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Interface-dominated materials such as nanocrystalline thin films have emerged as an enthralling class of materials able to engineer functional properties of transition metal oxides widely used in energy and information technologies. In particular, it has been proved that strain-induced defects in grain boundaries of manganites deeply impact their functional properties by boosting their oxygen mass transport while abating their electronic and magnetic order. In this work, the origin of these dramatic changes is correlated for the first time with strong modifications of the anionic and cationic composition in the vicinity of strained grain boundary regions. We are also able to alter the grain boundary composition by tuning the overall cationic content in the films, which represents a new and powerful tool, beyond the classical space charge layer effect, for engineering electronic and mass transport properties of metal oxide thin films useful for a collection of relevant solid state devices.

Strain effects on epitaxial thin films of LaNiO3 grown on different single crystalline substrates are studied by Raman scattering and first-principles simulation. New Raman modes, not present in bulk or fully-relaxed films, appear under both compressive and tensile strains, indicating symmetry reductions. Interestingly, the Raman spectra and the underlying crystal symmetry for tensile and compressively strained films are different. Extensive mapping of LaNiO3 phase stability is addressed by simulations, showing that a variety of crystalline phases are indeed stabilized under strain which may impact the electronic orbital hierarchy. The calculated Raman frequencies reproduce the principal features of the experimental spectra, supporting the validity of the multiple strain-driven structural transitions predicted by the simulations., Comment: 18 pages, 7 figures

Polarization dependent Raman scattering experiments realized on single GaAs nanowires with different percentages of zinc-blende and wurtzite structure are presented. The selection rules for the special case of nanowires are found and discussed. In the case of zinc-blende, the transversal optical mode E1(TO) at 267 cm-1 exhibits the highest intensity when the incident and analyzed polarization are parallel to the nanowire axis. This is a consequence of the nanowire geometry and dielectric mismatch with the environment, and in quite good agreement with the Raman selection rules. We also find a consistent splitting of 1 cm-1 of the E1(TO). The transversal optical mode related to the wurtzite structure, E2H, is measured between 254 and 256 cm-1, depending on the wurtzite content. The azymutal dependence of E2H indicates that the mode is excited with the highest efficiency when the incident and analyzed polarization are perpendicular to the nanowire axis, in agreement with the selection rules. The presence of strain between wurtzite and zinc-blende is analyzed by the relative shift of the E1(TO) and E2H modes. Finally, the influence of the surface roughness in the intensity of the longitudinal optical mode on {110} facets is presented., Comment: 28 pages, 12 figures. to be published in Phys. Rev. B

The structural and optical properties of 3 different kinds of GaAs nanowires with 100% zinc-blende structure and with an average of 30% and 70% wurtzite are presented. A variety of shorter and longer segments of zinc-blende or wurtzite crystal phases are observed by transmission electron microscopy in the nanowires. Sharp photoluminescence lines are observed with emission energies tuned from 1.515 eV down to 1.43 eV when the percentage of wurtzite is increased. The downward shift of the emission peaks can be understood by carrier confinement at the interfaces, in quantum wells and in random short period superlattices existent in these nanowires, assuming a staggered band-offset between wurtzite and zinc-blende GaAs. The latter is confirmed also by time resolved measurements. The extremely local nature of these optical transitions is evidenced also by cathodoluminescence measurements. Raman spectroscopy on single wires shows different strain conditions, depending on the wurtzite content which affects also the band alignments. Finally, the occurrence of the two crystallographic phases is discussed in thermodynamic terms., Comment: 24 pages

We report on the structural and magnetic characterization of (110) and (001) La2/3Ca1/3MnO3 (LCMO) epitaxial thin films simultaneously grown on (110) and (001)SrTiO3 substrates, with thicknesses t varying between 8 nm and 150 nm. It is found that while the in-plane interplanar distances of the (001) films are strongly clamped to those of the substrate and the films remain strained up to well above t=100 nm, the (110) films relax much earlier. Accurate determination of the in-plane and out-of-plane interplanar distances has allowed concluding that in all cases the unit cell volume of the manganite reduces gradually when increasing thickness, approaching the bulk value. It is observed that the magnetic properties (Curie temperature and saturation magnetization) of the (110) films are significantly improved compared to those of (001) films. These observations, combined with 55Mn-nuclear magnetic resonance data and X-ray photoemission spectroscopy, signal that the depression of the magnetic properties of the more strained (001)LCMO films is not caused by an elastic deformation of the perovskite lattice but rather due to the electronic and chemical phase separation caused by the substrate-induced strain. On the contrary, the thickness dependence of the magnetic properties of the less strained (110)LCMO films are simply described by the elastic deformation of the manganite lattice. We will argue that the different behavior of (001) and (110)LCMO films is a consequence of the dissimilar electronic structure of these interfaces., Comment: 16 pages, 15 figures