钙钛矿型锰氧化物(La$lt;sub$gt;0.8$lt;/sub$gt;Eu$lt;sub$gt;0.2$lt;/sub$gt;)$lt;sub$gt;4/3$lt;/sub$gt;Sr$lt;sub$gt;5/3$lt;/sub$gt;Mn$lt;sub$gt;2$lt;/sub$gt;O$lt;sub$gt;7$lt;/sub$gt;的磁性和电性研究

采用传统固相反应法制备钙钛矿型锰氧化物 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇多晶样品, X-射线衍射分析表明, 样品(La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇结构呈现良好的单相. 通过磁化强度随温度的变化曲线(M-T)、不同温度下磁化强度随磁场的变化曲线(M-H)和电子自旋共振谱发现: 在300 K以下, 随着温度的降低, 样品先后经历了二维短程铁磁有序转变 (T_C^2D ≈ 282 K)、三维长程铁磁有序转变(T_C^3D ≈ 259 K)、奈尔转变(T_N ≈ 208K)和电荷有序转变(T_CO ≈ 35 K); 样品 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇在T_N以下, 主要处于反铁磁态; 在T_C^3D达到370 K时, 样品处于铁磁-顺磁共存态, 在370 K以上时样品进入顺磁态. 此外, 分析电阻率随温度的变化曲线(ρ-T)得到: 样品在金属-绝缘转变温度(T_P ≈ 80 K)附近出现最大磁电阻值, 其位置远离T_C^3D, 表现出非本征磁电阻现象, 其磁电阻值约为61%. 在T_CO以下, 电阻率出现明显增长, 这是由于温度下降使原本在高温部分巡游的e_g电子开始自发局域化增强所致. 通过对 (La_0.8Eu_0.2)_4/3Sr_5/3Mn₂O₇的ρ-T 曲线拟合, 发现样品在高温部分的导电方式基本遵循小极化子的导电方式. 关键词： 磁性 电性 金属-绝缘转变温度 电子自旋共振     

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.     

钙钛矿锰氧化物(La_(1-x)Eu_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.15)的磁性和电性研究

通过传统固相反应法制备了钙钛矿锰氧化物(La1-xEux)4/3Sr5/3Mn2O7(x=0,0.15)多晶样品,并且对其磁性和电性进行了研究.磁性测量表明:随着温度的降低,样品经历了一个复杂的转变过程,在温度为T*时经历二维短程铁磁有序转变,在温度为TC时进入三维长程铁磁态.随着Eu的掺杂,T*和TC减小,并且样品(La0.85Eu0.15)4/3Sr5/3Mn2O7在低温区表现出自旋玻璃行为.电性质测量表明:在母体La4/3Sr5/3Mn2O7中La位掺杂Eu后电阻率明显变大,金属绝缘转变温度TMI降低,磁电阻峰值增大.这些影响归因于较小的Eu3+离子替代La3+离子导致平均离子半径减小,晶格发生畸变.此外,较小的Eu3+离子优先占据层间岩盐层的R-site,使La3+,Sr3+,Eu3+离子在(La0.85Eu0.15)4/3Sr5/3Mn2O7中的分布更加有序,所以x=0.15的样品的ρ-T曲线只有一个峰.     

双层钙钛矿(La_(1-x)Gd_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.05)的相分离

采用传统固相反应法制备(La1-xGdx)4/3Sr5/3Mn2O7(x=0,0.05)多晶样品,并通过测量样品的磁化强度与温度的变化曲线(M-T曲线)、电子自旋共振谱(ESR谱)和电阻率与温度的变化曲线(ρ-T曲线),研究了x=0和x=0.05样品的相分离现象.研究结果表明,两样品在低温部分出现了反铁磁与铁磁相互竞争的现象,体现出团簇自旋玻璃态的特征.x=0和x=0.05样品分别在125—375 K和100—375 K范围内观察到类Griffiths相,同时发现掺杂使得三维铁磁有序温度(T3Dc0≈125 K和T3Dc1≈100 K)降低,而对类Griffiths温度(TG≈375 K)没有明显影响.在TG温度以上两样品均表现出纯顺磁特性.其电特性表明,x=0样品在整个测量范围内出现两次绝缘-金属转变,这是由钙钛矿锰氧化物共生现象所致.而x=0.05样品只出现一次绝缘-金属转变,表明掺杂能抑制共生现象的产生.通过对ρ-T曲线的拟合发现两样品在高温部分的导电方式基本都遵循三维变程跳跃的导电方式.     

