arXiv subjects

Robert. J. Cava

Publications and source records attributed to Robert. J. Cava.

5 recordsLinked to original sources

arXiv2023

Hidden Hydroxides in KOH-Grown BaNiO3 Crystals: A Potential Link to Their Catalytic Behavior

The hexagonal perovskite BaNiO3, prepared via non-ceramic approaches, is known to act as a good catalyst for the oxygen-evolution reaction (OER) in alkaline media. Here we report our observation that BaNiO3 synthesized via KOH flux growth and high O2 pressure ceramic synthesis have different magnetic properties. We show that this is because the KOH flux-grown crystals made in open-air are actually a hydroxide-containing form of BaNiO3 that can be dried upon annealing in O2 flow. This work not only unveils a previously unknown aspect of the BaNiO3 OER catalyst and offers some insights into the underlying mechanism, but also suggests that hydroxide ions may be present in other hexagonal perovskite oxides prepared in wet conditions.

cond-mat.mtrl-sci↗

arXiv2023

Electron Doping of a Double Perovskite Flat-band System

Electronic structure calculations indicate that the Sr2FeSbO6 double perovskite has a flat-band set just above the Fermi level that includes contributions from ordinary sub-bands with weak kinetic electron hopping plus a flat sub-band that can be attributed to the lattice geometry and orbital interference. To place the Fermi energy in that flat band, electron doped samples with formulas Sr2-xLaxFeSbO6 (0 < x < 0.3) were synthesized and their magnetism and ambient temperature crystal structures determined by high-resolution synchrotron X-ray powder diffraction. All materials appear to display an antiferromagnetic-like maximum in the magnetic susceptibility, but the dominant spin coupling evolves from antiferromagnetic to ferromagnetic on electron doping. Which of the three sub-bands or combinations is responsible for the behavior has not been determined.

cond-mat.mtrl-sci↗

arXiv2021

Stability and superconductivity of 4d and 5d transition metal high-entropy alloys

We report the synthesis of new equimolar high-entropy alloys (HEAs) formed from five or six 4d/5d transition metals that are each from a different Group of the Periodic Table. These include MoReRuRhPt and MoReRuIrPt, which have a valence electron count (VEC) of 8 and crystallise in the hexagonal close-packed (hcp) structure, making them isoelectronic and isostructural to the elements Ru and Os and the high-pressure phase of the well-known HEA CrMnFeCoNi. Analogous HEAs with VECs of 7, 6 and 5 crystallise with multiple phases, which we rationalise using the atomic size difference, $δ$, and the electronegativity difference, $Δ$$χ$, of the constituent elements. Finally, we find our hcp and mixed hcp-$σ$ phase HEAs to be superconductors, and compare their critical temperatures to those of isostructural elements and other HEAs that have recently been reported.

cond-mat.mtrl-sci↗

arXiv2018

A Family of Pb-based Superconductors with Variable Cubic to Hexagonal Packing

We describe three previously unreported superconductors, BaPb3, Ba0.89Sr0.11Pb3 and Ba0.5Sr0.5Pb3. These three materials, together with SrPb3, form a distinctive isoelectronic family of intermetallic superconductors based on the stacking of Pb planes, with crystal structures that display a hexagonal to cubic perovskite-like progression, as rarely seen in metals. The superconducting transition temperatures (Tc) are similar for all - 2.2 K for BaPb3, 2.7 K for Ba0.89Sr0.11Pb3 and 2.6 K for Ba0.5Sr0.5Pb3, and the previously reported Tc of SrPb3, ~ 2 K, is confirmed. The materials are moderate coupling superconductors, and calculations show that the electronic densities of states at the Fermi energy are primarily contributed by Pb. The observations suggest that the Pb-stacking variation has only a minor effect on the superconductivity.

cond-mat.supr-con↗

arXiv2011

Electron doped Ca10(Pt3As8)(Fe2As2)5 and Ca10(Pt4As8)(Fe2As2)5 - High Tc superconductors with skutterudite intermediary layers

It has been argued that the very high transition temperatures of the highest Tc cuprate superconductors are facilitated by enhanced CuO2 plane coupling through the (Bi,Tl,Hg)-O intermediary layers. Whether enhanced coupling through intermediary layers can also influence Tc in the iron arsenide superconductors has never been tested due the lack of appropriate systems for study. Here we report the crystal structures and properties of two iron arsenide superconductors, Ca10(Pt3As8)(Fe2As2)5 (the 10-3-8 phase) and Ca10(Pt4As8)(Fe2As2)5 (the 10-4-8 phase). Based on -Ca-(PtnAs8)-Ca-Fe2As2- layer stacking, the most important difference in the structures lies in the structural and electronic characters of the intermediary platinum arsenide layers. Electron doping through partial substitution of Pt for Fe in the Fe2As2 layers leads to Tc of 11 K in the 10-3-8 phase and 25 K in the 10-4-8 phase. Using the chemical concepts of Zintl ion electron counting and the stability of Pt in the 5d8 configuration we argue that the dramatic difference in Tc arises because the intermediary layer is semiconducting in the 10-3-8 phase but metallic in the 10-4-8 phase, leading to enhanced interlayer coupling in the 10-4-8 phase. The results suggest that metallic intermediary layers may offer a new road to higher Tc in iron arsenide superconductors.

cond-mat.supr-con↗