Atomic Layer Deposition of Cobalt Using H2-, N2-, and NH3-Based Plasmas: On the Role of the Co-reactant

This work investigates the role of the co-reactant for the atomic layer deposition of cobalt (Co) films using cobaltocene (CoCp2) as the precursor. Three different processes were compared: an AB process using NH3 plasma, an AB process using H2/N2 plasma, and an ABC process using subsequent N2 and H2 plasmas. A connection was made between the plasma composition and film properties, thereby gaining an understanding of the role of the various plasma species. For NH3 plasma, H2 and N2 were identified as the main species apart from the expected NH3, whereas for the H2/N2 plasma, NH3 was detected. Moreover, HCp was observed as a reaction product in the precursor and co-reactant subcycles. Both AB processes showed self-limiting half-reactions and yielded similar material properties, that is, high purity and low resistivity. For the AB process with H2/N2, the resistivity and impurity content depended on the H2/N2 mixing ratio, which was linked to the production of NH3 molecules and related radicals. The ABC process resulted in high-resistivity and low-purity films, attributed to the lack of NHx,x≤3 species during the co-reactant exposures. The obtained insights are summarized in a reaction scheme where CoCp2 chemisorbs in the precursor subcycle and NHx species eliminate the remaining Cp in the consecutive subcycle.