铁电相Tb2(MoO4)3晶体的生长和缺陷研究

钼酸铽[Tb2(MoO4)3]是一种具有铁电、铁弹和顺磁等多种性质的功能晶体.采用提拉法,沿[001]方向生长了φ25 mm×20 mm的铁电相Tb2(MoO4)3晶体.采用化学腐蚀法、扫描电子显微镜(SEM)观察了晶体中的缺陷,结果显示,晶体中的主要缺陷是位错、镶嵌物.高分辨X射线衍射(摇摆曲线)实验表明所生长的Tb2(MoO4)3晶体具有很好的晶格完整性.     

单一基质Na2Ca3Si2O8∶Tb3+,Eu3+荧光粉发光性质和能量传递的研究

通过传统的高温固相法成功的制得了一系列紫外激发的硅酸盐荧光粉Na2 Ca3 Si2O8∶Tb3+,Eu3+.X射线衍射(XRD)研究表明所制得的荧光粉为纯相.在Na2Ca3Si2O8∶Tb3+,yEu3+荧光粉体系中,随着Eu3+的掺杂浓度增大,发射光谱中Tb3的特征峰发光强度降低而Eu3+的不断升高,并且荧光寿命不断减小,说明了Tb3+和Eu3之间能量传递方式是交换相互作用,能量传递效率(ET)达到了15.8;.此外,通过CIE色坐标观察到,随着Eu3+浓度的增加,样品从绿色变成黄色,最终变成红色.由于它多彩的颜色变化,所以它是一种用于制作多彩LED的良好材料.     

狄拉克材料SrMnBi2的单晶制备与物理性质研究

在真空密封的石英管中运用高温助溶剂方法制备出各向异性狄拉克材料SrMnBi2的高品质单晶样品.通过X射线衍射(XRD)、扫描电镜-能量色散X射线光谱仪系统(SEM-EDX)、磁性测量系统(MPMS)和综合物性测量系统(PPMS)等多种测试技术手段综合研究了高品质SrMnBi2单晶样品的晶体结构、化学组成、电学和磁性等性质.结果表明:狄拉克材料SrMnBi2在晶体结构上是一个典型的层状结构化合物,物理性质上是一个反铁磁(TN=290K)金属,具有狄拉克材料的典型特征.     

Tb∶Lu2SiO5光学薄膜的结构演变和发光性能

采用溶胶-凝胶法结合旋涂工艺在单晶硅(111)上制备了Tb3+离子不同掺杂浓度的硅酸镥光学薄膜(Tb∶Lu2SiO5),利用热重差热分析(TG-DSC)、X射线衍射(XRD)、傅里叶红外光谱仪(FTIR)、原子力显微镜(AFM)和紫外可见荧光光谱(PL)对Tb∶Lu2SiO5薄膜的不同温度热处理的结构演变和发光性能进行了表征.研究结果表明Tb∶Lu2SiO5光学薄膜表面均匀、平整、无裂纹,薄膜样品从800℃开始晶华,1100 ℃时晶化完全.Tb∶Lu2SiO5的发光性能表现为Tb3+离子的4f→5d和5D4(5D3)→7FJ(J =6,5,4,3)跃迁结果(监测波长分别为480～650 nm和350～470 nm),激发主峰位于～240 nm,发射光谱主峰为542 nm的绿光发射.研究表明Tb3掺杂浓度对Tb∶Lu2SiO5光学薄膜的发光强度会产生明显影响,掺杂15mol;的Tb3+时,Tb∶Lu2SiO5薄膜的发光强度最强.     

新型( Yb3+,La3+)∶Gd2SiO5和(Yb3+,Tb3+)∶GdTaO4单晶生长及分凝研究

采用提拉法生长了尺寸为φ30 mm × 50 mm的(Yb3+,La3+)∶Gd2SiO5单晶和尺寸为φ24 mm×57 mm的( Yb3+,Tb3)∶GdTaO4单晶,用X射线荧光法测量了掺杂样品的组分浓度在晶体中的分布,拟合了掺杂离子的有效分凝系数,结果表明:Yb3+在Gd2SiO5晶体中的分凝系数为1.185(15),接近单位1,而La3+则为0.68 (10),偏离单位1较多,对晶体的光学均匀性会有较大的影响;Yb3+和Tb3+在GdTaO4中的分凝系数为0.84(14)和0.84(5),接近单位1,对晶体的光学均匀性影响较小.     

