尖晶石铁氧体TixNi1-xFe2O4中阳离子分布和Ti离子磁矩的实验研究

采用固相反应法制备了系列样品Ti_xNi_1-xFe₂O₄ (x=0.0, 0.1, 0.2, 0.3, 0.4). 室温下的X射线衍射谱表明样品全部为(A)[B]₂O₄型单相立方尖晶石结构, 属于空间群Fd3m. 样品的晶格常数随Ti掺杂量的增加而增大. 样品在10 K温度下的比饱和磁化强度σ_S随着Ti掺杂量x的增加逐渐减小. 研究发现, 当Ti掺杂量x≥ 0.2时, 磁化强度σ随温度T的变化曲线出现两个转变温度T_L和T_N. 当温度低于T_N时, 磁化强度明显减小; 当温度达到T_N时, dσ/dT具有最大值. σ-T曲线的这些特征表明, 由于Ti掺杂在样品中出现了附加的反铁磁结构. 这说明样品中的Ti离子不是无磁性的+4价离子, 而是以+2和+3价态存在, 其离子磁矩的方向与Fe和Ni离子的磁矩方向相反. 利用本课题组提出的量子力学方势垒模型拟合样品在10 K温度下的磁矩, 得到了Ti, Fe和Ni三种阳离子在(A)位和[B]位的分布情况, 并发现在所有掺杂样品中, 80%的Ti离子以+2价态占据尖晶石结构的[B]位.     

Dy,Co共掺杂对BiFeO3陶瓷磁特性和磁相变温度Tc的影响

采用快速液相烧结法制备BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0, 0.05, 0.1, 0.15)陶瓷样品. 实验结果表明: 所有样品的主衍射峰与纯相BiFeO₃相符合且具有良好的晶体结构, 随着Co³⁺掺杂量的增大, Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品的主 衍射峰由双峰(104)与(110)逐渐重叠为单峰(110), 当掺杂量x>0.05时, 样品呈现正方晶系结构; SEM形貌分析可知: Dy³⁺, Co³⁺共掺杂使BiFeO₃晶粒尺度由原来的3—5 μ减小到约1 μ. 室温下, BiFeO₃样品表现出较弱的铁磁性, 随着Dy³⁺和Co³⁺掺杂, BiFeO₃样品的铁磁性显著提高. 在外加磁场为30 kOe的作用下, Bi_0.95Dy_0.05Fe_1-xCo_xO₃ (x=0.05, 0.1, 0.15)的M_r分别为0.43, 0.489, 0.973 emu/g; M_S分别为0.77, 1.65, 3.08 emu/g. BiFeO₃和Bi_0.95Dy_0.05Fe_1-xCo_xO₃样品磁矩M随着温度T的升高而逐渐减小, Dy掺杂使BiFeO₃样品的T_N由644 K升高到648 K, 而T_C基本没有变化. Dy和Co共掺杂导致BiFeO₃样品磁相变温度T_C由870 K降低到780 K, 其T_C变化主要取决于Fe-O-Fe反铁磁超交换作用的强弱和磁结构的相对稳定性. 关键词： 铁磁电材料 磁滞回线 磁相变温度     

