RESUMEN
A transition-metal oxide of PbCu3Mn4O12 was prepared at 1523 K and 10 GPa. An A-site-ordered quadruple perovskite structure with the space group Im3Ì is assigned for this compound. Based on bond-valence-sum calculations and X-ray absorption spectroscopy, the charge combination is determined to be PbCu32+Mn44+O12. Due to Cu2+(↑)-Mn4+(↓) antiferromagnetic coupling, a near-room-temperature ferrimagnetic phase transition is observed at approximately 287 K. PbCu3Mn4O12 exhibits a semiconducting electric transport property with the energy band gap Eg ≈ 0.2 eV. In addition, considerable low-field magnetoresistance effects are observed at lower temperatures. This study provides an intrinsic near-room-temperature ferrimagnetic semiconductor that exhibits potential applications in next-generation spintronic devices.
RESUMEN
An AA'3B4O12-type A-site-ordered quadruple perovskite oxide AgMn7O12 was prepared by high-pressure and high-temperature methods. At room temperature, the compound crystallizes into a cubic Im3Ì symmetry with a charge distribution of AgMn33+Mn43.5+O12. With the temperature decreasing to TCO,OO ≈ 180 K, the compound undergoes a structural phase transition toward a monoclinic C2/m symmetry, giving rise to a B-site charge- and orbital-ordered AgMn33+Mn23+Mn24+O12 phase. Moreover, this charge-/orbital-ordered main phase coexists with the initial cubic AgMn33+Mn43.5+O12 phase in the wide temperature range we measured. The charge-/orbital-ordered phase shows two antiferromagnetic phase transitions near 125 and 90 K, respectively. Short-range ferromagnetic correlations are found to occur for the initial B-site mixed cubic phase around 35 K. Because of the robust phase separation, considerable magnetoresistance effects are observed below TCO,OO in AgMn7O12.
RESUMEN
An AA'3B2B'2O12-type quadruple perovskite oxide of CaCu3Cr2Re2O12 was synthesized at 18 GPa and 1373 K. Both an A- and B-site ordered quadruple perovskite crystal structure was observed, with the space group Pn-3. The valence states are verified to be CaCu32+Cr23+Re25+O12 by bond valence sum calculations and synchrotron X-ray absorption spectroscopy. The spin interaction among Cu2+, Cr3+, and Re5+ generates a ferrimagnetic transition with the Curie temperature (TC) at about 360 K. Moreover, electric transport properties and specific heat data suggest the presence of a half-metallic feature for this compound. The present study provides a promising quadruple perovskite oxide with above-room-temperature ferrimagnetism and possible half-metallic properties, which shows potential in the usage of spintronic devices.
RESUMEN
α-CdFe2O4 stabilizes its normal spinel structure due to the covalent Cd-O bond, in which all the connections between adjacent FeO6 octahedral are edge-shared, forming a typical geometrically frustrated Fe3+ magnetic lattice. As the high-pressure methods were utilized, the post-spinel phase ß-CdFe2O4 with a CaFe2O4-type structure was synthesized at 8 GPa and 1373 K. The new polymorph has an orthorhombic structure with the space group Pnma and an 11.5% higher density than that of its normal spinel polymorph (α-CdFe2O4) synthesized at ambient conditions. The edge-shared FeO6 octahedra form zigzag S = 5/2 spin ladders along the b-axis dominating its low-dimensional magnetic properties at high temperatures and a long-range antiferromagnetic ordering with a high Néel temperature of TN1 = 350 K. Further, the rearrangement of magnetic ordering was found to occur around TN2 = 265 K, below which the competition of two phases or several couplings induce complex antiferromagnetic behaviors.
