EP1162289A1 - Bain pour l'electrodeposition de palladium et processus pour l'electrodeposition - Google Patents

Bain pour l'electrodeposition de palladium et processus pour l'electrodeposition Download PDF

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Publication number
EP1162289A1
EP1162289A1 EP01304721A EP01304721A EP1162289A1 EP 1162289 A1 EP1162289 A1 EP 1162289A1 EP 01304721 A EP01304721 A EP 01304721A EP 01304721 A EP01304721 A EP 01304721A EP 1162289 A1 EP1162289 A1 EP 1162289A1
Authority
EP
European Patent Office
Prior art keywords
metal
sulfonic acid
electroplating bath
electroplating
bath according
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.)
Withdrawn
Application number
EP01304721A
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German (de)
English (en)
Inventor
Conor Anthony Dullaghan
Joseph Anthony Abys
Peter Epstein
Joseph John Maisano
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.)
Nokia of America Corp
Original Assignee
Lucent Technologies 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 Lucent Technologies Inc filed Critical Lucent Technologies Inc
Publication of EP1162289A1 publication Critical patent/EP1162289A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
    • 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

  • the present invention is related to electroplating and, more particularly, to an electroplating salt, bath and process.
  • Precious metals are used in a.variety of industrial applications including electrical circuits as electrical contact surfaces, conducting paths and heat sinks.
  • Various properties of precious metals make their use in such applications highly advantageous. These properties include physical and chemical stability, high electrical conductivity, low porosity, and high thermal conductivity.
  • Precious metals are often used in high-density circuits such as integrated circuits because of one or more of the properties set forth above.
  • One problem with precious metal electroplating processes involves the selection of a suitable compound to supply the plating metal initially to the bath.
  • the compound should be stable, easily made in reasonably pure form and readily soluble in the electroplating bath.
  • the problem is particularly difficult where rapid, high quantity palladium electroplating is being carried out. In this case, relatively large amounts of palladium metal are being plated out and therefore large amounts of palladium must be added to the bath. Under these circumstances, high solubility and high rate of solubility is extremely important.
  • an electroplating bath includes a metal-sulfonic acid complex wherein the metal is a precious metal, and free sulfonic acid.
  • precious metals include Pd, Au, Hard Au (with Ni or Co as hardening agents), Pt, Rh, Ru, Ag and alloys thereof.
  • the sulfonic acid may for example be methane sulfonic acid (MSA).
  • MSA methane sulfonic acid
  • the resulting bath may have a pH less than 2.5, particularly less than 1.0.
  • the electroplating bath may include only a single additive, such as a brightener or brightening agent.
  • the electroplating bath may also include an alloying metal-sulfonic acid complex.
  • the bath for plating an Pd-Ni alloy may include a Pd-sulfonic acid complex and a Ni-sulfonic acid complex. The concentration of the two metal complexes is largely dictated by the desired percentage composition of the alloy.
  • a process of electroplating a metal on an object involves maintaining an object to be plated in a solution including a metal-sulfonic acid complex having a precious metal, and free sulfonic acid while providing current through the bath.
  • the object may be pre-dipped in sulfonic acid.
  • the precious metal may be Pd which is immersion deposited on a substrate, such as Cu or an alloy thereof
  • a metal salt for use in an electroplating bath to electroplate Pd or Pd alloys is provided.
  • the chemical formula for the Pd salt may be expressed as follows: Pd(NH 3 ) x MSA 2 wherein x is in the range of 0 to 4.