纳米微粒BaFe12O19掺杂对单畴超导块材GdBa2Cu3O7-δ性能的影响

磁通钉扎性能对GdBa₂Cu₃O_7-δ超导块材的实际应用具有重要的影响, 而引入合适的第二相粒子可以改善GdBa₂Cu₃O_7-δ 超导块材的磁通钉扎性能.本文采用顶部籽晶熔融织构法成功地制备出纳米微粒BaFe₁₂O₁₉(<100 nm)掺杂的超导块材, 样品的最终组分为Gd123+ 0.4 Gd211+ x BaFe₁₂O₁₉ (x=0, 0.2 mol%, 0.4 mol%, 0.8 mol%)+ 10 wt%Ag₂O+ 0.5 wt%Pt. 通过研究不同掺杂量的BaFe₁₂O₁₉微粒对GdBa₂Cu₃O_7-δ 超导块材微观结构和超导性能的影响, 结果表明当掺杂量为0.2 mol%时, 样品的临界电流密度几乎在整个外加磁场下都有明显的提高.在零场下, 临界电流密度达到5.5× 10⁴ A/cm². 纳米微粒BaFe₁₂O₁₉不仅可以保持掺杂前的化学组成, 作为有效的钉扎中心存在于超导块材中, 并且能够改善Gd₂BaCuO₅粒子的分布和细化Gd₂BaCuO₅粒子, 使Gd₂BaCuO₅粒子的平均粒径由未掺杂时的1.4 μ m减小到掺杂后的0.79 μ m, 进而提高了超导块材的临界电流密度和俘获磁场, 明显提高了GdBa₂Cu₃O_7-δ 超导块材的超导性能.临界温度T_C也有所提升, 并能够维持在92.5 K左右. 该结果为进一步研究纳米磁通钉扎中心的引入并改善GdBa₂Cu₃O_7-δ 超导块材的性能有着重要的意义.     

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.     

柠檬酸掺杂的MgB2超导体钉扎机理的研究

本文研究了柠檬酸掺杂的MgB₂超导材料的J_c-B行为及其钉扎机理.在纯MgB₂多晶样品中,δT_c钉扎起主要作用,而在掺杂的样品中,则是δl钉扎和δT_c钉扎共同作用,并且δl钉扎机理占主要作用,其贡献比重随着掺杂量的增加而增加.从J_c-B行为和钉扎行为的分析都可以得到 关键词： 柠檬酸 2')" href="#">MgB₂ T_c钉扎')" href="#">δT_c钉扎 l钉扎')" href="#">δl钉扎     

Ti1－xCrxO2±δ体系的相关系、晶体结构和磁性能研究

采用溶胶凝胶法制备了Ti_1-xCr_xO_2±δ体系系列样品.利用扫描电子显微镜(SEM)，X射线光电子能谱(XPS)，粉末X射线衍射分析(XRD)方法研究了Ti_1-xCr_xO_2±δ系列样品的颗粒尺寸、形貌、组分化学态、相关系和固溶区范围；并利用超导量子干涉磁强计对样品的磁性能进行了研究.采用Rietveld结构精修的方法研究了Cr的不同掺杂量对TiO₂晶体结构的影响，研究表明，1000℃烧结的样品的固溶区范围是x=0—0.03，为金红石单相；随着Cr掺杂量的增加，金红石相晶胞参数规律性地减小；当x>0.03，为金红石相和CrO₂相两相共存.综合XRD和磁性测量结果，500℃烧结的样品的固溶区范围是x=0—0.02，为锐钛矿单相；随着Cr掺杂量的增加，锐钛矿相晶胞参数规律性地减小；当x≥0.04，为锐钛矿相和绿铬矿相(Cr₂O₃)两相共存.XPS实验结果表明，500℃和1000℃退火的样品中Cr都是以Cr⁺³和Cr⁺⁶两种化学态存在，1000℃烧结的样品中可能有更多的Cr³⁺转化为Cr⁶⁺.根据M-H和M-T曲线的测试结果发现，本文500℃烧结的Ti_1-xCr_xO_2±δ体系样品当x=0—0.02时，为室温铁磁性.当x≥0.04时，由铁磁相和顺磁相所组成，在低温下有较强的铁磁性；室温下主要是顺磁相，铁磁相只占据很小的体积分数. 关键词： 1-xCr_xO_2±δ体系')" href="#">Ti_1-xCr_xO_2±δ体系 相关系 固溶区 磁性能     

