EP0375179B1 - Copper plating process for difficult to plate metals - Google Patents

Copper plating process for difficult to plate metals Download PDF

Info

Publication number
EP0375179B1
EP0375179B1 EP19890312444 EP89312444A EP0375179B1 EP 0375179 B1 EP0375179 B1 EP 0375179B1 EP 19890312444 EP19890312444 EP 19890312444 EP 89312444 A EP89312444 A EP 89312444A EP 0375179 B1 EP0375179 B1 EP 0375179B1
Authority
EP
European Patent Office
Prior art keywords
litre
bath
per litre
copper plating
copper
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
EP19890312444
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0375179A2 (en
EP0375179A3 (en
Inventor
Issa Said Mahmoud
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.)
International Business Machines Corp
Original Assignee
International Business Machines Corp
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 International Business Machines Corp filed Critical International Business Machines Corp
Publication of EP0375179A2 publication Critical patent/EP0375179A2/en
Publication of EP0375179A3 publication Critical patent/EP0375179A3/en
Application granted granted Critical
Publication of EP0375179B1 publication Critical patent/EP0375179B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium
    • 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
    • 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
    • C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel

Definitions

  • the present invention relates to an electroplating bath composition suitable for electroplating extremely electropositive metals such as aluminium and tungsten.
  • Strongly electropositive metals such as aluminium and tungsten are quite difficult to electroplate. Such metals have a strong affinity for atmospheric oxygen. This characteristic creates an ever present compacted oxide layer at the metal surface. Such a layer forms within seconds after a fresh surface of these metals is exposed to oxygen. The oxide layer renders plating these metals very difficult; and if plating occurs, in many cases, the adhesion is quite poor.
  • the present invention provides a process including a bath formulation for depositing copper on difficult to plate metals such as aluminium and tungsten.
  • the bath formulation of the present invention is an acid copper bath and includes additives for specific purposes.
  • the process of the present invention requires no surface preparation or etching prior to plating, thereby reducing the amount of chemical waste attendant to the process. Further, the present invention provides for oxide removal from difficult to plate metals in the plating tank so that there is minimal opportunity for new oxide to form on clean surfaces, thereby enabling the establishment of excellent metallic bonds between the electrodeposited copper and base metal.
  • the inventive process provides higher yields, better adhesion while minimizing the cost associated with waste treatment.
  • the preferred aqueous plating solution contains sulphuric acid, 0.5-0.75 moles per litre; hydrated copper sulphate, 0.3-0.5 moles per litre; urea, 1-2 grammes per litre; a wetting agent, 1-2 millilitres per litre; sulphonic acid, 1-2 grammes per litre; and deionized water, 800-1000 millilitres.
  • the preferred solution composition includes 0.5 mol. hydrated copper sulphate, 0.4 mol. sulphuric acid, 1 gramme urea, 1 gramme Beta-phenylethyltosylate (an ester of a sulphonic acid) and sufficient water to make one litre of solution.
  • Preparation of the bath is preferably carried out as follows. About 700 millilitres of deionised or distilled water is measured into a 2000 ml beaker, to which is added the above bath constituents in the order listed with continuous agitation. Subsequently enough water is added to make one litre of solution which is then filtered to remove any undissolved reagents.
  • Urea is included for its properties as a levelling agent.
  • Sulphonic acid is used for its brightening properties.
  • Sulphonic acids of the ester type, particularly of the tosyl and mesyl types, are well suited for use in the present plating bath solution.
  • Suitable wetting agents include cationic surfactants such as sodium lauryl sulphate.
  • the bath is prepared by adding all of the chemicals in the order listed to the deionized water.
  • the solution is mixed and filtered if need be to remove any undissolved particles.
  • Metals to be plated are first cleaned to remove soil, dirt and other surface contaminants, then rinsed in deionized water. The metals are then placed in the plating tank containing the prepared bath.
  • the parts remain in the plating solution for 2 to 3 minutes before a negative bias is applied to commence electroplating of copper.
  • a negative bias is applied to commence electroplating of copper.
  • Normal plating process parameters include a bath temperature in the range of 20-30 degrees Celsius, at a current density of 108-216 amperes per square metre (10-20 amperes per square foot) With continuous, strong agitation.
  • the duration of the plating step is variable, depending on the desired copper thickness.
  • the sulphuric acid concentration in the plating bath is sufficient for removing the oxide layers during the 2-3 minute soak before introduction of current. No extensive surface preparation or etching is required before plating, thereby reducing the number of steps and the amount of chemical waste generated and the cost attendant thereto.
  • Aluminium and tungsten workpieces were cleaned in a mild alkaline cleaner and then plated in the following solution: Sulphuric acid, 75 grammes/litre Hydrated Copper sulphate, 72 grammes/litre Urea (levelling agent), 1 gramme/litre Sulphonic acid (brightener), 1 gramme/litre Sodium lauryl sulphate surfactant, 1 gramme/litre Deionized water, 1 litre
  • the workpieces were immersed in this solution for 2-3 minutes prior to biasing.
  • Plating was carried out at room temperature and at 108 amperes per square metre (10 amperes per square foot) for 20 minutes.
  • the copper deposits were smooth and free of defects such as skip plating. Testing for adhesion strength by both cross-cut and quench method showed no adhesion failures.
  • Example 2 Another example of this invention was carried out in a similar manner as Example 1, except the amount of sulphuric acid was reduced to 50 grammes/litre. Again the quality and adhesion of the copper deposit were similar to Example 1.
  • Example 2 In another example the conditions were as in Example 1 except that the amount of hydrated copper sulphate was 50 grammes/litre. The electrodeposits were smooth, free of skip plating and had excellent adhesion.
  • Coupons of tungsten which showed slight blue colour (tungsten oxide) were cleaned and then plated as in Example 1. Subsequent adhesion testing showed poor adhesion. However, when the coupons were first positively biased for 1 minute, then plated in the negative bias, the plated coupons showed good adhesion.

