Multiferroics, defined for those multifunctional materials in which two or more kinds of fundamental ferroicities coexist, have become one of the hottest topics of condensed matter physics and materials science in recent years. The coexistence of several order parameters in multiferroics brings out novel physical phenomena and offers possibilities for new device functions. The revival of research activities on multiferroics is evidenced by some novel discoveries and concepts, both experimentally and theoretically. In this review, we outline some of the progressive milestones in this stimulating field, especially for those single-phase multiferroics where magnetism and ferroelectricity coexist. First, we highlight the physical concepts of multiferroicity and the current challenges to integrate the magnetism and ferroelectricity into a single-phase system. Subsequently, we summarize various strategies used to combine the two types of order. Special attention is paid to three novel mechanisms for multiferroicity generation: (1) the ferroelectricity induced by the spin orders such as spiral and E-phase antiferromagnetic spin orders, which break the spatial inversion symmetry; (2) the ferroelectricity originating from the charge-ordered states; and (3) the ferrotoroidic system. Then, we address the elementary excitations such as electromagnons, and the application potentials of multiferroics. Finally, open questions and future research opportunities are proposed.

Multiferroicity: the coupling between magnetic and polarization orders

The manipulation of magnetic properties by an electric field in magnetoelectric multiferroic materials has driven significant research activity, with the goal of realizing their transformative technological potential. Here, we review progress in the fundamental understanding and design of new multiferroic materials, advances in characterization and modelling tools to describe them, and the exploration of devices and applications. Focusing on the translation of the many scientific breakthroughs into technological innovations, we identify the key open questions in the field where targeted research activities could have maximum impact in transitioning scientific discoveries into real applications. Magnetoelectric multiferroics, where magnetic properties are manipulated by electric field and vice versa, could lead to improved electronic devices. Here, advances in materials, characterisation and modelling, and usage in applications are reviewed.

Advances in magnetoelectric multiferroics.

A2B′B″O6 perovskites: A review

The immense potential of colossal permittivity (CP) materials for use in modern microelectronics as well as for high-energy-density storage applications has propelled much recent research and development. Despite the discovery of several new classes of CP materials, the development of such materials with the required high performance is still a highly challenging task. Here, we propose a new electron-pinned, defect-dipole route to ideal CP behaviour, where hopping electrons are localized by designated lattice defect states to generate giant defect-dipoles and result in high-performance CP materials. We present a concrete example, (Nb+In) co-doped TiO₂ rutile, that exhibits a largely temperature- and frequency-independent colossal permittivity (> 10(4)) as well as a low dielectric loss (mostly < 0.05) over a very broad temperature range from 80 to 450 K. A systematic defect analysis coupled with density functional theory modelling suggests that 'triangular' In₂(3+)Vo(••)Ti(3+) and 'diamond' shaped Nb₂(5+)Ti(3+)A(Ti) (A = Ti(3+)/In(3+)/Ti(4+)) defect complexes are strongly correlated, giving rise to large defect-dipole clusters containing highly localized electrons that are together responsible for the excellent CP properties observed in co-doped TiO₂. This combined experimental and theoretical work opens up a promising feasible route to the systematic development of new high-performance CP materials via defect engineering.

Electron-pinned defect-dipoles for high-performance colossal permittivity materials

Multiferroics, compounds with both magnetic and ferroelectric orders, are believed to be a key material system to achieve cross-control between magnetism and electricity in a solid with minute energy dissipation. Such a colossal magnetoelectric (ME) effect has been an issue of keen interest for a long time in condensed matter physics as well as a most desired function in the emerging spin-related electronics. Here we begin with the basic mechanisms to realize multiferroicity or spin-driven ferroelectricity in magnetic materials, which have recently been clarified and proved both theoretically and experimentally. According to the proposed mechanisms, many families of multiferroics have been explored, found (re-discovered), and newly developed, realizing a variety of colossal ME controls. We overview versatile multiferroics from the viewpoints of their multiferroicity mechanisms and their fundamental ME characteristics on the basis of the recent advances in exploratory materials. One of the new directions in multiferroic science is the dynamical ME effect, namely the dynamical and/or fast cross-control between electric and magnetic dipoles in a solid. We argue here that the dynamics of multiferroic domain walls significantly contributes to the amplification of ME response, which has been revealed through the dielectric spectroscopy. Another related issue is the electric-dipole-active magnetic resonance, called electromagnons. The electromagnons can provide a new stage of ME optics via resonant coupling with the external electromagnetic wave (light). Finally, we give concluding remarks on multiferroics physics in the light of a broader perspective from the emergent electromagnetism in a solid as well as from the possible application toward future dissipationless electronics.

