US3751289A - Method of preparing surfaces for electroplating - Google Patents

Method of preparing surfaces for electroplating Download PDF

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US3751289A
US3751289A US00173645A US3751289DA US3751289A US 3751289 A US3751289 A US 3751289A US 00173645 A US00173645 A US 00173645A US 3751289D A US3751289D A US 3751289DA US 3751289 A US3751289 A US 3751289A
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copper
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grams per
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acid
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US00173645A
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D Arcilesi
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M&T HARSHAW
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M&T Chemicals Inc
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34Pretreatment of metallic surfaces to be electroplated
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/38Coating with copper
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/22Secondary treatment of printed circuits
    • H05K3/24Reinforcing the conductive pattern
    • H05K3/244Finish plating of conductors, especially of copper conductors, e.g. for pads or lands

Abstract

This invention relates to adherent copper films formed by immersion, or electrolytically on metallic objects from an aqueous solution of (1) a nonoxidizing acid, (2) a copper salt of a nonoxidizing acid, and (3) a polyether exhibiting at least 5 ether oxygen atoms per molecule; to processes for coating said films; and to compositions for the deposition of said adherent copper films.

Description

Unite States Patent [1 1 Arcilesi 1 1 METHOD OF PREPARING SURFACES FOR ELECTROPLATING [75] Inventor: Donald A. Arcilesi, Detroit, Mich.
[73] Assignee: M & T Chemicals Inc., Greenwich,
Conn.
[22] Filed: Aug. 20, 1971 [21] Appl. N0.: 173,645
1451 Aug. 7, 1973 2,472,393 6/1949 Avallone et al .1 106/1 X 3,620,822 11/1971 Oei i l 117/130 R 3,661,597 5/1972 Gullu 117/130 F. X
Primary Examiner-Ralph S. Kendall Att0rneyKenneth G. Wheeless et a1.
[57] ABSTRACT This invention relates to adherent copper films formed by immersion, or electrolytically on metallic objects from an aqueous solution of (l) a nonoxidizing acid, (2) a copper salt of a nonoxidizing acid, and (3) a polyether exhibiting at least 5 ether oxygen atoms per molecule; to processes for coating said films; and to compositions for the deposition of said adherent copper films.
26 Claims, N0 Drawings METHOD OF PREPARING SURFACES FOR ELECTROPLATING plating steel or ferrous articles such as automobile bumper bars, hubcaps, printing rolls, etc., a preliminary copper strike from a cyanide bath or a nickel strike from an acidic nickel plating bath is first used to avoid poorly adherent immersion deposits before acid copper plating.
After strike deposition'from a cyanide bath, the work must be thoroughly rinsed, dipped in a dilute solution of hydrochloric or sulfuric acid to neutralize any undissolved alkaline material, and rinsed again before plating in the acid bath. After nickel strike or nickel chloride immersion dip, thorough rinsing is required to prevent the drag-in of chloride into the acid copper bath. Neither the cyanide copper strike nor the nickel strike produce deposits in deeply recessed areas such as the inside of tubes; consequently a loosely adherent copper deposit forms in these areas on subsequent plating from an acid copper bath. I
lt is an object of this invention to provide an adherent copper film on metallic objects which effects good adhesion of subsequent copper deposits from copper plating baths, even in deeply recessed areas such as the inside of tubes. It is another object of this invention to provide an adherent copper film such that the work does not have to be rinsed between the strike or immersion dip and the acid copper plating baths, as is necessary after conventional strikes. It is an object of this invention to prevent formation of badly adherent copper electrodeposits. Other objects of this invention will be apparent from the following description.
This invention is directed to a process for coating metal surfaces with a copper film prior to the electrodeposition of copper from copper plating baths comprising treating said metal surface in a solution containing 0.01 to 10 grams per liter of a copper salt of a nonoxidizing acid; 0.1 grams per liter to 500 grams per liter of a nonoxidizing acid; and 0.1 to 100 grams per liter of a polyether containing at least ether oxygen atoms per molecule, thereby obtaining a copper film effecting good copper plate adherence on basis metals from copper plating baths. Copper salts operable in'the practice of this invention include copper sulfate, 'copper fluoborate, and copper phosphate.
Copper pretreatment'baths of this invention are distinguished from aqueous acidic copper plating'baths by their deficiency of copper. Typical amounts of copper include about 0.025 to 2.5 grams per liter as metallic copper (preferably 0.025 to 0.625 grams per liter); 'or 0.1 to grams per liter as CuSOySl-bO or Cu(BF (preferably 0.1 to 2.5 grams per liter).