RESUMEN
CaCu3Mn2Te2O12 was synthesized using high-temperature and high-pressure conditions. The compound possesses an A- and B site ordered quadruple perovskite structure in Pn3Ì symmetry with the charge combination of CaCu32+Mn22+Te26+O12. A ferrimagnetic phase transition originating from the antiferromagnetic interaction between A' site Cu2+ and B site Mn2+ ions is found to occur at TC ≈ 100 K. CaCu3Mn2Te2O12 also shows insulating electric conductivity. Optical measurement demonstrates the energy bandgap to be about 1.9 eV, in agreement with the high B site degree of chemical order between Mn2+ and Te6+. The first-principles theoretical calculations confirm the Cu2+(↓)-Mn2+(↑) ferrimagnetic coupling as well as the insulating nature with an up-spin direct bandgap. The current CaCu3Mn2Te2O12 provides an intriguing example of an intrinsic ferrimagnetic insulator with promising applications in advanced spintronic devices.
RESUMEN
Scheelite-type HoCrO4 was prepared by treating the ambient-pressure zircon-type precursor phase under 8 GPa and 700 K. A long-range antiferromagnetic phase transition is found to occur at TN ≈ 23 K due to the spin order of Ho3+ and Cr5+ magnetic ions. However, the antiferromagnetic ground state is sensitive to an external magnetic field and a moderate field of about 1.1 T can induce a metamagnetic transition, giving rise to the presence of a large magnetization up to 8.5 µB/f.u. at 2 K and 7 T. Considerable linear magnetoelectric effect is observed in the antiferromagnetic state, while the induced electric polarization experiences a sharp increase near the critical field of the metamagnetic transition. Ferromagnetism and ferroelectricity thus rarely coexist under higher magnetic fields in scheelite-type HoCrO4. Moreover, a magnetic field also plays an important role in the longitudinal constriction of HoCrO4, and a significant magnetostrictive effect with a value of up to 300 ppm is observed at 2 K and 9 T, which can be attributed to the strong anisotropy of the rare-earth Ho3+ ion. Possible coupling between magnetoelectric and magnetoelastic effects is discussed.
RESUMEN
A 4H-type BaMnO3 single crystal was prepared by combining the floating zone method with high-pressure treatment at 5 GPa and 1023 K. The crystal crystallizes to a hexagonal structure with space group P63/mmc and lattice parameters a = 5.63723(5) Å and c = 9.22355(8) Å. In this structure, face-sharing MnO6 octahedral dimers connect with each other by corner O atoms along the c-axis direction, forming an -A-B-A-C-type 4H arrangement. A long-range antiferromagnetic (AFM) phase transition is found to occur at TN ≈ 263 K. When the synthesis pressure increases to 20 GPa, a new polymorphic phase is obtained. This higher-pressure phase still possesses the hexagonal P63/mmc symmetry, but the lattice parameters change to be a = 5.61349(2) Å and c = 13.66690(9) Å with a unit cell volume reduction of 2.05%. In this new phase, the c-axis MnO6 dimers are separated by MnO6 octahedral layers in the ab plane, forming an -A-B-C-A-C-B-type 6H structure. The 6H phase exhibits two long-range AFM orderings at TN1 ≈ 220 K and TN2 ≈ 25 K, respectively. The different magnetic properties are discussed on the basis of the detailed structural constitutions of 4H- and 6H-BaMnO3.
RESUMEN
B-site Os-doped quadruple perovskite oxides LaCu3Fe4-xOsxO12 (x = 1 and 2) were prepared under high-pressure and high-temperature conditions. Although parent compound LaCu3Fe4O12 experiences Cu-Fe intermetallic charge transfer that changes the Cu3+/Fe3+ charge combination to Cu2+/Fe3.75+ at 393 K, in the Os-doped samples, the Cu and Fe charge states are found to be constant 2+ and 3+, respectively, indicating the complete suppression of charge transfer. Correspondingly, Os6+ and mixed Os4.5+ valence states are determined by X-ray absorption spectroscopy for x = 1 and x = 2 compositions, respectively. The x = 1 sample crystallizes in an Fe/Os disordered structure with the Im3Ì space group. It experiences a spin-glass transition around 480 K. With further Os substitution up to x = 2, the crystal symmetry changes to Pn3Ì , where Fe and Os are orderly distributed in a rocksalt-type fashion at the B site. Moreover, this composition shows a long-range Cu2+(↑)Fe3+(↑)Os4.5+(↓) ferrimagnetic ordering near 520 K. This work provides a rare example for 5d substitution-suppressed intermetallic charge transfer as well as induced structural and magnetic phase transitions with high spin ordering temperature.
