Relativistic effects, including the Rashba effect, are increasingly seen as key ingredients in spintronics. A link between Rashba physics and the field of ferroelectrics is established by predicting giant Rashba spin-splitting in bulk GeTe (see the Figure showing the band-structure as well as in-plane and out- of-plane spin polarization for a constant energy cut).
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)SnI 3 , containing the planar formamidinium cation FA, (NH 2 CHNH 2 ) þ , 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 p/4, resulting in a highly tunable ferroelectricity appealing for multistate logic. Intriguingly, the relatively strong spin-orbit coupling in noncentrosymmetric (FA)SnI 3 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.
A comprehensive mapping of the spin polarization of the electronic bands in ferroelectric α-GeTe(111) films has been performed using a time-of-flight momentum microscope equipped with an imaging spin filter that enables a simultaneous measurement of more than 10.000 data points (voxels). A Rashba type splitting of both surface and bulk bands with opposite spin helicity of the inner and outer Rashba bands is found revealing a complex spin texture at the Fermi energy. The switchable inner electric field of GeTe implies new functionalities for spintronic devices. The strong coupling of electron momentum and spin in low-dimensional structures allows an electrically controlled spin manipulation in spintronic devices [1-4], e.g. via the Rashba effect [5]. The Rashba effect has first been experimentally demonstrated in semiconductor heterostructures, where an electrical field perpendicular to the layered structure, i.e. perpendicular to the electron momentum, determines the electron spin orientation relative to its momentum [6-8]. An asymmetric interface structure causes the necessary inversion symmetry breaking and accounts for the special spin-splitting of electron states, the Rashba effect [5], the size of which can be tuned by the strength of the electrical field. For most semiconducting materials the Rashba effect causes only a quite small splitting of the order of 10 −2 ˚ A −1 and thus requires experiments at very low temperatures [9-11] and also implies large lateral dimensions for potential spintronic applications. A considerably larger splitting has been predicted theoretically [12] and was recently found experimentally for the surface states of GeTe(111) [13, 14]. GeTe is a ferroelectric semiconductor with a Curie temperature of 700 K. Thus, besides the interface induced Rashba splitting, the ferroelectric properties also imply a broken inversion symmetry within the bulk and thus would allow for the electrical tuning of the bulk Rashba splitting via switching the ferroelectric polarization [12, 15, 16]. This effect is of great interest for non-volatile spin orbitronics [10]. For GeTe a bulk Rashba splitting of 0.19Å19Å −1 has been predicted theoretically [12]. Experimentally, bulk-Rashba bands are rare and have only been found in the layered polar semiconductors BiTeCl and BiTeI [17-20] that, however, are not switchable. A characterization of the ferroelectric properties and a measurement of the spin polarization of the surface states of GeTe(111) at selected k-points has been performed previously by force microscopy [21, 22] and spin-resolved angular resolved photoemission spectroscopy, respectively [13]. A recent experimental and theoretical study revealed that at the Fermi level the hybridization of surface and bulk states causes surface-bulk resonant states resulting in unconventional spin topologies with chiral symmetry [14]. Here, we demonstrate the spin structure of surface and bulk bands of the GeTe(111) surface using the novel pho-toemission technique of spin-resolved time-of-flight momentum microsco...
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.
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