Advances in ab-initio theory of multiferroics

Within the broad class of multiferroics (compounds showing a coexistence of magnetism and ferroelectricity), we focus on the subclass of ??improper electronic ferroelectrics??, i.e. correlated materials where electronic degrees of freedom (such as spin, charge or orbital) drive ferroelectricity. In particular, in spin-induced ferroelectrics, there is not only a coexistence of the two intriguing magnetic and dipolar orders; rather, there is such an intimate link that one drives the other, suggesting a giant magnetoelectric coupling. Via first-principles approaches based on density functional theory, we review the microscopic mechanisms at the basis of multiferroicity in several compounds, ranging from transition metal oxides to organic multiferroics to organic-inorganic hybrids.     

Multiferroic materials and magnetoelectric physics: symmetry,entanglement, excitation,and topology

Multiferroics are those materials with more than one ferroic order, and magnetoelectricity refers to the mutual coupling between magnetism (spins and/or magnetic field) and electricity (electric dipoles and/or electric field). In spite of the long research history in the whole twentieth century, the discipline of multiferroicity has never been so highly active as that in the first decade of the twenty-first century, and it has become one of the hottest disciplines of condensed matter physics and materials science. A series of milestones and steady progress in the past decade have enabled our understanding of multiferroic physics substantially comprehensive and profound, which is further pushing forward the research frontier of this exciting area. The availability of more multiferroic materials and improved magnetoelectric performance are approaching to make the applications within reach. While seminal review articles covering the major progress before 2010 are available, an updated review addressing the new achievements since that time becomes imperative. In this review, following a concise outline of the basic knowledge of multiferroicity and magnetoelectricity, we summarize the important research activities on multiferroics, especially magnetoelectricity and related physics in the last six years. We consider not only single-phase multiferroics but also multiferroic heterostructures. We address the physical mechanisms regarding magnetoelectric coupling so that the backbone of this divergent discipline can be highlighted. A series of issues on lattice symmetry, magnetic ordering, ferroelectricity generation, electromagnon excitations, multiferroic domain structure and domain wall dynamics, and interfacial coupling in multiferroic heterostructures, will be revisited in an updated framework of physics. In addition, several emergent phenomena and related physics, including magnetic skyrmions and generic topological structures associated with magnetoelectricity will be discussed. The review is ended with a set of prospectives and forward-looking conclusions, which may inevitably reflect the authors' biased opinions but are certainly critical.     

钙钛矿超晶格的演生磁电物性

钙钛矿过渡金属氧化物中存在诸多自由度（如晶格、电荷、自旋和轨道）,这些自由度 之间的相互耦合以及相互竞争会诱导出很多奇异物性,如高温超导、庞磁电阻效应、多铁性等, 这些物性在量子器件的发展过程中扮演了重要的角色。在此基础上,若再将不同特性的氧化物材 料耦合在一起形成超晶格,通过界面处的晶格重组与电子重组,体系可呈现出更加丰富的物理和 更多可调控的性能。本综述主要关注钙钛矿超晶格中的磁电物性。首先介绍了超晶格中磁性调控 的几种物理机制,然后对超晶格中的杂化非本征铁电性以及电子铁电性进行了重点讨论,最后围 绕超晶格中的磁电耦合效应进行了讨论和总结。     

Multiferroicity induced by dislocated spin-density waves

We uncover a new pathway towards multiferroicity, showing how magnetism can drive ferroelectricity without relying on inversion symmetry breaking of the magnetic ordering. Our free-energy analysis demonstrates that any commensurate spin-density-wave ordering with a phase dislocation, even if it is collinear, gives rise to an electric polarization. Because of the dislocation, the electronic and magnetic inversion centers do not coincide, which turns out to be a sufficient condition for multiferroic coupling. The novel mechanism explains the formation of multiferroic phases at the magnetic commensurability transitions, such as the ones observed in YMn(2)O(5) and related compounds. We predict that in these multiferroics an oscillating electrical polarization is concomitant with the uniform polarization. On the basis of our theory, we put forward new types of magnetic materials that are potentially ferroelectric.     

