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Magnetic-Field-Induced Change of Magneto-Electric Coupling in the in Molecular Multiferroic (ND4)2[FeCl5(D2O)]

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 Publication date 2016
  fields Physics
and research's language is English




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Our results describe an unprecedented example of change in the mechanism of magnetically-induced electric polarization from spin current to spin-dependent p-d hybridization model. We have followed the evolution of the magnetic structures of (ND4)2[FeCl5 D2O] compound using single crystal neutron diffraction under external magnetic field. The spin arrangements change from incommensurate cycloidal to commensurate distorted-cycloidal and finally to quasi-collinear. The determination of the magnetic structures allows us to explain the observed electric polarization in the different ferroelectric phases. Two different magneto-electric coupling mechanisms are at play: the spin-current mechanism for external magnetic field below 5 T, and the spin dependent p-d hybridization mechanism for magnetic field above this value, being this compound the first example reported presenting this sequence of magneto-electric coupling mechanisms.



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Neutron spherical polarimetry, which is directly sensitive to the absolute magnetic configuration and domain population, has been used in this work to unambiguously prove the multiferroicity of (ND4)2[FeCl5(D2O)]. We demonstrate that the application of an electric field upon cooling results in the stabilization of a single-cycloidal magnetic domain below 6.9 K, while poling in the opposite electric field direction produces the full population of the domain with opposite magnetic chirality. We prove the complete switchability of the magnetic domains at low temperature by the applied electric field, which constitutes a direct proof of the strong magnetoelectric coupling. Additionally, we refine the magnetic structure of the ordered ground state, determining the underlying magnetic space group consistent with the direction of the ferroelectric polarization, and we provide evidence of a collinear amplitude-modulated state with magnetic moments along the a-axis in the temperature region between 6.9 and 7.2 K.
The number of magnetoelectric multiferroic materials reported to date is scarce, as magnetic structures that break inversion symmetry and induce an improper ferroelectric polarization typically arise through subtle competition between different magnetic interactions. The (NH4)2[FeCl5(H2O)] compound is a rare case where such improper ferroelectricity has been observed in a molecular material. We have used single crystal and powder neutron diffraction to obtain detailed solutions for the crystal and magnetic structures of (NH4)2[FeCl5(H2O)], from which we determined the mechanism of multiferroicity. From the crystal structure analysis, we observed an order-disorder phase transition related to the ordering of the ammonium counterion. We have determined the magnetic structure below TN, at 2K and zero magnetic field, which corresponds to a cycloidal spin arrangement with magnetic moments contained in the ac-plane, propagating parallel to the c-axis. The observed ferroelectricity can be explained, from the obtained magnetic structure, via the inverse Dzyaloshinskii-Moriya mechanism.
We investigate the electronic structure and the ferroelectric properties of the recently discovered multiferroic ScFeO$_3$ by means of ab-initio calculations. The $3d$ manifold of Fe in the half-filled configuration naturally favors an antiferromagnetic ordering, with a theoretical estimate of the antiferromagnetic Neel temperature in good agreement with the experimental values. We find that the inversion symmetry-breaking is driven by the off-centering of Sc atoms, which results in a large ferroelectric polarization of $sim$105,$mu$C/cm$^{2}$. Surprisingly the ferroelectric polarization is sensitive to the local magnetization of the Fe atoms resulting in a large negative magnetoelectric interaction. This behavior is unexpected in type-I multiferroic materials because the magnetic and ferroelectric orders are of different origins.
We performed elastic neutron scattering measurements on the charge- and magnetically-ordered multiferroic material LuFe(2)O(4). An external electric field along the [001] direction with strength up to 20 kV/cm applied at low temperature (~100 K) does not affect either the charge or magnetic structure. At higher temperatures (~360 K), before the transition to three-dimensional charge-ordered state, the resistivity of the sample is low, and an electric current was applied instead. A reduction of the charge and magnetic peak intensities occurs when the sample is cooled under a constant electric current. However, after calibrating the real sample temperature using its own resistance-temperature curve, we show that the actual sample temperature is higher than the thermometer readings, and the intensity reduction is entirely due to internal sample heating by the applied current. Our results suggest that the charge and magnetic orders in LuFe(2)O(4) are unaffected by the application of external electric field/current, and previously observed electric field/current effects can be naturally explained by internal sample heating.
Neutron diffraction is used to probe the (H,T) phase diagram of magneto-electric (ME) LiNiPO4 for magnetic fields along the c-axis. At zero field the Ni spins order in two antiferromagnetic phases. One has commensurate (C) structures and general ordering vectors (0,0,0), the other one is incommensurate (IC) with ordering vector (0,q,0). At low temperatures the C order collapses above 12 Tesla and adopts an IC structure with modulation vector parallel to (0,q,0). We show that C order is required for the ME effect and establish how electric polarization results from a field-induced reduction of the total magneto-elastic energy.
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