EP0536170A1 - Combinaison de bains aqueux pour le depot de l'or sans courant. - Google Patents

Combinaison de bains aqueux pour le depot de l'or sans courant.

Info

Publication number
EP0536170A1
EP0536170A1 EP91910402A EP91910402A EP0536170A1 EP 0536170 A1 EP0536170 A1 EP 0536170A1 EP 91910402 A EP91910402 A EP 91910402A EP 91910402 A EP91910402 A EP 91910402A EP 0536170 A1 EP0536170 A1 EP 0536170A1
Authority
EP
European Patent Office
Prior art keywords
gold
combination
bath
nickel
salts
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.)
Granted
Application number
EP91910402A
Other languages
German (de)
English (en)
Other versions
EP0536170B1 (fr
Inventor
Renate Gesemann
Juergen Spindler
Falk Richter
Renate Broulik
Klaus Janotta
Robert Ruether
Manfred Dettke
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.)
Atotech Deutschland GmbH and Co KG
Original Assignee
Schering AG
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 Schering AG filed Critical Schering AG
Publication of EP0536170A1 publication Critical patent/EP0536170A1/fr
Application granted granted Critical
Publication of EP0536170B1 publication Critical patent/EP0536170B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents

Definitions

  • the invention relates to a combination of aqueous baths for electroless gold plating and the use of this combination.
  • Electroless gold baths containing the anion disulfitoaurate - (I) are known from the publications DD-PS 150 762, DD-PS 240 915 or DD-PS 244 768. Furthermore, electroless gold baths containing potassium dicyanoaurate (I) are described in the documents DD-PS 273 651 or US Pat. No. 3,506,462. Difficulties with gold plating arise with the deposition on nickel layer surfaces. Either there is no deposition on nickel or nickel alloy surfaces (US Pat. No. 1,322,203) or it is a cementation deposition (US Pat. No. 3,123,484) which only allows the deposition of thin gold layers (DD-PS 265 915). Cementation of the gold also has the disadvantage that, with longer treatment times, the adhesion of the gold layers deteriorates.
  • Gold layer thicknesses of 0.2 - 3.0 ⁇ m are required for chip or wire bonding.
  • the electrolytes indicated for this with a high deposition rate are only stable to a limited extent (Rieh, D.W., Proc. Am.Elekctropl.Soc. 1971, p. 58 and US Pat. No. 4,169,171).
  • Alkaline soluble photoresists or varnishes are often used to cover surfaces that are not to be coated for selective coating tasks. It is therefore not possible to use gold electrolytes working in the alkaline range,> pH 9 (Dettke, electroless coating, Eugen G. Leuze Verlag 1988, pp. 74-78).
  • DD-PS 263 307 also describes a chemical-reductive gold bath with a high deposition rate.
  • the disadvantage of this bath is that a simultaneous cementation process takes place.
  • the object of the present invention is to achieve stable deposition of adhesive, bondable gold layers of> 0.2 ⁇ m with particularly short deposition times.
  • this object is achieved by a gold-electrolyte combination consisting of a prebath containing the anion disulfitoaurate-I ([Au (S0 3 ) 2 ] 3 ⁇ as the gold salt, an alkali and / or ammonium sulfite (S0 3 ) ⁇ as Stabilizer and a reducing agent, and a main bath containing the anion dicyanoaurate-I [Au (CN) 2 ] ⁇ as gold salt, thiourea or its derivatives as stabilizers and cobalt-II salts ⁇ optionally a complexing agent and optionally a nickel-II salt , solved.
  • a gold-electrolyte combination consisting of a prebath containing the anion disulfitoaurate-I ([Au (S0 3 ) 2 ] 3 ⁇ as the gold salt, an alkali and / or ammonium sulfite (S0 3 ) ⁇ as Stabilizer and
  • the gold electrolyte contained in the prebath, disulfitoaurate-I can be used in the form of its ammonium or alkali salts.
  • Suitable reducing agents for the preliminary bath are, for example, aldehyde and aledehyde-sulfite adducts.
  • Formaldehyde (methanal) and the adduct formaldehyde / sodium sulfite (Rongali ⁇ ) are particularly suitable.
  • a complexing agent for example ethylenediamine, can optionally be added to the prebath.
  • the gold anion used in the main bath can also be used in the form of its ammonium or alkali salts.
  • Thiourea or its derivatives are added to the main bath as stabilizers; for example thiosemicarbazide.
