US5730854A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Alkoxylated dimercaptans as copper additives and de-polarizing additives
Assignee: MacDermid Enthone Inc
•
Filing: 1996-05-30
•
Granted: 1998-03-24
•
Expires: 2016-05-30
Abstract
Abstract A copper electroplating process using alkoxylated dimercaptan ethers as an additive. The additives prevent dendritic formations which short out electrodes. Also provided is a method for polarizing the electrodes, allowing for current reduction and cost savings.
Inventors
- 👤 Sylvia Martin
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-29 05:00
CPC Classifications
C; C25; C25D; C25D3/00; C25D3/02; C25D3/38; C25C; C25C1/00; C25C1/12
Claims Analysis
Total Claims: 22
Claim 1
Independent Claim
70 words
A method for electroplating a copper deposit substantially free of dendrites, nodules and sulfur impurities, comprising: (1) providing an electroplating bath including ionic copper and an effective amount of an alkoxylated dimercaptan ether additive for inhibiting formation of dendrites and nodules, and reducing sulfur impurities; and (2) electroplating a copper deposit from said bath onto a cathode, wherein the resulting deposit is substantially free of dendrites, nodules and sulfur impurities.
Claim 2
Independent Claim
70 words
A method for electroplating a copper deposit substantially free of dendrites, nodules and sulfur impurities, comprising: (1) providing an electroplating bath including ionic copper and an effective amount of an alkoxylated dimercaptan ether additive for inhibiting formation of dendrites and nodules, and reducing sulfur impurities; and (2) electroplating a copper deposit from said bath onto a cathode, wherein the resulting deposit is substantially free of dendrites, nodules and sulfur impurities.
Claim 3
Dependent Claim
169 words
The method of claim 1 wherein said dimercaptan ether has the formula: HO--R.sub.1 -- O--R.sub.2 !.sub.n --S--Z--X--S-- R.sub.3 --O!.sub.m --R.sub.4 --OH wherein: R 1 , R 2 , R 3 and R 4 are selected from the group consisting of ethylene, propylene and butylene; Z is selected from the group consisting of R 5 --O--R 6 , R 5 --O--Y 1 , Y 1 --O--Y 2 and Y 1 --Y 2 , where R 5 is selected from the group consisting of ethylene, propylene, Y 1 and Y 2 . R 6 is selected from the group consisting of ethylene, propylene, Y 1 and Y 2 ; Y 1 is selected from the group consisting of R--OH and ##STR4## Y 2 is selected from the group consisting of R--OH and ##STR5## where R is selected from the group consisting of ethylene, propylene and butylene; X is selected from the group consisting of (O--R 5 ) p where p=0 to 3; and m+n is from about 8 to about 100.
Claim 4
Dependent Claim
14 words
The method of claim 2 wherein m+n is from about 8 to about 23.
Claim 5
Dependent Claim
14 words
The method of claim 2 wherein m+n is from about 13 to about 16.
Claim 6
Dependent Claim
23 words
The method of claim 2 wherein said additive is present in said bath in quantities of from about 5 to about 1000 mg/l.
Claim 7
Dependent Claim
23 words
The method of claim 2 wherein said additive is present in said bath in amounts of from about 20 to about 120 mg/l.
Claim 8
Dependent Claim
30 words
The method of claim 2 wherein a ductile bright satin copper deposit is plated by including from about 0.5 mg/l to about 60 mg/l of said additive in said bath.
Claim 9
Dependent Claim
34 words
The method of claim 2 wherein a functionally pure electrical grade copper plate is produced wherein the additive is found in the bath in an amount of from about 60 to about 1000 mg/l.
Claim 10
Dependent Claim
32 words
The method of claim 2 wherein said copper electroplating is an electrowinning process wherein the additive is found in the bath in an amount of from about 10 to about 300 mg/l.
Claim 11
Dependent Claim
78 words
The method of claim 1 wherein the additive is selected from the group consisting of: 1,6 dimercapto-2,4 dioxahexane ethoxylated with 16 moles of ethylene oxide; 1,8 dimercapto-3,6 dioxaoctane ethoxylated with 16 moles of ethylene oxide; 1,4 dimercapto-2 oxabutane ethoxylated with 20 moles of ethylene oxide; 1,11, dimercapto-3,5,9-trihydroxy-4,8 dioxa-undecane ethoxylated with 4 moles propylene oxide and 16 moles ethylene oxide; and 1,8 dimercapto-3,6 dioxa-octane alkoxylated with 2 moles butylene oxide 6 moles propylene oxide and 16 moles ethylene oxide.
Claim 12
Independent Claim
93 words
A method for electrorefining a fine-grained copper deposit substantially free of dendrites and nodules comprising: (1) providing a bath for electrorefining of a copper material, the bath including ionic copper and an effective amount of an alkoxylated dimercaptan ether additive for inhibiting formation of dendrites and nodules, and reducing sulfur impurities, and allowing said bath to be passed between a cathode and anode for deposition of a copper deposit on the cathode; and (2) providing an electroplating current to said anode and cathode for depositing a substantially sulfurfree copper deposit on said cathode.
