Synthesis, anion order and magnetic properties of RVO3−xNx perovskites (R = La, Pr, Nd; 0 ≤ x ≤ 1)

The rare earth vanadium oxynitride perovskites RVO3−xNx (R = La, Pr, Nd; 0 ≤ x ≤ 1) have been prepared by treatment of RVO4 precursors in NH3. The ammonolysis reactions proceed through an initial reduction of RVO4 precursors to RVO3 perovskites that are progressively nitrided and reoxidised to RVO3−xNx materials with varying proportions of V4+/V3+. Variable temperature neutron diffraction studies show that NdVO2N and PrVO2.24N0.76 have orthorhombic Pbnm symmetry between 3.5 and 300 K, but LaVO2.11N0.89 undergoes a broad Pbnm to Rc structural transition over this temperature range. In LaVO3−xNx samples the proportion of the Rc phase at room temperature increases with the nitrogen content. The partial anion order indicative of planes of cis-VN2 chains found in NdVO2N is also present in PrVO2.24N0.76, and is thus robust to the disorder created by non-stoichiometry. Magnetic measurements reveal spin freezing transitions at low temperatures in LaVO2.09N0.91 and PrVO2.24N0.76, but NdVO2N is paramagnetic.