Selective etch of metal nitride films
Processing methods comprising oxidizing a metal nitride film to form a metal oxynitride layer and etching the metal oxynitride layer with a metal halide etchant. The metal halide etchant can be, for example, WCl 5 , WOCl 4 or TaCl 5 . Methods of filling a trench with a seam-free gapfill are also described. A metal nitride film is deposited in the trench to form a seam and pinch-off an opening of the trench. The pinched-off opening is subjected to a directional oxidizing plasma and a metal halide etchant to open the pinched-off top and allow access to the seam.
1. A selective etch method comprising:
providing a substrate having a trench formed in a surface of the substrate, the trench having a bottom and sidewalls;
depositing a metal nitride film in the trench so that the metal nitride film grows in the trench forming a seam within the trench and metal nitride film near a top of the trench pinches off access to the seam;
exposing the metal nitride film to a directional oxidizing plasma to oxidize the metal nitride film near the top of the trench to form a metal oxynitride layer;
exposing the metal oxynitride layer to a metal halide etchant to etch the metal oxynitride layer from the metal nitride film to remove the pinch off of the trench and allow access to the seam; and
depositing additional metal nitride film in the trench to fill the seam.
2. The method of claim 1 , wherein the metal nitride film comprises one or more of TaN or TiN.
3. The method of claim 1 , wherein the oxidizing agent comprises one or more of air, O 2 , O 3 or H 2 O or combinations thereof.
4. The method of claim 1 , wherein the metal halide etchant comprises one or more of WCl 5 , WOCl 4 or TaCl 5 .
5. The method of claim 1 , wherein the metal oxynitride layer is formed in a self-limiting process.
6. The method of claim 1 , wherein the metal halide has an etch rate for the metal oxynitride layer that is greater than about 10 times the etch rate for the metal nitride film.
7. The method of claim 1 , wherein the etchant comprises substantially no plasma.
8. The method of claim 1 , wherein the metal halide etchant comprises halogen atoms consisting essentially of chlorine.
9. The method of claim 1 , wherein exposures to the oxidizing agent and metal halide etchant are repeated to remove a predetermined amount of the metal nitride film.
10. The method of claim 4 , wherein the metal halide etchant consists essentially of one or more of WCl 5 , WOCl 4 or TaCl 5 .
11. The method of claim 4 , wherein the metal halide etchant is a solid contained within an ampoule configured for vapor draw using a carrier gas at an ampoule temperature.
12. The method of claim 11 , wherein the metal halide etchant comprises WCl 5 and the ampoule temperature is in the range of about 110° C. to about 150° C.
13. The method of claim 11 , wherein the metal halide etchant comprises WOCl 4 and the ampoule temperature is in the range of about 50° C. to about 90° C.
14. The method of claim 11 , wherein the metal halide etchant comprises TaCl 5 and the ampoule temperature is in the range of about 80° C. to about 120° C.