Method of manufacturing semiconductor device
The present invention provides a technology capable of removing impurities remaining in a thin film when the film is formed and modifying a characteristic of the thin film according to a change in impurity concentration. There is provided a method of manufacturing a semiconductor device including: (a) repetitively supplying a plurality of gases including elements constituting a film in temporally separated pulses (in non-simultaneous manner) to form the film on the substrate; and (b) exciting a modifying gas including a reducing gas and at least one of a nitriding gas and an oxidizing gas by plasma and supplying the modifying gas excited by plasma to modify the film.
1. A method of manufacturing a semiconductor device, comprising:
(a) plasma-exciting a modifying gas comprising a reducing agent and an organic amine based gas nitriding agent; and
(b) modifying a conductive metal nitride film containing an impurity by supplying the modifying gas plasma-excited in (a) to the conductive metal nitride film,
wherein, in (b), the reducing agent plasma-excited in (a) is supplied first and the organic nitriding agent plasma-excited in (a) is supplied second.
2. The method of claim 1 , wherein, in (b), a supply of the organic nitriding agent plasma-excited in (a) is started after stopping a supply of the reducing agent plasma-excited in (a) is stopped.
3. The method of claim 1 , wherein a supply of the organic nitriding agent plasma-excited in (a) is started during a supply of the reducing agent plasma-excited in (a).
4. The method of claim 1 , wherein, in (b), a supply of the reducing agent plasma-excited in (a) is stopped during a supply of the organic nitriding agent plasma-excited in (a).
5. The method of claim 1 , wherein (b) comprises:
(b-1) removing the impurity from the conductive metal nitride film by supplying the reducing agent plasma-excited in (a); and
(b-2) injecting nitrogen contained in the organic nitriding agent into a portion of the conductive metal nitride film having the impurity removed by supplying the nitriding agent plasma-excited in (a).
6. The method of claim 1 , wherein, in (b), a crystallization of the conductive metal nitride film is stimulated by supplying the organic nitriding agent plasma-excited in (a).
7. The method of claim 1 , further comprising: (c) removing a residual gas remaining on the conductive metal nitride film after a supply of the modifying gas plasma-excited in (a) is stopped, wherein a cycle of alternately performing (b) and (c) is repeated.
8. The method of claim 7 , wherein a duration of the supply of the modifying gas plasma-excited in (a) is adjusted to control a resistivity of the conductive metal nitride film.
9. The method of claim 8 , wherein the duration of the supply of the modifying gas is adjusted by controlling a number of times the cycle is repeated.
10. The method of claim 7 , wherein the cycle is repeated two or more times.
11. The method of claim 1 , wherein the reducing agent is deuterium gas.
12. The method of claim 1 , wherein the organic nitriding agent is an ethylamine-based gas.
13. The method of claim 1 , wherein the organic nitriding agent is a propylamine-based gas.
14. The method of claim 1 , wherein the organic nitriding agent is an isobutylamine-based gas.
15. The method of claim 1 , wherein the reducing agent is NH 3 gas.
16. The method of claim 1 , wherein the reducing agent is H 2 O gas.