Fig. 2: Adsorption behaviour and blocking property of TMPMCT inhibitor.

a Surface reaction energy diagram of TMPMCT molecules on the TiO2 surface calculated by DFT. The structures below correspond to the Path 1. The dotted lines represent the reactions, where TS (transition states) structures were not calculated. Colours: Tisurf (light blue), TiTMPMCT (yellow green), Osurf (red), OTMPMCT (purple), C (brown), H (white pink). The corresponding chemical equations: Phy.: Cp(CH3)5Ti(OMe)3, Ads.: *-Cp(CH3)5Ti(OMe)3, 1OMe disso.: *-Cp(CH3)5Ti(OMe)2 + *-(OMe), 2OMe disso.: *-Cp(CH3)5Ti(OMe) + 2·*-(OMe), 3OMe disso.: *-Cp(CH3)5Ti + 3·*-(OMe). Phy. (Physisorption), Ads. (Adsorption), disso. (dissociation), surf (surface), * refers to adsorbed species. b WCA measurement with various exposure times of TMPMCT on the TiO2 surface. Fitting of the JMAK model (dashed lines) to the data (points with error bars) obtained from c the growth of subsequent TiO2 ALD on the TMPMCT inhibitor layer (20, 40 and 60 s), and d selectivity calculated from the thickness measured by ellipsometry. e Areal coverage of TMPMCT on the TiO2 surface (10 nm × 10 nm) using various impingement numbers calculated by MC simulation and the coverage of TDMAT on the TMPMCT-inhibited surface. f Adsorption mechanism of TMPMCT inhibitor. Unoccupied sites serve as starting points for the nucleation sites of TiO2 in subsequent ALD cycles. Source data are provided as a Source data file.