US20050016416A1 - Stabilizer for electroless copper plating solution - Google Patents
Stabilizer for electroless copper plating solution Download PDFInfo
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- US20050016416A1 US20050016416A1 US10/625,435 US62543503A US2005016416A1 US 20050016416 A1 US20050016416 A1 US 20050016416A1 US 62543503 A US62543503 A US 62543503A US 2005016416 A1 US2005016416 A1 US 2005016416A1
- Authority
- US
- United States
- Prior art keywords
- plating bath
- bath composition
- electroless copper
- copper plating
- composition according
- 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.)
- Abandoned
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- 238000007747 plating Methods 0.000 title claims abstract description 57
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 47
- 239000010949 copper Substances 0.000 title claims abstract description 47
- 239000003381 stabilizer Substances 0.000 title claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000004675 formic acid derivatives Chemical class 0.000 claims abstract description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019253 formic acid Nutrition 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 24
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- 239000008139 complexing agent Substances 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- -1 alkali metal salts Chemical class 0.000 claims description 4
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical group [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 15
- 238000000151 deposition Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- YYCULGQEKARBDA-UHFFFAOYSA-N copper;formaldehyde Chemical compound [Cu].O=C YYCULGQEKARBDA-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
- C23C18/405—Formaldehyde
Definitions
- This invention relates to an improved electroless copper plating solution for plating non-conductive surfaces, such as through holes in multi-layered printed circuit boards.
- the improved electroless copper plating solution contains a formate stabilizer to prevent autodecomposition of copper from the plating solution.
- electroless deposition of copper (here used to include copper alloys or intermetallics), i.e., the chemical plating of copper onto a catalytically active substrate surface by chemical reduction without the need for externally-applied electrical current, is a well-known process in extensive commercial use, particularly in the manufacture of printed circuit boards.
- electroless copper depositing baths are aqueous solutions containing a bath-soluble source of copper, a reducing agent for the copper ion, a complexing agent for the copper, and a source, if necessary, of acid or alkali to achieve the pH at which the bath is intended to operate.
- the baths may also include a stabilizer.
- Typical baths are based upon formaldehyde (or a precursor thereof) as the reducing agent, although other reducing agents, such as hypophosphite may also be used. See, e.g., U.S. Pat. No. 4,279,948 to Kukanskis et al., the subject matter of which is herein incorporated by reference in its entirety.
- Substrate surfaces to be electrolessly copper plated are clean, catalytically active surfaces.
- catalytic activation is by means of palladium/tin sols or solutions (see, e.g., U.S. Pat. Nos. 3,011,920 and 3,532,518, the subject matter of which is herein incorporated by reference in its entirety) which often require an acceleration step to expose and/or activate the catalytic species. See, e.g., U.S. Pat. No. 4,608,275 to Kukanskis, the subject matter of which is herein incorporated by reference in its entirety.
- electroless copper plating is in providing the requisite conductive metal surface in the through-holes which are provided in double-sided and multilayer printed circuits and through which conductive interconnection is achieved between or among circuit patterns on the opposed substrate and/or innerlayer surfaces.
- the integrity of the conductive metal layer provided on these through-hole surfaces in terms of its full coverage, adherence, and resistance to cracking or peeling under stress (particularly as will occur when components are later soldered to the printed circuit), is of critical importance in achieving useful printed circuit boards.
- Electroless copper plating baths of this type are prone to bath instability, particularly at operating temperatures above 120° F. Higher temperatures release dissolved oxygen, a primary electroless copper stabilizer, from the plating solution. A low dissolved oxygen content allows copper ions to shift between the +1 and +2 valence state, resulting in the spontaneous reduction of copper ions to metal. The metal may then catalyze additional copper reduction and result in run-away plating in the tank.
- the baths generally require the incorporation of “catalytic poisons” in carefully controlled trace amount to avoid spontaneous (bulk) decomposition.
- the plating bath must therefore always operate in a relatively narrow range between conditions which are conducive to satisfactory deposition on controlled areas of a substrate on the one hand, and random, unwanted, copper plate-out on tank walls, racks, etc., on the other.
