Using first-principles density functional theory, we have investigated the electronic and magnetic properties of recently synthesized and characterized 5d double-perovskites Sr2BOsO6 (B=Y, In, Sc). The electronic structure calculations show that in all compounds, the Os5+ (5d3) site is the only magnetically active one, while Y3+, In3+ and Sc3+ remain in nonmagnetic states, with Sc/Y and In featuring d0 and d10 electronic configurations, respectively. Our studies reveal the important role of closed-shell (d10) versus open-shell (d0) electronic configurations of the nonmagnetic sites in determining the overall magnetic exchange interactions. Although the magnetic Os5+ (5d3) site is the same in all compounds, the magnetic super-exchange interactions mediated by non-magnetic Y/In/Sc species are strongest for Sr2ScOsO6, weakest for Sr2InOsO6, and intermediate in case of the Y (d0), due to different energy overlaps between Os-5d and Y/In/Sc-d states. This explains the experimentally observed substantial differences in the magnetic transition temperatures of these materials, despite of an identical magnetic site and underlying magnetic ground state. Furthermore, short range Os-Os exchange-interactions are more prominent than long range Os-Os interactions in these compounds, which contrasts with the behavior of other 3d-5d double-perovskites.
We have investigated the structural and magnetic properties of antiferroelectric $A_2$CoTeO$_6$ perovskites with $A$ = Cd, Ca, Sr, Pb, and Ba. All compounds are antiferromagnetic at low temperatures, with the antiferromagnetic transition temperature slightly decreasing with decreasing ionic size of the $A$ cation. Such a decrease in antiferromagnetic interaction is not observed in $A^{2+}_2$Co$M^{6+}$O$_6$ materials with other $M^{6+}$ cations of similar ionic sizes, suggesting that Te$^{6+}$ cations affect the electronic and in turn the magnetic structure of the system.
Double perovskites extend the design space for new materials, and they often host phenomena that don't exist in their parent perovskite compounds. Here, we present a detailed first principles study of the correlated double perovskite Sr$_2$VNbO$_6$, where inter-cationic charge transfer and strength of electronic correlations depend strongly on the cation order. By using Density Functional Theory + Embedded Dynamical Mean Field Theory, we show that this compound has a completely different electronic structure than either of its parent compounds despite V and Nb being from the same group in the …
Polycrystalline samples of double perovskites Ba2BOsO6 (B = Sc, Y, In) were synthesized by solid state reactions. They adopt the cubic double perovskite structures (space group, Fm-3m) with ordered B and Os arrangements. Ba2BOsO6 (B = Sc, Y, In) show antiferromagnetic transitions at 93 K, 69 K, and 28 K, respectively. The Weiss-temperatures are -590 K for Ba2ScOsO6, -571 K for Ba2YOsO6, and -155 K for Ba2InOsO6. Sc3+ and Y3+ have the open-shell d0 electronic configuration, while In3+ has the closed-shell d10. This indicates that a d0 B-type cation induces stronger overall magnetic exchange int…
Here we show that the B-site cation (Fe/Mo) ordering in the double-perovskite magnetoresistor, Sr2FeMoO6, is controlled by either kinetics or thermal equilibrium depending on the temperature range. In order to enhance the ordering, long synthesis periods at moderate temperatures are thus required. Employment of a special oxygen-getter-controlled low-O2-pressure encapsulation technique for the sample synthesis enabled us to use long heating periods without evident evaporation of Mo, and thereby reach the thermal equilibrium state and a high degree of B-site cation order. For samples fired at 11…
Efficient thermoelectric materials should present large Seebeck coefficient, high electrical conductivity and low thermal conductivity. An enhanced Seebeck coefficient can be obtained from materials where the Fermi level can be aligned with a large and narrow peak of the density of states, particularly when a substantial band valley degeneracy occurs. A high electrical conductivity comes as a consequence of large conductive hopping paths between the atoms of the material. Both physical quantities can be decoupled and optimized independently if their origins can be ascribed to different sets of…
Due of its polymorphism, Mn$_2$FeSbO$_6$ can be synthesized at high pressures and temperatures as a ferrimagnetic ilmenite or an antiferromagnetic perovskite. The structural phase transformation is discussed in detail, and magnetic structures are proposed for both phases. The high-pressure Mn$_2$FeSbO$_6$ polymorph is a rare example of $A_2 B'B"$O$_6$ perovskite with solely Mn cations on the $A$-site. Fe and Sb cations are ordered on the $B$-sites. Theoretical calculations for the perovskite phase suggest a complex magnetic structure, holding an electronic polarization.
