Patent US5252196A successfully refreshed from Google Patents.
US5252196A
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Copper electroplating solutions and processes
Assignee: Shipley Co Inc
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Filing: 1991-12-05
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Granted: 1993-10-12
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Expires: 2011-12-05
Abstract
Abstract Compositions and processes for electrolytic plating. The compositions are characterized by critical amounts of one or more brightening and leveling agents. The compositions are particularly useful for plating through hole walls of printed circuit boards, including through holes having an aspect ratio equal or greater than about ten to one.
Inventors
- 👤 Wade Sonnenberg
- 👤 Gordon Fisher
- 👤 Roger F. Bernards
- 👤 Patrick Houle
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 18:57
CPC Classifications
C; C25; C25D; C25D3/00; C25D3/02; C25D3/38
Claims Analysis
Total Claims: 50
Claim 1
Independent Claim
64 words
An aqueous electroplating solution, comprising: at least one soluble copper salt, an electrolyte, and one or more brightening agents of the formula HS--R--SO 3 wherein R is substituted or unsubstituted aryl or substituted or unsubstituted alkyl, and wherein the concentration of said brightening agents of formula HS--R--SO 3 is from about 1 ppb to 250 ppb based on total weight of the electroplating solution.
Claim 2
Dependent Claim
64 words
An aqueous electroplating solution, comprising: at least one soluble copper salt, an electrolyte, and one or more brightening agents of the formula HS--R--SO 3 wherein R is substituted or unsubstituted aryl or substituted or unsubstituted alkyl, and wherein the concentration of said brightening agents of formula HS--R--SO 3 is from about 1 ppb to 250 ppb based on total weight of the electroplating solution.
Claim 3
Dependent Claim
38 words
The electroplating solution of claim 1 where the concentration of the brightening agent of the formula HS--R--SO 3 in the electroplating solution is from about 1 ppb to 100 ppb based on total weight of the electroplating solution.
Claim 4
Dependent Claim
31 words
The electroplating solution of claim 1 wherein R is selected from the group consisting of substituted or unsubstituted phenyl and substituted or unsubstituted alkyl having from 1 to 6 carbon atoms.
Claim 5
Dependent Claim
49 words
The electroplating solution of claim 1 where the one or more brightening agents comprise a brightening agent of the formula O 3 S--R--S--S--R 1 --SO 3 wherein R and R 1 are each independently selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl.
Claim 6
Dependent Claim
42 words
The electroplating solution of claim 4 where the concentration of the brightening agent of the formula O 3 S--R--S--S--R 1 --SO 3 in the electroplating solution is from about 10 ppb to 200 ppb based on total weight of the electroplating solution.
Claim 7
Dependent Claim
36 words
The electroplating solution of claim 4 wherein R and R 1 are each independently selected from the group consisting of substituted or unsubstituted phenyl and substituted or unsubstituted alkyl having from 1 to 6 carbon atoms.
Claim 8
Dependent Claim
27 words
The electroplating solution of claim 1 where the one or more brightening agents are selected from the group consisting of mercapto-propylsulfonic acid, mercapto-ethanesulfonic acid and bissulfopropyl disulfide.
Claim 9
Dependent Claim
115 words
The electroplating solution of claim 1 where the one or more brightening agents is a mixture of brightening agents, said mixture consisting essentially of one or more brightening agents of the formula HS--R--SO 3 wherein R is selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl, and one or more brightening agents of the formula O 3 S--R--S--S--R 1 --SO 3 wherein R and R 1 are each independently selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl, the concentration of said mixture in the electroplating solution being from about 1 ppb to 500 ppb based on total weight of the electroplating solution.
Claim 10
Dependent Claim
13 words
The electroplating solution of claim 1 further comprising one or more wetting agents.
Claim 11
Dependent Claim
18 words
The electroplating solution of claim 1 where the electrolyte is an acid used in combination with halide ions.
Claim 12
Dependent Claim
12 words
The electroplating solution of claim 1 where the electrolyte comprises a base.
Claim 13
Dependent Claim
11 words
The electroplating solution of claim 1 further comprising a leveling agent.
