Optimization of synthesis of the solid solution, Pb(Zr1–xTix)O3 on a single substrate using a high-throughput modified molecular-beam epitaxy technique

Synthesis of Pb(Zr1–xTix)O3 (PZT) on a single substrate using a high-throughput molecular-beam epitaxy technique was demonstrated. In situ synthesis of crystalline PZT at elevated substrate temperatures could not be achieved, as reevaporation of Pb (PbO) occurred and the partial pressure of O2 was insufficient to prevent formation of a PbPtx phase during deposition. Instead, ex situ postdeposition annealing was performed on PZT deposited at room temperature. Dense single phase PZT was prepared with a compositional range of 0.1 > x > 0.9, for film thicknesses up to 800 nm. Transmission electron microscopy revealed the grain size increased from 50 nm to ~0.5 µm with increasing Zr-concentration and became more columnar. Raman, x-ray diffraction, and scanning electron microscopy/energy dispersive spectroscopy results revealed a morphotropic phase boundary between rhombohedral and tetragonal phases occurred at x ~0.4 rather than at x = 0.47 in bulk ceramics. This was attributed to clamping arising from mismatch in thermal expansion between the film and substrate.