US2742413A - Bright copper plating bath - Google Patents

Bright copper plating bath Download PDF

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Publication number
US2742413A
US2742413A US348581A US34858153A US2742413A US 2742413 A US2742413 A US 2742413A US 348581 A US348581 A US 348581A US 34858153 A US34858153 A US 34858153A US 2742413 A US2742413 A US 2742413A
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US
United States
Prior art keywords
bath
copper
thiourea
plating bath
copper plating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US348581A
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English (en)
Inventor
Cransberg Rolf
Hendricus Andreas V Oosterhout
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
METALLIC INDUSTRY NV
N V Metallic Industry
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METALLIC INDUSTRY NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by METALLIC INDUSTRY NV filed Critical METALLIC INDUSTRY NV
Application granted granted Critical
Publication of US2742413A publication Critical patent/US2742413A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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

  • 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.
  • 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"
  • the invention is elucidated by the followingsiexarnpleszi' I Example I V
  • 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.
  • 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 III An acid copper bath of the following composition was prepared:
  • 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.
  • a bath according to claim 1, wherein said brightener is allylthiourea.
  • a bath according to claim 1, wherein said brightener is acetylthiourea.
  • a bath according to claim 1 hexamethylene tetramine.

Landscapes

  • 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)
US348581A 1952-07-05 1953-04-13 Bright copper plating bath Expired - Lifetime US2742413A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL2742412X 1952-07-05

Publications (1)

Publication Number Publication Date
US2742413A true US2742413A (en) 1956-04-17

Family

ID=19875526

Family Applications (2)

Application Number Title Priority Date Filing Date
US348582A Expired - Lifetime US2742412A (en) 1952-07-05 1953-04-13 Electrolytic deposition of copper
US348581A Expired - Lifetime US2742413A (en) 1952-07-05 1953-04-13 Bright copper plating bath

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US348582A Expired - Lifetime US2742412A (en) 1952-07-05 1953-04-13 Electrolytic deposition of copper

Country Status (4)

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US (2) US2742412A (US06623731-20030923-C00012.png)
BE (1) BE518440A (US06623731-20030923-C00012.png)
DE (2) DE940860C (US06623731-20030923-C00012.png)
NL (4) NL170871B (US06623731-20030923-C00012.png)

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
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
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 (de) * 1954-02-10 1957-04-25 Dehydag Gmbh Sparbeizmittel zum Schutze von Metallen bei der Behandlung mit sauren Mitteln
DE1007592B (de) * 1955-01-19 1957-05-02 Dehydag Gmbh Bad zur Herstellung von galvanischen Metallueberzuegen
US2853443A (en) * 1956-04-25 1958-09-23 Westinghouse Electric Corp Addition agent for acid copper electrolytes
BE565994A (US06623731-20030923-C00012.png) * 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
JPH02232391A (ja) * 1988-12-21 1990-09-14 Internatl Business Mach Corp <Ibm> アデイテイブ鍍金浴および方法
US6565729B2 (en) * 1998-03-20 2003-05-20 Semitool, Inc. Method for electrochemically depositing metal on a semiconductor workpiece
TW593731B (en) * 1998-03-20 2004-06-21 Semitool Inc Apparatus for applying a metal structure to a workpiece
US20100140098A1 (en) * 2008-05-15 2010-06-10 Solopower, Inc. Selenium containing electrodeposition solution and methods
JP2017503929A (ja) * 2013-11-25 2017-02-02 エンソン インコーポレイテッド 銅の電析

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 (US06623731-20030923-C00012.png) *
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 (US06623731-20030923-C00012.png) * 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
US6610191B2 (en) 1998-04-21 2003-08-26 Applied Materials, Inc. Electro deposition chemistry
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
US6571657B1 (en) 1999-04-08 2003-06-03 Applied Materials Inc. Multiple blade robot adjustment 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
US20030201184A1 (en) * 1999-04-08 2003-10-30 Applied Materials, Inc. Method and associated apparatus for tilting a substrate upon entry for metal deposition
US20020113039A1 (en) * 1999-07-09 2002-08-22 Mok Yeuk-Fai Edwin Integrated semiconductor substrate bevel cleaning apparatus and method
US20030213772A9 (en) * 1999-07-09 2003-11-20 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
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
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
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
NL84048C (US06623731-20030923-C00012.png)
NL81606C (US06623731-20030923-C00012.png)
BE518440A (US06623731-20030923-C00012.png)
DE940860C (de) 1956-03-29
DE962129C (de) 1957-04-18
NL170871B (nl)
US2742412A (en) 1956-04-17
NL170870B (nl)

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