Tb掺杂双层锰氧化物La_(4/3)Sr_(5/3)Mn_2O_7的磁熵变和电输运性质

研究了Tb掺杂对双层锰氧化物La_(4/3)Sr_(5/3)Mn_2O_7磁熵变和电输运性质的影响.样品采用传统固相反应法制备,两样品的名义组分可以表示为(La_(1-x)Tb_x)_(4/3)Sr_(5/3)Mn_2O_7(x=0,0.025),磁场为7 T时的最大磁熵变?S_M分别为-4.60 J/(kg·K)和-4.18 J/(kg·K).比较后发现,Tb元素的掺杂使得最大磁熵变值减小,但同时增大了相对制冷温区.电性测量结果表明,x=0.025的样品在高温区的导电机制可以用小极化子模型解释,与母体三维变程跳跃模型不同;当温度降低至三维长程铁磁有序温度(T_c~(3D))附近时,掺杂样品发生金属绝缘相变;掺杂后样品在T_c~(3D)附近,磁电阻取得极大值(约为56%),表明是本征磁电阻效应.     

High hydrostatic pressure effect on magnetic state of anion-deficient La0.70Sr0.30MnOx perovskite manganites

The magnetic state of La_0.70Sr_0.30MnO_x (x=2.85, 2.80) anion-deficient manganites is studied experimentally under hydrostatic pressure up to 5.2 GPa. These materials possessing the properties of a spin-glass state. The La_0.70Sr_0.30MnO_2.85 exhibits a coexistence of the rhombohedral (R3¯c) and tetragonal (I4/mcm) crystal structures and below T_f 50 K the spin-glass state is formed. The La_0.70Sr_0.30MnO_2.80 exhibits the tetragonal (I4/mcm) crystal structure. For this compound a phase-separated magnetic state below T_f is formed, involving coexistence of C-type antiferromagnetic (AFM) clusters within spin-glass matrix. In both compounds the crystal structure and magnetic states remain stable upon compression. Under the hydrostatic pressure up to 1 GPa, the La_0.70Sr_0.30MnO_2.85 is a spin glass with a smeared phase transition to the paramagnetic state. The freezing temperature T_f of the magnetic moments of the ferromagnetic clusters increases at a rate of 4.30 K/GPa and the magnetic ordering temperature T_MO increases at a rate of 12.90 K/GPa. The enhancement of the ferromagnetic properties of La_0.70Sr_0.30MnO_2.85 anion-deficient manganite under hydrostatic pressure is explained by the redistribution of oxygen vacancies and a decrease in the unit cell parameters.     

(1-x)Sr_3Sn_2O_7+xCa_3Mn_2O_7陶瓷合成及其光电性能

为了寻求新的非常规多铁性材料,采用固相合成方法制备具有Ruddlesden-Popper结构的(1-x)Sr_3Sn_2O_7+x Ca_3Mn_2O_7(SSO+CMO)(x=0,0.05,0.10,0.15,0.20)系列陶瓷.通过X射线衍射、紫外可见光谱和磁性测量,发现SSO+CMO陶瓷为单一正交相结构,空间群为A21am.随着掺杂量x的增加,样品的晶胞参数和体积相应地减小;在室温不同频率下,样品的介电常数和介电损耗随着频率增加而减小,且在x=0.1时有弱的铁磁性.     

Temperature dependence of ESR anisotropy in La7/8Sr1/8MnO3

We report X-ray diffraction, DC-susceptibility, electron spin resonance (ESR), and dilatometry measurements carried out on an La_7/8Sr_1/8MnO₃ single crystal. Thermal expansion was measured along different crystallographic axes using a three-terminal dilatometer. The sharp anomalies observed in the temperature dependence of Δl/l allowed us to locate the Jahn–Teller transition at T_JT=285(1) K. ESR experiments were carried out in the paramagnetic regime from 220 to 570 K, at 9.4 GHz. We measured the ESR line width ΔH_pp(T) with the magnetic field parallel to the crystallographic directions [1 0 0] and [0 0 1], referred to the orthorhombic (Pbnm) axes. We correlate the temperature dependence of ΔH_pp with the structural changes of the lattice.     

