Exploring nanoscale magnetism in advanced materials with polarized X-rays

Nanoscale magnetism is of paramount scientific interest and high technological relevance. To control magnetization on a nanoscale, both external magnetic fields and spin polarized currents, which generate a spin torque onto the local spin configuration, are being used. Novel ideas of manipulating the spins by electric fields or photons are emerging and benefit from advances in nano-preparation techniques of complex magnetic materials, such as multiferroics, ferromagnetic semiconductors, nanostructures, etc.Advanced analytical tools are needed for their characterization. Polarized soft X-rays using X-ray dichroism effects are used in a variety of spectroscopic and microscopic techniques capable of quantifying in an element, valence and site-sensitive way basic properties of ferro(i)- and antiferromagnetic systems, such as spin and orbital moments, nanoscale spin configurations and spin dynamics with sub-ns time resolution. Future X-ray sources, such as free electron lasers will provide an enormous increase in peak brilliance and open the fs time window to studies of magnetic materials. Thus fundamental magnetic time scales with nanometer spatial resolution can be addressed.This review provides an overview and future opportunities of analytical tools using polarized X-rays by selected examples of current research with advanced magnetic materials.     

Possible valence-bond condensation in the frustrated cluster magnet LiZn2Mo3O8

The emergence of complex electronic behaviour from simple ingredients has resulted in the discovery of numerous states of matter. Many examples are found in systems exhibiting geometric magnetic frustration, which prevents simultaneous satisfaction of all magnetic interactions. This frustration gives rise to complex magnetic properties such as chiral spin structures, orbitally driven magnetism, spin-ice behaviour exhibiting Dirac strings with magnetic monopoles, valence-bond solids and spin liquids. Here we report the synthesis and characterization of LiZn(2)Mo(3)O(8), a geometrically frustrated antiferromagnet in which the magnetic moments are localized on small transition-metal clusters rather than individual ions. By doing so, first-order Jahn-Teller instabilities and orbital ordering are prevented, allowing the strongly interacting magnetic clusters in LiZn(2)Mo(3)O(8) to probably give rise to an exotic condensed valence-bond ground state reminiscent of the proposed resonating valence-bond state. Our results also link magnetism on clusters to geometric magnetic frustration in extended solids, demonstrating a new approach for unparalleled chemical control and tunability in the search for collective, emergent electronic states of matter.     

磁性多层膜研究进展:理论和实验

详细叙述了磁性多层膜研究的理论和实验进展，在不同的磁性多层膜材料中，大量实验事实证明和理论预示磁性多层膜具有独特的物理性质，如维度磁性、界面各向异性、耦合作用、巨磁阻、层间交换作用振荡和磁性量子隧道效应等等，因而，磁性多层膜是理论研究和技术应用的重要课题。     

Magnetism in nanoclusters and cluster-assembled thin films

Increasing attention has been focused on the magnetic behavior of nanoparticles with diameters of 1-5 nm (approximately 50-5000 atoms). In this size range fundamental magnetic parameters such as the orbital and spin magnetic moments per atom deviate significantly from bulk values, and studying clusters addresses fundamental problems in mesoscopic magnetism, which is not as well understood as in either the atomic or the bulk regimes. There is also a growing realization of the enormous industrial potential of materials built by depositing preformed nanoclusters instead of atoms. If the clusters are size-selected and deposited in conjunction with an atomic vapor of a matrix material, it is possible to produce granular films in which there is independent control over the particle size and volume fraction. Using this technique, it also becomes possible to make granular mixtures of miscible materials. This unprecendented degree of control over the properties of the films holds the promise of new magnetic materials with "engineered properties." To fully realize this potential requires a greater understanding of not only the individual particles, but also how they interact in dense assemblies. There has been great progress in understanding some aspects of the magnetic behavior of nanoclusters and cluster-assembled materials. The mechanisms that generate spin and orbital moments that are enhanced by up to 36 and 200%, respectively, relative to the bulk in isolated clusters are well understood as is the dynamical behavior of the magnetic moment. Not so well understood is the observed magnetic anisotropy, which often has a different symmetry than the bulk. In dense assemblies, the nature of the interparticle coupling and the relative importance of dipolar and exchange interactions also require further research.     

