Method for etching high dielectric constant materials and for cleaning deposition chambers for high dielectric constant materials

• US 20040011380A1
• Filed: 04/10/2003
• Published: 01/22/2004
• Est. Priority Date: 07/18/2002
• Status: Abandoned Application

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Versum Materials US Inc.
• Inventors: Ji, Bing, Karwacki, Eugene Joseph Jr., Pearlstein, Ronald Martin, Wu, Dingjun, Motika, Stephen Andrew
• Application Number:
  US10/410,803
• Publication Number:
  US 20040011380A1
• Time in Patent Office: Days
• US Class Current: 134/1.1
• CPC Class Codes: B08B 7/00 Cleaning by methods not provided for in a single other subclass or a single group in this subclass
• CPC Class Codes: B08B 7/0035 by radiant energy, e.g. UV, laser, light beam or the like
• CPC Class Codes: C23C 16/4405 Cleaning of reactor or parts inside the reactor by using reactive gases

Abstract

A process for the removal of a substance from a substrate for etching and/or cleaning applications is disclosed herein. In one embodiment, there is provided a process for removing a substance having a dielectric constant greater than silicon dioxide from a substrate by reacting the substance with a reactive agent that comprises at least one member from the group consisting a halogen-containing compound, a boron-containing compound, a hydrogen-containing compound, nitrogen-containing compound, a chelating compound, a carbon-containing compound, a chlorosilane, a hydrochlorosilane, or an organochlorosilane to form a volatile product and removing the volatile product from the substrate to thereby remove the substance from the substrate.

Claims

1. A process for cleaning a substance from a reactor surface, said process comprising:

providing a reactor containing the reactor surface, wherein;

(a) the reactor surface is at least partially coated with a film of the substance;

(b) the substance is at least one member selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, or a laminate comprising at least one layer selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, a nitrogen containing Group 13 metal oxide, or a nitrogen containing Group 13 metal silicate; and

(c) the substance has a dielectric constant greater than the dielectric constant of silicon dioxide;

reacting the substance with a reactive agent to form a volatile product, wherein the reactive agent comprises at least one member selected from the group consisting of a halogen-containing compound;

a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and

removing the volatile product from the reactor to thereby remove the substance from the surface.

2. The process of claim 1, wherein the reactor is an atomic layer deposition reactor.

3. The process of claim 1, wherein the substance is at least one member selected from the group consisting of Al₂O₃, HfO₂, ZrO₂, HfSi_xO_y, and ZrSi_xO_y wherein x is a number greater than 0 and y is 2x +2, and any of the aforementioned compounds containing nitrogen.

4. The process of claim 1 wherein the reactive agent is at least one member selected from the group consisting of BCl₃, COCl₂, HCl, Cl₂, ClF₃, and NF_zCl_3-z, where z is an integer from 0 to 2.

5. The process of claim 4, wherein the reactive agent is COCl₂ formed by an in situ reaction of CO and Cl₂.

6. The process of claim 4, wherein the reactive agent is BCl₃.

7. The process of claim 1 wherein the reactive agent is a carbon-containing compound having the formula C_xH_yCl_z, wherein x is a number ranging from 1 to 6, y is a number ranging from 0 to 13, and z is a number ranging 1 from 14.

8. The process of claim 1, wherein the reactive agent is conveyed to the substance from a gas cylinder, a safe delivery system or a vacuum delivery system.

9. The process of claim 1, wherein the reactive agent is formed in situ by a point-of-use generator.

10. The process of claim 1, wherein the substance is contacted with the reactive agent diluted with an inert gas diluent.

11. A process for removing a substance from at least a portion of the surface of a reaction chamber, the process comprising:

providing a reaction chamber wherein at least a portion of the surface is at least partially coated with the substance and wherein the substance has a dielectric constant of 4.1 or greater and is at least one member of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, or a laminate comprising at least one layer of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate;

introducing a reactive agent into the reaction chamber wherein the reactive agent comprises at least one member selected from the group consisting of a halogen-containing compound;

a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound;

exposing the reactive agent to one or more energy sources sufficient to react the substance with the reactive agent and form a volatile product; and

removing the volatile product from the reaction chamber.

