Giant Modulation of Microstructure and Ferroelectric/Piezoelectric Responses in Pb(Zr,Ti)O₃ Ultrathin Films via Single-Pulse Femtosecond Laser

Ferroelectric oxides, such as Pb(Zr,Ti)O₃ (PZT), have been shown to maintain stable ferroelectricity even in ultrathin film configurations. However, achieving controllable modulation of microstructure and physical responses in these ultrathin films remains challenging, limiting their potential applications in modern nanoelectronics and optoelectronics. Here, we propose a single-pulse femtosecond (fs) laser micromachining technique for high-precision engineering of microstructure and ferroelectric/piezoelectric responses in ultrathin PZT films. The results show that various microstructures can be selectively fabricated through precise control of fs laser fluence. Specifically, nano-concave arrays are formed via low-fluence laser irradiation, which is mainly attributed to the fs laser peening effect. In contrast, nano-volcano (nano-cave) structures are generated when the laser fluence is close to or reaches the ablation threshold. Additionally, applying an fs laser pulse with fluence exceeding a critical threshold enables the formation of nano-cave structures with controlled depth and width in PZT/Pt/SiO₂ multilayers. Piezoresponse force microscopy measurements demonstrate that the laser peening process significantly enhances the piezoelectric response while exerting minimal influence on the coercive field of PZT thin films. This improvement is attributed to the enhanced electromechanical energy transfer and concentrated compressive stresses distribution in PZT thin films resulting from the laser peening effect. Our study not only offers an effective strategy for microstructure and property engineering in ferroelectric materials at the nanoscale but also provides new insights into the underlying mechanism of ultrafast laser processing in ferroelectric thin films.