Claim 13
Independent Claim
93 words
A method for electrorefining a fine-grained copper deposit substantially free of dendrites and nodules comprising: (1) providing a bath for electrorefining of a copper material, the bath including ionic copper and an effective amount of an alkoxylated dimercaptan ether additive for inhibiting formation of dendrites and nodules, and reducing sulfur impurities, and allowing said bath to be passed between a cathode and anode for deposition of a copper deposit on the cathode; and (2) providing an electroplating current to said anode and cathode for depositing a substantially sulfurfree copper deposit on said cathode.
Claim 14
Dependent Claim
168 words
The method of claim 8 wherein the additive has the formula: HO--R.sub.1 -- O--R.sub.2 !.sub.n --S--Z--X--S-- R.sub.3 --O!.sub.m --R.sub.4 --OH wherein: R 1 , R 2 , R 3 and R 4 are selected from the group consisting of ethylene, propylene and butylene; Z is selected from the group consisting of R 6 --O--R 6 , R 5 --O--Y 1 , Y 1 --O--Y 2 and Y 1 --R 2 , where R 5 is selected from the group consisting of ethylene, propylene, Y 1 and Y 2 . R 6 is selected from the group consisting of ethylene, propylene, Y 1 and Y 2 ; Y 1 is selected from the group consisting of R--OH and ##STR6## Y 2 is selected from the group consisting of R--OH and ##STR7## where R is selected from the group consisting of ethylene, propylene and butylene; X is selected from the group consisting of (O--R 5 ) p where p=0 to 3; and m+n is from about 8 to about 100.
Claim 15
Dependent Claim
78 words
The method of claim 12 wherein the additive is selected from the group consisting of: 1,6 dimercapto-2,4 dioxahexane ethoxylated with 16 moles of ethylene oxide; 1,8 dimercapto-3,6 dioxaoctane ethoxylated with 16 moles of ethylene oxide; 14 dimercapto-2 oxabutane ethoxylated with 20 moles of ethylene oxide; 1,11, dimercapto-3,5,9-trihydroxy-4,8 dioxa-undecane ethoxylated with 4 moles propylene oxide and 16 moles ethylene oxide; and 1,8 dimercapto-3,6 dioxa-octane alkoxylated with 2 moles butylene oxide 6 moles propylene oxide and 16 moles ethylene oxide.
Claim 16
Dependent Claim
14 words
The method of claim 12 wherein m+n is from about 8 to about 23.
Claim 17
Dependent Claim
14 words
The method of claim 12 wherein m+n is from about 13 to about 16.
Claim 18
Dependent Claim
20 words
The method of claim 12 wherein the additive is used in amounts of from about 5 to about 1000 mg/l.
Claim 19
Dependent Claim
20 words
The method of claim 12 wherein said additive is present in amounts of from about 20 to about 200 mg/l.
Claim 20
Dependent Claim
103 words
The method of claim 12 wherein the bath further comprises a de-polarizing additive having the formula: A--R.sub.7 --(S).sub.n --R.sub.6 --Q--O.sub.3 B wherein: R 7 and R 6 are alkylene groups having from about 1 to about 6 carbons; A is selected from the group consisting of hydrogen, sulfonate, phosphonate, an alkaline metal sulfonate or phosphonate, an ammonium salt of a sulfonate or phosphonate, an acid of a sulfonate or phosphonate, and an alkali; n=1-3; B is selected from the group consisting of H, a group I or group II metal ion and an ammonium ion; and Q is selected from S or P.
Claim 21
Dependent Claim
21 words
The method of claim 18 wherein the depolarizing additive is used in amounts of from about 0.01 to about 25 mg/l.
Claim 22
Dependent Claim
101 words
The method of claim 18 wherein the additive is selected from the group consisting of: HO 3 P--(CH 2 ) 3 --S--S--(CH 2 ) 3 --PO 3 H; HO 3 S--(CH 2 ) 4 --S--S(CH 2 ) 4 --SO 3 H; NaO 3 S--(CH 2 ) 3 --S--S--(CH 2 ) 3 --SO 3 Na; HO 3 S--(CH 2 ) 2 --S--S(CH 2 ) 2 --SO 3 H; CH 3 --S--S--CH 2 --SO 3 H; NaO 3 --(CH 2 ) 3 --S--S--S--(CH 2 ) 3 --SO 3 Na; (CH 2 ) 2 --CH--S--S--(CH 2 ) 2 --SO 3 H; and mixtures thereof.
References Cited (Backward Citations)
US3328273A
Cited
US3502551A
Cited
US3784454A
Cited
US3770597A
Cited
US3743584A
Cited
US3987246A
Cited
US3770598A
Cited
US3985784A
Cited
US4110176A
Cited
US4292155A
Cited
US4272335A
Cited
US4336114A
Cited
US4347108A
Cited
US4376685A
Cited
US4683036A
Cited
US4861438A
Cited
US5219523A
Cited
US5417841A
Cited
US5236626A
Cited
US5238554A
Cited
US5200057A
Cited
US5151170A
Cited
US5256275A
Cited
US5328589A
Cited
US5458746A
Cited
US5425873A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2001-03-23 | 2001-09-22 | 2002-03-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2005-03-23 | 2005-09-22 | 2006-03-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2009-03-23 | 2009-09-22 | 2010-03-24 | $7700.00 | Window Closed / Lapsed |