EP0107109B1 - Electrolytic copper plating solutions and a method for their application - Google Patents

Electrolytic copper plating solutions and a method for their application Download PDF

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Publication number
EP0107109B1
EP0107109B1 EP83109814A EP83109814A EP0107109B1 EP 0107109 B1 EP0107109 B1 EP 0107109B1 EP 83109814 A EP83109814 A EP 83109814A EP 83109814 A EP83109814 A EP 83109814A EP 0107109 B1 EP0107109 B1 EP 0107109B1
Authority
EP
European Patent Office
Prior art keywords
hydrogen
alkali metal
copper
magnesium
electroplating solution
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
Application number
EP83109814A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0107109A3 (en
EP0107109A2 (en
Inventor
John Houman
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.)
Shipley Co Inc
Original Assignee
LeaRonal Inc
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 LeaRonal Inc filed Critical LeaRonal Inc
Priority to AT83109814T priority Critical patent/ATE32611T1/de
Publication of EP0107109A2 publication Critical patent/EP0107109A2/en
Publication of EP0107109A3 publication Critical patent/EP0107109A3/en
Application granted granted Critical
Publication of EP0107109B1 publication Critical patent/EP0107109B1/en
Expired 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 invention relates to electrolytic copper plating solutions and a method for their application.
  • the invention relates especially to the electrodeposition of copper for decorative use and more particularly to the electrodeposition of copper on substrates having sharp corners such as formed by the holes drilled into copper clads for the production of printed circuit boards.
  • Circuit boards are generally prepared by laminating copper clad to both sides of a plastic sheet such as an epoxy-glass. Holes are then drilled through the copper clad and the plastic, exposing the plastic. The exposed plastic must then be plated to effect conductivity from one side of the board to the other. This is generally accomplished by treating the plastic with an activator by well known processes, subjecting the entire circuit board to electroless deposition of copper to render the areas receptive to electrolytic copper depositions, and then plating the board and the internal surfaces of the holes by electrodeposition of copper. The sharp corners formed by the perimeter of the holes adjacent the top and bottom of the board must also be plated. This can be accomplished by many different copper electroplating solutions presently on the market, but the copper plate at the corners has a tendency to develop cracks when the boards are subjected to thermal shock necessitated by further processing of the boards.
  • This invention relates to acid copper electroplating solutions comprising a soluble copper salt, free acid and a solution obtainable by reacting
  • the invention also comprises a method of electroplating substrates having sharp corners to prevent the formation of cracks at the corners due to thermal shock, using the electroplating copper solution according to the invention.
  • R, and R 2 are lower alkyl radicals with 1 to 6 carbon atoms, a hydrogen atom or mixtures thereof
  • R 4 is an alkali metal, hydrogen, 1/2 magnesium, or the groups SX or SSX, wherein X is an alkali metal, hydrogen or 1/2 magnesium, or wherein R 3 is an aromatic, heterocyclic or alicyclic radical containing 3 to 12 carbon atoms, and R 4 represents an alkali metal, hydrogen, 1/2 magnesium, or the groups SX or SSX where X is an alkali metal, hydrogen or 1/2 magnesium.
  • the compounds found to be the most advantageous to date are the soduim salts obtained from the following compounds: tetraalkylthiuram disulfide, wherein R, and R 2 are methyl or ethyl or mixtures thereof, 2,2'-dithio-bisbenzothiazole, and 2-mercaptobenzothiazole
  • R, and R 2 are methyl or ethyl or mixtures thereof
  • 2,2'-dithio-bisbenzothiazole 2,2'-dithio-bisbenzothiazole
  • 2-mercaptobenzothiazole When reacting compounds such as (3) and (4) with sodium hydroxide, the compounds are split, predominantly but not exclusively between the -S-S- bond forming the sodium salts.
  • formula (3) wherein R is ethyl
  • after reaction with sodium hydroxide would form predominantly two moles of plus minor amounts of and and formulas (4) and (5) would form with minor amounts of
  • the sodium salts of the compounds (3), (4) and (5) can readily be prepared by known means by heating the compounds dissolved in a solvent such as methanol (preferably under reflux) with sodium hydroxide.
  • a solvent such as methanol (preferably under reflux) with sodium hydroxide.
  • the compound of formulas (3), (4) and (5) are available commercially and marketed under the marks TUADS O , ALTAX° and CAPTAX O , respectively, by R. T. Vanderbilt Company, Inc.
  • the second reactant is an alkylene sulfide compound having terminal acid group(s).
  • This compound corresponds to the general formula wherein R i , R 2 and X have the meaning as defined above.
  • alkylene sulfide di(sodium 3-sulfonate-1-propyl) sulfide:
  • the third reactant is acrylamide.
  • reaction solution The product resulting from these reactions is hereinafter referred to as "reaction solution”.
  • the invention includes the use of oxyalkylene polymers as brightening and leveling agents in combination with the "reaction solution".
