EP3002350B1 - Cyanidfreie galvanische bäder für weisse bronze basierend auf kupfer (i) ionen - Google Patents

Cyanidfreie galvanische bäder für weisse bronze basierend auf kupfer (i) ionen Download PDF

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EP3002350B1
EP3002350B1 EP15185289.4A EP15185289A EP3002350B1 EP 3002350 B1 EP3002350 B1 EP 3002350B1 EP 15185289 A EP15185289 A EP 15185289A EP 3002350 B1 EP3002350 B1 EP 3002350B1
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Prior art keywords
copper
bath
tin
ions
electroplating
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French (fr)
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EP3002350A1 (de
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Adolphe Foyet
Jonas Guebey
Margit Clauss
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Rohm and Haas Electronic Materials LLC
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Rohm and Haas Electronic Materials LLC
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    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance

Definitions

  • the present invention is directed to cyanide-free electroplating baths for white bronze based on copper (I) ions. More specifically, the present invention is directed to cyanide-free electroplating baths for white bronze based on copper (I) ions which are stable and electroplate bright white bronze deposits.
  • White bronze is commonly used in decorative and sanitary industries as material for nickel replacement.
  • bronze is 40% to 70% by weight copper with the remainder tin or tin and silver or tin and zinc. It is hard enough, provides adequate wear and corrosion resistance such that it may be substituted for nickel in both decorative and sanitary functions.
  • most industrial white bronze is not only toxic due to cyanide content but also has a relatively slow plating speed of 0.1 ASD to around 2 ASD with a low current efficiency ranging from 50% to 80%.
  • U.S. 7,780,839 to Egli et al. is a cyanide-free white bronze which may be used as an alternative to conventional cyanide containing white bronze electroplating baths. Although the plating speed of this electrolyte is significantly improved over many conventional white bronze electroplating baths, the white bronze deposit may be slightly brittle and unable to pass abrasion tests. It may also be difficult to plate finishing top layers such as gold, chrome (III) or (VI), palladium or silver on white bronze.
  • the general process involves degreasing the article using a conventional degreasing formulation, rinsing with water followed by a thick copper plate for leveling purposes and then electroplating white bronze from a cyanide containing bath, rinsing with water, then plating a gold, chrome (III) or (VI), palladium or silver finish on the white bronze.
  • a cyanide-free white bronze electroplating bath is used as in U.S. 7,780,839 , an extra step is typically needed prior to plating the finishing layer.
  • An organic film of unknown composition may form on the white bronze after electroplating diminishing the surface appearance of the white bronze.
  • An ultrasonic rinse or cathodic degreasing step is then included in the process to remove the film prior to plating the finishing layer. This extra step reduces the efficiency and increases the cost of the overall process because ultrasonic equipment must be installed or in the case of cathodic degreasing separate tanks with current suppliers is needed. Accordingly, there is still a need for an improved white bronze electroplating bath and process.
  • EP 2 565 297 discloses electroplating baths that comprise one or more sources of copper ions, one or more sources of tin ions and one or more mercaptans selected from mercaptotriazoles and mercaptotetrazoles.
  • JP 2001 234387 discloses the use of thioethane compounds such as 3,6-dithione-1,8-diol as a whisker inhibiting agent in tin and tin-alloy electroplating baths.
  • An electroplating bath includes copper (I) ions, one or more sources of alloying tin ions, optionally one or more sources of alloying silver ions, one or more compounds having a formula: X-S-Y (I) wherein X and Y may be the same or different and may be substituted or unsubstituted phenol groups, HO-R- or -R'S-R"-OH wherein R, R' and R" may be the same or different and are linear or branched alkylene radicals having 1 to 20 carbon atoms; and one or more tetrazoles wherein a mole ratio of the one or more tetrazoles to the copper (I) ions in the electroplating bath is ⁇ 1 and a mole ratio of the one or more tetrazoles to the one or more compounds of formula (I) is 0.05 to 4, the electroplating bath is cyanide-free.
  • a method of electroplating includes contacting a substrate with an electroplating bath comprising copper (I) ions, one or more sources of alloying tin ions, optionally one or more sources of alloying silver ions, one or more compounds having a formula: X-S-Y (I) wherein X and Y may be the same or different and may be substituted or unsubstituted phenol group, HO-R- or -R'S-R"-OH wherein R, R' and R" may be the same or different and may be linear or branched alkylene radicals having 1 to 20 carbon atoms; and one or more tetrazoles, wherein a mole ratio of the one or more tetrazoles to the copper (I) ions in the electroplating bath is ⁇ 1 and a mole ratio of the one or more tetrazoles to the one or more compounds of formula (I) is 0.05 to 4, the electroplating bath is cyanide-free; and electroplating a
  • the cyanide-free copper alloy electroplating baths deposit a bright, white bonze copper/tin alloy or cooper/tin/silver alloy.
