Surface Phase Transitions in BiFeO3 Below Room Temperature

We combine a wide variety of experimental techniques to analyze two heretofore mysterious phase transitions in multiferroic bismuth ferrite at low temperature. Raman spectroscopy, resonant ultrasound spectroscopy, electron paraelectric resonance, x-ray lattice constant measurements, conductivity and dielectric response, and specific heat and pyroelectric data have been collected for two different types of samples: single crystals and, in order to maximize surface/volume ratio to enhance surface phase transition effects, BiFeO${}_{3}$ nanotubes were also studied. The transition at $T$ $=$ 140.3 K is shown to be a surface phase transition, with an associated sharp change in lattice parameter and charge density at the surface. Meanwhile, the 201 K anomaly appears to signal the onset of glassy behavior.