Use of an inhibitor molecule in chemical vapor deposition to afford deposition of copper on a metal substrate with no deposition on adjacent SIO2 substrate

Patent metadata

Field	Value
Publication number	US-10103057-B2
Application number	US-201514937790-A
Country	US
Kind code	B2
Filing date	Nov 10, 2015
Priority date	Nov 11, 2014
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

Provided herein are methods for selectively forming layers of metal films on one portion of a substrate while leaving adjacent portions of the substrate uncoated. The methods provide for selectively depositing metal films on a conductive surface, such as ruthenium oxide, disposed on or near an insulating portion of the substrate, such as a silicon dioxide (SiO 2 ) surface. The invention provides methods to simultaneously contact the substrate surface with both the precursor gas and the inhibitor agent leading to the selective formation of metal nuclei on the conductive portion of the substrate. In the methods described, nuclei are selectively formed by a disproportionation reaction occurring on the conductive portion of the substrate but not on the insulating portion of the substrate.

First claim

We claim:

1. A method for selectively forming a layer on a substrate, the method comprising:
(a) providing the substrate having a receiving surface with at least one conductive portion and at least one insulating portion;
(b) contacting the receiving surface of the substrate with a precursor gas, wherein accommodation of the precursor gas by the substrate results in formation of nuclei of deposited material on the conductive portion of the receiving surface of the substrate;
(c) contacting the nuclei on the conductive portion of the receiving surface with the precursor gas; wherein accommodation of the precursor gas by the nuclei, the substrate or both the nuclei and the substrate results in growth of the nuclei at a growth rate; and
(d) contacting the nuclei, the substrate or both the nuclei and the substrate with an inhibitor agent, wherein accommodation of the inhibitor agent by the nuclei, the substrate or both the nuclei and the substrate provides for selective formation of the layer on the conductive portion of the substrate and the growth rate being at least 100 times faster on the conductive portion than on the insulating portion; wherein:
step (d) is capable of being performed independently of step (b);
a partial pressure of said inhibitor agent above said receiving surface is greater than a partial pressure of said precursor gas above said receiving surface by a factor greater than or equal to 5; and
when said partial pressure of said inhibitor agent above said receiving surface is less than or equal to 2 mTorr, said receiving surface has a temperature less than or equal to 180° C.

2. The method of claim 1 , wherein said precursor gas and said inhibitor agent are simultaneously contacted with said receiving surface of said substrate.

3. The method of claim 1 , wherein said nuclei are selectively formed by a disproportionation reaction occurring on said conductive portion but not on said insulating portion of said substrate.

4. The method of claim 1 , wherein said receiving surface has a temperature selected from the range of 50° C. to 400° C.

5. The method of claim 1 , wherein said layer is a contiguous layer or a discontinuous layer.

6. The method of claim 1 , wherein the conductive portion comprises a conductive metal oxide.

7. The method of claim 6 , wherein said conductive portion has a formula of M y O x , where M is selected from the group consisting of Ru, Ti, In, Sn, Zn or combinations thereof and x and y are numbers selected from 1 to 3.

8. The method of claim 7 , wherein a ratio of y:x is selected from 1:1 to 1:3.

9. The method of claim 6 , wherein said conductive metal oxide portion comprises a compound selected from the group consisting of RuO 2 , TiO 2 , In 2 O 3 , SnO 2 , ZnO and combinations thereof.

10. The method of claim 6 , wherein said conductive metal oxide portion is prepared by oxidation of a metal layer formed on said insulating portion of the substrate.

11. The method of claim 1 , wherein said conductive portion has a thickness selected from the range of 0.1 nm to 1000 nm.

12. The method of claim 1 , wherein said conductive portion covers less than or equal to 99.5% of said receiving surface.

13. The method of claim 1 , wherein said conductive portion is formed on said substrate via a process selected from the group consisting of physical vapor deposition, chemical vapor deposition, atomic layer deposition, electrochemical deposition, photolithography, shadow masking, ion beam etching, chemical etching and combinations thereof.