  • the copper alloy electroplating baths are stable over prolonged periods of time and deposit copper/tin alloys and copper/tin/silver alloys with high current efficiencies and high plating speeds in contrast to many conventional copper alloy baths which electroplate white bronze.
  • the copper/tin alloys and copper/tin/silver alloys electroplated from the baths have good ductility, thermal stability and abrasion resistance.
  • the copper/alloys may be directly plated with gold, chrome (III) or (VI), palladium and silver finishing layers without many of the conventional post-treatment steps of conventional processes such as ultrasonic rinse or cathodic degreasing. Therefore, the cyanide-free copper alloy electroplating bath enables more efficient processes than many conventional cyanide-free white bronze processes and may be used for nickel replacement.
  • °C degrees Centigrade
  • mL milliliter
  • L liter
  • mg milligrams
  • DI de-ionized
  • ⁇ m microns
  • mol mole
  • wt% percent by weight
  • Ah ampere hours
  • %CE percent current efficiency
  • rpm revolutions per minute
  • IEC International Electrochemical Commission
  • XRF X-ray fluorescence
  • ASTM American standard testing method.
  • Electroplating potentials are provided with respect to a hydrogen reference electrode. Relating to the electroplating process, the terms “depositing”, “coating”, “electroplating” and “plating” are used interchangeably throughout this specification.
  • “Halide” refers to fluoride, chloride, bromide and iodide. All percentages are by weight, unless otherwise noted. All numerical ranges are inclusive and combinable in any order, except where it is logical that such numerical ranges are construed to add up to 100%.
  • the copper (I), silver, tin, and copper (I) and tin alloy electroplating baths are substantially free of cyanide. Cyanide is primarily avoided by not employing any silver or tin salts or other compounds in the baths which include the CN - anion.
  • the copper (I), silver, tin and copper (I) and tin alloy electroplating baths are also substantially free of copper (II) ions to enable the copper alloy electroplating baths to plate a bright white bronze deposit.
  • Sources of copper (I) ions include, but are not limited to cuprous salts such as cuprous oxide, cuprous chloride, cuprous bromide, cuprous iodide and cuprous ammonium salts such as cuprous ammonium chloride.
  • the copper (I) salts are generally commercially available or may be prepared by methods described in the literature. When cuprous oxide is used, alkane or aryl sulfonic acids or mixtures thereof are preferably included in the bath. Sufficient amounts of one or more copper (I) salts are included in the baths such that the amount of copper (I) ions may range from 0.5 g/L to 150 g/L, preferably 10 g/L to 50 g/L.
  • Sources of tin ions include, but are not limited to salts, such as tin halides, tin sulfates, tin alkane sulfonates, tin alkanol sulfonates, and acids.
  • tin halide it is typical that the halide is chloride.
  • the tin compound is preferably tin sulfate, tin chloride or a tin alkane sulfonate, and more preferably tin sulfate or tin methane sulfonate.
  • the tin compounds are generally commercially available or may be prepared by methods known in the literature.
  • the tin salts are readily water-soluble.
  • the amount of tin salts used in the bath depends on the desired composition of the alloy to be deposited and operating conditions. Sufficient amounts of tin salts are included in the baths to provide tin ions which may range from 1 g/L to 100 g/L, preferably from 5 g/L to 50 g/L.
  • Sources of silver ions include, but are not limited to silver halides, silver gluconate, silver citrate, silver lactate, silver nitrate, silver sulfates, silver alkane sulfonates and silver alkanol sulfonates.
  • the halide is chloride.
  • the silver salts are silver sulfate, a silver alkane sulfonate or mixtures thereof.
  • the silver salts are generally commercially available or may be prepared by methods described in the literature.
  • the silver salts are readily water-soluble.
  • the amounts of the one or more silver salts used in the baths depend, for example, on the desired alloy composition to be deposited and operating conditions. Sufficient amounts of silver salts are included in the baths to provide silver ions which may range from 0.01 g/L to 100 g/L, preferably from 0.5 g/L to 50 g/L.
  • the copper (I) alloy electroplating baths include one or more sulfur compounds having formula: X-S-Y (I) where X and Y may be substituted or unsubstituted phenol groups, HO-R- or -R'-S-R"-OH where R, R' and R" are the same or different and are linear or branched alkylene radicals having 1 to 20 carbon atoms.
  • Substituent groups on the phenol include, but are not limited to linear or branched (C 1 -C 5 )alkyl. Such compounds may function as complexing agents for copper (I) ions.
  • Examples of such compounds where X and Y are the same are 4,4'-thiodiphenol, 4,4'-thiobis(2-methyl-6-tert-butylphenol) and thiodiethanol.
  • the compounds When X and Y are different, the compounds preferably have the following general formula: HO-R-S-R'-S-R"-OH (II) wherein R, R' and R" are the same or different and are linear or branched alkylene radicals having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably R and R" have 2 to 10 carbon atoms and R' has 2 carbon atoms.
