stilbazolium tosylate (DAST) single crystals grown by nucleation reduction method

Good quality single crystal 4-dimethylamino-N-methyl 4-stilbazolium tosylate (DAST) has been grown by novel nucleation reduction method instead of regular slope nucleation technique (SNT). The grown crystal was subjected to high resolution X-ray diffraction (HRXRD) studies, the perfection of the crystal was found to be better than the crystal grown by slope nucleation technique and slow cooling method. The UV-vis-NIR spectrum was recorded for the grown crystal and relative second harmonic generation (SHG) efficiency was investigated to explore the nonlinear optical (NLO) property. The dielectric and thermal behaviour of the crystal were also studied. The nuclear magnetic resonance (NMR) studies also performed for the identification of different modes present in the compound. The photoluminescence and mechanical were carried out and the results were discussed in detail.     

大尺寸硅酸铋晶体的原料合成、晶体生长及闪烁性能研究

以Si(OC₂H₅)₄和Bi(NO₃)₃·5H₂O作为前驱体、柠檬酸作为溶剂, 按化学计量比配料, 采用溶胶-凝胶法合成并经高温烧结制备了纯相Bi₄Si₃O₁₂多晶粉末, 每批次可合成250 g。以此为原料、<001 >取向BSO为籽晶, 在坩埚下降炉内生长了BSO晶体, 讨论了晶体的析晶行为, 获得了30 mm × 30 mm × 210 mm的高质量BSO晶体。闪烁性能测试表明, 该晶体能量分辨率为18.9%, 光输出为同等条件下CSI(T1)晶体的7.2%。     

Crystal growth and scintillation characteristics of the Nd doped LiLuF4 single crystals

Sixty millimeter diameter single crystal of Nd³⁺ doped LiLuF₄ was successfully grown by the Czochralski technique. No remarkable absorption due to unfavorable impurities was observed from optical absorption measurements in the vacuum ultra-violet spectral region. The high crystallinity and homogeneous luminescence characteristics were found from X-ray rocking curve and cathode-ray luminescence respectively. X-ray excited luminescence spectrum was measured and the significant 4f²5d-4f³ luminescence at 182 nm was observed in the grown crystal. The pulse height spectrum was taken upon γ-ray irradiation. As a result, the grown crystals demonstrated sufficient response to the γ-ray showing the light yield of 420 ± 30 photons/MeV. The decay curve under α-ray irradiation was also investigated and described by two component decay kinetics which consists of the decay constants of 34 and 450 ns.     

Growth and characterizations of Ba2Ti2Fe2As4O single crystals

Abstract

Single crystals of a new iron-based superconductor Ba₂Ti₂Fe₂As₄O have been grown successfully via a Ba₂As₃-flux method in a sealed evacuated quartz tube. Bulk superconductivity with T_c ～ 21.5 K was demonstrated in resistivity and magnetic susceptibility measurements after the as-grown crystals were annealed at 500 °C in vacuum for a week. X-ray diffraction patterns confirm that the annealed and the as-grown crystals possess the identical crystallographic structure of Ba₂Ti₂Fe₂As₄O. Energy-dispersive x-ray spectra indicate that partial Ti/Fe substitution exists in the [Fe₂As₂] layers and the annealing process redistributes the Ti within the Fe-plane. The ordered Fe-plane stabilized by annealing exhibits superconductivity with magnetic vortex pinned by Ti.     

Growth and Optical Studies of a Novel Organometallic Complex NLO Crystal: Tetrathiourea Cadmium(II) Tetrathiocyanato Zinc(II)

Tetrathiourea cadmium(II) tetrathiocyanato Zinc(II) (TCTZ) single crystals were grown in acetone-water mixture solvent using slow solvent evaporation technique and their optical property was studied for the first time. Both thiourea and thiocyanate ligands were combined with the transition metal ions Cd²⁺ and Zn²⁺. The nonlinear optical (NLO) efficiency of TCTZ crystal was tested and measured using Kurtz and Perry technique. The dielectric behavior of the sample was also studied.     

Growth and characterization of Bi2Sr2Ca1Cu2O8+x single crystals

High-quality single crystals are well suited to the investigation of some intrinsic material properties. A modified Bridgman method using a sharp temperature gradient (300°C/cm) was used to grow Bi₂Sr₂Ca₁Cu₂O_8+x single crystals. Although the samples were contained in alumina ampoules, no aluminium contamination of the samples was detected. Blade-shaped crystals up to 7–8 mm length and 3–4 mm width could be grown by this method, although extraction from the matrix was difficult. Electron diffraction patterns of the [001] zone axis revealed a high degree of crystallinity. The narrowness of the superconducting transition temperature, as determined by ac susceptibility, also suggests the existence of well-formed crystalline domains. In order to determine the relative orientation of the crystalline domains, electron channeling patterns were recorded from several consecutive growth steps from a fracture surface. The poor contrast of these and Kikuchi patterns suggests the presence of a stacking structure. The results showed a [100] growth direction and (001) cleavage plane. Reversible oxygen loss at the peritectic decomposition temperature of 863°C was observed. Knoop indentation measurements showed that the crystals were quite soft, having a microhardness of 0.44 GPa.