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Patent US4755265A successfully refreshed from Google Patents.
US4755265A
Expired / Lapsed
US
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Processes for the deposition or removal of metals
Assignee: Entek Corp
•
Filing: 1987-03-03
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Granted: 1988-07-05
•
Expires: 2007-03-03
Abstract
Abstract Methods for depositing metals on or removing metals from substrates are provided which involve the use of electrolytic cells comprising an anode and cathode, sulfuric acid, and a chalcogen-containing compound soluble in said bath and having the empirical formula ##STR1## wherein X is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is hydrogen or a monovalent organic radical, and R 5 is a divalent organic radical, in which the molar ratio of the chalcogen compound to sulfuric acid is about 1 or more, and the molar ratio of water to the combination of acid and chalcogen compound is about 20 or less. These methods enable the use of higher concentrations of strong acids than would otherwise be possible, minimize hydrogen and/or oxygen evolution at the electrodes with attendant advantages, and are useful for electroplating (including immersion plating), electroforming, electrolytic machining, electropolishing, electrolytic roughening, anodizing and electrowinning among others.
Inventors
- 👤 Donald C. Young
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-08 21:50
CPC Classifications
B; B01; B01J; B01J31/00; B01J31/02; B01J31/0234; B01J31/0235; B01J31/0245; B01J31/0249; C; C23; C23C; C23C18/00; C23C18/16; C23C18/31; C23C18/38; C25; C25D; C25D3/00; C25D3/02; C25D3/38; C25F; C25F5/00; H; H05; H05K; H05K3/00; H05K3/02; H05K3/06; H05K3/07
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
159 words
A method for electrolytically plating a metal on an electrically conductive substrate which method comprises suspending said electrically conductive substrate as a cathode in an electrolytic cell comprising an anode and said cathode immersed in an electrically conductive bath comprising platable metal ions, sulfuric acid and a chalcogen-containing compound soluble in said bath and having the empirical formula ##STR5## wherein X is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is about 1 to about 10, and the molar ratio of water to the combination of said sulfuric acid and said chalcogen-containing compound is about 20 or less.
Claim 2
Independent Claim
159 words
A method for electrolytically plating a metal on an electrically conductive substrate which method comprises suspending said electrically conductive substrate as a cathode in an electrolytic cell comprising an anode and said cathode immersed in an electrically conductive bath comprising platable metal ions, sulfuric acid and a chalcogen-containing compound soluble in said bath and having the empirical formula ##STR5## wherein X is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is about 1 to about 10, and the molar ratio of water to the combination of said sulfuric acid and said chalcogen-containing compound is about 20 or less.
Claim 3
Dependent Claim
30 words
The method defined in claim 1 wherein said chalcogen-containing compound comprises urea, and the molar ratio of said urea to said sulfuric acid is about 1 to less than 5.
Claim 4
Dependent Claim
47 words
The method defined in claim 1 wherein said chalcogen-containing compound comprises a member selected from the group consisting of urea, thiourea, formamide, and combinations thereof, and the molar ratio of water to the combination of said chalcogen-containing compound and said sulfuric acid is about 10 or less.
Claim 5
Dependent Claim
35 words
The method defined in claim 1 wherein said substrate comprises a metal which is less noble than said platable metal ions, and said substrate is immersion plated with said ions while suspended in said bath.
Claim 6
Dependent Claim
57 words
The method defined in claim 4 wherein said chalcogen-containing compound comprises a member selected from the group consisting of urea, formamide, thiourea, and combinations thereof, and said platable metal ions comprise ions selected from the group consisting of zinc, chromium, nickel, gold, silver, indium, iron, copper, lead, platinum, palladium, rhodium, ruthenium, iridium, osmium, tin, and combinations thereof.
Claim 7
Dependent Claim
25 words
The method defined in claim 4 wherein said chalcogen-containing compound comprises urea, and the molar ratio of urea to sulfuric acid is less than 5.
Claim 8
Dependent Claim
25 words
The method defined in claim 1 which further comprises the step of impressing a direct current voltage across said electrically conductive substrate and an anode.
Claim 9
Dependent Claim
17 words
The method defined in claim 1 wherein said bath comprises less than about 1 weight percent water.
Claim 10
Dependent Claim
24 words
The method defined in claim 1 wherein the [H 2 O]/[chalcogen compound][H 2 SO 4 ] molarity product ratio is about 50 or less.
Claim 11
Dependent Claim
24 words
The method defined in claim 1 wherein the [H 2 O]/[chalcogen compound][H 2 SO 4 ] molarity product ratio is about 25 or less.
