US3664933A - Process for acid copper plating of zinc - Google Patents

Process for acid copper plating of zinc Download PDF

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Publication number
US3664933A
US3664933A US834909A US3664933DA US3664933A US 3664933 A US3664933 A US 3664933A US 834909 A US834909 A US 834909A US 3664933D A US3664933D A US 3664933DA US 3664933 A US3664933 A US 3664933A
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United States
Prior art keywords
copper
grams per
per liter
zinc
immersion
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Expired - Lifetime
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US834909A
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English (en)
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Richard J Clauss
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FIRST CITY NATIONAL BANK OF MIDLAND
OMI International Corp
Udylite Corp
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Udylite Corp
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Assigned to OXY METAL INDUSTRIES CORPORATION reassignment OXY METAL INDUSTRIES CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). 4-09-74 Assignors: OXY METAL FINISHING CORPORATION
Assigned to HOOKER CHEMICALS & PLASTICS CORP. reassignment HOOKER CHEMICALS & PLASTICS CORP. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: OXY METAL INDUSTRIES CORPORATION
Assigned to OCCIDENTAL CHEMICAL CORPORATION reassignment OCCIDENTAL CHEMICAL CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). EFFECTIVE MARCH 30, 1982. Assignors: HOOKER CHEMICAS & PLASTICS CORP.
Assigned to OMI INTERNATIONAL CORPORATION reassignment OMI INTERNATIONAL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: OCCIDENTAL CHEMICAL CORPORATION
Assigned to MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF reassignment MANUFACTURERS HANOVER TRUST COMPANY, A CORP OF SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: INTERNATIONAL CORPORATION, A CORP OF DE
Assigned to FIRST CITY NATIONAL BANK OF MIDLAND,, TULLOS, MADGE, S. reassignment FIRST CITY NATIONAL BANK OF MIDLAND, ASSIGNMENT OF 1/4 OF ASSIGNORS INTEREST Assignors: TULLOS, MIKE S.
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated

Definitions

  • ABSTRACT A process for the acid copper plating of zinc, particularly complex zinc parts having recessed areas, wherein a displacement copper deposit is formed on the zinc surface by treatment with an immersion copper plating bath and, thereafter, the thus-plated surface is electroplated with copper from an acid copper electroplating bath.
  • This invention relates to a method for the copper plating of zinc surfaces and more particularly it relates to an improved process for the copper electroplating of complex zinc dicastings having recessed areas.
  • Acid copper electroplating baths have long been used in industry, particularly in the decorative field as an undercoat for nickel-chromium deposits. With the development in recent years of processes which will produce a fully bright, ductle, high leveling copper deposit, there has been an even wider use of acid copper plating solutions. With such solutions, it is now possible to process large zinc components from the leveling acid copper solutions directly to nickel and chromium plating baths, without the necessity for finishing the die casting to the degree formerly required.
  • Another object of the present invention is to provide an improved process for forming an adherent deposit from an acid copper plating solution, even in recessed areas of complex zinc parts.
  • a further object of the present invention is to provide an improved immersion plating composition for forming a displacement copper coating on zinc surfaces, prior to the electrodeposition of copper from an acid copper plating solution.
  • the present invention includes applying an electrolytic copper strike to the zinc surface, treating the thus-strike plated zinc surface with an immersion copper plating bath, forming a displacement copper deposit on the zinc surface and, thereafter, electrodepositing copper on the thus-treated surface from an aqueous acidic copper electroplating bath.
  • an adherent copper plate is obtained from the acid copper plating bath over the entire zinc surface being treated, even in those areas, such as recesses and blind holes, which receive little or no electrical current.
  • the zinc surface is desirably cleaned, using various conventional cleaning techniques, prior to treatment with the plating solutions of the present invention.
  • cleaning techniques may utilize alkaline, acidic, or organic solvent cleaning compositions, and may include spraying, scrubbing, vapor degreasing, ultrasonic cleaning, steam cleaning, and the like.
  • the various conventional copper strike plating baths such as the copper cyanide baths, may be used.
  • Such baths generally contain copper cyanide, an alkali metal cyanide, and an alkali metal hydroxide. Additionally, such baths may also contain Rochelle salts or other addition agents which may aid in the operation of the bath by modifying the structure of the deposits, retarding carbonate buildup in the bath, or assisting in anode corrosion.
  • the operation of such copper strike baths is conventional and well known to those in the art. Typically, these baths are operated at temperatures of from room temperature up to about 70" C. for plating times of about 9% to 4 minutes at a tank voltage of from about 4 to 6 volts.
  • the copper strike plate may be either copper or a copper alloy, e.g., brass, or the like.
  • the zinc surfaces are treated with an immersion copper plating bath.
  • Various immersion copper plating baths which will form a displacement copper deposit on the zinc surfaces may be used for this purpose, provided, however, that the plating solution does not unduly attack the zinc surface being treated, while still providing sufiicient attack of the surface that the formation of the desired displacement copper deposit can be effected in a reasonable period of time.
  • the immersion copper plating solutions used may be either acidic or alkaline solutions and may be operated over a wide range of pH values. In general, it has been found that better control of these plating solutions, and hence a more satisfactory displacement copper deposit is formed, where the solutions used are those containing a complex or chelate of copper, rather than merely simple copper salts.
  • Such solutions may contain a water soluble copper salt, a primary complexing agent for cupric ions, an alkali metal hydroxide, and an accelerator and/or secondary complexing agent for cuprous ions.
  • Typical of the water soluble copper salts which may be used in such copper immersion plating solutions are copper sulfate, which is preferred, copper chloride, copper acetate, copper carbonate and the like.
  • the solutions will contain the copper salts in amounts giving a copper metal content within the range of about 8 to 30 grams per liter, with amounts within the range of about 12 to 24 grams per liter being preferred.
  • complexing agents which will complex the cupric ions in the immersion plating solution
  • Typical of such complexing agents are the alkaline metal gluconates, such as sodium gluconate, citric acid, tartrates, such as Rochelle salts, ethylene diamine, diethylene triamine, diethanol glvoxime, ethylene diamine tetraacetic acid, lactonitrile and the like.
  • such complexing agents are included in the plating solution in amounts within the range of about 30 to 350 grams per liter, with amounts within the range of about 60 to 280 grams per liter being preferred.
  • alkali metal hydroxides such as sodium hydroxide
  • alkali metal carbonates may also be used.
  • alkaline materials are desirably present in the plating bath in amounts within the range of about 5 to grams per liter and preferably in amounts within the range of about 10 to 60 grams per liter.
  • the immersion copper plating baths for use in the method of the present invention also desirably contain a component which acts to accelerate the plating action of the bath and a component which acts to complex any cuprous ions formed during plating.
  • the alkali metal chlorides such as sodium chloride, or the alkaline earth metal chlorides, such as magnesium chloride, have been found to be particularly preferred accelerating materials.
  • the alkali metal cyanides such as sodium cyanide, have been found to give excellent results, although similar results are also obtained when using ammonium hydroxide.
  • the accelerator is desirably present in the bath in amounts within the range of about to 70 grams/liter, with amounts within the range of about to 50 grams/liter being preferred.
  • the cuprous ion complexing agent is present in the bath in amounts within the range of about 0.2 to 5 grams/liter, with amounts within the range of about 0.5 to 2.5 grams/liter being preferred.
  • Exemplary of particularly preferred immersion copper plating baths of the above type is a bath wich is an aqueous solution containing the following components in the amounts indicated:
  • these immersion copper plating baths may be operated over a relatively wide pH range, depending upon the quantity and type of the components which are used to formulate the bath. pH values for the plating bath within the range of about 4 to 13 are typical, although in many instances, pH values on the acid side of from about 5 to 6 or on the alkaline side or from about 10 to 13, are preferred.
  • the copper strike electroplated zinc surface is contacted, preferably by immersion with the immersion copper plating bath for a period sufiicient to form the desired displacement copper deposit on the surface.
  • the immersion copper plating solution is at an elevated temperature, temperatures within the range of about 45 to 70 C. being typical, and the contact times used are desirably from about 2 to 5 minutes. It is to be appreciated, however, that in some instances, depending upon the specific operating conditions used, temperatures and times which are outside of these ranges may also be utilized to produce satisfactory results.
  • the immersion copper plating bath may be operated as a still bath or it may be agitated, using mechanical agitation or air agitation, whichever is desired.
  • the immersion copper plating solution is maintained in contact with the zinc surfaces being treated for a period sufficient to produce a displacement copper coating on the surface having a thickness of from about five to thirty-five millionths of an inch. It is found that the displacement copper coatings produced are quite porous and this inherent porosity permits a controlled attack by the subsequently applied acid copper plating solution through the pores, to produce a second adherent copper layer. Although it is important that the displacement copper deposit formed from the immersion copper plating solution have some porosity, where the porosity is too great, the subsequently applied acid copper electroplating solution may corrode the zinc surface too rapidly through these pores at too many points, resulting in undercutting of the immersion copper displacement deposit with resulting poor adhesion of the total copper deposit.
  • the above techniques may not be sufficient to effect the desired reduction in the porosity in the immersion copper deposit.
  • various immersion nickel plating baths may be used, such baths are desirably aqueous solutions having a pH of from about 3 to 5 and containing up to about 500 grams per liter of nickel chloride, up to about 300 grams per liter nickel sulfate, up to about grams per liter sodium chloride and up to about 45 grams per liter boric acid.
  • the im mersion nickel plating bath contains from about 60 to 200 grams per liter nickel chloride, from about 75 to grams per liter nickel sulfate, from about 20 to 40 grams per liter boric acid and up to about 60 grams per liter of sodium chloride.
  • the zinc surfaces which have been previously given a copper or nickel electro strike plate and the displacement copper coating, are contacted, preferably by immersion, with the immersion nickel plating solution.
  • this immersion nickel plating solution is at a temperature within the range of about 25 to 60 C., temperatures of from about 40 to 55 C. being typical, and the contact times are typically within the range of about 1 to 3 minutes.
