This paper was selected as Featured ARTICLES YOU MAY BE INTERESTED IN Interrelation between domain structures and polarization switching in hybrid improper ferroelectric Ca 3 (Mn,Ti) 2 O 7

Recently, two-dimensional van der Waals ferroelectrics have been receiving much interest with continuous exploration of the underlying physics and device applications. While α-In2Se3 in an atomically thin crystal form is believed to have nonzero out-of-plane polarization, its ferroelectric (FE) instability in competition with the antiferroelectric (AFE) ground state is highly concerned. Along this line, a bilayer α-In2Se3 structure should be a good object for clarifying this issue since it is the simplest 2D lattice accommodating an AFE state, possibly allowing the AFE–FE competition. In this work, we employ the first-principles calculation to investigate the lattice and electronic structures of bilayer α-In2Se3, and special attention is paid to the FE instability in competition with the AFE ground state. It is found that the energy difference between the AFE ground state and FE state is small, thereby allowing an electric field modulation of the AFE–FE inter-conversion. More importantly, the Hyed–Scuseria–Ernzerhof algorithm predicts that the FE state is indeed semiconducting rather than metallic, removing the inconsistency between experimental observation and theoretical prediction. The spin–orbital coupling effect can further enlarge the bandgap and drive the indirect-to-direct bandgap transition, and thus appears to be an important ingredient of the underlying physics.

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Ca3Ti2O7 is an experimentally confirmed hybrid improper ferroelectric material, in which the electric polarization is induced by a combination of the coherent TiO6 octahedral rotation and tilting. In this work, we investigate the tuning of ferroelectricity of Ca3Ti2O7 using iso-valent substitutions on Ca-sites. Due to the size mismatch, larger/smaller alkaline earths prefer A'/A sites respectively, allowing the possibility for site-selective substitutions.Without extra carriers, such site-selected iso-valent substitutions can significantly tune the TiO6 octahedral rotation and tilting, and thus change the structure and polarization. Using the first-principles calculations, our study reveals that three substituted cases (Sr, Mg, Sr+Mg) show divergent physical behaviors. In particular, (CaTiO3)2SrO becomes non-polar, which can reasonably explain the suppression of polarization upon Sr substitution observed in experiment. In contrast, the polarization in (MgTiO3)2CaO is almost doubled upon substitutions, while the estimated coercivity for ferroelectric switching does not change. The (MgTiO3)2SrO remains polar but its structural space group changes, with moderate increased polarization and possible different ferroelectric switching paths. Our study reveals the subtle ferroelectricity in the A3Ti2O7 family and suggests one more practical route to tune hybrid improper ferroelectricity, in addition to the strain effect.

The topologically protected vortex–antivortex (V–AV) domain structure in ferroelectric hexagonal manganites has been highly concerned recently, but its stability against intrinsic defects remains to be understood, given the claim that a topological structure would be robust against defects and other perturbations. In fact, it is also known that the V–AV structure is sensitive to the sample quality, and such a well-developed structure is hardly observed in thin films and defective single crystals. In this work, we investigate the influence of anti-trimer point defects on the stability of the V–AV domain structure by employing the phase-field simulation based on the Landau–Devonshire phenomenological theory. It is revealed that the characteristic V–AV structure essentially relies on the anti-trimer point defects under consideration. These defects lower the trimerization transition temperature on one hand and produce pinning effect on the vortex cores/walls on the other hand. However, the V–AV structure does remain robust if the anti-trimer magnitude of these defects is relatively weak but will be eventually destroyed if the anti-trimer magnitude is strong.

In Landau-Devonshire phase transition theory, the order parameter represents a unique property for a disorder-order transition at the critical temperature. Nevertheless, for a phase transition with more than one order parameter, such behaviors can be quite different and system-dependent in many cases. In this work, we investigate the temperature (T) and electric field (E) dependence of the two order parameters in improper ferroelectric hexagonal manganites, addressing the phase transition from the high-symmetry P6 3 /mmc structure to the polar P6 3 cm structure. It is revealed that the trimerization as the primary order parameter with two components: the trimerization amplitude Q and phase U, and the spontaneous polarization P emerging as the secondary order parameter exhibit quite different stability behaviors against various T and E. The critical exponents for the two parameters Q and P are 1/2 and 3/2, respectively. As temperature increases, the window for the electric field E enduring the trimerization state will shrink. An electric field will break the Z 2 part of the Z 2 ÂZ 3 symmetry. The present work may shed light on the complexity of the vortex-antivortex domain structure evolution near the phase transition temperature.

In this work, we investigated the nanoscale conduction and charge transport characteristics of epitaxial VO2 thin films around the metal-insulator transition (MIT) using the Hall transport measurement and conduction atomic force microscopy. Unlike the conventional oxides, the VO2 thin films show unique transport characteristics. First, the dominant carrier type shows a critical change from electron to hole during the MIT sequence (cooling sequence) or from hole to electron during the reverse MIT sequence (heating sequence). Second, the carrier density measured during the MIT sequence is higher than that measured during the reverse MIT sequence, evidenced with a clear thermal hysteresis. Third, the volume fraction (area percentage) of the nanoscale high-conduction phase also shows a thermal hysteresis, evidenced with a larger volume fraction of the high-conduction region in the MIT sequence than the reverse MIT sequence. The first-principles calculations indicate that the dominant carrier is the hole in the monoclinic phase, while it is the electron in the rutile phase, suggesting that the unique charge transport characteristics are attributed to the structural phase transition. Our work provides a deep insight into the nanoscale conduction and charge transports in VO2 thin films.

Magnetically induced ferroelectric polarization in rare-earth RMn2O5 manganites is believed to originate from the symmetric exchange striction associated with a specific antiferromagnetic phase in the low temperature (T) region and would be irrelevant with electropoling in the high-T paramagnetic-paraelectric phase region. In this work, we demonstrate that low-T pyroelectric polarization of GdMn2O5 single crystals along the b axis in the antiferromagnetic phase exhibits remarkable dependence on the electropoling history imposed in the high-T paramagnetic-paraelectric phase. In particular, the high-T electropoling results in a reversal of ferroelectric polarization in the low-T region, which can be flopped back by the electropoling being sustained in the low-T ferroelectric region. The existence of an electrically polarizable magnetic cluster state in the high-T paramagnetic-paraelectric region is proposed based on a combination of experimental observations and first-principles calculations. An intrinsic correlation between the low-T antiferromagnetic ordering and the high-T polarizable state is discussed. The present experiments unveil the emergent phenomena on multiferroicity of RMn2O5 and suggest an alternative scenario for electrocontrol of magnetism.