Claim 12
Dependent Claim
49 words
The method defined in claim 1 wherein said bath comprises urea, and at least a portion of said sulfuric acid is present in said bath as a member selected from the group consisting of the monourea adduct of sulfuric acid, the diurea adduct of sulfuric acid, and combinations thereof.
Claim 13
Independent Claim
164 words
A method for electrolytically removing a metal from an electrically conductive substrate which method comprises employing said substrate as the anode in an electrolytic cell comprising said anode and a cathode immersed in an electrically conductive bath comprising sulfuric acid and chalcogen-containing compound soluble in said bath and having the empirical formula ##STR6## wherein X is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is about 1 to about 10, and the molar ratio of water to the combination of said sulfuric acid and said chalcogen-containing compound is about 20 or less, and impressing a voltage differential across said cathode and said anode.
Claim 14
Independent Claim
164 words
A method for electrolytically removing a metal from an electrically conductive substrate which method comprises employing said substrate as the anode in an electrolytic cell comprising said anode and a cathode immersed in an electrically conductive bath comprising sulfuric acid and chalcogen-containing compound soluble in said bath and having the empirical formula ##STR6## wherein X is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is about 1 to about 10, and the molar ratio of water to the combination of said sulfuric acid and said chalcogen-containing compound is about 20 or less, and impressing a voltage differential across said cathode and said anode.
Claim 15
Dependent Claim
44 words
The method defined in claim 12 wherein said chalcogen-containing compound comprises a member selected from the group consisting of urea, thiourea, formamide, and combinations thereof, and the molar ratio of said chalcogen-containing compound to said sulfuric acid is about 1 to less than 5.
Claim 16
Dependent Claim
28 words
The method defined in claim 12 wherein the molar ratio of water to the combination of said chalcogen-containing compound and said sulfuric acid is about 10 or less.
Claim 17
Dependent Claim
11 words
The method defined in claim 12 which comprises electromachining said substrate.
Claim 18
Dependent Claim
11 words
The method defined in claim 12 which comprises electropolishing said substrate.
Claim 19
Dependent Claim
11 words
The method defined in claim 12 which comprises electroroughening said substrate.
Claim 20
Dependent Claim
11 words
The method defined in claim 12 which comprises anodizing said substrate.
Claim 21
Dependent Claim
16 words
The method defined in claim 12 wherein said bath comprises less than 1 weight percent water.
Claim 22
Dependent Claim
24 words
The method defined in claim 12 wherein the [H 2 O]/[chalcogen compound][H 2 SO 4 ] molarity product ratio is about 50 or less.
Claim 23
Dependent Claim
23 words
The method defined in claim 12 wherein the H 2 O]/[chalcogen compound][H 2 SO 4 molarity product ratio is about 25 or less.
Claim 24
Dependent Claim
49 words
The method defined in claim 12 wherein said bath comprises urea, and at least a portion of said sulfuric acid is present in said bath as a member selected from the group consisting of the monourea adduct of sulfuric acid, the diurea adduct of sulfuric acid, and combinations thereof.
Claim 25
Dependent Claim
30 words
The method defined in claim 12 wherein at least a portion of said sulfuric acid is present in said bath in the form of an adduct with said chalcogen compound.
Claim 26
Independent Claim
134 words
A method for electrolytically plating a metal on an electrically conductive substrate, which method comprises suspending said electrically conductive substrate as a cathode in an electrolytic cell comprising an anode and said cathode immersed in an electrolytic bath comprising sulfuric acid, a chalcogen-containing compound selected from the group consisting of urea, formamide, thiourea, and combinations thereof, and a metal ion platable on said substrate, wherein the molar ratio of said chalcogen-containing compound to said sulfuric acid is within the range of about 1 to about 10, the molar ratio of water to the combination of said chalcogen-containing compound and said sulfuric acid is about 20 or less, the [H 2 O]/[chalcogen compound][H 2 SO 4 molarity product ratio is about 50 or less, and causing said platable metal ion to plate on said substrate.
Claim 27
Independent Claim
134 words
A method for electrolytically plating a metal on an electrically conductive substrate, which method comprises suspending said electrically conductive substrate as a cathode in an electrolytic cell comprising an anode and said cathode immersed in an electrolytic bath comprising sulfuric acid, a chalcogen-containing compound selected from the group consisting of urea, formamide, thiourea, and combinations thereof, and a metal ion platable on said substrate, wherein the molar ratio of said chalcogen-containing compound to said sulfuric acid is within the range of about 1 to about 10, the molar ratio of water to the combination of said chalcogen-containing compound and said sulfuric acid is about 20 or less, the [H 2 O]/[chalcogen compound][H 2 SO 4 molarity product ratio is about 50 or less, and causing said platable metal ion to plate on said substrate.
