狄拉克材料BaMnBi2的单晶制备和物理性质研究

在本工作中,我们成功制备了层状过渡金属磷族化合物BaMnBi2单晶样品,并研究了该化合物的磁学性质和电学输运性质.准二维化合物BaMnBi2具有四方晶体结构,主要包含有两个Bi四方格子层和一个共边的MnBi4四面体层.磁化率显示BaMnBi2在TN ＝288 K以下发生反铁磁相变,并表现出很强的磁各向异性.在反铁磁相变温度TN 以上,磁化率随温度呈线性关系,暗示体系在顺磁态具有很强的反铁磁关联.电阻率随温度变化曲线和在磁场下电阻率随角度的变化曲线都表明BaMnBi2具有准二维的电子结构.磁场导致的金属-绝缘体转变和低温下大的非饱和线性磁阻,与Bi四方格子层存在狄拉克费米子是一致的.     

狄拉克材料CaMnBi2的单晶制备与物理性质研究

采用高温助溶剂方法制备出各向异性狄拉克材料CaMnBi2的高质量大尺寸单晶样品.综合运用X射线衍射(XRD)、扫描电镜-能量色散X射线光谱仪系统(SEM-EDX)、综合物性测量系统(PPMS)等测试手段对CaMnBi2高质量单晶样品的晶体结构、化学成分、电学、磁学和热学性质进行了系统的研究.结果表明:CaMnBi2的晶体结构是由MnBi(1)四面体层、Ca原子层以及Bi(2)四方格子层构成,它们按照MnBi(1)-Ca-Bi (2)-Ca-MnBi(1)的顺序沿c轴方向堆垛形成“三明治”型层状结构;这些不同的结构层对物理性质有不同的作用,其中Bi(2)四方格子层对电输运性质和狄拉克电子起主要作用,而MnBi(1)层中Mn2+对磁学性质的起着决定作用.这两个功能层的共同作用下该材料具有层状准二维电子系统的典型特征,并且表现出金属反铁磁(TN=270 K)行为.     

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.     

光学浮区法生长Bi2Sr(Ca)2Co2Oy晶体及电输运性质研究

采用光学浮区法生长了层状过渡金属氧化物Bi2Sr2-xCazCo2Oy(x=0,2)晶体.通过XRD,SEM和TEM结构表征,表明了生长的晶体为层状晶体,并确定了晶体生长的方向垂直与c轴.研究了晶体的热电性能,包括Bi2Ca2Co2Oy和Bi2Sr2Co2Oy晶体ab面的Seeback系数和电阻率,表明了Bi2Ca2Co2Oy具有较好的热电势和电导,并分析了电输运性能与晶体失配结构的关系.     

高分子辅助化学溶液沉积法制备La0.7Sr0.3MnO3/Si薄膜及电磁输运研究

利用高分子辅助化学溶液沉积法在Si(100)衬底上外延生长La0.7Sr0.3MnO3薄膜.并利用X射线衍射仪结果、扫描电子显微镜结果和电阻率-温度曲线(ρ-T曲线)结果、磁电阻(MR)曲线结果对其晶体结构、表面形貌和电磁输运机制进行了研究.结果显示实验制备的La0.7Sr0.3MnO3薄膜为赝立方钙钛矿多晶结构,薄膜表面均匀平滑,结晶性好,晶粒尺寸约为50~70 nm.随着温度降低,薄膜电输运机制从绝缘体行为向转变金属导电行为.金属绝缘转变转变点温度(TMI)随磁场的增加而升高,在0 T和1 T分别为TMI=238K、246 K.电输运测试结果说明,低温(TTMI)时薄膜按照绝热近似的小极化子输运.     

镧钙锰氧陶瓷转变温度各向异性的研究

为了进一步提高La-Ca-Mn-O体系巨磁阻陶瓷的转变温度,利用固相反应法制备了La_(0.67)Ca_(0.33)MnO_3巨磁阻陶瓷柱状(φ13 mm×8 mm)样品,研究了不同切型对转变温度的各向异性的影响.通过R-T曲线测量发现沿与样品压力轴垂直和平行的方向切割制成的样品,在零磁场和施加0.5 T的磁场强度时转变温度均相差80 K.利用XRD和SEM研究了样品的相结构和微观结构,初步解释了转变温度差异的机理.     

