GB2085924A - Bath and process for high speed nickel electroplating - Google Patents
Bath and process for high speed nickel electroplating Download PDFInfo
- Publication number
- GB2085924A GB2085924A GB8132066A GB8132066A GB2085924A GB 2085924 A GB2085924 A GB 2085924A GB 8132066 A GB8132066 A GB 8132066A GB 8132066 A GB8132066 A GB 8132066A GB 2085924 A GB2085924 A GB 2085924A
- Authority
- GB
- United Kingdom
- Prior art keywords
- nickel
- electroplating
- bath
- stress
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000009713 electroplating Methods 0.000 title claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000080 wetting agent Substances 0.000 claims abstract description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000007747 plating Methods 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims 4
- 229910001453 nickel ion Inorganic materials 0.000 claims 4
- 125000005619 boric acid group Chemical group 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 1
- 238000004070 electrodeposition Methods 0.000 claims 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 1
- 150000002815 nickel Chemical class 0.000 abstract description 2
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 abstract 1
- SHHKMWMIKILKQW-UHFFFAOYSA-N 2-formylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C=O SHHKMWMIKILKQW-UHFFFAOYSA-N 0.000 abstract 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 abstract 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229960003975 potassium Drugs 0.000 description 2
- UPPLJLAHMKABPR-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;nickel(2+) Chemical compound [Ni+2].[Ni+2].[Ni+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O UPPLJLAHMKABPR-UHFFFAOYSA-H 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SQXDIYWBFJJRGX-UHFFFAOYSA-N benzenesulfonyl formate Chemical compound O=COS(=O)(=O)C1=CC=CC=C1 SQXDIYWBFJJRGX-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- FJIUUBZGIYMKFS-UHFFFAOYSA-N dioxoruthenium oxygen(2-) titanium(4+) Chemical compound [Ru](=O)=O.[O-2].[O-2].[Ti+4] FJIUUBZGIYMKFS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Cosmetics (AREA)
Abstract
An electroplating bath for producing a semi-bright, ductile, low- stressed nickel deposit, for use with insoluble anodes, comprises a nickel salt such as nickel sulphate, carbonate or citrate, an electrolyte such as boric or citric acid or salt thereof, and as organic brightener and wetting agent, o-formyl benzene sulphonic acid or salt thereof, and potassium perfluoroalkyl sulfonate.
Description
SPECIFICATION
Bath and process for high speed nickel electroplating
The present invention relates to a nickel plating bath and to a process for using it.
It is known in electrolytic nickel plating systems to use soluble anodes. The use of soluble anodes was prescribed because of the belief that organic additives in the bath would break down in the presence of insoluble anodes. It was also known that the stress of the nickel deposit was adversely affected by insoluble anodes. For various commerical reasons it would be highly desirable to use insoluble anodes in a nickel electroplating system without encountering break down of organic additives or stressed nickel deposits.
United States patents relating to nickel plating include U.S. Patents 2,228,991 (Freed); 2,409,119 (Freed); 2,409,120 (Freed et al.); 2,485,149 (Freed et al.); and 2,998,360 (Castellano). As far as can be determined, these patents involve the use of a conventional or modified consumable anode. See, for example, page 2, column 2, lines 53 to 64, of U.S.
Patent 2,228,991.
The present invention relates to a new and improved electroplating bath for use with insoluble anodes and can be operated at relatively high speeds to produce nickel deposits which are also relatively stress-free. The insoluble anodes which can be employed in the process of this invention are, for example, platinized titanium, pltinized tantalum, platinized columbium (niobium) as well as a platinum metal anode itself. Additionally, titanium anodes having mixed oxide coatings, such as ruthenium dioxide-titanium dioxide coatings, may also be used.
The electroplating bath of this invention contains certain selected additives which have been found to have markedly increased resistance to breakdown during operations carried out in the presence of insoluble anodes as compared to conventional nickel brighteners. In addition to a conventional nickel source, e.g. nickel, sulphate, and an electrolyte conducting or buffering agent such as boric acid, the electroplating bath will contain ortho-formyl benzene sulphonic acid as the brightener and a blend of potassium perfluoro-alkyl sulphonates sold under the trade name designation of FC 98 as the wetting agent.
In general, the electroplating baths of the present invention will be formulated as follows:
Component Concentration (g/l)
Nickel Salt 30 to 105 (as Ni)
Electrolyte 20 to 100
O-formyl benzene sulphonic acid 0.25 to 3.0
FC 98 0.02 to 0.2
The preferred sources of the nickel metal ions are nickel sulphate, nickel citrate, and nickel carbonate. These salts are preferably employed in an amount of from 1 35 to 470 g/l to provide the desired nickel metal ion concentration.
