Considering this information and the homogeneous growth from the first ALD cycle on, we exclude the possibility that the defect OH species are the primary nucleation sites for TDMAH in the first half cycle. Instead, we propose that the nucleation on CoO(111) again occurs in the form of a Lewis acid-base reaction, similar to our observation on CoO(100). The appearance of additional IR signals in the first half cycle that do not originate from the -NMe2 ligands (neither bound to Hf nor bound to Co) indicates that follow-up reactions occur on the CoO(111) surface.