Polyethers whic h may be used according to the process of the invention have at least 5 ether oxygen atoms and include polyethers of the formulae:
where R' is a monovalent radical such as H, alkyl, alkenyl, alkynyl, alkylaryl, arylalkyl or a heterocyclic radical; and R" is a mvalent aliphatic, aromatic or heterocyclic radical; m=2 to and properties.
The polyethers of this invention may be derived from 1,2 olefin oxides such as ethylene oxide, propylene oxide, 1,2 butylene oxide, etc.; from 4- and S-membered ring cyclic ethers such as ox'etane, -2,3- dichlo'rom'ethyloxetane, etc.; from glycidyl'esters and eth'ers such 'as allyLgIycidyl ether, glycidyl acetate, and phenyl glycidyl ether and mixtures of the foregoing.
TABLE I CH3 CH3 CH3 3 I I I I CH CH2 CH CH;
0 o I m I wherein m n 30, or wherein m n 15, or wherein m n 10;
CH3 CH3 7 I I on c CH2 0 0 (CH CHQ H CH3 CH3 wherein x 9 1.0, or wherein x 30, or wherein x +0;
I1 C 1 +1 ('3 CH3 N 4011 011 0) H 1 y (cn cu m u wherein x 9 1.2, and y z 15;
wherein x is about 3 and y is about 3-;
HO(C H O) H wherein x is about 13; I
HO('C H O) H wherein xis about 33;
HO(C H O) H wherein x is about 12;
CH CH I I CH3CHZC CH2 CH2 C CHZCHQ CH CH Cl-IZ CH2 CHCH f CHCH CH CH wherein "m about 12-15 and n hbout 1-2;
1. Excellent adhesion of subsequent copper deposits over a wide concentration range of the constituents of the invented solution used as an immersion dip prior to copper plating.
2. The concentration ranges and the reliability were I greatly increased by making the work cathodic and using the invented solution as a strike bath.
3. In contrast to cyanide or nickel strikes one can get good adhesion even if current is not used. Therefore, we can get good adhesion even in very deeply recessed areas such as the inside of a tube.
4. Work does not have to be rinsed between the strike or immersion dip of this invention and the acid copper plating bath, as it does after conventional strikes. It may be cycled directly from the coating solution of this invention to the plating bath.
The nonoxidizing acids of this invention are preferably sulfuric acid H SO and fluoboric acid HBF The immersion baths of this invention should be at a temperature of 10 C to 60 C, (preferably 20 C to 40 C). While this invention is completely operable without the use of current as shown by examples hereinafter, this invention may also be practiced with current for instance a cathode current density of 0.1 to 60 amperes per square decimeter. With agitation is not necessary for the practice of the invention, air agitation, volume agitation, and mechanical agitation may be used with no deleterious effect.
This invention according to one of its aspects, is the deposition of a film of copper from a solution comprising 0.01 grams per liter to 10 grams per liter of a copper salt selected from the group consisting of copper sulfate, copper phosphate and copper fluoborate, 0.1 grams per liter to 500 grams per liter of a nonoxidizing acid, and 0.1 grams per liter to 100 grams per liter of a polyether containing at least 5 ether oxygen atoms per molecule; and after deposition of said strike coating of copper, electrodepositing copper thereon from an aqueous copper plating bath.
Optionally, the copper strike of this invention may be desposited electrolytically at a temperature of C to 60 C, with the use of a current density of l asd to asd. The first step, the essence of the invention, is
to form a thin, dense, strongly adherent layer or strike coating. Under the above conditions, the strike coating is formed in from 20 seconds to 3 minutes depending upon the current density, the copper ion concentration, and various additives of the strike solution.
For electrodeposition of bright, strongly leveled, ductile copper, the article is transferred from the strike bath of this invention to an aqueous acidic copper plating bath containing chloride ions and organic additives without permitting the article to dry and without rinising it.