RESUMEN
Spin state transitions and intermetallic charge transfers can essentially change material structural and physical properties while excluding external chemical doping. However, these two effects have rarely been found to occur sequentially in a specific material. In this article, we show the realization of these two phenomena in a perovskite oxide PbCoO3 with a simple ABO3 composition under high pressure. PbCoO3 possesses a peculiar A- and B-site ordered charge distribution Pb2+Pb4+3Co2+2Co3+2O12 with insulating behavior at ambient conditions. The high spin Co2+ gradually changes to low spin with increasing pressure up to about 15 GPa, leading to an anomalous increase of resistance magnitude. Between 15 and 30 GPa, the intermetallic charge transfer occurs between Pb4+ and Co2+ cations. The accumulated charge-transfer effect triggers a metal-insulator transition as well as a first-order structural phase transition toward a Tetra.-I phase at the onset of â¼20 GPa near room temperature. On further compression over 30 GPa, the charge transfer completes, giving rise to another first-order structural transformation toward a Tetra.-II phase and the reentrant electrical insulating behavior.
RESUMEN
An ilmenite-like monoclinic phase of HgMnO3 with space group P21/c was prepared using high-pressure and high-temperature methods at 18 GPa and 1473 K. The MnO6 octahedra form a two-dimensional (2D) network in the bc plane, leading to a long-range antiferromagnetic ordering with a low Néel temperature of TN â¼ 32 K. As the synthesis pressure increases to 20 GPa, a new perovskite-like rhombohedral phase with space group R3Ì c was found to occur. The rhombohedral phase exhibits a three-dimensional (3D) network for the MnO6 octahedra, giving rise to an antiferromagnetic ordering at TN â¼ 60 K. X-ray absorption spectroscopy confirms the invariable Mn4+ charge state in these two polymorphic phases, in agreement with the Curie-Weiss and bond valence sum analysis. HgMnO3 provides an interesting example to study the magnetic properties from 2D to 3D by varying synthesis pressure.
RESUMEN
A new oxide, LaMn3Co2Mn2O12, was synthesized under high-pressure (7 GPa) and high-temperature (1423 K) conditions. The compound crystallizes in an AA'3B4O12-type quadruple perovskite structure with space group Im3Ì . The Rietveld structural analysis combined with soft X-ray absorption spectroscopy reveals the charge combination to be LaMn3+3Co2+2Mn4+2O12, where the La3+ and Mn3+ are 1:3 ordered respectively at the A and A' sites, whereas the Co2+ and Mn4+ are disorderly distributed at the B site. This is in sharp contrast to R2Co2+Mn4+O6 (R = La and rare earth) double perovskites, in which the Co2+ and Mn4+ charge states are always orderly distributed with a rocksalt-type fashion, giving rise to a long-range magnetic ordering. As a result, LaMn3Co2Mn2O12 displays spin glassy magnetic properties due to the random Co2+ and Mn4+ distribution, as demonstrated by dc and ac magnetic susceptibility as well as specific heat measurements. Possible factors that affect the B-site degree of order in perovskite structures are discussed.
