Impact of A-Site Cation Deficiency on Charge Transport in La0.5−xSr0.5FeO3−d

The electrical conductivity of La0.5−xSr0.5FeO3−δ, investigated as a function of the nominal cation deficiency in the A-sublattice, x, varying from 0 to 0.02, has demonstrated a nonlinear dependence. An increase in the x value from 0 to 0.01 resulted in a considerable increase in electrical conductivity, which was shown to be attributed mainly to an increase in the mobility of the charge carriers. A combined analysis of the defect equilibrium and the charge transport in La0.5−xSr0.5FeO3−δ revealed the increase in the mobility of oxygen ions, electrons, and holes by factors of ~1.5, 1.3, and 1.7, respectively. The observed effect is assumed to be conditioned by a variation in the oxide structure under the action of the cationic vacancy formation. It was found that the cation deficiency limit in La0.5−xSr0.5FeO3−δ did not exceed 0.01. A small overstep of this limit was shown to result in the formation of (Sr,La)Fe12O19 impurity, which even in undetectable amounts reduced the conductivity of the material. The presence of (Sr,La)Fe12O19 impurity was revealed by X-ray diffraction on the ceramic surface after heat treatment at 1300 °C. It is most likely that the formation of traces of the liquid phase under these conditions is responsible for the impurity migration to the ceramic surface. The introduction of a cation deficiency of 0.01 into the A-sublattice of La0.5−xSr0.5FeO3−δ can be recommended as an effective means to enhance both the oxygen ion and the electron conductivity and improve ceramic sinterability.

Cationic-vacancy-induced room-temperature ferromagnetism in transparent, conducting anatase Ti 1− x Ta x O 2 ( x ∼0.05) thin films

We report room-temperature ferromagnetism (FM) in highly conducting, transparent anatase Ti 1− x Ta x O 2 ( x ∼0.05) thin films grown by pulsed laser deposition on LaAlO 3 substrates. Rutherford backscattering spectrometry (RBS), X-ray diffraction, proton-induced X-ray emission, X-ray absorption spectroscopy (XAS) and time-of-flight secondary-ion mass spectrometry indicated negligible magnetic contaminants in the films. The presence of FM with concomitant large carrier densities was determined by a combination of superconducting quantum interference device magnetometry, electrical transport measurements, soft X-ray magnetic circular dichroism (SXMCD), XAS and optical magnetic circular dichroism, and was supported by first-principles calculations. SXMCD and XAS measurements revealed a 90 per cent contribution to FM from the Ti ions, and a 10 per cent contribution from the O ions. RBS/channelling measurements show complete Ta substitution in the Ti sites, though carrier activation was only 50 per cent at 5 per cent Ta concentration, implying compensation by cationic defects. The role of the Ti vacancy ( V Ti ) and Ti 3+ was studied via XAS and X-ray photoemission spectroscopy, respectively. It was found that, in films with strong FM, the V Ti signal was strong while the Ti 3+ signal was absent. We propose (in the absence of any obvious exchange mechanisms) that the localized magnetic moments, V Ti sites, are ferromagnetically ordered by itinerant carriers. Cationic-defect-induced magnetism is an alternative route to FM in wide-band-gap semiconducting oxides without any magnetic elements.