Electrolytes which are most useful for the present purpose include boric acid and citric acid.
The preferred amounts used in preparing the electroplating baths of this invention will range from 22.5 to 45 g/l. The use of boric acid is especially preferred.
The organic components of the bath are usually the brighteners and the wetting agents. In formulating the special electroplating bath of this invention the specific brightener employed is ortho-formyl benzene sulphonic acid. The required wetting agent is FC 98, a tradenamed product marketed by the Minnesota Mining a Manufacturing Company.
For most purposes the pH of the electroplating bath is adjusted to a range of 2 to 5, preferably 2.5 to 4.5. The compounds which may be used to effect the pH adjustment include nickel carbonate, sulphuric acid, potassium citrate, and citric acid.
The baths of the present invention may be operated at temperatures of 46 to 57"C and at a relatively high current density of up to 1000 ASF (110 ASD), and preferably about 100 to 600
ASF (11 to 66 ASD). The ability to use such high current densities is another important advantage of the electroplating baths of the present invention.
Nickel deposits on various substrates when utilizing the baths of this invention are characterized by being semi-bright, ductile, and low-stressed. Heretofore such properties could only be obtained by the use of consumable anodes in nickel electroplating systems.
The invention may be put into practice in various ways and one specific embodiment will be described to illustrate the invention with reference to the accompanying example.
EXAMPLE
An electroplating bath was formulated from the following ingredients:
Components Concentration g/l
Nickel Sulphate 75 (as Ni)
Boric Acid 40 Oformyl benzene sulphonic acid 1.5 FC98 0.1
"Blend of potassium perfluoroalkyl sulphonates. Prior to use sufficient nickel carbonate was added to the bath to adjust the pH to about 2.5. The bath was used in a conventional electroplating bath with platinized titanium anodes to coat copper at 55"C and 500 ASF (55
ASD). The resulting nickel deposit was semi-bright and ductile. Further analysis indicated lowstress in the deposit. In utilizing this bath substantially no break down of the. organic additives present in the bath was noted.
Claims (14)
1. A process for electroplating a workpiece having a conductive surface with a semi-bright, ductile, low-stress or stress-free nickel deposit which comprises contacting the workpiece as the cathode with a plating bath comprising a source of nickel ions, an electrolyte, and ortho-formyl benzene sulphonic acid or a salt thereof, and carrying out electroplating using insoluble anodes.
2. A process as claimed in Claim 1 in which the electrolyte comprises borixc acid or citric acid or salts thereof.
3. A process as claimed in Claim 1 or Claim 2 in which the plating bath also contains a wetting agent comprising at least one potassium perflluoroalkyl sulphonate.
4. A process as claimed in Claim 1, 2 or 3 in which the source of nickel ions in the plating bath comprises nickel sulphate.
5. A process as claimed in Claim 1, 2, 3 or 4 in which the electrolyte is boric acid.
6. A process as claimed in any one of Claims 1 to 5 in which the plating bath has a pH of 2.5 to 4.5.
7. A process as claimed in any one of Claims 1 to 6 in which the electroplating is carried out at a current density of up to 1000 ASF (110 ASD).
8. A process as claimed in Claim 7 in which the electroplating is carried out at a current density of 100 to 600 ASF (11 to 66 ASD).
9. A process as claimed in Claim 1 substantially as specifically described herein with reference to the Example.
1 0. An article whenever provided with a semi-bright, ductile, low-stress or stress-free nickel deposit by a process as claimed in any one of Claims 1 to 9.
11. An electroplating bath suitable for use with insoluble anodes in the electrodeposition of semi-bright, ductile and low-stress or stress-free nickel deposits, the said bath comprising a source of nickel ions; an electrolyte comprising boric acid or citric acid or salts thereof; orthoformyl benzene sulphonic acid or a salt thereof as a brightener; and a wetting agent comprising a blend of portassium perflouroalkyl sulphonates.
1 2. An electroplating bath as claimed in Claim 11 in which the source of nickel ions comprises nickel sulphate.
1 3. An electroplating bath as claimed in Claim 11 or Claim 1 2 in which the electrolyte is boric acid.
