Atomic layer deposition (ALD) of titanium dioxide (TiO2) high-κ dielectric films on brominated Ge substrates using titanium tetrachloride and water has been studied. A strong temperature dependence was observed for the TiO2 deposition rate. An accelerated growth rate was measured for the first 15 ALD cycles at 300 °C; this effect is attributed to bromine desorption and resultant deposition on halide-free Ge. Results suggest that TiO2 films were deposited with no interfacial oxide layer at 300 °C. The films were in a crystalline anatase phase at 300 °C, and were amorphous when deposited at 100 °C.