On the basis of successful first-principles predictions of new functional ferroelectric materials, a number of new ferroelectrics have been experimentally discovered. Using trilinear coupling of two types of octahedron rotation, hybrid improper ferroelectricity has been theoretically predicted in ordered perovskites and the Ruddlesden-Popper compounds (Ca3Ti2O7, Ca3Mn2O7 and (Ca/Sr/Ba)3(Sn/Zr/Ge)2O7). However, the ferroelectricity of these compounds has never been experimentally confirmed and even their polar nature has been under debate. Here we provide the first experimental demonstration of room-temperature switchable polarization in bulk crystals of Ca3Ti2O7, as well as Sr-doped Ca3Ti2O7. Furthermore, (Ca, Sr)3Ti2O7 is found to exhibit an intriguing ferroelectric domain structure resulting from orthorhombic twins and (switchable) planar polarization. The planar domain structure accompanies abundant charged domain walls with conducting head-to-head and insulating tail-to-tail configurations, which exhibit a conduction difference of two orders of magnitude. These discoveries provide new research opportunities, not only for new stable ferroelectrics of Ruddlesden-Popper compounds, but also for meandering conducting domain walls formed by planar polarization.
Magnetoelectric (ME) effect is recognized for its utility for low-power electronic devices. Largest ME coefficients are often associated with phase transitions in which ferroelectricity is induced by magnetic order. Unfortunately, in these systems, large ME response is revealed only upon elaborate poling procedures. These procedures may become unnecessary in single-polar-domain crystals of polar magnets. Here we report giant ME effects in a polar magnet Fe2Mo3O8 at temperatures as high as 60 K. Polarization jumps of 0.3 μC/cm2, and repeated mutual control of ferroelectric and magnetic moments with differential ME coefficients on the order of 104 ps/m are achieved. Importantly, no electric or magnetic poling is needed, as necessary for applications. The sign of the ME coefficients can be switched by changing the applied “bias” magnetic field. The observed effects are associated with a hidden ferrimagnetic order unveiled by application of a magnetic field.
Combining high resolution scanning tunneling microscopy and first principles calculations, we identified the major native defects, in particular the Se vacancies and Se interstitial defects, that are responsible for the bulk conduction and nanoscale potential fluctuations in single crystals of archetypal topological insulator Bi_{2}Se_{3}. Here it is established that the defect concentrations in Bi_{2}Se_{3} are far above the thermodynamic limit, and that the growth kinetics dominate the observed defect concentrations. Furthermore, through careful control of the synthesis, our tunneling spectroscopy suggests that our best samples are approaching the intrinsic limit with the Fermi level inside the band gap without introducing extrinsic dopants.
Sr Sn O is the first room-temperature ferroelectric Sn insulator with switchable electric polarization. The ferroelastic twin domains are observed using a polarized optical microscope. The polarization hysteresis loop clearly demonstrates the ferroelectric property. Intriguing polarization switching kinetics are observed through an in situ poling process using a dark-field transmission electron microscopy technique.
The hexagonal phase of LuFeO 3 is a rare example of a multiferroic material possessing a weak ferromagnetic moment, which is predicted to be switchable by an electric field. We stabilize this structure in bulk form though Mn and Sc doping, and determine the complete magnetic and crystallographic structures using neutron-scattering and magnetometry techniques. The ferroelectric P 6 3 cm space group is found to be stable over a wide concentration range, ordering antiferromagnetically with Néel temperatures that smoothly increase following the ratio of c to a (c/a) lattice parameters up to 172 K, the highest found in this class of materials to date. The magnetic structure for a range of temperatures and dopings is consistent with recent studies of high quality epitaxial films of pure hexagonal LuFeO 3 including a ferromagnetic moment parallel to the ferroelectric axis. We propose a mechanism by which room-temperature multiferroicity could be achieved in this class of materials.
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