Additive For Copper Plating And Process For Producing Electronic Circiut Substrate Therewith

Abstract

An additive for copper plating comprising, as an effective ingredient, a nitrogen-containing biphenyl derivative represented by the following formula (I):

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[FIG. 1] FIG. 1 is a view schematically showing a cross section of filled metal wirings by an existent technique.

[FIG. 2] FIG. 2 is a view schematically showing the state of a substrate before treatment with the method of the invention.

[FIG. 3] FIG. 3 is a view schematically showing the state of a substrate after treatment with the method of the invention.

[FIG. 4] FIG. 4 is a view showing cross sectional observation images (200×) of blind via holes of an IC substrate after plating in Example 1. In the drawing, (a) is specimen 1, and (b) is specimen 2.

[FIG. 5] FIG. 5 is a view showing cross sectional observation images (200×) of through holes of an IC substrate after plating according to Example 2.

[FIG. 6] FIG. 6 is a view showing cross sectional observation images (200×) of blind via holes of an IC substrate after plating according to Example 3. In the drawings, (a) is specimen 1, and (b) is specimen 2.

[FIG. 7] FIG. 7 is a view showing cross sectional observation images (200×) of the blind via holes of the IC substrate of specimen 1 after plating in Example 4.

DESCRIPTION OF THE REFERENCE NUMERALS AND SIGNS

101: material103: blind via105: metal layer111: void113: seam115: super filling401: substrate403: blind via405: through hole410: additive411: surface413: bottom

Claims

1. An additive for copper plating comprising, as an effective ingredient, a nitrogen-containing biphenyl derivative represented by the following formula (I):

2. An additive for copper plating according to claim 1 for use in filling microholes or microgrooves.

3. An additive for copper plating according to claim 1 or 2, wherein a nitrogen-containing biphenyl derivative is added such that its concentration in a basic composition copper plating solution is from 0.01 to 1,000 mg/L.

4. An additive for copper plating according to claim 1 or 2, wherein a nitrogen-containing biphenyl derivative is added such that its concentration in a basic composition copper plating solution is from 20 to 100 mg/L.

5. A copper plating solution formed by adding an additive for copper plating comprising, as an effective ingredient, a nitrogen-containing biphenyl derivative represented by the following formula (I):

6. A copper plating solution according to claim 5, for filling microholes or microgrooves.

7. A copper plating solution according to claim 5 or 6, wherein the addition amount of the nitrogen-containing biphenyl derivative is such that its concentration in the basic composition copper plating solution is from 0.01 to 1,000 mg/L.

8. A copper plating solution according to claim 5 or 6, wherein the addition amount of the nitrogen-containing biphenyl derivative is such that its concentration in the basic composition copper plating solution is from 20 to 100 mg/L.

9. A copper plating solution according to any one of claims 5 to 8, wherein copper sulfate, copper carbonate, copper oxide, copper chloride, copper pyrophosphate, copper alkane sulfonate, copper alkanol sulfonate, copper acetate, copper citrate, copper tartarate is used as a copper ion source.

10. A copper plating solution according to any one of claims 5 to 8, wherein copper sulfate is used as a copper ion source.

11. A copper plating solution according to claim 10, wherein copper sulfate pentahydrate as the copper ion source is used within a range from 100 to 300 g/L (25 to 75 g/L copper ion concentration) in the basic composition copper plating solution.

12. A copper plating solution according to claim 10, wherein copper sulfate pentahydrate as a copper ion source is used within a range from 200 to 250 g/L (50 to 62.5 g/L copper ion concentration) in the basic composition copper plating solution.

13. A copper plating solution according to any one of claims 5 to 12, wherein a halogen ion is further contained as an electrolyte.

14. A copper plating solution according to claim 13, wherein the halogen ion is a chlorine ion and the concentration thereof in the basic composition copper plating solution is from 10 to 100 mg/L.

15. A copper plating solution according to any one of claims 5 to 14, wherein at least one acid is contained as an anionic ingredient source.

16. A copper plating solution according to claim 15, wherein the acid is sulfuric acid and the concentration thereof in the basic composition copper plating solution is from 18 g/L −150 g/L.

17. A copper plating solution according to claims 5 to 16, wherein at least one sulfur-containing compound is further contained.

18. A copper plating solution according to claim 17, wherein one or more sulfur-containing compounds are selected from the group consisting of sulfoalkyl sulfonic acids and salts thereof, bissulfo organic compounds, and dithiocarbamic acid derivatives, and the concentration of the compound is from 0.1 to 200 mg/L.

19. A copper plating solution according to any one of claims 5 to 18, wherein at least one polymeric hydrocarbon compound is further contained.

20. A copper plating solution according to claim 19, wherein the concentration of the polymeric hydrocarbon compound in the basic composition copper plating solution is from 10 to 2,000 mg/L.

21. A copper plating solution according to claim 19 or 20, wherein the polymeric hydrocarbon compound is a compound represented by the following formula (IX):

22. A copper plating solution according to claim 19 or 20, wherein one or more polymeric hydrocarbon compounds are selected from the group consisting of 1,3-dioxolane polymer, polyethylene glycol, polypropylene glycol, pluronic type surfactant, polypropylenepropanol, polyethylene glycol derivatives such as polypethylene glycol/glyceryl ether and polyethylene glycol/dialkyl ether, and oxyalkylene polymers.

23. A method of manufacturing an electronic circuit substrate having a fine copper wiring circuit, which comprises electroplating using an electronic circuit substrate in which microholes or microgrooves in the shape of electronic circuit wirings are formed on the surface as a cathode in a copper plating solution containing a copper ion ingredient, an anion ingredient, and a nitrogen-containing biphenyl derivative represented by the following formula (I):