Effect of nitrogen containing plasmas on interface stability of hafnium oxide ultrathin films on Si(100)

Abstract

Hafnium oxide dielectric thin films were deposited by metalorganic chemical vapor deposition with Hf (IV) t-butoxide and either an O2, N2, or N2O plasma in a 1:1 ratio with helium. Films approximately 5nm thick were analyzed using angle-resolved x-ray photoelectron spectroscopy (XPS) and variable angle ellipsometry before and after heat treatment in an ultrahigh vacuum up to 470°C. Interdiffusion and/or reaction of the film with the silicon substrate, as measured by an increase in thickness and an increase in Si-O type bonding at the interface was most apparent with O2 plasma deposited films and least observed with N2 plasma deposited films. Also, the Hf(4f) XPS peak shifts toward higher binding energy after anneals for the N2 and N2O plasma deposited films indicates further oxidation of the film. In contrast, oxygen plasma deposited films do not exhibit a Hf(4f) peak shift. These results provide evidence that high-κ film∕substrate stability may be controlled by applying appropriate plasma chemistry.