Effect of deposition temperature and thermal annealing on the dry etch rate of a-C: H films for the dry etch hard process of semiconductor devices

The effect of deposition and thermal annealing temperatures on the dry etch rate of a-C:H films was investigated to increase our fundamental understanding of the relationship between thermal annealing and dry etch rate and to obtain a low dry etch rate hard mask. The hydrocarbon contents and hydrogen concentration were decreased with increasing deposition and annealing temperatures. The I(D)/I(G) intensity ratio and extinction coefficient of the a-C:H films were increased with increasing deposition and annealing temperatures because of the increase of sp2 bonds in the a-C:H films. There was no relationship between the density of the unpaired electrons and the deposition temperature, or between the density of the unpaired electrons and the annealing temperature. However, the thermally annealed a-C:H films had fewer unpaired electrons compared with the as-deposited ones. Transmission electron microscopy analysis showed the absence of any crystallographic change after thermal annealing. The density of the as-deposited films was increased with increasing deposition temperature. The density of the 600 °C annealed a-C:H films deposited under 450 °C was decreased but at 550 °C was increased, and the density of all 800 °C annealed films was increased. The dry etch rate of the as-deposited a-C:H films was negatively correlated with the deposition temperature. The dry etch rate of the 600 °C annealed a-C:H films deposited at 350 °C and 450 °C was faster than that of the as-deposited film and that of the 800 °C annealed a-C:H films deposited at 350 °C and 450 °C was 17% faster than that of the as-deposited film. However, the dry etch rate of the 550 °C deposited a-C:H film was decreased after annealing at 600 °C and 800 °C. The dry etch rate of the as-deposited films was decreased with increasing density but that of the annealed a-C:H films was not. These results indicated that the dry etch rate of a-C:H films for dry etch hard masks can be further decreased by thermal annealing of the high density, as-deposited a-C:H films. Furthermore, not only the density itself but also the variation of density with thermal annealing need to be elucidated in order to understand the dry etch properties of annealed a-C:H films. - Highlights: ► A-C:H(amorphous carbon) films are grown for using hard mask in dry etch process by plasma-enhanced chemical vapor deposition and annealed. ► Physical, chemical and mechanical properties of grown amorphous carbon films are changed by hydrogen and hydrocarbon contents, be determined by deposition and annealing temperature. ► Dry etch rate of a-C:H films is decreased and the film density increased through thermal annealing with high density, low hydrogen content, as-deposited film.