Spontaneous polarization and pyroelectric effect in the improper ferroelectrics-ferroelastics Gd2(MoO4)3 and Tb2(MoO4)3 at low temperatures

Abstract

The experimental variations in the spontaneous polarization ΔPs(T) and pyroelectric coefficient γs(T) for Gd2(MoO4)3 (GMO) and Tb2(MoO4)3 (TMO) at low temperatures reported here differ from those for intrinsic ferroelectrics. A fundamental difference is found in the repolarization behavior of samples of GMO and TMO at fixed temperatures of 300 and 4.2 K. While the single domain formation temperature essentially has no effect on the measurements for TMO, a fundamental difference is observed in the case of GMO: single domain formation in the latter at 4.2 K leads to an order of magnitude increase in ΔPs at T > 85 K and distinct anomalies are observed in γs(T), at one of which the pyroelectric coefficient reaches a record peak of 3 × 10−4 C/(m2·K) at T = 25 K. At T = 200 K the pyroelectric coefficients equal −1.45 and −1.8 in units of 10−6 C/(m2·K). Based on these results and taking published data on the rotational structural transformation in the (001) plane and symmetry considerations into account, we propose a crystal physical model for GMO-type improper ferroelectrics consisting of four mesotetrahedra, each of which is made up of three different types (a, b, c) of MoO4 coordination tetrahedra. The physical significance of the pseudodeviator coefficient Q12*, which initiates the phase transition at T > 433 K from one non-centrally symmetric phase (mm2) into another (4¯2m), is discussed in terms of this model.