Claim 14
Dependent Claim
35 words
The electroplating solution of claim 12 where the leveling agent contains a group of the formula N--R--S, where R is selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl.
Claim 15
Dependent Claim
46 words
The electroplating solution of claim 12 where the leveling agent is present in the electroplating solution in a concentration, based on total weight of the electroplating solution, in a range equal to 1 ppm or less divided by the Leveler Potency Constant of the leveling agent.
Claim 16
Dependent Claim
12 words
The electroplating solution of 12 further comprising one or more wetting agents.
Claim 17
Dependent Claim
12 words
The electroplating solution of 12 further comprising one or more wetting agents.
Claim 18
Dependent Claim
27 words
The electroplating solution of claim 12 where the leveling agent-brightener w/w ratio is less than about 20:1 divided by the Leveler Potency Constant of the leveling agent.
Claim 19
Dependent Claim
27 words
The electroplating solution of claim 12 where the leveling agent-brightener w/w ratio is less than about 5:1 divided by the Leveler Potency Constant of the leveling agent.
Claim 20
Dependent Claim
12 words
The electroplating solution of claim 12 where the leveling agent is 1-(2-hydroxyethyl)-2-imidazolidinethione.
Claim 21
Dependent Claim
33 words
The electroplating solution of claim 18 where the leveling agent is present in the electroplating solution in a concentration of less than about 1 ppm based on total weight of the electroplating solution.
Claim 22
Dependent Claim
33 words
The electroplating solution of claim 18 where the leveling agent is present in the electroplating solution in a concentration of less than about 500 ppb based on total weight of the electroplating solution.
Claim 23
Dependent Claim
33 words
The electroplating solution of claim 18 where the leveling agent is present in the electroplating solution in a concentration of less than about 200 ppb based on total weight of the electroplating solution.
Claim 24
Dependent Claim
17 words
The electroplating solution of claim 18 where the leveling agent-brightener w/w ratio is less than about 20:1.
Claim 25
Dependent Claim
17 words
The electroplating solution of claim 18 where the leveling agent-brightener w/w ratio is less than about 5:1.
Claim 26
Dependent Claim
82 words
A process for electrodepositing copper on a substrate, comprising: electrolytically depositing copper on the substrate from an aqueous electroplating solution, the solution comprising at least one soluble copper salt, an electrolyte, and one or more brightening agents of the formula HS--R--SO 3 wherein R is substituted or unsubstituted aryl or substituted or unsubstituted alkyl, and wherein the concentration of said brightening agents of formula HS--R--SO 3 is from about 1 ppb to 250 ppb based on total weight of the electroplating solution.
Claim 27
Dependent Claim
82 words
A process for electrodepositing copper on a substrate, comprising: electrolytically depositing copper on the substrate from an aqueous electroplating solution, the solution comprising at least one soluble copper salt, an electrolyte, and one or more brightening agents of the formula HS--R--SO 3 wherein R is substituted or unsubstituted aryl or substituted or unsubstituted alkyl, and wherein the concentration of said brightening agents of formula HS--R--SO 3 is from about 1 ppb to 250 ppb based on total weight of the electroplating solution.
Claim 28
Dependent Claim
11 words
The process of claim 24 where the substrate has irregular topography.
Claim 29
Dependent Claim
37 words
The process of claim 24 where the concentration of the brightening agent of the formula HS--R--SO 3 in the electroplating solution is from about 1 ppb to 100 ppb based on total weight of the electroplating solution.
Claim 30
Dependent Claim
16 words
The process of claim 24 where the substrate is a printed circuit board having through holes.
Claim 31
Dependent Claim
22 words
The process of claim 27 where the through holes have an aspect ratio equal to or greater than about ten to one.
Claim 32
Dependent Claim
108 words
The process of claim 27 where the one or more brightening agents is a mixture of brightening agents, said mixture consisting essentially of (1) one or more brightening agents of the formula HS--R--SO 3 wherein R is selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl, and (2) one or more brightening agents of the formula O 3 S--R--S--S--R 1 --SO 3 wherein R and R 1 are each independently selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl, the concentration of said mixture in the electroplating solution being from about 1 ppb to 500 ppb.
