Magnetic Structures and Magnetic Phase Diagram of the Mixed-Valence Iron Phosphate Fe7(PO4)6.

Mixed-valence iron compounds are fascinating materials exemplified by ferrimagnetic Fe3O4, multiferroic LuFe2O4, and a pigment Fe4[Fe(CN)6]3. Mixed-valent iron (oxy)phosphates also provide a large variety of different connections between magnetic ions, which are responsible for complex magnetism. Fe7(PO4)6 (Fe32+Fe43+(PO4)6) has well-defined Fe2+ and Fe3+ sites and shows two antiferromagnetic transitions at TN1 = 47 K and TN2 = 16 K. Here, we investigated magnetic structures of Fe7(PO4)6 (at zero magnetic field) using neutron powder diffraction and constructed a temperature-magnetic-field phase diagram. Below TN1, magnetic propagation vector is k1 = (1/2, 0, 1/2), and magnetic moments on Fe3+ sites are nearly fully ordered; while moments on Fe2+ sites are significantly reduced. Below TN2, the second propagation vector appears k2 = (0, 1/2, 0) and coexists with k1; moments on Fe2+ sites are fully ordered (at 2 K) reaching 4.5 μB suggesting noticeable spin-orbital contributions. Coexistence of two propagation vectors and triclinic symmetry results in variations of total magnetic moments on each site. Magnetic measurements up to 300 kOe detected one field-induced transition near 55.5 kOe. Data showed that TN1 is nearly magnetic-field independent up to 90 kOe, while a more complex behavior was observed near TN2 at magnetic fields around 50 kOe.