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1.
Nat Commun ; 10(1): 5144, 2019 11 13.
Artigo em Inglês | MEDLINE | ID: mdl-31723139

RESUMO

The Dresselhaus and Rashba effects are well-known phenomena in solid-state physics, in which spin-orbit coupling splits spin-up and spin-down energy bands of nonmagnetic non-centrosymmetric crystals. Here, we discuss a phenomenon we dub band splitting with vanishing spin polarizations (BSVSP), in which, as usual, spin-orbit coupling splits the energy bands in nonmagnetic non-centrosymmetric systems. Surprisingly, however, both split bands show no net spin polarization along certain high-symmetry lines in the Brillouin zone. In order to rationalize this phenomenon, we propose a classification of point groups into pseudo-polar and non-pseudo-polar groups. By means of first-principles simulations, we demonstrate that BSVSP can take place in both symmorphic (e.g., bulk GaAs) and non-symmorphic systems (e.g., two dimensional ferroelectric SnTe). Furthermore, we identify a linear magnetoelectric coupling in reciprocal space, which could be employed to tune the spin polarization with an external electric field. The BSVSP effect and its manipulation could therefore form the basis for future spintronic devices.

2.
Phys Rev Lett ; 121(2): 027601, 2018 Jul 13.
Artigo em Inglês | MEDLINE | ID: mdl-30085752

RESUMO

Previous studies showed that, as ferroelectric films become thinner, their Curie temperature (T_{c}) and polarization below T_{c} both typically decrease. In contrast, a recent experiment [Chang et al., Science 353, 274 (2016)SCIEAS0036-807510.1126/science.aad8609] observed that atomic-thick SnTe films have a higher T_{c} than their bulk counterpart, which was attributed to extrinsic effects. We find, using first-principles calculations, that the 0-K energy barrier for the polarization switching (which is a quantity directly related to T_{c}) is higher in most investigated defect-free SnTe ultrathin films than that in bulk SnTe, and that the 5-unit-cell (UC) SnTe thin film has the largest energy barrier as a result of an interplay between hybridization interactions and Pauli repulsions. Further simulations, employing a presently developed effective Hamiltonian, confirm that freestanding, defect-free SnTe thin films have a higher T_{c} than bulk SnTe, except for the 1-UC case. Our work, therefore, demonstrates the possibility to intrinsically enhance ferroelectricity of ultrathin films by reducing their thickness.

3.
Nano Lett ; 18(5): 2751-2758, 2018 05 09.
Artigo em Inglês | MEDLINE | ID: mdl-29380606

RESUMO

The electric and nonvolatile control of the spin texture in semiconductors would represent a fundamental step toward novel electronic devices combining memory and computing functionalities. Recently, GeTe has been theoretically proposed as the father compound of a new class of materials, namely ferroelectric Rashba semiconductors. They display bulk bands with giant Rashba-like splitting due to the inversion symmetry breaking arising from the ferroelectric polarization, thus allowing for the ferroelectric control of the spin. Here, we provide the experimental demonstration of the correlation between ferroelectricity and spin texture. A surface-engineering strategy is used to set two opposite predefined uniform ferroelectric polarizations, inward and outward, as monitored by piezoresponse force microscopy. Spin and angular resolved photoemission experiments show that these GeTe(111) surfaces display opposite sense of circulation of spin in bulk Rashba bands. Furthermore, we demonstrate the crafting of nonvolatile ferroelectric patterns in GeTe films at the nanoscale by using the conductive tip of an atomic force microscope. Based on the intimate link between ferroelectric polarization and spin in GeTe, ferroelectric patterning paves the way to the investigation of devices with engineered spin configurations.

4.
Inorg Chem ; 56(1): 197-207, 2017 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-27935298

RESUMO

A study of the magnetic structure of the [NH2(CH3)2]n[FeIIIMII(HCOO)6]n niccolite-like compounds, with MII = CoII (2) and MnII (3) ions, has been carried out using neutron diffraction and compared with the previously reported FeII-containing compound (1). The inclusion of two different metallic atoms into the niccolite-like structure framework leads to the formation of isostructural compounds with very different magnetic behaviors due to the compensation or not of the different spins involved in each lattice. Below TN, the magnetic order in these compounds varies from ferrimagnetic behavior for 1 and 2 to an antiferromagnetic behavior with a weak spin canting for 3. Structure refinements of 2 and 3 at low temperature (45 K) have been carried out combining synchrotron X-ray and high-resolution neutron diffraction in a multipattern approach. The magnetic structures have been determined from the difference patterns between the neutron data in the paramagnetic and the magnetically ordered regions. These difference patterns have been analyzed using a simulated annealing protocol and symmetry analysis techniques. The obtained magnetic structures have been further rationalized by means of ab initio DFT calculations. The direction of the magnetic moment of each compound has been determined. The easy axis of the MII for compound 1 (FeII) is along the c axis; for compound 2 (CoII), the moments are mainly within the ab plane; finally, for compound 3 (MnII), the calculations show that the moments have components both in the ab plane and along the c axis.

