Neutron Powder Diffraction and Magnetic Study of Perovskites Pb(Mn1/2nb1/2)O-3 and Pb(Mn1/4fe1/4nb1/2)O-3

The structural and magnetic properties of the complex metal oxides Pb(Mn1/2Nb1/2)O3 (PMNO) and Pb(Mn1/4Fe1/4Nb1/2)O3 (PMFNO), which belong to a class of disordered perovskites have been studied. The magnetic susceptibilities of PMNO showed hysteresis between field cooled and zero-field cooled conditions below the transition of 15K, suggesting that the material has a spin-glass feature. Neutron diffraction patterns of PMNO showed no evidence of a long-range magnetic ordering at 1.5K, which is consistent with spin-glass behavior. Rietveld refinements of neutron powder diffraction data collected at different temperatures between 1.5 and 700K have been carried out in order to extract structural information. The crystal structure of this compound is cubic (space group Pm3¯m) within the whole temperature interval. The Mn and Nb ions were found to be disordered over the perovskite B-sites. The main feature of this structure is the positional disorder at the Pb site, the importance of which in connection with the ferroic transitions is briefly discussed. The Pb cations show a positional disorder shifting from their high-symmetry positions along the [111] direction. The effect of Fe-doping on PMNO has been studied. The substitution of Fe at the Mn site in PMFNO results in a small changes of the magnetic properties without significant differences in the crystal structures. The factors governing the observed structural and magnetic properties of PMNO and PMFNO are discussed and compared with those of other quaternary Mn-containing perovskites. For the PbB3+1/2Nb1/2O3 series with the isomorphous substitution B3+, graphs of average lattice parameters of the perovskite phase and the temperatures of ferroelectric and magnetic phase transitions as functions of the B3+ cation radius were constructed and are discussed. Influence of A-cation sublattice on magnetic properties is also considered.