  • this treatment with the immersion nickel plating solution, in combination with the immersion copper plating solution, it is possible to obtain satisfactory results with shorter contact times in the immersion copper plating solution than are possible when using this solution alone.
  • total contact times in the two immersion plating solutions of from about 2 to 4 minutes have been found to be typical.
  • the zinc surface is then electroplated, using an acid copper plating bath.
  • acid copper electroplating baths as are known to those in the art, may be used for the application of the copper electroplate in accordance with the method of the present invention.
  • such acid copper electroplating baths are aqueous acidic solutions of copper sulfate, copper fluoborate, copper nitrate, copper sulfamate, the copper alkyl sulfonates and disulfonates and the like.
  • such acid copper plating baths will also contain one or more additives which are effective in improving the lustre, leveling, ductility, and the like of the copper electroplate obtained.
  • Typical of such acid copper electroplating baths and the additives which they may contain are the plating baths described in U.S. Pat. Nos. 2,707,166; 3,267,010; and 3,288,690. It is to be appreciated, of course, that other acid copper electroplating baths, other than those specifically set forth, may also be used to effect the desired copper plating of the zinc surfaces.
  • the copper electroplate is applied to the zinc surfaces by the electrolysis of the acid copper electroplating baths in the conventional manner, as is known to those in the art.
  • such baths will be operated so as to produce a copper plate having a thickness of from about 0.0002 to .0015 inches, typical operating conditions to produce such a plate including bath temperatures of from about 18 to 60 C., average current densities of from about 15 to 300 amps/square foot and plating times of from about 10 to 40 minutes.
  • the thus-copper electroplating surfaces may then, if desired, be further electroplated with nickel and/or chromium to produce the final plated zinc parts.
  • the copper electroplate produced by the electrolysis of the acid copper plating bath, in accordance with the method of the present invention, is found to be bright, ductle, and adherent. Moreover, the adherency of this copper plate is found to be excellent, even in cavities and other recessed areas of the zinc surface where there is very low or even no current density during the electroplating process.
  • EXAMPLE 1 A hollow zinc die cast nozzle approximately 6 inches in length and open at both ends was plated for 2 minutes in a standard copper cyanide strike solution, followed by a 2- minute immersion copper deposit from a solution of the following composition:
  • EXAMPLE 2 Another hollow zinc die cast nozzle was processed exactly as above but the 2-minute immersion copper treatment was omitted. After plating in the acid copper solution, the deposit on the inside of the nozzle was rough and loosely adherent copper flaked off the zinc surface.
  • EXAMPLE 3 Zinc die cast mirror support arms having a deep cavity completely closed at one end even given a 2-minute copper strike deposit from an alkaline copper solution followed by a six minute immersion treatment in a solution of the following composition:
  • EXAMPLE 5 Similar zinc die cast support arms were processed as in Example 3 but the copper immersion treatment was omitted. After acid copper plating for 15 minutes, the inside surfaces of the casting were covered with rough, loosely adherent deposits which readily flaked loose.
  • a process for the copper electroplating of complex zinc die castings having recessed areas which comprises applying an electrolytic copper strike to the zinc surface to be treated, treating the thus-strike plated zinc surface with an immersion copper plating bath, forming a displacement copper deposit on the uncoated, recessed, zinc surface and, thereafter, electrodepositing copper on the thus-treated surfaces from an aqueous acidic copper electroplating bath.
  • the immersion copper plating bath is an aqueous solution comprising from about 8 to 30 grams per liter of copper supplied by a water soluble copper salt, from about 30 to 350 grams per liter of a primary complexing agent for cupric ions, from about 5 to 80 grams per liter of an alkali metal hydroxide, from about 5 to 70 grams per liter of an accelerator selected from alkali metal chlorides and from about 0.2 to 5 grams per liter of a secondary complexing agent selected from alkali metal cyanides and ammonium hydroxide.
  • a process for the copper electroplating of complex zinc die castings having recessed areas which comprises applying an electrolytic copper strike to the zinc surface to be treated, treating'the thus strike plated zinc surface with an immersion copper plating bath which is an aqueous solution comprising from about 8 to 30 grams per liter of copper supplied by a trodepositing copper on the thus treated surfaces from aqueous acidic copper electroplating bath.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Chemically Coating (AREA)
  • Electroplating Methods And Accessories (AREA)
US834909A 1969-06-19 1969-05-19 Process for acid copper plating of zinc Expired - Lifetime US3664933A (en)

