钙钛矿锰氧化物(La1-xGdx)4/3Sr5/3Mn2O7 (x=0, 0.025) 磁性和输运性质研究

采用传统的高温固相烧结法制备了双层钙钛矿锰氧化物(La_1-xGd_x)_4/3Sr_5/3Mn₂ O₇ (x=0, 0.025)多晶样品. 通过X射线衍射仪研究发现样品为Sr₃Ti₂O₇型四方结构, 空间群为I4/mmm; 磁性测量表明, Gd³⁺掺杂后的样品(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂O₇的三维磁有序转变温度(T_C1^3D)、磁化强度(M)均降低, 这是由于Gd³⁺的掺杂引起晶格的畸变, 从而使得晶格常数发生改变, 减弱了铁磁耦合而导致的; 通过电子自旋共振谱测量发现, 在T_C^3D<T<300 K温度范围内, 两样品在顺磁的基体上均有短程的铁磁团簇存在, 出现了相分离现象. 电性测量表明: 两样品分别在T_C1^3D (La_4/3Sr_5/3Mn₂O₇ 样品的三维磁有序转变温度, T_C0^3D)<T<300 K温度范围内均以三维变程跳跃的方式导电, 分析得出Gd³⁺的掺杂使得载流子局域长度的减小. 这表明载流子需要吸收更多的能量才能克服晶格的束缚进行跳跃, 因此(La_0.975Gd_0.025)_4/3Sr_5/3Mn₂ O₇ 样品的电阻较高.     

First-principles investigation of A-B intersite charge transfer and correlated electrical and magnetic properties in BiCu3Fe4O12

First-principles calculations using the augmented plane wave plus local orbitals method, as implemented in the WIEN2K code, have been carried out to study the A-B intersite charge transfer and the correlated electrical and magnetic properties of the perovskite BiCu(3)Fe(4)O(12), especially as regards the charge transfer. The results indicate that the charge transfer between A-site Cu and B-site Fe is by way of O 2p orbitals, and during this process orbital hybridization plays an important role. More importantly, the charge transfer is of 3d(9) + 4d(5)L(0.75) →3d(9)L + 4d(5) type (here L denotes an oxygen hole or a ligand hole). During this process, the magnetic interaction experiences a transition from Cu-Fe ferrimagnetic coupling to G-type antiferromagnetic coupling within B-site Fe with paramagnetic Cu(3+). As to electrical property, it undergoes a metal to insulator transition. All our calculated results are consistent with the available experimental results.     

Structural phase transition and magnetic properties of layered organic-inorganic hybrid compounds: p-Haloanilinium tetrachlorocuparate(II)

Compounds of the general formula A₂CuCl₄, (where A = 4-fluoroanilinium (1) and 4-chloroanilinium (2)) were prepared, structurally characterized and their thermal and magnetic properties studied. These compounds have a layered structure, distorted perovskite, where layers of CuCl₄²⁻ are sandwiched between a 4-haloanilinium cation bilayer. A single crystal X-ray diffraction study on (4-fluoroanilinium)₂CuCl₄, (1), shows that it crystallizes in the monoclinic P2₁/c space group with cell dimensions a = 15.5113(5) Å, b = 7.3788(2) Å, c = 7.0929(2) Å, β = 99.004(2)°, volume 801.81(4) Å³ at 150 K. Compound 2, (4-chloroanilinium)₂CuCl₄, crystallizes isostructurally to 1 at RT, but at 150 K it adopts the Pccn space group. This structural transition for 2 is reversible, and has been observed using Differential Scanning Calorimetric (DSC) measurements. The dc-magnetic studies using a SQUID magnetometer suggest that both compounds are soft ferromagnets and show an onset of long range magnetic ordering below 9 K. The ac-susceptibility measurements confirm the presence of this ferromagnetic ordering in both the compounds.     

The ferroelectric phase of CdTiO3: A powder neutron diffraction study

The synthesis of bulk samples of polycrystalline CdTiO₃ in both the rhombohedral ilmenite and orthorhombic perovskite forms is described and the structures of these have been refined using powder neutron diffraction data. This involved the preparation of samples enriched in ¹¹⁴Cd. Cooling perovskite-type CdTiO₃ to 4 K induces a ferroelectric phase transition, with the neutron data suggesting the low temperature structure is in Pna2₁. Mode analysis shows the polar mode to be dominant at low temperatures. The ilmenite-structure of CdTiO₃ is compared with that of ZnTiO₃. The refined scattering length of the ¹¹⁴Cd is estimated to be 5.56 fm. Attempts to dope CdTiO₃ with Ca and Sr are described.     

Single-crystal X-ray diffraction at megabar pressures and temperatures of thousands of degrees

The most reliable information about crystal structures and their response to changes in pressure and temperature is obtained from single-crystal diffraction experiments. We have developed a methodology to perform single-crystal X-ray diffraction experiments in laser-heated diamond anvil cells and demonstrate that structural refinements and accurate measurements of the thermal equation of state of metals, oxides and silicates from single-crystal intensity data are possible in pressures ranging up to megabars and temperatures of thousands of degrees. A new methodology was applied to solve the in situ high pressure, high temperature structure of iron oxide and study structural variations of iron and aluminum bearing silicate perovskite at conditions of the Earth's lower mantle.     