Ambient Degradation‐Induced Spin Paramagnetism in Phosphorene

The sizeable direct bandgap, high mobility, and long spin lifetimes at room temperature offer black phosphorus (BP) potential applications in spin‐based semiconductor devices. Toward these applications, a critical step is creating a magnetic response in BP, which is arousing much interest. It is reported here that ambient degradation of BP, which is immediate and inevitable and greatly changes the semiconducting properties, creates magnetic moments, and any degree of degradation leads to notable paramagnetism. Its Landau factor g measured is ≈1.995, revealing that the magnetization mainly results from spin rather than orbital moments. Such magnetism most likely results from the unsaturated phosphorus in the vacancies which are stabilized by O adatoms. It can be tuned by changing any one of the ambient factors of ambient temperature, humidity, and light intensity, and can be stabilized by exposing BP in argon. The findings highlight the importance of evaluating the effect of ambient degradation‐induced magnetism on BP's spin‐based devices. The work seems an essential milestone toward the forthcoming research upsurge on BP's magnetism.     

Concept of impurity-dislocation magnetism in III�CV compound semiconductors

The ability of dislocations to attract impurity atoms is examined from the viewpoint of the feasibility to produce linear, extended magnetic structures in transition-metal-doped diamagnetic III?CV compound semiconductor hosts. To understand the possible formation mechanisms and expected properties of such structures, we analyze a number of experimental studies that address the precipitation of magnetically inactive atoms onto edge dislocations in metals and semiconductors. The general trends identified are used in analysis of the properties of magnetically active atoms located around dislocations. We examine the feasibility of creating novel magnetic semiconductors in which transition-metal-doped dislocations would serve as magnetic memory cells. The research direction addressed in this paper is defined as the concept of impurity-dislocation magnetism in III?CV compound semiconductors.     

铁基超导体的磁性研究

介绍了超导电性的发展简史及其广阔用途,介绍了铁基超导体的结构分类和物质的磁性分类;以BaFe2As2为例综述了铁基超导体中铁磁和超导共存的研究现状,同时以SmOCoAs为例研究了1111相中丰富的磁结构,从而阐明磁性在铁基超导电性研究中的重要地位;最后针对高温超导微观机理研究和超导新材料探索提出了见解.     

有机磁性结构型化合物的研究进展

有机磁性材料因其具有质轻、结构多样性、易用化学方法合成、并且还可以通过引入特定的官能团而产生新功能等特性，在超高频装置、高密度存贮材料、吸波材料、微电子工业和宇航等领域具有广阔的应用前景。介绍了磁性的本质与来源，分别从纯有机磁性化合物和金属有机磁性化合物两方面对结构型磁性化合物进行综述，重点阐述金属有机磁性化合物中的桥联型、二茂金属类、席夫碱型以及含双噻唑环类磁性化合物的发展及其性能研究，并提出了结构型磁性化合物的理论与应用研究方向。     

Magnetic Plasmon Networks Programmed by Molecular Self‐Assembly

Nanoscale manipulation of magnetic fields has been a long‐term pursuit in plasmonics and metamaterials, as it can enable a range of appealing optical properties, such as high‐sensitivity circular dichroism, directional scattering, and low‐refractive‐index materials. Inspired by the natural magnetism of aromatic molecules, the cyclic ring cluster of plasmonic nanoparticles (NPs) has been suggested as a promising architecture with induced unnatural magnetism, especially at visible frequencies. However, it remains challenging to assemble plasmonic NPs into complex networks exhibiting strong visible magnetism. Here, a DNA‐origami‐based strategy is introduced to realize molecular self‐assembly of NPs forming complex magnetic architectures, exhibiting emergent properties including anti‐ferromagnetism, purely magnetic‐based Fano resonances, and magnetic surface plasmon polaritons. The basic building block, a gold NP (AuNP) ring consisting of six AuNP seeds, is arranged on a DNA origami frame with nanometer precision. The subsequent hierarchical assembly of the AuNP rings leads to the formation of higher‐order networks of clusters and polymeric chains. Strong emergent plasmonic properties are induced by in situ growth of silver upon the AuNP seeds. This work may facilitate the development of a tunable and scalable DNA‐based strategy for the assembly of optical magnetic circuitry, as well as plasmonic metamaterials with high fidelity.     