Pechini法合成Bi2Sr2CaCu2O8+δ超导薄膜的研究

采用Pechini法在STO(100)单晶基底上制备Bi2Sr2CaCu2O8+δ(Bi2212)超导薄膜.重点研究了金属离子比例与预处理温度对Bi2212薄膜相组成及表面形貌的影响.结果表明,适当增加初始计量中Ca的摩尔比,有利于纯相的形成.预处理温度不仅影响样品的表面形貌,同时对相纯度的影响也很显著.较佳条件下,1108 K温度下热处理10 min可制备具有c轴外延取向的纯Bi2212相薄膜.     

(Na1/2Bi1/2)TiO3-(Na1/2Bi1/2)(Zn1/3Nb2/3)O3无铅压电陶瓷的介电特性研究

采用固相合成法制备了(1-x)(Na1/2Bi1/2)TiO3-x(Na1/2Bi1/2)(Zn/23Nb2/3)O3(简写为(1-x)NBT-xNBZN)无铅压电陶瓷.研究了该体系陶瓷晶体结构、弥散相变特征与介电弛豫行为.X射线衍射分析表明,所研究的组成均能够形成纯钙钛矿(ABO3)型固溶体.当x≥0.5%摩尔分数时,该体系陶瓷具有三方、四方共存的晶体结构.材料的介电常数-温度曲线显示陶瓷具有两个介电反常峰Tf和Tm.修正的居里-外斯公式较好的描述了陶瓷弥散相变特征,弥散指数随x的增加而增加.x≤0.5%摩尔分数的陶瓷仅在低温介电反常峰Tf附近表现出明显的频率依赖性,随x的增加,陶瓷材料在室温和低温介电反常峰Tf之间都表现出明显的频率依赖性.根据有序-无序转变和宏畴.微畴转变理论探讨了该体系陶瓷介电弛豫特性的机理.     

0．94Na1／2Bi1／2TiO3—0．06BaTiO3无铅压电单晶的生长及电学性能研究

采用坩埚下降法成功生长出尺寸达φ15 mm×50 mm的0.94Na1/2Bi1/2TiO3-0.06BaTiO3(NBBT94/6)无铅压电单晶.利用X射线荧光沿纵向对晶体棒成分分析表明:Na 、Bi3 、Ti4 离子的含量沿纵向波动较小,而Ba2 离子的含量却波动较大.XRD结构分析表明,晶体棒的中、下部分属于三方相钙钛矿结构,而上部转变为四方相钙钛矿结构.详细研究晶体棒中部0.952Na1/2Bi1/2TiO3-0.048BaTiO3(NBBT95.2/4.8)的介电及压电行为表明:非自发极化方向[001]、[110]样品的退极化温度Td分别为200℃和150℃,具有明显的结晶学方向依赖性,且在Td附近表现出典型的介电弛豫行为;在3～5 kV/mm电压极化下,[001]、[110]方向样品的最大压电系数d33分别为165 pC/N、110 pC/N,机电耦合系数kt分别为49.8%、45.0%.     

Bi2 S3/TiO2复合光催化剂的制备及光催化还原Cr(Ⅵ)性能研究

环境中污染物的低耗能绿色处理方法,特别是环境中重金属Cr(Ⅵ)的绿色处理方法,是近年来的热点研究领域.本文首先制备了TiO2单晶颗粒,之后与不同量的Bi2 S3进行复合,制备了Bi2 S3/TiO2复合光催化材料.研究了不同的Bi2 S3复合量对所制备样品的组成、形貌、结构和光催化还原Cr(Ⅵ)性能的影响.通过XRD、SEM、TEM、DRS、SPV等方法对样品进行了表征.研究结果表明,TiO2表面复合有棒状的Bi2 S3,复合样品对Cr(Ⅵ)的可见光光催化还原效率明显高于纯TiO2,其中0.02 mol/L的Bi(NO3)3反应液制备的复合样品具有最高光催化还原效率.对样品催化机理研究表明,Bi2 S3/TiO2复合材料的带隙随着Bi2 S3含量的增加而变窄,对可见光的吸收和利用效率明显提高;并且TiO2与Bi2 S3的复合,可以减弱光生电子和空穴的复合,从而有效地利用了光生电子,提高了样品对Cr(Ⅵ)的光催化还原效率.     

