Dissociative ionization and electron beam induced deposition of tetrakis(dimethylamino)silane, a precursor for silicon nitride deposition

Motivated by the use of tetrakis(dimethylamino)silane (TKDMAS) to produce silicon nitride-based deposits and its potential as a precursor for Focused Electron Beam Induced Deposition (FEBID), we have studied its reactivity towards low energy electrons in the gas phase and the composition of its deposits created by FEBID. While no negative ion formation was observed through dissociative electron attachment (DEA), significant fragmentation was observed in dissociative ionization (DI). Appearance energies (AEs) of fragments formed in DI were measured and are compared to the respective threshold energies calculated at the DFT and coupled cluster (CC) levels of theory. The average carbon and nitrogen loss per DI incident is calculated and compared to its deposit composition in FEBID. We find that hydrogen transfer reactions and new bond formations play a significant role in the DI of TKDMAS. Surprisingly, a significantly lower nitrogen content is observed in the deposits than is to be expected from the DI experiments. Furthermore, a post treatment protocol using water vapour during electron exposure was developed to remove the unwanted carbon content of FEBIDs created from TKDMAS. For comparison, these were also applied to FEBID deposits formed with tetraethyl orthosilicate (TEOS). In contrast, effective carbon removal was achieved in post treatment of TKDMAS, while his approach only marginally affected the composition of deposits made with TEOS.

Automated summary

Motivated by the potential use in Focused Electron Beam Induced Deposition (FEBID), the reactivity of tetrakis(dimethylamino)silane (TKDMAS) towards low energy electrons and the composition of its deposits were studied. Significant fragmentation was observed in dissociative ionization (DI), with hydrogen transfer reactions and new bond formations playing a significant role. However, the nitrogen content in the deposits was surprisingly lower than expected. A post treatment protocol using water vapor was developed to remove unwanted carbon content in FEBIDs created from TKDMAS.