Claim 33
Dependent Claim
48 words
The process of claim 27 where the one or more brightening agents comprise a brightening agent of the formula O 3 S--R--S--S--R 1 --SO 3 wherein R and R 1 are each independently selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl.
Claim 34
Dependent Claim
41 words
The process of claim 30 where the concentration of the brightening agent of the formula O 3 S--R--S--S--R 1 --SO 3 in the electroplating solution is from about 1 ppb to 500 ppb based on total weight of the electroplating solution.
Claim 35
Dependent Claim
41 words
The process of claim 30 where the concentration of the brightening agent of the formula O 3 S--R--S--S--R 1 --SO 3 in the electroplating solution is from about 10 ppb to 200 ppb based on total weight of the electroplating solution.
Claim 36
Dependent Claim
10 words
The process of claim 27 further comprising a leveling agent.
Claim 37
Dependent Claim
26 words
The process of claim 33 where the leveling agent-brightener w/w ratio is less than about 20:1 divided by the Leveler Potency Constant of the leveling agent.
Claim 38
Dependent Claim
26 words
The process of claim 33 where the leveling agent-brightener w/w ratio is less than about 5:1 divided by the Leveler Potency Constant of the leveling agent.
Claim 39
Dependent Claim
30 words
The process of claim 33 where copper is deposited at a current density of about 30 ASF or greater and the leveling agent-brightener w/w ratio is less than about 0.5:1.
Claim 40
Dependent Claim
45 words
The process of claim 33 where the leveling agent is present in the electroplating solution in a concentration, based on total weight of the electroplating solution, in a range equal to 1 ppm or less divided by the Leveler Potency Constant of the leveling agent.
Claim 41
Dependent Claim
50 words
The process of claim 36 where the leveling agent is present in the electroplating solution in a concentration of less than about 1 ppm, and the leveling agent-brightener w/w ratio is equal to a value of less than about 20 divided by the Leveler Potency Constant of the leveling agent.
Claim 42
Dependent Claim
16 words
The process of claim 33 where the electroplating solution further comprises one or more wetting agents.
Claim 43
Dependent Claim
34 words
The process of claim 33 where the leveling agent is 1-(2-hydroxyethyl)-2-imidazolidinethione and is present in the electroplating solution in a concentration of less than about 1 ppm based on total weight of the solution.
Claim 44
Dependent Claim
31 words
The process of claim 40 where the leveling agent is present in the electroplating solution in a concentration of less than about 500 ppb based on total weight of the solution.
Claim 45
Dependent Claim
31 words
The process of claim 40 where the leveling agent is present in the electroplating solution in a concentration of less than about 200 ppb based on total weight of the solution.
Claim 46
Dependent Claim
16 words
The process of claim 40 where the leveling agent-brightener w/w ratio is less than about 20:1.
Claim 47
Dependent Claim
16 words
The process of claim 40 where the leveling agent-brightener w/w ratio is less than about 5:1.
Claim 48
Dependent Claim
30 words
The process of claim 40 where copper is deposited at a current density of about 30 ASF or greater and the leveling agent-brightener w/w ratio is less than about 0.5:1.
Claim 49
Dependent Claim
80 words
An aqueous electroplating solution, comprising: at least one soluble copper salt, an electrolyte, and one or more brightening agents, at least of one of said one or more brightening agents having the structural formula HS--R--SO 3 wherein R is selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl, and wherein the concentration of said brightening agent of the structural formula HS--R--SO 3 in the electroplating solution is from about 1 ppb to 250 ppb.
Claim 50
Dependent Claim
80 words
An aqueous electroplating solution, comprising: at least one soluble copper salt, an electrolyte, and one or more brightening agents, at least of one of said one or more brightening agents having the structural formula HS--R--SO 3 wherein R is selected from the group consisting of substituted or unsubstituted aryl and substituted or unsubstituted alkyl, and wherein the concentration of said brightening agent of the structural formula HS--R--SO 3 in the electroplating solution is from about 1 ppb to 250 ppb.
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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) | 1996-10-11 | 1997-04-12 | 1997-10-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2000-10-11 | 2001-04-12 | 2001-10-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2004-10-11 | 2005-04-12 | 2005-10-12 | $7700.00 | Window Closed / Lapsed |