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US4877450A
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Formaldehyde-free electroless copper plating solutions
Assignee: Shipley Co Inc
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Filing: 1989-02-23
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Granted: 1989-10-31
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Expires: 2009-02-23
Abstract
Abstract This invention relates to a formaldehyde-free electroless copper plating solution, containing a solution soluble divalent copper compound in a concentration between about 1/2 and 2 g/l; a reducing agent for the copper compound in an amount of between about 1 and 3 g/l; a complexing and chelating agent mixture of between about 5 and 100 ml/l of an alkanol amine having at least one alkyl group with one to three carbon atoms and between about 1 and 10 g/l of an ethylene diamine compound of the formula ##STR1## wherein R is an alkyl moiety having between 1 and 3 carbon atoms and X is --OH or --COOH; the solution preferably having a pH between about 7 and 8.5 and a temperature preferably between about 130° and 150° F., with the complexing and chelating agent mixture being present to provide stability to the solution and to enable the solution to provide a uniform plating rate of copper upon a substrate which is immersed therein.
Inventors
- 👤 William R. Brasch
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-07 18:29
CPC Classifications
C; C23; C23C; C23C18/00; C23C18/16; C23C18/31; C23C18/38; C23C18/40
Claims Analysis
Total Claims: 27
Claim 1
Independent Claim
136 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound; an amine borane reducing agent for said copper compound; a complexing and chelating agent mixture of an amine alkanol compound having at least one alkyl group of 1 to 3 carbon atoms and an ethylene diamine compound of the formula ##STR4## wherein R is an alkyl moeity having between 1 and 3 carbon atoms and X is --OH or --COOH; said solution having a pH above about 6 but less than about 9 and a temperature above about 125° F. but below about 165° F., said complexing and chelating agent mixture being present in an amount sufficient to provide stability to the solution and to enable the solution to provide a uniform plating rate of copper upon a substrate which is immersed therein.
Claim 2
Dependent Claim
136 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound; an amine borane reducing agent for said copper compound; a complexing and chelating agent mixture of an amine alkanol compound having at least one alkyl group of 1 to 3 carbon atoms and an ethylene diamine compound of the formula ##STR4## wherein R is an alkyl moeity having between 1 and 3 carbon atoms and X is --OH or --COOH; said solution having a pH above about 6 but less than about 9 and a temperature above about 125° F. but below about 165° F., said complexing and chelating agent mixture being present in an amount sufficient to provide stability to the solution and to enable the solution to provide a uniform plating rate of copper upon a substrate which is immersed therein.
Claim 3
Dependent Claim
28 words
The solution of claim 1 wherein the reducing agent is dimethylamine borane and is present in the solution in a concentration of between about 1 and 3 g/l.
Claim 4
Dependent Claim
25 words
The solution of claim 1 wherein the amine alkanol compound is present in the solution in a concentration of between about 5 and 100 ml/l.
Claim 5
Dependent Claim
17 words
The solution of claim 1 wherein the amine alkanol compound is a mono-, di- or tri-ethanol amine.
Claim 6
Dependent Claim
25 words
The solution of claim 1 wherein the ethylene diamine compound is present in the solution in a concentration of between about 1 and 10 g/l.
Claim 7
Dependent Claim
25 words
The solution of claim 1 wherein the ethylene diamine compound is hydroxyethyl ethylene diamine triacetic acid; tetrahydroxy ethylene diamine; or dihydroxymethyl ethylene diamine diacetic acid.
Claim 8
Dependent Claim
25 words
The solution of claim 1 further comprising one or more addition agents for improving the characteristics of the solution or the resultant electroless copper deposit.
Claim 9
Dependent Claim
25 words
The solution of claim 1 wherein the pH range is between 7.5 and 8 and wherein the temperature is between about 130° and 150° F.
Claim 10
Dependent Claim
22 words
The solution of claim 8 which further comprises an acid in an amount sufficient to adjust the pH to the desired range.
Claim 11
Dependent Claim
26 words
The solution of claim 1 wherein the copper compound is present in an amount which provides a copper ion concentration of between 1/2 and 2 g/l.
Claim 12
Dependent Claim
166 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound in an amount which provides a copper ion concentration of between about 1/2 and 2 g/l; an amine borane reducing agent for said copper compound in a concentration of between about 1 and 3 g/l; a complexing and chelating agent mixture of between about 5 and 100 ml/l of an amine alkanol compound having at least one alkyl group of one to three carbon atoms and between about 1 and 10 g/l of an ethylene diamine compound of the formula ##STR5## wherein R is an alkyl moeity having between 1 and 3 carbon atoms, and X is --OH or --COOH; said solution having a pH between about 7 and 8.5 and a temperature between about 130° and 150°0 F.; said complexing and chelating agent mixture being present to provide stability to the solution and to enable the solution to provide a uniform plating rate of copper upon a substrate which is immersed therein.
Claim 13
Dependent Claim
166 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound in an amount which provides a copper ion concentration of between about 1/2 and 2 g/l; an amine borane reducing agent for said copper compound in a concentration of between about 1 and 3 g/l; a complexing and chelating agent mixture of between about 5 and 100 ml/l of an amine alkanol compound having at least one alkyl group of one to three carbon atoms and between about 1 and 10 g/l of an ethylene diamine compound of the formula ##STR5## wherein R is an alkyl moeity having between 1 and 3 carbon atoms, and X is --OH or --COOH; said solution having a pH between about 7 and 8.5 and a temperature between about 130° and 150°0 F.; said complexing and chelating agent mixture being present to provide stability to the solution and to enable the solution to provide a uniform plating rate of copper upon a substrate which is immersed therein.
