Oxide electrodes as barriers to hydrogen damage of Pb(Zr,Ti)O3-based ferroelectric capacitors

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Abstract
The ferroelectric properties of Pb(Zr,Ti)O3 films are known to degrade when subjected to forming gas anneals. In an earlier publication we established that although there may be loss of oxygen and lead during forming gas anneal, the primary mechanism for loss of ferroelectricity is the incorporation of hydrogen and subsequent formation of [OH]−1 bonds between the ionized hydrogen and oxygen ions along the polarization axis in the octahedra. In this study, we show that (La,Sr)CoO3 oxide electrodes can act as a diffusion barrier to hydrogen during forming gas anneals. Forming gas anneal at lower temperatures such as 200 and 300 °C does not lead to a measurable loss of polarization. There is some loss of polarization during forming gas anneals at 450 °C for 12 h, however the capacitors still exhibit ferroelectric properties. The capacitors show no fatigue up to 1011 cycles, no imprint, good logic state retention characteristics, and similar slopes for the pulse width dependent polarization values before and after forming gas anneal in the measured range. More importantly, we have demonstrated that even a bare La0.5Sr0.5CoO3 top electrode can prevent the complete loss of ferroelectricity during forming gas treatment.