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Bright copper plating bath

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Publication number
US2742413A
US2742413A US34858153A US2742413A US 2742413 A US2742413 A US 2742413A US 34858153 A US34858153 A US 34858153A US 2742413 A US2742413 A US 2742413A
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copper
bath
thiourea
acid
according
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Expired - Lifetime
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Cransberg Rolf
Hendricus Andreas V Oosterhout
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METALLIC INDUSTRY NV
N V Metallic Industry
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METALLIC INDUSTRY NV
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/38Electroplating: Baths therefor from solutions of copper

Description

Unitedtsratesfi Patent Claims priority, application Netherlands July5j1952 9 Claims. (ClIZM -SZ) The electrolytic deposition of copper is an operation. whichds appliedv very frequently.- in the. metal industry and is carried out either to embellish the surface of the treatedwbjects or to increase the corrosion resistance thereof," while the electro-de'posited" copper als'o serves as a base for a further treatment such-as the electrolytic depositionof nickel. ln'pra'ctice hig'hdemands are made on the appearance of the treated objects'so' that theseup" till now had to be ground and polished in an earlier-or later stageofthe'treatment which entails a number of operations, of whiehithe cost connect'ed therewith form a greatpart of the total cost of the surface:treatment,.theelectrolytic deposition of copper formsa-part of I Mdstelectfolyti'ci baths have the property that they do not fill up unevennesses in -the' metalsurface such as scratches and-the like but rather accentuate them, .and especially the baths for the electro-deposition of bright metal layers, from which a very fine crystalline metal deposit is precipitated, have the property that they, besides covering the uneven metal surface with a bright metal layer, also cover the unevennesses only with a thin layer, due to which the latter, although lustrous, remain visible in an undiminished degree.

It has now been found that the acid copper bath in so far makes a favorable exception on the baths, that it has some filling action, in other words, partially fills up gaps, pits and other unevennesses in the surface so that one aimed at improving the filling action of the copper bath, while maintaining other favorable properties such as the capacity to deposit a soft coating on the metal, etc.

It has been proposed to meet the above-described need by adding an organic substance to the copper bath. It is known e. g. from the U. S. P. 1,903,860 to add thiourea or a water-soluble derivative of thiourea, such as methylthiourea, to metal baths. It has been found, however, that the copper coating which is precipitated from the copper baths thus prepared, is very hard, so that it easily springs off on bending and moreover has a very small lustrous range which is considered as a very serious drawback of these baths. Moreover, the action of a copper bath containing exclusively thiourea as an organic compound decreases very soon. 7

It has now been found that a soft copper layer is obtained if the combination of thiourea or a water-soluble derivative of thiourea and a water-soluble heterocyclic nitrogen compound is added to an acid copper bath. The bath thus prepared displays moreover an excellent filling capacity and has a wide lustrous range.

According to the invention objects, particularly metal objects, are electrolytically provided with a copper deposit with the aid of an acid bath by using a bath con taining the combination of a water-soluble derivative of thiourea and a water-soluble heterocyclic nitrogen compound.

The invention extends to the preparation of an acid copper bath containing the combination of thiourea or a added tothe-bath in combination with the heterocyclic nitrogen compounds allyl thiourea is preferred as well" I 2,742,413 Patented Apr. 17,1956

water-soluble "derivative of thiourea and a water-soluble heterocyclic"nitrogencompound, as well'as to objects electrolyticallyprovided with a copper layer with the aidbf are bath:

Of themvatensoluble hetero'cyclic nitrogen compounds which are*used'in combinatiomwith thiourea or a watersoluble iderivative' of thiourea in theacid copper bath,

compoundsioflthe :xanthine group, particularly-the methyl 1 nonro1ogues'; --sueh as caffeine (l,3;7-trimethylxanthine),-

theophyllirie (1,3-dimethylxanthine) and" theobromine (3,f7-'dimethy1xanthine) are preferred," as well as hexa-=- methylene itetr'ami'ne; morpholine' and pyridine; as well as the ring systems, containing the pyridine nucleus,-=such as quinoline.

Of the'water-soluble thiourea derivatives -which are as acetylthiourea, ,while the thiourea itself, possible;

still exceeds in activity, these two. above-mentioned thiourea derivatives.