导模提拉法生长Tb3Sc2Al3O12(TSAG)晶体及性质表征

本文采用导模提拉法成功生长了Tb3Sc2Al3O12 (TSAG)晶体,并对所生长晶体进行了物相分析和单晶结构分析,探讨了多晶原料的烧结温度对晶体颜色的影响.Sc3+和Al3+的浓度分布测试表明,导模提拉法能较好地克服因分凝效应引起的Sc3+浓度分布不均,可以生长获得浓度分布均匀的TSAG晶体.磁光性能测试表明,Sc3+掺入对晶体在400～1100 nm波长范围内的磁光性能影响不大,所生长TSAG晶体的费尔德常数仅比Tb3Al5O12 (TAG)晶体低6; ～8;.     

铁电相Tb2（M0O4）3晶体的生长和缺陷研究

钼酸铽[Tb2（M0O4）3]是一种具有铁电、铁弹和顺磁等多种性质的功能晶体。采用提拉法,沿[001]方向生长了Ф25mm×20mm的铁电相Tb2（M0O4）3晶体。采用化学腐蚀法、扫描电子显微镜（SEN）观察了晶体中的缺陷,结果显示,晶体中的主要缺陷是位错、镶嵌物。高分辨X射线衍射（摇摆曲线）实验表明所生长的Tb2（M0O4）3晶体具有很好的晶格完整性。     

SiO2@Gd2O3∶Tb3+核壳微球的可控合成及发光性能研究

采用简便的尿素辅助沉淀法将Gd2O3∶Tb3+成功包覆在二氧化硅微球表面合成了尺寸均匀的球形SiO2@Gd2O3∶Tb3核壳发光材料,解决了稀土发光材料普遍存在的形貌可控性差和颗粒尺寸不均一等问题.利用XRD、SEM、红外光谱和荧光光谱等表征测试了样品的形貌、结构和发光性能.SEM照片和尺寸分布图显示,SiO2@Gd2O3∶Tb3+粒子呈现均匀球形形貌,分散性良好,粒径约(608 +18) nm.XRD图谱分析表明,600℃煅烧后,壳层Gd(OH)3CO3完全转变为立方相Gd2O3,结晶性良好,无杂相生成.同时,结合红外光谱推测了SiO2@Gd2O3∶Tb3核壳微球的形成机理,并得出Gd2O3∶Tb3+壳层主要以Si-O-Gd键形式连接在二氧化硅微球表面.在240 nm紫外光激发下,SiO2@Gd2O3∶Tb3核壳微球呈现绿光发射,其中,位于540 nm处的主峰归属于Tb3+的5D4→7F5能级跃迁.不同Tb3掺杂浓度下的发射光谱表明,当Tb3+掺杂浓度为4mol;时,SiO2@Gd2O3∶Tb3+核壳微球的发射强度达到最大值,寿命为1.55 ms,色坐标位于绿色区域,展现了良好的绿光发光性能.     

溶胶-凝胶法制备ZnAl2O4∶Tb3+薄膜及其光学性能研究

使用溶胶-凝胶法在硅片衬底上制备出不同浓度Tb3+掺杂的ZnAl2O4∶Tb3+薄膜,使用X射线衍射(XRD)、热重-示差扫描量热(TG-DSC)、扫描电镜(SEM)以及荧光光谱分析(PL)进行了表征.结果表明,在700 ℃煅烧温度下得到的ZnAl2O4∶Tb3+薄膜能够形成良好的锌铝尖晶石物相.700℃煅烧所得样品以薄膜形态附着在硅片衬底上,薄膜表面存在小尺寸裂纹,且与衬底之间附着良好.在232 nm紫外光激发下,样品的发射光谱由位于489 nm、543 nm、587 nm和620 nm的四个发射峰组成,分别对应Tb3+的5D4→7F1(J=6,5,4,3)的跃迁,并且当Tb3+掺杂浓度为5at;时,样品的发光强度达到最大值,继续增加Tb3+浓度,则会发生浓度猝灭现象,发光强度降低.     

FeYO3/Y2O3:1;Eu3+,1;Tb3+粉体的制备及其磁性研究

以FeCl2和KOH为原料采用水热法制备Fe3 O4粉体,然后以氧化钇、氧化铕和氧化铽为原料制备Eu3+,Tb3+共掺杂的Y2 O3荧光粉体,并通过XRD对粉体的物相结构进行分析;然后以三聚氰胺以及所制备的Fe3 O4和Y2 O3:Eu3+,Tb3+粉体为原料,采用微波烧结法在Ar气氛下制备FeYO3/Y2 O3:1;Eu3+,1;Tb3+粉体,并对其磁学性能进行了研究.研究结果表明:当Fe3 O4,Y2 O3:1;Eu3+,1;Tb3+和三聚氰胺比例为1:3:4时,所制备的FeYO3/Y2 O3:1;Eu3+,1;Tb3+粉体的磁力饱和强度为12.299 emu·g-1,磁力最强.     

