Hypothetic impact of chemical bonding on the moisture resistance of amorphous SixNyHz by plasma-enhanced chemical vapor deposition

Abstract

The relationship between the microstructure of silicon nitride and its sensitivity to moisture was studied. The effectiveness of Si-H rich and N-H rich silicon nitride layers was measured under attack from water in vapor and liquid states. For water vapor attack, samples are exposed to vapor at 85 °C with a relative humidity of 85% during 1600 hours; for liquid water attack, samples are dipped in water at 60, 85 and 100 °C for 200 hours. The water resistance of the Si-H rich and N-H rich silicon nitride layers was evaluated by measuring: (i) the thickness of the silicon dioxide formed after their oxidation with water vapor, (ii) the rate of dissolution of the silicon nitride in liquid water and (iii) the corresponding activation of energy. This evaluation was performed by coupling spectroscopic ellipsometry, infra-red and X-ray photoelectron spectrometry analyses. The results revealed that for Si-H rich layer, 10 nm of silicon dioxide was formed during the water vapor attack; for liquid water attack, a high activation energy (0.88 eV) and a low dissolution rate were observed regardless of the water temperature. For N-H rich layers, approximatively 6–8 nm of silicon dioxide was formed and a low activation energy (0.64 eV) with a high dissolution rate were observed. All of these observations lead to the conclusion that the N-H rich layers could be less resistant to moisture because the isoelectronic relationship between Si2N-H and −H2O+ facilitated their deterioration in water. Moreover, a higher rate of nanoporosity for N-H rich layers than Si-H rich layer could complete this hypothesis.