Role of defects on the magnetic behaviour of the geometrically frustrated spinel ZnFe2O4

Defective zinc ferrites ZnFe2O4-delta obtained by vacuum annealing bulk Zn-ferrite at different temperatures TAnn were investigated by using XANES at Zn-K, Fe-K and XMCD at Fe-L-2,L-3 edges, static and dynamic magnetic measurements. The cation inversion that confers to the starting ferrite a weak ferromagnetic response is progressively lost when T-Ann surpasses 250 degrees C. Consequently, there is a detriment of the magnetic response that reaches its lower value for T-Ann around 370 degrees C, being the latter coincident with a negligible non-equilibrium occupancy. Above T-An (n) over tilde 450 degrees C the ferrite progressively enhances its magnetic response. In such case, even though Zn and Fe occupy non-equilibrium sites at surface regions, the deficiency of oxygen predominates over inversion and the former triggers an increment of the magnetic coupling between Fe3+ at octahedral spinel sites. We discuss the magnetic results that account for spin-glass and/or cluster-glass behavior of this geometrically frustrated compound as due to the randomness and frustration introduced by local defects. (C) 2018 Elsevier B.V. All rights reserved.