Claim 28
Independent Claim
132 words
A method for electrolytically depositing a metal on a substrate which comprises employing said substrate as a cathode in an electrolytic cell comprising an anode and said cathode immersed in an anhydrous, electrically conductive bath comprising platable metal ions, sulfuric acid and a chalcogen-containing compound soluble in said bath and having the empirical formula ##STR7## wherein X is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, R 5 is selected from divalent organic radicals, and the molar ratio of said chalcogen-containing compound to said acid is about 1 to about 10.
Claim 29
Independent Claim
132 words
A method for electrolytically depositing a metal on a substrate which comprises employing said substrate as a cathode in an electrolytic cell comprising an anode and said cathode immersed in an anhydrous, electrically conductive bath comprising platable metal ions, sulfuric acid and a chalcogen-containing compound soluble in said bath and having the empirical formula ##STR7## wherein X is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, R 5 is selected from divalent organic radicals, and the molar ratio of said chalcogen-containing compound to said acid is about 1 to about 10.
Claim 30
Dependent Claim
15 words
The method defined in claim 25 wherein said metal is selected from aluminum and titanium.
Claim 31
Dependent Claim
12 words
The method defined in claim 25 wherein said chalcogen-containing compound comprises urea.
Claim 32
Independent Claim
160 words
A method for electrolytically depositing a metal on or removing a metal from the substrate which method comprises conducting said metal deposition or removal in an electrolytic bath comprising sulfuric acid and a chalcogen-containing compound soluble in said bath and having the empirical formula ##STR8## wherein X is S or O, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is at least about 1, the molar ratio of water to the combination of said acid and said chalcogen-containing compound is about 20 or less, and the [H 2 O]/[chalcogen compound][H 2 SO 4 molarity product ratio is about 50 or less.
Claim 33
Independent Claim
160 words
A method for electrolytically depositing a metal on or removing a metal from the substrate which method comprises conducting said metal deposition or removal in an electrolytic bath comprising sulfuric acid and a chalcogen-containing compound soluble in said bath and having the empirical formula ##STR8## wherein X is S or O, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is at least about 1, the molar ratio of water to the combination of said acid and said chalcogen-containing compound is about 20 or less, and the [H 2 O]/[chalcogen compound][H 2 SO 4 molarity product ratio is about 50 or less.
Claim 34
Dependent Claim
12 words
The method defined in claim 28 wherein said chalcogen-containing compound comprises urea.
Claim 35
Independent Claim
180 words
A method for immersion plating platable metal ions on a substrate which comprises a metal less noble than said platable metal ions, which method comprises suspending said substrate in an electrolyte containing said platable metal ions, sulfuric acid, and a chalcogen-containing compound soluble in said bath and having the empirical formula: ##STR9## wherein X is is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is at least about 1, the molar ratio of water to the combination of said sulfuric acid and said chalcogen-containing compound is about 20 or less, and the [H 2 O]/[chalcogen compound][H 2 SO 4 ] molarity product ratio is about 50 or less, under conditions sufficient to plate said metal ions on said substrate.
Claim 36
Independent Claim
180 words
A method for immersion plating platable metal ions on a substrate which comprises a metal less noble than said platable metal ions, which method comprises suspending said substrate in an electrolyte containing said platable metal ions, sulfuric acid, and a chalcogen-containing compound soluble in said bath and having the empirical formula: ##STR9## wherein X is is a chalcogen, each of R 1 and R 2 is selected from hydrogen, NR 3 R 4 and NR 5 , at least one of R 1 and R 2 is other than hydrogen, each of R 3 and R 4 is selected from hydrogen and monovalent organic radicals, and R 5 is selected from divalent organic radicals, the molar ratio of said chalcogen-containing compound to said sulfuric acid is at least about 1, the molar ratio of water to the combination of said sulfuric acid and said chalcogen-containing compound is about 20 or less, and the [H 2 O]/[chalcogen compound][H 2 SO 4 ] molarity product ratio is about 50 or less, under conditions sufficient to plate said metal ions on said substrate.
Claim 37
Dependent Claim
12 words
The method defined in claim 30 wherein said chalcogen-containing compound comprises urea.
Claim 38
Dependent Claim
12 words
The method defined in claim 31 wherein said bath is substantially anhydrous.
Claim 39
Dependent Claim
17 words
The method defined in claim 31 wherein said bath comprises about 1 weight percent water or less.
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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) | 1991-07-05 | 1992-01-04 | 1992-07-05 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1995-07-05 | 1996-01-04 | 1996-07-05 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1999-07-05 | 2000-01-04 | 2000-07-05 | $7700.00 | Window Closed / Lapsed |