The invention is elucidated by the followingsiexarnpleszi' I Example I V Am -"acid copper batha of the following composition was preparedt cuso s aq.... a.;-fi.. ==a..a..agr/l 200 HaSQt. g. /Lt... ,Thiourea g 10 Pyridine mg./l 40 This bath was brought at a temperature of 30 C. and was kept in motion by blowing in a current of air. The anode was of copper. As the cathode a 50 cm. long iron tube with a diameter of 3.5 cm. and a wall thickness of 2 mm. was connected after it having been subjected as a short pretreatment in a cyanidic copper bath to a socalled copper strike" in which a copper layer of very slight thickness was deposited on the outer wall and on a small part of the inner surface adjacent to the ends. The cathode current density of the main treatment in 1 the acid copper bath according to the invention was adjusted to 8 a./dm. and in 20 minutes 32; of copper was deposited on the tube. The copper layer was soft and lustrous, and the numerous unevennesses originally present on the surface of the tube, had substantially disappeared after the electro-deposition of the copper in the above-described bath.

' Example II An acid copper bath of the following composition was prepared: 7

015045 aq g./l. 250 H2804 ..g./l 2,0 Ammonium sulphate g./l 20 Acetyl thiourea mg./1 20 Caffeine rng./l 50 In this bath an iron plate of 4.5 x 25 dm. was provided with a copper layer at a bath temperature of 25 C. and

Example III An acid copper bath of the following composition was prepared:

Copper fiuoborate ..g./l 400 Fluoboric acid g./l 50 Thiourea mg./l 12 Hexamethylene tetramine mg./l 800 An acid copper bath of the following composition was prepared:

CuSO4.5 aq g./l 250 H2804 g./l 20 Ammonium sulphate g./l 20 Allyl thiourea mg./l 20 Morpholine mg./l 45 A number of small iron plates of 6 x 6 cm. (thickness 0.2 cm.) which had been ground with emery beforehand were provided with a copper layer during 40 minutes at 26 C. in the above-mentioned bath which was kept in motion with air. The cathode current density amounted to 6 a./dm. and the duration of the treatment was 35 minutes. The thickness of the layer was 4211.,

but it is more important that nothing could be seen anymore of the grinding scratches originally present.

What is claimed is:

1. A bright copper plating bath comprising copper sulfate, sulfuric acid, a brightener in proportion of 5 to mg. per liter of solution, said brightener being selected from the group consisting of thiourea, allylthiourea and acetylthiourea, and a filler selected from the group consisting of xanthine and its methyl homologues, hexamethylene tetramine, pyridine and morpholine.

2. A bath according to claim 1, wherein said brightener is thiourea.

3. A bath according to claim 1, wherein said brightener is allylthiourea.

4. A bath according to claim 1, wherein said brightener is acetylthiourea.

5. A bath according to claim 1, wherein said filler is xanthine.

6. A bath according to claim 1, caffeine.

7. A bath according to claim 1, theobromine.

8. A bath according to claim 1, theophylline.

9. A bath according to claim 1, hexamethylene tetramine.

wherein said filler is wherein said filler is wherein said filler is wherein said filler is References Cited in the file of this patent UNITED STATES PATENTS 2,391,289 Beaver Dec. 18, 1945 2,700,020 Pierce Jan. 18, 1955 FOREIGN PATENTS 461,186 Canada Nov. 22, 1949

Claims (1)

1. A BRIGHT COPPER PLATING BATH COMPRISING COPPER SULFATE, SULFURIC ACID, A BRIGHTENER IN PORPORTION OF 5 TO 50 MG. PER LITER OF SOLUTION, SAID BRIGHTENER BEING SELECTED FROM THE GROUP CONSISTING OF THIOUREA, ALLYLTHIOUREA AND ACETYL.THIOUREA, AND A FILLER SELECTED FROM THE GROUP CONSISTING OF XANTHINE AND ITS METHYL HOMOLOGUES, HEXAMETHYLENE TETRAMINE, PYRIDINE AND MORPHOLINE.
US2742413A 1952-07-05 1953-04-13 Bright copper plating bath Expired - Lifetime US2742413A (en)

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US2742412A Expired - Lifetime US2742412A (en) 1952-07-05 1953-04-13 Electrolytic deposition of copper

