The magnetoelectric effect--the induction of magnetization by means of an electric field and induction of polarization by means of a magnetic field--was first presumed to exist by Pierre Curie, and subsequently attracted a great deal of interest in the 1960s and 1970s (refs 2-4). More recently, related studies on magnetic ferroelectrics have signalled a revival of interest in this phenomenon. From a technological point of view, the mutual control of electric and magnetic properties is an attractive possibility, but the number of candidate materials is limited and the effects are typically too small to be useful in applications. Here we report the discovery of ferroelectricity in a perovskite manganite, TbMnO3, where the effect of spin frustration causes sinusoidal antiferromagnetic ordering. The modulated magnetic structure is accompanied by a magnetoelastically induced lattice modulation, and with the emergence of a spontaneous polarization. In the magnetic ferroelectric TbMnO3, we found gigantic magnetoelectric and magnetocapacitance effects, which can be attributed to switching of the electric polarization induced by magnetic fields. Frustrated spin systems therefore provide a new area to search for magnetoelectric media.

There has been increasing interest in phenomena emerging from relativistic electrons in a solid, which have a potential impact on spintronics and magnetoelectrics. One example is the Rashba effect, which lifts the electron-spin degeneracy as a consequence of spin-orbit interaction under broken inversion symmetry. A high-energy-scale Rashba spin splitting is highly desirable for enhancing the coupling between electron spins and electricity relevant for spintronic functions. Here we describe the finding of a huge spin-orbit interaction effect in a polar semiconductor composed of heavy elements, BiTeI, where the bulk carriers are ruled by large Rashba-like spin splitting. The band splitting and its spin polarization obtained by spin- and angle-resolved photoemission spectroscopy are well in accord with relativistic first-principles calculations, confirming that the spin splitting is indeed derived from bulk atomic configurations. Together with the feasibility of carrier-doping control, the giant-Rashba semiconductor BiTeI possesses excellent potential for application to various spin-dependent electronic functions.

The evolution of spin-and orbital-ordered states has been investigated for a series of insulating perovskites RMnO3 (R=La,Pr,Nd,...). RMnO3 with a large GdFeO3-type distortion is regarded as a frustrated spin system having ferromagnetic nearest-neighbor and antiferromagnetic (AF) nextnearest-neighbor (NNN) interactions within a MnO2 plane. The staggered orbital order associated with the GdFeO3-type distortion induces the anisotropic NNN interaction, and yields unique sinusoidal and up-up-down-down AF ordered states in the distorted perovskites with e 1 g configuration. and e 1 g t 6 2g configurations, respectively, the e g orbital is doubly degenerate and the t 2g orbital degree of freedom is quenched. It is widely recognized that the layered-type (A-type) antiferromagnetic (AF) structure in LaMnO 3 is understood from the view point of the anisotropic superexchange (SE) interaction under the directional order of orbital [1,2]. On the other hand, the spin structure in nickelates (R =La) is distinct from the A-type AF; the socalled "up-up-down-down"-type one where two Ni sites of "up" spins are followed by two sites of "down" spins along the principal axes in the cubic unit cell. Origin of this unusual magnetic order has been a long-standing question, as well as its relations to metal-insulator transition, orbital order (OO), and charge disproportionation [3][4][5]. Recently, a similar spin structure, i.e. the up-up-down-down order in a MnO 2 plane (E-type AF order in the Wollan-Koehler notation [6]), is found in a manganite, HoMnO 3 [7] with a significantly distorted perovskite structure. This has to be a bridge between the well-understood A-type AF in manganites and the unique magnetic ground state in nickelates.In this Letter, we examine systematically the magnetic and orbital structures in a series of RMnO 3 as a function of the ionic radius (r R ) of R. The most significant effect on the crystal structure by decreasing r R is an enhancement of the cooperative rotation of the MnO 6 octahedra (the GdFeO 3 -type distortion) characterized by the decrease of Mn-O-Mn bond angle φ. Let us first summarize in Fig. 1 the orbital (a) and spin (b) ordering temperatures (T OO and T N , respectively) on Mn sites of RMnO 3 as a function of φ, which is based on both the present and former studies [7][8][9][10]. Here, we adopt the φ at room temperature [11]. The T OO monotonically increases with decreasing r R , while the magnetic transition occurs from the A-type AF to the E-type one through the incommensurate structure. We argue that the combination of OO and next-nearest-neighbor (NNN) SE interaction brings about a nontrivial effect on the magnetic ground state in the systems with the orbital degeneracy and the large GdFeO 3 -type distortion. Microscopic calculation shows that the magnetism in this system is mapped onto the frustrated spin model which well reproduces the phase diagram of RMnO 3 .A series of RMnO 3 (R=La−Dy) crystals were grown by the floating zone method. We made powder x-ray diffraction measurements on th...

