(La1-xCex)2/3Ca1/3MnO3体系的输运性质和反常磁特性研究

本文报告了对Ce掺杂锰氧化物(La1-xCex)2/3Ca1/3MnO3 (x=0～1.0)系列样品的输运特性和反常磁特性的研究结果.实验表明,Ce掺杂对Tc有明显的抑制作用,整体上电阻率随Ce掺杂含量增加而上升,在外加磁场时表现出极大的磁电阻效应.磁化强度随温度变化的曲线出现了两个转变,高温处对应于Mn离子磁矩的铁磁金属转变,低温处的转变则对应于Ce离子磁矩自旋有序排列的形成.表明Ce掺杂引起样品中铁磁双交换作用和反铁磁超交换作用之间的竞争,Ce离子与Mn离子有很强的相互作用.随Ce掺杂含量的增加,铁磁有序转变温度下降,而反铁磁有序转变温度则向高温处移动,铁磁区域明显减小.     

(La_(1-x)Ce_x)_(2/3)Ca_(1/3)MnO_3体系的结构和输运性质研究

对Ce掺杂锰氧化物 (La1 -xCex) 2 3Ca1 3MnO3(x =0— 1.0 )多晶样品的结构和输运性质系统研究的结果 .实验表明 ,在低掺杂浓度下 ,样品呈现完整的正交钙钛矿结构 ;随掺杂浓度的增加 ,有少量CeO2 杂相出现 ,同时伴随有Ce3 和Ce4 离子两种价态的涨落和Mn2 Mn3 Mn4 混合价态的共存 ,Ce掺杂导致的体系无序度增加 ,使得绝缘体 -金属 (I M)和顺磁 -铁磁 (PM FM)转变温度向低温方向移动 .有趣的是 ,Ce掺杂样品的电阻率测量I M转变峰值温度TIM 较PM FM转变温度Tc 为高 ,其差值ΔT(=TIM -Tc)随Ce掺杂含量的增加而增加 ,最大差值ΔT达 5 0K .各样品的磁电阻则随温度的降低而增加 ,在Tc 附近MR达到最大值 ,且随Ce掺杂含量增加Tc 附近的MR最大值迅速增加 ,达到 10 4 %以上 ,表现出很强的庞磁电阻效应 .在x≥ 0 .7时 ,磁电阻效应则表现出反常减小 .整体上而言 ,各样品的磁特性与输运行为间有较强的关联 ,电输运特性可用双交换作用模型进行很好的解释 ,在高温区满足热激活模型 .最后 ,在Ce掺杂对Tc 和MR的影响机理方面进行了初步讨论 .     

钙钛矿型锰氧化物(La_(0.8)Eu_(0.2))_(4/3)Sr_(5/3)Mn_2O_7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(La0.8Eu0.2)4/3Sr5/3Mn2O7多晶样品,X-射线衍射分析表明,样品(La0.8Eu0.2)4/3Sr5/3Mn2O7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(T2D C≈282K)、三维长程铁磁有序转变(T3D C≈259K)、奈尔转变(T N≈208K)和电荷有序转变(T CO≈35K);样品(La0.8Eu0.2)4/3Sr5/3Mn2O7在T N以下,主要处于反铁磁态;在T3D C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≈80K)附近出现最大磁电阻值,其位置远离T3D C,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(La0.8Eu0.2)4/3Sr5/3Mn2O7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.     

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.     

Mn 位 Al 掺杂的六角结构 YMn1-xAlxO3(0≤x ≤0.1)单晶的磁性及受挫调制

用光学浮区法生长了 Mn 位 Al 掺杂的六角结构 YMn1 -x Alx O3 系列单晶样品, 对该样品的掺杂效应及磁受挫性质进行了研究. 结果发现, 在 YMnO3 的 Mn3 + 位掺入不同浓度的非磁性 Al3 + 离子对样品的磁化特性有很大的影响. 随着掺杂浓度的增加, 居里-外斯温度明显降低, 磁性受挫因子f 减小, 反铁磁转变温度向低温方向移动.由于 Al3 + 离子半径比 Mn3 + 小, 掺杂使得系统的晶格常数变小, Mn-Mn 键长变短, 最终导致交换积分减小. 另外, 由于非磁性的 Al3 + 离子部分替代 Mn3 + 离子直接破坏了 Mn3 + 离子间的交换路径, 结果使得体系的几何受挫被抑制,反铁磁转变温度降低, Mn3 + - Mn3 + 之间的 AFM 相互作用被大大削弱.     