Magnetic transition behavior of perovskite manganites Nd_(0.5)Sr_(0.3)Ca_(0.2)MnO_3 polycrystalline

A polycrystalline sample Nd_(0.5)Sr_(0.3)Ca_(0.2)MnO_3 is prepared by the conventional solid state reaction method. The structure and magnetic properties are investigated with x-ray diffraction(XRD) patterns, a superconducting quantum interference device(SQUID), and electron spin resonance(ESR). The sample is in single phase with the space group Pbnm symmetry. With the decrease of temperature, Nd_(0.5)Sr_(0.3)Ca_(0.2)MnO_3 undergoes three magnetic transitions: ferromagnetic transition at TC≈ 210 K, charge-ordering at TCO≈ 175 K, and antiferromagnetic transition at TN= 155 K. In addition, the activation energy Ea ≈ 52.78 me V can be extracted by curve fitting.     

Structural modulation and physical properties of cobalt-doped layered La_2M_5As_3O_2(M=Cu,Ni) compounds

We investigate the structural variation and physical properties of layered La_2M_5As_3O_2(M=Cu,Ni) compound upon Co doping. It is found that the substitution of Co ion just induces the monotonous change of lattice constants without observing the anomalous kink in superconducting La_2(Cu~(1-x)Nix)_5 As_3O_2 solid-solutions. Meanwhile, this doping barely changes As–As bond length in [M_5As_3]~(2-) subunit(±2%), being significantly smaller than 7% shrinkage of that in La_2(Cu~(1-x)Nix)_5 As_3 O_2. Therefore, the doping dependence of crystal structure exhibits similar trend with Ba~(1-x)K_xFe_2 As_2 without the interference of As1–As 2 bonding, implying that the Co substitution for Cu/Ni is hole-doped. In terms of physical property, La2(Cu1-xCox)~5As_3O_2 turns into itinerant ferromagnetic metal, while La2(Ni1-x Cox)5 As3 O2 shows paramagnetism and suppressed structural phase transition upon Co-doping. The distinct structural variation and absence of superconductivity provide important clues to understand the effect of As–As bond in [M_5 As_3]~(2-) subunit.     

Magnetic pair making and breaking effect of Ru in La0.7Sr0.3Mn0.9Ru0.1O3 and La0.5Sr0.5Co0.9Ru0.1O3

The substitutional effect of Ru on the magnetic and transport properties of double exchange ferromagnets, La_0.7Sr_0.3MnO₃ and La_0.5Sr_0.5CoO₃ has been investigated. It is found that substitution of 10% Ru at the Mn site of La_0.7Sr_0.3MnO₃ decreases the Curie temperature by 20 K than that of the parent compound. However, a large decrease in the Curie temperature, ΔT_c80 K and the system undergoes a transition from metallic state to insulating state is observed when 10% Ru is doped in La_0.5Sr_0.5CoO₃. The marginal effect of Ru in the Mn–O–Mn sublattice in comparison to the Co–O–Co sublattice could be due to the magnetic exchange interaction between Mn and Ru by virtue of the fact that Ru exhibits variable valence states, Ru⁺⁴/Ru⁺⁵. The e_g and t_2g parentage of Ru⁺⁵ is similar to Mn⁺⁴ and therefore, Ru⁺⁵ ion appears to participate in the double exchange mediated ferromagnetic (FM) interaction. On the other hand, Ruthenium (IV) ion disrupts an intermediate spin state of cobalt (Co⁺³: t_2g⁵e_g¹), forcing a double exchange FM state to anti-FM state.     

