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Publication numberUS3767539 A
Publication typeGrant
Publication dateOct 23, 1973
Filing dateOct 4, 1971
Priority dateOct 29, 1970
Also published asCA967110A1, DE2053860A1, DE2053860B2, DE2053860C3
Publication numberUS 3767539 A, US 3767539A, US-A-3767539, US3767539 A, US3767539A
InventorsClauss W, Todt H
Original AssigneeSchering Ag
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Acid galvanic copper bath
US 3767539 A
Abstract
Acid aqueous electrolytes for the deposition of bright, low-tension, ductile copper coatings containing organo selenium compounds are used.
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United States Patent Clauss et al.

{45] Oct. 23, 1973 ACID GALVANIC COPPER BATH lnventors: Wolfgang Clauss; Hans-Giinther Todt, both of Berlin, Germany Schering AG, Berlin and Bergkamen, Germany Filed: Oct. 4, 1971 Appl. No.: 186,548

Assignee:

Foreign Application Priority Data Oct. 29, 1970 Germany P 20 53 860.7

US. Cl. 204/52 R, 204/DIG. 2 2 Int. Cl C23!) 5/20 Field of Search 204/52 R, 52 Y, 44;

OTHER PUBLICATIONS H. Koretzky, IBM Tech. Disclosure Bulletin, Vol. 9, No. 11, Apr.l967.

Primary ExaminerG. L. Kaplan Attorney-Joseph F. Padlon [57] ABSTRACT Acid aqueous electrolytes for the deposition of bright, low-tension, ductile copper coatings containing organo selenium compounds are used.

5 Claims, No Drawings ACID GA-LVANIC COP-PER BATH The invention relates to an acid aqueous electrolyte for the deposition of bright, low-tension, ductile copper coatings.

It is known that certain organic substances can be added in small quantities to acid copper electrolytes, particularly the most widely used sulfuric acid types, in order to obtain bright copper coatings instead of a crystalline, dull deposition. There have been proposed for this-purpose chiefly organic thio compounds, such as thio-alkanosulfonic acids (German Pat. No. 1,037,801), derivatires of acid sulfur containing phosphorus derivatives (German Pat. No. 1,168,208, No. 1,196,464, No. 1,201,152), and organic sulfides containing at least one sulfonic acid in mixture or in chemical bond with a polyether (German Pat. application No. 1,521,062).

These thio compounds, however, often adversely affect the working of the acid electrolytes and the properties of the copper precipitates deposited therefrom. Thus, for example, in certain current density ranges the deposits turn out with black streaks due to the formation of copper sulfide, or there are deposited coatings having a high hardness or high internal'macro tensions, which show an inferior corrosion behavior, especially under mechanical stresses. Many of the organic thio compounds, moreover, are very critical in their proportioning and must be added to the electrolyte in a very narrow concentration range if coatings with constant properties are to be obtained.

The problem underlying the invention herein, therefore, is to prevent the formation of black, streaky depositions and to make possible the precipitation of lustrous, low tension and ductile copper depositions of high anti-corrosion value over a wide current density range.

This problem is solved according to the present invention by using an acid aqueous copper electrolyte which is characterized by a content of at least one compound of the general formula in which R and R are identical or different and represent possibly a monoor'multi-substituted aromatic, aliphatic, cycloaliphatic, araliphatic, or heterocyclic hydrocarbon radical, at least one of the two radicals containing a sulfonic acid group, or in whichR has the above-stated meaning and R represents the cyanide or the sulfonic acid group and n is equal to l or 2, or the salts thereof.

Especially suitable for this invention are, as additions, those compounds wherein the above general formula, R is phenyl, nitrophenyl, alkylphenyl, alkoxyphenyl, carboxyphenyl, carbmethoxyphenyl, dimethylaminophenyl, alkylmercaptophenyl, aminophenyl, alkyl containing preferably 2 to 8 carbon atoms, benzyl, phenoxyalkyl, sulfonlanyl, furyl, cyclohexylalkyl, pyridylalkyl, carboxyalkyl, dihydroxpropyl, sulfoalkyl containing preferably 2 to 6 carbon atoms, sulfophenyl, alkoxy-sulfophenyl, alkylmercapto-sulfophenyl, halogen-sulfophenyl, sulfonaphthyl, disulfonaphthyl or sulfophenyl-alkyl, R represents sulfoalkyl containing preferably 2 to 6 carbon atoms, sulfophenyl, alkoxysulfophenyl, alkylmercapto-sulfophenyl, halogensulfophenyl, sulfonaphthyl, disulfonaphthyl or sulfophenylalkyl, and n is 1 or 2, or in which R represents sulfoalkyl containing preferably 2 to 6 carbon atoms,

sulfophenyl, alkoxysulfophenyl, alkylmercaptosulfophenyl, halogen-sulfophenyl, sulfonaphthyl, disulfonaphthyl, sulfophenylalkyl, R represents the cyanide or the sulfonic acid group, and n is the number 1 The compounds to be used according to the invention are known in themselves or can be produced by methods known in themselves, as described for example in HOUBEN-WEYL Methoden der organischen Chemie, volume 9 (1955), pages 972 1002 and pages 1,086 1,099.

