热处理对钙钛矿锰氧化物La_(0.95)Sr_(0.05)MnO_3离子价态和磁结构的影响

对于磁性氧化物的磁有序,传统的观点用超交换相互作用(SE)和双交换相互作用(DE)模型进行解释,其出发点都建立在全部氧离子是-2价的基础上.例如,对于LaMnO_3,认为其中的La和Mn都处于+3价,用SE模型解释相邻Mn~(3+)离子间的反铁磁序;当以二价的Sr离子替代一部分La离子后,认为等量的Mn~(3+)离子变为Mn~(4+)离子,用DE模型解释相邻Mn~(3+)和Mn~(4+)离子间的铁磁序.然而,事实上在氧化物中存在一部分负一价氧离子.Cohen[Nature 358 136]利用密度泛函理论计算了BaTiO_3的价电子态密度,结果得到只有Ba离子的化合价与传统观点相同,为+2价;而Ti和0分别为+2.89价和-1.63价,不是传统观点的+4价和-2价,但是与多年来关于氧化物电离度的研究[Rev.Mod.Phys.42 317]和X射线光电子谱(XPS)的研究结果相符合.本文经过不同热处理条件制备了名义成分为La_(0.95)Sr_(0.05)MnO_3的三个样品,通过对样品的XPS分析,发现样品中不存在Mn~(4+)离子,只存在Mn2+和Mn~(3+)离子,平均价态随热处理程序的增加而升高.尽管三个样品有相同的晶体结构,但磁矩明显不同.对于这样的性能,不能用SE和DE模型解释其磁结构.利用本课题组最近在研究尖晶石结构铁氧体磁有序过程中提出的O 2p巡游电子模型解释了这种现象,利用样品在10 K的磁矩估算出的Mn离子平均价态变化趋势与XPS分析结果一致.O 2p巡游电子模型的出发点建立在氧化物中存在一部分负一价氧离子的基础上,这是其与SE和DE模型的根本区别.     

磁性二维材料的近期研究进展

具有磁各向异性的二维磁性材料可在有限温度下和单层极限下形成磁有序,其宏观磁性与层数、堆叠形式等密切相关且其磁交换作用可被多种外场调控.这些新奇特性赋予了二维磁性材料丰富的物理内涵和潜在的应用价值,受到了研究者的广泛关注.本文着重介绍近年来二维磁体在实验和理论计算两方面的研究进展,首先从几种二维磁性材料中常见的磁交换机制出发,随后以组分作为分类依据,详细介绍一些主要二维磁体的几何和电子结构以及它们的磁耦合方式;在此基础上,再讨论如何通过外部(外场和界面)和内部(堆叠和缺陷)两类方式调控二维磁体的电子结构和磁性;继而探讨如何利用这两类调控方式,将上述材料应用于实际自旋电子学器件以及磁存储等方面的潜力;最后总结和展望了目前二维磁性材料遇到的困难和挑战以及未来可能的研究方向.     

La$lt;sub$gt;0.4$lt;/sub$gt;Ca$lt;sub$gt;0.6$lt;/sub$gt;MnO$lt;sub$gt;3$lt;/sub$gt;中Mn-位Fe和Cr掺杂对磁性质的影响

研究了Fe和Cr掺杂对La_0.4Ca_0.6MnO₃ 中电荷有序反铁磁基态的调控作用. 磁性质的测量结果表明, 两种离子掺杂均能有效抑制原型样品中的长程电荷有序相, 但是Fe离子掺杂样品均具有反铁磁的基态, 而Cr掺杂样品中则出现了显著的铁磁性. 结合电输运测量结果显示, Cr掺杂引起的铁磁态同时具有金属性, 表明其中是电子双交换作用占主导. 对比两种掺杂离子的电子结构发现, Cr离子空的e_g电子轨道促进了电子双交换作用, 而Fe掺杂则只是引入了不同的自旋交换作用, 导致自旋无序. 关键词： 磁性氧化物 反铁磁     