The physics of magnetic materials from ab-initio calculations

Recent advances on ab-initio computation of physical properties of magnetic materials are reviewed. The emphasis is put forward regarding the new development of the electronic structure methods, namely the calculation of magnetic anisotropy energy, X-ray magnetic dichroism, non-collinear magnetism, spin density wave, and spin fluctuations in materials. These theoretical advances have lead to new levels of understanding of magnetic materials. In particular, new results on magnetic anisotropy, surface and interface magnetism, and magnetic alloys will be briefly discussed.     

WC基高锰钢结硬质合金的异常碎裂机理研究

对成分为:w(WC)=75.0%～90.0%,w(Mn):w(C)≥10,w(Ni)=3.0%～5.0%,w(Fe)为余量的合金进行了脆性断裂的机理研究。通过对合金的磁性测量、X射线衍射能谱、金相显微镜和断口电镜扫描等的分析,发现有磁性的合金其内部化学成分发生了变化,导致其组织结构发生变化,脆性增大,无加工硬化;而无磁性的合金具有明显的加工硬化。进一步的研究还发现,磁性强弱与WC晶粒的大小有关,晶粒粗大的磁性强,从而可以认定,磁性可作为该类合金适用性的一种表征值。     

Transport and Optical Properties of Diluted Magnetic Semiconductors

We investigated the transport and optical properties of diluted magnetic semiconductors theoretically by using a simple model where carriers move in a single band. In this model the carrier feels a nonmagnetic potential at a magnetic impurity site, and its spin interacts with the localized spins of the magnetic impurities through exchange interactions. The electronic states of a carrier were calculated by using the coherent potential approximation (CPA). The magnetism was investigated by minimizing the free-energy and the electrical conductivity was calculated by using the Kubo formula. We examined the results in several typical cases which correspond to (Ga_1–xMn_x)As with x = 0.05.     

Multiferroics: a magnetic twist for ferroelectricity

Magnetism and ferroelectricity are essential to many forms of current technology, and the quest for multiferroic materials, where these two phenomena are intimately coupled, is of great technological and fundamental importance. Ferroelectricity and magnetism tend to be mutually exclusive and interact weakly with each other when they coexist. The exciting new development is the discovery that even a weak magnetoelectric interaction can lead to spectacular cross-coupling effects when it induces electric polarization in a magnetically ordered state. Such magnetic ferroelectricity, showing an unprecedented sensitivity to ap plied magnetic fields, occurs in 'frustrated magnets' with competing interactions between spins and complex magnetic orders. We summarize key experimental findings and the current theoretical understanding of these phenomena, which have great potential for tuneable multifunctional devices.     

Magnetic effects at the interface between non-magnetic oxides

The electronic reconstruction at the interface between two insulating oxides can give rise to a highly conductive interface. Here we show how, in analogy to this remarkable interface-induced conductivity, magnetism can be induced at the interface between the otherwise non-magnetic insulating perovskites SrTiO3 and LaAlO3. A large negative magnetoresistance of the interface is found, together with a logarithmic temperature dependence of the sheet resistance. At low temperatures, the sheet resistance reveals magnetic hysteresis. Magnetic ordering is a key issue in solid-state science and its underlying mechanisms are still the subject of intense research. In particular, the interplay between localized magnetic moments and the spin of itinerant conduction electrons in a solid gives rise to intriguing many-body effects such as Ruderman-Kittel-Kasuya-Yosida interactions, the Kondo effect and carrier-induced ferromagnetism in diluted magnetic semiconductors. The conducting oxide interface now provides a versatile system to induce and manipulate magnetic moments in otherwise non-magnetic materials.     