In accordance with certain of its aspects this invention provides a process for electrodepositing bright copper from aqueous acidic baths comprising buffing the metal surface, cleaning by immersing the pretreated metal surface in an organic solvent; electrolytically degreasing said surface electrolytically in alkaline solution; rinsing, immersing in an acid bath thereby obtaining a bright, clean metal surface; depositing on said surface a strike coating of copper from a solution cohtaining 0.01 grams per liter to 10 grams per liter of a copper salt; 0.1 grams per liter to 500 grams per liter of nonoxidizing acid; and 0.1 gram per liter to 100 grams per liter of a polyether containing at least 5 ether oxygen atoms per molecule; and electrodepositing on said copper film a relatively thicker layer of bright, strongly leveled, ductile copper from a copper plating bath containing suitable combinations of addition agents.
Typical copper plating baths which may be employed to electrodeposit adherent thicker copper over the copper film of this invention include the following:
TABLE 11 grams per (preferably) Compound liter grams per liter sulfate CuSO,-5H,O 150-300 220 Bath Cl 5-100 mg/l. 20-40 mg/l.
Fluoborate Cu(B )2 -600 224 Bath HBF, l-60 3.5
H,BO 0-30 15 Cl 5-100 mg/l. 20-40 mg/l.
The basis metals which may be pretreated with the process of this invention include ferrous metals, such as steel, iron, etc.; zinc and its alloys including zinc-base die-cast articles; nickel, including'nickel alloys with other metals such as cobalt, iron, chromium, aluminum, including its alloys.
For the purpose of providing those skilled in the art with a better understanding of this invention, the following examples are set forth.
EXAMPLE 1 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 1 gram per liter of cupric sulfate pentahydrate (CuSO,'5H O) and 100 grams per liter of sulfuric acid (H 80 and 16 grams per liter of an ethoxylated propoxylated lauryl alcohol (MW 1020), having the following structure CH (CH 0C l-l,,), -,(OC,H OH, at 24 C, with an applied cathodic potential sufficient to produce an average current density of 8.0 asd after the panel was half immersed. After 30 seconds the panel was transferred to an acid copper plating bath where it was plated with copper to an average thickness of 75 microns.
The edgesof the panel were ground down to the steel. The copperwas easily, pulled off the top of the panel but could not be pulled off the bottom half, which had been treated in the above solution, indicating excellent adhesion.
Other panels were done without current in the above treatment solution and/or with water rinsing between the treatment solution and the plating bath and the plated deposits still had excellent adhesion to the panel. However, under some conditions it is advantageous to use current in the treatment solution and water rinse.
EXAMPLE 2 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 1 gram per liter cupric sulfate pentahydrate (CuSO '5l-l O) and 60 grams per liter of sulfuric acid (H 80 and 1 gram per liter of ethoxylated propoxylated lauryl alcohol (MW 1020), having the following structure CH;,(CH,),,(OC- l-l (OC H,) Ol-I, at 24 C, with an applied cathodic potential sufficient to produce an average current density of 8.0 asd after the panel was half immersed. After 30 seconds the panel was transferred to an acid copper plating bath where it was plated with copper to an average thickness of 75 microns.
The edges of the panel were ground down to the steel. The copper was easily pulled off the top of the panel but could not be pulled off the bottom half, which had been treated in the above solution, indicating excellent adhesion.
EXAMPLE 3 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and cm long, half of it was immersed into an aqueous solution containing 0.1 grams per liter of cupric sulfate pentahydrate (CuSO -5 H 0) and 60 grams per liter of sulfuric acid (H 80 and 10 grams per liter of ethoxylated propoxylated lauryl alcohol (MW 1020), having the following structure CH (CH (OC l-l (OC,,H,,) OH, at 24 C, with an applied cathodic potential sufficient to produce an average current density of 8.0 asd after the panel was half immersed. After seconds the panel was transferred to an acid copper plating bath where it was plated with copper to an average thickness of 75 microns.
The edges of the panel were ground down to the steel. The copper was easily pulled off the top of the panel but could not be pulled off the bottom half, which had been treated in the above solution, indicating excellent adhesion.
EXAMPLE 4 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 1 gram per liter of cupric sulfate pentahydrate (CuSO -SH O) and l00 grams per liter of phosphoric acid (H PO and l6 grams per liter of an ethoxylated propoxylated lauryl alcohol (MW 1020), having the following structure CH3(CH2)1,(OC2H4)15(OC3H )OH, at 24 C, with an applied cathodic potential sufficient to produce an average current density of 8.0 asdaf ter the panel was half immersed. After 30 seconds the panel was transferred to an acid copper plating bath where it was plated with copper to an average thickness of 75 microns.
The edges of the panel were ground down to the steel. The copper was easily pulled off the top of the panel but could not be pulled off the bottom half, which had been treated in the above solution, indicating excellent adhesion.
