US3878066A - Bath for galvanic deposition of gold and gold alloys - Google Patents

Bath for galvanic deposition of gold and gold alloys Download PDF

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Publication number
US3878066A
US3878066A US394959A US39495973A US3878066A US 3878066 A US3878066 A US 3878066A US 394959 A US394959 A US 394959A US 39495973 A US39495973 A US 39495973A US 3878066 A US3878066 A US 3878066A
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Prior art keywords
bath
gold
grams per
per liter
group
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US394959A
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Manfred Dettke
Karl-Hans Fuchs
Rolf Ludwig
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FUCHS KARL#HANS
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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
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/62Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • 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
    • C25D3/48Electroplating: Baths therefor from solutions of gold

Definitions

  • the invention relates to a bath for the galvanic deposition of gold coatings and gold alloy coatings, containing a combination of organic compounds on a base of aldehydes and nitrogen compounds with arsenic compounds.
  • an object of the present invention to avoid the disadvantages of the known electrolytes and to provide galvanic baths from which smooth coatings of gold and the alloys can be deposited.
  • a bath which is characterized by a content of t A. at least one compound of the general formula R CHO in which R signifies hydrogen, methyl or the group -CHO, or one of its addition compounds and B. at least one compound of the general formula in which the radicals R are identical or different and represent hydrogen, possibly alkyl substituted by hydroxy groups with preferably 1 to 4 carbon atoms or aryl and R alkylidene radicals with preferably 1 to 5 carbon atoms, in and n being or representing integers from 1 to 3, or one of their salts and C. at least one alkali salt of arsenic or arsenous acid,
  • radicals R signify for example methyl, ethyl, propyl, butyl or isobutyl
  • the radicals R signify methylene, ethylidene, propylidene, butylidene, pentylidene and the like, the alkyl radicals being preferably substituted with up to 2 hydroxy groups.
  • the components (A), (B) and (C) seem to influence each other synergistically in the bath, for when used alone they are completely ineffective.
  • concentrations required for a high-gloss gold deposition or a chromatic gold alloy deposition are, for the aldehydes, i.e., component A, about 0.005 to 50 g/liter, for the nitrogen compounds, i.e., component B, about 0.1 to 50 g/liter, and for the arsenic compounds, i.e., component C, about 0.001 to g/liter.
  • aldehyde components there are suitable preferably formaldehyde, acetaldehyde and glyoxal, which can be used per se or in the form of their addition compounds, i.e., as bisulfites.
  • Nitrogen compounds that are especially suitable are hydrazine or methyl hydrazine, which are to be used according to invention either by themselves or in the form of their salts, such as the chlorides or sulfates, or alone or in a mixture with one another.
  • hydrazine or methyl hydrazine which are to be used according to invention either by themselves or in the form of their salts, such as the chlorides or sulfates, or alone or in a mixture with one another.
  • prropyl hydrazine as well as phenyl hydrazine and the substitution products thereof and their salts have proved to be suitable.
  • nitrogen compounds that may be used according to the invention are, for example, N-(3-propy1- 5 l,2-diol)-diethylene triamine, triethylene tetramine,
  • ethylene diamine, diethylene triamine, triethylenetetramine and tetraethylene pentamine of which the first two in particular have been found to be very favorable with respect to their smoothing action.
  • these compounds can be used by themselves as such, as well as in the form of their salts, for example, the chlorides or acetates.
  • Suitable arsenic compounds that are effective are the alkali salts of arsenic and arsenous acid, such as sodium and potassium arsenate or arsenite.
  • an aqueous solution which contains a water-soluble gold salt, preferably a complex compound of gold, in particular potassium dicyanoaurate (I), in concentrations of about 1 to 50 g/liter.
  • a water-soluble gold salt preferably a complex compound of gold, in particular potassium dicyanoaurate (I), in concentrations of about 1 to 50 g/liter.
  • 1f gold alloy coatings are to be deposited, there are added to the bath the alloy metals silver, copper, zinc, cadmium, manganese, cobalt, nickel, palladium, indium, antimony 'or tin, in the form of their watersoluble compounds, preferably in the form of the complex compounds, such as the chelate or the cyano complexes, in total concentrations of about 0.01 to 200 g/liter.
