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.
ABSTRACT
We present the frequency study of electric conductivity in the superprotonic single crystal in a wide temperature range covering the superprotonic phase I and the low conducting, ferroelastic phase II. The data below microwave frequencies are analyzed using the Summerfield scaling method to check for presence of the first universality. The scaled conductivity obtained from the raw experimental data plotted versus scaled frequency do not show the universality because it contains, in a low temperature range, steps related to relaxational dielectric contribution. The contribution, evidenced by a temperature study of frequency dependence of εâ³, presumably comes from polar ammonia and therefore does not reflect properties of the hopping motion of mobile ions. To get rid of it, the conductivity is calculated using the impedance data obtained from the fitting procedure of the Nyquist plots. The resulting scaled ac conductivity plot forms a single curve in a wide temperature range. Thus, (NH4)3H(SO4)2 meets criteria for the first universality, despite the fact that it undergoes the structural, superionic phase transition in the temperature range studied.
ABSTRACT
The proton conducting crystal (NH4)3H(SeO4)2 is examined to check whether the first universality of conductivity spectra is sensitive to subtle changes in the crystal structure and proton dynamics caused by external pressure. The ac conductivity was measured along the trigonal c axis by means of impedance spectroscopy, in the frequency range from 100 Hz to 1 MHz, at temperatures 250 K < T < 330 K and pressures 0.1 < p < 380 MPa. The ac conductivity characteristics were analyzed using the Summerfield scaling procedure. In the temperature range of the experiment the master curve is strongly disturbed by the structural phase transition at Tc1 = 273 K but the scaled spectra superimpose within the temperature range of each individual phase (below and above Tc1). The effect of pressure on the scaled conductivity spectra considered separately for each of the studied phases is similar to that caused by temperature. This means that both stimuli give rise to an acceleration of the dynamics of protons and consequently to an increase in conductivity. The evolution of the scaled conductivity spectra with pressure close to the phase boundary between the triclinic, ferroelastic phase III (P1[combining macron]) and the trigonal, superionic phase II (R3[combining macron]) points to the mixing of phase III with inclusions of phase II.