Thus the alkylor aryl-selenoalkylsulfonic acids can be prepared by reaction of the respective alkali selenolates with sulfoalkyl halides.

The symmetrical sulfoalkylor sulfoaryl-diselenides are formed, for example, by hydrolysis of the respective selenoxyanates of the alkali-alkyl-selenosulfates.

Alkylselenocyanates and, or, respectively, alkylselenosulfates are formed by reaction of alkyl halides with alkali-selenocyanates or selenosulfates.

Aromatic selenocyanates are formed by reaction of corresponding diazonium slats with alakliselenocyanates.

The characterized compounds are used as such or better in the form of their salts, e.g. the alkali, ammonium or amino salts. As an example there may be named the sodium, potassium, ammonium and triethylammonium salt. The following table lists compounds to be used according to the invention:

1. [K038 (OHzMzSez Di-(6-potassiumsulfohexyD- diselenide.

Di-(4p0tassiumsuliobutyD- diselenide.

Di-(3-potassiumsulfopropyD- diselenide.

Di-(3-sulfopr0pyl) diselenide.

5 [N H4038 (CH2)3]2$82 Di-(3-ammoniumsuliopropyD- diselenide.

Di-(3-triethylammoniumsulfopropyD- diselenide.

Di-(3-methyl-3- sodiumsulfopropyl); diselemde.

Di-(2-sodiumsulfoethyD- diselenide.

Di-(4-sodiumsulfophenyD- diselenide.

Di-(4-sodiumsulfophenyl)- diselenide.

Di-(3-sodiumsuliophenyD- diselenide.

(Naoasom) set NaOaS Se:

11 SO Na SOIaNa SiOaNa CHJS Di-(4-sodiumsulfo- 3-chlor-pheuyl)- diselenide.

ergo-@m-wmnsouc Hooc@se(o11msoma @OCHrCHzSMCHQaSOaNa mN--se(cm).soma

' @SeCHz-CH:SOzNa @sewnmsoma H CHr-SKCHzhSOaNfl CH2Se(CH2)aS sK Di-(7-sodiumsulfonaphthyi- 2)-disolonide.

Di-(6,8-disodiumsulfonaphthyi- 2)-diselenide.

phenyiselenoy propylsulionate of sodium.

-(p-nitrophenylseleno)-propylsulionate of potassium.

-(p-mothylphenylselen)-propyisulfonate of potassium.

-(p-methoxyphenylselen0)- propyisulfonate of potassium.

-(p-carboxyphenylseieno)-propyisuifonate of sodium.

-(benzyiseieno)- propylsulfonate of sodium.

henoxethylseleno)-propylsu1- fonate of sodium.

-(4-aminophen 1. 3O 4 seieno)-propylsulfonate of sodium.

3-(p-carbmethoxyphenylseleno)- propylsulfonate of potassium.

3-(p-dimethylaminophenylse- 1eno)-propy1- sulfonato of potassium.

2-(phenylseleno)- othyisulfonate of sodium.

4-(phenylseleno)- butylsulfonate of sodium.

3-(sulioianyiscleno)-propylsuifonato of potassium.

3-(iurylselono)- propyisulfonate of sodium.

3-(m-methylmercaptophenyi seleno)-propyisulfonate of potassium 3-(cyc1ohexyimethylseleno)-propy1- sulfonate of sodium.

3-(3-pyn'dylmethylseieno)-propyisulfonate of potassium.

Bis(4-sodiumsuifobutyD-selenide.

Bis-(3-sodiumsuifopropyD-seienide. Bis-(2-potassiumsulioethyD- seienide.

(ethylselono)- propylsulfonatc of sodium.

3-(propy1selono)- propylsulionato of sodium.

3-(octylscieno)- propylsulfonato of potassium.

3-(2-carboxyothylsolon0)-propylsulfonato of potassium.

3-(2,3-dihydroxypropylseieno)- propylsulfonate of potassium.