  • the alloy metals silver, copper, zinc, cadmium, manganese, cobalt, nickel, palladium, indium, antimony 'or tin, in the form of their watersoluble compounds, preferably in the form of the complex compounds, such as the chelate or the cyano complexes, in total concentrations of about 0.01 to 200 g/liter.
  • the complex compounds such as the chelate or the cyano complexes
  • the bath contains boric acid and a polyvalent alcohol, preferably ethylene glycol, namely more particularly in a ratio by weight of about 1:1 to 1:2 and in a concentration of about to 200 g/liter of boric acid or of about 10 to 2000 g/liter of alcohol.
  • a polyvalent alcohol preferably ethylene glycol
  • the bath may contain common conducting salts, for example ammonium sulfate or alkali salts of sulfuric acid, nitric acid or hydrochloric acid, pH-regulating substances, appropriately the organic and/or inorganic buffer mixtures commonly used for this purpose such as, mixtures of citric acid and potassium citrate or sodium hydrophosphate and sodium dihydrophosphate as well as surface-active substances, such as ethylhexylsu lfate and N- ethoxyhexylamine.
  • common conducting salts for example ammonium sulfate or alkali salts of sulfuric acid, nitric acid or hydrochloric acid, pH-regulating substances, appropriately the organic and/or inorganic buffer mixtures commonly used for this purpose such as, mixtures of citric acid and potassium citrate or sodium hydrophosphate and sodium dihydrophosphate as well as surface-active substances, such as ethylhexylsu lfate and N- ethoxyhexylamine.
  • the pH value of the bath may .be from about 5 to 10, preferably 6.8 to 7.5. It is operated appropriately at temperatures of about to 70 C, preferably at temperatures between to C, current densities from about 0.1 to 5 amp.dm being used.
  • the bath according to the invention is suitable in particular for the galvanic deposition of high-gloss gold coatings and chromatic gold alloy coatings with excellent smoothing appearance.
  • Another advantage of the invention consists in the extraordinary adhesion of the coatings, which, surprisingly, far exceeds that of the coatings produced by the usual, known methods.
  • the lead containing brass alloy which is very difficult to galvanize or plate, can be gold plated directly without the previous deposition of an intermediate layer by means of the bath according to this invention resulting in a substantial saving of material and time.
  • bath of the invention permits the use of high current densities and at good current efficiency shorter exposure times, whence special advantages result for the practice.
  • pH value 6.8 which is adjusted with sulfuric acid
  • Applicable current density from 0.1 to maximum 2.0 amp.dm Temperature: to 70 C
  • This electrolyte composition according to the invention is suitable for the deposition of nearly 24 carat gold.
  • the coatings deposited from this electrolyte are of high luster, saturated gold color, and have a hardness of about 170 microvickers.
  • lead containing brass With the electrolyte, lead containing brass can be proviced, without an intermediate layer, with a gold coating which is of high luster from about 8 micron on.
  • EXAMPLE 2 g/liter Potassium dicyanoaurate (l), K(Au(CN) 12.0 Ammonium sulfate, (NHQ SO 70.0 Boric acid, H 30 40.0 Ethylene glycol, HOCH -CH OH 80.0 Copper sulfate, CuSO '5 H O 8.0 Ethylene diamine tetraceticacid dipotassium salt 9.5 Formaldehyde, CH O 5.0 Hydrazine hydrate N H 'H O 12.0 Sodium arsenite, Na ASO 0.045
  • carat coatings By means of this electrolyte, about 18 carat coatings can be deposited, which have the color of rolled gold.
  • the coatings are of high gloss and tarnish resistant.
  • Applicable current density From 0.1 to 1.5 amp/dm Temperature: 20 to 60 C Rate of deposition at l amp.dm 1 micron in 4 minutes. Intensive agitation of electrolyte or cathode is effected.
  • Thiselectrolyte furnishes light yellow, about 20 carat coatings.