  • a process of synthesizing a metal salt for use in supplying a plating metal to an electroplating bath may involve mixing sulfonic acid with a source of metal ions to form a slurry, the metal being a precious metal; filtering the slurry to collect the precious metal-sulfonic acid salt; washing the collected salt with alcohol; and drying the washed salt.
  • the mixing may occur at approximately room temperature.
  • the present invention is directed to a metal composition, particularly a metal complex of methane sulfonic acid (MSA), for supplying a plating metal to an electroplating bath and a process of synthesizing the metal-MSA complex.
  • MSA methane sulfonic acid
  • the present invention is further directed to an electroplating bath including a metal complex of sulfonic acid and a process of employing such a bath to electroplate precious metals on an object (e.g., a substrate).
  • precious metals include Pd, Au, Hard Au (with Ni or Co as hardening agents), Pt, Rh, Ru, Ag and alloys thereof.
  • metal complexes of a sulfonic acid may generally be employed to supply a plating metal to an electroplating bath to electroplate precious metals onto a surface of an object.
  • a process to form the metal-sulfonic acid complex is provided herein which results in high yields of the metal salt with little or minimal waste of the underlying metal.
  • metal-sulfonic acid complexes Through the use of such metal-sulfonic acid complexes, it is possible to obtain a very acidic bath for electroplating precious metals which is particularly suitable in plating a strike or underlayer onto an object. Additionally, the metal-sulfonic acid complex provides an electrolytic bath or solution which requires less chemicals and additives, reduces contamination or the likelihood of contamination of the main plating tank, produces quality-grade plated products, and may reduce the overall costs in maintaining the main plating tanks.
  • an electrolytic bath or solution for plating precious metals onto a surface of an object.
  • the bath or solution comprises a metal-sulfonic acid complex or salt wherein the metal is a precious metal, and free sulfonic acid.
  • the bath may also include an alloying metal-sulfonic acid complex or salt for plating precious metal alloys.
  • Such an arrangement provides for an acidic bath with a pH level less than 2.5, preferably less than 1.0.
  • the bath or solution may be limited only to a single additive, such as a brightening agent or brighteners or other well known plating additives.
  • a single additive such as a brightening agent or brighteners or other well known plating additives.
  • additive systems for Pd plating can typically be grouped in to two classes.
  • Class I - are generally unsaturated sulfonic compunds where unsaturation is in the alpha- or beta -position with respect to the sulfonic group.
  • Such compounds have the formula A - SO 3 - B where A is an aryl or alkylene group, substituted or unsubstituted, and B may be OH, OR, OM, NH2, etc.
  • a process of plating precious metals is provided herein.
  • the plating process generally involves maintaining an object (e.g., a substrate) to be plated in a bath or solution containing metal-sulfonic acid complex wherein the metal is a precious metal, while providing a current through the bath.
  • the bath may further include an alloying metal-sulfonic acid complex.
  • the process may be employed to deposit a strike or underlayer of a precious metal.
  • an electrolyte or salt and a process of manufacturing thereof are provided for use in plating precious metals, such as Pd.
  • the Pd electrolyte or salt may comprise a palladium-amine methane sulfonic acid complex: Pd(NH 3 ) x MSA 2 where
  • a metal-sulfonic acid salt provides various benefits and advantages over current approaches.
