Tailoring the electrocaloric effect by internal bias fields and field protocols

TL;DR

This paper investigates how internal bias fields in ferroelectrics influence the electrocaloric effect, revealing complex dependencies and proposing strategies to optimize cooling and heating responses through field protocols.

Contribution

It introduces an analytical model and simulations to understand and manipulate the electrocaloric effect via internal bias fields and field protocols in ferroelectrics.

Findings

Internal bias fields can reverse the sign of the electrocaloric response.

The electrocaloric effect depends complexly on field protocol and internal/external field strength.

Design strategies are proposed to optimize electrocaloric cooling and heating responses.

Abstract

In acceptor doped ferroelectrics and in ferroelectric films and nanocomposites, defect dipoles, strain gradients, and the electric boundary conditions at interfaces and surfaces often impose internal bias fields. In this work we delicately study the impact of internal bias fields on the electrocaloric effect (ECE), utilizing an analytical model and \emph{ab initio}-based molecular dynamics simulations. We reveal the complex dependency of the ECE on field protocol and 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.