Multiferroics of spin origin

Many transition-metal oxides show very large (“colossal”) magnitudes of the dielectric constant and thus have immense potential for applications in modern microelectronics and for the development of new capacitance-based energy-storage devices In the present work, we thoroughly discuss the mechanisms that can lead to colossal values of the dielectric constant, especially emphasising effects generated by external and internal interfaces, including electronic phase separation In addition, we provide a detailed overview and discussion of the dielectric properties of CaCu3Ti4O12 and related systems, which is today’s most investigated material with colossal dielectric constant Also a variety of further transition-metal oxides with large dielectric constants are treated in detail, among them the system La2−xSrxNiO4 where electronic phase separation may play a role in the generation of a colossal dielectric constant

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Colossal dielectric constants in transition-metal oxides

Combining the efforts of physicists, materials scientists, economists and resource-strategy researchers opens up an interdisciplinary route enabling the substitution of rare elements by more abundant ones, serving as a guideline for the development of novel materials.

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The route to resource-efficient novel materials

The search for new materials with extremely high ("colossal") dielectric constants, required for future electronics, is one of the most active fields of modern materials science. However, the applicability of the colossal-epsilon' materials, discovered so far, suffers from the fact that their dielectric constant, epsilon', only is huge in a limited frequency range below about 1 MHz. In the present report, we show that the dielectric properties of La15/8Sr1/8NiO4 surpass those of other materials. Especially, epsilon' retains its colossal magnitude of >10000 well into the GHz range. This material is prone to charge order and this spontaneous ordering process of the electronic subsystem can be assumed to play an important role in the generation of the observed unusual dielectric properties.

Colossal dielectric constant up to GHz at room temperature

The applicability of recently discovered materials with extremely high (“colossal”) dielectric constants, required for future electronics, suffers from the fact that their dielectric constant e′ only is huge in a limited frequency range below about 1 MHz. In the present report, we show that the dielectric properties of a charge-ordered nickelate, La15/8Sr1/8NiO4, surpass those of other materials. Especially, e′ retains its colossal magnitude of >10 000 well into the gigahertz range.

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Colossal dielectric constant up to gigahertz at room temperature

Multiferroics, showing simultaneous ordering of electrical and magnetic degrees of freedom, are remarkable materials as seen from both the academic and technological points of view. A prominent mechanism of multiferroicity is the spin-driven ferroelectricity, often found in frustrated antiferromagnets with helical spin order. There, as for conventional ferroelectrics, the electrical dipoles arise from an off-centre displacement of ions. However, recently a different mechanism, namely purely electronic ferroelectricity, where charge order breaks inversion symmetry, has attracted considerable interest. Here we provide evidence for ferroelectricity, accompanied by antiferromagnetic spin order, in a two-dimensional organic charge-transfer salt, thus representing a new class of multiferroics. We propose a charge-order-driven mechanism leading to electronic ferroelectricity in this material. Quite unexpectedly for electronic ferroelectrics, dipolar and spin order arise nearly simultaneously. This can be ascribed to the loss of spin frustration induced by the ferroelectric ordering. Hence, here the spin order is driven by the ferroelectricity, in marked contrast to the spin-driven ferroelectricity in helical magnets.

Stephan Krohns

Papers

Colossal dielectric constants in transition-metal oxides

The route to resource-efficient novel materials

Colossal dielectric constant up to GHz at room temperature

Colossal dielectric constant up to gigahertz at room temperature

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism