Intrinsic Ferroelectricity in Charge-Ordered Magnetite

Single crystalline magnetite Fe 3 O 4 was investigated at low temperatures in the charge ordered state by electric measurements and time-resolved diffraction with voltage applied in-situ. Dielectric spectroscopy indicates relaxor ferroelectric characteristics, with polarization switching observably only at sufficiently low temperatures and in a suitably chosen time-window. PUND measurements with a ms time scale indicate a switchable polarization of about 0 . 6 μ C / cm 2 . Significant switching occurs only above a threshold field of about 3 kV / mm , and it occurs with a time delay of about 20 μ s . The time-resolved diffraction experiment yields, for sufficiently high voltage pulses, a systematic variation by about 0 . 1 % of the intensity of the ( 2 , 2 ˉ , 10 ˉ ) Bragg reflection, which is attributed to structural switching of domains of the non-centrosymmetric C c structure to its inversion twins, providing proof of intrinsic ferroelectricity in charge ordered magnetite