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Register a new userLaSrVMoO$_6$: A case study for $A$-site covalency-driven local cationic order in double perovskites
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An unusual atomic scale chemical fluctuation in LaSrVMoO$_6$, in terms of narrow patches of La,V and Sr,Mo-rich phases, has been probed in detail to understand the origin of such a chemical state. Exhaustive tuning of the equilibrium synthesis parameters showed that the extent of phase separation can never be melted down below an unit cell dimension making it impossible to achieve the conventional $B$-site ordered structure, which establishes that the observed `inhomogeneous patch-like structure with minimum dimension of few angstroms is a reality in LaSrVMoO$_6$. Therefore, another type of local chemical order, hitherto unknown in double perovskites, gets introduced here. X-ray diffraction, electron microscopy elemental mapping, magnetic, and various spectroscopic studies have been carried out on samples, synthesized under different conditions. These experimental results in conjunction with {it ab-initio} electronic structure calculation revealed that it is the energy stability, gained by typical La-O covalency as in LaVO$_3$, that leads to the preferential La,V and Sr,Mo ionic proximity, and the consequent patchy structure.
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Recent experimental and theoretical work has shown that the double perovskite NaLaMnWO$_6$ exhibits antiferromagnetic ordering owing to the Mn $d$ states, and computational studies further predict it to exhibit a spontaneous electric polarization due to an improper mechanism for ferroelectricity [King textit{et al., Phys. Rev. B}, 2009, textbf{79}, 224428; Fukushima textit{et al., Phys. Chem. Chem. Phys.}, 2011, textbf{13}, 12186], which make it a candidate multiferroic material. Using first-principles density functional calculations, we investigate nine isostructural and isovalent $AA^{prime}$MnWO$_6$ double perovskites ($A$=Na, K, and Rb; $A^{prime}$=La, Nd, and Y) with the aim of articulating crystal-chemistry guidelines describing how to enhance the magnitude of the electric polarization through chemical substitution of the $A$-site while retaining long-range magnetic order. We find that the electric polarization can be enhanced by up to 150% in compounds which maximize the difference in the ionic size of the $A$ and $A^{prime}$ cations. By examining the tolerance factors, bond valences, and structural distortions (described by symmetry-adapted modes) of the nine compounds, we identify the atomic scale features that are strongly correlated with the ionic and electronic contributions to the electric polarization. We also find that each compound exhibits a purely electronic remnant polarization, even in the absence of a displacive polar mode. The analysis and design strategies presented here can be further extended to additional members of this family ($B$=Fe, Co, etc.), and the improper ferroelectric nature of the mechanism allows for the decoupling of magnetic and ferroelectric properties and the targeted design of novel multiferroics.
Given the consensus that pressure improves cation order in most of known materials, a discovery of pressure-induced disorder could require reconsideration of order-disorder transition in solid state physics/chemistry and geophysics. Double perovskites Y2CoIrO6 and Y2CoRuO6 synthesized at ambient pressure show B-site order, while the polymorphs synthesized at 6 and 15 GPa are partially-ordered and disordered respectively. With the decrease of ordering degrees, the lattices are shrunken and the crystal structures alter from monoclinic to orthorhombic symmetry. Correspondingly, long-range ferrimagnetic order in the B-site ordered phases are gradually overwhelmed by B-site disorder. Theoretical calculations suggest that unusual unit cell compressions under external pressures unexpectedly stabilize the disordered phases of Y2CoIrO6 and Y2CoRuO6.
Solar thermochemical hydrogen production (STCH) is a renewable alternative to hydrogen produced using fossil fuels. While serial bulk experimental methods can accurately measure STCH performance, screening chemically complex materials systems for new promising candidates is more challenging. Here we identify double-site Ce-substituted (Ba,Sr)MnO3 oxide perovskites as promising STCH candidates using a combination of bulk synthesis and high-throughput thin film experiments. The Ce substitution on the B-site in 10H-BaMnO3 and on the A-site in 4P-SrMnO3 lead to 2-3x higher hydrogen production compared to CeO2, but these bulk single-site substituted perovskites suffer from incomplete reoxidation. Double-site Ce substitution on both A- and B-site in (Ba,Sr)MnO3 thin films increases Ce solubility and extends the stability of 10H and 4P structures, which is promising for their thermochemical reversibility. This study demonstrates a high-throughput experimental method for screening complex oxide materials for STCH applications.
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We report the comprehensive experimental results identifying the magnetic spin ordering and the magnetization dynamics of a double perovskite Pr2CoFeO6 by employing the (dc and ac) magnetization, powder neutron diffraction (NPD) and X-ray magnetic circular dichroism (XMCD) techniques. X-ray diffraction and neutron diffraction studies revealed that Pr2CoFeO6 adopts a B-site disordered orthorhombic structure with space group Pnma. Additionally, ab initio band structure calculations performed on this system suggested an insulating anti-ferromagnetic (Fe-Fe) ground state. Magnetometry study showed the system to possess a spectrum of interesting magnetic phases including long range antiferromagnetic (canted) spin ordering (TN ~269 K), Griffiths phase, re-entrant cluster glass (RCG) (TG~ 34 K) and exchange bias. However, the NPD study divulged the exhibition of a long range G-type (below TN ~269 K) of spin ordering by Fe spins. Spin dynamics study by ac susceptibility technique confirmed the system possessing long range ordering at higher temperatureundergoes a RCG transition at ~34 K. Existence of Griffiths phase was confirmed by non-analytic field variation of magnetization and Heisenberg type temporal spin relaxation above long range ordering temperature TN ~269 K. The anti-site disorder related to the B-sites (Co/Fe) is found to be the main driving force forthe observed multiple magnetic phases. Furthermore, the electronic structure probed by the X-ray absorption spectroscopy (XAS) study suggested a nominal valance state of +3 for both of the B-site ions (Co/Fe) which in turn triggered the anti-site disorder in the system. Magnetic, XRD, NPD and XAS analysis yielded a low spin state (LS) for the Co3+ ions. The random non-magnetic dilution of magnetic Fe3+ (HS) ions by Co3+ (LS) ions essentially played a crucial role in manifesting the magnetic properties of the system.
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