- stabilizers can be added to the plating solution.
- stabilizers that have been suggested for use in electroless copper plating solutions include cyanide and surfactants such as polyethyleneglycolstearylamine (U.S. Pat. No. 3,804,638), polyethylene oxide, polyethylene glycol, polyether, polyester, etc.
- Choosing a proper stabilizer is essential to proper operation of the plating bath.
- the stabilizer is prone to absorption onto the surface of plating film, disturbing deposition of copper and retarding the plating rate.
- development of techniques satisfying the plating rate, mechanical strength of plating film, and stability of plating solution at the same time has been in keen demand.
- the improved electroless copper plating bath composition of the invention generally comprises:
- a formate salt or neutralized? formic acid to a traditional formaldehyde-type electroless copper plating bath composition can provide bath stability at the elevated temperatures required for plating, preferably temperatures above 120° F.
- a preferred formate salt is sodium formate.
- the preferred reducing agent for the plating solution is formaldehyde or a formaldehyde precursor.
- Suitable formaldehyde precursors for use in electroless copper plating baths would generally be known to one skilled in the art. Hypophosphites may also be used.
- Proper pH level of the copper bath is important to the operability of the plating bath.
- the pH is normally maintained in the alkaline range, generally between 11 and 13. If adjustment of pH is needed, any standard base may be employed to return the level to correct operating range. Commonly used pH adjusters include sodium hydroxide and potassium hydroxide.
- Effective complexing agents include N-hydroxyethyl ethylenediamine triacetic acid (HEEDTA), ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and alkali metal salts of these. Tartates and salts of therefore are also used.
- the plating composition is preferably subjected to air agitation during use.
- Plating time may range from about a few minutes to several hours depending upon the thickness required.
- a standard copper plating bath is made up as follows: Copper Sulfate 4 g/l copper Formaldehyde 5 g/l Ethylenediaminetetraacetic acid (EDTA) 50 g/l Sodium Hydroxide 20 g/l 2,2,-bipyridine 5 ppm
- the plating solution starts to form copper in solution when the composition is heated to between 155 and 160° F. for one hour.
- Example 2 The same copper plating bath solution as in Example 1 was prepared, except that 10 grams/liter of sodium formate was added to the bath composition.
- the plating solution remained stable at temperatures between 155 and 160° F., even when air agitation was interrupted for short periods of time.
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
Abstract
An improved electroless copper plating bath solution comprising a stabilizer selected from the group consisting of formate salts and formic acid. The addition of the formate salt or formic acid to the plating solution provides increased bath stability at the elevated operating conditions of the plating bath, preventing copper from spontaneously decomposing from the plating solution.
Description
- This invention relates to an improved electroless copper plating solution for plating non-conductive surfaces, such as through holes in multi-layered printed circuit boards. The improved electroless copper plating solution contains a formate stabilizer to prevent autodecomposition of copper from the plating solution.
- The electroless deposition of copper (here used to include copper alloys or intermetallics), i.e., the chemical plating of copper onto a catalytically active substrate surface by chemical reduction without the need for externally-applied electrical current, is a well-known process in extensive commercial use, particularly in the manufacture of printed circuit boards. Typically, electroless copper depositing baths are aqueous solutions containing a bath-soluble source of copper, a reducing agent for the copper ion, a complexing agent for the copper, and a source, if necessary, of acid or alkali to achieve the pH at which the bath is intended to operate. The baths may also include a stabilizer. Typical baths are based upon formaldehyde (or a precursor thereof) as the reducing agent, although other reducing agents, such as hypophosphite may also be used. See, e.g., U.S. Pat. No. 4,279,948 to Kukanskis et al., the subject matter of which is herein incorporated by reference in its entirety.