深红色Mg_(1+y)Al_(2-x)O_4:xMn~(4+),yMg~(2+)荧光粉的合成与发光性质

采用高温固相法在空气气氛中合成了新型Mg_(1+y)Al_(2-x)O_4:xMn~(4+),yMg~(2+)深红色荧光粉.利用X射线衍射仪、扫描电子显微镜和荧光光谱仪表征荧光粉的晶体结构和形貌,并分析了发光性质,讨论了掺杂不同浓度Mn4+和过量Mg2+对样品发光强度的影响.结果表明,在300 nm波长激发下样品发射652 nm波长的红光,归因于Mn~(4+)的~2Eg—~4A_(2g)跃迁, Mn~(4+)的最佳掺杂浓度为0.14%.采用Blasse公式计算了Mn~(4+)-Mn~(4+)之间能量传递的临界距离,讨论了可能的能量传递过程和引起浓度淬灭的原因,采用Tanabe-Sugano能级图从理论上计算和分析了Mn~(4+)的d~3电子构型的晶体场强度大小.过量Mg~(2+)可以提高荧光粉的发光强度,同时导致了荧光寿命的缩短,荧光衰减曲线呈单指数变化.探讨了过量Mg~(2+)增强发光强度的机理,阐述了深红色荧光粉MgAl_2O_4:Mn~(4+)发光效率提高的原因.     

Co掺杂对La5/8Ca3/8MnO3体系铁磁有序的影响与电子的局域化效应

系统研究了强关联锰氧化物La5/8Ca3/8Mn1-xCoxO3(x=0,0.05)体系的结构和输运特性.结果表明,样品均为很好的正交O′单相结构,Mn位5%Co掺杂明显影响了样品铁磁-顺磁(FM-PM)转变和金属-绝缘体(M-I)转变,M-I转变温度TM-I从未掺杂时的271K降至227K,对应的峰值电阻率ρp增大;随着TM-I的降低,Tc同时降低,磁电阻MR%亦相应增加;La5/8Ca3/8MnO3样品在Tc以下表现出长程铁磁有序态,Mn位5%Co掺杂样品则表现为团簇玻璃型短程铁磁有序行为.证明Co掺杂引起电子的局域化效应乃是导致体系输运行为发生变化的主要原因.同时,从Mn3 -O2--Mn4 双交换(DE)作用和超交换(SE)相互作用机制等出发,对样品的输运行为、CMR效应以及与Co掺杂之间的关联进行了讨论.     

Y_3Fe_(5-x)Mn_xO_(12)的磁结构和磁性能

对多晶Y_3Fe_(5-x)Mn_xO_(12)(x=0.05和0.09),得到300K下的中子衍射曲线。发现当x=0.05时,Mn~(3+)离子占据16a和24d位置的几率分别为0.72和0.28;当x=0.09时,Mn~(3+)离子全部占据16a位置;还得到两种组分16a和24d位置各自的磁矩值。 在外磁场(800—10KOe)下测量Y_3Fe_(5-x)Mn_xO_(12)(x=0—0.11)的磁化曲线,温度范围是1.5—300K。得到饱和磁矩值;并利用趋近饱和定律确定1.5K下的磁晶各向异性常数k_1值,发现|K_1|值随含锰量增加而减小。     

Pb掺杂对Cd_2Ru_2O_7反常金属态的调控

具有烧绿石结构的Cd_2Ru_2O_7在形成长程反铁磁序的同时进入反常的金属态.采用高压高温方法制备了一系列Pb掺杂的Cd_(2-x)Pb_xRu_2O_7(0≤x≤2)多晶样品,并系统研究了其晶体结构和电阻率、磁化率、热电势等物理性质.尽管Pb_2Ru_2O_7是泡利顺磁金属,但少量Pb~(2+)掺杂的样品Cd1.8Pb0.2Ru2O7却呈现出明显的金属-绝缘体转变,与施加静水压和少量Ca~(2+)掺杂的效果类似.通过与类似的烧绿石Ru~(5+)氧化物进行对比,提出Cd_2Ru_2O_7中的Ru~(5+)-4d~3电子态恰好处于巡游到局域过渡的区域,少量Pb~(2+)掺杂造成的晶格无序增强了电子的局域性,使得形成反铁磁序的同时伴随出现了金属-绝缘体转变.这表明具有烧绿石结构的Ru~(5+)氧化物是研究巡游-局域电子转变的理想材料体系.     

Pr(Sr_(0.2)Ca_(0.8))_2Mn_2O_7纳米颗粒的磁性研究

采用溶胶-凝胶法成功制备了双层钙钛矿锰氧化物Pr(Sr0.2Ca0.8)2Mn2O7纳米颗粒样品,并研究了样品的相结构和显微形貌及样品的磁性.X射线衍射分析结果表明样品中没有出现明显的杂相,SEM分析晶粒平均尺寸约为35nm,EDS测得的样品原子百分比表明成分基本没有偏析,Scherrer公式计算晶粒平均尺寸与SEM测试结果相同约为35nm.在场冷(field cooling FC)和零场冷(zero field cooling ZFC)模式测得的磁化强度-温度(M~T)曲线上,没有观察到300K时电荷有序转变;通过不同温度下磁化强度-磁场强度(M~T)曲线可以清楚的看出,Pr(Sr0.2Ca0.8)2Mn2O7纳米样品在5K和77K时都表现出铁磁行为,表明样品中铁磁(ferromagnetic FM)团簇磁矩已经开始有序排列形成铁磁态.     