Ga2O3组分对Tm3+掺杂GeO2-Ga2O3-Li2O-BaO-La2O3玻璃的光谱性能影响

制备了Tm³⁺(8.0mol%)掺杂(77-x)GeO₂-xGa₂O₃-8Li₂O-10BaO-5La₂O₃(x=4,8,12,16)系列玻璃.系统地研究了Ga₂O₃从4mol%变化到16mol%时,玻璃的光谱性质与热学性质的变化规律.差热分析表明,随着Ga₂O₃含量的增加,锗酸盐玻璃的热稳定性增加.运用Judd-Ofelt(J_O)理论计算得到了Tm³⁺在不同Ga₂O₃含量的GeO₂-Ga₂O₃-Li₂O-BaO-La₂O₃玻璃中的J-O强度参数(Ω₂,Ω₄,Ω₆)及Tm³⁺各激发能级的自发跃迁概率、荧光分支比以及辐射寿命等光谱参量.在808nm激光二极管的激发下,测试并分析了Ga₂O₃对Tm³⁺荧光光谱特性的影响.随着Ga₂O₃从4mol%增加到16mol%,Tm³⁺在1.8μm处的荧光强度呈现先减弱后增强的特性.当Ga₂O₃含量大约在12mol%时,Tm³⁺在1.8μm处的荧光强度最弱,受激发射截面达到最小.还初步讨论了Ga₂O₃对玻璃结构与光谱参数的影响规律. 关键词： 3+掺杂锗酸盐玻璃')" href="#">Tm³⁺掺杂锗酸盐玻璃 光谱性能 Judd-Ofelt参数 热稳定性     

La0.4Ca0.6MnO3系统中Mn位Fe和Cr掺杂效应的比较性研究

利用固相反应法制备了Mn位Fe³⁺和Cr³⁺掺杂的系列锰氧化物La_0.4Ca_0.6(Mn_1-x(y)B_x(y))O₃ (B=Fe³⁺ (0≤x≤0.1); Cr³⁺ (0≤y≤0.1)) 多晶样品,研究了掺杂对样品输运性质的影响.实验结果表明两种离子具有截 关键词： 锰氧化物 反铁磁 磁电阻效应     

Er3+/Yb3+共掺碲硼硅酸盐玻璃的光谱性质和热稳定性研究

制备了系列Er³⁺/Yb³⁺共掺碲硼硅酸盐玻璃样品(85-x)TeO₂-15B₂O₃-xSiO₂ (TBS x=0,5,10,15,20 mol%).测试和分析了样品的吸收光谱、荧光光谱、能级寿命、红外透射光谱及差热特性.并通过对Er³⁺离子⁴I_13/2→⁴I_15/2跃迁发射谱线的高斯拟合，设计了一个简单的四能级结构估算了Er³⁺离子⁴I_13/2和⁴I_15/2能级在碲硼硅酸盐中的Stark分裂情况.研究表明SiO₂的引入能有效地改善玻璃的热稳定性和光谱性能，玻璃析晶温度T_x与玻璃转变温度T_g之差(ΔT=T_x-T_g)可达178℃，说明碲硼硅酸盐是一种适合于光纤拉制的玻璃基质材料.比较了不同基质玻璃中Er³⁺离子的荧光半高宽和受激发射截面，结果表明TBS玻璃系统具有较好的带宽性能，是一种优良的宽带光纤放大器候选基质材料. 关键词： 碲硼硅酸盐 热稳定性 高斯拟合 -基')" href="#">OH^-基     

自旋梯状化合物Sr14(Cu1-yFey)24O41的拉曼散射谱研究

利用常规的固相合成法制备了三种Sr₁₄(Cu_1-yFe_y)₂₄O₄₁(y=0,0.03,0.05)多晶样品,其中y=0.03是单纯Fe³⁺掺杂,y=0.05是Fe³⁺和Fe²⁺混合掺杂.在100—1500cm^-1频移范围内测量了这三种样品的偏 关键词： 拉曼散射 电输运性质 自旋梯状化合物     

Trapping mechanism of superconductivity suppression induced by Pr substitution in the Ho1−xPrxBa2Cu3O7−δ system

