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  1. 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 expectedmore » 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.« less
  2. Magnetoelectric materials have great potential to revolutionize electronic devices due to the coupling of their electric and magnetic properties. Thickness varying La 0.7Sr 0.3MnO 3 (LSMO)/PbZr 0.2Ti 0.8O 3 (PZT) heterostructures were built and measured in this article by valence sensitive x-ray absorption spectroscopy. The sizing effects of the heterostructures on the LSMO/PZT magnetoelectric interfaces were investigated through the behavior of Mn valence, a property associated with the LSMO magnetization. Here, we found that Mn valence increases with both LSMO and PZT thickness. Piezoresponse force microscopy revealed a transition from monodomain to polydomain structure along the PZT thickness gradient. Themore » ferroelectric surface charge may change with domain structure and its effects on Mn valence were simulated using a two-orbital double-exchange model. The screening of ferroelectric surface charge increases the electron charges in the interface region, and greatly changes the interfacial Mn valence, which likely plays a leading role in the interfacial magnetoelectric coupling. The LSMO thickness dependence was examined through the combination of two detection modes with drastically different attenuation depths. The different length scales of these techniques' sensitivity to the atomic valence were used to estimate the depth dependence Mn valence. Finally, a smaller interfacial Mn valence than the bulk was found by globally fitting the experimental results.« less

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