14. An electroplating bath as claimed in Claim 11, 12 or 13 having a pH of 2.5 to 4.5.
1 5. An electroplating bath as claimed in Claim 11 substantially as specifically described herein with reference to the Example.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19989480A | 1980-10-23 | 1980-10-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2085924A true GB2085924A (en) | 1982-05-06 |
| GB2085924B GB2085924B (en) | 1983-06-02 |
Family
ID=22739453
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8132066A Expired GB2085924B (en) | 1980-10-23 | 1981-10-23 | Bath and process for high speed nickel electroplating |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS6020475B2 (en) |
| AU (1) | AU527954B2 (en) |
| BE (1) | BE890836A (en) |
| BR (1) | BR8106819A (en) |
| CA (1) | CA1180677A (en) |
| CH (1) | CH649579A5 (en) |
| DE (1) | DE3139641C2 (en) |
| DK (1) | DK422181A (en) |
| ES (1) | ES506173A0 (en) |
| FR (1) | FR2492849A1 (en) |
| GB (1) | GB2085924B (en) |
| HK (1) | HK66786A (en) |
| IT (1) | IT1171598B (en) |
| NL (1) | NL8104808A (en) |
| SE (1) | SE8106250L (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2164953A (en) * | 1984-10-01 | 1986-04-03 | Omi Int Corp | Zinc-alloy plating |
| CN112323096A (en) * | 2020-09-23 | 2021-02-05 | 河北东恩企业管理咨询有限公司 | Preparation method of sulfur-nickel-containing round cake |
| EP4050628A4 (en) * | 2019-10-24 | 2023-01-11 | Iljin Materials Co., Ltd. | Nickel foil for production of thin-film capacitor, and manufacturing method for same |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1162505A (en) * | 1980-10-31 | 1984-02-21 | Donald R. Rosegren | Process for high speed nickel and gold electroplate system |
| JP4904933B2 (en) * | 2005-09-27 | 2012-03-28 | 日立電線株式会社 | Nickel plating solution and manufacturing method thereof, nickel plating method and copper foil for printed wiring board |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3334032A (en) * | 1964-05-08 | 1967-08-01 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
| US3697391A (en) * | 1970-07-17 | 1972-10-10 | M & T Chemicals Inc | Electroplating processes and compositions |
| ZA721964B (en) * | 1971-04-01 | 1972-12-27 | M & T Chemicals Inc | Nickel plating |
-
1981
- 1981-09-24 DK DK422181A patent/DK422181A/en not_active Application Discontinuation
- 1981-09-25 AU AU75676/81A patent/AU527954B2/en not_active Ceased
- 1981-09-25 CA CA000386693A patent/CA1180677A/en not_active Expired
- 1981-10-06 DE DE3139641A patent/DE3139641C2/en not_active Expired
- 1981-10-09 ES ES506173A patent/ES506173A0/en active Granted
- 1981-10-13 JP JP56163363A patent/JPS6020475B2/en not_active Expired
- 1981-10-21 IT IT49529/81A patent/IT1171598B/en active
- 1981-10-22 FR FR8119853A patent/FR2492849A1/en active Granted
- 1981-10-22 BR BR8106819A patent/BR8106819A/en not_active IP Right Cessation
- 1981-10-22 SE SE8106250A patent/SE8106250L/en unknown
- 1981-10-22 CH CH6755/81A patent/CH649579A5/en not_active IP Right Cessation
- 1981-10-22 BE BE0/206326A patent/BE890836A/en not_active IP Right Cessation
- 1981-10-23 NL NL8104808A patent/NL8104808A/en not_active Application Discontinuation
- 1981-10-23 GB GB8132066A patent/GB2085924B/en not_active Expired
-
1986
- 1986-09-11 HK HK667/86A patent/HK66786A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2164953A (en) * | 1984-10-01 | 1986-04-03 | Omi Int Corp | Zinc-alloy plating |
| EP4050628A4 (en) * | 2019-10-24 | 2023-01-11 | Iljin Materials Co., Ltd. | Nickel foil for production of thin-film capacitor, and manufacturing method for same |
| CN112323096A (en) * | 2020-09-23 | 2021-02-05 | 河北东恩企业管理咨询有限公司 | Preparation method of sulfur-nickel-containing round cake |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5794589A (en) | 1982-06-12 |
| BR8106819A (en) | 1982-07-06 |
| DE3139641A1 (en) | 1982-09-30 |
| HK66786A (en) | 1986-09-18 |
| SE8106250L (en) | 1982-04-24 |
| IT1171598B (en) | 1987-06-10 |
| CA1180677A (en) | 1985-01-08 |
| NL8104808A (en) | 1982-05-17 |
| DK422181A (en) | 1982-04-24 |
| JPS6020475B2 (en) | 1985-05-22 |
| FR2492849A1 (en) | 1982-04-30 |
| DE3139641C2 (en) | 1986-07-31 |
| FR2492849B1 (en) | 1984-11-23 |
| CH649579A5 (en) | 1985-05-31 |
| AU7567681A (en) | 1982-04-29 |
| BE890836A (en) | 1982-04-22 |
| AU527954B2 (en) | 1983-03-31 |
| ES8302802A1 (en) | 1983-01-16 |
| ES506173A0 (en) | 1983-01-16 |
| GB2085924B (en) | 1983-06-02 |
| IT8149529A0 (en) | 1981-10-21 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19931023 |