US 3784454 A
Brightener compositions for aqueous copper pyrophosphate electroplating electrolyte consisting essentially of (1) a heterocyclic brightening additive selected from the group consisting of mercaptothiazoles, mercaptobenzthiazoles, mercaptothiadiazoles, mercaptopyrimidines, and mercaptoiminazoles, and (2) an auxiliary brightener selected from the group of step plating inhibitors consisting of imino diacetic acid, malonic acid, cinammic acid, aurine tricarboxylic acid, aliphatic dicarboxylic acids having at least seven carbon atoms, salts of the aforesaid acids and hydroxyethyl cellulose, said auxiliary brightener being in a proportion of from 3:1 to 3:4 based on the weight of said heterocyclic brightener.
Description (OCR text may contain errors)
United States Patent [191 Lyde [ Jan. 8, 1974 ADDITIVE FOR THE ELECTRODEPOSITION OF COPPER Derek Martin Lyde, Stourbridge, England  Assignee: Alhreght & Wilson Limited, Oldbury, near Birmingham, Warwickshire, England  Filed: Dec. 16, 1971  Appl. No.: 209,004
Related U.S. Application Data  Division of Ser. No. 63,954, Aug. 14, 1970, Pat. No. 3,674,660, which is a continuation-in-part of Ser. No. 724,225, April 25, 1968, abandoned.
 Foreign Application Priority Data May 1, 1967 Great Britain 19989/67  us. Cl. 204/52 R, 204/010. 2 511 int. Cl C23b 5/46 58 Field of Search 204/52 R, 52 Y, mo. 2,
204/43, 44, 45 R, 46, 47, 48, 49, 50 R, 50 Y, 53, 54 R, 54 L, 55 R, 55 Y  References Cited UNITED STATES PATENTS 2,700,019 l/l955 Jernstedt el: al 204/52 R Primary ExaminerG. L. Kaplan Attorney-Herbert H. Goodman 5 7] ABSTRACT Brightener compositions for aqueous copper pyro phosphate electroplating electrolyte consisting essen proportion of from 3:1 to 3:4 based on the weight of said heterocyclic brightener.
14 Claims, No Drawings 1 ADDITIVE FOR THE ELECTRODEPOSITION OF COPPER This is a division of application Ser. No. 63,954, filed Aug. 14, 1970, now US. Pat. No. 3,674,660 which in turn was a continuation-in-part of application Ser. No. 724,225, filed Apr. 25, 1968 and now abandoned.
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(P O-,) 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 finisheswhich 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 favour 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 =N- or -N- grouping) or a sulphur atom. Examples of these mercapto-heterocyclic compounds are described in UK. Specification 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 hydroxy-aliphatic 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 polarisation. 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. Cetainly 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 electro plating 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, Z-mercaptobenzthiazole, 2- mercaptothiadiazole, Z-mercaptopyrimidine, 2-
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(P 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 examplified: by the mercapto-thiazole compounds described in Specification No. 940,282, for example 2- mercapto- 1 3-thiazole and Z-mercapto-benthiazole; by the Z-mercapto-l, 3,4-thiadiazole compounds described in Specification No. 939,997, for example 2,5- 2-mercapto-5- methylmercapto-l,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 2-mercaptol -methyliminazole, 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:
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 watersoluble 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 alkonyl-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 0.00] grams per litre of the total weight of electrolyte and preferably from i to mg. per litre. The optimum concentration may vary from 2 to 4 mg. per litre 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 pyrphosphate as those conventionally employed, for example as described in the above-mentioned 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 ineffective. 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-l,3,4-thiadiazole, 6 ppm. 2- mercaptobenzimidazole and 10 ppm. 2- 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 Hull 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;
1. Cinnamic acid 2. Aurine tricarboxylic acid 3. Hydroxyethyl cellulose 4. lminodiacetic acid 5. Malonic acid 6. Sebacic acid 7. Azelaic acid 8. Suberic acid 9. Maleic anhydride/polyisobutylene adduct (Na salt) Oxalic acid Citric acid Tartaric acid Formic acid Acetic acid Propionic acid Benzoic acid Phthalic acid Examples 1 to 9 provided excellent specular brightness with improved levelling 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.
1. ln brightening compositions for addition to aqueous copper pyrophosphate electroplating solutions and consisting essentially of a heterocyclic brightener selected from the known group consisting of 2- mercaptothiazole, Z-mercaptobenzthiazole, 2- mercaptothiadiazole, 2-mercaptopyrimidines, 2- mercapto iminazole, substituted homologs of the aforesaid heterocyclic brighteners and derivatives which form the aforesaid compounds on dissolution in an aqueous copper pyrophosphate electroplating solution, the improvement which consists in that thebrightening composition contains, in addition to the heterocyclic brightener, an auxiliary brightener selected from the group of step plating inhibitors consisting of imino diacetic acid, malonic acid, cinammic acid, aliphatic dicarboxylic acids having at least seven carbon atoms, salts of the aforesaid acids and hydroxyethyl cellulose.
2. An improved brightening composition according to claim 1 wherein the auxiliary brightener is present in a proportion of from 3:1 to 3:4 based on the weight of heterocyclic brightener.
3. Brightener compositions for aqueous copper pyrophosphate electroplating electrolyte consisting essentially of 1 a heterocyclic brightening additive selected from the group consisting of mercaptothiazoles, mercaptobenzthiazoles, mercaptothiadiazoles, mercaptopyrimidines, and mercaptoiminazoles, and (2) an auxiliary brightener selected from the group of step plating inhibitors consisting of imino diacetic acid, malonic acid, cinammic acid, aurine tricarboxylic acid, aliphatic dicarboxylic acids having at least seven carbon atoms, salts of the aforesaid acids, an adduct of maleic acid with a polyolephine having from 30 to carbon atoms and hydroxyethyl cellulose, said auxiliary brightener being in a proportion of from 3:1 to 3:4 based on the weight of said heterocyclic brightener.
4. The brightener compositions of claim 3 wherein said heterocyclic brightener is selected from the group consisting of Z-mercaptothiazole, 2- mercaptobenzthiazole, Z-mercaptothiadiazoles, 2- mercaptopyrimidine, and Z-mercaptoiminazole.
5. The brightener compositions of claim 4 wherein said auxiliary brightener is an adduct of maleic acid with a polyolephine having from 30 to 150 carbon atoms.
6. The brightener compositions of claim 4 wherein said polyolephine is polyisobutylene.
7. The brightener compositions of claim 4 wherein said auxiliary brightener is sebacic acid.
said auxiliary brightener is maloniic acid.
. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,784 5 Dated January 8 1974 I Inventor) DEREK MARTIN LYDE It is certified that error appears in the above-identified patent and that said Letters Patent are hereby orrected as shown below:
In Column '5, line 1 3 "Claim 4" should be cla. 'i.m 5-.
Signedland sealed this 16th day of July 1974.
(SEAL) I Attest;
MCCOY M. GIBSON, JR. Q. MARSHALL DANN, I
Attesting Officer Commissioner ofPatents FORM PO-1050 (IO-69) USCOMM-DC 60376-PQ9 W 11.5. GOVERNMENT 'RINTING OFFICE: "ll 0-366-334,