Absence of Ferromagnetism in Mn-doped Tetragonal Zirconia

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 address 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.