An accelerative increase of the effective electron mobility with Mo content in SrFe1−xMoxO3−δ is due to progressive formation of the Sr2FeMoO6 ordered areas with high electron mobility.
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.
23 February 2018 in Journal of Electronic Materials
The structure, oxygen non-stoichiometry, and defect equilibrium in perovskite-type PrBa1−xSrxFe2O6−δ (x = 0, 0.25, 0.50) synthesized at 1350 °C were studied. For all compositions, X-ray diffraction testifies to the formation of a cubic structure (S.G. ), but an electron diffraction study reveals additional diffuse satellites around each Bragg spot, indicating the primary incommensurate modulation with wave vectors about ±0.43. The results were interpreted as a sign of the short-order in both A-cation and anion sublattices in the areas of a few nanometers in size, and of an intermediate state before the formation of an ordered superstructure. An increase in oxygen deficiency was found to promote the ordering, whereas partial substitution of barium by strontium caused the opposite effect. The oxygen content in oxides as a function of oxygen partial pressure and temperature was measured by coulometric titration, and the data were used for the modeling of defect equilibrium in oxides. The simulation results implied oxygen vacancy ordering in PrBa1−xSrxFe2O6−δ that is in agreement with the electron diffraction study. Besides oxidation and charge disproportionation reactions, the reactions of oxygen vacancy distribution between non-equivalent anion positions, and their trapping in clusters with Pr3+ ions were taken into account by the model. It was demonstrated that an increase in the strontium content in Pr0.5Ba0.5−xSrxFeO3−δ suppressed ordering of oxygen vacancies, increased the binding energy of oxygen ions in the oxides, and resulted in an increase in the concentration of p-type carriers.