Magnetoelectric multiferroicity and quantum paraelectricity in hexaferrites

Multiferroic materials with coexisting ferroelectric and magnetic orders have attracted tremendous research interests because of their intriguing fundamental physics as well as potential applications in the next-generation multifunctional devices. Hexaferrites with conical magnetic structures are among the most promising single-phase multiferroics because strong magnetoelectric effects can be achieved in them from low temperatures up to room temperature in low magnetic fields. In this review, after briefly introducing the background on multiferroics and classification of hexaferrites, we summarize recent progress in multiferroic hexaferrites, including the mechanisms of spin-induced ferroelectricity, the magnetoelectric phase diagram, giant direct and converse magnetoelectric effects. Furthermore, we present a new mechanism of magnetic-ion-induced displacive polarization in hexaferrites, which leads to quantum paraelectricity and quantum electric-dipole liquid in M-type hexaferrites.     

Computational studies on magnetism and ferroelectricity

Magnetics, ferroelectrics, and multiferroics have attracted great attentions because they are not only extremely important for investigating fundamental physics, but also have important applications in information technology. Here, recent computational studies on magnetism and ferroelectricity are reviewed. We first give a brief introduction to magnets, ferroelectrics, and multiferroics. Then, theoretical models and corresponding computational methods for investigating these materials are presented. In particular, a new method for computing the linear magnetoelectric coupling tensor without applying an external field in the first principle calculations is proposed for the first time. The functionalities of our home-made Property Analysis and Simulation Package for materials (PASP) and its applications in the field of magnetism and ferroelectricity are discussed. Finally, we summarize this review and give a perspective on possible directions of future computational studies on magnetism and ferroelectricity.     

铋层状氧化物单晶薄膜多铁性研究进展

室温单相多铁材料非常稀缺,磁性元素掺杂的铋层状钙钛矿结构Aurivillius相氧化物是一类重要的单相室温多铁材料,但由于缺少单晶类样品,这一类多铁材料研究主要是围绕多晶类块体或者多晶薄膜展开,它们的磁、电等性能研究大都采用宏观探测方式,因此这类多铁材料的多铁性机理研究进行得非常困难.近年来在高质量单晶薄膜的基础上,研究了多种磁性元素掺杂和不同周期结构的铋层状氧化物多铁单晶薄膜.这些单晶薄膜在室温下大都具有层状面面内方向的铁电极化,以及比较小的室温磁化强度,低温区存在第二个磁性相变.通过X射线共振非弹性散射实验发现元素掺杂会改变金属和氧原子之间的氧八面体晶体场的劈裂,能够增强铁磁性.另一方面,通过极化中子反射实验发现薄膜主体的磁化强度远小于通常探测的宏观磁化强度,说明单晶薄膜中磁的来源及其磁电耦合机理和多晶块体很可能是不同的.铋层状单晶薄膜的多铁性对未来继续改善这类材料的多铁性能有很好的指导作用.     

Microscopic origin of magnetoelectric coupling in noncollinear multiferroics

An universal microscopic mechanism to understand the interplay between the electric and magnetic degrees of freedom in noncollinear multiferroics is developed. In a system with a strong spin-orbit coupling, we show that there is a pure electric mechanism that the ferroelectricity is generated by noncollinear magnetism through an electric current cancellation process, which saves the pure electric energy. This mechanism provides a simple estimation and sets a physical limitation of the value of ferroelectricity in noncollinear multiferroic materials.     

Modulation of physical properties of oxide thin films by multiple fields

Recent studies of the modulation of physical properties in oxide thin films by multiple fields are reviewed.Some of the key issues and prospects of this area of study are also addressed.Oxide thin films exhibit versatile physical properties such as magnetism,ferroelectricity,piezoelectricity,metal–insulator transition(MIT),multiferroicity,colossal magnetoresistivity,switchable resistivity.More importantly,the exhibited multifunctionality can be tuned by various external fields,which has enabled demonstration of novel electronic devices.     

Nanomagnetism in nanocrystalline multiferroic bismuth ferrite lead titanate films

Multiferroics conventionally refer to the materials exhibiting co-existing electric, magnetic, and structure order parameters. Interplay between ferroelectricity, magnetism, and ferroelasticity in a single phase makes multiferroics truly multifunctional providing control over magnetic and electric ordering by applying electric and magnetic fields, respectively. Incorporation of multiferroic-based components into nanoscale applications will enable additional degrees of freedom in manipulating with spin and charge not easily attainable otherwise. Multiferroic bismuth ferrite lead titanate has been chemically synthesized in form of nanocrystalline films. The morphology of the films revealed a single perovskite phase confined within crystalline grains of few tens of nm in size. The films were found to exhibit ferroelectricity and ferromagnetism with characteristic electric polarization and magnetization hysteresis loops, transformations associated with spin reorientation in an external magnetic field and the spin-glassy behavior well above the room temperature. High degree of magnetic frustration and disorder in the spin system spatially confined in the nanograins, distribution of the grains anisotropy axis, inter-grain interactions, and the effects of uncompensated spins on the large effective surface/interface favored by the nanocrystalline morphology were assumed to be responsible for the anomalous magnetic properties and glassy dynamics in the films.     

