Surface and bulk ferroelectric phase transition in super-tetragonal BiFeO 3 thin films

The temperature-dependent ferroelectric properties of super-tetragonal ${\mathrm{BiFeO}}_{3}$ are investigated using surface-sensitive low-energy electron microscopy (LEEM). We use epitaxial oxide ${\mathrm{BiFeO}}_{3}/{\mathrm{Ca}}_{0.96}{\mathrm{Ce}}_{0.04}{\mathrm{MnO}}_{3}$ bilayers grown by pulsed laser deposition on ${\mathrm{YAlO}}_{3}$ substrates. Ferroelectric, micrometer-scale domains are written by piezoresponse force microscopy and subsequently observed by LEEM from room temperature up to about 950 K. Kelvin probe force microscopy and LEEM spectroscopy reveal that the surface potential is efficiently (g50%) screened by adsorbates that are only released after annealing above 873 $\ifmmode\pm\else\textpm\fi{}$ 50 K in ultrahigh vacuum. The surface structure and chemistry of the ferroelectric thin films are analyzed using scanning transmission electron microscopy, electron energy loss spectroscopy, and x-ray photoelectron spectroscopy, discarding the occurrence of a putative ``skin layer'' effect. While its magnetic and structural transitions were reported in the literature, the true, ferroelectric Curie temperature of super-tetragonal ${\mathrm{BiFeO}}_{3}$ has not been determined so far. Here, we measure a Curie temperature of 930 $\ifmmode\pm\else\textpm\fi{}$ 30 K for the super-tetragonal ${\mathrm{BiFeO}}_{3}$ surface and corroborate it with volume-sensitive, temperature-dependent x-ray diffraction measurements. These results suggest that LEEM can be used as a powerful tool to probe surface charge and ferroelectric transitions in ultrathin films.