US2742412A - Electrolytic deposition of copper - Google Patents

Electrolytic deposition of copper Download PDF

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Publication number
US2742412A
US2742412A US348582A US34858253A US2742412A US 2742412 A US2742412 A US 2742412A US 348582 A US348582 A US 348582A US 34858253 A US34858253 A US 34858253A US 2742412 A US2742412 A US 2742412A
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US
United States
Prior art keywords
copper
thiourea
bath
group
water
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
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US348582A
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English (en)
Inventor
Cransberg Rolf
Hendricus Andreas Va Osterhout
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METALLIC INDUSTRY NV
N V Metallic Industry
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METALLIC INDUSTRY NV
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Publication of US2742412A publication Critical patent/US2742412A/en
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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 electrolytic deposition of copper is an operation which is applied very frequently in the metal industry and is carried out either to embellish the surface of the treated objects, or to increase the corrosion resistance thereof, while the electro-deposited copper also serves as a base for a further treatment such as the electrolytic ers mostly do cover the unevennesses in the metal surface but do not fill them up, so that they, although lustrous, yet remain visible.
  • the acid copper bath in so far makes a favorable exception that it has some filling action, but the copper baths proposed up till now do not have the combination of an excellently filling activity and the capacity of depositing a lustrous, soft copper layer.
  • objects are .electrolytically provided with a copper deposit with the aid of an acid bath by using a bath containing the combination of a substance selected from the group consisting of thiourea and the water-soluble derivatives of thiourea, and a substance selected from the group consisting of the water-soluble di or trivalent a1- cohols. and the water-soluble derivatives thereof.
  • the invention extends to the preparation of an acid copper bath containing the combination of a substance selected from the group consisting of thiourea and the water-soluble derivatives of thiourea, and a substance se- 2,742,412 Patented Apr. :17," 1956 di and trivalent alcohols and the water-soluble derivatives thereof, as-well as the objects electrolytically provided with a copper layer with the aid of the bath.
  • glycerol is preferred, while ethylene glycol monoethyl ether and diethylene glycol monobutyl ether as derivatives of the bivalent alcohols ethylene glycol and diethylene glycol are preferred, because the former of these two com pounds very much improves the adherence to the base and the latter excells by the combination of lustre and filling up capacity of the bath.
  • thiourea derivatives used in combination with the di or trivalent alcohols particularly allylthiourea and acetyl thiourea are preferred, while thiourea itself, if possible, still exceeds in activity these two derivatives.
  • the invention is elucidated by the following exam ples':
  • Example I An acid copper bath of the following composition was prepared:
  • Example II To the acid copper bath of Example I instead of the thiourea as much allylthiourea and instead of the glycerol mg./l. ethylene glycol monoethyl ether were added. A similar tube as in Example I was electrolytically provided with a copper layer in this bath. The
  • Example III sulfate, sulfuric acid, a brightener in a proportion of 5- 50 mgQ/liter, said brightener being selected from the group consisting of thiourea, allylthiourea and acetyl thiourea, and a filler selected fromthe group consisting of glycerol, glycol, ethylene glycol mono ethyl ether and diethylene glycol mono butyl ether.
  • a bath according to claim 1, wherein said filler is diethylene glycol mono butyl ether.

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  • 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)
US348582A 1952-07-05 1953-04-13 Electrolytic deposition of copper Expired - Lifetime US2742412A (en)

Applications Claiming Priority (1)

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

Publications (1)

Publication Number Publication Date
US2742412A true US2742412A (en) 1956-04-17

Family

ID=19875526

Family Applications (2)

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

Family Applications Before (1)

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

Country Status (4)

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US (2) US2742413A (US06623731-20030923-C00012.png)
BE (1) BE518440A (US06623731-20030923-C00012.png)
DE (2) DE940860C (US06623731-20030923-C00012.png)
NL (4) NL84048C (US06623731-20030923-C00012.png)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2853443A (en) * 1956-04-25 1958-09-23 Westinghouse Electric Corp Addition agent for acid copper electrolytes
US2903403A (en) * 1954-02-10 1959-09-08 Dehydag Gmbh Method of copper-plating metal surfaces
US2910413A (en) * 1955-01-19 1959-10-27 Dehydag Gmbh Brighteners for electroplating baths
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
EP0375180A2 (en) * 1988-12-21 1990-06-27 International Business Machines Corporation Additive plating bath and process
EP1064417A1 (en) * 1998-03-20 2001-01-03 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US20050245083A1 (en) * 1998-03-20 2005-11-03 Semitool, Inc. Apparatus and 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

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE565994A (US06623731-20030923-C00012.png) * 1957-04-16
NL238490A (US06623731-20030923-C00012.png) * 1958-04-26
US4009087A (en) * 1974-11-21 1977-02-22 M&T Chemicals Inc. Electrodeposition of copper
US6113771A (en) * 1998-04-21 2000-09-05 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
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
WO2001090446A2 (en) 2000-05-23 2001-11-29 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
EP1470268A2 (en) * 2000-10-03 2004-10-27 Applied Materials, Inc. Method and associated apparatus for tilting a substrate upon entry for metal deposition
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
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
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
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2389179A (en) * 1941-02-21 1945-11-20 Udylite Corp Electrodeposition of metals
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
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

Family Cites Families (9)

* 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
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
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
BE504701A (US06623731-20030923-C00012.png) * 1950-07-17
US2700020A (en) * 1952-06-02 1955-01-18 Houdaille Hershey Corp Plating copper

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2389179A (en) * 1941-02-21 1945-11-20 Udylite Corp Electrodeposition of metals
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
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

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2903403A (en) * 1954-02-10 1959-09-08 Dehydag Gmbh Method of copper-plating metal surfaces
US2910413A (en) * 1955-01-19 1959-10-27 Dehydag Gmbh Brighteners for electroplating baths
US2853443A (en) * 1956-04-25 1958-09-23 Westinghouse Electric Corp Addition agent for acid copper electrolytes
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
EP0375180A2 (en) * 1988-12-21 1990-06-27 International Business Machines Corporation Additive plating bath and process
EP0375180A3 (en) * 1988-12-21 1991-01-30 International Business Machines Corporation Additive plating bath and process
EP1064417A1 (en) * 1998-03-20 2001-01-03 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US20050139478A1 (en) * 1998-03-20 2005-06-30 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US20050150770A1 (en) * 1998-03-20 2005-07-14 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US20050173252A1 (en) * 1998-03-20 2005-08-11 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US20050245083A1 (en) * 1998-03-20 2005-11-03 Semitool, Inc. Apparatus and method for electrochemically depositing metal on a semiconductor workpiece
EP1064417A4 (en) * 1998-03-20 2006-07-05 Semitool Inc DEVICE AND METHOD FOR THE ELECTROLYTIC COATING OF COPPER TO A SEMICONDUCTOR WORKPIECE
US7332066B2 (en) 1998-03-20 2008-02-19 Semitool, Inc. Apparatus and 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
CN105917032A (zh) * 2013-11-25 2016-08-31 乐思股份有限公司 铜的电沉积

Also Published As

Publication number Publication date
DE940860C (de) 1956-03-29
BE518440A (US06623731-20030923-C00012.png)
DE962129C (de) 1957-04-18
US2742413A (en) 1956-04-17
NL84048C (US06623731-20030923-C00012.png)
NL170870B (nl)
NL170871B (nl)
NL81606C (US06623731-20030923-C00012.png)

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