Nucleation of HfO2 atomic layer deposition films on chemical oxide and H-terminated Si

HfO2 thin films have been deposited by an atomic layer deposition (ALD) process using alternating pulses of tetrakis-ethylmethylamino hafnium and H2O precursors at 250 °C. The as-deposited films are mainly amorphous and nearly stoichiometric HfO2 (O/Hf ratio ∼1.9) with low bonded carbon content (∼3 at. %). A comparison of the nucleation stage of the films on OH- and H-terminated Si(100) surfaces has been performed using Rutherford backscattering spectrometry, x-ray photoelectron spectroscopy (XPS), and spectroscopic ellipsometry (SE). We find for the initial 5–7 process cycles that the film nucleates more efficiently on the OH-terminated surface. However, after the 7th cycle both surfaces exhibit similar surface coverage, which takes about 40 cycles to reach a steady growth rate per cycle. Angle resolved XPS measurements reveal the formation of a ∼6 A interfacial layer after four ALD cycles on the H-terminated surface and the thickness of the interfacial layer does not change substantially between the 4th...