Origin of cathodic degradation and new phase formation at the La0.9Sr0.1MnO3/YSZ interface

New phase formation at the La_0.9Sr_0.1MnO₃/YSZ interface and its effects on the cathodic performances were studied at 900 °C in air. The resistance caused by the interfacial product layer kept increasing with time to reach up to 40% of the total resistance after 500 h. The interfacial product was identified as La₂Zr₂O₇ by XRD measurement. The electrical conductivity of La₂Zr₂O₇ (2.4 × 10⁻⁵ S cm⁻¹ at 1000 °C), measured by AC impedance and current interruption methods, was 4 to 7 orders of magnitude smaller than those of La_0.9Sr_0.1MnO₃ electrode or YSZ electrolyte. Either the electronic conductivity or the electrochemical O₂ reduction activity of La₂Zr₂O₇ was negligible. Combining these results, a conclusion was made that the cathodic degradation comes mainly from the growth of interfacial product layer and its contribution to the cell resistance increment is ohmic in nature.     

La1.3Sr1.7Mn2O7/SrTiO3-Nb异质结的整流和光伏特性

采用脉冲激光沉积法在SrTiO₃:0.7%Nb(100)单晶衬底上生长了La_1.3Sr_1.7Mn₂O₇(LSMO)薄膜, 并 研究了LSMO/SrTiO₃-Nb异质结的输运性质和光伏效应. 研究发现, 异质结具有良好的整流特征和明显的光生伏特效应. 在532 nm激光辐照下, 光生电压随温度升高先增大后减小, 并且在150 K达到最大值400 mV, 此温度点与LSMO薄膜发生金属-绝缘体转变的温度一致, 这表明异质结的光生伏特效应受LSMO薄膜内部的输运特征调控. 进一步, 从光生电压随时间的变化曲线中分析发现, 上升沿符合一阶指数函数, 这与载流子的迁移过程相关; 而下降沿符合二阶指数函数, 这与结两侧载流子的外部回路中和以及材料内部的电子-空穴湮灭有关. 值得注意的是, 上升沿和下降沿的时间常数均随着温度先增大后减小, 且最大值均出现在LSMO薄膜的金属-绝缘转变温度.     

红色荧光粉La2Mo2O9:Eu3+,W6+的制备及发光性能

采用高温固相法合成出La₂Mo₂O₉:Eu³⁺,W⁶⁺系列红色荧光粉,其结构为立方晶系的β- La₂Mo₂O₉。在395 nm光激发下,样品La_1.40Mo₂O₉:0.60Eu³⁺发射出很强的红光,最强发射峰位于616 nm处。适量地掺杂W⁶⁺离子可以提高样品的激发和发射强度,在395 nm光激发下,La_1.40Mo_1.84O₉:0.60Eu³⁺,0.16W⁶⁺荧光粉的Eu³⁺的⁵D₀→⁷F₂跃迁发射强度最大,是样品La_1.40Mo₂O₉:0.60Eu³⁺的1.23倍。最后,将La_1.40Eu_0.60Mo_1.84O₉:0.16W⁶⁺荧光粉与~395 nm发射的InGaN芯片一起制作成红光发光二极管(LED),该LED发射出很强的红光。     

Proper composition for superconductivity in Pb(Ba, Sr)2(Y, Ca)Cu3O7

Superconductivity and composition analysis of PbBaSr(Y, Ca)Cu₃O_y with fixed ratio of Sr/Ba = 1 were studied. Synthesis condition and superconductivity of Pb(Ba, Sr)₂(Y, Ca)Cu₃O_y with various ratio of Sr/Ba and Ca/Y were also studied. It was found that T_c increased with increasing Ca concentration, and that Sr-rich specimens allowed to contain more Ca. PbBa_0.8Sr_1.2Y_0.6Ca_0.4Cu₃O₇ showed superconductivity with zero-resistance temperature of 42 K, which was higher than PbBaSrY_0.7Ca_0.3Cu₃O₇ with maximum Ca content for Sr/Ba = 1. Decrease in averaged ionic radii of Ba and Sr in Sr-rich compositions would be favorable for the contraction of Cu-O bonds by hole-doping via Ca substitution for Y.     

