US3674660A - Electrodeposition of copper - Google Patents

Electrodeposition of copper Download PDF

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Publication number
US3674660A
US3674660A US63954A US3674660DA US3674660A US 3674660 A US3674660 A US 3674660A US 63954 A US63954 A US 63954A US 3674660D A US3674660D A US 3674660DA US 3674660 A US3674660 A US 3674660A
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United States
Prior art keywords
electrolyte
acid
brightener
auxiliary
auxiliary brightener
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Expired - Lifetime
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US63954A
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English (en)
Inventor
Derek Martin Lyde
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Solvay Solutions UK Ltd
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Albright and Wilson Ltd
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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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • ABSTRACT 30 Foreign A fi fl P -i it Data
  • a copper pyrophosphateelectroplating bath contains a known heterocychc additive in conjunction with an auxiliary y 1, 1967 Great Bmam 1 brightener selected from iminodiacetic acid, cinammic acid, aliphatic acid, diand polycarboxylic acids having at least i seven carbon atoms, salts of the aforesaid acids and hydrox- 58] g [52 R 52 44 1 yethylcellulose.
  • the auxiliary brightener prevents step plating which is normally caused by the presence of the heterocyclic brightener.
  • the present invention relates to improvements in the electrodeposition of copper.
  • a characteristic feature of these plating solutions is that in conjunction with suitable brightening additives they may be used to form highly specular mirror bright finishes which do not require subsequent mechanical polishing. In this they differ from the conventional acid copper plating systems and from copper cyanide systems, which produce matt finishes. Brighteners used in the former solutions are intended to improve the specularity of the bright finish whereas those used in the latter systems are designed to make the matt finish more amenable to mechanical polishing.
  • heterocyclic compounds have been proposed as brightener additives for alkaline pyrophosphate electroplating compositions and some of these have found particular favor in the art.
  • a group of these heterocyclic compounds is characterized by the presence of the grouping:
  • Some of the aforementioned specifications refer to the optional presence in the electroplating composition of other organic compounds, such as simple aliphatic or hydroxyaliphatic carboxylic acids including oxalic, citric, tartaric, acetic, propionic and phthalic acids and wetting agents. Certain of these compounds are stated, for example in specification No. 1,051,150, to improve the grain refinement of the electrodeposited material and to reduce the anodic polarization. These additives were originally described in the early work on copper pyrophosphate baths, before the advent of heterocyclic brighteners.
  • the heterocyclic brighteners have one disadvantage-they tend to cause a plating defect called step plating. This arises when in consequence of reduction of current density across the surface of the workpiece, such as commonly occurs in practice with contoured surfaces, the thickness of the coating varies. in normal plating there may be a continuous variation of the thickness of the coating across the surface without affecting the appearance or quality of the work. In step plating there is a sharp division between an area of relatively thick plating of high specular brightness and an area of relatively thin plating of inferior quality. This tendency can be avoided by keeping the concentration of heterocyclic brightener small, but that imposes limitations on the amount by which the specular brightness is improved.
  • An object of my invention is to inhibit the tendency of heterocyclic brighteners to cause step plating in copper pyrophosphate electroplating baths.
  • a further object of my invention is to provide copper pyrophosphate electroplating baths which produce work of improved specular brightness.
  • a further object of my invention is to provide copper pyrophosphate electroplating baths of improved levelling power.
  • the invention provides, in brightening compositions for addition to copper pyrophosphate electroplating baths and containing a heterocyclic brightener selected from the known group consisting of 2-mercaptothiazole, 2-mercap tobenzthiazole, Z-mercaptothiadiazole, Z-mercaptopyrimidine, Z-mercaptoiminazole, substituted homologs of the aforesaid heterocyclic brighteners and derivatives that form any of the aforesaid compounds when dissolved in copper pyrophosphate electroplating baths, the improvement which consists in that the brightening composition contains, in addition to the heterocyclic brightener, an auxiliary brightener selected from the group of step plating inhibitors consisting of aliphatic dicarboxylic and polycarboxylic acids having at least seven carbon atoms, malonic acid, cinammic acid, iminodiacetic acid,salts of the said acids and hydroxyethyl-cellulose.
  • a heterocyclic brightener selected from
  • the invention further provides an aqueous electrolyte for copper plating having dissolved therein a copper salt, an alkali metal pyrophosphate in an amount at least sufficient to form the complex X Cu(l O-,) where X represents an alkali metal, and a minor proportion of a brightening composition according to the invention.
  • the invention also provides a process for the electrodeposition of copper using an aqueous electrolyte of the invention.
  • heterocyclic brighteners for present use are exemplified by the mercapto-thiazole compounds described in specification No. 940,282, for example 2-mercapto-1, 3- thiazole and 2-mercapto-benthiazole; by the Z-mercapto- 1,3,4-thiadiazole compounds described in specification No. 939,997, for example 2,5-dimercapto-l,3,4-thiadiazole, 2- mercapto-5-methylmercapto-1,3,4-thiadiazole and 2-mercapto-5-n-butylmercapto-l,3,4-thiadiazole; and by the 2-mercapto-iminazole and Z-mercapto pyrimidines described in specification No.
