Phase transitions in BaCeO3: neutron diffraction and Raman studies

Polycrystalline samples and small single crystals of the perovskite BaCeO₃ were studied by neutron diffraction and Raman spectrometry between 300 and 1200 K. The controversy about the phase transitions originally deduced from our previous Raman study and those observed since by neutron diffraction by Knight has stimulated this work. Pretransitional effects which are detected by Raman much before long-range ordering takes place can partly explain the above disagreement. A continuous monitoring of the structural changes by neutron diffraction and by Raman spectroscopy including polarization analysis has allowed discussion of the transition mechanisms: The first transition Pnma–Imma takes place at 573 K and is of second order. Although some modes soften when the temperature is raised as in many of these perovskite compounds the transition is likely partly displacive partly order–disorder. The Raman modes which disappear transform in modes at the X point of the Brillouin zone of the Imma phase. The second transition Imma–Rc takes place at 673 K and is first order. The last transition Rc–Pm3m occurs above 1200 K and the transition temperature which can be deduced by extrapolation to zero Raman intensity is in good agreement with neutron results. This second order transition is progressive and begins at about 400 K, the intermediate Rc structure appearing as an attempt for slowing down the structural evolution toward the cubic perovskite form.