In a recent letter, it has been predicted within first principle studies that Mn-doped ZrO2 compounds could be good candidate for spintronics application because expected to exhibit ferromagnetism far beyond room temperature. Our purpose is to addres
s this issue experimentally for Mn-doped tetragonal zirconia. We have prepared polycrystalline samples of Y0.15(Zr0.85-yMny)O2 (y=0, 0.05, 0.10, 0.15 & 0.20) by using standard solid state method at equilibrium. The obtained samples were carefully characterized by using x-ray diffraction, scanning electron microscopy, elemental color mapping, X-ray photoemission spectroscopy and magnetization measurements. From the detailed structural analyses, we have observed that the 5% Mn doped compound crystallized into two symmetries (dominating tetragonal & monoclinic), whereas higher Mn doped compounds are found to be in the tetragonal symmetry only. The spectral splitting of the Mn 3s core-level x-ray photoelectron spectra confirms that Mn ions are in the Mn3+ oxidation state and indicate a local magnetic moment of about 4.5 {mu}B/Mn. Magnetic measurements showed that compounds up to 10% of Mn doping are paramagnetic with antiferromagnetic interactions. However, higher Mn doped compound exhibits local ferrimagnetic ordering. Thus, no ferromagnetism has been observed for all Mn-doped tetragonal ZrO2 samples.
Ab initio studies have theoretically predicted room temperature ferromagnetism in crystalline SnO2, ZrO2 and TiO2 doped with non magnetic element from the 1A column as K and Na. Our purpose is to address experimentally the possibility of magnetism in
both Sn1-xKxO2 and Sn1-xCaxO2 compounds. The samples have been prepared using equilibrium methods of standard solid state route. Our study has shown that both Sn1-xCaxO2 and Sn1-xKxO2 structure is thermodynamically unstable and leads to a phase separation, as shown by X-ray diffraction and detailed micro-structural analyses with high resolution transmission electron microscopy (TEM). In particular, the crystalline SnO2 grains are surrounded by K-based amorphous phase. In contrast to Ca: SnO2 samples we have obtained a magnetic phase in K: SnO2 ones, but no long range ferromagnetic order. The K: SnO2 samples exhibit a moments of the order of 0.2 {mu}B/K /ion, in contrast to ab-initio calculations which predict 3{mu}B, where K atoms are on the Sn crystallographic site. The apparent contradictions between our experiments and first principle studies are discussed.
Frequency and dc magnetic field dependences of dynamic susceptibility in diluted paramagnets LiYF$_4$:Ho$^{3+}$ have been measured at liquid helium temperatures in the ac and dc magnetic fields parallel to the symmetry axis of a tetragonal crystal la
ttice. Experimental data are analyzed in the framework of microscopic theory of relaxation rates in the manifold of 24 electron-nuclear sublevels of the lowest non-Kramers doublet and the first excited singlet in the Ho$^{3+}$ ground multiplet $^5I_8$ split by the crystal field of S$_4$ symmetry. The one-phonon transition probabilities were computed using electron-phonon coupling constants calculated in the framework of exchange charge model and were checked by optical piezospectroscopic measurements. The specific features observed in field dependences of the in- and out-of-phase susceptibilities (humps and dips, respectively) at the crossings (anti-crossings) of the electron-nuclear sublevels are well reproduced by simulations when the phonon bottleneck effect and the cross-spin relaxation are taken into account.
