Influence of Orbital Character on the Ground State Electronic Properties in the van Der Waals Transition Metal Iodides VI3 and CrI3.

Two-dimensional van der Waals magnetic semiconductors display emergent chemical and physical properties and hold promise for novel optical, electronic and magnetic "few-layers" functionalities. Transition-metal iodides such as CrI3 and VI3 are relevant for future electronic and spintronic applications; however, detailed experimental information on their ground state electronic properties is lacking often due to their challenging chemical environment. By combining X-ray electron spectroscopies and first-principles calculations, we report a complete determination of CrI3 and VI3 electronic ground states. We show that the transition metal-induced orbital filling drives the stabilization of distinct electronic phases: a wide bandgap in CrI3 and a Mott insulating state in VI3. Comparison of surface-sensitive (angular-resolved photoemission spectroscopy) and bulk-sensitive (X-ray absorption spectroscopy) measurements in VI3 reveals a surface-only V2+ oxidation state, suggesting that ground state electronic properties are strongly influenced by dimensionality effects. Our results have direct implications in band engineering and layer-dependent properties of two-dimensional systems.

Dirac semimetal phase and switching of band inversion in XMg2Bi2 (X = Ba and Sr).

Topological Dirac semimetals (TDSs) offer an excellent opportunity to realize outstanding physical properties distinct from those of topological insulators. Since TDSs verified so far have their own problems such as high reactivity in the atmosphere and difficulty in controlling topological phases via chemical substitution, it is highly desirable to find a new material platform of TDSs. By angle-resolved photoemission spectroscopy combined with first-principles band-structure calculations, we show that ternary compound BaMg2Bi2 is a TDS with a simple Dirac-band crossing around the Brillouin-zone center protected by the C3 symmetry of crystal. We also found that isostructural SrMg2Bi2 is an ordinary insulator characterized by the absence of band inversion due to the reduction of spin-orbit coupling. Thus, XMg2Bi2 (X = Sr, Ba, etc.) serves as a useful platform to study the interplay among crystal symmetry, spin-orbit coupling, and topological phase transition around the TDS phase.

Synthesis, Structure, and Anomalous Magnetic Ordering of the Spin-1/2 Coupled Square Tetramer System K(NbO)Cu4(PO4)4.

Quasi-zero-dimensional antiferromagnets with weakly coupled clusters of multiple spins can provide an excellent platform for exploring exotic quantum states of matter. Here, we report the synthesis and the characterization of a copper-based insulating antiferromagnet, K(NbO)Cu4(PO4)4. Single-crystal X-ray diffraction measurements reveal that the crystal structure belongs to the tetragonal space group P4/nmm, in which Cu2+ ions align to form a quasi-two-dimensional layer of spin-1/2 coupled square tetramers. The structure is quasi-isostructural to recently reported magnetoelectric antiferromagnets, A(TiO)Cu4(PO4)4 (A = Ba, Sr, and Pb) with the P4212 space group. Despite their structural similarities, whereas the antiferromagnetic transition in A(TiO)Cu4(PO4)4 produces conventional anomalies in magnetization and heat capacity, that in K(NbO)Cu4(PO4)4 has several unusual features such as an upturn in magnetic susceptibility and a very weak specific heat anomaly that corresponds to a spin entropy release as small as 3%. These results indicate that the magnetism of K(NbO)Cu4(PO4)4 is far different from that of A(TiO)Cu4(PO4)4 and suggest that the ground state is very close to a quantum nonmagnetic singlet state. The origin of the distinct magnetism in K(NbO)Cu4(PO4)4 is discussed in terms of structural modifications of a Cu4O12 unit forming a square tetramer. Our study demonstrates that the present material family, represented by an extended chemical formula A(BO)Cu4(PO4)4 (AB = KNb, BaTi, SrTi, and PbTi), has broad chemical controllability of their magnetism. This makes this system an attractive material platform to study the physics of quantum spin-1/2 coupled square tetramers.

Ultrathin Bismuth Film on High-Temperature Cuprate Superconductor Bi2Sr2CaCu2O8+δ as a Candidate of a Topological Superconductor.

One of the key challenges in condensed-matter physics is to establish a topological superconductor that hosts exotic Majorana fermions. Although various heterostructures consisting of conventional BCS (Bardeen-Cooper-Schrieffer) superconductors as well as doped topological insulators were intensively investigated, no conclusive evidence for Majorana fermions has been provided. This is mainly because of their very low superconducting transition temperatures ( Tc) and small superconducting-gap magnitude. Here, we report a possible realization of topological superconductivity at very high temperatures in a hybrid of Bi(110) ultrathin film and copper oxide superconductor Bi2Sr2CaCu2O8+δ (Bi2212). Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy, we found that three-bilayer-thick Bi(110) on Bi2212 exhibits a proximity-effect-induced s-wave energy gap as large as 7.5 meV which persists up to Tc of Bi2212 (85 K). The small Fermi energy and strong spin-orbit coupling of Bi(110), together with the large pairing gap and high Tc, make this system a prime candidate for exploring stable Majorana fermions at very high temperatures.

