Effects of plasma and vacuum-ultraviolet exposure on the mechanical properties of low-k porous organosilicate glass

The effects of plasma exposure and vacuum-ultraviolet (VUV) irradiation on the mechanical properties of low-k porous organosilicate glass (SiCOH) dielectric films were investigated. Nanoindentation measurements were made on SiCOH films before and after exposure to an electron-cyclotron-resonance plasma or a monochromatic synchrotron VUV beam, to determine the changes of film hardness, elastic modulus, and crack threshold due to these exposures. This permits the effects of ion bombardment and photon bombardment to be analyzed separately. The role of energetic ions was examined with a variety of inert plasma-exposure conditions. The role of VUV photons was analyzed as a function of synchrotron photon energy. It was found that both energetic ions and VUV photons with energies larger than the bond energy of the Si-O bond cause a significant increase in film hardness along with a smaller increase in elastic modulus and crack threshold. Differential Fourier transform infrared spectra and x-ray photoemission spectroscopy results show that the energetic ions affect the SiCOH properties mainly through physical bombardment, during which the ions transfer their momentum to the Si-O-Si backbone and transform them into more energetically stable Si-O-Si network structures. This results in the Si-O-Si network structures becoming densified. VUV photons assist reaction that increase the number of bridging O-3 Si-O-Si O-3 bonds and deplete nonbridging O-3 Si-O and C-Si O-3 bonds. This increased degree of cross linking in porous organosilicate dielectrics can substantially enhance their hardness and elastic modulus while showing no significant film shrinkage or densification. (C) 2014 AIP Publishing LLC.