14. The method of claim 1 , wherein said conductive portion is characterized by a conductivity greater than 100 S/m.

15. The method of claim 1 , wherein said conductive portion comprises a thin film structure.

16. The method of claim 1 , wherein said insulating portion is an oxide, a nitride or combinations thereof.

17. The method of claim 1 , wherein said insulating portion comprises SiO 2 or SiO x C y where x is a number between 1 and 2 and y is a number between 0 and 1.

18. The method of claim 17 , wherein said SiO 2 comprises thermal SiO 2 or porous, carbon-doped SiO 2 , or both.

19. The method of claim 1 , wherein said insulating portion of the substrate is prepared by thermal oxidation or nitridation of a silicon wafer.

20. The method of claim 1 , wherein said insulating portion has a thickness selected from the range of 0.1 nm to 1 mm.

21. The method of claim 1 , wherein said insulating portion is characterized by a conductivity less than 100 S/m.

22. The method of claim 1 , wherein said conductive portion and said insulating portion are in direct physical contact, direct thermal contact or direct electrical contact.

23. The method of claim 1 , wherein said conductive portion and said insulating portion are in indirect physical contact, indirect thermal contact or indirect electrical contact.

24. The method of claim 1 , wherein said conductive portion and said insulating portion are side-by-side.

25. The method of claim 1 , wherein said conductive portion is disposed on a surface of said insulating portion.

26. The method of claim 1 , wherein the precursor gas has a net sticking coefficient with respect to accommodation on the nuclei, and wherein accommodation of the inhibitor agent by the nuclei, the conductive portion of the substrate or both the nuclei and the conductive portion of the substrate results in a decrease of the net sticking coefficient of the precursor gas with respect to accommodation on the nuclei by a factor greater than or equal to 1.1.

27. The method of claim 1 , wherein the precursor gas has a partial pressure less than or equal to 1000 mTorr.

28. The method of claim 1 , wherein the precursor gas has a partial pressure selected from the range of 0.1 mTorr to 10 mTorr.

29. The method of claim 1 , wherein the precursor gas comprises Cu(hfac)(vtms), Cu(hfac)(MHY), iron complexes, titantium complexes, magnesium complexes, silver complexes and combinations thereof.

30. The method of claim 1 , wherein a growth rate of said layer decreases as a function of a partial pressure of said inhibitor agent.

31. The method of claim 1 , wherein the inhibitor agent has a partial pressure less than or equal to 1000 mTorr.

32. The method of claim 1 , wherein the inhibitor agent has a partial pressure selected from the range of 0.1 mTorr to 10 Torr.

33. The method of claim 1 , wherein said inhibitor agent is a neutral molecule.

34. The method of claim 1 , wherein said inhibitor agent is selected from the group consisting of VTMS, MHY, DMB and combinations thereof.

35. The method of claim 1 , wherein the inhibitor agent and the precursor gas are a combination selected from the group consisting of:
VTMS and Cu(hfac)(VTMS);
MHY and Cu(hfac)(VTMS);
VTMS and Cu(hfac)(MHY);
MHY and Cu(hfac)(MHY); and
combinations thereof.

36. The method of claim 1 , wherein said layer is an electrical conductor.

37. The method of claim 1 , wherein said layer comprises a metal.

38. The method of claim 37 , wherein said metal is selected from the group consisting of copper, ruthenium, titanium, TiN x , TaN x , HfB 2 and combinations thereof.

39. The method of claim 1 , wherein sai

Assignees

• Univ Illinois

Inventors

• Abelson John
• Babar Shaista
• Mohimi Elham
• Girolami Gregory

Classifications

• H10P14/432

  using selective deposition · CPC title

• H10W20/063

  by forming conductive members before forming protective insulating material · CPC title

• H10W20/045

  for deposition from the gaseous phase, e.g. for chemical vapour deposition [CVD] · CPC title

• H10W20/057 Primary

  by selectively depositing, e.g. by using selective CVD or plating · CPC title

• C23C16/18

  from metallo-organic compounds · CPC title