Infrared spectroscopy in KNbO₃through the successive ferroelectric phase transitions

Abstract

The temperature dependence of the infrared reflectivity spectra in KNbO3 is reported for the cubic, tetragonal and orthorhombic phases in a temperature range extending from 300 to 1200K. Spectra have been fitted with a model based on the factorised form of the dielectric function. The temperature dependence of the mode frequencies, the dampings and the oscillator strengths through the successive phase transitions is reported. The experimental data exhibit an unstable mode which decreases continuously in frequency upon cooling across the diverse transitions. The ionic effective charges, the spontaneous polarisation and the static dielectric constant are calculated from these data. All results are discussed in terms of a displacive/order-disorder crossover, which appears especially when the transition from the cubic to the tetragonal phase is approached. A particular phase transition mechanism is proposed, which leads to an understanding of the discrepancy between the experimental and the calculated values of the dielectric constant, the large damping of the soft mode, the incomplete softening of the unstable phonon and the special sequence of phase transitions.