Controlling the Polarization in Ferroelectric PZT Films via the Epitaxial Growth Conditions

The integration of thin-film ferroelectrics with reliable properties into oxide electronics requires accomplishing deterministic polarization states. Since ferroelectricity emerges during thin-film synthesis already, it is essential to elucidate how the interplay of different growth parameters affects the polarization. Here, the polarization of fully strained Pb(Zr0.2Ti0.8)O-3 (PZT) films is accessed in situ, during epitaxial growth. Surprisingly, it is found that the orientation of the out-of-plane polarization during growth may differ from the one after growth completion and it strongly depends on the substrate temperature and the oxygen partial pressure. Increasing the growth temperature and/or the oxygen partial pressure favors a uniform downward-oriented polarization, independent of the direction of polarization during growth. Specifically, for films with an emerging upward-oriented polarization, a polarization reversal and a downward-oriented polarization after cool-down is observed. The in situ measurements obtained by optical second harmonic generation (SHG) in conjunction with ex situ piezoresponse force microscopy (PFM) and X-ray diffraction (XRD) measurements point to the temperature- and pressure-dependent formation of a charged Pb defect gradient toward the film surface as the responsible mechanism for the polarization reorientation.