Bi4Si3O12晶体的水热法生长研究

采用水热法,以固相烧结的化学计量比(2Bi2 O3∶3SiO2)的玻璃态Bi4Si3O12做培养料,以NaOH溶液为矿化剂,研究了在水热体系下形成Bi4Si3O12晶体的相区.结果发现,在生长温度为380 ～ 500℃,矿化剂浓度为1.5 ～4 mol/L时,自发成核生成的晶粒均为Bi4Si3O12和Bi12SiO20两种物相.通过在矿化剂溶液中外加一定量的SiO2,得到完全纯相的Bi4Si3O12,并生长出尺寸超过8 mm的Bi4Si3O12单晶.无论在矿化剂溶液中是否添加SiO2,生长的Bi4Si3O12都呈四面体形状,显露面以{112}面族为主,Bi4Si3O12晶体的这一结晶习性能够用周期性键链(PBC)理论予以解释.     

稀土元素(Ce、Nd和Eu)掺杂Bi4Si3O12晶体的生长与性能

本文采用坩埚下降法生长出20mm×20mm×100mm优质Bi4Si3O12晶体及Ce、Nd和Eu掺杂Bi4Si3O12晶体.测试了晶体的透射光谱、能谱及光产额、FWHM能量分辨率和激发-发射光谱.总结并解释了掺杂影响Bi4Si3O12晶体闪烁性能的规律,探讨了掺杂改善晶体闪烁性能的可能性.     

Sm掺杂Bi4Ti3O12陶瓷晶体结构及电性能的研究

采用固相反应工艺制备了Sm3+掺杂层状结构无铅Bi4-xSmxTi3O12(x=0.00,0.25,0.50,0.75,1.00,1.25)介电陶瓷.利用XRD、SEM等测试方法研究了Sm掺杂量、烧结温度和保温时间对Bi4-xSmxTi3O12 (BST) 陶瓷晶体结构及电性能的影响.结果表明:所制备的Bi4-xSmxTi3O12陶瓷均具有单一正交相结构,BST陶瓷表面晶粒的显微形貌表现为随机排列的棒状结构.样品的铁电性能测试表明,Sm3+施主掺杂明显降低了BIT的电导率,随着Sm3+含量的增加,Sm3+逐渐有部分取代B位,由于Sm3+取代Ti4+大大降低了氧空位的浓度,使得氧空位对电畴的钉扎作用减弱,并且材料的剩余极化Pr也相应提高.     

(1-x)Bi4Ti3O12-xSrBi2Nb2O9铋层状铁电陶瓷结构与性能研究

采用传统固相法制备了(1-x)Bi4Ti3 O12-xSrBi2 Nb2 O9(BIT-SBN,x=0,0.025,0.050,0.100,0.150,0.200)铋层状无铅压电陶瓷.系统研究了SrBi2 Nb2 O9掺杂对Bi4Ti3 O12基陶瓷物相结构、微观结构以及jie电性能的影响.结果表明:所有陶瓷样品均为单一的铋层状结构;当SBN掺量为0.100时,样品具有最佳的电性能:d33=21 pC/N,相对密度ρ =98.1;,机电耦合系数kp=8.26;,εr=220,介电损耗tanδ =0.29;,剩余极化强度Pr=9.128 μC/cm2,Tc=594℃.同时,SBN的引入增强了样品的抗老化性和热稳定性.     

Sr和Nb复合掺杂Bi4Ti3O12基高温压电陶瓷的研究

采用传统固相法制备了Bi4Ti3O12 +0-91wt;Nb2O5+xwt; SrCO3(BTNO-Sr,0.00≤x≤1.50)层状压电陶瓷,研究了Sr掺杂对BTNO系陶瓷微观结构与电性能的影响.结果表明所有样品均为单一的铋层状结构相陶瓷.适量引入Sr能使BTNO系陶瓷的晶粒尺寸细化与均一,表现出介电弥散性,并改善其压电、机电和铁电性能.当x=0.50时,样品性能最佳:相对密度p=98.8;,压电常数d33=22 pC/N,平面机电耦合系数kp=9.5;,机械品质因子Qm =4462,剩余极化强度Pr=13.01μC/cm2,居里温度Tc=620℃.此外,介电性能和热稳定性能研究显示材料x=0.50具有好的压电稳定性,适合于制备高温高频压电器件.     