Pr concentration dependence of the superconducting transition temperature T_c in the Ho_1−xPr_xBa₂Cu₃O_7−δ system is determined from measurements of DC electrical resistance. This dependence coincides with that for the parallely studied Y_1−xPr_xBa₂Cu₃O_7−δ reference system. Both systems have the same value of the critical concentration x_c=0.58, in accordance with nearly equal ionic radii of Ho³⁺ and Y³⁺ ions. It has been shown that the T_c(x) curve can be described with a single mechanism based on a decreasing number of sheet holes trapped by Pr^IV-ions, if one takes also into account that the number of these ions changes with x.     

Influence of the Tl- and Hg-content on magnetic and transport properties of the Pb, Sr-doped Tl-1223 and Hg-1223 superconductors

The effects of the thallium and mercury content x on the as-sintered and post annealed samples of M_xPb_0.4Sr_1.6Ba_0.4Ca₂Cu₃O_8+δ {M: Tl (0.32≤x≤0.74) or Hg (0.18≤x≤0.68)} have been studied by magnetization and transport measurements. For Tl-1223 we have found the optimum Tl doping level to be x=0.53 regarding the grain properties, the content of superconducting phase, the first penetration field H_pl^wl, the transport (J_c^tr), magnetic intergrain (J_c^M) and intragrain (J_c^g) critical current densities. The critical temperature T_c of the as-sintered Tl-1223 sample decreased with increasing Tl content. Post-annealing in oxygen improved the T_c for Tl contents of x≥0.53 and had generally positive effects on the critical current densities. The intergrain properties of the Hg-1223 samples were much worse than those of the Tl-based superconductors.     

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.     

Temperature dependence of the critical current in YBa2Cu3O7−δ and Bi2Sr2Ca1Cu2O8 Josephson junctions

We have studied the stationary Josephson effect on YBa₂Cu₃O_7−δ (T_c=90 K) and Bi₂Sr₂Ca₁Cu₂ O₈ (T_c=80 K and 87 K for two samples of different origin) ceramic based junctions. The temperature dependence of the critical current near T_c has been found as I_c≈(T_c-T) for the Y-Ba-Cu-O samples indicating that they should be classified as S-N-I-N-S type junctions. The I-V curves of the Bi-Sr-Ca-Cu samples show the typical behaviour of S-I-S structures. Using Ambegaokar-Baratoff's theory for Bi₂Sr₂Ca₁Cu₂O₈, the temperature dependence of the superconducting state gap Δ(T) was calculated and it was evaluated that 1.452Δ(0)/k_BT_c3.5.     

Crystal structure, superconductivity and magnetic properties of the superconducting ferromagnets Gd1.4−xDyxCe0.6Sr2RuCu2O10 (x=0–0.6)

The structural, electrical and magnetic properties of the superconducting ferromagnets, Gd_1.4−xDy_xCe_0.6Sr₂RuCu₂O₁₀ (x=0–0.6) are systematically investigated as a function of Dy doping and temperature. These compounds are characterized by high temperature superconductivity (T_c ranging from 20 to 40 K depending upon the Dy content) co-existing with weak ferromagnetism with two magnetic transitions (T_M2 ranging from 95 to 106 K and T_M1 around 120 K). Doping with Dy gives no significant structural changes except for a minor change in the c/a ratio. However the superconducting transition temperature is significantly suppressed and magnetic ordering temperature enhanced on Dy doping. These effects are described and discussed.     

Synthesis and superconducting properties of the infinite-layer compounds Sr1−xLnxCuO2(Ln=La, Nd, Sm, Gd)

Infinite-layer-type superconductors Sr_1−xLn_xCuO₂ are synthesized under high pressure of 3 GPa for Ln=Sm, Gd as well as for Ln=La, Nd. Their chemical and superconducting properties are systematically studied as functions of doping concentration and the kind of lanthanide ion. As a result, it is demonstrated that the variation of these properties with doping concentration is similar for all the examined Ln³⁺ ions. The solubility limit lies at x ≈ 0.10. CuO₂ sheets are expanded with increasing x, while their spacing decreases. The T_c onset determined by magnetic measurements remains constant for any doping concentration; only the Meissner fraction increases with increasing x.     

