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Ratcliff, William D.

Publications and source records attributed to Ratcliff, William D..

Effects of dimensionality on the electronic structure of Ruddlesden-Popper chromates Sr n+1 ⁢Cr n ⁢O 3⁢n+1

Transition-metal oxides host a wide variety of electronic phenomena that can be significantly influenced by the effective dimensionality of the system under consideration. These include charge, spin, and orbital orderings, as well as unconventional superconductivity. In this context, the Ruddlesden-Popper chromates Sr n+1 Cr n O 3n+1 emerge as a particularly intriguing series of materials. Formally, the chromium atom displays a rather special 4+ oxidation state throughout the entire series. However, the effective dimensionality changes from quasi-2D to 3D as n increases from 1 to ∞. As a result, the insulating antiferromagnetic behavior observed for n = 1, 2, 3 transforms into itinerant antiferromagnetism with reduced transition temperature for the n = ∞ end member of the series, i.e., the perovskite SrCrO 3 . Further, distinct orbital orderings with exotic singlet states have been predicted for these systems. However, the lack of single-crystal bulk or thin-film samples has made experimental progress difficult. Here we demonstrate the synthesis of thin films of the perovskite SrCrO 3 and the associated layered chromates via oxide molecular beam epitaxy for n = 1 to n = 5. Our electrical transport measurements reveal a gradual evolution from a strongly insulating state in Sr 2 CrO 4 to a metallic state in the end member SrCrO 3 . X-ray absorption spectroscopy measurements demonstrate a varying hybridization strength of the Cr 4+ valence electrons across the series, helping to explain the trend in conduction. Finally, density functional theory calculations further confirm the observed transport trend and identify additional distortions present in the system.

36 MATERIALS SCIENCE↗

Antiferromagnetic metal phase in an electron-doped rare-earth nickelate

Long viewed as passive elements, antiferromagnetic materials have emerged as promising candidates for spintronic devices due to their insensitivity to external fields and potential for high-speed switching. Recent work exploiting spin and orbital effects has identified ways to electrically control and probe the spins in metallic antiferromagnets, especially in non-collinear or non-centrosymmetric spin structures. The rare-earth nickelate NdNiO 3 is known to be a non-collinear antiferromagnet in which the onset of antiferromagnetic ordering is concomitant with a transition to an insulating state. In this work, we find that for low electron doping, the magnetic order on the nickel site is preserved, whereas electronically, a new metallic phase is induced. We show that this metallic phase has a Fermi surface that is mostly gapped by an electronic reconstruction driven by bond disproportionation. Furthermore, we demonstrate the ability to write to and read from the spin structure via a large zero-field planar Hall effect. Our results expand the already rich phase diagram of rare-earth nickelates and may enable spintronics applications in this family of correlated oxides.

36 MATERIALS SCIENCE↗

Liberating a hidden antiferroelectric phase with interfacial electrostatic engineering

Antiferroelectric materials have seen a resurgence of interest because of proposed applications in a number of energy-efficient technologies. Unfortunately, relatively few families of antiferroelectric materials have been identified, precluding many proposed applications. Here, we propose a design strategy for the construction of antiferroelectric materials using interfacial electrostatic engineering. We begin with a ferroelectric material with one of the highest known bulk polarizations, BiFeO 3 . By confining thin layers of BiFeO 3 in a dielectric matrix, we show that a metastable antiferroelectric structure can be induced. Application of an electric field reversibly switches between this new phase and a ferroelectric state. The use of electrostatic confinement provides an untapped pathway for the design of engineered antiferroelectric materials with large and potentially coupled responses.

42 ENGINEERING↗

Intermediate Sr 2 Co 1.5 Fe 0.5 O 6-δ Tetragonal Structure between Perovskite and Brownmillerite as a Model Catalyst with Layered Oxygen Deficiency for Enhanced Electrochemical Water Oxidation

The generation of hydrogen in an environmentally benign way is highly essential to meet future energy demands. However, in the process of splitting water electrochemically, sluggish kinetics of the oxygen evolution reaction (OER) curtails its applicability, as it drags energy input. Herein, we synthesized SrCo-Fe-O oxides to optimize their OER activity by varying the Co/Fe ratio. Among them, Sr 2 Co 1.5 Fe 0.5 O 6-δ exhibited the best OER catalytic activity in the series, with an overpotential of 318 mV at 10 mA cm -2 and Tafel slope of 44.8 mV dec -1 . High-resolution neutron powder diffraction analysis identified an intermediate structure between the perovskite and brownmillerite, with alternating layers of disorderly orientated oxygen-deficient tetrahedra and fully stoichiometric octahedra. The unique stacking of tetrahedral and octahedral units facilitates desired interactions between the electrode surface and electrolyte. Theoretical calculations revealed that increased covalency of Co 3d and O 2p in Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide is another primary contributor to its augmented water oxidation ability. As a model for developing catalysts with such an intermediate structure, the synergetic effect of oxygen vacancy and hybridization between Co 3d and O 2p assured the Sr 2 Co 1.5 Fe 0.5 O 6-δ oxide as a better catalyst for its enhanced OER activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