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Oxide ABO₃ systems, such as the hexagonal manganites, exhibit complex polarization domain structures.  Underlying these domains are unique atomic configurations that determine the polarization.  We are examining the atomic-level structure utilizing electron and photon probes to determine how local structure and surface potential variations are connected to the observed polarization.  Sub-micron 2D mapping with depth sensitivity is used to connect the polarization with variations in electronic and atomic structure.