Giant pressure effect in oxygen deficient YBa2Cu3Ox

The pressure effect on T_c of polycrystalline and single crystalline YBa₂Cu₃O_x investigated as a function of oxygen content x by ac-susceptibility measurements under helium pressure. In the overdoped region x> 6.93 the single crystals show a negative dT_c/d p, as expected from the charge transfer model. For optimally doped samples with x = 6.93 we find dT_c/d P = 0.4 K/GPa which points to pressure effects on T_c aside from charge transfer. In the underdoped region x < 6.93 the dT_c/d p values obtained from the experiment depend strongly on the storage temperature of the sample during the experiment. When the samples are stored at temperatures well below 240 K throughout the entire experiment including pressure application and pressure release, dT_c/d p increases to approx. 7 K/GPa at x = 6.7 but with a further decrease of the oxygen content the dT_c/d p drops to approx. 2 K/GPa at x = 6.4. These effects are intrinsic to the YBa₂Cu₃O_x structure and can be explained by considering the anisotropic structure of YBa₂Cu₃O_x. The decrease of the c-axis lattice parameter results in a charge transfer to the CuO₂-planes mainly [1], whereas the compression of the a- and b-axis lattice parameter is known to produce different pressure effects which are responsible for the peak in dT_c/d p at x = 6.7 [2]. When pressure is changed at room temperature oxygen ordering effects occur which cause a relaxation of T_c to the equilibrium value T_c(p) at this pressure with a time constant depending on the oxygen content x. A decrease x results in a peak effect in dT_c/d p at x = 6.7 again, which is enhanced to approx. 12 K/GPa. If the oxygen content is decreased further, dT_c/d p first drops to 5 K/GPa at x = 6.6, but the increases to values of more than 20 K/GPa for x < 6.42. These giant pressure effects at low oxygen contents are mainly caused by a reversible T_c increase (dT_c/d p)_O due to pressure induced oxygen ordering via oxygen motion between unit cells.     

Thermal transport in the oxygenated magnetic superconductor, Eu1.5Ce0.5RuSr2Cu2O10+δ

The thermal conductivity and thermopower are reported for a hole doped Eu_1.5Ce_0.5RuSr₂Cu₂O_10+δ sample that has been annealed at 1100 K under an oxygen pressure of 54 atm. At T_c=45 K superconductivity and weak ferromagnetism coexist (T_m=180 K). Weak features in the thermopower, S(T), and thermal conductivity, κ(T), are observed both at T_m and at T^*=140 K. The thermopower begins to decrease sharply toward zero at T_c, and there is an extremely sharp increase of about 30% in the thermal conductivity at T_c. This “first order” transition may be related to the sudden appearance of a spontaneous vortex phase at T_c. A small shoulder is observed in κ(T) in the temperature range T=5–13 K.     

Magnetic properties of xFe2O3(1−x)[B2O3 · PbO] glasses

The magnetic measurements performed on xFe₂O₃(1-x)[B₂O₃ · PbO] glasses show that for x 5 mol.% Fe₂O₃ the thermal variation of reciprocal susceptibility obeys a Curie behaviour. For higher iron content, at T 50 K, a nonlinear variation, typical for systems with random distribution of exchange interactions is observed. At greater temperatures than 50 K a Curie-Weiss behaviour is shown. The composition dependence of the Curie constants is analysed in correlation with the number of Fe³⁺ and Fe²⁺ ions as determined from Mössbauer effect measurements. A comparison with the data obtained in case of xFe₂O₃(1-x)[3B₂O₃ · PbO] glasses is made.