Analytical reagent for acid copper sulfate solutions

• US 7,205,153 B2
• Filed: 04/11/2003
• Issued: 04/17/2007
• Est. Priority Date: 04/11/2003
• Status: Expired due to Fees

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Balisky, Todd Alan
• Primary Examiner(s): Soderquist; Arlen
• Application Number:
  US10/412,484
• Publication Number:
  US 20040203165A1
• Time in Patent Office: 1,467 Days
• Field of Search: 422/61, 422 75- 77, 436/43, 436 50- 51, 436/55, 436/73, 436/80, 436150-151, 436/166
• US Class Current: 436/80
• CPC Class Codes: G01N 31/16 using titration
• CPC Class Codes: Y10T 436/11 Automated chemical analysis
• CPC Class Codes: Y10T 436/115831 Condition or time responsive
• CPC Class Codes: Y10T 436/116664 with automated titrator
• CPC Class Codes: Y10T 436/17 Nitrogen containing

Abstract

Embodiments of the invention provide an analytical method and analytical reagent solutions for determining the concentration of electrolyte components, such as copper, acid and chloride constituents in an acid or basic metal plating bath using a chemical analyzer. Common methods for measuring the concentration of copper general require two reagent solutions/two steps. This invention provides a novel analytical reagent solution that simplifies the chelating, buffering, and cleaning functions of separate regent solutions required for measuring electrolyte concentration. This has the benefits of reducing chemical inventory and associated dispensing equipment, and thus reducing chemical consumption.

Claims

1. An analytical method for determining the concentration of a component in a plating bath, comprising:

providing an analytical reagent solution, wherein the analytical reagent solution comprises at least one chelating agent, at least one pH buffering agent, and water;

providing a testing solution having a portion of the plating bath therein;

measuring a series of chemical responses of the testing solution reacting with two or more doses of the analytical reagent solution; and

calculating the concentration of the component in the plating bath from the measurements of the series of chemical responses.

2. The method of claim 1, wherein the method is applied to at least one of titration and back titration.

3. The method of claim 1, wherein the component is copper.

4. The method of claim 1, wherein the at least one chelating agent is selected from the group consisting of ethelenediaminetetraacetic acid (H₄EDTA), ethelenediaminetetraacetic acid salts, ethelenediaminetetraacetic acid disodium salt (Na₂ H₂EDTA), tetrasodium ethelenediam inetetraacetic acid (Na₄EDTA), magnesium disodium ethelenediam inetetraacetic acid (MgNa₂EDTA), cyclohexanediaminetetraacetic acid (CDTA), N-2-hydroxyethyl-ethylenediamine-N,N,N′

-triacetic acid tri sodium salt (HEDTA), triethylene tetramine hexaacetic acid (TTHA), nitrilotriacetic acid (NTA), derivatives, hydrates, anhydrates, metal salts, and combinations thereof.

5. The method of claim 1, wherein the at least one pH buffering agent is selected from the group consisting of ammonia, ammonia chloride, sodium hydroxide, ammonium hydroxide, magnesium hydroxide, and calcium hydroxide, their derivatives, and combinations thereof.

6. The method of claim 1, wherein the at least one pH buffering agent is present in an amount sufficient to adjust the pH of the analytical reagent solution to a range of between about 7 and about 10.

7. The method of claim 1, wherein the at least one pH buffering agent is non-volatile.

8. The method of claim 1, wherein the analytical reagent solution further comprises at least one cleaning agent.

9. The method of claim 8, wherein the at least one cleaning agent is selected from the group consisting of amino acids, amine(—

NH2)-containing, thiol(—

SH) -containing, thio(—

SC)-containing, and thionate (—

SO)-containing compounds, their derivatives, and combinations thereof.

10. The method of claim 8, wherein the at least one cleaning agent is selected from the group consisting of glycine, glutamine, and derivatives thereof.

11. The method of claim 8, wherein the at least one cleaning agent is non-volatile.

12. An analytical method for determining the concentration of a component in a plating bath, comprising:

providing an analytical reagent solution, wherein the analytical reagent solution comprises,

at least one chelating agent selected from the group consisting of ethelenediaminetetraacetic acid (H₄EDTA), ethelenediaminetetraacetic acid salts, ethelenediaminetetraacetic acid disodium salt (Na₂ H₂EDTA), tetrasodium ethelenediaminetetraacetic acid (Na₄EDTA), magnesium disodium ethelenediaminetetraacetic acid (MgNa₂EDTA), cyclohexanediaminetetraacetic acid (CDTA), N-2-hydroxyethyl-ethylenediamine-N,N,N′

-triacetic acid tri sodium salt (HEDTA), triethylene tetramine hexaacetic acid (TTHA), nitrilotriacetic acid (NTA), derivatives, hydrates, anhydrates, metal salts, and combinations thereof;

at least one pH buffering agent selected from the group consisting of ammonia, ammonia chloride, a hydroxide salt solution, sodium hydroxide, ammonium hydroxide, magnesium hydroxide, and calcium hydroxide, and combinations thereof, in an amount sufficient to adjust the pH of the analytical reagent solution to a range of from about 7 to about 10; and

water;

providing a testing solution having a portion of the plating bath therein;

measuring a series of chemical responses of the testing solution reacting with two or more doses of the analytical reagent solution; and

calculating the concentration of the component in the plating bath from the measurements of the series of chemical responses.

