Ferroelectric phase transition in multiferroic Ge1-x Mn x Te driven by local lattice distortions.
ABSTRACT: The evolution of local ferroelectric lattice distortions in multiferroic Ge1-x Mn x Te is studied by x-ray diffraction, x-ray absorption spectroscopy and density functional theory. We show that the anion/cation displacements smoothly decrease with increasing Mn content, thereby reducing the ferroelectric transition from 700 to 100 K at x = 0.5, where the ferromagnetic Curie temperature reaches its maximum. First principles calculations explain this quenching by different local bond contributions of the Mn 3d shell compared to the Ge 4s shell in excellent quantitative agreement with the experiments.
Project description:Entanglement of the spin-orbit and magnetic order in multiferroic materials bears a strong potential for engineering novel electronic and spintronic devices. Here, we explore the electron and spin structure of ferroelectric ?-GeTe thin films doped with ferromagnetic Mn impurities to achieve its multiferroic functionality. We use bulk-sensitive soft-X-ray angle-resolved photoemission spectroscopy (SX-ARPES) to follow hybridization of the GeTe valence band with the Mn dopants. We observe a gradual opening of the Zeeman gap in the bulk Rashba bands around the Dirac point with increase of the Mn concentration, indicative of the ferromagnetic order, at persistent Rashba splitting. Furthermore, subtle details regarding the spin-orbit and magnetic order entanglement are deduced from spin-resolved ARPES measurements. We identify antiparallel orientation of the ferroelectric and ferromagnetic polarization, and altering of the Rashba-type spin helicity by magnetic switching. Our experimental results are supported by first-principles calculations of the electron and spin structure.
Project description:Responding to the rapidly increasing demand for efficient energy usage and increased speed and functionality of electronic and spintronic devices, multiferroic oxides have recently emerged as key materials capable of tackling this multifaceted challenge. In this paper, we describe the development of single-site manganese-based multiferroic perovskite materials with modest amounts of nonmagnetic Ti substituted at the magnetic Mn site in Sr1- x Ba x Mn1- y Ti y O3 (SBMTO). Significantly enhanced properties were achieved with ferroelectric-type structural transition temperatures boosted to ?430K. Ferroelectric distortions with large spontaneous polarization values of ?30?C/cm2, derived from a point charge model, are similar in magnitude to those of the prototypical nonmagnetic BaTiO3. Temperature dependence of the system's properties was investigated by synchrotron x-ray powder diffraction and neutron powder diffraction at ambient and high pressures. Various relationships were determined between the structural and magnetic properties, Ba and Ti contents, and T N and T C. Most importantly, our results demonstrate the large coupling between the magnetic and ferroelectric order parameters and the wide tunability of this coupling by slight variations of the material's stoichiometry.
Project description:Gd2(MoO4)3 (GMO) is a well-studied multiferroic material that exhibits full ferroelectric and ferroelastic behavior at room temperature. However, its difficult stabilization in thin films has prevented the study and exploitation of its multiferroic properties in different architectures. Here, we report on the study of GMO thin films deposited on Si(001) substrates by Pulsed Laser Deposition (PLD). The physicochemical properties of the films are discussed and studied. Results obtained by X-ray diffraction, X-ray photoelectron spectroscopy, high resolution transmission microscopy and second harmonic generation show that the orthorhombic (?'-GMO) multiferroic phase can be stabilized and homogenized by post deposition thermal reconstruction. Finally, the reconstruction process takes place via a complex surface mechanism with a clear leaf-like behavior.
Project description:Structural evolution and ferroelectric (FE)-to-antiferroelectric (AFE) transition behaviors were observed in Bi1-δFe0.95Mn0.05O3 (100)-textured films with a carefully controlled Bi deficiency concentration δ. Raman spectra revealed an orthorhombic structural transition induced by Mn substitution. The polarization-electric field hysteresis loops and capacitance-voltage loops of Bi1-δFe0.95Mn0.05O3 films clearly demonstrated antiferroelectric behavior with increasing δ. The responses of the domain structure of the Bi1-δFe0.95Mn0.05O3 film under positive and negative applied voltages directly suggested the coexistence of FE and AFE phases. The existence of (100) superstructure reflections and antiparallel displacements of the Bi atoms along the  direction observed by transmission electron microscopy unambiguously reveal the AFE phase. The chemical substitution-induced orthorhombic structural transition in BiFe0.95Mn0.05O3 film implies that as the δ concentration increases, the changes in Bi-O bonding and the stereochemical activity of Bi 6s lone pair affect both the ferroelectric distortion and the antiferrodistortive rotation and therefore drive the Bi1-δFe0.95Mn0.05O3 crystal lattice to form a PbZrO3-type orthorhombic phase with an AFE order. A continuing increase in Bi deficiency creates defect dipole complexes which produce an internal field leading to a preferred direction of the ferroelectric domain. The Bi deficiency in multiferroic BiFeO3 provides a new route by which to tune functionality.
Project description:Despite remarkable progress in developing multifunctional materials, spin-driven ferroelectrics featuring both spontaneous magnetization and electric polarization are still rare. Among such ferromagnetic ferroelectrics are conical spin spiral magnets with a simultaneous reversal of magnetization and electric polarization that is still little understood. Such materials can feature various multiferroic domains that complicates their study. Here we study the multiferroic domains in ferromagnetic ferroelectric Mn2GeO4 using neutron diffraction, and show that it features a double-Q conical magnetic structure that, apart from trivial 180o commensurate magnetic domains, can be described by ferromagnetic and ferroelectric domains only. We show unconventional magnetoelectric couplings such as the magnetic-field-driven reversal of ferroelectric polarization with no change of spin-helicity, and present a phenomenological theory that successfully explains the magnetoelectric coupling. Our measurements establish Mn2GeO4 as a conceptually simple multiferroic in which the magnetic-field-driven flop of conical spin spirals leads to the simultaneous reversal of magnetization and electric polarization.
