Ferroelectric thin films with complex composition of PNN–PZN–PMN–PZ–PT and excess NiO

Ferroelectric thin films of the 0.1Pb(Ni1/3Nb2/3)O3–0.35Pb(Zn1/3Nb2/3)O3–0.15Pb (Mg1/3Nb2/3)O3–0.1PbZrO3–0.3PbTiO3 (PNN–PZN–PMN–PZ–PT) complex oxide system were prepared on Pt/Ti/SiO2/Si substrates using a polymer-modified sol-gel method followed by a rapid thermal annealing (RTA) process. It was found that the addition of excess NiO is effective in stabilizing the perovskite phase while suppressing the pyrochlore phase. The crystalline structure and morphology of the films with different amounts of access NiO were studied with x-ray diffraction (XRD) and field-emission scanning electron microscopy (FE-SEM), respectively. The electrical properties, including dielectric, ferroelectric, and piezoelectric, showed a significant improvement with excess NiO. The film sample with 3 mol% of excess NiO exhibited optimized electrical properties. Different parameters, including tolerance factors on the basis of ionic radii, electronegativity differences between cations and anions, and oxygen bond valences, were applied to analyze the stability of the perovskite phase with different amount of excess NiO. Analysis results indicated that only the bond-valence theory could explain the effect of excess NiO on the stability of the perovskite phase under the assumption that the excess Ni2+ entered the A sites of the perovskite structure.