RESUMEN
A new 3d-5d hybridization oxide, CaCu3Mn2Os2O12 (CCMOO), was prepared by high-pressure and high-temperature synthesis methods. The compound crystallizes to an A-site-ordered but B-site-disordered quadruple perovskite structure with a space group of Im3Ì (No. 204). The charge states of the transition metals are determined to be Cu2+/Mn3.5+/Os4.5+ by X-ray absorption spectroscopy. Although most B-site-disordered perovskites possess lower spin-ordering temperatures or even nonmagnetic transitions, the current CCMOO displays a long-range ferrimagnetic phase transition with a critical temperature as high as â¼280 K. Moreover, a large saturated magnetic moment is found to occur [7.8 µB/formula units (f.u.) at 2 K]. X-ray magnetic circular dichroism shows a Cu2+(↑)Mn3.5+(↑)Os4.5+(↓) ferrimagnetic coupling. The corner-sharing Mn/OsO6 octahedra with mixed Mn and Os charge states make the compound metallic in electrical transport, in agreement with a specific heat fitting at low temperature. This work provides a rare example with high spin-ordering temperature and a large magnetic moment in B-site-disordered 3d-5d hybridization perovskite oxides.
RESUMEN
The rare physical property of negative thermal expansion (NTE) is intriguing because materials with a large NTE over a wide temperature range can serve as high-performance thermal expansion compensators. However, the applications of NTE are hindered by the fact that most of the available NTE materials show small magnitudes of NTE, and/or NTE occurs only in a narrow temperature range. Herein, for the first time, we investigated the effect of anion substitution instead of general Pb/Ti-site substitutions on the thermal expansion properties of a typical ferroelectric NTE material, PbTiO3. Intriguingly, the substitution of S for O in PbTiO3 further increases the tetragonality of PbTiO3. Consequently, an unusually enhanced NTE with an average volumetric coefficient of thermal expansion of îV = -2.50 × 10-5 K-1 was achieved over a wide temperature range (300-790 K), which is in contrast to that of pristine PbTiO3 (îV = -1.99 × 10-5 K-1, RT-763 K). The intensified NTE is attributed to the enhanced hybridization between Pb/Ti and O/S atoms by the substitution of S, as evidenced by our theoretical investigations. We therefore demonstrate a new technique for introducing mixed anions to achieve a large NTE over a wide temperature range in PbTiO3-based ferroelectrics.
RESUMEN
The concurrent presence of large electric polarization and strong magnetoelectric coupling is quite desirable for potential applications of multiferroics. In this paper, we report the growth of CdMn7O12single crystals by flux method under a high pressure of 8 GPa for the first time. An antiferromagnetic (AFM) order with a polar magnetic point group is found to occur at the onset temperature ofTN1= 88 K (AFM1 phase). As a consequence, the pyroelectric current emerges atTN1and gradually increases and reaches its maximum atTset= 63 K, at which the AFM1 phase finally settles down. BelowTset, CdMn7O12single crystal exhibits a large ferroelectric polarization up to 2640µC m-2. Moreover, the spin-induced electric polarization can be readily tuned by applying magnetic fields, giving rise to considerable magnetoelectric coupling effects. Thus, the current CdMn7O12single crystal acts as a rare multiferroic system where both large polarization and strong magnetoelectric coupling merge concurrently.
RESUMEN
The perovskite ABO3 family demonstrates a wide variety of structural evolutions and physical properties and is arguably the most important family of complex oxides. Chemical substitutions of the A- and/or B-site and modulation of oxygen content can effectively regulate their electronic behaviors and multifunctional performances. In general, the BO6 octahedron represents the main unit controlling the electronic and magnetic properties while the A-site ion is often not involved. However, a series of unconventional perovskite materials have been recently synthesized under high pressure, such as the s-d level controlled Pb-based perovskite family and quadruple perovskite oxides containing transition metal ions at the A-site. In these compounds, the intersite A-B correlations play an important role in electronic behaviors and further induce many emergent physical properties.