Phase diagram of the SrS–Ga2S3 system and its application to the single-crystal growth of SrGa2S4

Ce-doped SrGa₂S₄ compound is expected as a new host material of blue EL devices. However, the basic properties of bulk single crystals have not been fully clarified, since this compound has been mostly synthesized in the form of polycrystals or thin films. Here, we firstly present the pseudo-binary phase diagram of the SrS–Ga₂S₃ system constructed in accordance with our DTA data for single-crystal growth of SrGa₂S₄. It is shown that SrGa₂S₄ compound has a congruent melting point and a eutectic reaction in the side of excess of Ga₂S₃ concentration. On the basis of the phase diagram, single crystals of SrGa₂S₄ are grown using Ga₂S₃ as a self-flux in a horizontal Bridgman furnace. Colorless and transparent crystals having a typical size 2×2×2 mm³ are obtained.     

Growth by self-flux method and post-annealing effect of Bi2Sr2Ca1Cu2Ox single crystals

Post-annealing effects on superconducting characteristics have been studied in Bi₂Sr₂Ca₁Cu₂O_x single crystals grown by a conventional flux method. Also, favorable growth conditions and the effect of the pre-sintering process on the starting materials for flux growth have been examined. The best superconducting behavior is obtained in post-annealed crystals grown from pre-sintered powder materials. The critical current density J_c estimated from magnetization hysteresis in annealed crystals grown with pre-sintered materials is roughly 8×10⁵ A/cm² (Hc) and 5×10⁴ A/cm² (Hc) at 4.2 K at zero field.     

Single-crystal growth of sulphospinel CuIr2S4 from Bi solution

Single crystals of a sulphospinel CuIr₂S₄ have been grown from bismuth solution by a slow cooling method for the first time. The grown crystals have a maximum edge of about 1 mm in size and a mirror-like shining surface. Optimum growth conditions are fairly strict. The specific weight of starting materials for the crystal growth is found to be 0.30 g of CuIr₂S₄ and 10.0 g of Bi in order to obtain good quality crystals. The starting and finishing temperatures for the slow cooling step in the temperature control are 1000 and 500°C. The pertinent cooling rate is 2°C/h. Since the volume of bismuth itself expands in the transition from liquid phase to solid phase, a simple method of separation of the grown crystals from the liquid solution will be proposed for avoiding the mechanical damages to the grown crystals. The single crystals have the normal-spinel structure of the lattice constant a=9.849 Å at room temperature. A step-like anomaly in the susceptibility of the single crystals, corresponding to the metal–insulator transition in the resistivity, occurs much sharply than in the powder specimen.     

Study on phase diagram of Bi2O3---SiO2 system for Bridgman growth of Bi4Si3O12 single crystal

Phase relation of Bi₂O₃---SiO₂ system was evaluated experimentally from DTA and XRD measurements and its stable and metastable phase diagrams were proposed. Although BSO melts near-congruently at 1025°C in the stable phase equilibrium, its melt crystallizes to form metastable phase Bi₂SiO₅ in accordance with the metastable phase diagram while cooling. Therefore, BSO couldn't nucleate and crystallize spontaneously without crystal seed and only Bi₂SiO₅ crystallized at about 850°C with significant supercooling during Bridgman growth. BSO single crystal with 20×20×100mm³ was grown in a vertical Bridgman furnace with a BSO seed according to its phase diagram. The measuring results of scintillation properties of BSO specimen show that its decay constant is 91 ns (about 1/3 of BGO) and light output is 23% of BGO.     

Improved growth of PbI2 single crystals

The phase equilibrium and the crystallization process of lead iodide (PbI₂) melt have been primarily investigated according to the lead–iodine phase diagram. It is found that the iodine evaporation and the segregated lead deposition are the two important factors that affect the PbI₂ crystal quality. The new method of Pulling U-type quartz growth ampoule has been made to impede the decomposition of PbI₂ and the vaporization and condensation of iodine. An orange and translucent PbI₂ single crystal of large size was obtained by the improved growth method, i.e. U-type ampoule pulling. Resistivity of the as-grown crystal is up to 4×10¹¹ Ω cm, and IR transmission is up to 45% in the region from 7800 to 450 cm⁻¹. Therefore, the improved growth method is a promising convenient new method for the growth of high quality PbI₂ crystals.     

