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The atomic-scale response of dielectrics/ferroelectrics to electric fields is central to their functionality. Here we introduce an  in situ  characterization method that reveals changes in the local atomic structure in polycrystalline materials under fields. The method employs atomic pair distribution functions (PDFs), determined from X-ray total scattering that depends on orientation relative to the applied field, to probe structural changes over length scales from sub-Ångstrom to several nanometres. The PDF is sensitive to local ionic displacements and their short-range order, a key uniqueness relative to other techniques. The method is applied to representative ferroelectrics, BaTiO 3  and Na ½ Bi ½ TiO 3 , and dielectric SrTiO 3 . For Na ½ Bi ½ TiO 3 , the results reveal an abrupt field-induced monoclinic to rhombohedral phase transition, accompanied by ordering of the local Bi displacements and reorientation of the nanoscale ferroelectric domains. For BaTiO 3  and SrTiO 3 , the local/nanoscale structural changes observed in the PDFs are dominated by piezoelectric lattice strain and ionic polarizability, respectively.

Electric-field-induced local and mesoscale structural changes in polycrystalline dielectrics and ferroelectrics