Methods for selective deposition using self-assembled monolayers

1. A method of selectively depositing a layer atop a substrate having a metal surface comprising copper, cobalt, tungsten, or molybdenum, or combination thereof and an adjacent dielectric surface, consisting essentially of:

(a) during a semiconductor device fabrication comprising atomic layer deposition or chemical vapor deposition process, contacting the metal surface with, concurrently, one or more metal halides to convert a metal component of a surface metal oxide to volatile metal halide to form an exposed metal surface at a pressure in an amount of 1 to 15 Torr, at a first temperature of about 300 to about 400 degrees Celsius, wherein the one or more metal halides is a metal chloride comprising WClx, MoClx, or combinations thereof, wherein x is an integer, wherein forming the exposed metal surface consists of said contacting with metal halides, or said contacting with metal halides and contacting with diatomic hydrogen gas;

(b) growing an organosilane based self-assembled monolayer atop the dielectric surface; and

(c) selectively depositing a layer atop the exposed metal surface of the substrate, wherein the organosilane based self-assembled monolayer inhibits deposition of the layer atop the dielectric surface.

2. The method of claim 1 , wherein contacting the metal surface with one or more metal halides is performed at the first temperature of about 325 to about 375 degrees Celsius.

3. The method of claim 2 , wherein contacting the metal surface with one or more metal halides is performed together with further contacting the metal surface with hydrogen.

4. The method of claim 3 , wherein contacting the metal surface with one or more metal halides is performed for 5 to 20 minutes.

5. The method of claim 1 , wherein the one or more metal halides is a gas.

6. The method of claim 1 , wherein the contacting the metal surface with one or more metal halides is performed in an oxygen-free chamber.

7. The method of claim 1 , wherein contacting the metal surface with one or more metal halides forms an exposed metal surface atop the metal surface.

8. The method of claim 1 , wherein growing the organosilane based self-assembled monolayer comprises exposing the substrate to a gas comprising an organosilane.

9. The method of claim 1 , wherein the organosilane based self-assembled monolayer comprises a C-8 to C-30 alkyl chain.

10. The method of claim 1 , wherein growing the organosilane based self-assembled monolayer is performed at a first temperature of about 100 to about 200 degrees Celsius.

11. The method of claim 1 , wherein growing the organosilane based self-assembled monolayer is performed at a pressure in an amount of 10 to 350 Torr.

12. The method of claim 1 , wherein growing the organosilane based self-assembled monolayer is performed for a duration of about 2 to about 3 hours.

13. The method of claim 1 , wherein growing the organosilane based self-assembled monolayer is performed in an oxygen-free chamber.

14. The method of claim 1 , wherein the organosilane based self-assembled monolayer comprises tris(dimethylamino)octadecylsilane.

15. The method of claim 1 , further comprising heating the substrate to a temperature of about 500 to about 1000 degrees Celsius to remove the organosilane based self-assembled monolayer.

16. The method of claim 1 , wherein the metal surface is tungsten or molybdenum, or combinations thereof.

17. The method of claim 1 , wherein the metal surface is copper, cobalt, or combinations thereof.

18. The method of claim 1 , wherein the metal surface is tungsten, cobalt, or molybdenum, or combinations thereof.