US3674660A - Electrodeposition of copper - Google Patents
Electrodeposition of copper Download PDFInfo
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- 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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- 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
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- 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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Abstract
A copper pyrophosphate electroplating bath contains a known heterocyclic additive in conjunction with an auxiliary brightener selected from iminodiacetic acid, cinammic acid, aliphatic acid, di- and poly- carboxylic acids having at least seven carbon atoms, salts of the aforesaid acids and hydroxyethylcellulose. The auxiliary brightener prevents step plating which is normally caused by the presence of the heterocyclic brightener.
Description
& llmte States Patent [151 3,674,660
Lyde July 4, 1972 [54] ELECTRODEPOSITION OF COPPER [56] References Cited [72] Inventor: Derek Martin Lyde, Stourbridge, England UNITED STATES PATENTS 73 Assignee; m & Wilson Limited, Oldbury near 2,195,409 4/1940 Flett ..204/49 X Birmingham, England 3 3/1943 2,700,019 1/1955 I22] hled. Aug. 14, 1970 116L575 IZHQM 3,341,433 9/l967 [2| I Appl. No: 63,954
Primary ExaminerG. L. Kaplan Related Apphcamn Data Attorney-Herbert H. Goodman [63] Continuation-impart of Ser. No. 724,225, April 25,
1968. [57] 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.
13 Claims, No Drawings ELECTRODEPOSITION OF COPPER This application is a continuation-in-part application of copending application Ser. No. 724,225, filed Apr. 25, 1968, now abandoned. v
The present invention relates to improvements in the electrodeposition of copper.
It is known to carry out the electrodeposition of copper from alkaline solutions containing an alkali metal copper pyrophosphate complex of the formula X,Cu( 2 where X represents an alkali metal.
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.
Various 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:
contained in a fiveor six-membered heterocyclic ring system where Q represents a nitrogen atom (either as a =-=Nor N-grouping) or a sulphur atom. Examples of these mercaptoheterocyclic compounds are described in UK. Specifications Nos. 939,997; 940,282 and 1,051,150.
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. In practice, however, we have discovered that although these known carboxylic acid additives and wetting agents caused some slight improvements in the unbrightened copper pyrophosphate baths for which they were originally proposed, they do not produce any noticeable effect in the presence of heterocyclic brighteners. This may be because the heterocyclic brighteners introduce such a striking improvement in the specular brightness and appearance of the work as completely to overide any effects of these previously known additives. Certainly these additives, such as citric acid, have not in commercial practice been used in conjunction with the more successful 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.
I have discovered that certain compounds may be used as auxiliary brighteners in conjunction with heterocyclic brighteners to provide higher levels of specular brightness with negligible tendency to step plating. 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.
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.
The 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. Also included among the classes of brighteners are 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). For example there may be used mercapto salts, or heterocyclic disulphides containing the grouping:
(III) The auxiliary brighteners for present use are for the most part acids which will normally be used as sodium, potassium, or ammonium salts.
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. As examples of 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.
Normally 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. Normally 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.
It is preferred that 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.
The invention is illustrated by the following examples wherein there were employed electrolytes of the following constitution:
Copper pyrophosphate 94 g/l, potassium pyrophosphate 300 g/l, ammonia 1 g/l. 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.
Tests were repeated with the three standard electrolytes containing the following auxiliary brighteners at a concentration of 10 ppm;
. 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.
It was found that Examples 1 to 9, when tested in an electrolyte containing no heterocyclic brightener, either gave no detectable improvement, or else were actually disadvantageous.
We claim:
1. In 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 effective to inhibit step plating.
2. The electrolyte of claim 1 wherein said 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.
3. The electrolyte of claim 2 wherein said auxiliary brightener is an adduct of maleic acid with a polyolephine having from 30 to carbon atoms.
4. The electrolyte of claim 3 wherein said polyolephine is polyisobutylene.
5. The electrolyte of claim 2 wherein said auxiliary brightener is sebacic acid.
6. The electrolyte of claim 2 brightener is azelaic acid.
7. The electrolyte of claim 2 brightener is suberic acid.
8. The electrolyte of claim 2 brightener is cinnamic acid.
9. The electrolyte of claim 2 brightener is aurine tricarboxylic acid.
10. The electrolyte of claim 2 wherein brightener is hydroxyethyl cellulose.
11. The electrolyte of claim 2 wherein brightener is iminodiacetic acid.
12. The electrolyte of claim 9 wherein brightener is malonic acid.
13. In a process for electrodepositing bright copper from an 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 carbon atoms, salts of the aforesaid acids and hydroxyethyl cellulose.
wherein said auxiliary wherein said auxiliary wherein said auxiliary wherein said auxiliary said auxiliary said auxiliary said auxiliary
Claims (12)
- 2. The electrolyte of claim 1 wherein said heterocyclic brightener is selected from the group consisting of 2-mercaptothiazole, 2-mercaptonbenzthiazole, 2-mercaptothiadiazole, 2-mercaptopyrimidines, and 2-mercapto iminazole, in a concentration of from 1 to 10 ppm, and wherein said auxiliary brightener is in a concentration of from 2 to 100 ppm.
