Unusual glass-like systems - Relaxation dynamics of Cu⁺ ions in ferroelectric KTN crystals

We present a broadband dielectric spectroscopy study of potassium tantalate niobate (KTN) crystals, doped with varying amounts of Cu ions. The dielectric landscape in frequency and temperature is rich, with multiple processes in different temperature phases of the crystals. Of particular interest are the processes resulting from Cu and Nb ions in the paraelectric phase of the crystal and from Cu ions in the ferroelectric phase. The linear dependence of the ferroelectric transition temperature in KTN crystals (KTa_0.62Nb _0.38O₃Cu) on the concentration of Nb, as well as the dielectric behavior of the ferroelectric phase transition in these crystals, are well known. We concentrate of the dielectric relaxation resulting from the Cu ions in the crystal lattice. Cu dopants in very small concentrations have been added in the past to enhance the photorefractive properties of KTN crystals. However the small ionic radius of such dopants, relative to their lattice site, results in virtual dipoles exhibiting dielectric relaxation. The random nature of their distribution throughout the ordered KTN lattice leads to relaxation behavior reminiscent of glass formers. In particular Vogel Fulcher Tammann relaxation of these ions is evident in the paraelectric phase of the crystal. This cooperativity is broken at a critical temperature (T = 354 K) and the relaxation becomes Arrhenius in nature. An explanation in terms of Adam-Gibbs theory is presented where the cooperative cluster is realized by polarized Nb ions linking the widely space Cu ions. At the phase transition (T_c = 295.6 K) this relaxation is 'frozen' by large internal fields caused by the structural shift of the Nb ion in the unit cell. As the temperature drops the Cu ions undergo a reorganization about the multiwell potential leading to a saddle-like process characteristic of liquids in confined systems. An explanation for this behavior is proposed based on free volume concepts, where the relatively small ionic radius of the Cu ions provides the free volume for the relaxing species. The role of the oxygen octahedra as the relaxing species is discussed.