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Abstract: The design of active and durable catalysts for the H2O/O2 interconversion is one of the major challenges of electrocatalysis for renewable energy. The oxygen evolution reaction (OER) is catalyzed by SrRuO3 with low potentials (ca. 1.35 VRHE), but the catalyst’s durability is insufficient. Here we show that Na doping enhances both activity and durability in acid media. DFT reveals that whereas SrRuO3 binds reaction intermediates too strongly, Na doping of ~0.125 leads to nearly optimal OER activity. Na doping increases the oxidation state of Ru, thereby displacing positively O p-band and Ru d-band centers, weakening Ru-adsorbate bonds. The enhanced durability of Na-doped perovskites is concomitant with the stabilization of Ru centers with slightly higher oxidation states, higher dissolution potentials, lower surface energy and less distorted RuO6 octahedra. These results illustrate how high OER activity and durability can be simultaneously engineered by chemical doping of perovskites.

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Abstract: The effect of ion etching on exchange bias in IrMn3/Co70Fe30 bilayers is investigated. In spite of the reduction of saturation magnetization caused by the embedding of Ir from the capping layer into the Co70Fe30 layer during the etching process, the exchange bias in samples with the same thickness of the Co70Fe30 layer is reducing in proportion to the etching power. X-ray magnetic circular dichroism measurements revealed the emergence of an uncompensated Mn magnetization after etching, which is antiferromagnetically coupled to the ferromagnetic layer. This suggests etching induced formation of small interfacial FeMn regions which leads to the decrease of effective exchange coupling between ferromagnetic and antiferromagnetic layers.

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Abstract: The ground-state orbital occupancy of the Ru4+ ion in Ca2−xLaxRuO4[x=0, 0.05(1), 0.07(1), and 0.12(1)] was investigated by performing x-ray absorption spectroscopy (XAS) in the vicinity of the O K edge as a function of the angle between the incident beam and the surface of the single-crystal samples. A minimal model of the hybridization between the O 2p states probed at the K edge and the Ru 4d orbitals was used to analyze the XAS data, allowing the ratio of hole occupancies nxy/nyz,zx to be determined as a function of doping and temperature. For the samples displaying a low-temperature insulating ground state (x≤0.07), nxy/nyz,zx is found to increase significantly with increasing doping, with increasing temperature acting to further enhance nxy/nyz,zx. For the x=0.12 sample, which has a metallic ground state, the XAS spectra are found to be independent of temperature and not to be describable by the minimal hybridization model, while being qualitatively similar to the spectra displayed by the x≤0.07 samples above their insulating to metallic transitions. To understand the origin of the evolution of the electronic structure of Ca2−xLaxRuO4 across its phase diagram, we have performed theoretical calculations based on a model Hamiltonian, comprising electron-electron correlations, crystal field Δ, and spin-orbit coupling λ, of a Ru-O-Ru cluster, with realistic values used to parametrize the various interactions taken from the literature. Our calculations of the Ru hole occupancy as a function of Δ/λ provide an excellent description of the general trends displayed by the data. In particular they establish that the enhancement of nxy/nyz,zx is driven by significant modifications to the crystal field as the tetragonal distortion of the RuO6 octahedral changes from compressive to tensile with La doping. We have also used our model to show that the hole occupancy of the O 2p and Ru 4d orbitals displays the same general trend as a function of Δ/λ, thus validating the minimal hybridization model used to analyze the data. In essence, our results suggest that the predominant mechanism driving the emergence of the low-temperature metallic phase in La-doped Ca2RuO4 is the structurally induced redistribution of holes within the t2g orbitals, rather than the injection of free carriers.

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Abstract: Magnetic topological insulators (MTIs) are a novel materials class in which a topologically nontrivial electronic band structure coexists with long‐range ferromagnetic order. The ferromagnetic ground state can break time‐reversal symmetry, opening a gap in the topological surface states whose size is dependent on the magnitude of the magnetic moment. Doping with rare earth ions is one way to introduce higher magnetic moments into a material, however, in Bi2Te3 bulk crystals, the solubility limit is only a few percent. Using molecular beam epitaxy for the growth of doped (Sb,Bi)2(Se,Te)3 TI thin films, high doping concentrations can be achieved while preserving their high crystalline quality. The growth, structural, electronic, and magnetic properties of Dy, Ho, and Gd doped TI thin films will be reviewed. Indeed, high magnetic moments can be introduced into the TIs, which are, however, not ferromagnetically ordered. By making use of interfacial effects, magnetic long‐range order in Dy doped Bi2Te3, proximity‐coupled to the MTI Cr:Sb2Te3, has been achieved. Clearly, engineered MTI heterostructures offer new possibilities that combine the advantageous properties of different layers, and thus provide an ideal materials platform enabling the observation new quantum effects at higher temperatures.

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Abstract: We demonstrate the emergence and control of magnetic phases between magnetite (Fe3O4), a ferrimagnetic halfmetal, and SrTiO3, a transparent non-magnetic insulator considered the bedrock of oxide-based electronics. The Verwey transition (TV) was detected to persist from bulk-like down to ultrathin Fe3O4 films, decreasing from 117±4 K (38 nm) to 25±4 K (2 nm), respectively. Element-selective electronic and magnetic properties of the ultrathin films and buried interfaces are studied by angle-dependent HAXPES and XMCD techniques. We observe a reduction of Fe2+ ions with decreasing film thickness, accompanied by an increase of Fe3+ ions in both tetrahedral and octahedral sites, and conclude on the formation of a magnetically active ferrimagnetic 2 u.c. γ-Fe2O3 intralayer. In order to manipulate the interfacial magnetic phase, a postannealing process causes the controlled reduction of the γ-Fe2O3 that finally leads to stoichiometric and ferrimagnetic Fe3O4/SrTiO3 (001) heterointerfaces.