Multiple phase and dielectric transitions on a novel multi-sensitive [TPrA][M(dca)3] (M: Fe2+, Co2+ and Ni2+) hybrid inorganic–organic perovskite family

Abstract

The hybrid inorganic–organic [TPrA][M(dca)₃] (M: Fe²⁺, Co²⁺ and Ni²⁺) compounds, where TPrA is the tetrapropylammonium cation and dca is the dicyanamide anion, are unique multi-sensitive compounds that display multiple phases and dielectric transitions. These materials exhibit up to three first-order structural transitions (between the polymorphs I, Ia, Ib and II) associated with the same number of dielectric transitions in the temperature range of 210–360 K. The mechanisms responsible for these dielectric responses are found to be novel within the hybrid perovskites, involving ionic displacements of the A-site cations (TPrA) and order/disorder processes of the X anions (dca). In addition, the phase transitions and dielectric transition temperatures can be tuned by applying external hydrostatic pressure or by inducing internal pressure by modifying the tolerance factor through ionic substitution in the B-sites. This multi-sensitive response towards temperature, external and internal pressure opens up promising technological applications for this family of materials, such as dielectric transductors or multistimuli-sensors, whose response can be modulated in a wide range of temperatures and pressures.