  • R, R' and R" are the same or different and are linear or branched alkylene radicals having from 1 to 20 carbon atoms, preferably from 1 to 10 carbon atoms, more preferably R and R" have 2 to 10 carbon atoms and R' has 2 carbon atoms.
  • Such compounds are known as dihydroxy bis-sulfide compounds.
  • the dihydroxy bis-sulfide compounds are included in the alloy baths over the phenol containing compounds.
  • dihydroxy bis-sulfide compounds examples include 2,4-dithia-1,5-pentanediol, 2,5-dithia-1,6-hexanediol, 2,6-dithia-1,7-heptanediol, 2,7-dithia-1,8-octanediol, 2,8-dithia-1,9-nonanediol, 2,9-dithia-1,10-decanediol, 2,11-dithia-1,12-dodecanediol, 5,8-dithia-1,12-dodecanediol, 2,15-dithia-1,16-hexadecanediol, 2,21-dithia-1,22-doeicasanediol, 3,5-dithia-1,7-heptanediol, 3,6-dithia-1,8-octane
  • the copper (I) alloy baths also include one or more tetrazoles as complexing agents for the copper (I) ions.
  • tetrazoles are heterocyclic nitrogen compounds having five membered rings and at least one sulfur substituent on the ring.
  • the tetrazoles along with the compounds of formula (I) and (II) inhibit the copper (I) ions from oxidizing to copper (II) ions and stabilize the bath. Inhibiting of the oxidation of the copper (I) ions to copper (II) ions assists in enabling the formation of a copper/tin/silver or copper/tin alloy.
  • Tetrazoles are included in the bath such that the mole ratio of the tetrazoles to the copper (I) ions in the bath are ⁇ 1, preferably >1, more preferably >1 to 10, even more preferably >1 to 6 and most preferably 1.1 to 4.
  • the amount of tetrazoles included in the bath may range from 0.5 g/L to 500 g/L.
  • the tetrazoles are mercaptotetrazole compounds having the following formula: where M is hydrogen, NH 4 , sodium or potassium and R 1 is substituted or unsubstituted, linear or branched (C 2 -C 20 )alkyl, substituted or unsubstituted (C 6 - C 10 )aryl, preferably substituted or unsubstituted, linear or branched (C 2 -C 10 )alkyl and substituted or unsubstituted (C 6 )aryl, more preferably substituted or unsubstituted, linear or branched (C 2 -C 10 )alkyl.
  • Substituents include, but are not limited to alkoxy, phenoxy, halogen, nitro, amino, substituted amino, sulfo, sulfamyl, substituted sulfamyl, sulfonylphenyl, sulfonyl-alkyl, fluorosulfonyl, sulfoamidophenyl, sulfonamide-alkyl, carboxy, carboxylate, ureido carbamyl, carbamyl-phenyl, carbamylalkyl, carbonylalkyl and carbonylphenyl.
  • Preferred substituents include amino and substituted amino groups.
  • Examples of mercaptotetrazoles are 1-(2-diethylaminoethyl)-5-mercapto-1,2,3,4-tetrazole, 1-(3-ureidophenyl)-5-mercaptotetrazole, 1-((3-N-ethyl oxalamido)phenyl)-5-mercaptotetrazole, 1-(4-acetamidophenyl)-5-mercapto-tetrazole and 1-(4-carboxyphenyl)-5-mercaptotetrazo le.
  • the combination of one or more tetrazoles with compounds of formulae (I) or (II) provides stability to the alloy baths during storage or during electroplating as well as stable alloy compositions over the applicable current density range such that hard bright copper/tin/silver or copper/tin alloys may be deposited as a replacement for nickel in decorative or sanitary articles.
  • Suitable acids include, but are not limited to, arylsulfonic acids, alkanesulfonic acids, such as methanesulfonic acid, ethanesulfonic acid and propanesulfonic acid, aryl sulfonic acids such as phenylsulfonic acid and tolylsulfonic acid, and inorganic acids such as sulfuric acid, sulfamic acid, hydrochloric acid, hydrobromic acid and fluoroboric acid.
  • the acids are alkane sulfonic acids and aryl sulfonic acids. Although a mixture of acids may be used, it is typical that a single acid is used.
  • the acids are generally commercially available or may be prepared by methods known in the literature.
  • the amount of acid in the plating compositions may be in the range of 0.01 to 500 g/L or such as from 10 to 400 g/L.
  • use of the corresponding acid may be desired.
  • use of hydrochloric acid as the acid component may be desired.
  • Mixtures of acids also may be used.
  • one or more suppressors may be included in the baths. Typically they are used in amounts of 0.5 to 15 g/L or such as from 1 to 10 g/L.
  • Such suppressors include, but are not limited to alkanol amines, polyethyleneimines and alkoxylated aromatic alcohols.
