Method for depositing a silicon nitride film and film deposition apparatus

1. A method for depositing a silicon nitride film, comprising:

depositing a silicon nitride film by ALD in a depression formed in a surface of a substrate from a bottom surface and a lateral surface toward a center of the depression in a lateral direction so as to narrow a space at the center of the depression; wherein the silicon nitride film is deposited in the depression by: forming an adsorption inhibiting region in which a H group in an NH 2 group formed on a surface is replaced by a Cl group that inhibits adsorption of a silicon-containing gas that contains chlorine, on an upper portion in the depression by adsorbing a chlorine gas; adsorbing the silicon-containing gas on an NH 2 group on a region other than the adsorption inhibiting region in the depression by supplying the silicon-containing gas into the depression by chemical adsorption; and depositing a molecular layer of the silicon nitride film in which an NH 2 group is formed on a surface in the depression by supplying ammonia gas into the depression so as to cause the silicon-containing gas adsorbed on the depression to react with the ammonia gas, and periodically repeating: forming the adsorption inhibiting region on the upper portion in the depression; adsorbing the silicon-containing gas on the region other than the adsorption inhibiting region; and depositing the molecular layer of the silicon nitride film in the depression;

switching supply of nitriding gas from the ammonia gas to nitrogen gas at a final stage of filling the space at the center of the depression;

adsorbing a first nitrogen radical into the depression immediately before a stage of filling the space at the center with the silicon nitride film deposited toward the center of the depression;

adsorbing the silicon-containing gas on the first nitrogen radical in the depression by physical adsorption; and

supplying a second nitrogen radical into the depression so as to release the silicon-containing gas from the first nitrogen radical and to cause the released silicon-containing gas to react with the second nitrogen radical, thereby depositing a silicon nitride film by CVD to fill the space at the center.

2. The method for depositing the silicon nitride film according to claim 1 , wherein adsorbing the silicon-containing gas by physical adsorption and depositing the silicon nitride film to fill the space are repeated, thereby completely filling the space at the center.

3. The method for depositing the silicon nitride film according to claim 1 , wherein the ammonia gas is supplied as an ammonia plasma.

4. The method for depositing the silicon nitride film according to claim 3 , wherein the chlorine gas is made of a chlorine radical.

5. The method for depositing the silicon nitride film according to claim 4 ,

wherein the plasma for activating the chlorine gas to make the chlorine radical is remote plasma, and

wherein the ammonia plasma, the first nitrogen radical, and the second nitrogen radical are generated using inductively coupled plasma.

6. The method for depositing the silicon nitride film according to claim 1 ,

wherein depositing the silicon nitride film, switching supply of nitriding gas from the ammonia gas to nitrogen gas, adsorbing the first nitrogen radical into the depression, adsorbing the silicon-containing gas on the first nitrogen radical by physical adsorption, and supplying the second nitrogen radical into the depression are made a cycle, and the cycle is repeated multiple times depending on a depth range of the depression until filling up the depression.