Pyroelectric detection of spontaneous polarization in magnetite thin films

We have investigated the spontaneous polarization in Fe$_3$O$_4$ thin films by using dynamic and static pyroelectric measurements. The magnetic and dielectric behavior of Fe$_3$O$_4$ thin films grown on Nb:SrTiO$_3$(001) substrates was consistent with bulk crystals. The well-known metal-insulator (Verwey) transition was observed at 120 K. The appearance of a pyroelectric response in the Fe$_3$O$_4$ thin films just below the Verwey temperature shows that spontaneous polarization appeared in Fe$_3$O$_4$ at the charge ordering transition temperature. The polar state characteristics are consistent with bond- and site- centered charge ordering of Fe$^{2+}$ and Fe$^{3+}$ ions sharing the octahedral $B$ sites. The pyroelectric response in Fe$_3$O$_4$ thin films was dependent on the dielectric constant. Quasi-static pyroelectric measurement of Pd/Fe$_3$O$_4$/Nb:SrTiO$_3$ junctions showed that magnetite has a very large pyroelectric coefficient of 735 nC/cm$^{2}$K at 60 K.