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Understanding the mechanisms underlying a stable polarization at the surfaceof ferroelectric thin films is of particular importance both from a fundamentalpoint of view and to achieve control of the surface polarization itself. Inthis study, it is demonstrated that the X-ray standing wave technique allowsthe polarization near the surface of a ferroelectric thin film to be probeddirectly. The X-ray standing wave technique is employed to determine, withpicometer accuracy, Ti and Ba atomic positions near the surface of threedifferently strained $\mathrm{BaTiO_3}$ thin films grown on scandatesubstrates, with a $\mathrm{SrRuO_3}$ film as bottom electrode. This techniquegives direct access to atomic positions, and thus to the local ferroelectricpolarization, within the first 3 unit cells below the surface. By employingX-ray photoelectron spectroscopy, a detailed overview of the oxygen-containingspecies adsorbed on the surface, upon exposure to ambient conditions, isobtained. The combination of structural and spectroscopic information allows usto conclude on the most plausible mechanisms that stabilize the surfacepolarization in the three samples under study. The different amplitude andorientation of the local ferroelectric polarizations are associated withsurface charges attributed to the type, amount and spatial distribution of theoxygen-containing adsorbates.

Probing the Surface Polarization of Ferroelectric Thin Films by X-ray Standing Waves