Nd掺杂对磁控溅射Bi4-xNdxTi3O12铁电薄膜结构和性能的影响

采用磁控溅射工艺在p-Si衬底上制备了Bi4-xNdxTi3O12铁电薄膜,研究了Nd掺杂对Bi4-xNdxTi3O12薄膜微观结构、介电和铁电性能的影响.结果表明,Nd掺杂并未改变薄膜的晶格对称性,仍然保持Bi层状钙钛矿结构,但能在一定程度上抑制晶粒的生长,使薄膜的晶粒更加细小、均匀,同时能明显改善薄膜的介电、铁电性能.Nd掺杂量x=0.30 ～0.40时,Bi4-xNdxTi3O12薄膜的综合性能较好,其介电常数εr＞250,介电损耗tanδ ＜0.1,剩余极化Pr=20.6 μC/cm2,Ec＜ 150 kV/cm.Ag/Bi4-xNdxTi3O12/p-Si异质结顺时针回滞的C-V曲线表明该异质结可实现极化存储,其记忆窗口达1.6V.但掺杂量不宜过多,当Nd掺杂量达到0.45以后,薄膜的介电、铁电性能反而有所下降.     

Zn0.99Cu0.01Al2O4-SrTiO3微波陶瓷介电性能的研究

以分析纯Zn O、Cu O、Al2O3、Ti O2以及Sr CO3为原料,采用传统固相法制备了(1-x)Zn0.99Cu0.01Al2O4-x Sr Ti O3(ZCAST,x=0~0.045)微波介质陶瓷,利用X射线衍射仪、扫描电镜和网络分析仪对其结构、形貌和微波介电性能进行表征。研究了不同x值对ZCAST陶瓷相组成、显微结构以及微波介电性能的影响。结果表明,ZCAST陶瓷的体积密度、介电常数εr随着Sr Ti O3含量的增多而增大。当x=0.04具有最佳微波介电性能:介电常数εr=14.12,品质因数Q×f=28700 GHz,频率温度系数τf=-1.8×10-6/℃。     

Bi3Ti4O12/α-Bi2O3/TiO2复合光催化剂的制备及其可见光催化活性研究

以工业二氧化钛(TiO2)、五水合硝酸铋(Bi(NO3)3·5H2O)为原料制备了Bi3Ti4O12/α-Bi2O3/TiO2复合光催化剂.采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FT-IR)、紫外-可见吸收光谱(UV-Vis)、荧光光谱(PL)等表征方法对光催化剂结构进行分析,表明复合样品中形成了Bi3 Ti4 O12/α-Bi2 O3/TiO2异质结结构,其禁带宽度减小、吸收带边红移,光催化效率有明显提高.以亚甲基蓝为目标污染物评价其光催化活性,TiO2与Bi(NO3)3·5H2O质量比为1:2.5,煅烧温度为600℃,煅烧时间为5 h时,复合样品光催化活性最佳,在12 W LED灯下,180 min后对浓度为10 mg/L的亚甲基蓝溶液的去除率达96.8;.     

La3+掺杂Ca1-xLaxCu3Ti4O12陶瓷的制备及性能研究

采用固相反应法制备了La3+掺杂的CaCu3Ti4O12(CCTO)陶瓷,研究了La3+掺杂量对Ca1-xLaxCu3Ti4O12(x=0;,1;,3;,5;,7;)陶瓷物相结构、微观形貌和介电性能影响,对La3+掺杂影响CCTO陶瓷介电性能的机理进行了分析.结果表明:x为3;时,开始出现杂相;x高于5;时,陶瓷晶粒开始细化;La3+掺杂可以显著提高CaCu3Ti4O12陶瓷的介电常数,同时介电损耗在高频段也相应降低,从而有助于CCTO陶瓷的综合介电性能的提升.     

La、Nb掺杂对Bi4Ti3O12薄膜介电性能和C-V特性的影响

采用溶胶-凝胶工艺制备了Bi4-xLaxTi3O12和Bi4Ti3-yNbyO12铁电薄膜,研究了La、Nb掺杂对薄膜介电性能和C-V特性的影响.研究表明,在x<0.75、y<0.06范围内,随La、Nb掺杂量的增加, Bi4-xLaxTi3O12和Bi4Ti3-yNbyO12薄膜的介电常数和C-V特性曲线回滞窗口增大,介电损耗和漏电流密度减小.x>0.5时,Bi4-xLaxTi3O12薄膜可获得大于1.8 V的C-V回滞窗口,且经1010极化开关后其回滞窗口的减小未超过6;;而Nb掺杂对增大Bi4Ti3-yNbyO12薄膜C-V回滞窗口的作用更加明显,但经1010极化开关后,其回滞窗口的减小较为明显,并出现一定平移.     

