Giant Exchange-Bias-Like Effect at Low Cooling Fields Induced by Pinned Magnetic Domains in Y2 NiIrO6 Double Perovskite.

Exchange bias (EB) is highly desirable for widespread technologies. Generally, conventional exchange-bias heterojunctions require excessively large cooling fields for sufficient bias fields, which are generated by pinned spins at the interface of ferromagnetic and antiferromagnetic layers. It is crucial for applicability to obtain considerable exchange-bias fields with minimum cooling fields. Here, an exchange-bias-like effect is reported in a double perovskite, Y2 NiIrO6 , which shows long-range ferrimagnetic ordering below 192 K. It displays a giant bias-like field of 1.1 T with a cooling field of only 15 Oe at 5 K. This robust phenomenon appears below 170 K. This fascinating bias-like effect is the secondary effect of the vertical shifts of the magnetic loops, which is attributed to the pinned magnetic domains due to the combination of strong spin-orbit coupling on Ir, and antiferromagnetically coupled Ni- and Ir-sublattices. The pinned moments in Y2 NiIrO6 are present throughout the full volume, not just at the interface as in conventional bilayer systems.

Non-Centrosymmetric Sr2IrO4 Obtained Under High Pressure.

Sr2IrO4 with strong spin-orbit coupling and Hubbard repulsion (U) hosts Mott insulating states. The similar crystal structure and magnetic and electronic properties, particularly the d-wave gap observed in Sr2IrO4 enhanced the analogies to the cuprate high-Tc superconductor, La2CuO4. The incomplete analogy was due to the lack of broken inversion symmetry phases observed in Sr2IrO4. Here, under high-pressure and high-temperature conditions, we report a noncentrosymmetric Sr2IrO4. The crystal structure and its noncentrosymmetric character were determined by single-crystal X-ray diffraction and high-resolution scanning transmission electron microscopy. The magnetic characterization confirms the Ir4+ with S = 1/2 at low temperature in Sr2IrO4 with magnetic ordering occurring at around 86 K, where a larger moment is observed than the ambient pressure Sr2IrO4. Moreover, the resistivity measurement shows three-dimensional Mott variable-range hopping (VRH) existed in the system. This noncentrosymmetric Sr2IrO4 phase appears to be a unique material that offers a further understanding of high-Tc superconductivity.

Tl2Ir2O7: A Pauli Paramagnetic Metal, Proximal to a Metal Insulator Transition.

A polycrystalline sample of Tl2Ir2O7 was synthesized by high-pressure and high-temperature methods. Tl2Ir2O7 crystallizes in the cubic pyrochlore structure with space group Fd3̅m (No. 227). The Ir4+ oxidation state is confirmed by Ir-L3 X-ray absorption near-edge spectroscopy. Combined temperature-dependent magnetic susceptibility, resistivity, specific heat, and DFT+DMFT calculation data show that Tl2Ir2O7 is a Pauli paramagnetic metal, but it is close to a metal-insulator transition. The effective ionic size of Tl3+ is much smaller than that of Pr3+ in metallic Pr2Ir2O7; hence, Tl2Ir2O7 would be expected to be insulating according to the established phase diagram of the pyrochlore iridate compounds, A3+2Ir4+2O7. Our experimental and theoretical studies indicate that Tl2Ir2O7 is uniquely different from the current A3+2Ir4+2O7 phase diagram. This uniqueness is attributed primarily to the electronic configuration difference between Tl3+ and rare-earth ions, which plays a substantial role in determining the Ir-O-Ir bond angle, and the corresponding electrical and magnetic properties.

A combinatory ferroelectric compound bridging simple ABO3 and A-site-ordered quadruple perovskite.

The simple ABO3 and A-site-ordered AA'3B4O12 perovskites represent two types of classical perovskite functional materials. There are well-known simple perovskites with ferroelectric properties, while there is still no report of ferroelectricity due to symmetry breaking transition in A-site-ordered quadruple perovskites. Here we report the high pressure synthesis of an A-site-ordered perovskite PbHg3Ti4O12, the only known quadruple perovskite that transforms from high-temperature centrosymmetric paraelectric phase to low-temperature non-centrosymmetric ferroelectric phase. The coordination chemistry of Hg2+ is changed from square planar as in typical A-site-ordered quadruple perovskite to a rare stereo type with 8 ligands in PbHg3Ti4O12. Thus PbHg3Ti4O12 appears to be a combinatory link from simple ABO3 perovskites to A-site-ordered AA'3Ti4O12 perovskites, sharing both displacive ferroelectricity with former and structure coordination with latter. This is the only example so far showing ferroelectricity due to symmetry breaking phase transition in AA'3B4O12-type A-site-ordered perovskites, and opens a direction to search for ferroelectric materials.

