Proton dynamics in superprotonic Rb₃H(SeO₄)₂ crystal by broadband dielectric spectroscopy

Abstract

Broadband dielectric and AC conductivity spectra (1 Hz to 1 THz) of the superprotonic single crystal Rb3H(SeO4)2 (RHSe) along the c axis were studied in a wide temperature range 10 K < T < 475 K that covers the ferroelastic (T < 453 K) and superprotonic (T > 453 K) phases. A contribution of the interfacial electrode polarization layers was separated from the bulk electrical properties and the bulk DC conductivity was evaluated above room temperature. The phase transition to the superprotonic phase was shown to be connected with the steep but almost continuous increase in bulk DC conductivity, and with giant permittivity effects due to the enhanced bulk proton hopping and interfacial electrode polarization layers. The AC conductivity scaling analysis confirms validity of the first universality above room temperature. At low temperatures, although the conductivity was low, the frequency dependence of dielectric loss indicates no clear evidence of the nearly constant loss effect, so-called second universality. The bulk (intrinsic) dielectric properties, AC and DC conductivity of the RHSe crystal at frequencies up to 1 GHz are shown to be caused by the thermally activated proton hopping. The increase of the AC conductivity above 100 GHz could be assigned to the low-frequency wing of proton vibrational modes.