217 research outputs found
Orbital control in strained ultra-thin LaNiO/LaAlO superlattices
In pursuit of rational control of orbital polarization, we present a combined
experimental and theoretical study of single unit cell superlattices of the
correlated metal LaNiO and the band insulator LaAlO. Polarized x-ray
absorption spectra show a distinct asymmetry in the orbital response under
strain. A splitting of orbital energies consistent with octahedral distortions
is found for the case of compressive strain. In sharp contrast, for tensile
strain, no splitting is found although a strong orbital polarization is
present. Density functional theory calculations including a Hubbard U term
reveal that this asymmetry is a result of the interplay of strain and
confinement induces octahedral rotations and distortions and altered covalency
in the bonding across the interfacial Ni-O-Al apical oxygen, leading to a
charge disporportionation at the Ni sites for tensile strain.Comment: 4 pages. 5 figure
Spin-resolved photoelectron spectroscopy of Fe3O4 - Revisited
Recently Tobin et al (2007 J. Phys.: Condens. Matter 19 315218) reported on the spin-resolved photoemission study of Fe3O4(001) films, claiming magnetite being a case against half-metallicity. In the present communication we re-examine recent spin-resolved photoemission experiments on Fe3O4 and explain why their criticism is unfounded
Modulations in martensitic Heusler alloys originate from nanotwin ordering
Heusler alloys exhibiting magnetic and martensitic transitions enable applications like magnetocaloric refrigeration and actuation based on the magnetic shape memory effect. Their outstanding functional properties depend on low hysteresis losses and low actuation fields. These are only achieved if the atomic positions deviate from a tetragonal lattice by periodic displacements. The origin of the so-called modulated structures is the subject of much controversy: They are either explained by phonon softening or adaptive nanotwinning. Here we used large-scale density functional theory calculations on the Ni2MnGa prototype system to demonstrate interaction energy between twin boundaries. Minimizing the interaction energy resulted in the experimentally observed ordered modulations at the atomic scale, it explained that a/b twin boundaries are stacking faults at the mesoscale, and contributed to the macroscopic hysteresis losses. Furthermore, we found that phonon softening paves the transformation path towards the nanotwinned martensite state. This unified both opposing concepts to explain modulated martensite
Jahn-Teller stabilization of a "polar" metal oxide surface: Fe3O4(001)
Using ab initio thermodynamics we compile a phase diagram for the surface of
Fe3O4(001) as a function of temperature and oxygen pressures. A hitherto
ignored polar termination with octahedral iron and oxygen forming a wave-like
structure along the [110]-direction is identified as the lowest energy
configuration over a broad range of oxygen gas-phase conditions. This novel
geometry is confirmed in a x-ray diffraction analysis. The stabilization of the
Fe3O4(001)-surface goes together with dramatic changes in the electronic and
magnetic properties, e.g., a halfmetal-to-metal transition.Comment: 4 pages, 4 figure
Facet-Dependent Intrinsic Activity of Single Co<sub>3</sub>O<sub>4</sub> Nanoparticles for Oxygen Evolution Reaction
Deciphering the influence of nanocatalyst morphology on their catalytic activity in the oxygen evolution reaction (OER), the limiting reaction in water splitting process, is essential to develop highly active precious metal-free catalysts, yet poorly understood. The intrinsic OER activity of Co3O4 nanocubes and spheroids is probed at the single particle level to unravel the correlation between exposed facets, (001) vs. (111), and activity. Single cubes with predominant (001) facets show higher activity than multi-faceted spheroids. Density functional theory calculations of different terminations and reaction sites at (001) and (111) surfaces confirm the higher activity of the former, expressed in lower overpotentials. This is rationalized by a change in the active site from octahedral to tetrahedral Co and the potential-determining step from *OH to *O for the cases with lowest overpotentials at the (001) and (111) surfaces, respectively. This approach enables the identification of highly active facets to guide shape-selective syntheses of improved metal oxide nanocatalysts for water oxidation