Ultrathin Bismuth Film on 1T-TaS2: Structural Transition and Charge-Density-Wave Proximity Effect.

We have fabricated bismuth (Bi) ultrathin films on a charge-density-wave (CDW) compound 1T-TaS2 and elucidated electronic states by angle-resolved photoemission spectroscopy and first-principles band-structure calculations. We found that the Bi film on 1T-TaS2 undergoes a structural transition from (111) to (110) upon reducing the film thickness, accompanied by a drastic change in the energy band structure. We also revealed that while two-bilayer-thick Bi(110) film on Si(111) is characterized by a dispersive band touching the Fermi level ( EF), the energy band of the same film on 1T-TaS2 exhibits holelike dispersion with a finite energy gap at EF. We discuss the origin of such intriguing differences in terms of the CDW proximity effect.

Coupling Ferroelectricity with Spin-Valley Physics in Oxide-Based Heterostructures.

The coupling of spin and valley physics is nowadays regarded as a promising route toward next-generation spintronic and valleytronic devices. In the aim of engineering functional properties for valleytronic applications, we focus on the ferroelectric heterostructure BiAlO3/BiIrO3, where the complex interplay among a trigonal crystal field, layer degrees of freedom, and spin-orbit coupling mediates a strong spin-valley coupling. Furthermore, we show that ferroelectricity provides a nonvolatile handle to manipulate and switch the emerging valley-contrasting spin polarization.

Electronic ferroelectricity induced by charge and orbital orderings.

After the revival of the magnetoelectric effect which took place in the early 2000s, the interest in multiferroic materials displaying simultaneous presence of spontaneous long-range magnetic and dipolar order has motivated an exponential growth of research activity, from both the experimental and theoretical perspectives. Within this context, and relying also on the rigorous formulation of macroscopic polarization as provided by the Berry-phase approach, it has been possible to identify new microscopic mechanisms responsible for the appearance of ferroelectricity. In particular, it has been realized that electronic spin, charge and orbital degrees of freedom may be responsible for the breaking of the space-inversion symmetry, a necessary condition for the appearance of electric polarization, even in centrosymmetric crystal structures. In view of its immediate potential application in magnetoelectric-based devices, many efforts have been made to understand how magnetic orderings may lead to ferroelectric polarization, and to identify candidate materials. On the other hand, the role of charge and orbital degrees of freedom, which have received much less attention, has been predicted to be non-negligible in several cases. Here, we review recent theoretical advances in the field of so-called electronic ferroelectricity, focusing on the possible mechanisms by which charge- and/or orbital-ordering effects may cause the appearance of macroscopic polarization. Generally, a naive distinction can be drawn between materials displaying almost localized electrons and those characterized by a strong covalent character and delocalized electrons. As for the latter, an intuitive understanding of basic mechanisms is provided in the framework of tight-binding model Hamiltonians, which are used to shed light on unusual charge/orbital effects in half-doped manganites, whereas the case of magnetite will be thoroughly discussed in light of recent progress pointing to an electronic origin of its proposed ferroelectric and magnetoelectric properties.

Influence of lone pair doping on the multiferroic property of orthorhombic HoMnO3: ab initio prediction.

Using first principles density functional theory, we predict new multiferroic compounds Ho1/2A1/2MnO3 (A = As, Sb, Bi) with enhanced polarization. We find that doping of lone pair cations with different ionic radii, at the A-site of orthorhombic HoMnO3, results in a marked increase of the electronic polarization and its development along the b-axis. This development of electronic polarization along the b-axis is attributed to the breaking of the two-fold rotational symmetry which leads to the emergence of a polar b-axis. Furthermore, this symmetry breaking leads to the emergence of two inequivalent Mn ions (Mn(0) and Mn(1)) and the variance in their octahedral (Mn(0)O6 and Mn(1)O6) distortions. We rationalize the observed trends in the total polarization in terms of disparate eg electron hopping along the two different Mn(0) and Mn(1) chains. We expect large ionic polarization in the doped compounds due to the presence of 4s(2) As, 5s(2) Sb and 6s(2) Bi lone pairs, but surprisingly the effect of the lone pairs seems to be inactive. This is attributed to the strong GdFeO3 distortions exhibited by the MnO6 octahedron which hinders polar displacement of the lone pair cations.

Beyond standard local density approximation in the study of magnetoelectric effects in Fe/BaTiO3 and Co/BaTiO3 interfaces.

First-principles density functional theory (DFT) simulations for Fe/BaTiO(3) and Co/BaTiO(3) junctions have been performed with different treatments of the exchange-correlation potential, ranging from standard semilocal density approximations to a Hubbard-like approach and to hybrid functionals. With the aim of elucidating the role of correlations in the microscopic interplay between ferroelectricity and magnetism in the interfacial region, we find that, compared to standard DFT approximations, Hubbard-like approaches and hybrid functionals do not qualitatively modify the physical origin behind magnetoelectric effects driven by interfacial orbital hybridization. Rather, more accurate treatments of correlations for both Fe/BaTiO(3) and Co/BaTiO(3) interfaces predict a stronger change of the interface magnetization upon switching the direction of polarization in the ferroelectric layer.

