Defect ordering and defect–domain-wall interactions in PbTiO3: A first-principles study

The properties of ferroelectric materials, such as lead zirconate titanate (PZT), are heavily influenced by the interaction of defects with domain walls. These defects are either intrinsic or are induced by the addition of dopants. We study here PbTiO${}_{3}$ (the end member of a key family of solid solutions) in the presence of acceptor (Fe) and donor (Nb) dopants, and the interactions of the different defects and defect associates with the domain walls. For the case of iron acceptors, the calculations point to the formation of defect associates involving an iron substitutional defect and a charged oxygen vacancy (Fe${}_{\text{Ti}}^{\ensuremath{'}}$-V${}_{\mathrm{O}}^{{}^{\phantom{\rule{0.16em}{0ex}}..}}$). This associate exhibits a strong tendency to align in the direction of the bulk polarization; in fact, ordering of defects is also observed in pure PbTiO${}_{3}$ in the form of lead-oxygen divacancies. Conversely, calculations on donor-doped PbTiO${}_{3}$ do not indicate the formation of polar defect complexes involving donor substitutions. Last, it is observed that both isolated defects in donor-doped materials and defect associates in acceptor-doped materials are more stable at 180${}^{\ensuremath{\circ}}$ domain walls. However, polar defect complexes lead to asymmetric potentials at domain walls due to the interaction of the defect polarization with the bulk polarization. The relative pinning characteristics of different defects are then compared, to develop an understanding of defect--domain-wall interactions in both doped and pure PbTiO${}_{3}$. These results may also help in understanding hardening and softening mechanisms in PZT.