  • Suitable alkanol amines include, but are not limited to, substituted or unsubstituted methoxylated, ethoxylated, and propoxylated amines, for example, tetra (2-hydroxypropyl)ethylenediamine, 2- ⁇ [2-(dimethylamino)ethyl]-methylamino ⁇ ethanol, N,N'-bis(2-hydroxyethyl)-ethylenediamine, 2-(2-aminoethylamine)-ethanol, and combinations thereof.
  • Suitable polyethyleneimines include, but are not limited to, substituted or unsubstituted linear or branched chain polyethyleneimines or mixtures thereof having a molecular weight of from 800-750,000.
  • Suitable substituents include, for example, carboxyalkyl, for example, carboxymethyl, carboxyethyl.
  • Useful alkoxylated aromatic alcohols include, but are not limited to ethoxylated bis phenol, ethoxylated phenol, ethoxylated beta naphthol, and ethoxylated nonyl phenol.
  • one or more reducing agents can be added to the baths to assist in keeping the tin in a soluble, divalent state.
  • Suitable reducing agents include, but are not limited to hydroquinone, hydroquinone sulfonic acid, potassium salt and hydroxylated aromatic compounds, such as resorcinol and catechol.
  • Such reducing agents when used in the compositions are present in an amount of 0.01 to 20 g/L or such as from 0.1 to 5 g/L.
  • one or more conventional surfactants may be included in the baths.
  • Surfactants include, but are not limited to ethylene oxide and/or propylene oxide derivatives of aliphatic alcohols containing one or more alkyl group or ethylene oxide and or propylene oxide derivatives of aromatic alcohols.
  • the aliphatic alcohols may be saturated or unsaturated.
  • Such aliphatic and aromatic alcohols may be further substituted, for example, with sulfate or sulfonate groups.
  • Surfactants may be included in conventional amounts. In general, surfactants may be included in amounts of 0.1 g/L to 50 g/L.
  • alkoxylates such as the polyethoxylated amines JEFFAMINE T-403 or TRITON RW, or sulfated alkyl ethoxylates, such as TRITON QS-15, and gelatin or gelatin derivatives.
  • Alkoxylated amine oxides also may be included. Conventional amounts of such grain refiners may be used. Typically they are included in the baths in amounts of 0.5 g/l to 20 g/L.
  • grain refiners include, but are not limited to phenanthroline compounds such as 1,10-phenanthroline monohydrate, bismuth salts such as bismuth nitrate, bismuth acetate, bismuth tartrate and bismuth alkane sulfonates.
  • Indium salts such as indium chloride, indium sulfate and indium alkane sulfonates.
  • Antimony salts such as antimony lactate, antimony potassium tartrate.
  • Selenium and tellurium may be added as dioxides.
  • Iron salts such ferric bromide and anhydrous ferric chloride.
  • Cobalt salts such as cobaltous nitrate, cobaltous bromide and chloride.
  • Zinc salts such as zinc lactate and zinc nitrate.
  • Chromium salts such as chromous chloride and chromous formate.
  • Such grain refiners are included in conventional amounts. In general such grain refiners are included in amounts of 5ppm to 1000 ppm.
  • the electroplating baths are typically prepared by adding to a vessel one or more of the acids, one or more of the compounds of formula (I) and one or more tetrazoles followed by one or more of the solution soluble copper (I), silver and tin compounds, one or more optional additives, and the balance water.
  • the compounds of formula (II) and the tetrazoles are added to the vessel followed by copper (I) compounds and acid before silver and tin compounds.
  • undesired material can be removed, such as by filtration and then water is typically added to adjust the final volume of the bath.
  • the bath may be agitated by any known means, such as stirring, pumping, or recirculating, for increased plating speed.
  • the baths are acidic having a pH of less than 7, preferably less than 3.
  • the current density used to plate the copper alloys depends on the particular plating method. Generally, the current density is 0.01 ASD or more, preferably from 0.1 ASD to 10 ASD, more preferably from 1 ASD to 6 ASD.
  • the copper/tin/silver and copper/tin alloys may be electroplated at room temperature to 60° C, preferably from 30° C to 50° C. More preferably electroplating is done at temperatures of 30° C to 45° C.
  • the baths may be used to deposit copper/tin/silver and copper/tin alloys of various compositions.
  • the copper content of the copper/tin/silver alloys ranges from 40% to 60% by weight with tin in amounts of 15% to 50% by weight with the remainder silver.
  • the copper content of the copper/tin alloys ranges from 40% to 70% by weight with the remainder tin.
  • Such weights are based on measurements taken by either atomic adsorption spectroscopy ("AAS"), X-ray fluorescence (“XRF”), inductively coupled plasma (“ICP”) or differential scanning calorimetry (“DSC”).
  • the copper alloys also accept finishing layers of gold, silver, palladium and chromium.
  • a finishing layer of gold, silver, palladium or chromium (III) or (VI) may be directly plated on the bright white bronze without any preparatory or other intervening steps such as ultrasonic rinse or cathodic degreasing.