High-Pressure Synthesis of Double Perovskite Ba2NiIrO6: In Search of a Ferromagnetic Insulator.

Double perovskite oxides with d8-d3 electronic configurations are expected to be ferromagnetic from the Goodenough-Kanamori rules, such as ferromagnetic La2NiMnO6. In search of new ferromagnetic insulators, double perovskite Ba2NiIrO6 was successfully synthesized by high-pressure and high-temperature methods (8 GPa and 1573 K). Ba2NiIrO6 crystallizes in a cubic double perovskite structure (space group: Fm3̅m), with an ordered arrangement of NiO6 and IrO6 octahedra. X-ray absorption near-edge spectroscopy confirms the nominal Ni(II) and Ir(VI) valence states. Ba2NiIrO6 displays an antiferromagnetic order at 51 K. The positive Weiss temperature, however, indicates that ferromagnetic interactions are dominant. Isothermal magnetization curves at low temperatures support a field-induced spin-flop transition.

Ambient and High Pressure CuNiSb2: Metal-Ordered and Metal-Disordered NiAs-Type Derivative Pnictides.

The mineral Zlatogorite, CuNiSb2, was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb2-AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb2-AP crystallizes in the NiAs-derived structure (P3m1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb6 and CuSb6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure (P63/mmc, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb2-AP. The magnetic measurement indicates that CuNiSb2-AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb2-AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb2-8 GPa) was prepared by pressing CuNiSb2-AP at 700 °C and 8 GPa. However, the structures of single crystal and CuNiSb2-8 GPa are best fit with a disordered metal structure in the P3m1 space group, corroborated by transmission electron microscopy.

Universal A-Cation Splitting in LiNbO3-Type Structure Driven by Intrapositional Multivalent Coupling.

Understanding the electric dipole switching in multiferroic materials requires deep insight of the atomic-scale local structure evolution to reveal the ferroelectric mechanism, which remains unclear and lacks a solid experimental indicator in high-pressure prepared LiNbO3-type polar magnets. Here, we report the discovery of Zn-ion splitting in LiNbO3-type Zn2FeNbO6 established by multiple diffraction techniques. The coexistence of a high-temperature paraelectric-like phase in the polar Zn2FeNbO6 lattice motivated us to revisit other high-pressure prepared LiNbO3-type A2BB'O6 compounds. The A-site atomic splitting (∼1.0-1.2 Šbetween the split-atom pair) in B/B'-mixed Zn2FeTaO6 and O/N-mixed ZnTaO2N is verified by both powder X-ray diffraction structural refinements and high angle annular dark field scanning transmission electron microscopy images, but is absent in single-B-site ZnSnO3. Theoretical calculations are in good agreement with experimental results and suggest that this kind of A-site splitting also exists in the B-site mixed Mn-analogues, Mn2FeMO6 (M = Nb, Ta) and anion-mixed MnTaO2N, where the smaller A-site splitting (∼0.2 Šatomic displacement) is attributed to magnetic interactions and bonding between A and B cations. These findings reveal universal A-site splitting in LiNbO3-type structures with mixed multivalent B/B', or anionic sites, and the splitting-atomic displacement can be strongly suppressed by magnetic interactions and/or hybridization of valence bands between d electrons of the A- and B-site cations.

A Pressure-Induced Inverse Order-Disorder Transition in Double Perovskites.

Given the consensus that pressure improves cation ordering in most of known materials, a discovery of pressure-induced disordering could require recognition of an order-disorder transition in solid-state physics/chemistry and geophysics. Double perovskites Y2 CoIrO6 and Y2 CoRuO6 polymorphs synthesized at 0, 6, and 15 GPa show B-site ordering, partial ordering, and disordering, respectively, accompanied by lattice compression and crystal structure alteration from monoclinic to orthorhombic symmetry. Correspondingly, the long-range ferrimagnetic ordering in the B-site ordered samples are gradually overwhelmed by B-site disorder. Theoretical calculations suggest that unusual unit-cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2 CoIrO6 and Y2 CoRuO6 .

High-Pressure, High-Temperature Synthesis and Characterization of Polar and Magnetic LuCrWO6.