  • the coatings deposited from this electrolyte are high gloss and tarnish resistant.
  • Applicable current density from 0.2 to 1.0 amp/dm Temperature: 20 to C
  • the rate of deposition at l amp/dm is 1 micron in 8 minutes.
  • This electrolyte furnishes almost white, high-gloss coatings.
  • the deposited alloy is approximately 16 carat.
  • EXAMPLE 5 g/liter Potassium dicyanoaurate (l), K(Au(CN 15.0 Ammonium sulfate, (NH SO 80.0 Boric acid, H BO 50.0 Ethylene glycol, HOCH CH OH 100.0 Cobalt sulfate, CoSo '7H- O 3.0 Nickel sulfate NiSO '7l-l O 2.0 lndium sulfate, ln (SO.,);, 0.5 Methyl hydrazine CH -NHNH 0.1 Ethylene diamine tetracetic acid dipotassium salt 6.0 Formaldehyde, CH O 3.0 Sodium arsenite, Na;,AsO 0.3
  • Applicable current density from 0.1 to 2.5 amp/dm Temperature: 20 to 35 C Rate of deposition at 2 amp/dm: 1 micron in 2 minutes According to the invention an alloy of good electrical properties and excellent abrasive strength can be deposited with this bath.
  • the coatings are of high gloss and have a fineness of 23 carat.
  • the current efficiency is 40 to 60%.
  • the content of alloy metals can be greatly influenced by varying the current density and the speed of goods or by electrolyte agitation. From a layer thickness of about 5 micron on, a smoothing effect can already be observed.
  • An aqueous bath for the electrodeposition of gold or gold alloys having a high gloss said bath having a pH of from about 5 to 10 and an amount of components,-
  • A, B and C to provide a coating having high gloss and extraordinary adhesion said bath comprising A. from about 0.005 to 50 grams per liter of at least one compound of the general formula RCHO wherein R is selected from the group consisting of hydrogen, methyl, and the group CH0, and an aldehyde bisulfite addition compound thereof, and B. from about 0.1 to 50 grams per liter of at least one compound of the general formula R N(R'NR- ),,,--(R),,- NR in which each R is selected from the group consisting of hydrogen, alkyl having from 1 to 5 carbon atoms and hydroxy-substituted alkyl having from 1 to 5 carbon atoms, in and n is 0 or an integer from 1 to 3, and C. from about 0.001 to 5 grams per liter of at least one alkali metal salt of a member of the group consisting of arsenic acid and arsenious acid, and
  • a bath adding to claim 1 which contains about ID to 200 grams per liter of boric acid and about to 200 grams per liter of a polyvalent alcohol, the ratio of boric acid to polyvalent alcohol being from about lzl to about 1:2, by weight.
  • a bath according to claim 2 wherein the polyvalent alcohol is ethylene glycol.

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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)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Physical Vapour Deposition (AREA)
  • Chemically Coating (AREA)
US394959A 1972-09-06 1973-08-29 Bath for galvanic deposition of gold and gold alloys Expired - Lifetime US3878066A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2244434A DE2244434C3 (de) 1972-09-06 1972-09-06 Wäßriges Bad zur galvanischen Abscheidung von Gold und Goldlegierungen

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AU (1) AU469094B2 (US20100154141A1-20100624-C00001.png)
BE (1) BE804544A (US20100154141A1-20100624-C00001.png)
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CH (1) CH594746A5 (US20100154141A1-20100624-C00001.png)
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Cited By (44)

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US4062736A (en) * 1974-11-15 1977-12-13 Oxy Metal Industries Corporation Gold and gold alloy deposition
US4207149A (en) * 1974-12-04 1980-06-10 Engelhard Minerals & Chemicals Corporation Gold electroplating solutions and processes
US5024733A (en) * 1989-08-29 1991-06-18 At&T Bell Laboratories Palladium alloy electroplating process