Pseudo Jahn-Teller origin of perovskite multiferroics, magnetic-ferroelectric crossover, and magnetoelectric effects: the d0-d10 problem

The conditions of multiferroicity in d(n) perovskites are derived from the pseudo Jahn-Teller effect, due to which ferroelectric displacements are triggered by vibronic coupling between ground and excited electronic states of opposite parity but same spin multiplicity; it takes place for some specific d(n) configurations and spin states only. In combination with the high-spin-low-spin crossover effect this leads to a novel phenomenon, the magnetic-ferroelectric (multiferroics) crossover which predicts magnetoelectric effects with exciting functionalities including electric magnetization and demagnetization.     

钙钛矿型氧化物非常规铁电研究进展

钙钛矿型氧化物因具有丰富的磁性、铁电、力学和光学等诸多功能属性,在电子信息通信材料器件领域中有广阔的应用前景.在各种物理性质之中,铁电极化因其产生机制多样,并能与磁性和晶格应变相互耦合形成多铁性等特点,近十多年来一直被作为凝聚态物理研究的国际热点问题.与以自发极化作为初级序参量的常规铁电材料不同,非常规铁电材料中的铁电极化是被其他的序参量诱导而产生的.本综述围绕无机钙钛矿型氧化物非常规铁电体的研究进展进行了总结.回顾了该体系经典唯象理论和原子尺度的微观模型,有序排列的人工钙钛矿超晶格型结构,以及稀土正铁氧体单晶的反铁磁畴壁结构中非常规铁电的极化强度大小及其诱导机制,为系统理解非常规铁电提供了理论途径.     

Emergent ferroelectricity in disordered tri-color multilayer structure comprised of ferromagnetic manganites

Multiferroic materials,showing the coexistence and coupling of ferroelectric and magnetic orders,are of great technological and fundamental importance.However,the limitation of single phase multiferroics with robust magnetization and polarization hinders the magnetoelectric effect from being applied practically.Magnetic frustration,which can induce ferroelectricity,gives rise to multiferroic behavior.In this paper,we attempt to construct an artificial magnetically frustrated structure comprised of manganites to induce ferroelectricity.A disordered stacking of manganites is expected to result in frustration at interfaces.We report here that a tri-color multilayer structure comprised of non-ferroelectric La_(0.9)Ca_(0.1)MnO_3(A)/Pr_(0.85)Ca_(0.15)MnO_3(B)/Pr_(0.85)Sr_(0.15)MnO_3(C) layers with the disordered arrangement of ABC-ACBCAB-CBA-BAC-BCA is prepared to form magnetoelectric multiferroics.The multilayer film exhibits evidence of ferroelectricity at room temperature,thus presenting a candidate for multiferroics.     

Topology and ferroelectricity in group-V monolayers

The group-V monolayers(MLs) have been studied intensively after the experimental fabrication of two-dimensional(2D) graphene and black phosphorus. The observation of novel quantum phenomena, such as quantum spin Hall effect and ferroelectricity in group-V elemental layers, has attracted tremendous attention because of the novel physics and promising applications for nanoelectronics in the 2D limit. In this review, we comprehensively review recent research progress in engineering of topology and ferroelectricity, and several effective methods to control the quantum phase transition are discussed. We then introduce the coupling between topological orders and ferroelectric orders. The research directions and outlooks are discussed at the end of the perspective. It is expected that the comprehensive overview of topology and ferroelectricity in 2D group-V materials can provide guidelines for researchers in the area and inspire further explorations of interplay between multiple quantum phenomena in low-dimensional systems.     

Suppression of ferroelectricity and quantum fluctuations in Ru-doped TbMnO<Subscript>3</Subscript>

We investigate the effects of Ru-doping in polycrystalline TbMn_1−x Ru _x O₃ (x≤0.10) on the multiferroicity. It is observed that the Ru substitution gradually melts away the dielectric anomaly at the ferroelectric transition point and the ferroelectricity by suppressing the polarization, accompanied with a surprising low-temperature dielectric plateau. While it is reasonable to observe the significant suppression of ferroelectricity, owing to the fact that the Ru-doping disrupts the Mn spiral spin ordering and reduces the Mn–Mn spin angle, quantum fluctuations associated with the Ru substitution, responsible for the low-temperature dielectric plateau, seems to be significant.     