Structural changes during the crystallization of the Bi4Ge3O12 glasses

Bismuth-germanate glass ceramics with the composition 40% Bi₂O₃-60% GeO₂ (in molar percents) were prepared through controlled crystallization of melt-quenched glass. The Raman and FTIR spectra recorded in the as-made glasses show broad bands at 240, 400, 780 cm^− 1 and 400, 745 cm^− 1 have been assigned Ge-O bonds which appear right after preparation. X-ray diffraction has shown that the as-made glasses are amorphous, but after annealing above the crystallization temperature at 558 °C, BGO nano-crystallites with a size of about 50 nm precipitate in the glass matrix. The Raman and FTIR spectra reveal sharp peaks associated to the “internal” and “external vibrations” of GeO₄ tetrahedral groups inside the BGO nano-crystallites. In the glass ceramic sample the transparency region is shifted at longer wavelengths compared to as-made glass, due to the Rayleigh scattering on the BGO nano-crystallites.     

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.     

Y2O3-Al2O3-Nd2O3 phase diagram and the growth of (Y,Nd)3 Al5O12 single crystals

The optimum compositions of the melts used for the growth of yttrium-aluminum garnet (YAG) single crystals with different neodymium contents are determined using the phase diagram of the ternary system Y₂O₃-Al₂O₃-Nd₂O₃ with the binary sections Y₃Al₅O₁₂-Nd₂O₃ and Y₃Al₅O₁₂-Nd₃Al₅O₁₂. A number of melt compositions characterized by one garnet phase, namely, (Y,Nd)₃Al₅O₁₂, are established. Single crystals of yttrium-aluminum garnets with a high content of the activator (up to 2.6 wt % Nd) are grown by the Czochralski method. __________ Translated from Kristallografiya, Vol. 48, No. 5, 2003, pp. 945–949. Original Russian Text Copyright ? 2003 by Soboleva, Chirkin. Dedicated to the 60th Anniversary of the Shubnikov Institute of Crystallography of the Russian Academy of Sciences     

Synthesis and characteristics of Na-doped Bi4Ti3O12 thin films on Si substrate

Bi_3.25Na_2.25Ti₃O₁₂ thin films were prepared on p-Si(1 1 1) substrate by a metalorganic solution decomposition (MOSD) method. The structural characteristic and crystallization of the films were examined by X-ray diffraction. The current–voltage characteristic shows ohmic conductivity in the lower voltage range and space-charge-limited conductivity in the higher voltage range. The dielectric constant is 53 at a frequency of 100 kHz at room temperature and the dissipation factor exists at a minimal value of 0.02 at a frequency of 200 kHz. The retention time estimated by measuring capacitance is about 10⁶ s. Nonhysteretic C–V curves at various frequencies were also collected.     

Enantiomorphism of the Ca3Ga2Ge4O14 compound and comparison of the Ca3Ga2Ge4O14 and Sr3Ga2Ge4O14 structures

The absolute crystal structures of two enantiomorphic forms of the Ca₃Ga₂Ge₄O₁₄ crystals (a = 8.075(1) ?, c = 4.9723(6) ?, space group P321) with the positive and negative senses of the optical activity are determined using X-ray diffraction analysis. The final R factors are as follows: R = 1.75% and R _w = 2.57% for the crystal with the positive sense of the optical activity and R = 1.86% and R _w = 2.78% for the crystal with the negative sense of the optical activity. The replacement of the Ca²⁺ ions by larger Sr²⁺ ions (with the formation of the Sr₃Ga₂Ge₄O₁₄ compound) leads to an anisotropic expansion of the crystal lattice (with a more considerable increase in the lattice parameter a as compared to the lattice parameter c), a change in the occupation of the 1a and 3f positions by the Ga³⁺ and Ge⁴⁺ ions, and symmetrization of the octahedra and tetrahedra forming the structural framework. The shape of the dodecahedron changes so that its size along the polar electric axis 2 increases significantly. This change is the main factor responsible for the increase in the piezoelectric activity of the Sr₃Ga₂Ge₄O₁₄ compound as compared to the piezoelectric activity of the Ca₃Ga₂Ge₄O₁₄ compound. Original Russian Text ? B.V. Mill, A.A. Klimenkova, B.A. Maximov, V.N. Molchanov, D.Yu. Pushcharovsky, 2007, published in Kristallografiya, 2007, Vol. 52, No. 5, pp. 816–823.     