38.- C H Se(CHz);SO Na 30 CgHnSMCHDaSOaK As additives to be used according to the invention there are suitable also those compounds which contain, besides a sulfo group-containing organic radical at the selenium atom, the cyanide or the sulfonic acid group. These seleno-cyanates or selenosulfates split in the highly acid copper electrolytes to diselenides, which then constitute what are actually the active compounds. The following table lists some such selenocyanates and seleno-sulfates TABLE II p-(Sodiumsulfo)- benzyisolonocyanote.

NaOaS -CHzSeCN p-(Sodiumsuifo)- phenylsolenocyanato.

p-(Sodium sulfo)- benzylseionosulfonato of sodium.

7-(sodiumsuifo)-2- naphthylselenocyanato.

NaOsS- -SoCN NaOaS- SeCN S OaNfl 4-mcthoxy-3-sodiumsullo-phonylsclonocyanato.

CHaO- SeCN 14- S OaNa. 6,8-di-(sodiumsuiIo)-2- naphthylselenocyanate.

NaO S SeCN As electrolyte for the deposition of copper coatings with the addition of the substances according to the invention a sulfuric acid copper sulfate solution of the following composition is generally used:

Copper sulfate CuSO :5 H 125 to 2 60 g/liter Sulfuric acidT-IJSCQ 2010 85 gutter? Instead of copper sulfate, other copper salts may be used in toto or at least in part. The sulfuric acid may be replaced in part or entirely by fluoroboric acid, phosphoric acid and/or other acids. The electrolyte may be chloride-free or, and this is usually advantageous for improving the luster and the leveling, it may contain chlorides,such as alkali chlorides, or hydrochloric acid in quantities of from 0.001 to 0.2 g/liter.

The quantities in which the substances according to the invention must be added to the copper baths in order to achieve an improvement of the copper deposition are, surprisingly, very low and amount to about 0.0005 to 0.5 g/liter, preferably 0.0005 to 0.1 g/liter. With these additions one obtains a definite fining of the grain, in certain current density ranges even lustrous copper coatings.

The substances according to the invention are also especially suitable, in conjunction with other common luster-formers and/or wetting agents, for depositing high-luster coatings which show a great leveling of rugosities of the base material and yet are very ductile and possess a high extensibility.

As known additives which can be used together with the substances according to the invention there are suitable primarily oxygen-containing high-molecular compounds. The quantities of these substances that one adds to the copper electrolyte are about 0.01 to 20.0 g/liter, preferably 0.02 to 8.0 g/liter. Table III contains examples of oxygen-containing high-molecular compounds.

TABLE III Polyvinyl alcohol Carboxymethyl cellulose Polyethylene glycol Polypropylene glycol Stearic acid polyglycol ester Oleic acid polyglycol ester Stearyl alcohol polyglycol ether Nonylphenol-polyglycol ether Reaction products of alkylene oxides with amines. As additional compounds known in the art and which can be added to the copper electrolyte the following, for example, may be used:

Polymeric phenazonium compounds, polyalkyleni mines, polyvinylamines, polyvinylimidazol, polyvinylpyrrolidone, phenazine dyes as well as the organic thio-compounds already mentioned. The following examples will illustrate but not restrict the use of the substances according to the invention.

EXAMPLE 1 Copper sulfate (CuS0 .5H O) 220 g/liter Sulfuric acid, cone. 50 g/liter Di-(ILpotassiumsulfopropyl)-diselenide 0.05 g/liter Temperature: 25C Current density: 4.0 A/dm Stock is mixed by agitation EXAMPLE 2 Copper fluoroborate (Cu(BF 300 g/liter Fluoroboric acid 20 g/liter 2-(phenylseleno)-ethylsulfonate of sodium 03 g/liter Temperature: 25C Current density: 8.0 A/dm The electrolyte is agitated by injection of air EXAMPLE 3 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions Di-(3-sulfopropyl)diselenide Temperature: 22C

Current density: 4.0 A/dm" Stock is stirred or agitated EXAMPLE 4 Copper sulfate (CuSO .5H,O)

Sulfuric acid. conc.

Chloride ions Di-(3-potassiumsulfopropyl)-diselenide Polypropylene glycol Temperature: 26C

Current density: 5.0 A/dm The stock is mixed by injection of air EXAMPLE 5 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions Di-(d-sodiumsulfophenyl)-diselenide Monylphenol-polyglycol ether Temperature: 22C; Current desnity: 4.0

A/dm

Stock is agitated EXAMPLE 6 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions Di-(4-metl1oxy-3-sodiumsulfo-phenyl)- diselenide Polyethylene glycol Temperature: 22C

Current density: 5.0 A/dm The mixture is treated by injection of air EXAMPLE 7 Copper sulfate (CuSO .5H O) Sulfuric acid. conc.

