Impulsive Stimulated Raman Scattering Study of Soft Mode Dynamics in Ferroelectric Crystals

Abstract

Soft Modes, ISRS, and Perovskite Ferroelectrics The dynamics of cooperative ordering in crystals near structural phase transitions have long been elusive. Most picosecond and femtosecond time-resolved measurements have involved rapid laser heating of a sample whose phase transition (e.g. melting) dynamics are then monitored1. In this case many lattice degrees of freedom are excited, and little information is provided about the roles or dynamics of particular lattice motions. In structural phase transitions, the order parameter is described by one or a very few specific ("soft") lattice modes whose motions bring crystalline constituents from their initial positions into their positions in a new crystalline phase. Experimental characterization of the dynamics is possible in some cases through Raman spectroscopy, but often the highly damped character of the soft mode leads to a central peak in the Raman spectrum which cannot be analyzed accurately. In many cases it is not even possible to tell whether the ordering motion is a heavily damped vibration, Debye relaxation, or some combination of the two. This information is essential for understanding the microscopic mechanism of a transition since vibrational or relaxational character is an indication of ionic motion within a single potential energy minimum (i.e. a displacive transition) or hopping between different sites (an order-disorder transition) respectively.