  • 1,051,150 for example Z-mercapto-lmethyliminazole, 2-mercaptopyrimidine, 6-hydroxy-2 mercaptopyrimidine and 6-hydroxy-2-mercapto-4-methylpyrimidine.
  • precursors of the compounds described above By precursor is meant herein a compound which when dissolved in the copper pyrophosphate electrolyte provides in solution a compound containing the structure (II).
  • auxiliary brighteners for present use are for the most part acids which will normally be used as sodium, potassium, or ammonium salts.
  • organic diand poly-carboxylic acids or anhydrides thereof having more than seven carbon atoms there may be used, usually in the form of water-soluble salts, organic diand poly-carboxylic acids or anhydrides thereof having more than seven carbon atoms.
  • these compounds there can be mentioned suberic acid, azelaic acid, and sebacic acid as well as adducts of the type formed when a dienophilic carboxylic acid such as maleic anhydride is condensed with a conjugally unsaturated hydrocarbon such as polyiso-butylene, for example the alkylor alkenyl-substituted succinic acids and anhydrides wherein the alkyl or alkenyl group contains from 30-150 carbon atoms.
  • the heterocyclic brightening agent is employed in a proportion of at least 0.001 grams per liter of the total weight of electrolyte and preferably from 1 to mg. per liter.
  • the optimum concentration may vary from 2 to 4 mg. per liter depending upon the nature of the auxiliary brightener present.
  • the auxiliary brightener is employed in a proportion of from 1 ppm to saturation, preferably from 2 to 100 ppm, for example 3 to 6 ppm.
  • the copper plating electrolytes of the invention have a similar constitution with respect to the concentration of copper salt and pyrophosphate as those conventionally employed, for example as described in the abovementioned specifications. These electrolytes may contain other additives that are conventionally employed in this type of electrolyte in addition to the heterocyclic brighteners.
  • the electrolyte may be employed for plating metal articles in accordance with known procedures.
  • the invention is particularly surprising because the compounds which have been found effective are similar chemically to a number of compounds which had already been tested and found totally inefiective. These ineffective compounds include oxalic acid, tartaric acid, citric acid, formic acid, acetic acid, propionic acid, benzoic acid and phthalic acid.
  • Standard solutions were made by using 3 heterocyclic brighteners, namely 4 ppm. 2,5-dimercapto- 1,3,4-thiadiazole, 6 ppm. Z-mercaptobenzimidazole and 10 ppm.Z-mercaptobenzthiazole. The solutions were obtained at a pH of 8.8 at a temperature of 55 C.
  • Plating was carried out on brass panels in a standard l-lull cell with a mean current density of 30 amp per sq. ft. under air agitation.
  • Cinnamic acid Aurine tricarboxylic acid Hydroxyethyl cellulose lminodiacetic acid Malonic acid Sebacic acid Azelaic acid Suberic acid Maleic anhydride/polyisobutylene adduct (Na salt) 10. Oxalic acid 1 l. Citric acid 12. Tartaric acid 13. Formic acid 14. Acetic acid 15. Propionic acid 16. Benzoic acid 17. Phthalic acid Examples 1 to 9 provided excellent specular brightness with improved leveling and negligible step plating in each of the electrolytes. Comparative Examples 10 to 17 on the other hand, although providing high specular brightness in regions of high current density, gave rise to serious step plating.
  • a copper pyrophosphate electroplating electrolyte consisting essentially of an alkaline aqueous solution containing dissolved therein a copper salt and an alkali metal pyrophosphate in an amount at least sufiicient to form the complex salt X Cu(P O-,),, and a known heterocyclic brightening additive in an amount sufficient to provide bright electrodeposits selected from the group consisting of mercaptothiazoles, mercaptobenzthiazoles, mercaptothiadiazoles, mercaptopyrimidines, and mercaptoiminazoles, the improvement wherein said electrolyte also contains an auxiliary brightener selected from the group of step plating inhibitors consisting of imino diacetic acid, malonic acid, cinnamic acid, aurine tricarboxylic acid, aliphatic dicarboxylic acids having at least seven carbon atoms, salts of the aforesaid acids and hydroxyethyl cellulose in a concentration
  • heterocyclic brightener is selected from the group consisting of 2-mercaptothiazole, 2-mercaptonbenzthiazole, 2-mercaptothiadiazole, 2-mercaptopyrimidines, and Z-mercapto iminazole, in a concentration of from 1 to 10 ppm, and wherein said auxiliary brightener is in a concentration of from 2 to ppm.
  • auxiliary brightener is an adduct of maleic acid with a polyolephine having from 30 to carbon atoms.
  • the electrolyte of claim 2 brightener is azelaic acid.
  • the electrolyte of claim 2 brightener is suberic acid.
  • the electrolyte of claim 2 brightener is cinnamic acid.
  • the electrolyte of claim 2 brightener is aurine tricarboxylic acid.
  • aqueous copper phyrophosphate electrolyte wherein copper is electrodeposited from electrolyte consisting essentially of an alkaline aqueous solution containing dissolved therein a copper salt and an alkali metal pyrophosphate in an amount at least sufiicient to form the complex salt X Cu(P O and of a known heterocyclic brightening additive in an amount sufficient to provide bright electrodeposits selected from the group consisting of mercaptothiazoles, mercaptobenzthiazoles, mercaptothiadiazoles, mercaptopyrimidines, and mercaptoiminazoles, the improvement comprising admixing in said electrolyte at least one part per million of an auxiliary brightener selected from the group of step plating inhibitors consisting of imino diacetic acid, malonic acid, cinnimac acid, aurine tricarboxylic acid, aliphatic dicarboxylic acids having at least seven