- 3. The electrolyte of claim 2 wherein said auxiliary brightener is an adduct of maleic acid with a polyolephine having from 30 to 150 carbon atoms.
- 4. The electrolyte of claim 3 wherein said polyolephine is polyisobutylene.
- 5. The electrolyte of claim 2 wherein said auxiliary brightener is sebacic acid.
- 6. The electrolyte of claim 2 wherein said auxiliary brightener is azelaic acid.
- 7. The electrolyte of claim 2 wherein said auxiliary brightener is suberic acid.
- 8. The electrolyte of claim 2 wherein said auxiliary brightener is cinnamic acid.
- 9. The electrolyte of claim 2 wherein said auxiliary brightener is aurine tricarboxylic acid.
- 10. The electrolyte of claim 2 wherein said auxiliary brightener is hydroxyethyl cellulose.
- 11. The electrolyte of claim 2 wherein said auxiliary brightener is iminodiacetic acid.
- 12. The electrolyte of claim 9 wherein said auxiliary brightener is malonic acid.
- 13. In a process for electrodepositing bright copper from an 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 sufficient to form the complex salt X6Cu(P2O7)2, 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 carbon atoms, salts of the aforesaid acids and hydroxyethyl cellulose.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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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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Application Number | Title | Priority Date | Filing Date |
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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 |
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BE (1) | BE714454A (en) |
DE (1) | DE1771228C3 (en) |
ES (1) | ES353094A1 (en) |
FR (1) | FR1564283A (en) |
GB (1) | GB1235101A (en) |
NL (1) | NL6805947A (en) |
SE (1) | SE332744B (en) |
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JPS5167234A (en) * | 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 |
EP0442187B1 (en) * | 1990-02-16 | 1994-02-02 | 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 |
AU2003248060A1 (en) | 2003-07-11 | 2005-01-28 | Shishiai-Kabushikigaisha | Cooling fluid composition for fuel battery |
EP1698678A1 (en) * | 2003-12-25 | 2006-09-06 | Shishiai-Kabushikigaisha | Heat carrier composition |
WO2010055825A1 (en) * | 2008-11-11 | 2010-05-20 | ユケン工業株式会社 | Zincate zinc plating bath |
WO2010092579A1 (en) * | 2009-02-12 | 2010-08-19 | Technion Research & Development Foundation Ltd. | A process for electroplating of copper |
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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 |
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1967
- 1967-05-01 GB GB09989/67A patent/GB1235101A/en not_active Expired
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1968
- 1968-04-24 DE DE1771228A patent/DE1771228C3/en not_active Expired
- 1968-04-24 ES ES353094A patent/ES353094A1/en not_active Expired
- 1968-04-26 NL NL6805947A patent/NL6805947A/xx unknown
- 1968-04-30 FR FR1564283D patent/FR1564283A/fr not_active Expired
- 1968-04-30 SE SE05888/68A patent/SE332744B/xx unknown
- 1968-04-30 BE BE714454D patent/BE714454A/xx not_active IP Right Cessation
-
1970
- 1970-08-14 US US63954A patent/US3674660A/en not_active Expired - Lifetime
-
1971
- 1971-04-07 US US00132236A patent/US3729393A/en not_active Expired - Lifetime
- 1971-12-16 US US00209004A patent/US3784454A/en not_active Expired - Lifetime
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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)
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 (en) * | 2013-03-21 | 2013-06-26 | 山东金宝电子股份有限公司 | Mixed additive for removing internal stress of electrolytic copper foil and method for producing low-stress copper foil |
CN103173812B (en) * | 2013-03-21 | 2015-12-09 | 山东金宝电子股份有限公司 | A kind ofly eliminate the mixed additive of electrolytic copper foil internal stress and the method for the production of low-stress Copper Foil |
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 (en) | 1973-04-26 |
NL6805947A (en) | 1968-11-04 |
US3729393A (en) | 1973-04-24 |
SE332744B (en) | 1971-02-15 |
DE1771228B2 (en) | 1974-01-24 |
US3784454A (en) | 1974-01-08 |
GB1235101A (en) | 1971-06-09 |
FR1564283A (en) | 1969-04-18 |
BE714454A (en) | 1968-09-16 |
DE1771228C3 (en) | 1974-08-22 |
DE1796337A1 (en) | 1974-02-28 |
ES353094A1 (en) | 1969-10-01 |
DE1796337B2 (en) | 1976-09-02 |
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