  • the oxyalkylene polymers have been found to materially increase the brightness and leveling of the deposits.
  • the polyalkylene glycols such as polyethylene glycols, methoxy polyethylene glycols and the polypropylene glycols, have been found to be particularly advantageous.
  • the oxyethylene or oxypropylene polymers can be surfactants, anionic, nonionic or cationic. Anionic and nonionic are preferred. These types of surfactants are well known and lists of specific polymers can be obtained by consulting any standard text on the subject such as the various volumes of Kirk-Othmer Encyclopedia of Chemical Technology or the industrial literature. It is the presence of the ethylene oxide or propylene oxide groups that is most important. The compounds should have at least about 8 mols of ethylene and/or propylene oxide and be soluble in the bath solution. Combinations of polyethylene and polypropylene glycols and/or surfactants can also be used.
  • the amounts of the oxyalkylene polymers can be about the same as is usually employed in acid copper baths. A sufficient amount should, of course, be used to obtain the brightness and leveling desired which will in turn depend on the ultimate use intended. Generally about 0.1 to 0.5 g/I or ml/I can be employed.
  • the copper deposited according to this invention is useful as decorative use, in the electronic industry generally, and for the conduction of electricity on substrates that do not have sharp corners or on articles where thermal shock is not a problem.
  • the amounts of the reaction products employed in the acid copper plating solutions may therefore differ depending on the result desired, but in any event the amounts should be sufficient to improve the brightness and smoothness of the metallic deposits over that obtainable from the basic plating solutions.
  • the amounts should be sufficient to prevent cracks in the deposit at the corners when the plated substrate is subjected to thermal shock. As far as it is known today, the amounts to accomplish both of these results will be substantially the same.
  • the acid copper plating solutions to which the "reaction solution” can be added are conventional and well known.
  • the two essential constituents are a copper salt, such as copper sulfate, and an acid, such as sulfuric acid.
  • the salt furnishes the metal ions and the acid serves to reduce the resistivity or promote conductivity.
  • These baths typically contain between about 70-250 g/I of copper sulfate and 30 to 250 g/I of sulfuric acid.
  • reaction solution can be formed by dissolving compounds of formulas (1) and/or (2), such as tetralakylthiuram disulfide sodium salt in a suitable solvent, adding a bis(3-sulfoalkyl) disulfide salt to the reaction mixture together with acrylamide under reflux. Concentrated sulfuric acid is then added (dropwise in the laboratory) during the reflux and continued until gassing has ceased or no precipitate or turbidity is present.
  • the reactants can be the mixtures as described above.
  • the exact proportions of the reactants are not very critical but best results to date are obtained by using stoichiometric amounts.
  • the reaction can include additional reactants so long as they do not affect the function and advantageous properties of the resulting reaction solution. For example, 0.6 g of formaldehyde can be added to the methanol solution and reacted with the sodium hydroxide before the addition of the disulfide compound and the resulting reaction solution has substantially the same advantageous properties.
  • the plating bath was operated at 23.9°C (75°F) in a Hull cell with air agitation at a current of 2 amps for 10 minutes.
  • the plating bath in the 7.5 I (2 gallon) tank was operated at identical parameters, but at a current density of 1.6 A/dm 2 (15 ASF) for an hour.
  • Printed circuit boards with the holes drilled therein after being activated and electrolessly plated with copper were plated in this tank.
  • the copper deposit on the circuit board was smooth and semi-lustrous over current density range of 0.2-2.1 A/dm 2 (2 to 20 ASF) and showed no signs of corner cracks after thermal shock.
  • Example 2 The procedure of Example 2 was followed except that the following material was also incorporated into the plating bath:
  • the copper deposit on the plated material was very bright and leveled over a current density range of from 0.1-10.7 A/dm 2 (1 to 100 ASF) and showed no signs of corner cracks after thermal shock.
  • Example 2 The procedure of Example 2 was followed except that the following materials were also incorporated into the plating bath:
  • the deposit on the plated material was very bright and leveled in the current density range of from 0.1-10.7 A/dm 2 (1 to 100 ASF).
  • the deposit on the printed circuit board plated in the 7.5 1 (2 gallon) tank was very bright and leveled, and showed no signs of corner cracks after thermal shock.
  • the thermal shock test to which the plated boards are subjected in the above examples is conventional. After the boards are baked for about an hour at 150°C, they are cooled to room temperature and allowed to float on one side in molten solder at 288°C for 10 seconds, then turned over and allowed to float on the solder on the other side for 10 seconds. The boards are then removed and inspected for cracks.

