Selective deposition of thin film dielectrics using surface blocking chemistry

Patent metadata

Field	Value
Publication number	US-9911591-B2
Application number	US-201615142497-A
Country	US
Kind code	B2
Filing date	Apr 29, 2016
Priority date	May 1, 2015
Publication date	Mar 6, 2018
Grant date	Mar 6, 2018

Abstract

Methods of depositing a film selectively onto a first substrate surface relative to a second substrate surface. Methods include soaking a substrate surface comprising hydroxyl-terminations with a silylamine to form silyl ether-terminations and depositing a film onto a surface other than the silyl ether-terminated surface.

First claim

What is claimed is:

1. A method of depositing a film, the method comprising:
providing a substrate comprising a first substrate surface having a hydroxyl-terminated surface and a second substrate surface having a hydrogen-terminated surface;
exposing the substrate to a silylamide to react with the hydroxyl-terminated surface of the first substrate surface to form a first substrate surface having a silyl ether-terminated surface; and
exposing the substrate to one or more deposition gases to deposit a film on the second substrate surface selectively over the silyl ether-terminated surface of the first substrate surface,
wherein one or more of the first substrate surface and the second substrate surface comprises a dielectric.

2. The method of claim 1 , wherein the silylamide comprises an organic silylamide.

3. The method of claim 2 , wherein the organic silylamide comprises a silicon atom bonded to substantially only to carbon and/or nitrogen atoms.

4. The method of claim 2 , wherein the organic silylamide comprises substantially no Si—H or Si—OH bonds.

5. The method of claim 2 , wherein the organic silylamide comprises one or more of trimethylsilylamide, triethylsilylamide, ethyldimethylsilylamide and/or diethylmethylsilylamide.

6. The method of claim 1 , wherein the silylamide includes an amide comprising one or more of pyrrolidine, pyrrole, pyrazole, dimethylamine, diethylamine, ethylmethylamine, cyclic secondary amine, saturated cyclic amine and/or unsaturated cyclic amine.

7. The method of claim 1 , wherein the silylamide comprises one or more of 1-trimethylsilylpyrrolidine, 1-trimethylsilylpyrrole and/or 3,5-dimethyl-1-trimethylsilylpyrazole.

8. The method of claim 1 , wherein the first substrate surface comprises a dielectric.

9. The method of claim 1 , further comprising etching the silyl ether-terminated surface after a predetermined amount of film is deposited followed by re-exposure to the silylamine to re-form the silyl ether-terminated surface and additional film deposition.

10. The method of claim 9 , wherein the silyl ether-terminated surface is etched and re-formed after no more than 100 ALD cycles of deposition.

11. The method of claim 1 , wherein the substrate is exposed to the silylamide for a time in the range of about 10 seconds to about 60 minutes.

12. The method of claim 1 , wherein the film comprises SiN.

13. The method of claim 12 , wherein the film is deposited by atomic layer deposition comprising sequential exposure to a silicon-containing gas and a nitrogen-containing gas.

14. The method of claim 13 , wherein the silicon containing gas comprises one or more of silane, disilane, trisilane, monochlorosilane, dichlorosilane, trichlorosilane, silicon tetrachloride, hexachlorodisilane (HCDS), a halogenated carbosilane.

15. The method of claim 13 , wherein the nitrogen-containing gas comprises one or more of a nitrogen-containing plasma, ammonia, an amine, hydrazine and/or carbonitride.

16. A method of depositing a film, the method comprising:
providing a substrate comprising a first substrate surface having a hydroxyl-terminated surface and a second substrate surface having a hydrogen-terminated surface, one or more of the first substrate surface and the second substrate surface comprising a dielectric;
soaking the substrate with a silylamide to react with the hydroxyl-terminated surface of the first substrate surface to form a first substrate surface having a silyl ether-terminated surface; and
exposing to the substrate to one or more deposition gases to deposit a silicon nitride film on the second substrate surface selectively over the first substrate surface.

17. The method of claim 16 , wherein the silylamide comprises silicon atoms bonded to substantially only to carbon and/or nitrogen atoms and there are substantially no Si—H or Si—OH bonds, and the silylamide includes an amide comprising one or more of pyrrolidine, pyrrole, pyrazole, dimethylamine, diethylamine, ethylmethylamine, cyclic secondary amine, saturated cyclic amine and/or unsaturated cyclic amine.

18. The method of claim 17 , wherein the silylamide comprises one or more of 1-trimethylsilylpyrrolidine, 1-trimethylsilylpyrrole and/or 3,5-dimethyl-1-trimethylsilylpyrazole.

19. A method of depositing a film, the method comprising:
providing a substrate comprising a first substrate surface including a hydroxyl-terminated surface and a second substrate surface including a hydrogen-terminated surface, one or more of the first substrate surface and the second substrate surface comprising a dielectric;
soaking the substrate with a silylamide comprising one or more of 1-trimethylsilylpyrrolidine, 1-trimethylsilylpyrrole and/or 3 ,5-dimethyl- 1-trimethylsilylpyrazole to react with the hydroxyl-terminated surface of the first substrate surface to form a first substrate surface having a silyl ether-terminated surface; and
exposing to the substrate to one or more deposition gases to deposit a silicon nitride film on the second substrate surface selectively over the first substrate surface.

Assignees

• Applied Materials Inc

Inventors

• Thompson David
• Saly Mark
• Bhuyan Bhaskar Jyoti

Classifications

• H10P95/00

  Generic processes or apparatus for manufacture or treatments not covered by the other groups of this subclass · CPC title

• H10P72/0468

  comprising a chamber adapted to a particular process · CPC title

• H10P50/287 Primary

  by chemical means · CPC title

• H10P14/69433

  the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz · CPC title

• H10P14/6682

  the compound being a silane, e.g. disilane, methylsilane or chlorosilane · CPC title