EP1064417A1 (en) * 1998-03-20 2001-01-03 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US6197181B1 (en) 1998-03-20 2001-03-06 Semitool, Inc. Apparatus and method for electrolytically depositing a metal on a microelectronic workpiece
US20010032788A1 (en) * 1999-04-13 2001-10-25 Woodruff Daniel J. Adaptable electrochemical processing chamber
US6319387B1 (en) * 1998-06-30 2001-11-20 Semitool, Inc. Copper alloy electroplating bath for microelectronic applications
US6334937B1 (en) 1998-12-31 2002-01-01 Semitool, Inc. Apparatus for high deposition rate solder electroplating on a microelectronic workpiece
US20020022363A1 (en) * 1998-02-04 2002-02-21 Thomas L. Ritzdorf Method for filling recessed micro-structures with metallization in the production of a microelectronic device
US6365033B1 (en) 1999-05-03 2002-04-02 Semitoof, Inc. Methods for controlling and/or measuring additive concentration in an electroplating bath
US20020053509A1 (en) * 1996-07-15 2002-05-09 Hanson Kyle M. Processing tools, components of processing tools, and method of making and using same for electrochemical processing of microelectronic workpieces
US20020084183A1 (en) * 2000-03-21 2002-07-04 Hanson Kyle M. Apparatus and method for electrochemically processing a microelectronic workpiece
US20020084195A1 (en) * 1998-05-01 2002-07-04 Chen Linlin Automated chemical management system executing improved electrolyte analysis method
US20020112970A1 (en) * 1998-05-01 2002-08-22 Graham Lyndon W. Automated chemical management system having improved analysis unit
US20020125141A1 (en) * 1999-04-13 2002-09-12 Wilson Gregory J. Tuning electrodes used in a reactor for electrochemically processing a microelectronic workpiece
US20020139678A1 (en) * 1999-04-13 2002-10-03 Wilson Gregory J. Tuning electrodes used in a reactor for electrochemically processing a microelectronic workpiece
US20030020928A1 (en) * 2000-07-08 2003-01-30 Ritzdorf Thomas L. Methods and apparatus for processing microelectronic workpieces using metrology
FR2828889A1 (fr) * 2001-08-24 2003-02-28 Engelhard Clal Sas Bain electrolytique pour le depot electrochimique de l'or et de ses alliages
US20030062258A1 (en) * 1998-07-10 2003-04-03 Woodruff Daniel J. Electroplating apparatus with segmented anode array
US6565729B2 (en) 1998-03-20 2003-05-20 Semitool, Inc. Method for electrochemically depositing metal on a semiconductor workpiece
US6569297B2 (en) 1999-04-13 2003-05-27 Semitool, Inc. Workpiece processor having processing chamber with improved processing fluid flow
US6592736B2 (en) 2001-07-09 2003-07-15 Semitool, Inc. Methods and apparatus for controlling an amount of a chemical constituent of an electrochemical bath
US20030159277A1 (en) * 2002-02-22 2003-08-28 Randy Harris Method and apparatus for manually and automatically processing microelectronic workpieces
US20030217929A1 (en) * 2002-05-08 2003-11-27 Peace Steven L. Apparatus and method for regulating fluid flows, such as flows of electrochemical processing fluids
US20040023494A1 (en) * 1998-03-13 2004-02-05 Semitool, Inc. Selective treatment of microelectronic workpiece surfaces
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US20040228719A1 (en) * 1996-07-15 2004-11-18 Woodruff Daniel J. Transfer devices for handling microelectronic workpieces within an environment of a processing machine and methods of manufacturing and using such devices in the processing of microelectronic workpieces
US20050084987A1 (en) * 1999-07-12 2005-04-21 Wilson Gregory J. Tuning electrodes used in a reactor for electrochemically processing a microelectronic workpiece
US20050087439A1 (en) * 1999-04-13 2005-04-28 Hanson Kyle M. Chambers, systems, and methods for electrochemically processing microfeature workpieces
US20050092611A1 (en) * 2003-11-03 2005-05-05 Semitool, Inc. Bath and method for high rate copper deposition
