Synergistic Enhancement of Ferroelectricity in Eu/Fe Codoped BiNaTiO Thin Films: Mechanistic Insights via Luminescent Probing and Defect Engineering.

Defect engineering is a pivotal strategy for optimizing the polarization intensity in ferroelectrics. However, the synergistic effects of codoping transition metals and rare-earth ions into ferroelectric systems remain underexplored, and the resulting atomic-scale coupling mechanisms are not fully deciphered. This study demonstrates a synergistic enhancement of ferroelectric polarization in lead-free BiNaTiO (BNT) thin films through Eu/Fe codoping while elucidating the underlying mechanism via luminescent probing and simulation calculation. Remarkably, codoping achieves a 130.9% enhancement in saturated polarization (). The synergistic enhancement derives from the formation of [Eu-Fe] defect pairs and the amplification of [TiO] octahedral distortion. This local structural asymmetry variations are characterized by in situ luminescent probes of Eu and first-principles calculation. It is confirmed that the coupling mechanism is related with the [Eu-Fe] defect-pair-induced electron density redistribution and dipole-dipole coupling energy transfer process. These findings provide atomic-scale insights into rare-earth/transition-metal coupling mechanisms and advance defect engineering strategies for high-performance multifunctional ferroelectric devices.