Method of manufacturing semiconductor device and method of processing substrate and substrate processing apparatus

A method of processing a substrate, comprising:

• (a) supplying a monochloro-silane gas to a substrate disposed in a processing chamber;
• (b) supplying a plasma-excited hydrogen-containing gas to the substrate disposed in the processing chamber;
• (c) supplying a plasma-excited or heat-excited nitrogen-containing gas to the substrate disposed in the processing chamber;
• (d) supplying at least one of a plasma-excited nitrogen gas and a plasma-excited rare gas to the substrate disposed in the processing chamber;
• and
• (e) performing a cycle comprising the steps (a) through (d) a predetermined number of times to form a silicon nitride film on the substrate.

A substrate processing apparatus comprising:

• a processing chamber configured to accommodate a substrate;
• a first gas supply system configured to supply a monochloro-silane gas to a substrate accommodated in the processing chamber;
• a second gas supply system configured to supply a nitrogen-containing gas to a substrate accommodated in the processing chamber;
• a third gas supply system configured to supply a hydrogen-containing gas to a substrate accommodated in the processing chamber;
• a fourth gas supply system configured to supply at least one of a nitrogen gas and a rare gas to a substrate accommodated in the processing chamber;
• an excitation unit configured to plasma-excite or heat-excite a gas;
• and
• a controller configured to control the first gas supply system, the second gas supply system, the third gas supply system, the fourth gas supply system and the excitation unit to perform a cycle comprising supplying the monochloro-silane gas to a substrate accommodated in the processing chamber, supplying the hydrogen-containing gas plasma-excited by the excitation unit to the substrate accommodated in the processing chamber, supplying the nitrogen-containing gas plasma-excited or heat-excited by the excitation unit to the substrate accommodated in the processing chamber and supplying at least one of the nitrogen gas and the rare gas plasma-excited by the excitation unit to the substrate accommodated in the processing chamber to form a silicon nitride film on the substrate.