- Substrate surfaces to be electrolessly copper plated are clean, catalytically active surfaces. Typically, catalytic activation is by means of palladium/tin sols or solutions (see, e.g., U.S. Pat. Nos. 3,011,920 and 3,532,518, the subject matter of which is herein incorporated by reference in its entirety) which often require an acceleration step to expose and/or activate the catalytic species. See, e.g., U.S. Pat. No. 4,608,275 to Kukanskis, the subject matter of which is herein incorporated by reference in its entirety.
- Among the most important uses of electroless copper plating is in providing the requisite conductive metal surface in the through-holes which are provided in double-sided and multilayer printed circuits and through which conductive interconnection is achieved between or among circuit patterns on the opposed substrate and/or innerlayer surfaces. The integrity of the conductive metal layer provided on these through-hole surfaces, in terms of its full coverage, adherence, and resistance to cracking or peeling under stress (particularly as will occur when components are later soldered to the printed circuit), is of critical importance in achieving useful printed circuit boards.
- One type of commercially satisfactory electroless copper bath uses formaldehyde-type reducing agents and operate at high pH levels (11-13). These baths are inherently unstable over long periods of use and/or at elevated temperatures. Electroless copper plating baths of this type are prone to bath instability, particularly at operating temperatures above 120° F. Higher temperatures release dissolved oxygen, a primary electroless copper stabilizer, from the plating solution. A low dissolved oxygen content allows copper ions to shift between the +1 and +2 valence state, resulting in the spontaneous reduction of copper ions to metal. The metal may then catalyze additional copper reduction and result in run-away plating in the tank.
- The baths generally require the incorporation of “catalytic poisons” in carefully controlled trace amount to avoid spontaneous (bulk) decomposition. The plating bath must therefore always operate in a relatively narrow range between conditions which are conducive to satisfactory deposition on controlled areas of a substrate on the one hand, and random, unwanted, copper plate-out on tank walls, racks, etc., on the other.
- To prevent the spontaneous decomposition of the plating bath composition and thus prevent the valence shift in copper in the plating bath composition, stabilizers can be added to the plating solution. Examples of stabilizers that have been suggested for use in electroless copper plating solutions include cyanide and surfactants such as polyethyleneglycolstearylamine (U.S. Pat. No. 3,804,638), polyethylene oxide, polyethylene glycol, polyether, polyester, etc.
- Choosing a proper stabilizer is essential to proper operation of the plating bath. In some instances, the stabilizer is prone to absorption onto the surface of plating film, disturbing deposition of copper and retarding the plating rate. Thus, development of techniques satisfying the plating rate, mechanical strength of plating film, and stability of plating solution at the same time has been in keen demand.
- The invention relates to the discovery that the addition of a formate salt or formic acid to a traditional formaldehyde-type electroless copper plating solution provides increased stability at elevated operating conditions.
- The improved electroless copper plating bath composition of the invention generally comprises:
-
- a source of copper;
- a reducing agent;
- a complexing agent;
- a pH adjuster; and
- a stabilizer selected from the group consisting of formic acid and formate salts.
- The inventor has surprisingly discovered that the addition of a formate salt or neutralized? formic acid to a traditional formaldehyde-type electroless copper plating bath composition can provide bath stability at the elevated temperatures required for plating, preferably temperatures above 120° F. A preferred formate salt is sodium formate.
- While the mechanism of stability is not currently known, it is theorized that the formate may complex the copper, preventing the valence shift from +1 to +2 or that the reaction product of formaldehyde oxidation shifts the reaction equilibrium back towards the reactants.
- The copper source in the plating solution may be comprised of any available bath soluble copper salt. Copper chloride and copper sulfate are generally preferred because of availability, but nitrate, other halide, or organic copper compounds such as acetates can also be used.
- The preferred reducing agent for the plating solution is formaldehyde or a formaldehyde precursor. Suitable formaldehyde precursors for use in electroless copper plating baths would generally be known to one skilled in the art. Hypophosphites may also be used.
- Proper pH level of the copper bath is important to the operability of the plating bath. In formaldehyde-type electroless copper plating baths of the invention, the pH is normally maintained in the alkaline range, generally between 11 and 13. If adjustment of pH is needed, any standard base may be employed to return the level to correct operating range. Commonly used pH adjusters include sodium hydroxide and potassium hydroxide.
