Quantitative X‐Ray Spectrum Imaging of Lead Lanthanum Zirconate Titanate PLZT Thin‐Films

The high permittivity of Pb(Zr,Ti)O 3 and (Pb,La)(Zr,Ti)O 3 —PZT and PLZT, respectively—thin films and the flexibility of chemical solution deposition (CSD) make solution‐derived P(L)ZT thin films extremely attractive for integrated capacitor applications. However, Pb‐loss or cation segregation during processing results in degraded properties of the final film. Here, we have extended the use of multivariate statistical analysis (MSA) of energy‐dispersive spectroscopy (EDS) spectrum images (SIs) in scanning transmission electron microscopy (STEM) to allow the two‐dimensional (2D) quantitative analysis of cation segregation and depletion in P(L)ZT thin films. Quantified STEM‐EDS SIs allow high‐resolution (< ≈10 nm) quantification of these cation distributions. Surface Pb depletion is found after crystallization and is replenished by a unique post‐crystallization PbO overcoat+anneal processes. Zr/Ti and La segregation are found to develop in a decidedly nonplanar fashion during crystallization, especially in PLZT 12/70/30 material, highlighting the need for 2D analysis. Quantitative 2D chemical information is essential for improved processing of homogeneous P(L)ZT films with optimal electrical properties.