13. The method of claim 12, wherein the method is applied to an analytical technique selected from the group consisting of titration and back titration.

14. The method of claim 12, wherein the component is copper.

15. The method of claim 12, wherein the at least one analytical reagent solution further comprises at least one cleaning agent selected from the group consisting of amino acids, amine(—

NH2)-containing, thiol(—

SH)-containing, thio(—

SC) -containing, and thionate (—

SO)-containing compounds, their derivatives, and combinations thereof.

16. An analytical method for determining the concentration of a component in a plating bath, comprising:

combining two or more reagent solutions for at least one chelating and at least one buffering into one analytical reagent solution, wherein the analytical reagent solution comprises;

at least one chelating agent selected from the group consisting of ethelenediaminetetraacetic acid (H₄EDTA), ethelenediaminetetraacetic acid salts, ethelenediaminetetraacetic acid disodium salt (Na₂ H₂EDTA), tetrasodium ethelenediaminetetraacetic acid (Na₄EDTA), magnesium disodium ethelenediaminetetraacetic acid (MgNa₂EDTA), cyclohexanediaminetetraacetic acid (CDTA), N-2-hydroxyethyl-ethylenediamine-N,N,N′

-triacetic acid tri sodium salt (HEDTA), triethylene tetramine hexaacetic acid (TTHA), nitrilotriacetic acid (NTA), derivatives, hydrates, anhydrates, metal salts, and combinations thereof;

a pH buffering agent selected from the group consisting of ammonia, ammonia chloride, a hydroxide salt solution, sodium hydroxide, ammonium hydroxide, magnesium hydroxide, and calcium hydroxide, and combinations thereof, in an amount sufficient to adjust the pH of the analytical reagent solution to a range of from about 7 to about 10; and

water; and

performing an analytical technique for a portion of the plating bath using the analytical reagent solution to determine the concentration of the component.

17. The method of claim 16, wherein the analytical technique is selected from the group consisting of titration and back titration.

18. The method of claim 16, wherein the component is copper.

19. The method of claim 16, wherein the analytical reagent solution further comprises at least one cleaning agent selected from the group consisting of amino acids, amine(—

NH2)-containing, thiol(—

SH)-containing, thio(—

SC)-containing, and thionate (—

SO)-containing compounds, their derivatives, and combinations thereof.

20. An analytical method for determining the concentration of a component in a plating bath, comprising:

providing a testing solution having a portion of the plating bath therein;

adding a pre-dose volume of an analytical reagent solution to react with the testing solution;

adding one or more doses of a second volume of the analytical reagent solution to react with the testing solution;

measuring a series of chemical responses of the testing solution reacting with the analytical reagent solution;

obtaining an endpoint dose; and

calculating the concentration of the component in the plating bath from the measurements of the series of chemical responses and the endpoint dose, wherein the analytical reagent solution comprises;

at least one chelating agent selected from the group consisting of ethelenediaminetetraacetic acid (H₄EDTA), ethelenediaminetetraacetic acid salts, ethelenediaminetetraacetic acid disodium salt (Na₂ H₂EDTA), tetrasodium ethelenediaminetetraacetic acid (Na₄EDTA), magnesium disodium ethelenediaminetetraacetic acid (MgNa₂EDTA), cyclohexanediaminetetraacetic acid (CDTA), N-2-hydroxyethyl-ethylenediam me-N,N,N′

-triacetic acid tri sodium salt (HEDTA), triethylene tetramine hexaacetic acid (TTHA), nitrilotriacetic acid (NTA), derivatives, hydrates, anhydrates, metal salts, and combinations thereof;

at least one pH buffering agent selected from the group consisting of ammonia, ammonia chloride, a hydroxide salt solution, sodium hydroxide, ammonium hydroxide, magnesium hydroxide, and calcium hydroxide, and combinations thereof, in an amount sufficient to adjust the pH of the analytical reagent solution to a range of from about 7 to about 10; and

water.

21. The method of claim 20, wherein the pre-dose volume is larger then the second volume.

22. The method of claim 20, wherein the pre-dose volume is about 10 times to about 100 times the second volume.

23. The method of claim 20, wherein the method is applied to an analytical technique selected from the group consisting of titration and back titration.

24. The method of claim 20, wherein the component is copper.

25. The method of claim 20, wherein the analytical reagent solution further comprises at least one cleaning agent selected from the group consisting of amino acids, amine(—

NH2)-containing, thiol(—

SH)-containing, thio(—

SC)-containing, and thionate (—

SO)-containing compounds, and their derivatives and combinations thereof.