Large-scale integrated fabrication in a H2 containing atmosphere, for example, during the passivation process, can cause serious damage in metal/Pb(Zr,Ti)O3/metal capacitors (i.e., Pt/PZT/Pt capacitors). To reveal the cause of the H2 damage, we investigated the behavior of hysteresis curves and the leakage current of capacitors with a top electrode of Pt, Pd, Au, or Ag. Capacitors with a top electrode of Au or Ag are more resistant to the H2 annealing damage than those of Pt or Pd. We found that the H2 damage was strongly affected by the catalytic activity and adsorptive properties of the top electrode when exposed to H2.

One of the most serious forms of damage that occurs during the integration of Pt/PZT/Pt ferroelectric capacitors [where PZT is Pb(ZrxTi1−x)O3] is the disappearance of polarization hysteresis characteristics during the passivation process. The hydrogen content of the atmosphere during this process affects the ferroelectric capacitor characteristics. However, the PZT film itself is not damaged by annealing in a hydrogen-containing atmosphere even at 400 °C, whereas the Pt/PZT/Pt ferroelectric capacitor loses its polarization hysteresis characteristics at 300 °C. The top Pt electrode was found to induce this damage. Possible mechanisms such as stress and a chemical reaction with the Pt catalyst are discussed.

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We used a density functional method to investigate the mechanism of negative-bias temperature instability (NBTI) and resultant structural changes of Si/SiO2 and Si/SiOxNy interfaces. The reaction energies for the water- and hydrogen-originated instabilities of several interface defects show that water-originated reactions of oxygen and nitrogen vacancies occur most easily. The larger instability of the Si/SiOxNy interface, compared with the Si/SiO2 interface, can be understood in terms of the difference in reaction energies. According to the calculated nitrogen 1s core-level shifts of the nitrogen atoms at the Si/SiOxNy interface, it is possible to identify a NBTI-generated structure at the Si/SiOxNy interface by x-ray photoelectron spectroscopy.

The Pt/PbZrxTi1−xO3 (PZT) interfacial reaction caused by low-temperature (320 °C) annealing and resulting change in the surface Fermi level position (Schottky barrier height) has been studied by using in vacuo x-ray photoelectron spectroscopy (XPS). A thin (2 nm) Pt layer was deposited on a polycrystalline PZT film and annealed in 0.5-Torr H2 and O2 in a chamber connected to the XPS chamber. For the PZT samples annealed prior to Pt deposition, a small amount of metallic Pb was produced after the Pt deposition. The annealing also moved the surface Fermi level (EF) at the Schottky interface toward the conduction band minimum (EC) of PZT by 0.4 eV, as evidenced by the band-bending shift of the PZT core levels. Excess metallic states appeared in the valence-band spectra of an annealed bare PZT surface. There was no appreciable annealing-atmosphere dependence in the amount of metallic Pb produced and surface EF position at the PT/PZT interface. However, a clear annealing-atmosphere dependence was observed for the samples annealed after the Pt deposition. The H2 annealing enhanced the production of metallic Pb, whereas the O2 annealing suppressed the metallic Pb formation. The H2 annealing moved the surface EF toward EC by 1.0 eV, whereas the O2 annealing caused no measurable change in the surface EF position. The catalytic effect of Pt during the annealing was postulated to explain the observed annealing-atmosphere dependence.