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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)
US63954A 1967-05-01 1970-08-14 Electrodeposition of copper Expired - Lifetime US3674660A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB09989/67A GB1235101A (en) 1967-05-01 1967-05-01 Improvements relating to electrodeposition of copper

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US3674660A true US3674660A (en) 1972-07-04

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US63954A Expired - Lifetime US3674660A (en) 1967-05-01 1970-08-14 Electrodeposition of copper
US00132236A Expired - Lifetime US3729393A (en) 1967-05-01 1971-04-07 Electrodeposition of copper
US00209004A Expired - Lifetime US3784454A (en) 1967-05-01 1971-12-16 Additive for the electrodeposition of copper

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US00132236A Expired - Lifetime US3729393A (en) 1967-05-01 1971-04-07 Electrodeposition of copper
US00209004A Expired - Lifetime US3784454A (en) 1967-05-01 1971-12-16 Additive for the electrodeposition of copper

Country Status (8)

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US (3) US3674660A (en:Method)
BE (1) BE714454A (en:Method)
DE (1) DE1771228C3 (en:Method)
ES (1) ES353094A1 (en:Method)
FR (1) FR1564283A (en:Method)
GB (1) GB1235101A (en:Method)
NL (1) NL6805947A (en:Method)
SE (1) SE332744B (en:Method)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US5051154A (en) * 1988-08-23 1991-09-24 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
GB2262288A (en) * 1991-11-27 1993-06-16 Hitachi Metals Ltd Copper electroplated permanent magnet of rare-earth element/transition metal system
WO1997049549A1 (en) * 1996-06-26 1997-12-31 Park Electrochemical Corporation A process for producing polytetrafluoroethylene (ptfe) dielectric boards on metal plates
US20030010646A1 (en) * 1999-05-17 2003-01-16 Barstad Leon R. Electrolytic copper plating solutions
US20030094376A1 (en) * 2000-12-20 2003-05-22 Shipley Company, L.L.C. Electrolytic copper plating solution and method for controlling the same
US6709564B1 (en) * 1999-09-30 2004-03-23 Rockwell Scientific Licensing, Llc Integrated circuit plating using highly-complexed copper plating baths
CN103173812A (zh) * 2013-03-21 2013-06-26 山东金宝电子股份有限公司 一种消除电解铜箔内应力的混合添加剂及用于生产低应力铜箔的方法
SE2150946A1 (en) * 2021-07-15 2023-01-16 Seolfor Ab Compositions, methods and preparations of cyanide-free copper solutions, suitable for electroplating of copper deposits and alloys thereof

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5167234A (ja) * 1974-12-09 1976-06-10 Hitachi Ltd Pirorinsandometsukizeikahimakuboshiho
US4134803A (en) * 1977-12-21 1979-01-16 R. O. Hull & Company, Inc. Nitrogen and sulfur compositions and acid copper plating baths
US4877518A (en) * 1988-05-02 1989-10-31 Phillips Petroleum Company Ore flotation employing dimercaptothiadiazoles
US4966688A (en) * 1988-06-23 1990-10-30 Phillips Petroleum Company Ore flotation employing amino mercaptothiadiazoles
US4976826A (en) * 1990-02-16 1990-12-11 Furukawa Circuit Foil Co., Ltd. Method of making electrodeposited copper foil
US5252196A (en) * 1991-12-05 1993-10-12 Shipley Company Inc. Copper electroplating solutions and processes
US5730854A (en) * 1996-05-30 1998-03-24 Enthone-Omi, Inc. Alkoxylated dimercaptans as copper additives and de-polarizing additives
WO2005006476A1 (ja) 2003-07-11 2005-01-20 Shishiai-Kabushikigaisha 燃料電池用冷却液組成物
EP1698678A1 (en) * 2003-12-25 2006-09-06 Shishiai-Kabushikigaisha Heat carrier composition
JP5419021B2 (ja) * 2008-11-11 2014-02-19 ユケン工業株式会社 ジンケート型亜鉛めっき浴
WO2010092579A1 (en) * 2009-02-12 2010-08-19 Technion Research & Development Foundation Ltd. A process for electroplating of copper

