Effects of Remanent Polarization State and Internal Field in Ferroelctric Film on the Hydrogen-Induced Degradation Characteristics in Pt/Pb(Zr,Ti)O3/Pt Capacitor

Abstract

The ferroelectric properties of Pb(Zr,Ti)O<TEX>$_3$</TEX>[PZT] films degrade when the films with Pt top electrodes are annealed in hydrogen containing environment. This is due to the reduction activity of atomic hydrogen that is generated by the catalytic activity of the Pt top electrode. At the initial stage of hydrogen annealing, oxygen vacancies are formed by the reduction activity of hydrogen mainly at the vicinity of top Pt/PZT interface, resulting in a shift of P-E (polarization-electric field) hysteresis curve toward the negative electric field direction. As the hydrogen annealing time increases, oxygen vacancies are formed inside the PZT film by the inward diffusion of hydrogen ions, as a result, the polarization degrades significantly and the degree of P-E curve shift decreases gradually. The direction and the magnitude of the remnant polarization in the PZT film affect the motion of hydrogen ions which determines the degradation of polarization characteristics and the shift in the P-E hysteresis curve of the PZT capacitor during hydrogen annealing. When the remnant polarization is formed in the PZT film by applying a pre-poling voltage prior to hydrogen annealing, the direction of the P-E curve shift induced by hydrogen annealing is opposite to the polarity of the pre-poling voltage. The hydrogen-induced degradation behavior of the PZT capacitor is also affected by the internal field that has been generated in the PZT film by the charges located at the top interface prior to hydrogen annealing.