Coexistence of antiferrodistortive and ferroelectric distortions at the PbTiO₃ (001) surface

The c(2$\times$2) reconstruction of (001) PbTiO$_3$ surfaces is studied by means of first principles calculations for paraelectric (non-polar) and ferroelectric ([001] polarized) films. Analysis of the atomic displacements in the near-surface region shows how the surface modifies the antiferrodistortive (AFD) instability and its interaction with ferroelectric (FE) distortions. The effect of the surface is found to be termination dependent. The AFD instability is suppressed at the TiO$_2$ termination while it is strongly enhanced, relative to the bulk, at the PbO termination resulting in a c(2x2) surface reconstruction which is in excellent agreement with experiments. We find that, in contrast to bulk PbTiO$_3$, in-plane ferroelectricity at the PbO termination does not suppress the AFD instability. The AFD and the in-plane FE distortions are instead concurrently enhanced at the PbO termination. This leads to a novel surface phase with coexisting FE and AFD distortions which is not found in PbTiO$_3$ bulk.