Polarization landscape effects in soft X-ray-induced surface chemical decomposition of lead zirco-titanate, evidenced by photoelectron spectromicroscopy

The stability of thin films of lead zirco-titanate (PZT) under intense soft X-ray beams is investigated by time-resolved photoelectron spectromicroscopy with a lateral resolution below 1 micrometer. Surface dissociation is observed when samples are irradiated with intense (5 × 10²³ photons per s per m²) soft X-rays, with promotion of reduced lead on the surface. On areas exhibiting outwards polarization (P⁽⁺⁾), the reduced lead is formed at the expense of P⁽⁺⁾-PZT. On areas presenting co-existing P⁽⁺⁾ states with areas without out-of-plane polarization (P⁽⁰⁾), the reduced lead is formed at the expense of the P⁽⁰⁾-PZT component, while the P⁽⁺⁾-PZT remains constant. The main dissociation mechanism was found to be triggered by 'hot' electrons in the conduction band, with energies exceeding the surface dissociation energies. Dissociation occurs basically when the electron affinity is larger than the dissociation energy of PbO (for P⁽⁺⁾ areas) or PbO^- (for P⁽⁰⁾ areas). Such mechanisms may be adapted for dissociation of other molecules on surfaces of ferroelectric thin films or for quantifying the stability of ferroelectric surfaces interacting with other radiation, with applications in the fields of photocatalysis or photovoltaic devices.