  • Conventional gold, silver, palladium or chromium plating baths may be used along with conventional plating parameters.
  • Such finishing layers may range in thickness of 0.05 ⁇ m to 10 ⁇ m.
  • the copper alloy electroplating baths are stable over prolonged periods of time and deposit copper/tin alloys and copper/tin/silver alloys with high current efficiencies and high plating speeds in contrast to many conventional copper alloy baths which electroplate white bronze. Current efficiencies range from 90% to as high as 100% with a mean value of 95%.
  • the copper/tin alloys and copper/tin/silver alloys electroplated from the baths have good ductility, thermal stability and abrasion resistance.
  • the copper/alloys may be directly plated with gold, chrome (III) or (VI), palladium and silver finishing layers without many of the conventional post-treatment steps of conventional processes such as ultrasonic rinse or cathodic degreasing. Therefore, the cyanide-free copper alloy electroplating baths enable a more efficient process than many conventional cyanide-free white bronze processes and are suitable for nickel replacement such as for decorative and sanitary articles.
  • the pH of the bath was less than 1 as measured using a KNICK Instruments conventional laboratory pH meter.
  • the molar mass of the tetrazole compound, 3,6-dithia-1,8-octanediol and copper (I) ions was 173.24, 182.30 and 63.55 g/mol, respectively.
  • the mole ratio of the tetrazole to the cooper (I) ions in the bath was 1.2:1 and the mole ratio of the tetrazole to the 3,6-dithia-1,8-octandiolwas 1.3:1.
  • a brass panel having dimensions 10 x 7.5 x 0.025 cm was degreased cathodically at 4 ASD for 1 minute by using RONACLEANTM DLF cleaner solution (available from Dow Electronic Materials) and activated by immersing the substrate for 20 seconds in RONASALTTM 369 solution (available from Dow electronic Materials).
  • the panel was then placed in a Hull cell containing 250 mL of the white bronze bath.
  • a platinized titanium electrode was used as anode material.
  • the working bath temperature ranged from 35°C to 45°C with optimum panel brightness at around 40°C over a broad current density range.
  • the panel was electroplated with the white bronze bath at 0.5 A for 5 minutes. After the electroplating was complete the panels were removed from the plating cells and rinsed with DI water.
  • the deposit on the panel was bright at all of the following current densities of the Hull cell test: 0.05 ASD, 0.2 ASD, 0.5 ASD, 0.73 ASD, 1 ASD, 2 ASD and 2.5 ASD.
  • the pH of the bath was less than 1 as measured using a KNICK Instruments conventional laboratory pH meter.
  • the mole ratio of the tetrazole to the cooper (I) ions in the bath was 1.1:1 and the mole ratio of the tetrazole to the thiodiethanol was 0.4:1.
  • a brass panel having dimensions 10 x 7.5 x 0.025 cm was degreased cathodically at 4 ASD for 1 minute using RONACLEANTM DLF solution and activated by immersing the substrate for 20 seconds in RONASALTTM 369 solution.
  • the panel was then placed in a Hull cell containing 250 mL of the white bronze bath.
  • a platinized titanium electrode was used as anode material.
  • the working bath temperature ranged from 30°C to 40°C with an optimum at around 35°C.
  • the panel was electroplated with the white bronze bath at 0.5 A for 5 minutes. The baths appeared stable throughout electroplating and the deposits appeared bright at the following current densities of the Hull cell test: 0.05 ASD, 0.2 ASD, 0.5 ASD, 0.73 ASD, 1 ASD, 2 ASD and 2.5 ASD.
  • the white bronze copper/tin/silver alloy electroplating bath was prepared as described in Example 1 with the exception that the amount of 3,6-dithia-1,8-octanediol was varied as shown in Table 3 below.
  • the mole ratio of 1-(2-dimethylamino-ethyl)-5-mercapto-1,2,3,4-tetrazole to 3,6-dithia-1,8-octanediol was as shown in Table 3.
  • a plurality of brass panels having dimensions 10 x 7.5 x 0.025 cm was degreased and activated as described in Example 1 above. Each panel was then placed in separate Hull cells containing 250 mL of the white bronze bath. The pH of the bath was less than 1. A platinized titanium or bronze electrode was used as anode material. The working bath temperature ranged from 35°C to 45°C. The panels were electroplated with the white bronze bath at 1 A for 3 minutes. Throughout electroplating all of the baths appeared stable.
  • the panels were removed from the Hull cells, rinsed with DI water and their appearance was observed with the naked eye.
  • the copper/tin/silver electroplating bath which did not include the combination of 1-(2-dimethylamino-ethyl)-5-mercapto-1,2,3,4-tetrazole and 3,6-dithia-1,8-octanediol all showed undesirable matte deposits at all of the current densities.
  • the white bronze copper/tin alloy electroplating bath was prepared as described in Example 2 with the exception that the amount of thiodiethanol was varied as shown in Table 4 below.