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.     

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.     

Properties of nonstoichiometric Pr0.6−xSr0.4MnO3 as the cathodes of SOFCs

A series of samples Pr_0.6−xSr_0.4MnO₃ (x=0, 0.01, 0.05, 0.1, 0.15, 0.2) were synthesized by a solid state reaction method. Pr deficiency at the A site has a great effect on the properties of Pr_0.6−xSr_0.4MnO₃ as the cathode of SOFCs (solid oxide fuel cells). Compared to the commonly used La_0.6Sr_0.4MnO₃ and La_0.55Sr_0.4MnO₃ cathode, Pr_0.6−xSr_0.4MnO₃ is better in the properties of conductivity, overpotential and impedance. In all the samples, the one with x=0.05, Pr_0.55Sr_0.4MnO₃, revealed the best performance in the measured temperature range.     

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.     

Superconductivity due to charge transfer to the CuO2 sheet from the (Tl,Pb) O layer in Tl0.5Pb0.5Sr2−xNdxCuO5−δ

The superconductivity of Tl_0.5Pb_0.5Sr_2−xNd_xCuO_5−δ was observed for x ≥ 0.3, although the calculated Cu valence assuming Tl³⁺ and Pb⁴⁺ is slightly above or below 2.0. The binding energy of the Tl and Pb 4f core levels measured by XPS shifted to higher energy than those of Tl³⁺ and Pb⁴⁺ in the reference materials, showing that the Tl and Pb valences are lower than 3 + and 4 +, respectively. These observations strongly suggest that holes in the CuO₂ sheet are created by charge transfer from the (Tl,Pb)O layer, similar to the double-layered Tl---Ba cuprates.

In contrast, the temperature variation of electrical conductivity of Tl_0.5Pb_0.5Sr₂CuO_5−δ changed from metallic to semiconducting with increasing oxygen deficiency, δ, and no superconductivity was observed through any control of δ. Although XPS measurement also suggested that Tl and Pb valences lowered with increasing oxygen deficiency, δ, the reason why the system did not show superconductivity can be understood by the depletion of oxygen from the CuO₂ plane during deoxygenation.     

Spin-polarized tunneling in nanostructured La2/3Sr1/3MnO3

We present magnetic and transport properties of nanocrystalline La_2/3Sr_1/3MnO₃ powders prepared by a gel-combustion method using citric acid as the fuel. The coercive magnetic field H_c is significantly different to the field H_c^* for which the magnetoresistance (MR) is maximum. The MR at low fields (LFMR) exhibits a power-law dependence with magnetization, MR∝Mⁿ, with n=2.5–3.3 for temperatures ranging from 5 to 200 K. The results are discussed in terms of a distribution of particle size in our sample.     

Direct measurement of the magnetocaloric effect in La0.67Ca0.33MnO3

Polycrystalline perovskite La_0.67Ca_0.33MnO₃ was synthesized by a sol–gel method. Its adiabatic temperature change ΔT_ad induced by a magnetic field change was measured directly. At 268 K, near its Curie temperature T_C, ΔT_ad of La_0.67Ca_0.33MnO₃ induced by a magnetic field change of 2.02 T reaches 2.4 K. The latent heat Q and magnetic entropy change −ΔS_M induced by a magnetic field change were calculated from the temperature dependence of ΔT_ad and zero-field heat capacity C_p. The maximum values of Q and −ΔS_M in La_0.67Ca_0.33MnO₃ induced by a magnetic field change of 2.02 T are 1.85 J g⁻¹ and 6.9 J kg⁻¹ K⁻¹, respectively. The former is larger than the phase transition latent heat of heating or cooling, which is about 1.70 J g⁻¹.     

Low temperature magnetotransport properties of La0.55Ho0.15Sr0.3MnO3

Magnetotransport data measured in thin films of La_0.55Ho_0.15Sr_0.3MnO₃ down to very low temperatures (0.25 K) are reported. The samples presented colossal magnetoresistance with a T_C close to 200 K. A minimum in the resistance vs. T curve and a drop in the ZFC magnetization were also observed. It was also found a T-dependent relaxation effect after the magnetic field was either applied or removed. These results can be understood within the framework where electronic scattering occurs across magnetic domain walls in a reentrant spin-glassy-like phase.     

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.