Tungsten oxide processing

• US 8,951,429 B1
• Filed: 12/20/2013
• Issued: 02/10/2015
• Est. Priority Date: 10/29/2013
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Liu, Jie, Wang, Xikun, Park, Seung, Korolik, Mikhail, Wang, Anchuan, Ingle, Nitin K.
• Primary Examiner(s): CULBERT, ROBERTS P
• Application Number:
  US14/136,200
• Time in Patent Office: 417 Days
• Field of Search: 216/67, 216/76, 438/722
• US Class Current: 216/76
• CPC Class Codes: H01J 37/32357 Generation remote from the workpiece, e.g. down-stream
• CPC Class Codes: H01J 37/32449 Gas control, e.g. control of the gas flow
• CPC Class Codes: H01L 21/31122 of layers not containing Si, e.g. PZT, Al2O3

Abstract

Methods of selectively etching tungsten oxide relative to tungsten, silicon oxide, silicon nitride and/or titanium nitride are described. The methods include a remote plasma etch using plasma effluents formed from a fluorine-containing precursor in combination with ammonia (NH₃). Plasma effluents from the remote plasma are flowed into a substrate processing region where the plasma effluents react with the tungsten oxide. The plasmas effluents react with exposed surfaces and selectively remove tungsten oxide while very slowly removing other exposed materials. Increasing a flow of ammonia during the process removes a typical skin of tungsten oxide having higher oxidation coordination number first and then selectively etching lower oxidation tungsten oxide. In some embodiments, the tungsten oxide etch selectivity results partly from the presence of an ion suppression element positioned between the remote plasma and the substrate processing region.

Claims

1. A method of etching tungsten oxide, the method comprising:

flowing a fluorine-containing precursor and ammonia (NH₃) into a remote plasma region fluidly coupled to a substrate processing region via through-holes in a showerhead while forming a remote plasma in the remote plasma region to produce plasma effluents; and

etching the tungsten oxide from a substrate disposed within the substrate processing region by flowing the plasma effluents into the substrate processing region through the through-holes in the showerhead.

2. The method of claim 1 wherein the tungsten oxide comprises about 20% or more tungsten and about 60% or more oxygen.

3. The method of claim 1 wherein a flow rate of the ammonia (NH₃) is between about 75% and about 100% of the flow rate of the fluorine-containing precursor.

4. The method of claim 1 wherein the substrate is a patterned substrate which further comprises one or more exposed regions of tungsten, silicon nitride, silicon oxide or titanium nitride.

5. The method of claim 4 wherein the operation of etching the tungsten oxide comprises etching tungsten oxide faster than tungsten by a ratio of about 10:

1 or more, faster than silicon nitride by a ratio of about 20;

1 or more, faster than silicon oxide by a ratio of about 15;

1 or more or faster than titanium nitride by a ratio of about 20;

1 or more.

6. The method of claim 1 wherein a temperature of the substrate is greater than or about 30°

C. and less than or about 300°

C. during the etching operation.

7. A method of etching tungsten oxide, the method comprising:

flowing a fluorine-containing precursor and ammonia (NH₃) into a remote plasma region fluidly coupled to a substrate processing region via through-holes in a showerhead, wherein the fluorine-containing precursor and the ammonia are flowed at a first flow rate ratio (ammonia;

fluorine-containing precursor);

forming a remote plasma in the remote plasma region to produce plasma effluents from the fluorine-containing precursor and the ammonia (NH₃);

etching a first portion of the tungsten oxide from a substrate disposed within the substrate processing region by flowing the plasma effluents into the substrate processing region through the through-holes in the showerhead;

increasing flow rate ratio (ammonia;

fluorine-containing precursor) to a second flow rate ratio which is greater than the first flow rate ratio;

etching a second portion of the tungsten oxide from the substrate by continuing to flow plasma effluents into the substrate processing region.

8. The method of claim 7 wherein the first portion of the tungsten oxide has a W:

O atomic ratio of roughly 1;

3.

9. The method of claim 7 wherein the second portion of the tungsten oxide has a W:

O atomic ratio of roughly 1;

2.

10. The method of claim 7 wherein the second flow rate ratio exceeds the first flow rate ratio by at least 1%.

11. The method of claim 7 wherein the operation of increasing flow rate ratio comprises changing from the first flow rate ratio to the second flow rate ratio essentially in a single discrete step.

12. A method of etching tungsten oxide, the method comprising:

flowing nitrogen trifluoride (NF₃) at a nitrogen trifluoride flow rate and ammonia (NH₃) at a first ammonia flow rate into a remote plasma region fluidly coupled to a substrate processing region via through-holes in a showerhead;

forming a remote plasma in the remote plasma region to produce plasma effluents from the nitrogen trifluoride and the ammonia;

etching a first portion of the tungsten oxide from a substrate disposed within the substrate processing region by flowing the plasma effluents into the substrate processing region through the through-holes in the showerhead;

increasing the flow rate of the ammonia from the first ammonia flow rate to a second ammonia flow rate;

etching a second portion of the tungsten oxide from the substrate by continuing to flow plasma effluents into the substrate processing region.

13. The method of claim 12 wherein the first ammonia flow rate is between 75% and 92% of the nitrogen trifluoride flow rate.

14. The method of claim 12 wherein the second ammonia flow rate is between 90% and 97% of the nitrogen trifluoride flow rate.

15. The method of claim 12 wherein forming the remote plasma in the remote plasma region to produce plasma effluents comprises applying RF power between about 10 watts and about 2500 watts to the remote plasma region.