Effect of hydrogen on Pb(Zr,Ti)O3-based ferroelectric capacitors

The properties of ferroelectric films are known to degrade when subjected to hydrogen in forming gas anneals. Earlier studies have attributed this degradation to the loss of oxygen from these films during these anneals. In this study, we show that though oxygen is lost during forming gas annealing, hydrogen incorporation is the primary mechanism for the degradation of ferroelectric properties. Raman spectra obtained from the forming gas-annealed films show evidence of polar hydroxil [OH−] bonds in the films. The most probable site for hydrogen ions is discussed based on ionic radii, crystal structure, electrical properties, and Raman spectra. We propose that the hydrogen ion is bonded with one of the apical oxygen ions and prevents the Ti ion from switching. Pyroelectric measurements on forming gas-annealed capacitors confirm that the capacitors no longer possess spontaneous polarization.