The formation, phase relations, crystal chemistry and physical properties were investigated for the solid solution deriving from binary clathrate with a solubility limit of 8 Zn atoms per formula unit at 800 °C ( is a vacancy). Single-crystal x-ray data throughout the homogeneity region confirm the clathrate type I structure with cubic primitive space group type . Temperature-dependent x-ray spectra as well as heat capacity define a low-lying, almost localized, phonon branch, whereas neutron spectroscopy indicates a phonon mode with significant correlations. The transport properties are strongly determined by the Ge/Zn ratio in the framework of the structure. Increasing Zn content drives the system towards a metal-to-insulator transition; for example, shows metallic behaviour at low temperatures, whilst at high temperatures semiconducting features become obvious. A model based on a gap of the electronic density of states slightly above the Fermi energy was able to explain the temperature dependences of the transport properties. The thermal conductivity exhibits a pronounced low-temperature maximum, dominated by the lattice contribution, while at higher temperatures the electronic part gains weight. Zn-rich compositions reveal attractive Seebeck coefficients approaching −180 µV K−1 at 700 K.

Using neutron reflectometry and resonant x-ray techniques we studied the magnetic proximity effect (MPE) in superlattices composed of superconducting YBa2Cu3O7 and ferromagnetic-metallic La0.67Ca0.33MnO3 or ferromagnetic-insulating LaMnO(3+δ). We find that the MPE strongly depends on the electronic state of the manganite layers, being pronounced for the ferromagnetic-metallic La0.67Ca0.33MnO3 and almost absent for ferromagnetic-insulating LaMnO(3+δ). We also detail the change of the magnetic depth profile due to the MPE and provide evidence for its intrinsic nature.

We have investigated the structure and magnetism of self-assembled, 20 nm diameter iron oxide nanoparticles covered by an oleic acid shell for scrutinizing their structural and magnetic correlations. The nanoparticles were spin-coated on an Si substrate as a single monolayer and as a stack of 5 ML forming a multilayer. X-ray scattering (reflectivity and grazing incidence small-angle scattering) confirms high in-plane hexagonal correlation and a good layering property of the nanoparticles. Using polarized neutron reflectivity we have also determined the long range magnetic correlations parallel and perpendicular to the layers in addition to the structural ones. In a field of 5 kOe we determine a magnetization value of about 80% of the saturation value. At remanence the global magnetization is close to zero. However, polarized neutron reflectivity reveals the existence of regions in which magnetic moments of nanoparticles are well aligned, while losing order over longer distances. These findings confirm that in the nanoparticle assembly the magnetic dipole-dipole interaction is rather strong, dominating the collective magnetic properties at room temperature.

The magnetization reversal processes are discussed for exchangecoupled ferromagnetic hard/soft bilayers made from Co 0.66 Cr 0.22 Pt 0.12 (10 and 20 nm)/Ni (from 0 to 40 nm) films with out-of-plane and in-plane magnetic easy axes respectively, based on room temperature hysteresis loops and first-order reversal curve analysis. On increasing the Ni layer thicknesses, the easy axis of the bilayer reorients from out-of-plane to in-plane. An exchange bias effect, 2 consisting of a shift of the in-plane minor hysteresis loops along the field axis, was observed at room temperature after in-plane saturation. This effect was associated with specific ferromagnetic domain configurations experimentally determined by polarized neutron reflectivity. On the other hand, perpendicular exchange bias effect was revealed from the out-of-plane hysteresis loops and it was attributed to residual domains in the magnetically hard layer.