Atomic/molecular layer deposition of Ti-organic thin films from different aromatic alcohol and amine precursors

•Atomic/molecular layer deposition involves metal and organic precursors.•Different organic precursors are investigated together with TiCl4.•Both homobifunctional and heterobifunctional precursors are investigated.•Hydroxy groups are found more reactive than amino groups towards TiCl4.•Combining both hydroxy and amino groups yields most ideal surface reactions. Atomic/molecular layer deposition (ALD/MLD) processes based on TiCl4 as the metal source, and hydroquinone (HQ), 4-aminophenol (AP), p-phenylenediamine (PDA) or 4,4′-oxydianiline (ODA) as the organic precursor are systematically investigated to shed light on the factors affecting the inorganic-organic thin film growth. All the four ALD/MLD processes yield amorphous Ti-organic thin films which are here characterized by ex-situ X-ray reflectivity and Fourier transform infrared measurements for the film thickness and bonding scheme. First principles modelling results are presented to explore differences in the interaction of organic precursors with surface-bound TiCl4. For the TiCl4+AP process the high growth rate achieved, i.e. ca. 10 Å per one ALD/MLD cycle, essentially corresponds to the ideal thickness of the [Ti-O-C6H4N-Ti] building unit. For both the ODA- and PDA-based processes the growth rates are considerably lower, while the TiCl4+HQ process yields the hybrid film with an intermediate growth rate. We attribute these observations to (i) the higher reactivity of the OH groups in comparison to the NH2 groups towards TiCl4, and (ii) the higher tendency of a heterobifunctional organic precursor to orientate vertically and avoid unwanted double reactions on the surface.