Perovskite-like oxides $AB'_{1/2}B''_{1/2}$O$_3$ may experience different ordering degrees of $B$-cations, that can be varied by suitable synthesis conditions or post-synthesis treatment. In this work the earlier proposed statistical model of order-disorder phase transitions of $B$-cations is extended to account for the effect of pressure. Depending on composition, pressure is found to either increase or decrease the order-disorder phase transition temperature. The change of transition temperature due to pressure in many cases reaches several hundreds of kelvin at pressures accessible in labor…
The oxygen-exchange behavior has been studied in half-doped manganese and cobalt perovskite oxides. We have found that the oxygen diffusivity in Gd_{0.5}Ba_{0.5}MnO_{3-δ} can be enhanced by orders of magnitude by inducing crystallographic ordering among lanthanide and alkali-earth ions in the A-site sublattice. Transformation of a simple cubic perovskite, with randomly occupied A-sites, into a layered crystal GdBaMn_2O_{5+x} (or isostructural GdBaCo_2O_{5+x} for cobalt oxide) with alternating lanthanide and alkali-earth planes reduces the oxygen bonding strength and provides disorder-free chan…
Anisotropic superexchange interaction is one of the most important interactions in realizing exotic quantum magnetism, which is traditionally regarded to originate from magnetic ions and has no relation with the nonmagnetic ions. In our work, by studying a multi-orbital Hubbard model with spin-orbit coupling on both magnetic cations and nonmagnetic anions, we analytically demonstrate that the spin-orbit coupling on nonmagnetic anions alone can induce antisymmetric Dzyaloshinskii-Moriya interaction, symmetric anisotropic exchange and single ion anisotropy on the magnetic ions and thus it actual…
B-site ordered A$_2$B'B''O$_6$ double perovskites have a variety of applications as magnetic materials. Here we show that diamagnetic $d^{10}$ and $d^0$ B'' cations have a significant effect on the magnetic interactions in these materials. We present a neutron scattering and theoretical study of the Mn$^{2+}$ double perovskite Ba$_2$MnTeO$_6$ with a $4d^{10}$ Te$^{6+}$ cation on the B''-site. It is found to be a Type I antiferromagnet with a dominant nearest-neighbor $J_1$ interaction. In contrast, the $5d^0$ W$^{6+}$ analogue Ba$_2$MnWO$_6$ is a Type II antiferromagnet with a significant next…
A three-step route has been developed for the synthesis of a new oxygen-ordered double perovskite, BaYMn2O5.5 or Ba2Y2Mn4O11. (i) The A-site cation ordered perovskite, BaYMn2O5+d, is first synthesized at d ~ 0 by an oxygen-getter-controlled low-O2-pressure encapsulation technique utilizing FeO as the getter for excess oxygen. (ii) The as-synthesized, oxygen-deficient BaYMn2O5.0 phase is then readily oxygenated to the d ~ 1 level by means of 1-atm-O2 annealing at low temperatures. (iii) By annealing this fully-oxygenated BaYMn2O6.0 in flowing N2 gas at moderate temperatures the new intermediate…
We perform a comparative magnetic study on two series of rare-earth (RE) based double perovskite iridates RE2BIrO6 (RE=Pr,Nd,Sm-Gd;B=Zn,Mg), which show Mott insulating state with tunable charge energy gap from ~330 meV to ~560 meV by changing RE cations. For nonmagnetic RE=Eu cations, Eu2MgIrO6 shows antiferromagnetic (AFM) order and field-induced spin-flop transitions below Néel temperature (TN) in comparison with the ferromagnetic (FM)-like behaviors of Eu2ZnIrO6 at low temperatures. For magnetic-moment-containing RE ions, Gd2BIrO6 show contrasting magnetic behaviors with FM-like transition …