EXAMPLE 5 rent density of 8.0 asd after the panel was half immersed. After 30 seconds the panel was transferred to an acid copper plating bath where it was plated with copper to an average thickness of microns.
Thd edges of the panel were ground down to the steel. The copper was easily pulled off the top of the panel but could not be pulled off the bottom half. which had been treated in the above solution, indicating excellent adhesion.
EXAMPLE 6 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 0.5 grams per liter of CuSO '5l-l O and 100 grams per liter of H SO and 10 grams per liter of ethoxylated propoxylated lauryl alcohol (MW 1020), having the following structure C- H (CH (OC H (OC H OH, at 24 C, without current. After 20 seconds the panel was dipped into an acid copper plating bath for approximately one second and quickly rinsed in water. Then the panel was dried and a strip of Scotch brand pressure sensitive masking tape 202 was firmly applied to half the width of the panel along its entire length.
The tape was then peeled off the panel. The panel was then examined for bare steel and the tape was examined for copper flakes.
The tape test revealed excellent adhesion.
EXAMPLE 7 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 0.5 grams per liter of CuSO 5l-l O and 100 grams per liter of H SO and 10 grams per liter of polyethylene glycol (MW 1000) having the following structure H(OC H OH, at 24 C, without current. After 20 seconds the panel was dipped into an acid copper plating bath for approximately one second and quickly rinsed in water. Then the panel was dried and a strip of Scotch brand pressure sensitive masking tape 202 was firmly applied to half the width of the panel along its entire length.
The tape was then peeled off the panel. The panel was then examined for bare steel and the tape was examined for copper flakes.
The tape test revealed excellent adhesion.
EXAMPLE 8 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 0.5 grams per liter of CuSOySl-LO and 100 grams per liter of H and 10 grams per liter of polyethylene glycol (6000) having the following structure H(OC,H OH, at 24 C, with an applied cathodic potential sufficient to produce an average current density of 2.7 asd after the panel was half immersed. After 20 seconds the panel was dipped into an acid copper plating bath for approximately one second and quickly rinsed in water, Then the panel was dried and a strip of Scotch brand pressure sensitive masking tape 202 was firmly applied to half the width of the panel along its entire length.
The tape was peeled off the panel. The panel was then examined for bare steel and the tape was examined for copper flakes.
The tape test" revealed excellent adhesion.
13 EXAMPLE 9 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 0.5 grams per liter of CuSO,-H, O and 100 grams per liter of H,SO, and grams per liter of ethoxylated lauryl alcohol (MW 1286), having the following structure n- C,,H, OC,H,), OH, at 24 C, with an applied cathodic potential sufficient to produce an average current density of 2.7 asd after the panel was half immersed. After 20 seconds the panel was dipped into an acid copper plating bath for approximately one second and quickly rinsed in water. Then the panel was dried and a strip of Scotch brand pressure sensitive masking tape 202 was firmly applied to half the width of the panel along its 7 entire length.
The tape was then peeled off the panel. The panel was then examined for bare steel and the tape was examined for copper flakes.
The tape test revealed excellent adhesion.
EXAMPLE 10 After thoroughly pickling and cleaning a steel panel, 2.5 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 0.5 grams per liter of CuSO -5H O and 100 grams per liter H 80 and 10 grams per liter nonyl phenoxy polyoxyethylene ethanol (MW 1540), having the following structure EXAMPLE 11 After thoroughly pickling and cleaning a steel panel, 10 cm wide and 20 cm long, half of it was immersed into an aqueous solution containing 0.5 grams per liter CuSO -5H O and 100 grams per liter H 80 and 20 grams per liter ethoxylated propoxylated lauryl alcohol (MW 1020), having the following .structure 2)11(OC2H4)15(OC3H6)3OH at o C, an applied di mtsntia ,-s fl' s t ..tq PIQQQQ? an average current densityof 8.0 asd after the panel was half immersed. After 15 seconds the panel was rinsed tube was immersed into an aqueous solution containing 0.5 grams per liter CuSO '5H,O and 100 grams per liter l-l,SO and 20 grams per liter ethoxylated propoxylated lauryl alcohol (MW 1020), having the following structure CH;,(CH (OC,H,), (0C l-l Ol-l at 24 C, without current. After 20 seconds the tube was transferred to an acid copper plating bath and plated so that there was an average thickness of 25 microns of copper on the outside of the tube.