  • the mole ratio of 1-(2-dimethylamino-ethyl)-5-mercapto-1,2,3,4-tetrazole to thiodiethanol was as shown in Table 4.
  • a plurality of brass panels having dimensions 10 x 7.5 x 0.025 cm was degreased and activated as described in Example 2. Each panel was then placed in separate Hull cells containing 250 mL of the white bronze bath. A platinized titanium or bronze electrode was used as anode material. The working bath temperature ranged from 30°C to 40°C. The panels were electroplated with the white bronze bath at 1 A for 3 minutes. Throughout electroplating all of the baths appeared stable.
  • the panels were removed from the Hull cells, rinsed with DI water and their appearance was observed with the naked eye.
  • the copper/tin electroplating bath which did not include the combination of 1-(2-dimethylaminoethyl)-5-mercapto-1,2,3,4-tetrazole and thiodiethanol showed undesirable matte deposits at all of the current densities.
  • a plurality of brass panels having dimensions 10 x 7.5 x 0.025 cm was degreased and activated. Each panel was then placed in separate Hull cells containing 250 mL of one of the three copper/tin electroplating baths. The pH of the baths was less than 1.
  • a platinized titanium or bronze electrode was used as anode material. The working baths were maintained at 35°C during plating. The panels were electroplated with the copper/tin bronze baths at 1 A for 3 minutes. After the panels were electroplated they were rinsed with deionized water and observed with the naked eye for their appearance. The results for each bath are shown in Table 5a.
  • Comparative Baths 1 and 2 had good bright deposits for all current densities, Comparative Bath 3 had undesirable yellow bronze deposits due to greater than 70% copper content and a very low current efficiency of less than 30% as indicated by a thin deposit.
  • Comparative Baths 1 and 2 were allowed to idle 24 hours. A new set of panels were then electroplated with the Comparative Baths 1 and 2. Because of the poor results obtained from Comparative Bath 3, its plating performance was not tested for performance after 24 hours idling time. The results of Comparative Baths 1 and 2 are shown in Table 5b. Table 5b Comparative Bath Mole Ratio of Tetrazole:Thio-diethanol 0.05 ASD Deposit 0.5 ASD Deposit 1 ASD Deposit 2 ASD Deposit 4 ASD Deposit 1 0.84 Bright Matte Matte Matte Matte 2 0.42 Matte Matte Matte Matte Matte Matte
  • tin (II) ions in amounts of half the original concentration to the baths, the brightness was re-established; however, the tin (II) rapidly oxidized to tin (IV) as indicated by the orange color of the baths.
  • a steel panel 10 x 7.5 x 0.025 cm was immersed for one minute in 40% hydrochloric acid solution to remove the protective zinc layer on its surface.
  • the panel was degreased anodically at 3 ASD for one minute in RONACLEANTM DLF cleaning solution.
  • the panel was activated by immersion in RONASALTTM 369 solution, rinsed with DI water and placed in a Hull cell containing 250 ml of a white bronze bath as described in Example 1 above.
  • a platinized titanium electrode was used as an anode.
  • the mole ratio of the tetrazole to the cooper (I) ions in the bath was 1.2:1 and the mole ratio of the tetrazole to the 3,6-dithia-1,8-octandiol was 1.3:1.
  • the alloy composition was measured on steel Hull cells plated at a current of 0.5 A for 5 minutes at different current densities as shown in Table 6 below.
  • Metal content was measured by XRF using a FISCHERSCOPE X-Ray model XDV-SD from Helmut Fischer AG. This measurement was repeated on three different steel panels coated with the white bronze. The average metal content at each current density is shown in Table 6.
  • Table 6 Metal 0.05 ASD 0.1 ASD 0.5 ASD 1 ASD 1.5 ASD 2 ASD 2.5 ASD % Copper 50 49 48 48 48 48 49 % Tin 34 36 38 40 41 42 43 % Silver 16 15 14 12 11 10 8 All of the alloys had a bright appearance upon observation with the naked eye.
  • Example 1 One liter of the white bronze bath of Example 1 was introduced in a glass cell. Two platinized titanium anodes were placed in the cell. A steel cylindrical ring of 12 mm in diameter and 7 mm high was mounted on a rotating axis of an electrical motor. The rotation speed of the axis was fixed at 1000 rpm. The axis was immersed in the bath and electrical contact established between the electrodes. The current density was varied and the plating speeds were measured for a new electroplating bath as well as the same electroplating bath at different bath ages as shown in Table 7a. At each current density, the thickness of the bronze coating was measured by using XRF. The plating rate was calculated at each current density as the thickness in microns of white bronze plated divided by the plating time in minutes.
  • the plating speed was substantially stable with the bath age; however, the speed at most of the current densities was lower compared to the results in Table 7a. This showed that the current efficiency in the copper (II) Comparative Bath was lower than the bath of Example 1.
