Effect of structural in-depth heterogeneities on electrical properties of Pb(Zr0.52Ti0.48) O3 thin films as revealed by nano-beam X-ray diffraction

Abstract

A direct quantification of a structural in-depth composition in the lead zirconate titanate Pb(Zr,Ti)O3 thin films of morphotropic composition has been conducted using the newly available X-ray nano-pencil beam (i.e., beam size of 100 nm × 1 μm) diffraction approach. We tested two samples with different Zr/Ti chemical gradients. Here, we demonstrate the presence of a significant microstructural gradient between the rhombohedral and tetragonal phases through PbZrxTi1−xO3 (PZT) films with a 100 nm in-depth resolution. The phase gradient extends over around 350 nm, and it is repeated through the PZT film three times, which corresponds to the number of thermal annealings. Moreover, this microstructural gradient is in agreement with the Zr/Ti chemical gradient observed by the secondary ion mass spectroscopy (SIMS). Indeed, the quantity of tetragonal phases rises in the Ti-rich zones as revealed by SIMS, and the quantity of rhombohedral phases rises in the Zr-rich zones. We also demonstrated a huge difference in the in-depth phase variation between the two tested samples. The gradient free sample still contains 4.7% of phase variation through the film and the amplified gradient contains 9.6% of phase variation through the film. Knowing that the gradient free sample shows better electric and piezoelectric coefficients, one can draw a correlation between the chemical composition, crystallographic homogeneity, and electro-mechanical properties of the film. The more close the film is to the morphotropic composition and the more it is crystallographically homogeneous, the higher the piezoelectric coefficients of the PZT are. Finally, the adequate knowledge of phase variation and its relation to the fabrication technique are crucial for the enhancement of the PZT electro-mechanical properties. Our methodology and findings open up new perspectives in establishing a relevant quantitative feedback to reach an ultimate electro-mechanical coupling in the sol-gel PZT thin films.