磁性材料的磁结构、磁畴结构和拓扑磁结构

首先简要地介绍了磁性材料中磁结构、磁畴结构和拓扑磁结构以及相互之间的关系. 一方面, 磁畴结构由材料的磁结构、内禀磁性和微结构因素决定; 另一方面, 磁畴结构决定了材料磁化和退磁化过程以及技术磁性. 拓扑学与材料物理、材料性能的联系越来越紧密. 最近的研究兴趣集中在一些拓扑磁性组态, 如涡旋、磁泡、麦纫、斯格米子等. 研究发现这些拓扑磁结构的拓扑性质与磁性能密切相关. 然后从尺寸效应、缺陷、晶界三个方面介绍国际学术界在磁结构、磁畴结构和拓扑磁结构方面的进展. 最后介绍了在稀土永磁薄膜材料的微观结构、磁畴结构和磁性能关系、交换耦合纳米盘中的拓扑磁结构及其动力学行为方面的工作. 通过对文献的评述, 得到以下结论: 开展各向异性纳米复合稀土永磁材料的研究对更好地利用稀土资源具有重要的意义. 可以有目的地改变材料的微结构, 可控地进行磁性材料的磁畴工程, 最终获得优秀的磁性能. 拓扑学的概念正在应用于越来越多的学科领域, 在越来越多的材料中发现拓扑学的贡献. 研究磁畴结构、拓扑磁性基态或者激发态的形成规律以及动力学行为对理解量子拓扑相变以及其他与拓扑相关的物理效应是十分重要的. 也会帮助理解不同拓扑学态之间相互作用的物理机制及其与磁性能之间的关系, 同时拓展拓扑学在新型磁性材料中的应用.     

La_(0.4)Ca_(0.6)MnO_3中Mn-位Fe和Cr掺杂对磁性质的影响

研究了Fe和Cr掺杂对La0.4Ca0.6Mn O3中电荷有序反铁磁基态的调控作用.磁性质的测量结果表明,两种离子掺杂均能有效抑制原型样品中的长程电荷有序相,但是Fe离子掺杂样品均具有反铁磁的基态,而Cr掺杂样品中则出现了显著的铁磁性.结合电输运测量结果显示,Cr掺杂引起的铁磁态同时具有金属性,表明其中是电子双交换作用占主导.对比两种掺杂离子的电子结构发现,Cr离子空的e g电子轨道促进了电子双交换作用,而Fe掺杂则只是引入了不同的自旋交换作用,导致自旋无序.     

铁磁金属薄膜磁性的电场调制

文章主要介绍了Science上发表的Weisheit M 等人利用外加电场调制铁磁金属薄膜磁性的实验工作,该工作所用的实验方法简单、有效,为人们改变金属磁性开辟了一条崭新的道路,有序合金FePt和FePd具有垂直的磁晶各向异性,将它们置人碳酸丙烯脂的电解液中,利用铁磁薄膜和液体接触面形成的双电层电容结构,可以在样品表面产生很大的电场,从而可以调控金属薄膜费米面附近未成对的d电子的态密度.由于费米面附近电子填充数的变化,铁磁薄膜的磁晶各向异性也会受到调制,实验结果表明,-0.6mV的电压变化会导致厚度为2nm的FePt和FePd合金的矫顽力分别减少4.5%和增加1%,这是第一次观测到电场调控金属薄膜磁性的实验工作.     

非简并p型Hgi-xMnxTe单晶（z〉0.17）的负磁电阻机理研究

研究磁性半导体中负磁电阻产生机理对正确理解载流子与磁性离子间的sp．d磁交换作用是非常重要的．通过变温（10-300K）磁输运和变温（5-300K）磁化率实验研究了一系列不同Mn含量非简并P型Hgl-xMn。Te单晶佃〉0．17）的负磁电阻和顺磁增强效应．实验结果表明其负磁电阻与温度的关系和磁化率与温度的关系基本一致,两者都包含一个呈指数型变化的温度函数exp（-K／T）．根据磁性半导体的杂质能级理论,非简并P型H譬1-xMnxTe单晶在低磁场范围内出现负磁电阻效应的主要物理机理为外磁场的磁化效应使得受主杂质或受主型束缚磁极化子的有效电离能减小．     

非简并p型Hg1-xMnxTe单晶(x>0.17)的负磁电阻机理研究

研究磁性半导体中负磁电阻产生机理对正确理解载流子与磁性离子间的sp-d磁交换作用 是非常重要的.通过变温(10---300 K)磁输运和变温(5---300 K)磁化率实验研究了一系列不同Mn含量 非简并p型Hg_1-xMn_xTe单晶(x>0.17)的负磁电阻和顺磁增强效应. 实验结果表明其负磁电阻与温度的关系和磁化率与温度的关系基本一致, 两者都包含一个呈指数型变化的温度函数exp(-K/T).根据磁性半导体的杂质能级理论, 非简并p型Hg_1-xMn_xTe单晶在低磁场范围内出现负磁电阻效应的主要物理机理 为外磁场的磁化效应使得受主杂质或受主型束缚磁极化子的有效电离能减小.     

