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The properties of many materials can be strongly affected by the atomic valence of the contained individual elements, which may vary at surfaces and other interfaces. These variations can have a critical impact on material performance in applications. A non-destructive method for the determination of layer-by-layer atomic valence as a function of material thickness is presented for La0.7Sr0.3MnO3 (LSMO) thin films. The method utilizes a combination of bulk- and surface-sensitive X-ray absorption spectroscopy (XAS) detection modes; here, the modes are fluorescence yield and surface-sensitive total electron yield. The weighted-average Mn atomic valence as measured from the two modes are simultaneously fitted using a model for the layer-by-layer variation of valence based on theoretical model Hamiltonian calculations. Using this model, the Mn valence profile in LSMO thin film is extracted and the valence within each layer is determined to within an uncertainty of a few percent. The approach presented here could be used to study the layer-dependent valence in other systems or extended to different properties of materials such as magnetism.

We present an efficient parameterized tight-binding (TB) model which can induce the energy bands that are consistent with results from ab-initio calculations. Besides the comparison of our simple TB model to previous ones, we also supplement further neighbor interactions into the TB Hamiltonian to analyze the band structure and consider the impact of each type of TB parameters such as onsite and hopping energies, overlap terms of wave functions on the shape and position of the energy bands. Then a set of appropriate parameters is selected to reproduce reasonably important characteristics of the band structure captured by ab-initio calculations, particularly at the low energy region near the Fermi level, which is relevant for many applications. Moreover, the TB model is applied to predict the impact of a vertical electric field on the electronic properties and the thermoelectric Seebeck effect of penta-graphene. It unveils that the bandgap is strongly modulated under the external field and the intrinsic Seebeck coefficient of penta-graphene is found to be 67 times as high as that of graphene.

The Mn valence in thin film La0.7Sr0.3MnO3 was studied as a function of film thickness in the range of 1–16 unit cells with a combination of non-destructive bulk and surface sensitive X-ray absorption spectroscopy techniques. Using a layer-by-layer valence model, it was found that while the bulk averaged valence hovers around its expected value of 3.3, a significant deviation occurs within several unit cells of the surface and interface. These results were supported by first principles calculations. The surface valence increases to up to Mn3.7+, whereas the interface valence reduces down to Mn2.5+. The change in valence from the expected bulk value is consistent with charge redistribution due to the polar discontinuity at the film-substrate interface. The comparison with theory employed here illustrates how this layer-by-layer valence evolves with film thickness and allows for a deeper understanding of the microscopic mechanisms at play in this effect. These results offer insight on how the two-dimensional electron gas is created in thin film oxide alloys and how the magnetic ordering is reduced with dimensionality.

In strongly correlated oxides, heterostructures provide a powerful route to manipulate the charge, spin, orbital, and lattice degrees of freedom to create distinctive functionalities. In this work, we have achieved atomically precise interface control in YBa2Cu3O7−x/La0.7Ca0.3MnO3 (YBCO/LCMO) heterostructures and find a hidden effective doping. This mechanism is responsible for higher Tc in the sample with the MnO2-terminated interface than in that with the La0.7Ca0.3O-terminated interface. The MnO2-terminated sample also shows a larger magnetic moment of Mn together with a lower valence state. For more than a decade, the control of Tc in these heterostructures prior to this work has been solely via the variation of YBCO or LCMO thickness. This work hints at an alternative way of exploiting and exploring the interactions between superconductivity and magnetism in this system.

The coupling of the localized surface plasmon resonance of Au nanoparticles is utilized to deliver a visible-light stimulus to control conduction at the LaAlO3 /SrTiO3 interface. A giant photoresponse and the controllable metal-insulator transition are characterized at this heterointerface. This study paves a new route to optical control of the functionality at the heterointerfaces.