The tube was longitudinally cut in half and examined. The copper on the outside of the tube had excellent adhesion to the tube. And further, the inside of the tube also had a uniform adherent coating of copper in it.
EXAMPLE 13 (Control) After thoroughly pickling and cleaning a steel tube approximately 2.5 cm in diameter and cm long, the tube was given a strike from a typical cyanide copper strike solution for approximately 5 minutes at about 5.4 asd. The tube was then rinsed with water, dipped in a 2 percent (by volume) sulfuric acid solution, again rinsed with water and transferred to an acid copper plating bath and plated so that there was an average thickness of 25 microns of copper on the outside of the tube.
The tube was longitudinally cut in half and examined. The copper on the outside of the tube had excellent adhesion to the tube. But the copper on the inside of the tube was loose and flaky.
If one wanted to process this through other plating baths, e.g. a nickel plating bath, it would be very probable that the copper would flake off from the inside of the tube thereby contaminating the plating solution.
EXAMPLE 14 After thoroughly cleaning a zinc die cast automobile handle, it was immersed into an aqueous solution containing 1 gram per liter CuSO,'5H O and 60 grams per with water and transferred to a pyrophosphate copper P a i bath a 2 micrgns st q rsmasrlate 21?.-
The edges of the panel were ground down to the steel. The copper was easily pulled off the top of the panel but could not be pulled off the bottom half, which had been treated in the above solution, indicating excellent adhesion.
EXAMPLE l2 and cleaning a steel tube,
approximately 2.5 cm in diameter and 30 cm long,
liter H and 20 grams per liter of an ethoxylated propoxylated lauryl alcohol (MW 1020), having the following structure Cl-l -,(CH ,(OC l-l (OC H Ol-l, at 24 C, with an applied cathodic potential sufficient to produce an average current density of 8.0 asd after the handle was immersed. After 1 minute the handle was rinsed with water and transferred to a pyrophosphate copper plating bath where it was plated with copper to an average thickness of 7.5 microns. The handle was again rinsed with water and then transferred to an acid copper plating solution where an average thickness of 25 microns of copper was plated on it.
Both the appearance of the plated deposit and its adhesion to the basis metal were excellent.
Although this invention has been illustrated by reference to specific embodiments, modifications thereof which are clearly within the scope of the invention will be apparent to those skilled in the art.
1 claim:
1. A process for coating metal surfaces with an adherent copper film prior to the electrodeposition of copper from copper plating baths comprising treating said metal surface in an aqueous acidic solution consisting essentially of 0.01 to 10 grams per liter of a copper ll salt selected from the group consisting of copper sulfate, copper fluoborate and copper phosphate, 0.] grams per liter to 500 grams per liter of a nonoxidizing acid, and 0.1 to grams per liter of a polyether containing at least 5 ether oxygen atoms per molecule,
thereby obtaining an adherent film effecting good copper plate adhesion of subsequent heavier copper electrodeposits.
2. The process of claim I wherein said non-oxidizing acid is sulfuric acid.
3. The process of claim 1 wherein said non-oxidizing acid is fluoboric acid.
4. The process of claim 1 wherein said copper salt is copper sulfate.
5. The process of claim 1 wherein said copper salt is copper fluoborate.
6. The process of claim 1 wherein said copper salt is a copper phosphate.
7. The process of claim 1 wherein said polyether is polyethylene glycol.
8. The process of claim 7 wherein said polyethylene glycol is of the structure H(OC H OH.
9. The process of claim 1 wherein said polyether is ethoxylated propoxylated lauryl alcohol.
10. The process of claim 9 wherein said ethoxylated propoxylated lauryl alcohol is of the structure CH (C- 2)ll( 2 4 I5( 3 6)3 11. The process of claim 1 wherein said polyether is ethoxylated lauryl alcohol.
12. The process of claim 1 wherein said polyether is nonyl phenoxy polyoxyethylene ethanol.
13. The process of claim 1 wherein said copper film is an immersion coating.
14. The process of claim 1 wherein said metal surface is a ferrous metal.
15. A composition for the deposition ofa thin coating of copper from an aqueous acidic solution consisting essentially of 0.01 grams per liter to 10 grams per liter of a copper ll salt selected from the group consisting of copper sulfate, copper fluoborate and copper phosphate, 0.1 grams per liter to 500 grams per liter of a nonoxidizing acid, and 0.1 grams per liter to grams per liter of a polyether containing at least 5 ether oxygen atoms per molecule.