Chloride ions S-(phenylseleno)-propylsulfonate of sodium Carboxymethyl cellulose Temperature: 22C

Current density: 3.0 A/dm The stock is agitated EXAMPLE 8 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions 3-(benzylseleno)-propylsulfonate of sodium omega-potassiumsulfohexylselenocyanate Polyethyleneglycol Temperature: 25C

Current density: 5.0 A/dm The mixture is treated by injection of air EXAMPLE 9 EXAMPLE 10 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions 3-(sulfolanylselen0)-pr0pylsulfonate of potassium Stearyl alcohol polyglycol ether Temeprature: 25C

Current density: 4.0 A/dm The stock is mixed by agitation or stirring 200 glliter 60 g/liter 0.03 g/liter 0.08 g/liter 220 g/liter 60 g/liter 0.05 g/liter 0.0] g/liter 0.5 g/liter 220 g/liter 60 g/liter 0.05 g/liter 0.03 g/liter 4.0 g/liter 220 g/liter 60 g/liter 0.02 g/liter 0.02 g/liter 0.2 g/liter g/liter 30 g/liter 0.03 g/liter 0.1 g/liter 0.1 g/liter 220 g/liter 50 g/liter 0.08 g/liter 0.01 g/liter 0.02 g/liter 0.0] g/liter 220 g/liter 30 g/liter 10 g/liter 0.05 g/liter 0.04 yjlilcl l .H g/litcr 220 g/liter 60 g/liter 0.05 g/liter 0.06 g/liter 1.5 g/liter EXAMPLE 11 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions 3-(m-methylmercaptophenylseleno)-propylsulfonate of potassium Stearyl alcohol polyglycol ether Temperature: 25C

Current desnity: 4.0 A/dm The stock is mixed by stirring EXAMPLE 12 Copper sulfate (CuSO .SH,O)

Sulfuric acid, conc.

Chloride ions Bis-(4-sodiumsulfobutyl)-selenide omega-potassium sulfohexylselenosulfonate of potassium Polypropylene glycol Temperature: 25C

Current density: 5.0 A/dm The ingredients are mixed by injection of air EXAMPLE 13 Copper sulfate (CuSO,.5H O) Sulfuric acid, conc.

Chloride ions 3-(ethyleseleno)-propylsulfonate of sodium Nonylphenol-polyglycol ether Temperature: 25C

Current density: 5.0 A/dm The stock is mixed by agitation EXAMPLE 14 Copper sulfate (CuSO .5 H O) Sulfuric acid, conc.

Chloride ions 3-(octylseleno)propylsulfonate of potassium Polypropylene glycol Temperature: 30C

Current density: 5.0 A/dm The stock is mixed by stirring EXAMPLE 15 Copper sulfate (CuSO,.5H O) Sulfuric acid, conc.

Chloride ions omega-potassiumsulfoethylselenocyanate Stearic acid polyglycol ester Temperature: 25C

Current density: 4.0 A/dm;

The ingredients are mixed by injection of air EXAMPLE 16 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions omega-potassiumsulfoethylselenosulfonate of potassium Polyethylene glycol Temperature: 25C

Current density: 5.0 A/dm The ingredients are mixed by injection of air EXAMPLE 17 Copper sulfate (CuSO .5H,O)

Sulfuric acid, conc.

Chloride ions omega-potassium sulfoethylselenosulfonate of potassium Nonylphenol polyglycol ether Temperature: 25C

Current desnity: 4.0 A/drn The ingredients are mixed by injection of air EXAMPLE 18 Copper sulfate (CuSO .5H O) Sulfuric acid, conc.

