Microstructure and growth rate of chemical vapour deposited TiN films in a vertical cold wall reactor

TiN films were grown on SUS304 substrates heated by an induction furnace in a vertical cold wall reactor. Scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterize the microstructures of films obtained at different deposition conditions (temperature, gas flow rate and gas composition). Film structures obtained in the present vertical reactor had the following features compared with those in the tubular reactor: (1) Abnormally grown “star-shaped” crystals were observed on the surfaces of films deposited in the following ranges of total gas flow rate (Q_T), temperature (T) and partial pressures (P): 9.0×10⁻⁶ ≤ Q_T ≤ 1.6×10⁻⁵ m³ s⁻¹, 1223 ≤ T ≤ 1273 K, 0.92 ≤ P_TiCl4 ≤ 6.18 kPa, P_H2 = P_N2. The matrix grains were responsible for (211) preferred orientation. (2) Surface morphologies did not vary so much with P_TiCl4. On the other hand, a drastic change was brought about by adding HCl to the source gas, i.e., plate-shaped crystals dominated and the large “star-shaped” crystals were no longer present. (3) The apparent activation energy for deposition reaction was 230 kJ/mol (1173 ≤ T ≤ 1273 K) and 76.5 kJ/mol (1273 ≤ T ≤ 1373 K) at P_TiCl4 = 2.43 kPa and P_H2 = P_N2 = 49.45 kPa.