  • Cobalt-II salts are added to the electrolyte as an essential component of the main bath, for example cobalt-II halides, cobalt-II sulfate, cobalt-II nitrate, cobalt-II-for iate or cobalt-II-acetate.
  • a nickel salt for example a nickel (II) halide, with particular advantage nickel (II) chloride
  • nickel (II) chloride can be added to the main bath to increase the deposition rate.
  • This pickling solution consists of a hydroxycarboxylic acid or its salts and ammonium chloride. Examples of suitable hydroxycarboxylic acids are tartaric acid and citric acid.
  • the decapitation solution is to be used if the existing nickel or nickel alloy surface shows a high level of cementation during the gold coating and there is an additional dissolution of the nickel layer by the acidic electrolyte solution.
  • the dense gold layer protects the nickel surface from selective dissolution in the acidic gold main electrolyte.
  • the acidic gold main electrolyte is additionally stabilized by the use of thiourea or its derivatives, with stability remaining achieved by an adapted concentration of nickel ions (nickel chloride) in the electrolyte, which accelerates the catalytic reduction reaction and thus a deposition rate of 2 ⁇ m / h .
  • a pretreatment solution in the event of further gold plating of gold and / or gold-plated surfaces can accelerate the initial reaction of the deposition from the main gold.
  • the pretreatment solution consists of heavy metal ions, eg Ni 2+ ions in an acidic environment, which are adsorbed on the gold surface and change the surface potential.
  • the invention further relates to a method for gold deposition using the electrolyte combination according to the invention and optionally the decapitation solution.
  • the subject of the invention is particularly well suited for the deposition of gold layers on conductive ceramic chip carrier housings. They are meta11ized with chemical-reductive nickel-phosphor layers and gold (2-3 ⁇ ) as an external contact layer system.
  • the nickel-phosphor layer is first of all with the following
  • Chips were over 20 N. When using ultrasonic wire bonding, high strengths of the connecting wires were achieved (pull test 9.2 ⁇ 1.1 CN).
  • the adhesive strength of the Ni ⁇ Py-Au layer system was 1300 N / cm 2 with the forehead pull test.
  • Au wires bonded with the Thermosonic process (ff 20 ⁇ m) showed tear strengths of 9.1
  • a stripline circuit on Al 2 0 3 ceramic should be with the layer system Ni ⁇ P y -galv. Cu - Ni ⁇ P y -Au can be built.
  • the interconnect structure including galvanized copper, is produced using lift-off technology. After removing the photoresist, the layer system Ni ⁇ P y -galv. Copper coated with Ni ⁇ P y from an alkaline electrolyte and gold-plated with the combination according to the invention as follows:
  • Laser metalization produces a Ni ⁇ P y structure from an alkaline electrolyte on Al 0 3 ceramic. This structure is to be gold-plated for the production of wire bond islands.
  • the IC chip is attached by gluing.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Conductive Materials (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne la combinaison de bains aqueux pour le dépôt de l'or sans courant, de préférence pour le dépôt de l'or sur des couches de nickel ou d'alliages de nickel. La combinaison se compose d'un bain préalable et d'un bain principal, ainsi que, le cas échéant, d'une solution décapante et d'un traitement préalable. La couche d'or obtenue convient pour les connexions de pastilles et de fils.
EP91910402A 1990-06-28 1991-06-13 Combinaison des electrolytes d'or pour le depot de l'or sans courant Expired - Lifetime EP0536170B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4020795 1990-06-28
DE4020795A DE4020795C1 (fr) 1990-06-28 1990-06-28
PCT/DE1991/000498 WO1992000398A1 (fr) 1990-06-28 1991-06-13 Combinaison de bains aqueux pour le depot de l'or sans courant

Publications (2)

Publication Number Publication Date
EP0536170A1 true EP0536170A1 (fr) 1993-04-14
EP0536170B1 EP0536170B1 (fr) 1995-08-30

Family

ID=6409370

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91910402A Expired - Lifetime EP0536170B1 (fr) 1990-06-28 1991-06-13 Combinaison des electrolytes d'or pour le depot de l'or sans courant