  • the current efficiency of the white bronze electroplating bath of Example 1 was estimated as the experimental mass of the deposit divided by the theoretical mass all multiplied by 100.
  • the experimental mass was determined by measuring the weight difference of a brass panel 5 x 7.5 x 0.025 cm before and after white bronze plating.
  • the theoretical mass of the deposit was calculated based on the Faraday law and by taking into consideration the alloy composition. This method is described in " Frederick Adolph Lowenheim, Electroplating (1978) page 377; Library of Congress Cataloging, McGraw-Hill Book Company: ISBN 0-07-038836-9" .
  • the current efficiency was determined at a high current density of 2 ASD over a bath age of 0 Ah/L to 15 Ah/L. Multiple estimations were made over the life of the bath as shown in the graph of Figure 1 of % CE v. Bath age. The current efficiency ranged from 90% to 100% with an average of about 95%. Values above 100% were due to possible experimental error. The sustained high and stable current efficiency over the life of the bath indicated a very stable electroplating bath where undesired hydrogen evolution was insignificant.
  • Three brass panels 2 x 10 x 0.025 cm were electroplated with the white bronze electroplating bath of Example 1 and another three were electroplated with the copper (II) copper/tin bronze alloy bath of Table 8 below.
  • Two liters of each bronze bath were added into separate electrochemical cells.
  • Two white bronze anodes were also placed in the cells.
  • An electric current density of 1 ASD was applied between the anodes and the brass cathodes for 5 minutes to plate a 3 ⁇ m thick layer on each brass panel.
  • the plating time was 7 minutes for the formulation in Table 8. The deposits appeared bright.
  • the ductility of each plated brass panel was tested using a Bend-tester from SHEEN INSTRUMENTS Ltd. according to ASTM standard B 489-85. The average ductility for each set of three panels was determined. The average ductility for the white bronze of the bath from Example 1 was 1.2 % elongation. Above this value cracks were observed in the deposit. Cracks were observed at an elongation of 0.8% for the deposits from the formulation in Table 8. 0.8% is the lower scale for the ductility test when using the above instrument. The test was repeated except that the amount of white bronze electroplated on the brass panels was 6 ⁇ m. The average elongation for the bath from Example 1 was again 1.2% and cracks were observed at 0.8% from the sample plated from the bath of Table 8. The white bronze deposit from Example 1 showed improved ductility in contrast to the bath from Table 8.
  • the test was repeated at 200 °C for 2 hours.
  • the panels electroplated with the white bronze bath of Example 1 were once again bright as well as the control panels.
  • the panels that were electroplated with the bath from Table 8 and annealed had an intensive dark color.
  • the white bronze electroplated from the bath of Example 1 showed improved heat resistance over the conventional bath of Table 8.
  • Three brass panels 2 x 10 x 0.025 cm were electroplated with the white bronze electroplating bath of Example 1 and another three were electroplated with the copper (II) copper/tin bronze alloy bath of Example 9. Two liters of each bronze bath were added into separate electrochemical cells. Two white bronze anodes were also placed in the cells. An electric current density of 1 ASD was applied between the anodes and the brass cathodes for 5 minutes to plate a 3 ⁇ m thick layer on each brass panel. The deposits appeared bright.
  • RONAFLASHTM P pure gold electroplating bath available from Dow Electronic Materials, was placed in a separate electrochemical cell.
  • the white bronze plated brass panels were rinsed with DI water and introduced in the gold bath.
  • the panels were then electroplated with the gold without any further surface treatment or preparation before gold plating.
  • a current density of 1 ASD was applied for 40 seconds between the bronze coated brass panels and platinized titanium anode.
  • the panels were removed, rinsed with DI water and dried with pressurized air. All of the deposits had a shiny gold color appearance.
  • the panels were kept at room temperature in the open air for one month.
  • the samples plated with the bath of Example 1 were still shiny.
  • the panels which were electroplated with the bath of Example 9 appeared stained with several dull areas present on the surface.
  • Figure 3 is a photograph of one of the panels which was plated with the bath from Example 9 taken with the OLYMPUS BX60M optical microscope. Severe surface staining of the chrome deposit is apparent. The panels electroplated with the white bronze bath of Example 1 showed significant improvement in the ability to resist staining in contrast to the conventional bronze bath.

