The role of ultraviolet radiation during ultralow k films curing: Strengthening mechanisms and sacrificial porogen removal

Abstract

This work proposes a fundamental understanding of structural transformation occurring during porogen extraction from as-deposited ultralow k (ULK) materials when exposed to ultraviolet (UV) radiation during thermal curing. Specific explanations are provided for as deposited films at high temperature (T>250 °C). This temperature range is sufficient to assess thin-film stability. Two distinguished regimes were identified in the curing process. During the first stage, the film shrinks strongly in similar proportion to SiCH3 break. Preferential impact of UV radiation on hydrocarbon porogen bonds leads also to a break of SiCH3 structures. In this work, 5 min of curing is enough to remove the porogen and create the max of porosity (33%). After the porogen removal step, the porous film shrinks under UV radiation leading to an increase of SiOSi bond concentration. A structural rearrangement of the bulk is initiated since the porogen is totally evacuated from the film. The increase of normalized infrared SiOSi peak during UV curing (related in literature to an improvement of mechanical properties) is mainly due to film densification (a few SiOSi bonds creation). The origin of shrinkage is explained by the breaking of SiCH3 which could turn into a SiH bond leading to a free volume reduction within the film. In this case, a correlation is found between shrinkage and elastic modulus. The resulting SiOSi structure densification drives, at first order, the improvement of the mechanical properties. UV radiation exposure shows no effect in silanol condensation and acts mainly on the porogen decomposition and bulk densification. Si-CH2-Si structure formation, pointed out in the literature as a possible reaction way to enhance film crosslinking, is identified in the nuclear magnetic resonance (NMR) broadband spectrum of the ULK film. However, resulted NMR and infrared peaks intensities suggest its formation as a minor. This study gives a full understanding of UV curing impact on ULK films (k≤2.5) where structure densification is identified as a main process to enhance the film strength in addition to the crosslinking.