Optimization of energy storage and electrocaloric performance in Pb(Zr,Ti)O₃ via A-Site La and Bi Co-doping

Lead-based ferroelectrics are one of the most fascinating candidates in the field of state-of-the-art electronic technology. Their intriguing properties are further enriched via the realization of morphotropic phase boundaries. Moreover, the A-site chemical substitution provides insight into the emergence of various exotic phases. Here, we employ co-doping of La³⁺ and Bi³⁺ at the A-site of Pb(Zr,Ti)O₃ (PZT) ferroelectric to broaden the practical perspective of relaxor systems. Here, we emphasize that the A-site co-doping approach introduces technologically appealing amendments in the well-established temperature composition phase diagram of the PZT system. La³⁺ and Bi³⁺ doping favors the evolution of a novel response to thermal and field fluctuations. The maximum values of −ΔS are found to be ∼0.157, 0.118 and 0.176 J (kg·K)⁻¹ for x = 0.01, 0.02 and 0.03, respectively. We employ the electrocaloric characteristics and Arrott plot as probing tools. The observation of a negative electrocaloric effect and the systematic reversal of Arrott lines, followed by a poling effect on the dielectric constant, reveals the emergence of ergodic phase as a novel phase. This further reveals that the Bi doping approach leads to the emergence of exotic characteristics in the chemically modified PZT system. The maximum observed recoverable energy for the composition for x = 0.01 is 0.0479 J cm⁻³ at a temperature of 388 K.