We report electron spin resonance (ESR) spectroscopy results on the double perovskite Ba$_2$YIrO$_6$. On general grounds, this material is expected to be nonmagnetic due to the strong coupling of the spin and orbital momenta of Ir$^{5+}$ (5$d^4$) ions. However, controversial experimental reports on either strong antiferromagnetism with static order at low temperatures or just a weakly paramagnetic behavior have triggered a discussion on the breakdown of the generally accepted scenario of the strongly spin-orbit coupled ground states in the 5$d^4$ iridates and the emergence of a novel exotic ma…
ABO3 perovskite multiferroic La0.5Bi0.5Mn0.5Fe0.5O3.09 where the B-site cations is responsible for the magnetic properties and the A-site cation with lone pair electron is responsible for the ferroelectric properties was synthesized at normal conditions. This oxide exhibits a ferromagnetic transition around 240 K with a well defined hysteresis loop, and a significant reversible remnant polarization below 67K similar to ferroelectric behavior. The magnetic interaction is interpreted by the ferromagnetic Fe3+-O-Mn3+ and antiferromagnetic Fe3+(Mn3+)-O-Fe3+(Mn3+) interactions competed each other, …
Establishing the physical mechanism governing exchange interactions is fundamental for exploring exotic phases such as the quantum spin liquids (QSLs) in real materials. In this work, we address exchange interactions in Sr2CuTe$_{1-x}$W$_{x}$O, a series of double perovskites that realize the spin-1/2 square lattice and were suggested to harbor a QSL ground state arising from random distribution of non-magnetic ions. Our {\it ab initio} multi-reference configuration interaction calculations show that replacing Te atoms with W atoms changes the dominant couplings from nearest to next-nearest nei…
For 4$d^1$ and 5$d^1$ spin-orbit-coupled electron configurations, the notion of nonmagnetic j=3/2 quartet ground state discussed in classical textbooks is at odds with the observed variety of magnetic properties. Here we throw fresh light on the electronic structure of 4$d^1$ and 5$d^1$ ions in molybdenum- and osmium-based double-perovskite systems and reveal different kinds of on-site many-body physics in the two families of compounds: while the sizable magnetic moments and $g$ factors measured experimentally are due to both metal $d$-ligand $p$ hybridization and dynamic Jahn-Teller interacti…
We report a comprehensive investigation of Ln2NiIrO6 (Ln = La, Pr, Nd) using thermodynamic and transport properties, neutron powder diffraction, resonant inelastic x-ray scattering, and density functional theory (DFT) calculations to investigate the role of A-site cations on the magnetic interactions in this family of hybrid 3d-5d-4f compositions. Magnetic structure determination using neutron diffraction reveals antiferromagnetism for La2NiIrO6, a collinear ferrimagnetic Ni/Ir state that is driven to long range antiferromagnetism upon the onset of Nd ordering in Nd2NiIrO6, and a non-collinear…
A quantum spin liquid state has long been predicted to arise in spin-1/2 Heisenberg square-lattice antiferromagnets at the boundary region between Néel (nearest-neighbor interaction dominates) and columnar (next-nearest-neighbor dominates) antiferromagnetic order. However, there are no known compounds in this region. Here we use $d^{10}$-$d^0$ cation mixing to tune the magnetic interactions on the square lattice while simultaneously introducing disorder. We find spin-liquid-like behavior in the double perovskite Sr$_2$Cu(Te$_{0.5}$W$_{0.5}$)O$_6$, where the isostructural end phases Sr$_2$CuTeO…
The magnetism of the double perovskite compounds \SLFCOx\ ($x$ = 0, 1, 2) are contrasted using magnetization, neutron diffraction and electron paramagnetic resonance with the support from density functional theory calculations. \LFCO\ is identified as a long-range ordered antiferromagnet displaying a near-room temperature transition at $T_N$ = 270~K, accompanied by a low temperature structural phase transition at $T_S$ = 200~K. The structural phase transformation at $T_S$ occurs from $R\overline{3}c$ at 300~K to $Pnma$ at 200~K. The density functional theory calculations support an insulating …