  • the use of Pd-MSA salt provides a very acidic bath with a pH below at least 2.5, preferably below 1.0, which is particularly useful to plate a strike (e.g., a layer having an approximate thickness of 3-4 ⁇ -inches) as well as to plate other-types of metal layers having an approximate thickness of 10-20 ⁇ -inches.
  • the high acidity of the bath scrubs off the surface layer (e.g., an oxide layer) on the substrate to be plated without requiring additional chemicals or additives which typically increase the complexity and cost of the bath.
  • the bath may be limited to a single additive.
  • the Pd-MSA salt provides a plating bath which is particularly suitable for depositing a strike. This results in additional benefits including improved adhesion on easily passivated surfaces such as Ni, reduction of porosity of subsequent deposits and further protects the main plating bath from contamination caused by substrate corrosion and metal salts dragged-in from previous plating operations.
  • the Pd-MSA salt provides a plating bath that is compatible with other plating operations, such as non-halide and halide based chemistries, which may be performed by the main plating tank.
  • a reaction scheme of an alloying metal-MSA salt may generally be expressed as follows: [M][A]+MSA (excess) ⁇ [M][MSA]+MSA+HA where:
  • the bath or solution may be prepared by mixing a solution of the alloying metal-MSA complex together with a Pd-MSA complex and free MSA.
  • a mixed ligand system may also be employed as desired.
  • An appropriate ligand may be selected depending on the metals in the desired alloy.
  • the ligand for Pd is ammonia.
  • the general process for synthesizing a precious metal complex of sulfonic acid for use in supplying a precious metal plating metal to a bath may involve:
  • the remaining filtrates and alcohol may be collected and recycled accordingly.
  • the remaining filtrates were collected and sent to recycle for Pd recovery. If desired, the alcohol used to wash the product may also be recycled by evaporation and condensation using standard equipment.
  • the general process by which a precious metal may be electroplated onto an object (e.g., a substrate) through the use of a bath including metal-sulfonic salt for supplying the precious metal preferably involves:
  • the above electroplating process may be employed to immersion deposit Pd on a substrate, such as Cu or an alloy thereof.
  • the bath may be employed with various plating processes, such as low speed plating which is typical for rack mounted articles or high speed plating which is typical of reel-to-reel type continuous feeding for electronic components (e.g., connectors, printed circuit boards, printed wiring boards, etc.).
  • electronic components e.g., connectors, printed circuit boards, printed wiring boards, etc.
  • a composition of a bath or solution for electroplating Pd is provided.
  • the single additive may be a class I or II brightening agent (brightener), as discussed above.
  • Pd may be deposited at a pH below 1. [Pd(NH 3 ) 4 ]MSA 2 ; 0.5-20 g/L of Pd a single additive 0.5-10mL/L Free MSA 50-300 mL/L pH less than ( ⁇ ) 1 Temperature Room Temperature Current density 5-50 ASF Rotation 100-500 rpm
  • a composition of a bath or solution for electroplating Pd-Ni alloy is provided.
  • the single additive may be a class I or II brightening agent (brightener), as discussed above.
  • Pd-Ni alloy may be deposited at a pH below 1. [Pd(NH 3 ) 4 ]MSA 2 ; 0.5-20 g/L of Pd Ni[MSA] 0.5-20 g/l of Ni a single additive 0.5-10mL/L/L pH less than ( ⁇ ) 1 Temperature Room Temperature Current density 5-50 ASF Rotation 100-500 rpm
  • Figs. 3A-3D illustrate images obtained with a scanning electron microscope at different thickness levels at 2200x of Pd layer deposited on a substrate or object using the processes of Figs. 1 and 2. As shown, the deposited layer did not evidence any micro-cracking.
  • Ni and Cu were both added up to 50 ppm with no negative impact on deposit quality.
  • drag-in concerns from other plating operations up to 20 ml/l was deliberately added to both halide and non-halide systems with no resulting problems.

