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 degrees C. The as-deposited films are mainly amorphous and nearly stoichiometric HfO2 (O/Hf ratio similar to 1.9) with low bonded carbon content (similar to 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 similar to 6 angstrom 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 and the 50th process cycles as shown by transmission electron microscopy. Although the surface coverage is comparable for both starting surfaces, film measurements performed by SE suggest that thick films deposited on H-terminated Si are similar to 5 % thicker than similar films on the chemical oxide surface. Atomic force microscopy (AFM) measurements reveal higher surface roughness for the films deposited in the H-terminated surface. The SE and the AFM data are consistent with higher porosity for the films on H-terminated surfaces. (c) 2007 American Institute of Physics.