- Effective complexing agents include N-hydroxyethyl ethylenediamine triacetic acid (HEEDTA), ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid (NTA), and alkali metal salts of these. Tartates and salts of therefore are also used.
- The plating composition is preferably subjected to air agitation during use. Plating time may range from about a few minutes to several hours depending upon the thickness required.
- A standard copper plating bath is made up as follows:
Copper Sulfate 4 g/l copper Formaldehyde 5 g/l Ethylenediaminetetraacetic acid (EDTA) 50 g/l Sodium Hydroxide 20 g/l 2,2,-bipyridine 5 ppm - Even with air agitation, the plating solution starts to form copper in solution when the composition is heated to between 155 and 160° F. for one hour.
- The same copper plating bath solution as in Example 1 was prepared, except that 10 grams/liter of sodium formate was added to the bath composition. The plating solution remained stable at temperatures between 155 and 160° F., even when air agitation was interrupted for short periods of time.
Claims (12)
1. An improved electroless copper plating bath composition comprising:
a) a source of copper;
b) a reducing agent;
c) a complexing agent;
d) a pH adjuster; and
e) a stabilizer selected from the group consisting of formic acid and formate salts.
2. The improved electroless copper plating bath composition according to claim 1 , wherein said plating bath composition is maintained at a temperature above 120° F.
3. The improved electroless copper plating bath composition according to claim 2 , wherein said plating bath composition is maintained at a temperature above 155° F.
4. The improved electroless copper plating bath composition according to claim 1 , wherein said stabilizer is present in said plating bath composition at a concentration of about 5 to about 20 grams/liter.
5. The improved electroless copper plating bath composition according to claim 3 , wherein said stabilizer is present in said plating bath composition at a concentration of about 10 grams/liter.
6. The improved electroless copper plating bath composition according to claim 1 , wherein said plating bath composition is maintained at a pH between 11 and 13.
7. The improved electroless copper plating bath composition according to claim 1 , wherein said reducing agent is formaldehyde.
8. The improved electroless copper plating bath composition according to claim 1 , wherein said complexing agent is selected from the group consisting of N-hydroxyethyl ethylenediamine triacetic acid and alkali metal salts thereof, ethylenediamine tetraacetic acid and alkali metal salts thereof, nitrilotriacetic acid and alkali metal salts thereof, and tartates and salts thereof.
9. The improved electroless copper plating bath composition according to claim 1 , wherein said pH adjuster is selected from the group consisting of sodium hydroxide and potassium hydroxide
10. The improved electroless copper plating bath composition according to claim 1 , wherein said source of copper is selected from the group consisting of copper chloride and copper sulfate.
11. The improved electroless copper plating bath composition according to claim 1 , wherein said formate salt is sodium formate.
