posted on 2023-12-19, 18:33authored byHyeongjin Kim, Jieun Hyun, Gaeun Kim, Eunsang Lee, Yo-Sep Min
Titanicone, obtained through molecular
layer deposition (MLD) using
TiCl4 and ethylene glycol (EG), is often regarded as a
thin film of titanium ethylene glycolate [Ti(OCH2CH2O)2]. Nevertheless, titanicone exhibits a distinct
vulnerability to moisture, while single crystals of Ti(OCH2CH2O)2 remain stable, even in the presence
of water. To elucidate the origin of instability, we investigated
the pathway of chemical degradation for titanicone using in situ and
ex situ analytical methods such as Fourier transform infrared spectrometry,
quartz crystal microbalance, quadrupole mass spectrometry, and X-ray
photoelectron spectroscopy. Our analyses unveiled that the instability
of the MLD-grown titanicone film in the presence of water can be primarily
attributed to the high chlorine content present as Ti–Cl species
and the coexistence of single-reacted EG species as well as double-reacted
EG species, unlike in Ti(OCH2CH2O)2 crystals. Water molecules react with the Ti–Cl species, leading
to the formation of Ti–OH species and the release of HCl gas.
Furthermore, the single-reacted EG species undergo an intramolecular
cyclization reaction catalyzed by HCl, resulting in the formation
of Ti–OH and the liberation of ethylene oxide. Consequently,
when exposed to water, the MLD-grown titanicone turns into a water-stable
mixed film composed of TiO2 and Ti(OCH2CH2O)2.