Project description:Topological vortices with swirling ferroelectric, magnetic and structural anti-phase relationship in hexagonal RMnO3 (R = Ho to Lu, Y, and Sc) have attracted much attention because of their intriguing behaviors. Herein, we report the structure of multiferroic vortex domains in YMnO3 at atomic scale using state-of-the-art aberration-corrected scanning transmission electron microscopy (STEM). Two types of displacements were identified among six domain walls (DWs); six translation-ferroelectric domains denoted by α+, γ-, β+, α-, γ+ and β-, respectively, were recognized, demonstrating the interlocking nature of the anti-vortex domain. We found that the anti-vortex core is about four unit cells wide. In addition, we reconstructed the vortex model with three swirling pairs of DWs along the  direction. These results are very critical for the understanding of topological behaviors and unusual properties of the multiferroic vortex.
Project description:In this work, a high thermoelectric figure of merit, zT of 1.9 at 740 K is achieved in Ge1-xBixTe crystals through the concurrent of Seebeck coefficient enhancement and thermal conductivity reduction with Bi dopants. The substitution of Bi for Ge not only compensates the superfluous hole carriers in pristine GeTe but also shifts the Fermi level (EF) to an eligible region. Experimentally, with moderate 6-10% Bi dopants, the carrier concentration is drastically decreased from 8.7 × 1020 cm-3 to 3-5 × 1020 cm-3 and the Seebeck coefficient is boosted three times to 75 μVK-1. In the meantime, based on the density functional theory (DFT) calculation, the Fermi level EF starts to intersect with the pudding mold band at L point, where the band effective mass is enhanced. The enhanced Seebeck coefficient effectively compensates the decrease of electrical conductivity and thus successfully maintain the power factor as large as or even superior than that of the pristine GeTe. In addition, the Bi doping significantly reduces both thermal conductivities of carriers and lattices to an extremely low limit of 1.57 W m-1K-1 at 740 K with 10% Bi dopants, which is an about 63% reduction as compared with that of pristine GeTe. The elevated figure of merit observed in Ge1-xBixTe specimens is therefore realized by synergistically optimizing the power factor and downgrading the thermal conductivity of alloying effect and lattice anharmonicity caused by Bi doping.
Project description:Multiferroic materials with both ferroelectric and ferromagnetic orders provide a promising arena for the electrical manipulation of magnetization through the mutual correlation between those ferroic orders. Such a concept of multiferroics may expand to semiconductor with both broken symmetries of spatial inversion and time reversal, that is, polar ferromagnetic semiconductors. Here, we report the observation of current-driven magnetization switching in one such example, (Ge,Mn)Te thin films. The ferromagnetism caused by Mn doping opens an exchange gap in original massless Dirac band of the polar semiconductor GeTe with Rashba-type spin-split bands. The anomalous Hall conductivity is enhanced with increasing hole carrier density, indicating that the contribution of the Berry phase is maximized as the Fermi level approaches the exchange gap. By means of pulse-current injection, the electrical switching of the magnetization is observed in the (Ge,Mn)Te thin films as thick as 200 nm, pointing to the Rashba-Edelstein effect of bulk origin. The efficiency of this effect strongly depends on the Fermi-level position owing to the efficient spin accumulation at around the gap. The magnetic bulk Rashba system will be a promising platform for exploring the functional correlations among electric polarization, magnetization, and current.
Project description:Cross-coupling of ordering parameters in multiferroic materials by multiple external stimuli other than electric field and magnetic field is highly desirable from both practical application and fundamental study points of view. Recently, mechanical force has attracted great attention in switching of ferroic ordering parameters via electro-elastic coupling in ferroelectric materials. In this work, mechanical force induced both polarization and magnetization switching were visualized in a polycrystalline multiferroic Bi0.9La0.1FeO3 thin film using a scanning probe microscopy system. The piezoresponse force microscopy and magnetic force microscopy responses suggest that both the ferroelectric domains and the magnetic domains in Bi0.9La0.1FeO3 film could be switched by mechanical force as well as by electric field. High tip stress applied on our thin film is demonstrated as able to induce ferroelastic switching and thus induce both ferroelectric dipole and magnetic spin flipping, as a consequence of electro-elastic coupling and magneto-electric coupling. The demonstration of mechanical force control of both the ferroelectric and the magnetic domains at room temperature provides a new freedom for manipulation of multiferroics and could result in devices with novel functionalities.
Project description:We report on structural, magnetic, ferroelectric, and thermodynamic properties of polycrystalline orthorhombic manganites Dy(1-x)Ho(x)MnO(3) for Ho substitution levels 0 ≤ x ≤ 1. This system offers a possibility to systemically modulate the multiferroicity of RMnO(3) via tuning the A-site ionic radii as well as the A-site magnetism. The successive transition of the multiferroic ground state is traced from the bc-cycloidal (DyMnO(3)) to the E-type antiferromagnetic phase (HoMnO(3)). In the middle substitution range 0.4 < x < 0.5, the phase separation is prominent, which's residual may survive in an even wider range. Accompanied with the phase transition and phase separation, obvious enhancement of both the polarization and magnetoelectric response is observed. Our experimental study also confirmed that the rare earth (Dy/Ho)-Mn exchange striction is a crucial role in deciding the multiferroicity of manganites.