16. The composition of claim 15 wherein said nonoxidizing acid is sulfuric acid.
17. The composition of claim 15 wherein said nonoxidizing acid is fluoboric acid.
18. The composition of claim 15 wherein said copper salt is copper sulfate.
19. The composition of claim 15 wherein said copper salt is copper fluoborate.
20. The composition of claim 15 wherein said copper salt is copper phosphate.
21. The composition of claim 15 wherein said polyether is polyethylene glycol.
22. The composition of claim 21 wherein said polyethylene glycol is of the structure H(OC H OH.
23. The composition of claim 15 wherein said polyether is ethoxylated propoxylated lauryl alcohol.
24. The composition of claim 23 wherein said ethoxylated propoxylated lauryl alcohol is of the structure CH3(CH2)H(OCZH4)IS(OC3HG)SOH- 25. The composition of claim 15 wherein said polyether is ethoxylated lauryl alcohol.
26. The composition of claim 15 wherein said polyether is nonyl phenoxy polyoxyethylene ethanol.

Claims (25)

  1. 2. The process of claim 1 wherein said non-oxidizing acid is sulfuric acid.
  2. 3. The process of claim 1 wherein said non-oxidizing acid is fluoboric acid.
  3. 4. The process of claim 1 wherein said copper salt is copper sulfate.
  4. 5. The process of claim 1 wherein said copper salt is copper fluoborate.
  5. 6. The process of claim 1 wherein said copper salt is a copper phosphate.
  6. 7. The process of claim 1 wherein said polyether is polyethylene glycol.
  7. 8. The process of claim 7 wherein said polyethylene glycol is of the structure H(OC2H4)136OH.
  8. 9. The process of claim 1 wherein said polyether is ethoxylated propoxylated lauryl alcohol.
  9. 10. The process of claim 9 wherein said ethoxylateD propoxylated lauryl alcohol is of the structure CH3(CH2)11(OC2H4)15(OC3H6)3OH.
  10. 11. The process of claim 1 wherein said polyether is ethoxylated lauryl alcohol.
  11. 12. The process of claim 1 wherein said polyether is nonyl phenoxy polyoxyethylene ethanol.
  12. 13. The process of claim 1 wherein said copper film is an immersion coating.
  13. 14. The process of claim 1 wherein said metal surface is a ferrous metal.
  14. 15. A composition for the deposition of a thin coating of copper from an aqueous acidic solution consisting essentially of 0.01 grams per liter to 10 grams per liter of a copper II salt selected from the group consisting of copper sulfate, copper fluoborate and copper phosphate, 0.1 grams per liter to 500 grams per liter of a nonoxidizing acid, and 0.1 grams per liter to 100 grams per liter of a polyether containing at least 5 ether oxygen atoms per molecule.
  15. 16. The composition of claim 15 wherein said nonoxidizing acid is sulfuric acid.
  16. 17. The composition of claim 15 wherein said nonoxidizing acid is fluoboric acid.
  17. 18. The composition of claim 15 wherein said copper salt is copper sulfate.
  18. 19. The composition of claim 15 wherein said copper salt is copper fluoborate.
  19. 20. The composition of claim 15 wherein said copper salt is copper phosphate.
  20. 21. The composition of claim 15 wherein said polyether is polyethylene glycol.
  21. 22. The composition of claim 21 wherein said polyethylene glycol is of the structure H(OC2H4)136OH.
  22. 23. The composition of claim 15 wherein said polyether is ethoxylated propoxylated lauryl alcohol.
  23. 24. The composition of claim 23 wherein said ethoxylated propoxylated lauryl alcohol is of the structure CH3(CH2)11(OC2H4)15(OC3H6)3OH.
  24. 25. The composition of claim 15 wherein said polyether is ethoxylated lauryl alcohol.
  25. 26. The composition of claim 15 wherein said polyether is nonyl phenoxy polyoxyethylene ethanol.
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2242485A1 (en) * 1973-09-04 1975-03-28 Miele & Cie
JPS50130645A (en) * 1974-04-03 1975-10-16
EP0021757A1 (en) * 1979-06-15 1981-01-07 Hitachi, Ltd. Electroless copper plating solution
US4374709A (en) * 1980-05-01 1983-02-22 Occidental Chemical Corporation Process for plating polymeric substrates
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
FR2699556A1 (en) * 1992-12-23 1994-06-24 Enthone Omi Inc Baths for forming an electrolytic deposit of copper and process for electrolytic deposition using this bath.