Ferroelectricity due to orbital ordering in E-type undoped rare-earth manganites.

Aiming at understanding the origin of the electronic contribution to ferroelectric polarization in undoped manganites, we evaluate the Berry phase of orbital-polarizable Bloch electrons as an orbital ordering (OO) establishes in the background of an antiferromagnetic E-type configuration. The onset of OO is tuned by the Jahn-Teller (JT) interaction in a tight-binding model for interacting electrons moving along zigzag chains. A finite polarization is found as soon as the JT coupling is strong enough to induce OO, supporting the large electronic contribution predicted from first principles.

Interplay between charge order, ferroelectricity, and ferroelasticity: tungsten bronze structures as a playground for multiferroicity.

Charge order is proposed as a driving force behind ferroelectricity in iron fluoride K(0.6)Fe(0.6)(II)Fe(0.4)(III)F(3). By means of density functional theory, we propose several noncentrosymmetric d(5)/d(6) charge-ordering patterns, each giving rise to polarization with different direction and magnitude. Accordingly, we introduce the concept of "ferroelectric anisotropy" (peculiar to improper ferroelectrics with polarization induced by electronic degrees of freedom), denoting the small energy difference between competing charge-ordered states. Moreover, we suggest a novel type of charge-order-induced ferroelasticity: a monoclinic distortion is induced by a specific charge-ordering pattern, which, in turn, determines the direction of polarization. K(0.6)Fe(0.6)(II)Fe(0.4)(III)F(3) therefore emerges as a prototypical compound, in which the intimately coupled electronic and structural degrees of freedom result in a peculiar multiferroicity.

Exchange bias driven by the Dzyaloshinskii-Moriya interaction and ferroelectric polarization at G-type antiferromagnetic perovskite interfaces.

Exchange bias is usually rationalized invoking spin pinning effects caused by uncompensated antiferromagnetic interfaces. However, for compensated antiferromagnets other extrinsic factors, such as interface roughness or spin canting, have to be considered to produce a small uncompensation. As an alternative, here we propose two (related) possible mechanisms, driven by the intrinsic Dzyaloshinskii-Moriya interaction and ferroelectric polarization, for the explanation of exchange bias effects in perovskites with compensated G-type antiferromagnetism. One of the mechanisms is only active when a multiferroic material is involved and it is controllable by electric fields.

Magnetically induced ferroelectricity in TbMnO(3): inverse Goodenough-Kanamori interaction.

Improper ferroelectricity in magnets, as induced by non-centrosymmetric spin-, charge- or orbital-ordering, is a branch of the field of multiferroics having fascinating physics and a potentially important technological outcome. We focus here on ferroelectricity in orthorhombic TbMnO(3), where the magnetic field along the a-axis produces a polar collinear spin-arrangement with a rather large in-plane electric polarization. The mechanism, similar to that occurring in orthorhombic HoMnO(3) in the AFM-E phase, is efficiently driven by a large modification of the structural properties (such as MnO bond-lengths and Mn-O-Mn bond-angles) to favor e(g) electron hopping between Mn with parallel spins. A similar mechanism where the t(2g) states are involved is examined through a hypothetical collinear spin-structure, resulting in a weaker out-of-plane ferroelectric polarization.

Comparison in treatments of nonleukemic granulocytic sarcoma: report of two cases and a review of 72 cases in the literature.

BACKGROUND: The purpose of this study was to reveal the clinical characteristics of nonleukemic granulocytic sarcoma (GS) and an association between the therapeutic regimens and the nonleukemic period. METHOD: Clinical records of 2 patients reported here and 72 patients gathered using a literature search on Medline from other institutions were analyzed. The patients consisted of 57 patients who preceded acute nonlymphoblastic leukemia (ANLL) and 17 patients who did not develop ANLL. These patients were divided into 3 groups by therapeutic regimens; Group I included 12 patients who received only biopsy or surgical resection of the tumor, Group II was 20 patients who received local irradiation for the tumor, and Group III consisted of 42 patients who received systemic chemotherapy. The nonleukemic periods between these groups were compared. In Group III, the period in the patients who were treated with chemotherapy given to ANLL was compared with that in the patients who received chemotherapy used for malignant lymphoproliferative disorders (MLPDs). RESULTS: Thirty-five patients (47%) initially were misdiagnosed, and the disease was most often malignant lymphoma. Preferential sites of GS were the small intestine, mediastinum, epidural site, uterus, and ovary, which often are difficult for the detection and diagnosis in addition to the skin and lymph nodes known commonly. The nonleukemic period after the diagnosis of GS was significantly longer in Group III than in the other groups (median, 12 months in Group III vs. 3 and 6 months in Groups I and II, respectively). The aggressive chemotherapy given to ANLL led to a longer nonleukemic period than the chemotherapy used for MLPDs. CONCLUSIONS: To reduce the risk of subsequent ANLL in patients with nonleukemic GS, it is important that accurate histologic diagnosis is established initially for GS and that all isolated cases of GS, even those that appear to be cured by resection or irradiation of the tumor, are treated with intensive chemotherapy similar to that used to treat ANLL during the nonleukemic period as soon as possible.