Roles of plasma-generated vacuum-ultraviolet photons and oxygen radicals in damaging nanoporous low-k films

Abstract

One important class of low-k materials used as interconnect dielectrics employs methyl groups added to nanoporous SiO2 matrices. These carbon-doped oxide materials are known to be susceptible to damage from plasma species during various stages of plasma processing. Two key active species generated in O2 plasma are oxygen (O) radicals and vacuum-ultraviolet (VUV) photons. These species are known to cause carbon loss, resulting in damaging increases in dielectric constant throughout the film. However, the mechanisms through which this damage is incurred are poorly understood. By capping the substrate in different ways during plasma exposure, it is possible to expose films to either photons alone or O atoms alone. The authors report measurements of damage induced by VUV photons only, O radicals only, and the combination of O radicals and photons. Through HF stripping, they note that carbon extraction from photons and from radicals yields different outcomes; the profile of carbon concentration within the modified region is different for each case. Damage from photons alone can be modeled and model predictions are in good agreement with measurements. Damage from O atoms alone can only be modeled if it is assumed that the near-surface region has a significantly reduced diffusivity compared to the bulk of the film. Experiment and model agree that both photons alone and O radicals alone damage the material by removing carbon. When radicals and photons are present simultaneously during plasma exposure, however, more C removal appears to be occurring in the model than experimentally observed. Remarkably, if only radicals are exposed to the film after short (10–30 s) plasma exposures, very little additional damage is incurred during this radical-only exposure. The most straightforward interpretation of these results appears to be that photons combine synergistically with radicals in the pores to narrow the pores, thereby reducing film diffusivity in the C-poor, plasma-damaged regions.