Resumen de Synthesis and advanced structural and magnetic characterization of mesoporous transition metal–doped SnO? powders and films /
This Thesis dissertation covers the synthesis by means of nanocasting and evaporation–induced self–assembly (EISA) methods as well as the advanced characterization of Ni, Cu–doped mesoporous SnO2 powders and films. The origin of the magnetic properties in these materials is also discussed in detail.
Firstly, ordered mesoporous SnO2 powders doped with different Ni amounts were synthesized by nanocasting from mesoporous KIT–6 silica. Successful replication of the silica template was verified by scanning electron microscopy. No extra phases attributed to Ni or NiO were detected in the corresponding X–ray diffractograms except for the sample with the highest doping amount (e.g., 9 at.% Ni), for which NiO as secondary phase was observed. The oxidation state and spatial distribution of Ni in the powders was investigated by X–ray photoelectron spectroscopy and electron energy loss spectroscopy, respectively. Ni–containing powders exhibit ferromagnetic response at low and room temperatures, due to uncompensated spins at the surface of NiO nanoparticles and the occurrence of oxygen vacancies.
Secondly, continuous mesoporous Ni–doped SnO2 thin films were synthesized from variable [Ni(II)]/[Sn(IV)] molar ratios through a sol–gel based self–assembly process, using P–123 triblock copolymer as a structure directing agent. A deep structural characterization revealed a truly 3–D nanoporous structure with thickness in the range of 100–150 nm, and average pore size about 10 nm. Grazing incidence X–ray diffraction experiments indicated that Ni had successfully substituted Sn in the rutile–type lattice, although energy–dispersive X–ray analyses also revealed the occurrence of small NiO clusters in the films produced from high [Ni(II)]/[Sn(IV)] molar ratios. Interestingly, the magnetic properties of these mesoporous films significantly vary as a function of the doping percentage. The undoped SnO2 films exhibit a diamagnetic behaviour, whereas a clear paramagnetic signal with small ferromagnetic contribution dominates the magnetic response of the Ni–doped mesoporous films.
Thirdly, the magnetic properties of ordered mesoporous Cu–doped SnO2 powders, prepared by hard–templating from KIT–6 silica, were also studied. While Fe contamination or the presence of oxygen vacancies might be a plausible explanation of the room temperature ferromagnetism, the low–temperature ferromagnetism was mainly and uniquely assigned to the nanoscale nature of the formed antiferromagnetic CuO nanoparticles (uncompensated spins and shape–mediated spin canting). The reduced blocking temperature, which resided between 30 and 5 K, and small vertical shifts in the hysteresis loops confirmed size effects in the CuO nanoparticles.