A new polar and magnetic oxide, LuCrWO6, was synthesized under high pressure (6 GPa) and high temperature (1673 K). LuCrWO6 is isostructural with the previously reported polar YCrWO6 (SG: Pna21, no. 33). The ordering of CrO6 and WO6 octahedra in the edge-shared dimers induce the polar structure. The effective size of rare earth, Ln cation does not seem to affect the symmetry of LnCrWO6. Second harmonic generation measurements of LuCrWO6 confirmed the noncentrosymmetric character and strong piezoelectric domains are observed from piezoresponse force microscopy at room temperature. LuCrWO6 exhibits antiferromagnetic behavior, TN, of ∼18 K with a Weiss temperature of -30.7 K.

Nonmetallic metal toward a pressure-induced bad-metal state in two-dimensional Cu3LiRu2O6.

The novel two-dimensional honeycomb layered Cu3LiRu2O6 exhibits Pauli-like paramagnetic and Mott variable range hopping semiconduction behaviors, which contradict the large specific-heat Sommerfeld coefficient for metals, and indicate a possible spin-excitation induced nonmetallic metal. This nonmetallic feature can be significantly suppressed by pressure toward producing a bad-metal state, as reflected by the temperature-dependent resistivity response up to 35 GPa.

High-Pressure Synthesis and Ferrimagnetism of Ni3TeO6-Type Mn2ScMO6 (M = Nb, Ta).

The corundum-related oxides Mn2ScNbO6 and Mn2ScTaO6 were synthesized at high pressure and high temperature (6 GPa and 1475 K). Analysis of the synchrotron powder X-ray diffraction shows that Mn2ScNbO6 and Mn2ScTaO6 crystallize in Ni3TeO6-type noncentrosymmetric crystal structures with space group R3. The asymmetric crystal structure was confirmed by second harmonic generation measurement. X-ray absorption near-edge spectroscopies indicate formal valence states of Mn2+2Sc3+Nb5+O6 and Mn2+2Sc3+Ta5+O6, also supported by the calculated bond valence sums. Both samples are electrically insulating. Magnetic measurements indicate that Mn2ScNbO6 and Mn2ScTaO6 order ferrimagnetically at 53 and 50 K, respectively, and Mn2ScTaO6 is found to have a field-induced magnetic transition.

LaMn3Rh4O12: An Antiferromagnetic Quadruple Perovskite Synthesized at High Pressure.

A quadruple perovskite LaMn3Rh4O12 with A' = Mn and B = 4d transition metal was synthesized at high pressure (8 GPa) and temperature (1423 K) for the first time. Room temperature powder X-ray diffraction indicates that LaMn3Rh4O12 forms in cubic symmetry (Im3̅, a = 7.4997(1) Å). X-ray absorption near-edge spectroscopy shows predominantly Mn3+ and Rh3+ oxidation states. An antiferromagnetic transition at TN ∼ 41 K is corroborated by specific heat measurements. The resistivity measurements indicate a three-dimensional Mott variable-range hopping conduction mechanism between 300 and 160 K.

La1.5Sr0.5NiMn0.5Ru0.5O6 Double Perovskite with Enhanced ORR/OER Bifunctional Catalytic Activity.

Perovskites (ABO3) with transition metals in active B sites are considered alternative catalysts for the water oxidation to oxygen through the oxygen evolution reaction (OER) and for the oxygen reduction through the oxygen reduction reaction (ORR) back to water. We have synthesized a double perovskite (A2BB'O6) with different cations in A, B, and B' sites, namely, (La1.5Sr0.5)A(Ni0.5Mn0.5)B(Ni0.5Ru0.5)B'O6 (LSNMR), which displays an outstanding OER/ORR bifunctional performance. The composition and structure of the oxide has been determined by powder X-ray diffraction, powder neutron diffraction, and transmission electron microscopy to be monoclinic with the space group P21/ n and with cationic ordering between the ions in the B and B' sites. X-ray absorption near-edge spectroscopy suggests that LSNMR presents a configuration of ∼Ni2+, ∼Mn4+, and ∼Ru5+. This bifunctional catalyst is endowed with high ORR and OER activities in alkaline media, with a remarkable bifunctional index value of ∼0.83 V (the difference between the potentials measured at -1 mA cm-2 for the ORR and +10 mA cm-2 for the OER). The ORR onset potential ( Eonset) of 0.94 V is among the best reported to date in alkaline media for ORR-active perovskites. The ORR mass activity of LSNMR is 1.1 A g-1 at 0.9 V and 7.3 A g-1 at 0.8 V. Furthermore, LSNMR is stable in a wide potential window down to 0.05 V. The OER potential to achieve a current density of 10 mA cm-2 is 1.66 V. Density functional theory calculations demonstrate that the high ORR/OER activity of LSNMR is related to the presence of active Mn sites for the ORR- and Ru-active sites for the OER by virtue of the high symmetry of the respective reaction steps on those sites. In addition, the material is stable to ORR cycling and also considerably stable to OER cycling.

