Crystal Structure of Solid Solutions LA1-xRxFeO3 (r=PR, nD)


O.B. Pavlovska, L.O. Vasylechko

Lviv Polytechnic National University

Complex oxides with perovskite structure RFeO3, where R are rare earth metals, represent an important class of functional materials. RFeO3 compounds are used in thermoelectric devices, solid oxide fuel cells, as membranes for partial oxidation of methane and oxygen cleaning, as catalysts for CO oxidation and decomposition of NOx, and as sensory materials. Complementary, the interest in the rare earth ferrites is stimulated by their interesting fundamental physical properties, such as spin-reorientation phenomena and the para- to antiferomagnetic transitions occurred at elevated temperatures.
Samples with nominal compositions La1 xPrxFeO3 (x = 0.2, 0.7) and La1 xNdxFeO3 (x = 0.1, 0.8) were obtained by solid state reactions technique. Precursor oxides La2O3, Pr6O11, Nd2O3 and Fe2O3 were ball-milled in ethanol for 5 h, dried, pressed into pellets and annealed in air at 1473 K for 20 h. As-obtained product was repeatedly re-grinded and annealed in air at 1473 K for 20 h, after that slowly cooled to RT for 20 h. Phase and structural behaviour of new mixed LaFeO3–based ferrites was investigated by using both laboratory and synchrotron X-ray powder diffraction techniques. The latest one was applied for the samples adopting pseudo-tetragonal perovskite structure. Corresponding high-resolution X-ray synchrotron powder diffraction experiments were performed at ID22 beamline of the European Synchrotron Radiation Facilities (Grenoble, France) during beamtime allocated to the ESRF Experiment MA-2320.
Based on the experimental powder diffraction data, the unit cell dimensions, positional and displacement parameters of atoms in the La1 xPrxFeO3 and La1 xNdxFeO3 structures were derived by full profile Rietveld refinement technique.
According to the results obtained, all samples synthesized adopt orthorhombically distorted perovskite structure isotypic with GdFeO3. Structural parameters of La1 xPrxFeO3 and La1 xNdxFeO3 samples agree well with the data of "pure" La, Pr and Nd ferrites, thus proving formation of continuous solid solutions in the LaFeO3-PrFeO3 and LaFeO3-NdFeO3 systems. The unit cells dimensions of La1 xPrxFeO3 and La1 xNdxFeO3 decreases almost linearly with decreasing R-cation radii according to the Vegard’s rule. Peculiarity of both solid solutions is the lattice parameters crossover occurred at certain compositions and formation of dimensionally tetragonal (pseudo-tetragonal) structures. Despite of the observed phenomenon of the lattice crossover, the symmetry of La1 xPrxFeO3 and La1 xNdxFeO3 structure remain orthorhombic in whole concentration range.