Direct observation of magnetodielectric effect in type-I multiferroic PbFe0.5Ti0.25W0.25O3

In type-I multiferroics, where ferroelectricity and magnetism arise from different origins, the explicit measurement of magnetoelectric effect is commonly prohibited due to the weak magnetoelectric coupling. From our investigation of magnetic and dielectric properties in a perovskite PbFe_0.5Ti_0.25W_0.25O₃, we have directly demonstrated magnetic-field-driven change of dielectric constant in a highly non-linear fashion. Our result offers a potential utilization of magnetoelectric functionality in type-I multiferroics.     

Multiferroic properties of nanocrystalline BaTiO3

Some of the Multiferroics [H. Schmid, Ferroelectrics 162 (1994) 317] form a rare class of materials that exhibit magneto–electric coupling arising from the coexistence of ferromagnetism and ferroelectricity, with potential for many technological applications [J.F. Scott, Nat. Mater. 6 (2007) 256; N.A. Spaldin, M. Fiebig, Science 309 (2005) 391]. Over the last decade, an active research on multiferroics has resulted in the identification of a few routes that lead to multiferroicity in bulk materials [C. Ederer, N.A. Spaldin, Nat. Mater. 3 (2004) 849; D.V. Efremov, J. van den Brink, D.I. Khomskii, Nat. Mater. 3 (2004) 853; N. Hur, S. Park, P.A. Sharma, J.S. Ahn, S. Guha, S.W. Cheong, Nature 429 (2004) 392]. While ferroelectricity in a classic ferroelectric such as BaTiO₃ is expected to diminish with the reducing particle size, [C.H. Ahn, K.M. Rabe, J.M. Triscone, Science 303 (2004) 488; J. Junquera, P. Ghosez, Nature 422 (2003) 506] ferromagnetism cannot occur in its bulk form [N.A. Hill, J. Phys. Chem. B 104 (2000) 6694]. Here, we use a combination of experiment and first-principles simulations to demonstrate that multiferroic nature emerges in intermediate size nanocrystalline BaTiO₃, ferromagnetism arising from the oxygen vacancies at the surface and ferroelectricity from the core. A strong coupling between a surface polar phonon and spin is shown to result in a magnetocapacitance effect observed at room temperature, which can open up possibilities of new electro–magneto-mechanical devices at the nano-scale.     

磁致多铁性物理与新材料设计

磁致多铁材料是多铁性材料大家族中的后起之秀,其特色在于其铁电性起源于特定的磁序,因此其铁电性与磁性紧密关联,具有本征的强磁电耦合效应。目前对磁致多铁性的研究以基础物理为主。随着对磁致多铁现象背后物理机制认识的不断深入,不断有新的磁致多铁材料被设计、预言和发现,其性能也在不断地提高。文章简要介绍了磁致多铁材料所涉及的基本物理机制,并根据这些已知的规律,回顾了近年来寻找和设计新的磁致多铁材料的经验。     

激发态电荷转移有机体的多铁性研究

随着人们对多铁性的深入了解,越来越多不同类型的有机多铁材料被合成出来.激发态电荷转移有机体的电荷转移网络是由一个提供电子的分子(给体donor,D~+)和一个接受电子的分子(受体acceptor,A~-)有序排列后构成的.D~+A~-长程有序排列,其激发态(激子)具有较长寿命和±1/2自旋,这是产生室温铁电性和铁磁性的根本原因.激发态容易受外场刺激,因此光照、磁场、电场、应力等能够很好地调控这类材料的铁电极化、磁矩和相应的磁电耦合系数.激发态电荷转移有机体不仅大大丰富了室温多铁材料体系,而且可以为开发新型多功能电子器件提供材料基础和技术储备.     

Multiferroic RMnO3 thin films

Multiferroic materials have received an astonishing attention in the last decades due to expectations that potential coupling between distinct ferroic orders could inspire new applications and new device concepts. As a result, a new knowledge on coupling mechanisms and materials science has dramatically emerged. Multiferroic RMnO₃ perovskites are central to this progress, providing a suitable platform to tailor spin–spin and spin–lattice interactions.With views towards applications, the development of thin films of multiferroic materials have also progressed enormously and nowadays thin-film manganites are available, with properties mimicking those of bulk compounds. Here we review achievements on the growth of hexagonal and orthorhombic RMnO₃ epitaxial thin films and the characterization of their magnetic and ferroelectric properties, we discuss some challenging issues, and we suggest some guidelines for future research and developments.