Chloride ions p-(sodiumsulfo)-benzylselenocyanate Nonylpenol-polyglycol ether Temperature: 20C

Current density: 3.0 A/drn The ingredients are mixed by injection of air 220 g/liter 60 g/liter 0.05 g/liter 0.02 glliter 1.5 g/liter 220 g/liter 60 glliter 0.05 g/liter 0.01 g/liter 0.01 g/liter 0.3 g/liter 220 g/liter 60 g/liter 0.03 g/liter 0.08 g/liter 1.03 g/liter 220 g/liter 60 g/liter 0.03 g/liter 0.1 g/liter 0.3 g/liter 220 g/liter 60 g/liter 0.05 g/liter 0.05 g/liter 2.0 g/liter 220 g/liter 60 g/liter 0.05 g/liter 0.02 g/liter 2.0 g/liter 220 g/liter 60 g/liter 0.04 g/liter 0.03 g/liter 1.0 g/liter 200 g/liter 50 g/liter 0.06 g/liter 0.06 g/liter 2.0 g/liter Temperature: 25C Current density: 5.0 A/dm The ingredients are mixed by injection of air What is claimed is:

1. In an acidic electrolyte for the electrodeposition of copper essentially consisting of water, sources of copper ions and of hydrogen ions, and a brightening composition in an amount sufficient to increase the luster of copper electrodeposited from said electrolyte, the improvement in said brightening composition which comprises at least one compound of the formula R (Se), R or a salt thereof, the amount of said compound or salt being between 0.0005 g and 0.5 g per liter of said electrolyte, in said formula R, and R being identical or different, R being a radical of monoor multi-substituted aromatic, aliphatic, cycloaliphatic, araliphatic, or heterocyclic hydrocarbon, R being a radical of a monoor multi-substituted aromatic, aliphatic, cycloaliphatic, araliphatic, or heterocyclic hydrocarbon, cyano or the sulfonic acid group, at least one of said R and R containing a sulfonic acid group, and n being 1 or 2.

2. In an electrolyte as set forth in claim 1, the amount of said at least one compound being not more than 0.1 g per liter of said electrolyte.

3. In an electrolyte as set forth in claim 1, said sources having respective anionic moieties selected from the group consisting of sulfate, fluoborate, and phosphate.

4. Electrolyte according to claim 1, wherein R, is phenyl, nitrophenyl, alkylphenyl, alkoxyphenyl, carboxyphenyl, carbmethoxyphenyl, dimethylaminophenyl), alkylmercaptophenyl, aminophenyl, alkyl containing from 2 to 8 carbon atoms, benzyl, phenoxyalkyl, sulfolanyl, furyl, cyclohexylalkyl, pyridylalkyl, carboxyalkyl, dihydroxypropyl, sulfoalkyl containing 2 to 6 carbon atoms, sulfophenyl, alkoxysulfophenyl, alkylmercapto-sulfophenyl, halogen-sulfophenyl, sulfonaphthyl, di-sulfonaphthyl or sulfophenyl-alkyl, R is sulfoalkyl containing 2 to 6 carbon atoms, sulfophenyl, alkoxysulfophenyl, alkylmercapto-sulfophenyl, halogen-sulfophenyl, sulfonaphthyl, disulfonaphthyl or sulfophenylalkyl.

5. An electrolyte according to claim 1, wherein R is sulfoalkyl containing 2 to 6 carbons atoms, sulfophenyl, alkoxysulfophenyl, alkylmercapto-sulfophenyl, halogen-sulfophenyl, sulfonaphthyl, disulfonaphthyl, sulfonphenylalkyl, R is the cyanide or the sulfonic acid group, and n is the number 1.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3492135 *Apr 11, 1967Jan 27, 1970Schering AgStabilized bath for deposition of copper by chemical reduction
US3502551 *Aug 10, 1967Mar 24, 1970Schering AgAcid electrolyte for the deposition of bright,levelling copper coatings
US3664852 *Dec 30, 1969May 23, 1972Hooker Chemical CorpElectroless copper plating solution and process
Non-Patent Citations
Reference
1 *H. Koretzky, IBM Tech. Disclosure Bulletin, Vol. 9, No. 11, Apr. 1967.
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4417956 *Sep 28, 1982Nov 29, 1983Electrochemical Products, Inc.Alkaline plating baths and electroplating process
US4540473 *Nov 22, 1983Sep 10, 1985International Business Machines CorporationCopper plating bath having increased plating rate, and method
US6024857 *Oct 8, 1997Feb 15, 2000Novellus Systems, Inc.Electroplating additive for filling sub-micron features
US6284121Jul 15, 1999Sep 4, 2001Novellus Systems, Inc.Additive molecules are absorbed by exterior surface relative to interior
US6518182 *Nov 13, 2000Feb 11, 2003Ebara-Udylite Co., Ltd.Via-filling process
EP1485522A1 *Mar 18, 2003Dec 15, 2004Taskem, Inc.High speed acid copper plating
Classifications
U.S. Classification205/298, 205/294, 205/296
International ClassificationC25D3/38
Cooperative ClassificationC25D3/38
European ClassificationC25D3/38