Role of HCl in Atomic Layer Deposition of TiO2 Thin Films from Titanium Tetrachloride and Water

Atomic layer deposition (ALD) of $TiO_2$ thin film from $TiCl_4$ and $H_2O$ has been intensively studied since the invention of ALD method to grow thin films via chemical adsorptions of two precursors. However the role of HCl which is a gaseous byproduct in ALD chemistry for $TiO_2$ growth is still intriguing in terms of the growth mechanism. In order to investigate the role of HCl in $TiO_2$ ALD, HCl pulse and its purging steps are inserted in a typical sequence of $TiCl_4$ pulse-purge-$H_2O$ pulse-purge. When they are inserted after the first-half reaction (chemisorption of $TiCl_4$), the grown thickness of $TiO_2$ becomes thinner or thicker at lower or higher growth temperatures than $300^{\circ}C$, respectively. However the insertion after the second-half reaction (chemisorption of $H_2O$) results in severely reduced thicknesses in all growth temperatures. By using the result, we explain the growth mechanism and the role of HCl in $TiO_2$ ALD.