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  • 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)
  • Manufacturing Of Printed Wiring (AREA)

Claims (5)

  1. Ein Galvanisierbad, beinhaltend Kupfer(I)-lonen, eine oder mehrere Quellen von Zinnlegierungsionen, optional eine oder mehrere Quellen von Silberlegierungsionen, eine oder mehrere Verbindungen mit einer Formel

            X-S-Y     (I)

    wobei X und Y gleich oder unterschiedlich sein können und substituierte oder nichtsubstituierte Phenolgruppen, HO-R- oder -R'S-R"-OH sein können, wobei R, R' und R" gleich oder unterschiedlich sein können und lineare oder verzweigte Alkylenreste mit 1 bis 20 Kohlenstoffatomen sind; und ein oder mehrere Tetrazole, wobei ein Molverhältnis des einen oder der mehreren Tetrazole zu den Kupfer(I)-lonen in dem Galvanisierbad ≥ 1 ist und ein Molverhältnis des einen oder der mehreren Tetrazole zu der einen oder den mehreren Verbindungen der Formal (I) 0,05 bis 4 ist, wobei das Galvanisierbad frei von Cyanid ist; wobei das eine oder die mehreren Tetrazole eine folgende Formel aufweisen:
    Figure imgb0004
     wobei M Wasserstoff, NH4, Natrium oder Kalium ist und R1 substituiertes oder nichtsubstituiertes, lineares oder verzweigtes (C2-C20)-Alkyl oder substituiertes oder nichtsubstituiertes (C6-C10)-Aryl ist.
  2. Galvanisierbad gemäß Anspruch 1, wobei X und Y unterschiedlich sind und HO-R- oder -R'-S-R"-OH sind und R, R' und R" gleich oder unterschiedlich sein können.
  3. Ein Verfahren zum Galvanisieren, beinhaltend:
    a) In-Kontakt-Bringen eines Substrats mit einem Galvanisierbad, beinhaltend Kupfer(I)-lonen, eine oder mehrere Quellen von Zinnlegierungsionen, optional eine oder mehrere Quellen von Silberlegierungsionen, eine oder mehrere Verbindungen mit einer Formel

            X-S-Y     (I)

    wobei X und Y gleich oder unterschiedlich sein können und eine substituierte oder nichtsubstituierte Phenolgruppe, HO-R- oder -R'S-R"-OH sein können, wobei R, R' und R" gleich oder unterschiedlich sein können und lineare oder verzweigte Alkylenreste mit 1 bis 20 Kohlenstoffatomen sein können; und ein oder mehrere Tetrazole, wobei ein Molverhältnis des einen oder der mehreren Tetrazole zu den Kupfer(I)-lonen in dem Galvanisierbad ≥ 1 ist und ein Molverhältnis des einen oder der mehreren Tetrazole zu der einen oder den mehreren Verbindungen der Formal (I) 0,05 bis 4 ist, wobei das Galvanisierbad frei von Cyanid ist; wobei das eine oder die mehreren Tetrazole eine folgende Formel aufweisen:
    Figure imgb0005
     wobei M Wasserstoff, NH4, Natrium oder Kalium ist und R1 substituiertes oder nichtsubstituiertes, lineares oder verzweigtes (C2-C20)-Alkyl oder substituiertes oder nichtsubstituiertes (C6-C10)-Aryl ist; und
    b) Galvanisieren einer Kupfer-/Zinnlegierung oder optional einer Kupfer-/Zinn-/Silberlegierung auf das Substrat.
  4. Verfahren gemäß Anspruch 3, wobei X und Y unterschiedlich sind und HO-R- oder -R'-S-R"-OH sind und R, R' und R" gleich oder unterschiedlich sein können.
  5. Verfahren gemäß Anspruch 3, ferner beinhaltend das Galvanisieren einer Deckschicht aus Silber, Gold, Palladium oder Chrom auf die Kupfer-/Zinnlegierung oder die Kupfer-/Zinn-/Silberlegierung.
EP15185289.4A 2014-09-30 2015-09-15 Cyanidfreie galvanische bäder für weisse bronze basierend auf kupfer (i) ionen Active EP3002350B1 (de)

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US9984895B1 (en) * 2017-01-31 2018-05-29 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Chemical mechanical polishing method for tungsten
CN110678583B (zh) * 2017-06-01 2022-09-30 巴斯夫欧洲公司 包含流平剂的锡合金电镀组合物
CN108166029A (zh) * 2017-12-28 2018-06-15 广东达志环保科技股份有限公司 无氰白铜锡电镀液和电镀方法
DE102018126174B3 (de) * 2018-10-22 2019-08-29 Umicore Galvanotechnik Gmbh Thermisch stabile Silberlegierungsschichten, Verfahren zur Abscheidung und Verwendung
CN110117803B (zh) * 2019-05-14 2020-10-23 广州超邦化工有限公司 氯化钾无氰镉钛合金镀液、其制备方法和电镀工艺
US20210172082A1 (en) * 2019-12-10 2021-06-10 Rohm And Haas Electronic Materials Llc Acidic aqueous binary silver-bismuth alloy electroplating compositions and methods
KR102539397B1 (ko) * 2020-11-24 2023-06-02 주식회사 호진플라텍 도금피막 내 은 함량의 분포 편차가 개선된 웨이퍼 범프용 주석-은 합금 전기 도금액
WO2023285604A1 (en) 2021-07-15 2023-01-19 Seolfor Aktiebolag Electroplating compositions and methods for preparing the same

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