US20050230262A1 (en) * 2004-04-20 2005-10-20 Semitool, Inc. Electrochemical methods for the formation of protective features on metallized features
USRE38931E1 (en) * 1998-05-01 2006-01-10 Semitool, Inc. Methods for controlling and/or measuring additive concentration in an electroplating bath
US7020537B2 (en) 1999-04-13 2006-03-28 Semitool, Inc. Tuning electrodes used in a reactor for electrochemically processing a microelectronic workpiece
US7090751B2 (en) 2001-08-31 2006-08-15 Semitool, Inc. Apparatus and methods for electrochemical processing of microelectronic workpieces
US7264698B2 (en) 1999-04-13 2007-09-04 Semitool, Inc. Apparatus and methods for electrochemical processing of microelectronic workpieces
US7351315B2 (en) 2003-12-05 2008-04-01 Semitool, Inc. Chambers, systems, and methods for electrochemically processing microfeature workpieces
US7351314B2 (en) 2003-12-05 2008-04-01 Semitool, Inc. Chambers, systems, and methods for electrochemically processing microfeature workpieces
US7438788B2 (en) 1999-04-13 2008-10-21 Semitool, Inc. Apparatus and methods for electrochemical processing of microelectronic workpieces
US20080264774A1 (en) * 2007-04-25 2008-10-30 Semitool, Inc. Method for electrochemically depositing metal onto a microelectronic workpiece
US20100024930A1 (en) * 2006-10-03 2010-02-04 The Swatch Group Research And Development Ltd. Electroforming method and part or layer obtained via the method
US20100206739A1 (en) * 2007-09-21 2010-08-19 The Swatch Group Research And Development Ltd. Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids
US20110089040A1 (en) * 2009-10-15 2011-04-21 The Swatch Group Research And Development Ltd Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic materials
ITFI20120103A1 (it) * 2012-06-01 2013-12-02 Bluclad Srl Bagni galvanici per l'ottenimento di una lega di oro a bassa caratura e processo galvanico che utilizza detti bagni.
US11618951B2 (en) 2020-05-27 2023-04-04 Global Circuit Innovations Incorporated Chemical evaporation control system

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CH626410A5 (en) * 1977-09-07 1981-11-13 Metaux Precieux Sa Bath for the electrolytic deposition of gold or gold alloys and use of this bath
DE2800817C2 (de) * 1978-01-10 1982-11-04 Oxy Metal Industries Corp., 48089 Warren, Mich. Aldehydfreies wässriges Bad für die galvanische Abscheidung von Gold und dessen Legierungen sowie ein Verfahren zur Herstellung von Gold- und Goldlegierungsabscheidungen unter Verwendung dieses Bades
DE3020765A1 (de) * 1980-05-31 1981-12-10 Degussa Ag, 6000 Frankfurt Alkalisches bad zum galvanischen abscheiden niederkaraetiger rosa- bis gelbfarbener goldlegierungsschichten
JP5707912B2 (ja) * 2010-12-08 2015-04-30 東ソー株式会社 N−(ジヒドロキシアルキル)ジエチレントリアミン類の組成物、及びそれを用いた2−ヒドロキシ(アルキル)トリエチレンジアミン類の製造方
JP5687667B2 (ja) * 2012-08-21 2015-03-18 日本エレクトロプレイテイング・エンジニヤース株式会社 シアン系金−パラジウム合金めっき液及びめっき方法

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Publication number Priority date Publication date Assignee Title
US4062736A (en) * 1974-11-15 1977-12-13 Oxy Metal Industries Corporation Gold and gold alloy deposition
US4207149A (en) * 1974-12-04 1980-06-10 Engelhard Minerals & Chemicals Corporation Gold electroplating solutions and processes
US5024733A (en) * 1989-08-29 1991-06-18 At&T Bell Laboratories Palladium alloy electroplating process
US6921467B2 (en) 1996-07-15 2005-07-26 Semitool, Inc. Processing tools, components of processing tools, and method of making and using same for electrochemical processing of microelectronic workpieces
US20020053509A1 (en) * 1996-07-15 2002-05-09 Hanson Kyle M. Processing tools, components of processing tools, and method of making and using same for electrochemical processing of microelectronic workpieces