Bridgman growth of Bi4Si3O12 scintillation crystals and doped effects on radiation resistance

Ce, Nd and Eu doped BSO crystals 20×20× 100mm³ in size have been gown by vertical Bridgman method, and the doped effects on radiation resistance of BSO have also been studied for the first time. Nd and Eu dopns were found to improve the radiation resistance of BSO. However, Cc and Nd dopings degrade the light output of BSO except that Eu doping has almost no effect on it. Therefore, Eu may be the most promising dopant candidate for improving the scintillation properties of BSO crystal.     

Decrease in dielectric loss of CaCu3Ti4O12 by the addition of TeO2

CaCu₃Ti₄O₁₂ (CCTO) has challenged for the last few years the scientific community due to its large dielectric constant, which is almost temperature and frequency independent, from 100 K to 400 K and from 1 kHz to 1 MHz, respectively. This makes the material desirable for many electronic applications. However, the dissipation factor is very large, with tan δ values, at room temperature and 1 kHz, higher than 0.1.In our work we report how the addition of TeO₂ lowers the dielectric loss and, although there is a decrease of dielectric constant of doped samples relatively to the undoped one, high dielectric constant values are still being reached. The sample of doped CCTO with 1.5% of TeO₂ by weight, presents, at room temperature and 60 kHz, a large dielectric constant, over 3000, and a dissipation factor around 0.09, which represents a decrease on tan δ over 30% relatively to the CCTO undoped sample. Two relaxation processes were identified for all the samples, one at MHz region and the other one at low frequency region (< 1 kHz). DC bias voltage was applied up to 40 V and a strong dc bias influence on the low frequency region was observed both at dielectric and impedance responses of the undoped sample, which was much weaker than the dc bias effects on the 4% Te doped sample.Dielectric measurements will be discussed and correlated with the samples' microstructure, supported on internal barrier layer capacitance (IBLC) and surface barrier layer capacitance (SBLC) models.     

Simulation of fluid flow in Gd3Ga5O12 melts

Using water or water/glycerine solutions, it has been found possible to simulate the fluid flow seen in Gd₃Ga₅O₁₂ melts and therefore study the effect of crystal rotation and diameter on the fluid flow. It has been found that the flow within the crucible can be described as falling into one of three distinct types each of which has been observed during GGG growth and in other oxide systems. Furthermore, the generation of dislocations during growth and their distribution have been found to be related to the transition from one type of flow to another.     

The growth and structure of Pb3Ga2Ge4O14 and Ba3Ga2Ge4O14 single crystals

Conditions for the flux synthesis of Pb₃Ga₂Ge₄O₁₄ and Ba₃Ga₂Ge₄O₁₄ single crystals and their solid solutions Pb_{3 − x} Ba_xGa₂Ge₄O₁₄ are studied. Structural analysis showed that the Ga³⁺-and Ge⁴⁺-cation positions in flux-grown Pb₃Ga₂Ge₄O₁₄ and Ba₃Ga₂Ge₄O₁₄ single crystals are not mixed. __________ Translated from Kristallografiya, Vol. 49, No. 2, 2004, pp. 325–328. Original Russian Text Copyright ? 2004 by Bezmaternykh, Vasil’ev, Gudim, Temerov. This work was presented at the National Conference on Crystal Growth (NCCG-2002, Moscow).     

Optical properties of and concentration quenching in Bi2O3-B2O3-Ga2O3 glasses

Er₂O₃-doped Bi₂O₃-B₂O₃-Ga₂O₃ glasses were prepared by the conventional melt-quenching method, and the Er³⁺:⁴I_13/2 → ⁴I_15/2 fluorescence properties are studied for different Er³⁺ concentrations. when the Er₂O₃ concentration increases from 0.03 to 3.0 mol%, the measured lifetime of Er³⁺:⁴I_13/2 level decrease from 2.24 to 0.9 m s, and from 0.25 to 0.20 m s for the Er³⁺:⁴I_11/2 level. The fast energy migration among Er³⁺ ions cause the reduction of lifetime of the ⁴I_13/2 level, whereas the change in the ⁴I_11/2 level is mainly due to a cooperative upconversion process (⁴I_11/2, ⁴I_11/2) → (⁴F_7/2, ⁴I_15/2). Based on the dipole-dipole interaction theory, the interaction parameter, C_Er,Er, for the migration rate of Er³⁺:⁴I_13/2 ↔ ⁴I_13/2 was calculated to be 32 × 10⁻⁴⁰ cm⁶ s⁻¹.