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3075899A (en) * 1958-04-26 1963-01-29 Dehydag Gmbh Baths for the production of metal electroplates
US4009087A (en) * 1974-11-21 1977-02-22 M&T Chemicals Inc. Electrodeposition of copper
EP0952242A1 (en) * 1998-04-21 1999-10-27 Applied Materials, Inc. Electro deposition chemistry
US20020113039A1 (en) * 1999-07-09 2002-08-22 Mok Yeuk-Fai Edwin Integrated semiconductor substrate bevel cleaning apparatus and method
US6478937B2 (en) 2001-01-19 2002-11-12 Applied Material, Inc. Substrate holder system with substrate extension apparatus and associated method
US6551484B2 (en) 1999-04-08 2003-04-22 Applied Materials, Inc. Reverse voltage bias for electro-chemical plating system and method
US6571657B1 (en) 1999-04-08 2003-06-03 Applied Materials Inc. Multiple blade robot adjustment apparatus and associated method
US6576110B2 (en) 2000-07-07 2003-06-10 Applied Materials, Inc. Coated anode apparatus and associated method
US20030146102A1 (en) * 2002-02-05 2003-08-07 Applied Materials, Inc. Method for forming copper interconnects
US6610189B2 (en) 2001-01-03 2003-08-26 Applied Materials, Inc. Method and associated apparatus to mechanically enhance the deposition of a metal film within a feature
US20030201184A1 (en) * 1999-04-08 2003-10-30 Applied Materials, Inc. Method and associated apparatus for tilting a substrate upon entry for metal deposition
US20030201166A1 (en) * 2002-04-29 2003-10-30 Applied Materials, Inc. method for regulating the electrical power applied to a substrate during an immersion process
US20040020780A1 (en) * 2001-01-18 2004-02-05 Hey H. Peter W. Immersion bias for use in electro-chemical plating system
US20040200725A1 (en) * 2003-04-09 2004-10-14 Applied Materials Inc. Application of antifoaming agent to reduce defects in a semiconductor electrochemical plating process
US20040206628A1 (en) * 2003-04-18 2004-10-21 Applied Materials, Inc. Electrical bias during wafer exit from electrolyte bath
US6808612B2 (en) 2000-05-23 2004-10-26 Applied Materials, Inc. Method and apparatus to overcome anomalies in copper seed layers and to tune for feature size and aspect ratio
US20050092602A1 (en) * 2003-10-29 2005-05-05 Harald Herchen Electrochemical plating cell having a membrane stack
US20050092601A1 (en) * 2003-10-29 2005-05-05 Harald Herchen Electrochemical plating cell having a diffusion member
US6913680B1 (en) 2000-05-02 2005-07-05 Applied Materials, Inc. Method of application of electrical biasing to enhance metal deposition
US20060102467A1 (en) * 2004-11-15 2006-05-18 Harald Herchen Current collimation for thin seed and direct plating
US20060175201A1 (en) * 2005-02-07 2006-08-10 Hooman Hafezi Immersion process for electroplating applications

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE962489C (en) * 1954-02-10 1957-04-25 Dehydag Gmbh Sparbeizmittel for the protection of metals in the treatment with acid agents
DE1007592B (en) * 1955-01-19 1957-05-02 Dehydag Gmbh Bad for the production of galvanic Metallueberzuegen
US2853443A (en) * 1956-04-25 1958-09-23 Westinghouse Electric Corp Addition agent for acid copper electrolytes
BE565994A (en) * 1957-04-16
US2931760A (en) * 1957-09-25 1960-04-05 Leon R Westbrook Acid copper plating
US3770599A (en) * 1971-05-24 1973-11-06 Oxy Metal Finishing Corp Acid zinc plating baths
US4474649A (en) * 1982-06-21 1984-10-02 Asarco Incorporated Method of thiourea addition of electrolytic solutions useful for copper refining
JPH0317914B2 (en) * 1988-12-21 1991-03-11 Intaanashonaru Bijinesu Mashiinzu Corp
WO1999047731A1 (en) * 1998-03-20 1999-09-23 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US6565729B2 (en) * 1998-03-20 2003-05-20 Semitool, Inc. Method for electrochemically depositing metal on a semiconductor workpiece
US20100140098A1 (en) * 2008-05-15 2010-06-10 Solopower, Inc. Selenium containing electrodeposition solution and methods
WO2015077772A1 (en) * 2013-11-25 2015-05-28 Enthone Inc. Electrodeposition of copper

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
CA461186A (en) * 1949-11-22 John Franklin Beaver, Jr. Bright copper plating
US2700020A (en) * 1952-06-02 1955-01-18 Houdaille Hershey Corp Plating copper

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA477508A (en) * 1951-10-02 Brown Henry Electrodeposition of nickel from acid baths
DE104111C (en) *
US2196588A (en) * 1937-05-26 1940-04-09 Du Pont Electroplating
US2315802A (en) * 1940-04-20 1943-04-06 Harshaw Chem Corp Nickel plating
US2389179A (en) * 1941-02-21 1945-11-20 Udylite Corp Electrodeposition of metals
US2489538A (en) * 1941-05-24 1949-11-29 Gen Motors Corp Electrodeposition of copper
US2355505A (en) * 1941-10-03 1944-08-08 Purdue Research Foundation Electrodeposition of bright zinc
US2462870A (en) * 1942-07-09 1949-03-01 Gen Motors Corp Electrodeposition of copper
US2472393A (en) * 1944-09-25 1949-06-07 American Steel & Wire Co Process and bath for copper coating ferrous metal
BE504701A (en) * 1950-07-17

