Low-energy electron interaction and focused electron beam-induced deposition of molybdenum hexacarbonyl (Mo(CO)₆)

Motivated by the potential role of molybdenum in semiconductor materials, we present a combined theoretical and experimental gas-phase study on dissociative electron attachment (DEA) and dissociative ionization (DI) of Mo(CO)₆ in comparison to focused electron beam-induced deposition (FEBID) of this precursor. The DEA and DI experiments are compared to previous work, differences are addressed, and the nature of the underlying resonances leading to the observed DEA processes are discussed in relation to an earlier electron transmission study. Relative contributions of individual ionic species obtained through DEA and DI of Mo(CO)₆ and the average CO loss per incident are calculated and compared to the composition of the FEBID deposits produced. These are also compared to gas phase, surface science and deposition studies on W(CO)₆ and we hypothesize that reductive ligand loss through electron attachment may promote metal-metal bond formation in the deposition process, leading to further ligand loss and the high metal content observed in FEBID for both these compounds.