Mn2CoReO6: a robust multisublattice antiferromagnetic perovskite with small A-site cations.

Mn2CoReO6, the fourth known magnetic transition-metal-only double perovskite oxide (space group P21/n) was synthesized at high pressure and temperature (8 GPa, 1350 °C). Large structural distortions are induced by the small A-site Mn2+ cations. Mn2CoReO6 exhibits complex magnetic properties with a robust antiferromagnetic order (TN = 94 K) involving all cation sublattices.

Reversible Structural Transformation between Polar Polymorphs of Li2GeTeO6.

Li2GeTeO6 prepared at ambient pressure adopts the corundum derivative ordered ilmenite structure (rhombohedral R3). When heated at 1073 K and 3-5 GPa, the as-made Li2GeTeO6 can convert into a LiSbO3-derived Li2TiTeO6-type phase (orthorhombic Pnn2), which is the third LiSbO3-derived double A2BB'O6 phase in addition to Li2TiTeO6 and Li2SnTeO6. This Pnn2 Li2GeTeO6 phase spontaneously reverts to the R3 phase if annealed up to 1023 K at ambient pressure. Although the crystal structural analyses and second harmonic generation measurements clearly demonstrate the polar nature of both the R3 and Pnn2 phases, P( E) and dielectric measurements do not show any convincing ferroelectric response. Given the large estimated spontaneous polarization (17 and 80 µC/cm2), the absence of ferroelectric behavior could be attributed to the random domain distribution and leakage due to Li-ion migration.

Pressure-dependent X-ray diffraction of the multiferroics RMn2O5.

The room-temperature structural properties of the RMn2O5 multiferroics have been investigated under pressure, using powder X-ray scattering and density functional theory (DFT) calculations. It was possible to determine the lattice parameters and the main atomic positions as a function of pressure. Good agreement was observed between the X-ray and DFT results for most of the determined crystallographic data. From the DFT calculations, it was possible to infer the pressure evolution of the exchange interactions, and this analysis led to the conclusion that the onset of the q = (½, 0, ½) magnetic structure under pressure is related to the increase in the J1 super-exchange terms (due to the reduction in the Mn-O distances) compared with the Mn-R exchange interactions. In addition, the 1D antiferromagnetic character of the compounds should be reinforced under pressure.

High-Pressure Synthesis of Lu2NiIrO6 with Ferrimagnetism and Large Coercivity.

Double-perovskite Lu2NiIrO6 was synthesized at high pressure (6 GPa) and high temperature (1300 °C). Synchrotron powder X-ray diffraction indicates that its structure is a monoclinic double perovskite (space group P21/ n) with a small, 11% Ni/Ir antisite disorder. X-ray absorption near-edge spectroscopy measurements established Ni2+ and Ir4+ formal oxidation states. Magnetic studies indicate a ferrimagnetic transition at 207 K. The low-temperature magnetization curve of Lu2NiIrO6 features broad hysteresis with a coercive field as high as 48 kOe. These results encourage the search for hard magnets in the class of 3d/5d double-perovskite oxides.

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.

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.

Structure and Magnetic Behavior of Layered Honeycomb Tellurates, BiM(III)TeO6 (M = Cr, Mn, Fe).

New layered honeycomb tellurates, BiM(III)TeO6 (M = Cr, Mn, Fe) were synthesized and characterized. BiM(III)TeO6 (M = Cr, Fe) species crystallize in a trigonal space group, P3̅1c (No. 163), of edge-sharing M3+/Te6+O6 octahedra, which form honeycomb-like double layers in the ab plane with Bi3+ cations located between the layers. Interestingly, the structure of BiMnTeO6 is similar to those of the Cr/Fe analogues, but with monoclinic space group, P21/c (No. 14), attributed to the strong Jahn-Teller distortion of Mn3+ cations. The crystal structure of BiM(III)TeO6 is a superstructure of PbSb2O6-related materials (ABB'O6). The Cr3+ and Fe3+ cations are ordered 80% and 90%, respectively, while the Mn3+ ions are completely ordered on the B-site of the ABB'O6 structure. BiCrTeO6 shows a broad antiferromagnetic transition (AFM) at ∼17 K with a Weiss temperature (θ) of -59.85 K, while BiFeTeO6 and BiMnTeO6 show sharp AFM transitions at ∼11 K with θ of -27.56 K and at ∼9.5 K with θ of -17.57 K, respectively. These differences in the magnetic behavior are ascribed to the different concentration of magnetic nearest versus next-nearest neighbor interactions of magnetic cations due to the relative differences in the extent of M/Te ordering.