Oxide and metal removal

• US 10,465,294 B2
• Filed: 04/11/2016
• Issued: 11/05/2019
• Est. Priority Date: 05/28/2014
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Wang, Xikun, Liu, Jie, Wang, Anchuan, Ingle, Nitin K., Anthis, Jeffrey W., Schmiege, Benjamin
• Primary Examiner(s): Pham, Thomas T
• Application Number:
  US15/095,342
• Publication Number:
  US 20160222522A1
• Time in Patent Office: 1,303 Days
• Field of Search: 216 37, 216 67, 438712, 438745
• CPC Class Codes: C23F 1/12 Gaseous compositions
• CPC Class Codes: C23F 4/00 Processes for removing metallic material from surfaces, not provided for in group C23F1/00 or C23F3/00
• CPC Class Codes: H01J 2237/327 Arrangements for generating the plasma
• CPC Class Codes: H01J 2237/334 Etching
• CPC Class Codes: H01J 2237/3341 Reactive etching
• CPC Class Codes: H01J 37/32091 the radio frequency energy being capacitively coupled to the plasma
• CPC Class Codes: H01J 37/32357 Generation remote from the workpiece, e.g. down-stream
• CPC Class Codes: H01J 37/32422 Arrangement for selecting ions or species in the plasma
• CPC Class Codes: H01J 37/3244 Gas supply means
• CPC Class Codes: H01L 21/32135 by vapour etching only
• CPC Class Codes: H01L 21/32138 pre- or post-treatments, e.g. anti-corrosion processes

Abstract

Methods are described herein for etching metal films which are difficult to volatize. The methods include exposing a metal film to a chlorine-containing precursor (e.g. Cl₂). Chlorine is then removed from the substrate processing region. A carbon-and-nitrogen-containing precursor (e.g. TMEDA) is delivered to the substrate processing region to form volatile metal complexes which desorb from the surface of the metal film. The methods presented remove metal while very slowly removing the other exposed materials. A thin metal oxide layer may be present on the surface of the metal layer, in which case a local plasma from hydrogen may be used to remove the oxygen or amorphize the near surface region, which has been found to increase the overall etch rate.

Claims

1. A method of etching metal from a substrate, the method comprising:

flowing a hydrogen-containing precursor into a substrate processing region housing the substrate while forming a plasma of the hydrogen-containing precursor in the substrate processing region;

treating a metal oxide layer exposed on the substrate, wherein the metal oxide layer is overlying a metal layer on the substrate, and wherein the treating comprises removing or reducing the metal oxide layer to expose the metal layer underlying the metal oxide layer;

exposing a portion of the metal layer underlying the metal oxide layer;

subsequent to treating the metal oxide layer, flowing a halogen-containing precursor into the substrate processing region, wherein the substrate processing region is plasma-free during the flowing of the halogen-containing precursor;

subsequent to flowing the halogen-containing precursor, flowing a carbon-and-nitrogen-containing precursor into the substrate processing region, wherein the substrate processing region is plasma-free during the flowing of the carbon-and-nitrogen-containing precursor; and

removing a portion of the exposed portion of the metal layer from the substrate.

2. The method of claim 1 wherein the metal comprises at least one of cobalt and nickel.

3. The method of claim 1 wherein the metal consists of a single element.

4. The method of claim 1 wherein the hydrogen-containing precursor comprises H₂.

5. The method of claim 1 wherein the carbon-and-nitrogen-containing precursor comprises tetramethylethylenediamine.

6. The method of claim 1 wherein the carbon-and-nitrogen-containing precursor comprises a carbon-nitrogen single bond.

7. The method of claim 1 wherein the carbon-and-nitrogen-containing precursor comprises at least two methyl groups.

8. The method of claim 1 wherein the halogen-containing precursor comprises at least one of chlorine or bromine.

9. The method of claim 1 wherein the halogen-containing precursor is a homonuclear diatomic halogen.

10. The method of claim 1 wherein the carbon-and-nitrogen-containing precursor consists of carbon, nitrogen and hydrogen.

11. The method of claim 1 wherein a pressure within the substrate processing region is between about 0.01 Torr and about 10 Torr during one or more of flowing the hydrogen-containing precursor, flowing the halogen-containing precursor or flowing the carbon-and-nitrogen-containing precursor.

12. The method of claim 1 wherein forming the plasma to treat the metal oxide layer comprises applying a remote RF power between about 25 watts and about 1500 watts to the substrate processing region.

13. The method of claim 1 wherein forming the plasma to treat the metal oxide layer comprises forming a capacitive local plasma within the substrate processing region.

14. The method of claim 1 wherein a processing temperature of the substrate is greater than or about −

30°

C. and less than or about 400°

C. during the etching operation.

15. The method of claim 1, further comprising purging the substrate processing region with an inert gas prior to flowing the carbon-and-nitrogen-containing precursor into the substrate processing region to remove residual halogen-containing precursor from the substrate processing region.

16. A method of etching metal from a substrate, the method comprising:

transferring the substrate into a substrate processing region;

forming a plasma of a hydrogen-containing precursor in the substrate processing region to treat a metal oxide layer exposed on the substrate, wherein the metal oxide layer is overlying a metal layer on the substrate, and wherein treating the metal oxide layer comprises removing or reducing the metal oxide layer to expose the metal layer underlying the metal oxide layer;

exposing a portion of the metal layer underlying the metal oxide layer;

subsequently flowing a halogen-containing precursor into the substrate processing region while maintaining the substrate processing region plasma free;

purging the substrate processing region with an inert gas to remove the halogen-containing precursor from the substrate processing region;

flowing a carbon-and-nitrogen-containing precursor in to the substrate processing region while maintaining the substrate processing region plasma free; and

removing a portion of the exposed portion of the metal layer from the substrate.

17. The method of claim 16 further comprising purging the substrate processing region with an inert gas to remove the carbon-and-nitrogen-containing precursor from the substrate processing region and then repeating the operations of flowing the hydrogen-containing precursor, flowing the halogen-containing precursor, purging to remove the halogen-containing precursor and flowing the carbon-and-nitrogen-containing precursor.