Moisture Adsorption in Plasma-Damaged Porous Low-k Dielectrics

Plasma etch/ash processes can induce changes in low-k film surface/bulk chemistries and topographies resulting in increased water absorption, surface roughness, and metal intrusion. After ashing, the altered surface character of the low-k can impact wetting, adhesion, and, consequently, the resistance of subsequently deposited barrier layers. In this work, we describe the use of deuterium oxide as means of measuring moisture penetration into low-k films. Film chemistries have been monitored using grazing angle attenuated total reflectance (GATR) and transmission Fourier transform infrared spectroscopy (FTIR). To study moisture absorption in porous spin-on and CVD low-k films, unashed and ashed films have been exposed to D2O liquid and vapor treatments under “dry” nitrogen. The extent of D 2 O uptake, removal and exchange reactions has been studied using transmission and GATR FTIR methods because the D 2 O and O-D adsorption peaks are distinct from water and O-H as well as other low-k adsorptions. This method can be used to study Si-OH species because deuterium can exchange with hydrogen within silanols under ambient conditions while methyl groups are much less likely to exchange. Three different low-k films, a porous spin-on MSQ (k=2.2), a porous CVD (k=2.3), and an organosilicate glass (OSG, k=2.85) have been used. In FTIR spectra, unashed low-k films show minimal D 2 O adsorption. In MSQ hydrogen-ashed films, the data suggest the presence of deuterium oxide and O-D peaks. Further, D 2 O adsorption appears to be considerably higher for ashed films as would be expected due to the hydrophobicity of these films. In the CVD films, there does not appear to be as marked a difference. This method permits the introduction of a chemical “marker” into low-k wet and ambient processes allowing one to distinguish among adsorptions from different aqueous sources.