12. The process of claim 11, wherein the reactive agent is conveyed to the substance from a gas cylinder, a safe delivery system or a vacuum delivery system.

13. The process of claim 11, wherein the reactive agent is formed in situ by a point-of-use generator.

14. The process of claim 11, wherein the substance is contacted with the reactive agent diluted with an inert gas diluent.

15. The process of claim 11 wherein the reactive agent is deposited onto a nonreactive support.

16. The process of claim 11 wherein the reactive agent is exposed to one or more energy sources and the exposing step is conducted prior to the introducing step.

17. The process of claim 11 wherein the reactive agent is exposed to one or more energy sources and the exposing step is conducted during at least a portion of the introducing step.

18. The process of claim 11 wherein a temperature of the exposing step is at least 150°

C.

19. The process of claim 11 wherein a pressure of the exposing step is at least 10 mTorr.

20. An apparatus for removing a substance from at least one surface of a reactor, the apparatus comprising:

an at least one reactive agent selected from the group consisting of a halogen-containing compound;

a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and

a non-reactive support having the at least one reactive agent deposited thereupon.

21. A mixture for removing a substance from at least one surface of a reactor, the mixture comprising:

an at least one reactive agent selected from the group consisting of a halogen-containing compound;

a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and

an inert diluent.

22. A process for removing a substance from an at least one surface of a substrate, said process comprising:

providing the substrate wherein the substrate is at least partially coated with a film of the substance that is at least one member selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide other than Al₂O₃, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, or a laminate comprising at least one layer of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, or a nitrogen containing transition metal silicate; and

wherein the substance has a dielectric constant greater than a dielectric constant of silicon dioxide;

reacting the substance with a reactive agent to form a volatile product, wherein the reactive agent comprises at least one member from the group consisting of a halogen-containing compound ;

a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, or an organochlorosilane compound; and

removing the volatile product from the substrate to thereby remove the substance from the substrate.

23. The process of claim 22, wherein the substance is at least one member selected from the group consisting of HfO₂, ZrO₂, HfSi_xO_y, ZrSi_xO_y where x is greater than 0 and y is 2x +2, Al₂Si_wO_z, where w is greater than 0 and z is 2w +3, or any of the aforementioned compounds containing nitrogen.

24. The process of claim 22, wherein the substance is a laminate comprising layers of at least one material selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, a nitrogen containing Group 13 metal oxide, or a nitrogen containing Group 13 metal silicate.

25. The process of claim 22, wherein the reactive agent is at least one member selected from the group consisting of BCl₃, COCl₂, HCl, Cl₂, ClF₃, and NF_zCl_3-z, where z is an integer from 0 to 2.

26. The process of claim 25, wherein the substance is at least one member selected from the group consisting of HfO₂, ZrO₂, HfSi_xO_y, ZrSi_xO_y, where x is greater than 0 and y is 2x +2, Al₂Si_wO_z, where w is greater than 0 and z is 2w +3, or any of the aforementioned compounds containing nitrogen.

27. The process of claim 25, wherein the reactive agent is COCl₂ formed by an in situ reaction of CO and Cl₂.

28. The process of claim 25, wherein the reactive agent is BCl₃.

29. The process of claim 22 wherein the reactive agent is a carbon-containing compound having the formula C_xH_yCl_z, wherein x is a number ranging from 1 to 6, y is a number ranging from 0 to 13, and z is a number ranging 1 from 14.

30. The process of claim 22 wherein the reactive agent is conveyed to the substance from a gas cylinder, a safe delivery system or a vacuum delivery system.

31. The process of claim 22 wherein the reactive agent is formed in situ by a point-of-use generator.

32. The process of claim 22 wherein the substance is contacted with the reactive agent diluted with an inert gas diluent.

33. The process of claim 22, wherein the substance is coated on the substrate by atomic layer deposition.