US5417841A (en) * 1990-08-03 1995-05-23 Mcgean-Rohco, Inc. Copper plating of gravure rolls
US20050211564A1 (en) * 2004-03-29 2005-09-29 Taiwan Semiconductor Manufacturing Co., Ltd. Method and composition to enhance wetting of ECP electrolyte to copper seed
US20120217166A1 (en) * 2009-09-11 2012-08-30 Umicore Galvanotechnik Gmbh Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation
US20140262799A1 (en) * 2013-03-14 2014-09-18 Rohm And Haas Electronic Materials Llc Method of filling through-holes
US10512174B2 (en) 2016-02-15 2019-12-17 Rohm And Haas Electronic Materials Llc Method of filling through-holes to reduce voids and other defects
US10508357B2 (en) 2016-02-15 2019-12-17 Rohm And Haas Electronic Materials Llc Method of filling through-holes to reduce voids and other defects

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2472393A (en) * 1944-09-25 1949-06-07 American Steel & Wire Co Process and bath for copper coating ferrous metal
US2915414A (en) * 1957-06-05 1959-12-01 Henry H Hilemn Copper coating process
US3620822A (en) * 1968-11-22 1971-11-16 Hooker Chemical Corp Process of copper plating super-refined steel
US3661597A (en) * 1971-05-20 1972-05-09 Shipley Co Electroless copper plating

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2472393A (en) * 1944-09-25 1949-06-07 American Steel & Wire Co Process and bath for copper coating ferrous metal
US2915414A (en) * 1957-06-05 1959-12-01 Henry H Hilemn Copper coating process
US3620822A (en) * 1968-11-22 1971-11-16 Hooker Chemical Corp Process of copper plating super-refined steel
US3661597A (en) * 1971-05-20 1972-05-09 Shipley Co Electroless copper plating

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2242485A1 (en) * 1973-09-04 1975-03-28 Miele & Cie
JPS50130645A (en) * 1974-04-03 1975-10-16
EP0021757A1 (en) * 1979-06-15 1981-01-07 Hitachi, Ltd. Electroless copper plating solution
US4303443A (en) * 1979-06-15 1981-12-01 Hitachi, Ltd. Electroless copper plating solution
US4374709A (en) * 1980-05-01 1983-02-22 Occidental Chemical Corporation Process for plating polymeric substrates
US4376685A (en) * 1981-06-24 1983-03-15 M&T Chemicals Inc. Acid copper electroplating baths containing brightening and leveling additives
US5417841A (en) * 1990-08-03 1995-05-23 Mcgean-Rohco, Inc. Copper plating of gravure rolls
GB2273941A (en) * 1992-12-23 1994-07-06 Enthone Omi Inc Polyether additives for copper electroplating baths
FR2699556A1 (en) * 1992-12-23 1994-06-24 Enthone Omi Inc Baths for forming an electrolytic deposit of copper and process for electrolytic deposition using this bath.
GB2273941B (en) * 1992-12-23 1995-09-13 Enthone Omi Inc Functional fluid additives for acid copper electroplating baths
ES2088356A1 (en) * 1992-12-23 1996-08-01 Enthone Omi Inc Functional fluid additives for acid copper electroplating baths
DE4343946C2 (en) * 1992-12-23 1998-10-29 Enthone Omi Inc Galvanic copper bath and process for the galvanic deposition of copper
US20050211564A1 (en) * 2004-03-29 2005-09-29 Taiwan Semiconductor Manufacturing Co., Ltd. Method and composition to enhance wetting of ECP electrolyte to copper seed
US20120217166A1 (en) * 2009-09-11 2012-08-30 Umicore Galvanotechnik Gmbh Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation
US20140262799A1 (en) * 2013-03-14 2014-09-18 Rohm And Haas Electronic Materials Llc Method of filling through-holes
US9598787B2 (en) * 2013-03-14 2017-03-21 Rohm And Haas Electronic Materials Llc Method of filling through-holes
US10512174B2 (en) 2016-02-15 2019-12-17 Rohm And Haas Electronic Materials Llc Method of filling through-holes to reduce voids and other defects
US10508357B2 (en) 2016-02-15 2019-12-17 Rohm And Haas Electronic Materials Llc Method of filling through-holes to reduce voids and other defects

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