Tailoring crystallisation of anatase TiO2 ultra-thin films grown by atomic layer deposition using 2D oxides as growth template

Abstract

TiO2 ultrathin films are required in many material research areas. The anatase phase was found to be more stable in case of atomic layer deposition growth, nevertheless a critical thickness of around 10 nm appears necessary to obtain crystallization on native silicon oxide on Si (001). This work focuses on direct liquid injection Atomic Layer Deposition (ALD) of TiO2 films with thicknesses about some nanometers, using titanium tetra-isopropoxide as precursor and H2O as oxidant. A particular care to the treatment of ellipsometric measurements is employed. Below the threshold value, films remain amorphous unless the growth starts onto a crystalized surface, a thick TiO2 layer in our case. Here we propose and show the efficiency of 2-dimensional (2D) [Ca2Nb3O10]− and [Ti0.865O2]0.54− nanosheets as seeds at the surface for the crystallization and epitaxy of ultra-thin films of TiO2 below the critical thickness. Furthermore, we show that the structure of the 2D nanosheets determines the growth orientation of the epitaxial anatase, namely (010) for [Ti0.865O2]0.54−, and (100) for [Ca2Nb3O10]−. These results, based on the tailoring of crystal anisotropy via adapted 2D seed nanosheets and low temperature ALD, opens the way for opto-electronics applications of titanium oxide layers of a few unit cells.