(C2N2H10)2Mg(HP2O7)2·2H2O synthesis and crystal structure

(C₂N₂H₁₀)₂Mg(HP₂O₇)₂·2H₂O, is a new inorganic organic hybrid structure. It has been synthetized using wet chemistry. Its crystal structure consists of cis- and trans-edge sharing [MgO₄(H₂O)₂] octahedra resulting in chains, which are linked via [HP₂O₇] units to form [Mg(HP₂O₇)₂(H₂O)₂]⁴⁻ layers. The Mg²⁺ cations and the ethylendiammonium cations are located on centers of inversion. The ethylendiammonium cations are alternately located in the interlayer space. The cohesion of the crystal is well ensured by coulombic interactions between anions and cations and by several hydrogen bonds. The diphosphate anion shows an eclipsed conformation.     

Crystal structure of Rb2[GeO2(OH)2]·2H2O

Single crystals of Rb₂[GeO₂(OH)₂] · 2H₂O are studied by X-ray diffraction. The crystals belong to the orthorhombic system, sp. gr. Pna2₁, a = 13.523(6) Å, b = 8.143(4) Å, c = 13.407(6) Å, Z = 8, R ₁ = 0.0506. In [GeO₂(OH)₂]^2? anions, the Ge-O distances (1.71–1.73(1) Å) are shorter than the Ge-OH distances (1.76–1.80(1) Å). Anions are linked to each other by pairs of hydrogen bonds to form infinite chains. The chains are linked by hydrogen bonds involving water molecules to form a 3D structure. The assignment of the bands in the IR spectrum of the compound under study is performed.     

通过SiO2涂层改善BaSi2O2N2∶Eu2荧光粉的热性能

本文研究了SiO2涂层对BaSi2O2N2∶ Eu2蓝绿色荧光粉发光性能和热性能的影响.采用溶胶-凝胶法制备了SiO2包覆的BaSi2O2N2∶Eu2+蓝绿色荧光粉.实验结果表明,最佳镀膜量为6wt;,当镀膜量大于此值时,荧光粉亮度迅速降低.涂覆SiO2后,在150℃下BaSi2O2 N2∶Eu2荧光粉的热猝灭性能提高了2.4;,在500℃热降解后荧光粉的发光性能提高了15;.SiO2涂层显著提高了BaSi2O2N2∶Eu2+荧光粉的热稳定性.SiO2涂层的作用机理是在荧光粉表面和氧化气氛之间形成阻挡层,保护Eu2的发光中心在热加热过程中不被氧化.     

Optical properties of the germanate melilites Sr2MgGe2O7, Sr2ZnGe2O7 and Ba2ZnGe2O7

Refractive indices and their dispersion in the wavelength range from 365 nm to 2325 nm and transmission ranges of the tetragonal melilite‐type germanates Sr₂MgGe₂O₇, Sr₂ZnGe₂O₇ and Ba₂ZnGe₂O₇ were determined. The uniaxial positive crystals Sr₂MgGe₂O₇ and Ba₂ZnGe₂O₇ both offer the possibility for phase matched second harmonic generation, a detailed analysis of phase matching conditions is given. The refractive indices of Sr₂ZnGe₂O₇ show an isoindex (isotropic) point at 467 nm. The investigation was performed on Czochralski grown large single crystals. The crystal structure of all three germanates were determined by means of X ‐ray diffraction. The results corroborate unmodulated melilite‐type structures at room temperature. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Crystal structure of bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate, [C6H5CH2CHCH2CH2NH2CH2CH2]2HPO4·5H2O

The salt bis 4-benzyl piperidinium monohydrogenmonophosphate pentahydrate is orthorhombic with the following unit cell dimensions: a = 11.235(2) Å, b = 27.924(6) Å, c = 9.321(4) Å space group Pca2₁ with Z = 4. The structure was solved by the Patterson method and refined to final R value of 0.049 for 1802 independent reflections. The flack parameter is 0.14 with an e.s.d. of 0.23. The structure consists of infinite parallel two-dimensional [110] planes built of mutually connected ions and water molecules by strong O—H,...,O and N—H,...,O hydrogen bonding. There are no contacts other than normal van der Waals interactions between the layers.     