12. The improved electroless copper plating bath composition according to claim 1 , wherein said bath is air agitated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/625,435 US20050016416A1 (en) | 2003-07-23 | 2003-07-23 | Stabilizer for electroless copper plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/625,435 US20050016416A1 (en) | 2003-07-23 | 2003-07-23 | Stabilizer for electroless copper plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20050016416A1 true US20050016416A1 (en) | 2005-01-27 |
Family
ID=34080211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US10/625,435 Abandoned US20050016416A1 (en) | 2003-07-23 | 2003-07-23 | Stabilizer for electroless copper plating solution |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US20050016416A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070037623A1 (en) * | 2005-07-20 | 2007-02-15 | E-Pokerusa Inc. | System and method for skill based games of chance |
| JP6024044B2 (en) * | 2014-01-27 | 2016-11-09 | 奥野製薬工業株式会社 | Conductive film forming bath |
| TWI613321B (en) * | 2014-02-07 | 2018-02-01 | 石原化學股份有限公司 | Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method |
| US11982002B2 (en) * | 2017-08-28 | 2024-05-14 | Xiamen University | Method for anti-corrosion treatment of metallic copper-containing materials |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
| US3532518A (en) * | 1967-06-28 | 1970-10-06 | Macdermid Inc | Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions |
| US3804638A (en) * | 1969-10-16 | 1974-04-16 | Philips Corp | Electroless deposition of ductile copper |
| US4279948A (en) * | 1978-05-25 | 1981-07-21 | Macdermid Incorporated | Electroless copper deposition solution using a hypophosphite reducing agent |
| US4563217A (en) * | 1983-07-25 | 1986-01-07 | Hitachi, Ltd. | Electroless copper plating solution |
| US4608275A (en) * | 1983-07-01 | 1986-08-26 | Macdermid, Incorporated | Oxidizing accelerator |
| US4666744A (en) * | 1984-05-10 | 1987-05-19 | Kollmorgen Technologies Corporation | Process for avoiding blister formation in electroless metallization of ceramic substrates |
| US4695505A (en) * | 1985-10-25 | 1987-09-22 | Shipley Company Inc. | Ductile electroless copper |
| US5306336A (en) * | 1992-11-20 | 1994-04-26 | Monsanto Company | Sulfate-free electroless copper plating baths |
| US6174353B1 (en) * | 1994-12-27 | 2001-01-16 | Ibiden Co., Ltd. | Pretreating solution for electroless plating, electroless plating bath and electroless plating process |
| US20040197541A1 (en) * | 2001-08-02 | 2004-10-07 | Joseph Zahka | Selective electroless deposition and interconnects made therefrom |
-
2003
- 2003-07-23 US US10/625,435 patent/US20050016416A1/en not_active Abandoned
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3011920A (en) * | 1959-06-08 | 1961-12-05 | Shipley Co | Method of electroless deposition on a substrate and catalyst solution therefor |
| US3532518A (en) * | 1967-06-28 | 1970-10-06 | Macdermid Inc | Colloidal metal activating solutions for use in chemically plating nonconductors,and process of preparing such solutions |
| US3804638A (en) * | 1969-10-16 | 1974-04-16 | Philips Corp | Electroless deposition of ductile copper |
| US4279948A (en) * | 1978-05-25 | 1981-07-21 | Macdermid Incorporated | Electroless copper deposition solution using a hypophosphite reducing agent |
| US4608275A (en) * | 1983-07-01 | 1986-08-26 | Macdermid, Incorporated | Oxidizing accelerator |
| US4563217A (en) * | 1983-07-25 | 1986-01-07 | Hitachi, Ltd. | Electroless copper plating solution |
| US4666744A (en) * | 1984-05-10 | 1987-05-19 | Kollmorgen Technologies Corporation | Process for avoiding blister formation in electroless metallization of ceramic substrates |
| US4695505A (en) * | 1985-10-25 | 1987-09-22 | Shipley Company Inc. | Ductile electroless copper |
| US5306336A (en) * | 1992-11-20 | 1994-04-26 | Monsanto Company | Sulfate-free electroless copper plating baths |
| US6174353B1 (en) * | 1994-12-27 | 2001-01-16 | Ibiden Co., Ltd. | Pretreating solution for electroless plating, electroless plating bath and electroless plating process |
| US20040197541A1 (en) * | 2001-08-02 | 2004-10-07 | Joseph Zahka | Selective electroless deposition and interconnects made therefrom |
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| US20070037623A1 (en) * | 2005-07-20 | 2007-02-15 | E-Pokerusa Inc. | System and method for skill based games of chance |
| JP6024044B2 (en) * | 2014-01-27 | 2016-11-09 | 奥野製薬工業株式会社 | Conductive film forming bath |
| TWI613321B (en) * | 2014-02-07 | 2018-02-01 | 石原化學股份有限公司 | Aqueous copper colloidal catalyst solution for electroless copper plating and electroless copper plating method |
| US11982002B2 (en) * | 2017-08-28 | 2024-05-14 | Xiamen University | Method for anti-corrosion treatment of metallic copper-containing materials |
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