Synthesis and investigation of the complex copper oxides Bi2Sr2R2−xCexCu2O10+δ (R=rare earth)

Bi-2222 phases were prepared by solid state reactions and were studied using X-ray diffraction, chemical and EDS-analysis. Compounds with composition Bi₂Sr₂R_1.33Ce_0.67Cu₂O_10+δ were obtained for R=Pr, Nd, Sm-Er. The phases Bi₂Sr₂Cu₂O_10+δ with similar structure but without Ce were prepared for R = Pr, Sm-Dy. For Bi₂Sr₂Eu_2−xCe_xCu₂O_10+δ the solubility limit was determined and the effect of treatment under different oxygen pressures was investigated. Weak diamagnetic signals (<3%) were detected for some of these samples.     

Dynamical effects in magnetic and transport properties of phase separated La0.5Ca0.5Mn0.95Fe0.05O3

We have measured transport and magnetic properties of polycrystalline La_0.5Ca_0.5Mn_0.95Fe_0.05O₃, a phase separated manganite with ferromagnetic ground state. Cooling rate dependences and time relaxation were found; the coexistence of ferromagnetic and charge ordered regions determines a dynamics which influences physical properties. We show that a dynamical contribution to the resistivity can account for the observed cooling rate dependence and ageing effects on this phase separated manganite.     

Electrical transport and superconductivity in the Al2O3-Bi2Sr1.8Ca1.2Cu2Oy and MgO-Bi2Sr1.8Ca1.2Cu2Oy composites

We have measured the resistivities of Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites with the nominal Bi₂Sr_1.8Ca_1.2Cu₂O_y volume fraction, ₂₂₁₂, ranging from 0.15 to 1.00. For the Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu ₂O_y composites, we find for the samples with ₂₂₁₂≥0.6 that the superconducting transition temperature, T_c, is not disturbed by the addition of Al₂O₃. For ₂₂₁₂<0.3, no zero-resistivity state is observed. For the MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites, T_c is barely disturbed for the samples with ρ₂₂₁₂≥0.7. No superconducting state is observed for the samples with ρ₂₂₁₂<0.35. The variation of (300 K) with ρ₂₂₁₂ indicates a three-dimensional percolating Bi-Sr-Ca-Cu-O matrix occurring at ρ₂₂₁₂≈0.19 and ≈0.15 in Al₂O₃-Bi₂Sr_1.8Ca_1.2 Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y, respectively. Both resistivity and magnetization measurements suggest that the reactions of Bi₂Sr_1.8Ca_1.2Cu₂O_y with MgO are weaker than with Al₂O₃.     

A 62 K superconductor with an original structure: Sr4−xBaxTlCu2CO3O7

A new superconductor with an original structure, Sr_4−xBa_xTlCu₂CO₃O₇ has been isolated for 1≤x≤2. It crystallizes in a A-type space group with a=3.84 Å≈a_p, b≈8 × a_p, c≈17.0 Å. The HREM study of this new curprate shows that it derives from the Tl_0.5Pb_0.5Sr₄Cu₂CO₃O₇ structure by a shearing mechanism. Indeed, it can be described as ribbons of the latter structure, four octahedra thick, shifted c/2 with respect to each other. It results in infinite single perovskite layers waving along the (001) plane and connected through flat mixed layers [(TIO)₄(CO)₄]∞. This oxycarbonate can also be described as a 1201-type structure in which the [TIO]∞ layers are replaced by mixed [(TIO)₄(CO)₄]∞ layers. The susceptibility measurements show that this cuprate exhibits a significantly higher critical temperature than the 1201-cuprates. The T_{c onset} of the synthesized phase is 56 K and it can be increased up to 62 K by hydrogen annealing; in the same way, one observes a large Meissner volume fraction of 35% at 4.2 K.     

Evidence for pinning by (Sr,Ca)2CuOy particles in partial-melting processed bulk Bi2Sr2CaCu2O8+δ ceramics

Flux distributions of partial-melting processed Bi₂Sr₂CaCu₂O_8+δ ceramics are obtained using magneto-optic imaging. In remanent states (μ₀H_a=0 T), large amounts of trapped flux are observed along (Sr,Ca)₂CuO_y particles embedded in the Bi₂Sr₂CaCu₂O_8+δ matrix. Despite the relatively large size of these particles (up to 30 μm), the pinning effect is similar to that of Y₂BaCuO₅ particles in melt-processed YBa₂Cu₃O_7−δ. Furthermore, we discuss how the pinning capability of non-superconducting particles of different sizes and densities will show up in magneto-optic images.