Response of the Verwey transition in magnetite to controlled point-like disorder induced by 2.5 MeV electron irradiation

Abstract

Controlled point-like disorder induced by low temperature 2.5 MeV electron irradiation was used to probe the nature of the Verwey transition in magnetite, Fe3O4. Two large single crystals, one with optimal transition temperature, TV≈121 K, and another with TV≈109 K, as well as magnetite magnetosome nanocrystals harvested from the lysed cells of the marine magnetotactic vibrio Magnetovibrio blakemorei strain MV-1, TV≈110 K, were examined. Temperature-dependent resistivity is consistent with the semiconductor-to-semiconductor (insulator) sharp, step-like Verwey transition from a state with a small bandgap of around 60 meV to a state with a large bandgap of about 300 meV. The irradiation causes an up-shift of the resistivity curves above the transition without transition smearing or broadening. It also causes an apparent down-shift of the resistivity maximum at high temperatures. In the lower TV crystal, the electron irradiation drives the transition temperature into a “forbidden” interval of TV , believed to separate the first order from the second order phase transition. Contrary to this belief, the transition itself remains sharp and hysteretic without a significant change in the hysteresis width indicating the strong 1st order character of the Verwey transition for all TV values. The separate 2nd order - looking transition is likely due to sample inhomogeneities. We conclude that the sudden change of the bandgap accompanied (or driven) by the monoclinic distortion and the change of magnetic anisotropy is the reason for the Verwey transition in magnetite and the effect of additional disorder is mostly in the smearing of the sharp gap edges near the Fermi level.