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Tailoring the electrocaloric effect by internal bias fields and field protocols
Defect dipoles, strain gradients, and the electric boundary conditions at interfaces and surfaces often impose internal bias fields in acceptor-doped ferroelectrics, ferroelectric films, nanocomposites, and multilayers. In this work, we study the impact of internal bias fields on the electrocaloric effect (ECE), utilizing an analytical model and ab-initio-based molecular-dynamics simulations. We reveal the complex dependency of the ECE on field protocol and the relative strength of internal and external fields. The internal fields may even reverse the sign of the response (inverse or negative ECE). We explore the transition between conventional and inverse ECE and discuss reversible and irreversible contributions to the field-induced specific entropy change. Most importantly, we predict design routes to optimize the cooling and heating response for small external fields by the combination of internal field strengths and the field-loading protocol.