Country Status (9)

Country Link
US (1) US5320667A (fr)
EP (1) EP0536170B1 (fr)
JP (1) JPH0649947B2 (fr)
KR (1) KR930701639A (fr)
CN (1) CN1060504A (fr)
AT (1) ATE127166T1 (fr)
CA (1) CA2086341C (fr)
DE (2) DE4020795C1 (fr)
WO (1) WO1992000398A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4241657C1 (de) * 1992-12-04 1994-07-14 Atotech Deutschland Gmbh Verfahren zur Erzeugung homogener Goldschichten aus stromlosen Goldbädern und Verwendung des Verfahrens
US5803957A (en) * 1993-03-26 1998-09-08 C. Uyemura & Co.,Ltd. Electroless gold plating bath
CN1131894C (zh) * 1994-12-27 2003-12-24 揖斐电株式会社 化学镀用的前处理液、化学镀浴槽和化学镀方法
DE19652991A1 (de) * 1996-12-13 1998-06-18 Albert Thorp Gmbh Verfahren zur zumindest teilweisen Goldbeschichtung eines Trägers
DE19745602C1 (de) * 1997-10-08 1999-07-15 Atotech Deutschland Gmbh Verfahren und Lösung zur Herstellung von Goldschichten
DE19745601C2 (de) * 1997-10-08 2001-07-12 Fraunhofer Ges Forschung Lösung und Verfahren zum stromlosen Abscheiden von Goldschichten sowie Verwendung der Lösung
WO2004108987A1 (fr) * 2003-06-05 2004-12-16 Nikko Materials Co., Ltd. Solution de placage d'or autocatalytique
CN1981347A (zh) * 2004-07-15 2007-06-13 积水化学工业株式会社 导电性微粒、导电性微粒的制造方法、和各向异性导电材料
JP5116956B2 (ja) * 2005-07-14 2013-01-09 関東化学株式会社 無電解硬質金めっき液
DE102009041264A1 (de) 2009-09-11 2011-03-24 IPHT Jena Institut für Photonische Technologien e.V. Verfahren zur Herstellung von optisch aktiven Nanostrukturen

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3506462A (en) * 1966-10-29 1970-04-14 Nippon Electric Co Electroless gold plating solutions
DD150762B1 (de) * 1980-04-17 1987-05-13 Falk Richter Cyanidfreies bad fuer die stromlose goldabscheidung
DD240915B1 (de) * 1983-12-22 1988-05-25 Falk Richter Cyanidfreies bad zur stromlosen abscheidung von hartgoldschichten
CN1003524B (zh) * 1985-10-14 1989-03-08 株式会社日立制作所 无电浸镀金溶液
DD244768B1 (de) * 1985-12-24 1990-08-08 Liebknecht Mikroelektron Verfahren zur erhaltung der loetfaehigkeit von nickelschichten
DD263307A1 (de) * 1987-08-17 1988-12-28 Mittweida Ing Hochschule Chemisch-reduktives goldbad mit hoher abscheidungsrate
DD273651A1 (de) * 1988-07-05 1989-11-22 Robotron Elektronik Bad zur chemischen vergoldung
US5130168A (en) * 1988-11-22 1992-07-14 Technic, Inc. Electroless gold plating bath and method of using same
DE4021681A1 (de) * 1989-07-12 1991-03-14 Kojima Chemicals Co Ltd Nichtelektrolytische goldplattierloesung
US4978559A (en) * 1989-11-03 1990-12-18 General Electric Company Autocatalytic electroless gold plating composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9200398A1 *

Also Published As

Publication number Publication date
CA2086341A1 (fr) 1991-12-29
US5320667A (en) 1994-06-14
DE4020795C1 (fr) 1991-10-17
CA2086341C (fr) 1998-03-31
JPH05506887A (ja) 1993-10-07
WO1992000398A1 (fr) 1992-01-09
JPH0649947B2 (ja) 1994-06-29
ATE127166T1 (de) 1995-09-15
DE59106385D1 (de) 1995-10-05
EP0536170B1 (fr) 1995-08-30
CN1060504A (zh) 1992-04-22
KR930701639A (ko) 1993-06-12

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