The first examples of single crystal epitaxial thin films of a high entropy perovskite oxide are synthesized. Pulsed laser deposition is used to grow the configurationally disordered ABO3 perovskite, Ba(Zr0.2Sn0.2Ti0.2Hf0.2Nb0.2)O3, epitaxially on SrTiO3 and MgO substrates. X-ray diffraction and scanning transmission electron microscopy demonstrate that the films are single phase with excellent crystallinity and atomically abrupt interfaces to the underlying substrates. Atomically-resolved electron energy loss spectroscopy mapping shows a uniform and random distribution of all B-site cations. …
The role of rare-earth (R) ions on the magnetodielectric (MD) coupling is always intriguing and markedly different for different systems. Although many reports are available concerning this aspect in frustrated 3d-transition metal oxides, no such reports exist on higher d (4d/5d)-orbital based systems due to the rare availability of highly insulating 4d/5d-systems. Here, we systematically investigated the magnetic, dielectric, ferroelectric and magnetodielectric behavior of the 6H-perovskites Ba3RRu2O9 for different R-ions, namely, R= Sm, Tb and Ho, which magnetically order at 12, 9.5 and 10.2…
Anti-site disordering in Sr2FeMoO6 double perovskites (containing Mo atoms at Fe positions, and viceversa) has recently been shown to have a dramatic influence in their magnetic and magnetotransport properties. In the present study, two polycrystalline Sr2FeMoO6 samples showing different degrees of anti-site disorder (a nominally 'ordered' sample with 70% of cationic ordering and a nominally 'disordered' sample with 18% of cationic ordering) have been examined by magnetic measurements and neutron powder diffraction (NPD) techniques in the 15-500K temperature range. Our main finding is that the…
In the family of double perovskites, colossal magnetoresistance (CMR) has been so far observed only in half-metallic ferrimagnets such as the known case Sr$_2$FeMoO$_6$ where it has been assigned to the tunneling MR at grain boundaries due to the half-metallic nature. Here we report a new material-Tl$_2$NiMnO$_6$, a relatively ordered double perovskite stablized by the high pressure and high temperature synthesis-showing CMR in the vicinity of its Curie temperature. We explain the origin of such effect with neutron diffraction experiment and electronic structure calculations that reveal the ma…
Remarkably, doping isovalent $d^{10}$ and $d^0$ cations onto the $B$'' site in $A_2B$'$B$''O$_6$ double perovskites has the power to direct the magnetic interactions between magnetic $B$' cations. This is due to changes in orbital hybridization, which favors different superexchange pathways, and leads to the formation of alternative magnetic structures depending on whether $B$'' is $d^{10}$ or $d^0$. Furthermore, the competition generated by introducing mixtures of $d^{10}$ and $d^0$ cations can drive the material into the realms of exotic quantum magnetism. Here, a W$^{6+}$ $d^0$ dopant was i…
Local configurational disorder can have a dominating role in the formation of macroscopic functional responses in strongly correlated materials. Here, we use entropy-stabilization synthesis to create single crystal epitaxial ABO3 perovskite thin films with equal atomic concentration of 3d transition metal cations on the B-site sublattice. X-ray diffraction, atomic force microscopy, and scanning transmission electron microscopy of La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 (L5BO) films demonstrate excellent crystallinity, smooth film surfaces, and uniform mixing of the 3d transition metal cations througho…
