Unveiling the Hidden Entropy in ZnFe2O4

The antiferromagnetic (AFM) transition of the normal ZnFe2O4 has been intensively investigated with results showing a lack of long-range order, spin frustrations, and a "hidden" entropy in the calorimetric properties for inversion degrees delta approximate to 0 or delta = 0. As delta drastically impacts the magnetic properties, it is logical to question how a delta value slightly different from zero can affect the magnetic properties. In this work, (Zn1-delta Fe delta)[Zn delta Fe2-delta]O-4 with delta = 0.05 and delta = 0.27 have been investigated with calorimetry at different applied fields. It is shown that a delta value as small as 0.05 may affect 40% of the unit cells, which become locally ferrimagnetic (FiM) and coexists with AFM and spin disordered regions. The spin disorder disappears under an applied field of 1 T. Mossbauer spectroscopy confirms the presence of a volume fraction with a low hyperfine field that can be ascribed to these spin disordered regions. The volume fractions of the three magnetic phases estimated from entropy and hyperfine measurements are roughly coincident and correspond to approximately 1/3 for each of them. The "hidden" entropy is the zero point entropy different from 0. Consequently, the so-called "hidden" entropy can be ascribed to the frustrations of the spins at the interphase between the AFM-FiM phases due to having delta approximate to 0 instead of ideal delta = 0.