The valley degree of freedom of electrons is attracting growing interest as a carrier of information in various materials, including graphene, diamond and monolayer transition-metal dichalcogenides. The monolayer transition-metal dichalcogenides are semiconducting and are unique due to the coupling between the spin and valley degrees of freedom originating from the relativistic spin-orbit interaction. Here, we report the direct observation of valley-dependent out-of-plane spin polarization in an archetypal transition-metal dichalcogenide--MoS2--using spin- and angle-resolved photoemission spectroscopy. The result is in fair agreement with a first-principles theoretical prediction. This was made possible by choosing a 3R polytype crystal, which has a non-centrosymmetric structure, rather than the conventional centrosymmetric 2H form. We also confirm robust valley polarization in the 3R form by means of circularly polarized photoluminescence spectroscopy. Non-centrosymmetric transition-metal dichalcogenide crystals may provide a firm basis for the development of magnetic and electric manipulation of spin/valley degrees of freedom.

A bulk material comprising stacked nanosheets of nickel bis(dithiolene) complexes is investigated. The average oxidation number is -3/4 for each complex unit in the as-prepared sample; oxidation or reduction respectively can change this to 0 or -1. Refined electrical conductivity measurement, involving a single microflake sample being subjected to the van der Pauw method under scanning electron microscopy control, reveals a conductivity of 1.6 × 10(2) S cm(-1), which is remarkably high for a coordination polymeric material. Conductivity is also noted to modulate with the change of oxidation state. Theoretical calculation and photoelectron emission spectroscopy reveal the stacked nanosheets to have a metallic nature. This work provides a foothold for the development of the first organic-based two-dimensional topological insulator, which will require the precise control of the oxidation state in the single-layer nickel bisdithiolene complex nanosheet (cf. Liu, F. et al. Nano Lett. 2013, 13, 2842).

We study superconducting FeSe (T c = 9 K) exhibiting the tetragonal-orthorhombic structural transition (T s ~ 90 K) without any antiferromagnetic ordering, by utilizing angle-resolved photoemission spectroscopy. In the detwinned orthorhombic state, the energy position of the d yz orbital band at the Brillouin zone corner is 50 meV higher than that of d xz , indicating the orbital order similar to NaFeAs and BaFe 2 As 2 families. Evidence of orbital order also appears in the hole bands at the Brillouin zone center. Precisely measured temperature dependence using strain-free samples shows that the onset of the orbital ordering (T o ) occurs very close to T s , thus suggesting that the electronic nematicity above T s is considerably weaker in FeSe compared to BaFe 2 As 2 family.

No abstract

We investigate the electronic reconstruction across the tetragonal-orthorhombic structural transition in FeSe by employing polarization-dependent angle-resolved photoemission spectroscopy (ARPES) on detwinned single crystals. Across the structural transition, the electronic structures around the  and M points are modified from four-fold to two-fold symmetry due to the lifting of degeneracy in d xz /d yz orbitals.The d xz band shifts upward at the  point while it moves downward at the M point, suggesting that the electronic structure of orthorhombic FeSe is characterized by a momentum-dependent sign-changing orbital polarization. The elongated directions of the elliptical Fermi surfaces (FSs) at the  and M points are rotated by 90 degrees with respect to each other, which may be related to the absence of the antiferromagnetic order in FeSe. Keywords: PACS:Most of the parent compounds of the iron-based superconductors show the tetragonal-orthorhombic structural transition at T s and the stripe-type antiferromagnetic (AFM) order below T N ( T s ) [1,2]. Near the structural transition, an orbital order defined by the inequivalent electron occupation of 3d xz (xz) and 3d yz (yz) orbitals [3][4][5], has been reported by ARPES [6,7] and X-ray linear dichroism measurements [8] in several parent compounds. Experimental and theoretical studies suggested that the structural transition is caused by the electronic nematicity of the spin [9,10] or orbital [11][12][13] degrees of freedoms. Since superconductivity develops when such complex ordered states are suppressed, it is crucial to understand how the phase transitions couple to each other.In Ba(Fe,Co) 2 As 2 , the spin-driven nematicity has been suggested from the phase diagram in which T s and T N closely follow each other as the carrier is doped [14]. The scaling behavior between the nematic fluctuation and spin fluctuation was also reported by the nuclear magnetic resonance (NMR) and shear modulus measurements [10]. On the other hand, in NaFeAs, the orbital-driven nematicity has been proposed by ARPES [11]. In this compound, the structural transition at T s = 54 K is well separated from the AFM transition at T N = 43 K. Inequivalent shift in the xz/yz orbital bands appearing above T s changes the FSs from four-fold to two-fold symmetric shape [11,15], which may be a possible trigger of the stripe type AFM order and the orthorhombicity [11,16]. The variety of iron-based