CaTiO3基微波介质陶瓷的频率温度稳定性

通过对克劳修斯-莫索蒂方程的近似, 分析了钙钛矿结构微波介质陶瓷频率温度系数 (τ_f) 的主要影响因素, 发现改变材料介电响应中离子位移极化和电子位移极化的比例, 可调节频率温度系数的正负与大小. 通过电子结构计算和容忍因子分析, 预测引入(Zn_1/3Nb_2/3)⁴⁺对具有正温度系数 的CaTiO₃进行B位取代将提高材料电子极化响应比例, 调节τ_f由正变负. 采用偏铌酸盐为前驱体, 通过固相反应法合成了Ca[(Zn_1/3Nb_2/3)_xTi_(1-x)]O₃钙钛矿结构陶瓷, 并对其进行结构分析和性能测试, 实验结果与理论分析一致, 获得了具有近零频率温度系数的Ca[(Zn_1/3Nb_2/3)_0.7Ti_0.3]O₃介质陶瓷材料. 关键词： B位复合钙钛矿陶瓷 谐振频率温度稳定性 极化机理 6八面体倾斜')" href="#">BO₆八面体倾斜     

Effect of Cu doping on the magnetic and electrical properties of n=2 Ruddlesden-Popper manganates

A series of polycrystalline Cu-doped n=2 Ruddlesden-Popper manganates La1.2Sr1.8CuzMn（2-x）O7 （x=0, 0.04, 0.13） were synthesized by the solid state reaction method. The effect of Cu doping on the magnetic and transport properties has been studied. It is found that Cu substitution for Mn greatly affects the magnetic and electrical properties of the parent phase La1.2Sr1.8Mn2O7. With the increase of Cu content, the system undergoes a transition from longrange ferromagnetic order to the spin glass state and further to an antiferromagnetic order. A little of Cu dopant can lead to the samples showing semiconductor or insulator behaviour in the whole observed temperature range while the parent phase has a metal-insulator transition. These samples show colossal magnetoresistance at low temperatures and the value of it decreases with increasing Cu content.     

Structural, magnetic and transport properties of double perovskite compounds (Sr2−3xLa2xBax)FeMoO6

The crystal structure and magnetic properties of a series of ordered double perovskite oxides (Sr_2−3xLa_2xBa_x)FeMoO₆ (0x0.3) have been investigated. X-ray powder diffraction reveals that the crystal structure of the compounds changes from a tetragonal I4/m lattice to a cubic lattice around x=0.2. Though the nominal average size of the A site cation of (Sr_2−3xLa_2xBa_x)FeMoO₆ is designed to be almost independent of x, the refinements of the crystal structure show that the lattice constants increase with x in both the tetragonal and the cubic phase regions due to electron doping. As the x increases, the degree of cationic ordering on the B site is decreased pronouncedly, while the Curie temperature of the compounds is nearly unchanged. The saturation magnetization of the compounds decreases with x and shows a linear dependence on the degree of cation ordering. The resistivity of the parent compound shows a semiconducting behavior below room temperature, but those of the doped samples exhibit a metal–semiconductor transition. A correlation between the resistivity and metal-semiconducting transition temperature (T_M−S) is observed. The resistivity and T_M−S of the compounds decrease with x for x0.2 and increase for x0.2. Magnetoresistance of the compounds is reduced by the La/Ba doping. All these observations can be understood based on the interplay of the electron doping, change in bandwidth and the anti-site defect concentration.     

Electromagnetic Properties of Lanthanum Manganese Oxides Doped with Iron

The mechanism of GMR effects in La(Mn_1–x Fe _x )O₃ (x=0, 0.01, 0.03) oxides has been investigated by means of magnetic measurements, resistivity measurements in magnetic field and Mössbauer spectroscopy. For the x=0.01 sample, the GMR behavior is similar to that of the conventional (La, A)MnO₃ (A: divalent cations) oxides. For the x=0.03 sample, even though the temperature dependence of the Mössbauer spectra was similar to that of the x=0.01 sample, the mechanism for the occurrence of the GMR effect seems to be different. The x=0 sample shows a similar behavior to the x=0.03 sample. A thermal stabilization of spin fluctuation is proposed for the x=0 and x=0.03 sample.     

用XRD和TPR技术考察制备方法和灼烧温度对钙钛矿型结构形成以及性质的影响

本文用柠檬酸络合物分解法、碳酸盐共沉淀分解法、硝酸盐直接分解法和陶瓷法合成了轻、重稀土钙钛矿型氧化物LnMnO_3(Ln=Sm.Er).用X-射线衍射(XRD)和程序升温还原(TPR)技术考察了制备方法和灼烧温度对钙钛矿型结构形成的影响.实验结果表明,用柠檬酸络合物分解法可以在较低的温度下得到单一相的钙钛矿氧化物,而陶瓷法的灼烧温度比其他方法所需的温度要高得多。不同方法得到的产物SmMmO_3对CO氧化反应的活性为:柠檬酸法～碳酸盐法～硝酸盐法>陶瓷法。实验表明,TPR技术在某些体系中可作为灵敏的物相分析辅助手段,它可在制备或反应过程中原位观察体系结构的变化,实验中观察到,稀土氧化物能促进某些过渡金属氧化物在稀土氧化物表面分散,能阻止它们形成晶态.本文还讨论了钙钛矿型氧化物的形成机理,提出了过渡金属氧化物的扩散是形成钙钛矿结构反应速率的决定步骤观点。