US20040228719A1 (en) * 1996-07-15 2004-11-18 Woodruff Daniel J. Transfer devices for handling microelectronic workpieces within an environment of a processing machine and methods of manufacturing and using such devices in the processing of microelectronic workpieces
US20050051436A1 (en) * 1998-02-04 2005-03-10 Semitool, Inc. Method of submicron metallization using electrochemical deposition of recesses including a first deposition at a first current density and a second deposition at an increased current density
US6753251B2 (en) 1998-02-04 2004-06-22 Semitool, Inc. Method for filling recessed micro-structures with metallization in the production of a microelectronic device
US20020022363A1 (en) * 1998-02-04 2002-02-21 Thomas L. Ritzdorf Method for filling recessed micro-structures with metallization in the production of a microelectronic device
US20060208272A1 (en) * 1998-02-04 2006-09-21 Semitool, Inc. Method for filling recessed micro-structures with metallization in the production of a microelectronic device
US7144805B2 (en) 1998-02-04 2006-12-05 Semitool, Inc. Method of submicron metallization using electrochemical deposition of recesses including a first deposition at a first current density and a second deposition at an increased current density
US20020102837A1 (en) * 1998-02-04 2002-08-01 Ritzdorf Thomas L. Method for filling recessed micro-structures with metallization in the production of a microelectronic device
US7244677B2 (en) 1998-02-04 2007-07-17 Semitool. Inc. Method for filling recessed micro-structures with metallization in the production of a microelectronic device
US6806186B2 (en) 1998-02-04 2004-10-19 Semitool, Inc. Submicron metallization using electrochemical deposition
US20040023494A1 (en) * 1998-03-13 2004-02-05 Semitool, Inc. Selective treatment of microelectronic workpiece surfaces
US7399713B2 (en) 1998-03-13 2008-07-15 Semitool, Inc. Selective treatment of microelectric workpiece surfaces
EP1064417A4 (en) * 1998-03-20 2006-07-05 Semitool Inc DEVICE AND METHOD FOR THE ELECTROLYTIC COATING OF COPPER TO A SEMICONDUCTOR WORKPIECE
US20040035708A1 (en) * 1998-03-20 2004-02-26 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US6811675B2 (en) 1998-03-20 2004-11-02 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
EP1064417A1 (en) * 1998-03-20 2001-01-03 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US6197181B1 (en) 1998-03-20 2001-03-06 Semitool, Inc. Apparatus and method for electrolytically depositing a metal on a microelectronic workpiece
US6277263B1 (en) 1998-03-20 2001-08-21 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US7115196B2 (en) 1998-03-20 2006-10-03 Semitool, Inc. Apparatus and method for electrochemically depositing metal on a semiconductor workpiece
US7332066B2 (en) 1998-03-20 2008-02-19 Semitool, Inc. Apparatus and method for electrochemically depositing metal on a semiconductor workpiece
US20040092065A1 (en) * 1998-03-20 2004-05-13 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
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NL7312310A (US20100154141A1-20100624-C00001.png) 1974-03-08
IT995275B (it) 1975-11-10
DE2244434B2 (de) 1981-02-19
AT322935B (de) 1975-06-10
DE2244434C3 (de) 1982-02-25
DD106060A5 (US20100154141A1-20100624-C00001.png) 1974-05-20
SE387372B (sv) 1976-09-06
AU5977073A (en) 1975-03-06
DE2244434A1 (de) 1974-03-21
CH594746A5 (US20100154141A1-20100624-C00001.png) 1978-01-31
JPS5421820B2 (US20100154141A1-20100624-C00001.png) 1979-08-02
ZA737128B (en) 1974-08-28
IE38198L (en) 1974-03-06
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IE38198B1 (en) 1978-01-18
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FR2197997B1 (US20100154141A1-20100624-C00001.png) 1976-11-19
CA1019276A (en) 1977-10-18
AU469094B2 (en) 1976-02-05
SU549089A3 (ru) 1977-02-28
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GB1438521A (en) 1976-06-09

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