Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond: Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden-Popper Phases.

Hybrid improper ferroelectricity, which utilizes nonpolar but ubiquitous rotational/tilting distortions to create polarization, offers an attractive route to the discovery of new ferroelectric and multiferroic materials because its activity derives from geometric rather than electronic origins. Design approaches blending group theory and first principles can be utilized to explore the crystal symmetries of ferroelectric ground states, but in general, they do not make accurate predictions for some important parameters of ferroelectrics, such as Curie temperature ( TC). Here, we establish a predictive and quantitative relationship between TC and the Goldschmidt tolerance factor, t, by employing n = 2 Ruddlesden-Popper (RP) A3B2O7 as a prototypical example of hybrid improper ferroelectrics. The focus is placed on an RP system, (Sr1- xCa x)3Sn2O7 ( x = 0, 0.1, and 0.2), which allows for the investigation of the purely geometric (ionic size) effect on ferroelectric transitions, due to the absence of the second-order Jahn-Teller active (d0 and 6s2) cations that often lead to ferroelectric distortions through electronic mechanisms. We observe a ferroelectric-to-paraelectric transition with TC = 410 K for Sr3Sn2O7. We also find that the TC increases linearly up to 800 K upon increasing the Ca2+ content, i.e., upon decreasing the value of t. Remarkably, this linear relationship is applicable to the suite of all known A3B2O7 hybrid improper ferroelectrics, indicating that the  TC correlates with the simple crystal chemistry descriptor, t, based on the ionic size mismatch. This study provides a predictive guideline for estimating the TC of a given material, which would complement the convergent group-theoretical and first-principles design approach.

A(II)GeTeO6 (A = Mn, Cd, Pb): Non-Centrosymmetric Layered Tellurates with PbSb2O6-Related Structure.

A(II)GeTeO6 (A = Mn, Cd, Pb), new non-centrosymmetric (NCS) honeycomb-layered tellurates, were synthesized and characterized. A(II)GeTeO6 (A = Mn, Cd, Pb) crystallize in trigonal space group P312 (No. 149) of edge-sharing Ge4+O6 and Te6+O6 octahedra, which form honeycomb-like-layers in the ab-plane with A(II) (A = Mn, Cd, Pb) cations located between the layers. Their crystal structures are PbSb2O6-related, and the ordering of Ge4+ and Te6+ in octahedral environment breaks the inversion symmetry of the parent PbSb2O6 structure. The size of A(II) cation in six coordination is an important factor to stabilize PbSb2O6-based structure. Temperature-dependent optical second harmonic generation measurements on A(II)GeTeO6 confirmed non-centrosymmetric character in the entire scanned temperature range (0 to 600 °C). The materials exhibit a powder SHG efficiency of ∼0.37 and ∼0.21 times of KH2PO4 for PbGeTeO6 and CdGeTeO6, respectively. Magnetic measurements of MnGeTeO6 indicate anti-ferromagnetic order at TN ≈ 9.4 K with Weiss temperature of -22.47 K.

Spatio-temporal symmetry - crystallographic point groups with time translations and time inversion.

The crystallographic symmetry of time-periodic phenomena has been extended to include time inversion. The properties of such spatio-temporal crystallographic point groups with time translations and time inversion are derived and one representative group from each of the 343 types has been tabulated. In addition, stereographic symmetry and general-position diagrams are given for each representative group. These groups are also given a notation consisting of a short Hermann-Mauguin magnetic point-group symbol with each spatial operation coupled with its associated time translation.

Magnetostriction-polarization coupling in multiferroic Mn2MnWO6.

Double corundum-related polar magnets are promising materials for multiferroic and magnetoelectric applications in spintronics. However, their design and synthesis is a challenge, and magnetoelectric coupling has only been observed in Ni3TeO6 among the known double corundum compounds to date. Here we address the high-pressure synthesis of a new polar and antiferromagnetic corundum derivative Mn2MnWO6, which adopts the Ni3TeO6-type structure with low temperature first-order field-induced metamagnetic phase transitions (T N = 58 K) and high spontaneous polarization (~ 63.3 µC·cm-2). The magnetostriction-polarization coupling in Mn2MnWO6 is evidenced by second harmonic generation effect, and corroborated by magnetic-field-dependent pyroresponse behavior, which together with the magnetic-field-dependent polarization and dielectric measurements, qualitatively indicate magnetoelectric coupling. Piezoresponse force microscopy imaging and spectroscopy studies on Mn2MnWO6 show switchable polarization, which motivates further exploration on magnetoelectric effect in single crystal/thin film specimens.