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)
  • Chemically Coating (AREA)
EP83109814A 1982-09-30 1983-09-30 Electrolytic copper plating solutions and a method for their application Expired EP0107109B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83109814T ATE32611T1 (de) 1982-09-30 1983-09-30 Elektrolytische kupferplattierungsloesungen und verfahren fuer ihre anwendung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US42905582A 1982-09-30 1982-09-30
US429055 1982-09-30

Publications (3)

Publication Number Publication Date
EP0107109A2 EP0107109A2 (en) 1984-05-02
EP0107109A3 EP0107109A3 (en) 1984-07-25
EP0107109B1 true EP0107109B1 (en) 1988-02-24

Family

ID=23701587

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83109814A Expired EP0107109B1 (en) 1982-09-30 1983-09-30 Electrolytic copper plating solutions and a method for their application

Country Status (5)

Country Link
EP (1) EP0107109B1 (ja)
JP (1) JPS59501829A (ja)
AT (1) ATE32611T1 (ja)
DE (2) DE3375732D1 (ja)
WO (1) WO1984001393A1 (ja)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4490220A (en) * 1982-09-30 1984-12-25 Learonal, Inc. Electrolytic copper plating solutions
DE3721985A1 (de) * 1987-06-30 1989-01-12 Schering Ag Waessriges saures bad zur galvanischen abscheidung glaenzender und eingeebneter kupferueberzuege
DE4032864A1 (de) * 1990-10-13 1992-04-16 Schering Ag Saures bad zur galvanischen abscheidung von kupferueberzuegen und verfahren unter verwendung dieser kombination
DE19758121C2 (de) * 1997-12-17 2000-04-06 Atotech Deutschland Gmbh Wäßriges Bad und Verfahren zum elektrolytischen Abscheiden von Kupferschichten
JP4115240B2 (ja) * 2002-10-21 2008-07-09 日鉱金属株式会社 特定骨格を有する四級アミン化合物及び有機硫黄化合物を添加剤として含む銅電解液並びにそれにより製造される電解銅箔
DE10337669B4 (de) * 2003-08-08 2006-04-27 Atotech Deutschland Gmbh Wässrige, saure Lösung und Verfahren zum galvanischen Abscheiden von Kupferüberzügen sowie Verwendung der Lösung
DE102005011708B3 (de) 2005-03-11 2007-03-01 Atotech Deutschland Gmbh Polyvinylammoniumverbindung und Verfahren zu deren Herstellung sowie diese Verbindung enthaltende saure Lösung und Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2888390A (en) * 1956-11-08 1959-05-26 Anaconda Co Electrolytic refining of copper
US2954331A (en) * 1958-08-14 1960-09-27 Dayton Bright Copper Company Bright copper plating bath
US3328273A (en) * 1966-08-15 1967-06-27 Udylite Corp Electro-deposition of copper from acidic baths
JPS4931183B1 (ja) * 1969-12-19 1974-08-20
JPS4931406B1 (ja) * 1970-02-19 1974-08-21
DE2746938C2 (de) * 1977-10-17 1987-04-09 Schering AG, 1000 Berlin und 4709 Bergkamen Wäßriges saures Bad zur galvanischen Abscheidung von glänzenden und rißfreien Kupferüberzügen und Verwendung dieses Bades
US4134803A (en) * 1977-12-21 1979-01-16 R. O. Hull & Company, Inc. Nitrogen and sulfur compositions and acid copper plating baths

Also Published As

Publication number Publication date
EP0107109A3 (en) 1984-07-25
EP0107109A2 (en) 1984-05-02
JPS6250559B2 (ja) 1987-10-26
DE3375732D1 (en) 1988-03-31
ATE32611T1 (de) 1988-03-15
WO1984001393A1 (en) 1984-04-12
JPS59501829A (ja) 1984-11-01
DE107109T1 (de) 1985-02-14

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