磁性材料磁有序的分子场来源

对于磁性材料磁有序能的来源,即外斯分子场来源,本文提出一个模型:在磁性金属和合金中的相邻离子实之间,以及磁性氧化物的相邻阴阳离子间,其外层轨道上高速运动的电子分别有一定概率形成三种不同的状态.1)具有一定寿命的自旋相反的电子对,称为外斯电子对(WEP);2)距离很近且自旋方向相同的电子,容易发生互相交换,交换前后电子的自旋方向保持不变;3)当一个离子外层轨道有2个电子,其相邻的离子外层轨道只有1个电子时,前者多出的电子可以跃迁到后者的轨道上,并且保持自旋方向不变.我们认为,WEP两个电子间的静磁吸引能是分子场(即磁有序能)的主要来源.进而,推导出WEP的能量表达式、两电子的平衡间距和最大间距,探讨了在几种钙钛矿结构锰氧化物中形成外斯电子对的概率,用以解释居里温度附近晶格常数随温度变化的特点.结果表明这个模型是合理的.     

基于机器学习的无机磁性材料磁性基态分类与磁矩预测

磁性材料是信息时代重要的基础材料,不同的磁性基态是磁性材料广泛应用的前提,其中铁磁基态是高性能磁性材料的关键要求.本文针对材料项目数据库中的无机磁性材料数据,采用机器学习技术实现无机磁性材料铁磁、反铁磁、亚铁磁和顺磁基态的分类以及无机铁磁性材料磁矩的预测.提取了材料的元素和结构属性特征,通过两步式特征选择方法分别为磁性基态分类和磁矩预测筛选了20个材料特征,发现材料特征中的电负性、原子磁矩和原子外围轨道未充满电子数对两种磁性性能具有重要贡献.基于机器学习的随机森林算法,构建了磁性基态分类模型和磁矩预测模型,采用10折交叉验证的方法对模型进行定量评估,结果表明所构建的模型具有足够的精度和泛化能力.在测试检验中,磁性基态分类模型的准确率为85.23%,精确率为85.18%,召回率为85.04%, F1分数为85.24%;磁矩预测模型的拟合优度为91.58%,平均绝对误差为0.098μB/atom.本研究为无机铁磁性材料的高通量分类筛选与磁矩预测提供了新的方法和选择,可为新型无机磁性材料的设计研发提供参考.     

Co50Fe50-xSix合金的结构相变和磁性

利用实验测量和理论计算相结合的方法,研究了介于B2结构CoFe低有序合金和L21结构Co2FeSi高有序合金之间的Co50Fe50-xSix合金的结构相变、磁相变、分子磁矩和居里温度.采用考虑Coulomb相互作用的广义梯度近似（GGA＋U）方法计算了合金的能带结构.研究发现,合金出现较强的原子有序倾向,表现出较强的共价成相作用.合金的晶格常数、磁矩、居里温度随Si含量的增加而线性地降低,极限成分Co2FeSi合金的分子磁矩和居里温度分别达到5.92μB和777℃.原子尺寸效应导致合金晶格发生变化,但并未成为居里温度和分子磁矩变化的主导因素.分子磁矩的变化符合Slater-Pauling原理,但发现原子磁矩的变化并非线性,据此提出了共价成相对磁性影响的观点.采用Stearns理论解释了居里温度的变化趋势,排除了原子间距对居里温度的主导影响作用.能带计算的结果还表明,Co2FeSi作为半金属材料并非十分完美,可能在实际应用中会出现自旋极化率降低的问题.发现该系列合金的结构相变和磁相变随着成分的变化聚集在窄小的成分和温度范围内.     

The influence of 3d transition metal substitution on the magnetic properties of MnGaGe

A study has been made of the effect of 3d transition element substitution on the magnetic moment and Curie temperature of MnGaGe. Substitution of 3d elements with atomic number less than Mn (i.e. Ti, V, or Cr) cause relatively small changes in magnetic properties, whereas substitution of Fe, Co, Ni and Cu cause a large reduction in moment and Curie temperature, e.g. substitution of 5 at.% Fe for Mn causes the moment to decrease by 30 per cent. The moment and ferromagnetism of MnGaGe are described in terms of a band model involving both strongly correlated and intinerant 3d electrons. The effect of 3d element substitution may be qualitatively understood in terms of this model.     

On the velocity of sound in an itinerant-electron antiferromagnet

The longitudinal sound velocity in an itinerant-electron antiferromagnet is studied, using a jellium model for the ions and a two-sub-band model for the itinerant electrons with an energy gap caused by the antiferromagnetic spin ordering. It is shown that the longitudinal sound velocity decreases with decreasing temperature, due to the electron-photon interaction. The exchange interaction between itinerant electrons is seen to play a particularly important role in the phonon softening phenomena for such a system; and although the model is a great simplification of reality it gives reason to believe that the observed elastic anomalies in the face-centred-cubic 3d transition metal alloys are directly related to their tendency towards antiferromagnetism.     