5.
Inorg Chem ; 56(1): 33-41, 2017 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-27626290

RESUMO

High-quality single crystals of perovskite-like (CH3NH3)3Bi2I9 hybrids have been synthesized, using a layered-solution crystal-growth technique. The large dielectric constant is strongly affected by the polar ordering of its constituents. Progressive dipolar ordering of the methylammonium cation upon cooling below 300 K gradually converts the hexagonal structure (space group P63/mmc) into a monoclinic phase (C2/c) at 160 K. A well-pronounced, ferrielectric phase transition at 143 K is governed by in-plane ordering of the bismuth lone pair that breaks inversion symmetry and results in a polar phase (space group P21). The dielectric constant is markedly higher in the C2/c phase above this transition. Here, the bismuth lone pair is disordered in-plane, allowing the polarizability to be substantially enhanced. Density functional theory calculations estimate a large ferroelectric polarization of 7.94 µC/cm2 along the polar axis in the P21 phase. The calculated polarization has almost equal contributions of the methylammonium and Bi3+ lone pair, which are fairly decoupled.

6.
Adv Mater ; 29(3)2017 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-27859857

RESUMO

The topological properties of lead-tin chalcogenide topological crystalline insulators can be widely tuned by temperature and composition. It is shown that bulk Bi doping of epitaxial Pb1-x Snx Te (111) films induces a giant Rashba splitting at the surface that can be tuned by the doping level. Tight binding calculations identify their origin as Fermi level pinning by trap states at the surface.

7.
Phys Rev Lett ; 117(7): 076401, 2016 Aug 12.
Artigo em Inglês | MEDLINE | ID: mdl-27563977

RESUMO

By means of density functional theory based calculations, we study the role of spin-orbit coupling in the new family of ABC hyperferroelectrics [Garrity, Rabe, and Vanderbilt Phys. Rev. Lett. 112, 127601 (2014)]. We unveil an extremely rich physics strongly linked to ferroelectric properties, ranging from the electric control of bulk Rashba effect to the existence of a three-dimensional topological insulator phase, with concomitant topological surface states even in the ultrathin film limit. Moreover, we predict that the topological transition, as induced by alloying, is followed by a Weyl semimetal phase of finite concentration extension, which is robust against disorder, putting forward hyperferroelectrics as promising candidates for spin-orbitronic applications.

8.
Sci Rep ; 6: 28618, 2016 06 28.
Artigo em Inglês | MEDLINE | ID: mdl-27350083

RESUMO

The development of high efficiency perovskite solar cells has sparked a multitude of measurements on the optical properties of these materials. For the most studied methylammonium(MA)PbI3 perovskite, a large range (6-55 meV) of exciton binding energies has been reported by various experiments. The existence of excitons at room temperature is unclear. For the MAPbX3 perovskites we report on relativistic Bethe-Salpeter Equation calculations (GW-BSE). This method is capable to directly calculate excitonic properties from first-principles. At low temperatures it predicts exciton binding energies in agreement with the reported 'large' values. For MAPbI3, phonon modes present in this frequency range have a negligible contribution to the ionic screening. By calculating the polarization in time from finite temperature molecular dynamics, we show that at room temperature this does not change. We therefore exclude ionic screening as an explanation for the experimentally observed reduction of the exciton binding energy at room temperature and argue in favor of the formation of polarons.

9.
Adv Mater ; 28(3): 560-5, 2016 Jan 20.
Artigo em Inglês | MEDLINE | ID: mdl-26599640

RESUMO

Photoelectron spectroscopy in combination with piezoforce microscopy reveals that the helicity of Rashba bands is coupled to the nonvolatile ferroelectric polarization of GeTe(111). A novel surface Rashba band is found and fingerprints of a bulk Rashba band are identified by comparison with density functional theory calculations.

10.
J Phys Chem Lett ; 6(12): 2223-31, 2015 Jun 18.
Artigo em Inglês | MEDLINE | ID: mdl-26266595

RESUMO

Ferroelectricity in halide perovskites currently represents a crucial issue, as it may have an important role for the enhancement of solar cells efficiency. Simulations of ferroelectric properties based on density functional theory are conceptually more demanding compared with "conventional" inorganic ferroelectrics due to the presence of both organic and inorganic components in the same compound. Here we present a detailed study focused on the prototypical CH3NH3PbI3 perovskite. By using density functional theory combined with symmetry mode analysis, we disentangle the contributions of the methylammonium cations and the role of the inorganic framework, therefore suggesting possible routes to enhance the polarization in this compound. Our estimate of the polarization for the tetragonal phase at low temperature is ∼4.42 µC/cm(2), which is substantially lower than that of traditional perovskite oxides.