Identification of a new family of diphosphate compounds, AI2BII3(P2O7)2: Structures of Ag2Co3(P2O7)2, Ag2Mn3(P2O7)2, and Na2Cd3(P2O7)2

Syntheses and single-crystal X-ray structural results are reported for three new mixed diphosphates of the family A^I ₂B^II ₃(P₂O₇)₂; Ag₂Co₃(P₂O₇)₂ (I), Ag₂Mn₃(P₂O₇)₂ (II), and Na₂Cd₃(P₂O₇)₂ (III). All crystallize in the triclinic system, space group P1 bar: (I) a = 5.351(4), b = 6.375(4), c = 16.532(4) Å, = 80.83(6) = 81.45(4), = 72.87(5)°, V = 528.9(6) ų, Z = 2, D _calc = 4.649 mg/m³, R/Rw = 0.0428/0.0548 for 3949 obs. reflns; (II) a = 5.432(7), b = 6.619(6), c = 16.51(3) Å, = 80.78(8) = 82.43(9), = 72.82(7)°, V = 557.7(13) ų, Z = 2, D _calc = 4.338 mg/m³, R/Rw = 0.0679/0.1303 for 2100 obs. reflns and (III) a = 5.67(3), b = 7.08(4), c = 7.90(4) Å, = 77.0(2), = 82.5(2), = 67.8(2)°, V = 286(3) ų, Z = 2, D _calc = 4.249 mg/m³, R/Rw = 0.0307/0.0342 for 1945 obs. reflns. (I) and (II) are isostructural but (III) is of a different type. All three structures are characterized by layers of P₂O₇ groups alternating with layers of mixed metal atoms. Differences are seen in the conglomerate bonding patterns of B atoms and in the irregular geometry of Ag in (I) and (II) compared to the octahedral bonding seen for Na in (III). The differences in structure may be understood in terms of the ratios of the ionic radii of A and B atoms.     

Synthesis and characterization of (NH4)2CuBr2Cl2·2H2O crystals

Single crystals of a new compound, (NH₄)₂CuBr₂Cl₂.2H₂O, were grown from saturated aqueous solution at room temperature by slow evaporation method. The grown crystals were characterized through elemental, powder XRD, thermal and DSC analyses and FTIR and far IR spectra. The elemental analysis and the decomposition pattern formulated using the TG‐DTG studies confirm the stoichiometry of the compound. The crystallinity of the compound is confirmed from the powder XRD pattern. A preliminary single crystal X‐ray diffraction structural analysis reveals that the title compound belongs to the orthorhombic system with a = 7.7466 Å, b = 7.783 Å and c = 8.1211 Å. The low temperature DSC shows thermal anomalies at –161.1, –156.5, –152.4, –145.2, –134, –18.5, and 1.4°C during the heating run and at –4.3, –54.8, –66.1, –90.6, –109.7 and –147.2 °C during the cooling run. The thermal hysterses indicate first order phase transitions in the title compound at these temperatures. The FTIR spectra were used to assign the characteristic vibrational frequencies due to NH₄⁺, CuX₄^2– ions and other chemical bonds. The effect of substitution of two bromine atoms on the phase transitions of a closely related crystal, diammonium tetrachloro cuprate dihydrate is also discussed. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Oxygen-conducting compounds with La2Mo2O9 structure in the ternary system La2Mo2O9-Sm2W2O9-Sm2Mo2O 9 + : Synthesis and properties

Polycrystalline samples in the ternary system La₂Mo₂O₉-Sm₂W₂O₉-Sm₂Mo₂O ₉ ⁺ were synthesized in air. The region of the existence of compounds with the lanthanum molybdate (La₂Mo₂O₉) structure in this system was determined. The polymorphism of the synthesized compounds was studied. Doping with samarium or with samarium and tungsten was shown to lead to the suppression of the transition between the monoclinic and cubic phases α → β and the appearance of the transition β _ms → β between two cubic phases. In samples with a high samarium content, the phase transition β _ms → β manifests itself as significant anomalies in the temperature dependences of the dielectric permeability and electric conductivity. An increase in the concentration of samarium in the samples leads to a substantial decrease in the conductivity compared with the nondoped compound La₂Mo₂O₉.     

Structure of {Pb[S2CN(C2H5)2]2(1,10-phenanthroline)}2

Lead (II) nitrate reacts with 1,10-phenanthroline and sodium diethyldithiocarbamate in water to produce yellow bisdiethyldithiocarbamata 1,10-phenanthroline lead(II). Crystals from water are triclinic, space group $P\bar 1$ (#2),a=10.53(2) Å,b=11.050(12)Å,c=24.74 (3) Å, α=94.71 (9)⁰, β=98.15(11)^o, γ=114.11(9)^o,V=2569(6) ų,Z=2. Each lead atom has approximate pentagonal pyramid coordination geometry through the nitrogens of a phenathroline and sulfurs of two dithiocarbamates. Additionally, complexes form loose dimers in which lead atoms are weakly coordinated to a sulfur in an adjacent complex. IR and proton nmr spectrum of the complex are consistent with the solid state structure.