Crystal growth of ferroelastic K2Cd2(SO4)3 and the K2SO4-CdSO4 phase diagram

Crystals of congruently melting K₂Cd₂(SO₄)₃ (having the langbeinite structure with a ferroelastic transition temperature of 156°C) were grown by the Bridgman and Czochralski techniques. The former yielded colorless crystals when using oxygen under pressure; the latter yielded tan crystals of slightly smaller unit cell volume and are assumed to be oxygen deficient. The ferroelastic transition was studied by thermal expansion measurements. Reexamination of the phase diagram showed the existence of a previously unreported phase K₆Cd(SO₄)₄ which is stable only between 520°C and the melting point of about 890°C.     

Growth of new spinel compounds CuInSnS4 and CuIn11S17

Two new spinel structure compounds CuInSnS₄ and CuIn₁₁S₁₇ are reported. The latter has the same composition formula as the superionic distorted defect spinel compound β-alumina. They were prepared by the reaction of alloys of the metals with sulphur vapour. The lattice parameters are 10.4938 ± 0.0002 and 10.73004 ± 0.0003 Å respectively. Single crystals of CuInSnS₄ were grown by temperature gradient annealing of powdered CuInSnS₄ at 680°C. Well faceted {111} habit crystals were produced and examined by electron probe microanalysis to confirm the composition. It is thought that these crystals grew by chemical diffusion and vapour growth in the vapour state controlled mode.     

Growth and properties of Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 single crystals directly from melt

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by a modified Bridgman method directly from melt using an allomeric Pb[(Mg_1/3Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal as a seed. X-ray diffraction (XRD) measurement confirmed that the as-grown PZNT91/9 single crystals are of pure perovskite structure. Electrical properties and thermal stabilization of PZNT91/9 crystals grown directly from melt exhibit different characters from those of PZNT91/9 crystals grown from flux, although segregation and the variation of chemical composition are not seriously confirmed by X-ray fluorescence analysis (XPS). The [0 0 1]-oriented PZNT91/9 crystals cut from the middle part of the as-grown crystal boules exhibit broad dielectric-response peaks at around 105 °C, accompanied by apparent frequency dispersion. The values of piezoelectric constant d₃₃, remnant polarization P_r, and induced strain are about 1800–2200 pC/N, 38.8 μC/cm², and 0.3%, respectively, indicating that the quality of PZNT crystals grown directly from melt can be comparable to those of PZNT91/9 single crystals grown from flux. However, further work deserves attention to improve the dielectric properties of PZNT crystals grown directly from melt. Such unusual characterizations of dielectric properties of PZNT crystals grown directly from melt are considered as correlating with defects, microinhomogeneities, and polar regions.     

Growth of single crystals of NaH2PO4 (NaDP), NaH2PO4 · H2O (NaDP · H2O), and NaH2PO4 · 2H2O (NaDP · 2H2O) sodium dihydrogenphosphate based on the analysis of the Na2O-P2O5-H2O phase diagram

The crystallization conditions for the NaH₂PO₄, NaH₂PO₄ · H₂O, and NaH₂PO₄ · 2H₂O solid phases have been established from the analysis of the phase diagram of solubility of the ternary Na₂O-P₂O₅-H₂O system in the temperature range from 0 to 100°C. Based on these data, the methods for growing sodium dihydrogenphosphate single crystals of the above compositions are developed. The initial components for preparing mother solutions were H₃PO₄ and NaOH solutions taken in certain weight ratios. For the first time, NaDP, NaDP · H₂O, and NaDP · 2H₂O single crystals were grown on a seed by the method of temperature decrease. The habits of the NaDP and NaDP · H₂O single crystals are determined. __________ Translated from Kristallografiya, Vol. 47, No. 5, 2002, pp. 937–944. Original Russian Text Copyright ? 2002 by Soboleva, Voloshin.     

Solution growth of CuGaS2 and CuGaSe2 using CuI solvent

The phase diagrams of the CuGaS₂-CuI and CuGaSe₂-CuI pseudobinary systems are investigated. Both systems show eutectic behavior; liquids along the liquids curves for solute concentrations of more than 15 mol% are shown to be single phase and solids in equilibrium with the liquids are demonstrated to be CuGaS₂ and CuGaSe₂ chalcopyrite compounds. On the basis of the results, bulk crystals of CuGaS₂ and CuGaSe₂ are prepared from CuI solutions using the Bridgman technique. The photoluminescence spectra of these crystals are nearly the same as those of the crystals grown by iodine transport method.