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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)
EP01304721A 2000-06-08 2001-05-29 Bain pour l'electrodeposition de palladium et processus pour l'electrodeposition Withdrawn EP1162289A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US590234 1984-03-20
US59023400A 2000-06-08 2000-06-08

Publications (1)

Publication Number Publication Date
EP1162289A1 true EP1162289A1 (fr) 2001-12-12

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EP (1) EP1162289A1 (fr)
JP (1) JP2002060989A (fr)
KR (1) KR20010112499A (fr)
HK (1) HK1038383A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3417097B1 (fr) * 2016-02-16 2021-04-07 LumiShield Technologies Incorporated Dépôt électrochimique d'éléments en milieu aqueux

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098656A (en) * 1976-03-11 1978-07-04 Oxy Metal Industries Corporation Bright palladium electroplating baths
US4244739A (en) * 1978-07-25 1981-01-13 Roberto Cagnassi Catalytic solution for the electroless deposition of metals
US4465563A (en) * 1982-12-22 1984-08-14 Learonal, Inc. Electrodeposition of palladium-silver alloys
US4673472A (en) * 1986-02-28 1987-06-16 Technic Inc. Method and electroplating solution for deposition of palladium or alloys thereof
JPH0841676A (ja) * 1994-08-01 1996-02-13 Ebara Yuujiraito Kk 非シアン性貴金属めっき浴
JPH10204676A (ja) * 1996-11-25 1998-08-04 C Uyemura & Co Ltd 錫−銀合金電気めっき浴及び錫−銀合金電気めっき方法
US6099713A (en) * 1996-11-25 2000-08-08 C. Uyemura & Co., Ltd. Tin-silver alloy electroplating bath and tin-silver alloy electroplating process
WO2000056952A1 (fr) * 1999-03-19 2000-09-28 Technic, Incorporated Bain galvanoplastique
DE19928047A1 (de) * 1999-06-19 2000-12-21 Gerhard Hoffacker Schadstoffarme bis schadstoffreie wäßrige Systeme zur galvanischen Abscheidung von Edelmetallen und Edelmetall-Legierungen
US6165342A (en) * 1996-07-23 2000-12-26 Degussa Huls Aktiengesellschaft Cyanide-free electroplating bath for the deposition of gold and gold alloys
US6251249B1 (en) * 1996-09-20 2001-06-26 Atofina Chemicals, Inc. Precious metal deposition composition and process

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2403399A1 (fr) * 1977-09-19 1979-04-13 Oxy Metal Industries Corp Bains de revetement electrolytique de palladium brillant
US4478692A (en) * 1982-12-22 1984-10-23 Learonal, Inc. Electrodeposition of palladium-silver alloys

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4098656A (en) * 1976-03-11 1978-07-04 Oxy Metal Industries Corporation Bright palladium electroplating baths
US4244739A (en) * 1978-07-25 1981-01-13 Roberto Cagnassi Catalytic solution for the electroless deposition of metals
US4465563A (en) * 1982-12-22 1984-08-14 Learonal, Inc. Electrodeposition of palladium-silver alloys
US4673472A (en) * 1986-02-28 1987-06-16 Technic Inc. Method and electroplating solution for deposition of palladium or alloys thereof
JPH0841676A (ja) * 1994-08-01 1996-02-13 Ebara Yuujiraito Kk 非シアン性貴金属めっき浴
US6165342A (en) * 1996-07-23 2000-12-26 Degussa Huls Aktiengesellschaft Cyanide-free electroplating bath for the deposition of gold and gold alloys
US6251249B1 (en) * 1996-09-20 2001-06-26 Atofina Chemicals, Inc. Precious metal deposition composition and process
JPH10204676A (ja) * 1996-11-25 1998-08-04 C Uyemura & Co Ltd 錫−銀合金電気めっき浴及び錫−銀合金電気めっき方法
US6099713A (en) * 1996-11-25 2000-08-08 C. Uyemura & Co., Ltd. Tin-silver alloy electroplating bath and tin-silver alloy electroplating process
WO2000056952A1 (fr) * 1999-03-19 2000-09-28 Technic, Incorporated Bain galvanoplastique
DE19928047A1 (de) * 1999-06-19 2000-12-21 Gerhard Hoffacker Schadstoffarme bis schadstoffreie wäßrige Systeme zur galvanischen Abscheidung von Edelmetallen und Edelmetall-Legierungen

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
MASAKI S: "Mirror-Bright Silver Plating from a Cyanide-Free Bath", METAL FINISHING, ELSEVIER SCIENCE PUBLISHING, NEW YORK, NY, US, vol. 96, no. 1, 1998, pages 16,18 - 20, XP004113126, ISSN: 0026-0576 *
PATENT ABSTRACTS OF JAPAN vol. 1996, no. 06 28 June 1996 (1996-06-28) *
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 13 30 November 1998 (1998-11-30) *
TETSUYA KONDO ET AL: "SILVER PLATING FROM SILVER METHANESULFONATE-POTASSIUM IODIDE BATH", METAL FINISHING, ELSEVIER SCIENCE PUBLISHING, NEW YORK, NY, US, vol. 89, no. 10, 1 October 1991 (1991-10-01), pages 32 - 36, XP000261679, ISSN: 0026-0576 *

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KR20010112499A (ko) 2001-12-20
JP2002060989A (ja) 2002-02-28
HK1038383A1 (zh) 2002-03-15

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