Understanding how individual dopants or substitutional atoms interact with host lattices enables us to manipulate, control, and improve the functionality of materials. However, because of the intimate coupling among various degrees of freedom in multiferroics, the atomic-scale influence of individual foreign atoms has remained elusive. Here, we unravel the critical roles of individual Sc substitutional atoms in modulating ferroelectricity at the atomic scale of typical multiferroics, Lu1-xScxFeO3, by combining advanced microscopy and theoretical studies. Atomic variations in polar displacement of intriguing topological vortex domains stabilized by Sc substitution are directly correlated with Sc atom-mediated local chemical and electronic fluctuations. The local FeO5 trimerization magnitude and Lu/Sc-O hybridization strength are found to be significantly reinforced by Sc, clarifying the origin of the strong dependence of improper ferroelectricity on Sc content. This study could pave the way for correlating dopant-regulated atomic-scale local structures with global properties to engineer emergent functionalities of numerous chemically doped functional materials.
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