11.
Phys Rev Lett ; 115(3): 037602, 2015 Jul 17.
Artigo em Inglês | MEDLINE | ID: mdl-26230826

RESUMO

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.

12.
J Phys Condens Matter ; 27(28): 283202, 2015 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-26125654

RESUMO

The design and discovery of new multiferroics, or materials that display both ferroelectricity and long-range magnetic order, is of fundamental importance for new electronic technologies based on low-power consumption. Far too often, however, the mechanisms causing these properties to arise are incompatible or occur at ordering temperatures below room temperature. One design strategy which has gained considerable interest is to begin with a magnetic material, and find novel ways to induce a spontaneous electric polarization within the structure. To this end, anharmonic interactions coupling multiple lattice modes have been used to lift inversion symmetry in magnetic dielectrics. Here we provide an overview of the microscopic mechanisms by which various types of cooperative atomic displacements result in ferroelectricity through anharmonic multi-mode coupling, as well as the types of materials most conducive to these lattice instabilities. The review includes a description of the origins of the displacive modes, a classification of possible non-polar lattice modes, as well as how their coupling can produce spontaneous polarizations. We then survey the recent improper ferroelectric literature, and describe how the materials discussed fall within a proposed classification scheme, offering new directions for the theoretical design of magnetic ferroelectrics. Finally, we offer prospects for the future discovery of new magnetic improper ferroelectrics, as well as detail remaining challenges and open questions facing this exciting new field.

13.
Sci Rep ; 5: 11285, 2015 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-26067146

RESUMO

By addressing the interplay between substitutional disorder and spin-orbit-coupling in chalcogenide alloys, we predict a strong robustness of spectral features at the Fermi energy. Indeed, supplementing our state of the art first-principles calculations with modeling analysis, we show that the disorder self-energy is vanishingly small close to the band gap, thus i) allowing for bulk Rashba-like spin splitting to be observed in ferroelectric alloys by means of Angle Resolved PhotoEmission Spectroscopy, and ii) protecting the band-character inversion related to the topological transition in recently discovered Topological Crystalline Insulators. Such a protection against strong disorder, which we demonstrate to be general for three dimensional Dirac systems, has potential and valuable implications for novel technologies, as spintronics and/or spinorbitronics.

14.
Dalton Trans ; 44(23): 10644-53, 2015 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-25579503

RESUMO

Recent experimental and theoretical work has shown that the double perovskite NaLaMnWO(6) exhibits antiferromagnetic ordering owing to the Mn d states, and computational studies further predict it to exhibit a spontaneous electric polarization due to an improper mechanism for ferroelectricity [King et al., Phys. Rev. B: Condens. Matter, 2009, 79, 224428; Fukushima et al., Phys. Chem. Chem. Phys., 2011, 13, 12186], which make it a candidate multiferroic material. Using first-principles density functional calculations, we investigate nine isostructural and isovalent AA'MnWO(6) double perovskites (A = Na, K, and Rb; A' = La, Nd, and Y) with the aim of articulating crystal-chemistry guidelines describing how to enhance the magnitude of the electric polarization through chemical substitution of the A-site while retaining long-range magnetic order. We find that the electric polarization can be enhanced by up to 150% in compounds which maximize the difference in the ionic size of the A and A' cations. By examining the tolerance factors, bond valences, and structural distortions (described by symmetry-adapted modes) of the nine compounds, we identify the atomic scale features that are strongly correlated with the ionic and electronic contributions to the electric polarization. We also find that each compound exhibits a purely electronic remnant polarization, even in the absence of a displacive polar mode. The analysis and design strategies presented here can be further extended to additional members of this family (B = Fe, Co, etc.), and the improper ferroelectric nature of the mechanism allows for the decoupling of magnetic and ferroelectric properties and the targeted design of novel multiferroics.

15.
Nat Commun ; 5: 5900, 2014 Dec 23.
Artigo em Inglês | MEDLINE | ID: mdl-25533044

RESUMO

Ferroelectricity is a potentially crucial issue in halide perovskites, breakthrough materials in photovoltaic research. Using density functional theory simulations and symmetry analysis, we show that the lead-free perovskite iodide (FA)SnI3, containing the planar formamidinium cation FA, (NH2CHNH2)(+), is ferroelectric. In fact, the perpendicular arrangement of FA planes, leading to a 'weak' polarization, is energetically more stable than parallel arrangements of FA planes, being either antiferroelectric or 'strong' ferroelectric. Moreover, we show that the 'weak' and 'strong' ferroelectric states with the polar axis along different crystallographic directions are energetically competing. Therefore, at least at low temperatures, an electric field could stabilize different states with the polarization rotated by π/4, resulting in a highly tunable ferroelectricity appealing for multistate logic. Intriguingly, the relatively strong spin-orbit coupling in noncentrosymmetric (FA)SnI3 gives rise to a co-existence of Rashba and Dresselhaus effects and to a spin texture that can be induced, tuned and switched by an electric field controlling the ferroelectric state.