热处理工艺对尖晶石型Ni0.5Zn0.45Co0.05Fe2O4静磁性能的影响

利用溶胶凝胶法制备了尖晶石型 Ni0.5Zn0.45Co0.05Fe2O4 纳米颗粒,设置了3种热处理工艺,发现随着热处理温度的提高,热处理时间的延长,颗粒长大,静磁性能提高。当热处理温度为800℃,保温8h,材料具有比较好的静磁性能（Ms=30.241Oe,Hc=73.261 emg/g,μi=0.210）。另外,将前驱体在磁场条件下热处理,得到颗粒尺寸比同种热处理工艺未加磁场条件下的大,并且静磁性能有了比较大的提高,其比饱和磁化强度甚至比在更高热处理温度,更长热处理时间下制备的NiZnCo铁氧体大。     

ZnO基稀磁半导体磁性机理研究进展

稀磁半导体是指在非磁性化合物半导体中通过掺杂引入部分磁性离子所形成的一类新型功能材料.目前,稀磁半导体的磁性来源和机理一直是该领域的研究热点,掺杂的磁性离子通过怎样的交换方式实现铁磁性一直存有争议.本文对近几年来ZnO基稀磁半导体磁性机理研究进展作一综述,着重阐述了代表性的RRKY理论、平均场理论、双交换理论和磁极子理论,对实验和理论方面的热点和存在问题作一评价,对磁性理论的研究提出了新思路.     

纳米磁性材料及其应用

纳米磁性材料是纳米材料中最早进入工业化生产,应用十分广泛的一类功能材料,纳米磁性材料的特性不同于常规的磁性材料,其原因在于与磁性相关联的特征物理长庆恰好处于纳米量级,例如,磁单畴尺寸,超顺磁性临界尺寸,交换作用长度,以主电子平均自由路磁程自由路程等大致处于1－100nm量级,当磁性体的尺寸与这些特征物理长度相当时,就会呈现反常的磁学与电学性质,利用这些新特性,已涌现出一系列新材料与众多应用。     

Atomistic modeling of materials properties by Monte Carlo Simulation

In order to optimize materials properties, in many cases a deeper understanding of the relationship between the chemical-atomistic structure and the physical properties of the solid and fluid phases of the material is necessary. Monte Carlo simulation is a tool that allows the reliable calculation of thermodynamic properties of strongly interacting many-body condensed matter systems. Given a model of effective interatomic or intermolecular interactions (drawn either from quantum-chemical-type interactions or from analysis of suitable experimental data), macroscopic bulk properties of a material can be simulated, as well as interfacial phenomena and certain kinds of slow dynamic processes (of relaxational or diffusive type). After a brief review of the foundations of this approach in statistical mechanics, the wide potential of this method is illustrated with examples taken from magnetism, metallurgy and amorphous polymeric materials. Strengths and limitations of this atomistic approach towards modeling materials properties are discussed and directions of future research are spelled out.     

磁性多层膜的研究进展

磁性研究是个古老而又暂新的课题，目前，随着信息产业的发展，磁性多层膜领域的研究正在引起人们更多的重视，综述了磁性多层膜领域的若干进展，认为该领域的研究主要集中在多磁性多层膜的结构研究，磁学特性的研究以及多层膜理论计算领域等几个方面。     

Robust Room-Temperature Ferromagnetism with Giant Anisotropy in Nd-Doped ZnO Nanowire Arrays

As an important class of spintronic material, ferromagnetic oxide semiconductors are characterized with both charge and spin degrees of freedom, but they often show weak magnetism and small coercivity, which limit their applications. In this work, we synthesized Nd-doped ZnO nanowire arrays which exhibit stable room temperature ferromagnetism with a large saturation magnetic moment of 4.1 μ(B)/Nd as well as a high coercivity of 780 Oe, indicating giant magnetic anisotropy. First-principles calculations reveal that the remarkable magnetic properties in Nd-doped ZnO nanowires can be ascribed to the intricate interplay between the spin moments and the Nd-derived orbital moments. Our complementary experimental and theoretical results suggest that these magnetic oxide nanowires obtained by the bottom-up synthesis are promising as nanoscale building blocks in spintronic devices.