In this article, we examine the initial polarization of PbTiO3 thin films grown epitaxially on SrRuO3 electrodes. It is found that the as-grown predominant polarization is directed toward the SrRuO3 bottom electrode in films thinner than 20 nm and directed toward the top surface in thicker films. The data is interpreted in terms of a Landau–Ginzburg–Devonshire model for a semiconducting ferroelectric with asymmetric boundary conditions. Based on the measured hysteresis loops and the stability of the two polarization directions with time, it is concluded that charged defects serve to impose a preferential downward polarization in very thin films.
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