Volatility Differences in Actinide and Lanthanide N,N-Dimethylaminodiboranates as CVD Precursors: A DFT Study

Vlaisavljevich, B.; Miró, P.; Koballa, D.; Todorova, T.; Daly, S. R.; Girolami, G. S.; Cramer, C. J.; Gagliardi, L.
J. Phys. Chem. C 2012, 116, 23194 (doi:10.1021/jp305691y).

N,N-Dimethylaminodiboranate complexes with praseodymium, samarium, erbium, and uranium, which are potential chemical vapor deposition precursors for the deposition of metal boride and oxide thin films, have been investigated by density functional theory calculations (DFT) guided by field-ionization mass spectroscopy experiments. The calculations indicate that the volatilities of these complexes are correlated with the M-H bond strengths, as determined by Mayer bond order analysis. The geometries of the gas phase monomeric, dimeric, and trimeric species seen in field-ionization mass spectroscopy experiments were identified using DFT calculations, and the relative stabilities of these oligomers were assessed in order to understand how the lanthanide aminodiboranates depolymerize to their respective volatile forms during sublimation.