RESUMEN
Topology, an important branch of mathematics, is an ideal theoretical tool to describe topological states and phase transitions. Many topological concepts have found their physical entities in real or reciprocal spaces identified by topological invariants, which are usually defined on orientable surfaces, such as torus and sphere. It is natural to investigate the possible physical realization of more intriguing non-orientable surfaces. Herein, we show that the set of spin-induced ferroelectric polarizations in cubic perovskite oxides AMn3Cr4O12 (A = La and Tb) reside on the topological Roman surface-a non-orientable two-dimensional manifold formed by sewing a Möbius strip edge to that of a disc. The induced polarization may travel in a loop along the non-orientable Möbius strip or orientable disc, depending on the spin evolution as controlled by an external magnetic field. Experimentally, the periodicity of polarization can be the same or twice that of the rotating magnetic field, which is consistent with the orientability of the disc and the Möbius strip, respectively. This path-dependent topological magnetoelectric effect presents a way to detect the global geometry of a surface and deepens our understanding of topology in both mathematics and physics.
RESUMEN
Half metals, in which one spin channel is conducting while the other is insulating with an energy gap, are theoretically considered to comprise 100% spin-polarized conducting electrons, and thus have promising applications in high-efficiency magnetic sensors, computer memory, magnetic recording, and so on. However, for practical applications, a high Curie temperature combined with a wide spin energy gap and large magnetization is required. Realizing such a high-performance combination is a key challenge. Herein, a novel A- and B-site ordered quadruple perovskite oxide LaCu3 Fe2 Re2 O12 with the charge format of Cu2+ /Fe3+ /Re4.5+ is reported. The strong Cu2+ (↑)Fe3+ (↑)Re4.5+ (↓) spin interactions lead to a ferrimagnetic Curie temperature as high as 710 K, which is the reported record in perovskite-type half metals thus far. The saturated magnetic moment determined at 300 K is 7.0 µB f.u.-1 and further increases to 8.0 µB f.u.-1 at 2 K. First-principles calculations reveal a half-metallic nature with a spin-down conducting band while a spin-up insulating band with a large energy gap up to 2.27 eV. The currently unprecedented realization of record Curie temperature coupling with the wide energy gap and large moment in LaCu3 Fe2 Re2 O12 opens a way for potential applications in advanced spintronic devices at/above room temperature.
RESUMEN
PbMO3 (M = 3d transition metals) family shows systematic variations in charge distribution and intriguing physical properties due to its delicate energy balance between Pb 6s and transition metal 3d orbitals. However, the detailed structure and physical properties of PbFeO3 remain unclear. Herein, we reveal that PbFeO3 crystallizes into an unusual 2ap × 6ap × 2ap orthorhombic perovskite super unit cell with space group Cmcm. The distinctive crystal construction and valence distribution of Pb2+0.5Pb4+0.5FeO3 lead to a long range charge ordering of the -A-B-B- type of the layers with two different oxidation states of Pb (Pb2+ and Pb4+) in them. A weak ferromagnetic transition with canted antiferromagnetic spins along the a-axis is found to occur at 600 K. In addition, decreasing the temperature causes a spin reorientation transition towards a collinear antiferromagnetic structure with spin moments along the b-axis near 418 K. Our theoretical investigations reveal that the peculiar charge ordering of Pb generates two Fe3+ magnetic sublattices with competing anisotropic energies, giving rise to the spin reorientation at such a high critical temperature.
RESUMEN
A new 3d-5d hybridized quadruple perovskite oxide, CaCu3Mn2Ir2O12, was synthesized by high-pressure and high-temperature methods. The Rietveld structure analysis reveals that the compound crystallizes in an [Formula: see text]-type perovskite structure with space group Im-3, where the Ca and Cu are 1:3 ordered at fixed atomic positions. At the B site the 3d Mn and the 5d Ir ions are disorderly distributed due to the rare equal +4 charge states for both of them as determined by x-ray absorption spectroscopy. The competing antiferromagnetic and ferromagnetic interactions among Cu2+, Mn4+, and Ir4+ ions give rise to spin glass behavior, which follows a conventional dynamical slowing down model.