16.
Sci Rep ; 4: 6062, 2014 Aug 14.
Artigo em Inglês | MEDLINE | ID: mdl-25317819

RESUMO

The coexistence of both electric and magnetic orders in some metal-organic frameworks (MOFs) has yielded a new class of multiferroics beyond inorganic materials. However, the coupling between two orders in multiferroic MOFs has not been convincingly verified yet. Here we present clear experimental evidences of cross coupling between electric and magnetic orders in a multiferroic MOF [(CH3)2NH2]Fe(HCOO)3 with a perovskite structure. The dielelectric constant exhibit a hump just at the magnetic ordering temperature TN. Moreover, both the direct (magnetic field control of dielectric properties) and converse (electric field control of magnetization) magnetoelectric effects have been observed in the multiferroic state. This work opens up new insights on the origin of ferroelectricity in MOFs and highlights their promise as magnetoelectric multiferroics.

17.
Phys Rev Lett ; 113(25): 256403, 2014 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-25554898

RESUMO

We study with first-principles methods the interplay between bulk and surface Dirac fermions in three dimensional Dirac semimetals. By combining density functional theory with the coherent potential approximation, we reveal a topological phase transition in Na_{3}Bi_{1-x}Sb_{x} and Cd_{3}[As_{1-x}P_{x}]_{2} alloys, where the material goes from a Dirac semimetal to a trivial insulator upon changing Sb or P concentrations. Tuning the composition allows us to engineer the position of the bulk Dirac points in reciprocal space. Interestingly, the phase transition coincides with the reversal of the band ordering between the conduction and valence bands.

18.
J Am Chem Soc ; 135(48): 18126-30, 2013 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-24191632

RESUMO

We perform density functional theory calculations on a recently synthesized metal-organic framework (MOF) with a perovskite-like topology ABX3, i.e., [CH3CH2NH3]Mn(HCOO)3, and predict a multiferroic behavior, i.e., a coexistence of ferroelectricity and ferromagnetism. A peculiar canted ordering of the organic A-cation dipole moments gives rise to a ferroelectric polarization of ~2 µC/cm(2). Starting from these findings, we show that by choosing different organic A cations, it is possible to tune the ferroelectric polarization and increase it up to 6 µC/cm(2). The possibility of changing the magnitude and/or the canting of the organic molecular dipole opens new routes toward engineering ferroelectric polarization in the new class of multiferroic metal-organic frameworks.

19.
Inorg Chem ; 52(20): 11850-8, 2013 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-24090277

RESUMO

A new orthorhombic phase, MnCrO4, isostructural with MCrO4 (M = Mg, Co, Ni, Cu, Cd) was prepared by evaporation of an aqueous solution, (NH4)2Cr2O7 + 2 Mn(NO3)2, followed by calcination at 400 °C. It is characterized by redox titration, Rietveld analysis of the X-ray diffraction pattern, Cr K edge and Mn K edge XANES, ESR, magnetic susceptibility, specific heat and resistivity measurements. In contrast to the high-pressure MnCrO4 phase where both cations are octahedral, the new phase contains Cr in a tetrahedral environment suggesting the charge balance Mn(2+)Cr(6+)O4. However, the positions of both X-ray absorption K edges, the bond lengths and the ESR data suggest the occurrence of some mixed-valence character in which the mean oxidation state of Mn is higher than 2 and that of Cr is lower than 6. Both the magnetic susceptibility and the specific heat data indicate an onset of a three-dimensional antiferromagnetic order at TN ≈ 42 K, which was confirmed also by calculating the spin exchange interactions on the basis of first principles density functional calculations. Dynamic magnetic studies (ESR) corroborate this scenario and indicate appreciable short-range correlations at temperatures far above TN. MnCrO4 is a semiconductor with activation energy of 0.27 eV; it loses oxygen on heating above 400 °C to form first Cr2O3 plus Mn3O4 and then Mn1.5Cr1.5O4 spinel.

20.
J Phys Condens Matter ; 25(6): 066001, 2013 Feb 13.
Artigo em Inglês | MEDLINE | ID: mdl-23306031

RESUMO

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.


Assuntos
Compostos de Bário/química , Cobalto/química , Campos Eletromagnéticos , Compostos Ferrosos/química , Titânio/química , Modelos Químicos , Teoria Quântica
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