Several authors have reported successful ALD growth of TiO₂ or TiN using TiCl₄
as a precursor and H₂O or N₂/H₂ as the reactant. However, the corrosive nature
of the HCl reaction by-product and/or the presence of small amounts of chlorine
in the film can be a drawback for certain applications. In this work, the metal
organic precursor tetrakis-dimethyl-amido titanium (Ti(N(CH₃)₂)₄, usually
abbreviated as TDMAT) was used for ALD growth of TiO₂ and TiN films. Oxygen,
water vapor, nitrogen or ammonia were used as reactants. The reactant was
flowing either directly into the ALD chamber (for thermal ALD) or through a
home-made inductively coupled RF plasma source for plasma enhanced ALD
(PE-ALD).

The kinetics of both thermal and plasma enhanced ALD were studied systematically
as a function of deposition temperature in the range of 50 °C to 350 °C. X-ray
reflectivity (XRR), x-ray diffraction (XRD) and x-ray photo-electron
spectroscopy (XPS) were used to characterize the thickness, crystallinity and
chemical composition of the films after growth.

Thermal ALD with H₂O and PE-ALD with O₂ or H₂O resulted in the deposition of
TiO₂ films. The as deposited films were amorphous, but could be crystallized
into the anatase phase after post-annealing at about 450 °C. Surprisingly, the
growth rate of thermal ALD with TDMAT and H₂O was observed to increase for
decreasing substrate temperatures, with a maximum rate of 0.14nm/cycle at a
substrate temperature of 50 °C.

Plasma enhanced ALD with N₂ or NH₃ resulted in the growth of TiN films at a rate
between 0.5 and 1 Angstrom per cycle. TiN films with a resistivity of about 1100 µOhm cm could be grown at temperatures between 150 and 300 °C

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