Digital modulation of the nickel valence state in a cuprate-nickelate heterostructure
Layer-by-layer oxide molecular beam epitaxy has been used to synthesize
cuprate-nickelate multilayer structures of composition
(LaCuO)/LaO/(LaNiO). In a combined experimental and
theoretical study, we show that these structures allow a clean separation of
dopant and doped layers. Specifically, the LaO layer separating cuprate and
nickelate blocks provides an additional charge that, according to density
functional theory calculations, is predominantly accommodated in the
interfacial nickelate layers. This is reflected in an elongation of bond
distances and changes in valence state, as observed by scanning transmission
electron microscopy and x-ray absorption spectroscopy. Moreover, the predicted
charge disproportionation in the nickelate interface layers leads to a
thickness-dependent metal-to-insulator transition for , as observed in
electrical transport measurements. The results exemplify the perspectives of
charge transfer in metal-oxide multilayers to induce doping without introducing
chemical and structural disorder
Termination control of electronic phases in oxide thin films and interfaces: LaAlO 3/SrTiO 3(001)
A wealth of intriguing properties emerge in the seemingly simple system composed of the band insulators LaAlO 3 and SrTiO 3 such as a two-dimensional electron gas, superconductivity and magnetism. In this paper, we review the current insight obtained from first principles calculations on the mechanisms governing the behaviour of thin LaAlO 3 films on SrTiO 3(001). In particular, we explore the strong dependence of the electronic properties on the surface and interface termination, the finite film thickness, lattice polarization and defects. A further aspect that is addressed is how the electronic behaviour and functionality can be tuned by an SrTiO 3 capping layer, adsorbates and metallic contacts. Lastly, we discuss recent reports on the coexistence of magnetism and superconductivity in this system for what they might imply about the electronic structure of this system
Interface magnetism in Fe2O3/FeTiO3-heterostructures
To resolve the microscopic origin of magnetism in the Fe2O3/FeTiO3-system, we
have performed density functional theory calculations taking into account
on-site Coulomb repulsion. By varying systematically the concentration,
distribution and charge state of Ti in a hematite host, we compile a phase
diagram of the stability with respect to the end members and find a clear
preference to form layered arrangements as opposed to solid solutions. The
charge mismatch at the interface is accommodated through Ti4+ and a
disproportionation in the Fe contact layer into Fe2+, Fe3+, leading to
uncompensated moments in the contact layer and giving first theoretical
evidence for the lamellar magnetism hypothesis. This interface magnetism is
associated with impurity levels in the band gap showing halfmetallic behavior
and making Fe2O3/FeTiO3 heterostructures prospective materials for spintronics
applications.Comment: 4 pages, 3 figure
Built-in and induced polarization across LaAlO/SrTiO heterojunctions
Ionic crystals terminated at oppositely charged polar surfaces are inherently
unstable and expected to undergo surface reconstructions to maintain
electrostatic stability. Essentially, an electric field that arises between
oppositely charged atomic planes gives rise to a built-in potential that
diverges with thickness. In ultra thin film form however the polar crystals are
expected to remain stable without necessitating surface reconstructions, yet
the built-in potential has eluded observation. Here we present evidence of a
built-in potential across polar \lao ~thin films grown on \sto ~substrates, a
system well known for the electron gas that forms at the interface. By
performing electron tunneling measurements between the electron gas and a
metallic gate on \lao ~we measure a built-in electric field across \lao ~of 93
meV/\AA. Additionally, capacitance measurements reveal the presence of an
induced dipole moment near the interface in \sto, illuminating a unique
property of \sto ~substrates. We forsee use of the ionic built-in potential as
an additional tuning parameter in both existing and novel device architectures,
especially as atomic control of oxide interfaces gains widespread momentum.Comment: 6 pages, 4 figures. Submitted to Nature physics on May 1st, 201
- …