Claim 14
Dependent Claim
12 words
The solution of claim 11 wherein the reducing agent is dimethylamine borane.
Claim 15
Dependent Claim
17 words
The solution of claim 11 wherein the amine alkanol compound is a mono-, di- or tri-ethanol amine.
Claim 16
Dependent Claim
25 words
The solution of claim 11 wherein the ethylene diamine compound is hydroxyethyl ethylene diamine triacetic acid; tetrahydroxy ethylene diamine; or dihydroxymethyl ethylene diamine diacetic acid.
Claim 17
Dependent Claim
25 words
The solution of claim 11 further comprising one or more addition agents for improving a characteristic of the solution or the resultant electroless copper deposit.
Claim 18
Dependent Claim
22 words
The solution of claim 11 which further comprises an acid in an amount sufficient to adjust the pH to the desired range.
Claim 19
Dependent Claim
25 words
The solution of claim 11 wherein the amine alkanol compound is present in the solution in a concentration of between about 25 and 75 ml/l.
Claim 20
Dependent Claim
25 words
The solution of claim 11 wherein the ethylene diamine compound is present in the solution in an amount of between about 4 and 6 g/l.
Claim 21
Dependent Claim
132 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound; dimethyl amine borane as a reducing agent for said copper compound; and one of a complexing agent, a chelating agent or a mixture thereof; said solution having a pH of between 7.5 and 8 and a temperature between about 130° and 150° F., said complexing or chelating agent being present to provide stability to the solution and to enable the solution to provide at the stated pH range a uniform plating rate of copper upon a substrate which is immersed therein without appreciable loss of the reducing agent due to extraneous reactions other than the reaction required for electrolessly depositing copper, said solution being substantially free of ammonium ions so as to avoid generating ammonium fumes during electroless plating.
Claim 22
Dependent Claim
132 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound; dimethyl amine borane as a reducing agent for said copper compound; and one of a complexing agent, a chelating agent or a mixture thereof; said solution having a pH of between 7.5 and 8 and a temperature between about 130° and 150° F., said complexing or chelating agent being present to provide stability to the solution and to enable the solution to provide at the stated pH range a uniform plating rate of copper upon a substrate which is immersed therein without appreciable loss of the reducing agent due to extraneous reactions other than the reaction required for electrolessly depositing copper, said solution being substantially free of ammonium ions so as to avoid generating ammonium fumes during electroless plating.
Claim 23
Dependent Claim
104 words
The solution of claim 19 wherein the copper compound is present in an amount which provides a copper ion concentration of between about 1/2 and 2 g/l, the reducing agent is present in an concentration of between about 1 and 3 g/l, and the complexing and chelating mixture is a mixture of an amine alkanol compound in a concentration of between about 5 and 100 ml/l and an ethylene diamine compound of the formula ##STR6## wherein R is an alkyl moeity having between 1 and 3 carbon toms, and x is --OH or --COOH in a concentration of between bout 1 and 10 g/l.
Claim 24
Dependent Claim
116 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound; dimethyl amine borane as a reducing agent for said copper compound; and one of a complexing agent, a chelating agent or a mixture thereof; said solution having a pH of between 7.5 and less than 8 and a temperature between about 130° and 150° F., said complexing or chelating agent being present to provide stability to the solution and to enable the solution to provide at the stated pH range a uniform plating rate of copper upon a substrate which is immersed therein without appreciable loss of the reducing agent due to extraneous reactions other than the reaction required for electrolessly depositing copper.
Claim 25
Dependent Claim
116 words
A formaldehyde-free electroless copper plating solution comprising: a solution soluble divalent copper compound; dimethyl amine borane as a reducing agent for said copper compound; and one of a complexing agent, a chelating agent or a mixture thereof; said solution having a pH of between 7.5 and less than 8 and a temperature between about 130° and 150° F., said complexing or chelating agent being present to provide stability to the solution and to enable the solution to provide at the stated pH range a uniform plating rate of copper upon a substrate which is immersed therein without appreciable loss of the reducing agent due to extraneous reactions other than the reaction required for electrolessly depositing copper.
Claim 26
Dependent Claim
137 words
A formaldehyde-free electroless copper plating solution comprising: between about 1/2 and 2 g/l of copper ions from a solution soluble divalent copper compound; between about 1 and 3 g/l of dimethyl amine borane as a reducing agent for said copper compound; one of a complexing agent, a chelating agent or a mixture thereof; and an acid to adjust the pH of said solution to between 7.5 and 8, said solution having a temperature between about 130° and 150° F., said complexing or chelating agent being present to provide stability to the solution and to enable the solution to provide at the stated pH range a uniform plating rate of copper upon a substrate which is immersed therein without appreciable loss of the reducing agent due to extraneous reactions other than the reaction required for electrolessly depositing copper.
Claim 27
Dependent Claim
137 words
A formaldehyde-free electroless copper plating solution comprising: between about 1/2 and 2 g/l of copper ions from a solution soluble divalent copper compound; between about 1 and 3 g/l of dimethyl amine borane as a reducing agent for said copper compound; one of a complexing agent, a chelating agent or a mixture thereof; and an acid to adjust the pH of said solution to between 7.5 and 8, said solution having a temperature between about 130° and 150° F., said complexing or chelating agent being present to provide stability to the solution and to enable the solution to provide at the stated pH range a uniform plating rate of copper upon a substrate which is immersed therein without appreciable loss of the reducing agent due to extraneous reactions other than the reaction required for electrolessly depositing copper.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1992-10-30 | 1993-05-01 | 1993-10-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1996-10-30 | 1997-05-01 | 1997-10-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2000-10-30 | 2001-05-01 | 2001-10-31 | $7700.00 | Window Closed / Lapsed |