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA461186A (en) * 1949-11-22 John Franklin Beaver, Jr. Bright copper plating
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
US2700020A (en) * 1952-06-02 1955-01-18 Houdaille Hershey Corp Plating copper

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3075899A (en) * 1958-04-26 1963-01-29 Dehydag Gmbh Baths for the production of metal electroplates
US4009087A (en) * 1974-11-21 1977-02-22 M&T Chemicals Inc. Electrodeposition of copper
EP0952242A1 (en) * 1998-04-21 1999-10-27 Applied Materials, Inc. Electro deposition chemistry
US6113771A (en) * 1998-04-21 2000-09-05 Applied Materials, Inc. Electro deposition chemistry
US6350366B1 (en) 1998-04-21 2002-02-26 Applied Materials, Inc. Electro deposition chemistry
US20030205474A1 (en) * 1998-04-21 2003-11-06 Applied Materials, Inc. Electro deposition chemistry
US6610191B2 (en) 1998-04-21 2003-08-26 Applied Materials, Inc. Electro deposition chemistry
US6551484B2 (en) 1999-04-08 2003-04-22 Applied Materials, Inc. Reverse voltage bias for electro-chemical plating system and method
US6571657B1 (en) 1999-04-08 2003-06-03 Applied Materials Inc. Multiple blade robot adjustment apparatus and associated method
US20030201184A1 (en) * 1999-04-08 2003-10-30 Applied Materials, Inc. Method and associated apparatus for tilting a substrate upon entry for metal deposition
US20030213772A9 (en) * 1999-07-09 2003-11-20 Mok Yeuk-Fai Edwin Integrated semiconductor substrate bevel cleaning apparatus and method
US20020113039A1 (en) * 1999-07-09 2002-08-22 Mok Yeuk-Fai Edwin Integrated semiconductor substrate bevel cleaning apparatus and method
US6913680B1 (en) 2000-05-02 2005-07-05 Applied Materials, Inc. Method of application of electrical biasing to enhance metal deposition
US6808612B2 (en) 2000-05-23 2004-10-26 Applied Materials, Inc. Method and apparatus to overcome anomalies in copper seed layers and to tune for feature size and aspect ratio
US6576110B2 (en) 2000-07-07 2003-06-10 Applied Materials, Inc. Coated anode apparatus and associated method
US6610189B2 (en) 2001-01-03 2003-08-26 Applied Materials, Inc. Method and associated apparatus to mechanically enhance the deposition of a metal film within a feature
US20040020780A1 (en) * 2001-01-18 2004-02-05 Hey H. Peter W. Immersion bias for use in electro-chemical plating system
US6478937B2 (en) 2001-01-19 2002-11-12 Applied Material, Inc. Substrate holder system with substrate extension apparatus and associated method
US20030146102A1 (en) * 2002-02-05 2003-08-07 Applied Materials, Inc. Method for forming copper interconnects
US6911136B2 (en) 2002-04-29 2005-06-28 Applied Materials, Inc. Method for regulating the electrical power applied to a substrate during an immersion process
US20030201166A1 (en) * 2002-04-29 2003-10-30 Applied Materials, Inc. method for regulating the electrical power applied to a substrate during an immersion process
US20040200725A1 (en) * 2003-04-09 2004-10-14 Applied Materials Inc. Application of antifoaming agent to reduce defects in a semiconductor electrochemical plating process
US20040206628A1 (en) * 2003-04-18 2004-10-21 Applied Materials, Inc. Electrical bias during wafer exit from electrolyte bath
US20050092601A1 (en) * 2003-10-29 2005-05-05 Harald Herchen Electrochemical plating cell having a diffusion member
US20050092602A1 (en) * 2003-10-29 2005-05-05 Harald Herchen Electrochemical plating cell having a membrane stack
US20060102467A1 (en) * 2004-11-15 2006-05-18 Harald Herchen Current collimation for thin seed and direct plating
US20060175201A1 (en) * 2005-02-07 2006-08-10 Hooman Hafezi Immersion process for electroplating applications

Also Published As

Publication number Publication date Type
DE940860C (en) 1956-03-29 grant
BE518440A (en) grant
NL170870B (en) application
NL170871B (en) application
US2742412A (en) 1956-04-17 grant
NL81606C (en) grant
NL84048C (en) grant
DE962129C (en) 1957-04-18 grant

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