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US83490969A 1969-06-19 1969-06-19

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JP (1) JPS4843787B1 (ja)
BE (1) BE751427A (ja)
CA (1) CA924670A (ja)
DE (1) DE2026698A1 (ja)
FR (1) FR2046885B1 (ja)
GB (1) GB1294027A (ja)
NL (1) NL7008864A (ja)

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4272570A (en) * 1980-04-11 1981-06-09 Sunbeam Corporation Provision of surface layers of copper or copper alloyed with zinc on die castings of zinc or zinc alloys
US4454168A (en) * 1982-09-29 1984-06-12 E. I. Du Pont De Nemours And Company Printed circuits prepared from metallized photoadhesive layers
US5558759A (en) * 1994-07-26 1996-09-24 Sargent Manufacturing Company Metal finishing process
EP1064417A1 (en) * 1998-03-20 2001-01-03 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US6180179B1 (en) * 1997-06-02 2001-01-30 Nihon Parkerizing Co., Ltd. Displace deposition-plated and doping-modified metal material and process for producing same
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
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
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
US6541188B2 (en) * 2001-05-11 2003-04-01 Kodak Polychrome Graphics Llc Developer for alkaline-developable lithographic printing plates
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
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
US20040038052A1 (en) * 2002-08-21 2004-02-26 Collins Dale W. Microelectronic workpiece for electrochemical deposition processing and methods of manufacturing and using such microelectronic workpieces
US6806186B2 (en) 1998-02-04 2004-10-19 Semitool, Inc. Submicron metallization using electrochemical deposition
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
US20050092611A1 (en) * 2003-11-03 2005-05-05 Semitool, Inc. Bath and method for high rate copper deposition
US20050214460A1 (en) * 2002-05-22 2005-09-29 Pascal Doppelt Method of depositing copper on a support
US20050230262A1 (en) * 2004-04-20 2005-10-20 Semitool, Inc. Electrochemical methods for the formation of protective features on metallized features
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
US20060280872A1 (en) * 2005-06-10 2006-12-14 Enthone Inc. Method for direct metallization of non-conducting substrates
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
US7585398B2 (en) 1999-04-13 2009-09-08 Semitool, Inc. Chambers, systems, and methods for electrochemically processing microfeature workpieces
WO2011029507A1 (en) * 2009-09-11 2011-03-17 Umicore Galvanotechnik Gmbh Process for the electrolytic copper plating of zinc diecasting having a reduced tendency to blister formation
US11618951B2 (en) 2020-05-27 2023-04-04 Global Circuit Innovations Incorporated Chemical evaporation control system
US11661666B2 (en) 2019-10-10 2023-05-30 The Boeing Company Electrodeposited zinc and iron coatings for corrosion resistance

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DE112020007889T5 (de) 2020-12-28 2023-11-02 Mitsubishi Electric Corporation Bildverarbeitungseinrichtung, programm und bildverarbeitungsverfahren

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Cited By (68)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4272570A (en) * 1980-04-11 1981-06-09 Sunbeam Corporation Provision of surface layers of copper or copper alloyed with zinc on die castings of zinc or zinc alloys
US4454168A (en) * 1982-09-29 1984-06-12 E. I. Du Pont De Nemours And Company Printed circuits prepared from metallized photoadhesive layers
US5558759A (en) * 1994-07-26 1996-09-24 Sargent Manufacturing Company Metal finishing 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
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
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
US6180179B1 (en) * 1997-06-02 2001-01-30 Nihon Parkerizing Co., Ltd. Displace deposition-plated and doping-modified metal material and process for producing same
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
US6806186B2 (en) 1998-02-04 2004-10-19 Semitool, Inc. Submicron metallization using electrochemical deposition
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
US7399713B2 (en) 1998-03-13 2008-07-15 Semitool, Inc. Selective treatment of microelectric workpiece surfaces
US20040023494A1 (en) * 1998-03-13 2004-02-05 Semitool, Inc. Selective treatment of microelectronic workpiece surfaces
US7115196B2 (en) 1998-03-20 2006-10-03 Semitool, Inc. Apparatus and method for electrochemically depositing metal on a semiconductor workpiece
US20040040857A1 (en) * 1998-03-20 2004-03-04 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
EP1064417A1 (en) * 1998-03-20 2001-01-03 Semitool, Inc. Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US20030141194A1 (en) * 1998-03-20 2003-07-31 Chen Linlin Apparatus and method for electrolytically depositing copper on a semiconductor workpiece
US6638410B2 (en) 1998-03-20 2003-10-28 Semitool, Inc. Apparatus and method for electrolytically depositing copper 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
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CA924670A (en) 1973-04-17
GB1294027A (en) 1972-10-25
JPS4843787B1 (ja) 1973-12-20
FR2046885A1 (ja) 1971-03-12
DE2026698A1 (de) 1971-01-07
FR2046885B1 (ja) 1974-05-24
BE751427A (fr) 1970-12-03

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