Robust half-metallic character and large oxygen magnetism in a perovskite cuprate

The new perovskite cuprate material Sr8CaRe3Cu4O24, which behaves ferrimagnetically and shows an unusually high Curie temperature (T(C) approximately 440 K), is found from density-functional theory calculation to display several surprising properties after hole doping or chemical substitution: (1) Half metal (HM) is realized by replacing Re with W or Mo while T(C) remains high; (2) hole-doped Sr8CaRe3Cu4O24 is also HM with high T(C). Moreover, we find that the O atoms will carry a large magnetic moment after hole doping, which is in sharp contrast to the generally accepted concept that magnetism in solids requires partially filled shells of d or f electrons in cations. The material Sr8CaRe3Cu4O24 is therefore expected to provide a very useful platform for material design and development.     

Critical scattering of low-energy electrons by a ferromagnet in the neighborhood of the curie point

It is found that the temperature dependence of the intensity of Bragg maxima arising upon diffraction of low-energy electrons elastically reflected from the (100) plane of a nickel crystal exhibits a critical singularity in the neighborhood of the Curie point. A theory is suggested which describes this effect as the scattering of incident electrons from critical fluctuations of magnetic moment. A comparison is made of the experimentally and theoretically obtained temperature dependences of the intensity of magnetic scattering of electrons, for both three-and two-dimensional models of magnetic ordering. For these models, the radius of interatomic spin-exchange interaction is estimated.     

Correlation between valence electronic structure and magnetic properties in RCo_5(R=rare earth) intermetallic compound

The magnetisms of RCo_5(R = rare earth) intermetallics are systematically studied with the empirical electron theory of solids and molecules(EET).The theoretical moments and Curie temperatures agree well with experimental ones.The calculated results show strong correlations between the valence electronic structure and the magnetic properties in RCo_5 intermetallic compounds.The moments of RCo_5 intermetallics originate mainly from the 3d electrons of Co atoms and 4f electrons of rare earth,and the s electrons also affect the magnetic moments by the hybridization of d and s electrons.It is found that moment of Co atom at 2c site is higher than that at 3g site due to the fact that the bonding effect between R and Co is associated with an electron transformation from 3d electrons into covalence electrons.In the heavy rare-earth-based RCo_5 intermetallics,the contribution to magnetic moment originates from the 3d and 4f electrons.The covalence electrons and lattice electrons also affect the Curie temperature,which is proportional to the average moment along the various bonds.     

Analysis of the valence electronic structures and calculation of the physical properties of Fe,Co, and Ni

The valence electronic structures of Fe, Co and Ni have been investigated with Empirical Electron Theory of Solids and Molecules. The magnetic moments, Curie temperature, cohesive energy and melting point have been calculated according to the valence electronic structure. These calculations fit the experimental data very well. Based on the calculations, the magnetic moments are proportional to the number of 3d magnetic electrons. Curie temperatures are related to the magnetic electrons and the bond lengths between magnetic atoms. Cohesive energies increase with the increase of the number of covalent electrons, and the decrease of the number of magnetic and dumb pair electrons. The melting point is mainly related to the number of covalent electron pairs distributed in the strongest bond. The contribution from the lattice electrons is very small, the dumb pair electrons weaken the melting point; however, the contribution to melting point of the magnetic electrons can be neglected. It reveals that the magnetic and thermal properties are closely related to the valence electronic structures, and the changes or transitions between the electrons obviously affect the physical properties. Supported by the National High Technology Development Program of China (Grant No. 2007AA03Z458)     

Cu cap layer on Ni8/Cu(001): reorientation and TC-shift

Adding a non-magnetic Cu overlayer on Ni₈/Cu(001) is known to induce the reorientation of the magnetic easy axis from in-plane to out-of-plane and to reduce the Curie temperature. In this paper both effects are described on the same footing using an effective Heisenberg trilayer. The model takes into account thermal fluctuations of the magnetization and allows to separate explicitly between two possible mechanisms behind the experimental observations, namely between a reduction of the magnetic moment by hybridization and a lattice relaxation at the Ni/Cu interface. Ferromagnetic resonance data for the reorientation and the decreased Curie temperature due to the Cu cap layer are best reproduced by assuming a reduction of the magnetic moment at the interface by ≈1/3.     

Helicoidal ordering in iron perovskites

We study the double exchange in transition metal oxides with itinerant and localized electrons. We show that the charge transfer energy Delta and the oxygen-oxygen hopping amplitude t(pp) have a strong effect on magnetic ordering: while for Delta>0 the ground state is ferromagnetic, for negative Delta and large t(pp) the double exchange gives rise to an incommensurate helicoidal ordering of local spins, observed, e.g., in the iron perovskites SrFeO3 and CaFeO3. For negative Delta, the metal-insulator transition into a charge-ordered state has little effect on magnetic ordering. This explains the difference in magnetic and transport properties of ferrates and manganites.