Etching liquid for film of multilayer structure containing copper layer and molybdenum layer

Patent metadata

Field	Value
Publication number	US-9580818-B2
Application number	US-201113805118-A
Country	US
Kind code	B2
Filing date	May 27, 2011
Priority date	Jun 18, 2010
Publication date	Feb 28, 2017
Grant date	Feb 28, 2017

Abstract

The present invention relates to an etching solution for a multilayer thin film containing a copper layer and a molybdenum layer, and a method of etching a multilayer thin film containing a copper layer and a molybdenum layer using the etching solution. There are provided an etching solution for a multilayer thin film containing a copper layer and a molybdenum layer, including (A) an organic acid ion supply source containing two or more carboxyl groups and one or more hydroxyl groups in a molecule thereof, (B) a copper ion supply source and (C) an ammonia and/or ammonium ion supply source, the etching solution having a pH value of from 5 to 8, and an etching method using the etching solution.

First claim

The invention claimed is:

1. An etching solution, comprising:
(A) an organic acid ion supply source comprising two or more carboxyl groups and a hydroxyl group in a molecule thereof;
(B) a copper ion supply source; and
(C) at least one selected from the group consisting of an ammonia and ammonium ion supply source;
wherein the etching solution has a pH value of from 5 to 8,
the molar ratio of the organic acid ion supply source (A) to the copper ion supply source (B) is from 0.2 to 3.0,
the content of the copper ion supply source (B) in the etching solution is in a range of from 0.2 to 1 mol/kg-etching solution, and
the content of (C) in the etching solution is in a range of from 0.5 to 10 mol/kg-etching solution.

2. The etching solution of claim 1 , wherein the organic acid ion supply source (A) is citric acid, tartaric acid, malic acid, an ammonium salt of citric acid, an ammonium salt of tartaric acid, an ammonium salt of malic acid, or any mixture thereof.

3. The etching solution claim 1 , wherein the copper ion supply source (B) is copper, copper sulfate, copper nitrate, or any mixture thereof.

4. The etching solution of claim 1 , wherein the at least one selected from ammonia and ammonium ion supply source (C) is selected from the group consisting of ammonia, ammonium sulfate, ammonium nitrate, ammonium citrate, ammonium tartarate, ammonium malate, or any mixture thereof.

5. A method of etching a multilayer thin film comprising a copper layer and a molybdenum layer, the method comprising:
contacting an object to be etched with the etching solution of claim 1 .

6. The method of claim 5 , wherein the multilayer thin film comprises the molybdenum layer and the copper layer laminated on the molybdenum layer.

7. The etching solution of claim 1 , wherein the molar ratio of the organic acid ion supply source (A) to the copper ion supply source (B) is from 0.4 to 1.5.

8. The etching solution of claim 1 , wherein the content of the copper ion supply source (B) in the etching solution is in a range of from 0.3 to 0.8 mol/kg-etching solution.

9. The etching solution of claim 1 , wherein the content of the at least one selected from the group consisting of ammonia and ammonium ion supply source (C) in the etching solution is in a range of from 1.5 to 4 mol/kg-etching solution.

10. The etching solution of claim 1 , further comprising:
a pH controlling agent (D), which is ammonia, potassium hydroxide, or sulfuric acid.

11. The etching solution of claim 1 , having a pH value from 6 to 8.

12. The etching solution of claim 1 , consisting essentially of water and:
(A) said organic acid ion supply source comprising two or more carboxyl groups and a hydroxyl group in a molecule thereof;
(B) said copper ion supply source;
(C) said at least one selected from the group consisting of ammonia and ammonium ion supply source; and
(D) a pH controlling agent.

13. The etching solution of claim 1 , wherein
the etching solution comprises of from 0.26 to 1.56 mol of the organic acid ion supply source (A) per 1 kg of the etching solution,
a molar ratio of the organic acid ion supply source (A) to the copper ion supply source (B) is from 0.42 to 2.49, and
the etching solution comprises of from 2.2 to 6.8 mol of the at least one selected from the group consisting of ammonia and ammonium ion supply source (C) per 1 kg of the etching solution.

14. The etching solution of claim 2 , wherein
the etching solution comprises of from 0.26 to 1.56 mol of the organic acid ion supply source (A) per 1 kg of the etching solution,
a molar ratio of the organic acid ion supply source (A) to the copper ion supply source (B) is from 0.42 to 2.49, and
the etching solution comprises of from 2.2 to 6.8 mol of the at least one selected from the group consisting of ammonia and ammonium ion supply source (C) per 1 kg of the etching solution.

15. The etching solution of claim 1 , wherein
the etching solution comprises of from 0.26 to 0.86 mol of the organic acid ion supply source (A) per 1 kg of the etching solution,
a molar ratio of the organic acid ion supply source (A) to the copper ion supply source (B) is from 0.42 to 1.38, and
the etching solution comprises of from 2.2 to 3.1 mol of the at least one selected from the group consisting of ammonia and ammonium ion supply source (C) per 1 kg of the etching solution.

16. The etching solution of claim 2 , wherein
the etching solution comprises of from 0.26 to 0.86 mol of the organic acid ion supply source (A) per 1 kg of the etching solution,
a molar ratio of the organic acid ion supply source (A) to the copper ion supply source (B) is from 0.42 to 1.38, and
the etching solution comprises of from 2.2 to 3.1 mol of the at least one selected from the group consisting of ammonia and ammonium ion supply source (C) per 1 kg of the etching solution.

17. The etching solution of claim 1 , wherein
the organic acid ion supply source (A) is citric acid, tartaric acid, malic acid, an ammonium salt of citric acid, an ammonium salt of tartaric acid, an ammonium salt of malic acid, or any mixture thereof,
the copper ion supply source (B) is copper, copper sulfate, copper nitrate, or any mixture thereof, and
the at least one selected from ammonia and ammonium ion supply source (C) is selected from the group consisting of ammonia, ammonium sulfate, ammonium nitrate, ammonium citrate, ammonium tartarate, ammonium malate, or any mixture thereof.

Assignees

• Tamai Satoshi
• Okabe Satoshi
• Matsubara Masahide
• Yube Kunio
• Mitsubishi Gas Chemical Co

Inventors

• Tamai Satoshi
• Okabe Satoshi
• Matsubara Masahide
• Yube Kunio

Classifications

• H10P50/667

  by liquid etching only · CPC title

• C23F1/18 Primary

  for etching copper or alloys thereof · CPC title

• H01L21/32134

  Electricity · mapped topic

• C23F1/14 Primary

  Aqueous compositions · CPC title

• C23F1/10 Primary

  Etching compositions (C23F1/44 takes precedence) · CPC title