Electronic self-doping of Mo-states in A2FeMoO6 (A=Ca, Sr and Ba) half-metallic ferromagnets - a Nuclear Magnetic Resonance study

A systematic study of (A,A')2FeMoO6 (A,A'=Ca, Sr, Ba) ferromagnetic oxides with double perovskite structure has been performed using 95,97Mo and 57Fe NMR spectroscopy. These oxides are isoelectronic but have substantially different Curie temperatures. The NMR analysis provides clear evidence that the magnetic moment at Mo sites is not constant but varies sensitively with the ionic size of the alkaline ions. The 95,97Mo frequency, and thus the electronic charge at Mo ions, is found to be smaller in Ba and Ca than in Sr-based oxides. The charge release from Mo sites is accompanied by an uptake at Fe sites, and thus a self-doping Fe-Mo process is observed. This process is controlled by relevant structural parameters: the Fe-O-Mo bond length and bending. A clear relationship between the Curie temperature and the magnetic moment and thus electron density at Mo sites has been disclosed. The relevance of these findings for the understanding of ferromagnetic coupling in double perovskites is discussed.Comment: 26 pages, 8 figure

Layered oxychalcogenide in the Bi–Cu–O–Se system as good thermoelectric materials

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Corrosion of titanium and zirconium under Ar irradiation in the low MeV range: an XPS and SE study

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Photoswitchable 11 nm CsCoFe Prussian Blue Analogue Nanocrystals with High Relaxation Temperature

International audiencePhotoswitchable 11 nm nanocrystals with the coordination network Cs{Co[Fe(CN)6]} were obtained using a template-free method. The nanocrystals were recovered from the colloidal solutions as solid materials surrounded by cetyltrimethylammonium (CTA) cations or embedded in the organic polymer polyvinylpyrrolidone (PVP). Complementary magnetic, spectroscopic, and structural techniques, including EPR spectroscopy, reveal a majority (∼70%) of the low-spin and photoactive diamagnetic CoIIIFeII pairs located in the core of the nanocrystals and a mixture of CoIIFeII and CoIIFeIII species present mainly within the shell of the objects. While bulk compounds with similar vacancy concentration do not exhibit noticeable photoinduced charge transfer, the observed photoactivity of the nanocrystals is ascribed to their nanometric size. The relaxation temperature of the photoinduced state shifts upward by ∼55 K when PVP is replaced by CTA. This is ascribed to the larger rigidity of the dense CsCoFe_CTA material, whose metastable state is lower than that for CsCoFe_PVP, leading to a larger relaxation energy barrier and, therefore, to a higher relaxation temperature