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)
EP19890312444 1988-12-21 1989-11-29 Copper plating process for difficult to plate metals Expired - Lifetime EP0375179B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28999388A 1988-12-21 1988-12-21
US289993 1988-12-21

Publications (3)

Publication Number Publication Date
EP0375179A2 EP0375179A2 (en) 1990-06-27
EP0375179A3 EP0375179A3 (en) 1991-01-30
EP0375179B1 true EP0375179B1 (en) 1994-05-25

Family

ID=23114070

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19890312444 Expired - Lifetime EP0375179B1 (en) 1988-12-21 1989-11-29 Copper plating process for difficult to plate metals

Country Status (3)

Country Link
EP (1) EP0375179B1 (enrdf_load_stackoverflow)
JP (1) JPH02232390A (enrdf_load_stackoverflow)
DE (1) DE68915519T2 (enrdf_load_stackoverflow)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2818294A1 (fr) * 2000-12-15 2002-06-21 Thomson Csf Revetement metallique conducteur anticorrosion, procede de fabrication dudit revetement, et produit utilise dans ledit procede
RU2194098C1 (ru) * 2001-06-29 2002-12-10 Калининградский государственный университет Электролит блестящего меднения
JP2010150622A (ja) * 2008-12-26 2010-07-08 Hitachi Ltd めっき液，凸状金属構造体を有する導電体基板、及び、その製造方法
CN103668355B (zh) * 2013-12-06 2016-05-11 南京三乐电子信息产业集团有限公司 一种行波管钨螺旋线表面的镀铜方法
FR3053352A1 (fr) 2016-07-04 2018-01-05 Airbus Safran Launchers Sas Composition de protection anticorrosion
DE102016113641A1 (de) 2016-07-25 2018-01-25 Christian-Albrechts-Universität Zu Kiel Aluminium-Kupfer-Konnektor aufweisend eine Heterostruktur und Verfahren zur Herstellung der Heterostruktur
CN107447239B (zh) * 2017-08-21 2018-08-28 安徽省含山县兴建铸造厂 一种耐腐蚀防振锤的制备方法

Also Published As

Publication number Publication date
JPH02232390A (ja) 1990-09-14
DE68915519T2 (de) 1994-12-01
EP0375179A2 (en) 1990-06-27
EP0375179A3 (en) 1991-01-30
JPH0317913B2 (enrdf_load_stackoverflow) 1991-03-11
DE68915519D1 (de) 1994-06-30

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