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2195409A (en) * 1936-07-31 1940-04-02 Nat Aniline & Chem Co Inc Electrodeposition
US2437865A (en) * 1943-09-25 1948-03-16 United Chromium Inc Method of electrodepositing copper and baths and compositions therefor
US2700019A (en) * 1951-07-05 1955-01-18 Westinghouse Electric Corp Acid copper plating
US3161575A (en) * 1960-07-23 1964-12-15 Albright & Wilson Mfg Ltd Copper pyrophosphate electroplating solutions
US3341433A (en) * 1964-05-01 1967-09-12 M & T Chemicals Inc Electrodeposition of nickel

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2195409A (en) * 1936-07-31 1940-04-02 Nat Aniline & Chem Co Inc Electrodeposition
US2437865A (en) * 1943-09-25 1948-03-16 United Chromium Inc Method of electrodepositing copper and baths and compositions therefor
US2700019A (en) * 1951-07-05 1955-01-18 Westinghouse Electric Corp Acid copper plating
US3161575A (en) * 1960-07-23 1964-12-15 Albright & Wilson Mfg Ltd Copper pyrophosphate electroplating solutions
US3341433A (en) * 1964-05-01 1967-09-12 M & T Chemicals Inc Electrodeposition of nickel

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4948474A (en) * 1987-09-18 1990-08-14 Pennsylvania Research Corporation Copper electroplating solutions and methods
US5051154A (en) * 1988-08-23 1991-09-24 Shipley Company Inc. Additive for acid-copper electroplating baths to increase throwing power
GB2262288A (en) * 1991-11-27 1993-06-16 Hitachi Metals Ltd Copper electroplated permanent magnet of rare-earth element/transition metal system
US5314756A (en) * 1991-11-27 1994-05-24 Hitachi Metals, Ltd. Permanent magnet of rare-earth-element/transition-metal system having improved corrosion resistance and manufacturing method thereof
GB2262288B (en) * 1991-11-27 1995-10-11 Hitachi Metals Ltd Permanent magnet of rare-earth element/transition metal system
WO1997049549A1 (en) * 1996-06-26 1997-12-31 Park Electrochemical Corporation A process for producing polytetrafluoroethylene (ptfe) dielectric boards on metal plates
US20030010646A1 (en) * 1999-05-17 2003-01-16 Barstad Leon R. Electrolytic copper plating solutions
US6709564B1 (en) * 1999-09-30 2004-03-23 Rockwell Scientific Licensing, Llc Integrated circuit plating using highly-complexed copper plating baths
US20030094376A1 (en) * 2000-12-20 2003-05-22 Shipley Company, L.L.C. Electrolytic copper plating solution and method for controlling the same
US6881319B2 (en) * 2000-12-20 2005-04-19 Shipley Company, L.L.C. Electrolytic copper plating solution and method for controlling the same
CN103173812A (zh) * 2013-03-21 2013-06-26 山东金宝电子股份有限公司 一种消除电解铜箔内应力的混合添加剂及用于生产低应力铜箔的方法
CN103173812B (zh) * 2013-03-21 2015-12-09 山东金宝电子股份有限公司 一种消除电解铜箔内应力的混合添加剂及用于生产低应力铜箔的方法
SE2150946A1 (en) * 2021-07-15 2023-01-16 Seolfor Ab Compositions, methods and preparations of cyanide-free copper solutions, suitable for electroplating of copper deposits and alloys thereof
SE545031C2 (en) * 2021-07-15 2023-03-07 Seolfor Ab Compositions, methods and preparations of cyanide-free copper solutions, suitable for electroplating of copper deposits and alloys thereof

Also Published As

Publication number Publication date
DE1771228A1 (de) 1973-04-26
DE1796337A1 (de) 1974-02-28
DE1771228B2 (de) 1974-01-24
US3784454A (en) 1974-01-08
DE1771228C3 (de) 1974-08-22
BE714454A (en:Method) 1968-09-16
GB1235101A (en) 1971-06-09
SE332744B (en:Method) 1971-02-15
DE1796337B2 (de) 1976-09-02
NL6805947A (en:Method) 1968-11-04
FR1564283A (en:Method) 1969-04-18
ES353094A1 (es) 1969-10-01
US3729393A (en) 1973-04-24

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