WO2004005589A1 - Bath for gold electrodeposition - Google Patents

Bath for gold electrodeposition Download PDF

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Publication number
WO2004005589A1
WO2004005589A1 PCT/CH2003/000400 CH0300400W WO2004005589A1 WO 2004005589 A1 WO2004005589 A1 WO 2004005589A1 CH 0300400 W CH0300400 W CH 0300400W WO 2004005589 A1 WO2004005589 A1 WO 2004005589A1
Authority
WO
WIPO (PCT)
Prior art keywords
gold
bath
bismuth
bath according
sulfite
Prior art date
Application number
PCT/CH2003/000400
Other languages
French (fr)
Inventor
Pierre Laude
Pierre-André AEBY
Original Assignee
Metalor Technologies International S.A.
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 Metalor Technologies International S.A. filed Critical Metalor Technologies International S.A.
Priority to EP03729763A priority Critical patent/EP1520063B1/en
Priority to AT03729763T priority patent/ATE307918T1/en
Priority to AU2003240347A priority patent/AU2003240347A1/en
Priority to DE60302074T priority patent/DE60302074T2/en
Publication of WO2004005589A1 publication Critical patent/WO2004005589A1/en

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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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold

Definitions

  • the present invention relates to the field of baths for electrolytic deposits. It relates, more particularly, to a sulphite gold bath of the type used to deposit layers of gold that are both ductile and thick, that is to say typically more than 200 ⁇ m. These deposits are particularly well suited, in particular, to the production of conductive protuberances, known under the name of "bumps", used to connect electronic chips.
  • gold has been present in electrolytic baths in the form of cyanide complexes, such as (Au (CN) 2 ) " .
  • cyanide complexes such as (Au (CN) 2 ) " .
  • Toxicity being a very relative concept, we will define as toxic a harmful substance in the quantities used for the intended application and as non-toxic a substance not presenting no harmfulness for this application.
  • metal layer be particularly ductile, regular, with fine grains and having a very low hardness.
  • the sulphite gold baths currently known provide deposits that are too hard, which requires additional heat treatment to soften them.
  • they use toxic grain refiners, containing arsenic or thallium.
  • the solutions obtained are aggressive and attack the substrates, especially when it comes to photoresists.
  • the main object of the present invention is to provide a sulphite gold bath free of toxic compounds and making it possible to deposit particularly tender, without having to use a subsequent heat treatment.
  • the pH of the bath obtained is neutral and the solution does not attack the photoresists commonly used.
  • the bath according to the invention is of the type comprising, in solution in water, gold sulfite, a grain refiner chosen from soluble compounds of bismuth, tin, tellurium and selenium, a complexing agent and a conductive salt.
  • This bath is characterized in that it further comprises amidosulfonic acid.
  • the bath for electrolytic deposition of gold according to the invention comprises:
  • a phosphonic acid derivative for example, the product known as Dequest 2010, used as complexing agent, - from 20 to 100 g / L of ammonium sulfite, used as conductive salt for plating, and
  • the bath comprises: - 10 g / L of gold, in the form of gold sulfite,
  • the bath obtained uses neither toxic gold salt, nor toxic grain refiner.
  • it makes it possible to obtain tender deposits, typically having a hardness of between 50 and 70 Vickers, without the need for any heat treatment.
  • the solution obtained does not attack the substrates on which bumps are commonly deposited and its pH is typically between 6.7 and 7.5.

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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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

The invention relates to a bath for gold electrodeposition, comprising, in solution in water, gold sulphite, a grain refiner which is selected from soluble compounds of bismuth, tin, tellurium and selenium, a complex-forming agent and a conducting salt. The invention is characterised in that it also comprises amidosulphonic acid.

Description

BAIN POUR DEPOT ELECTROLYTIQUE D'OR BATH FOR ELECTROLYTIC GOLD DEPOSIT
La présente invention se rapporte au domaine des bains pour dépôts électrolytiques. Elle concerne, plus particulièrement, un bain d'or sulfitique du type de ceux employés pour déposer des couches d'or à la fois ductiles et épaisses, c'est-à-dire typiquement de plus de 200 μm. Ces dépôts sont particulièrement bien adaptés, notamment, à la réalisation de protubérances conductrices, connues sous le nom de "bumps", utilisées pour connecter des puces électroniques. Pendant longtemps, l'or a été présent dans les bains électrolytiques sous la forme de complexes cyanures, comme (Au(CN)2)". Cependant, malgré la qualité des dépôts obtenus, la toxicité des cyanures a conduit à la recherche d'autres produits et des solutions de complexes solubles de sulfites d'or leur ont été substituées. La toxicité étant une notion très relative, on définira comme toxique une substance nocive dans les quantités utilisées pour l'application visée et comme non-toxique une substance ne présentant pas de nocivité pour cette application.The present invention relates to the field of baths for electrolytic deposits. It relates, more particularly, to a sulphite gold bath of the type used to deposit layers of gold that are both ductile and thick, that is to say typically more than 200 μm. These deposits are particularly well suited, in particular, to the production of conductive protuberances, known under the name of "bumps", used to connect electronic chips. For a long time, gold has been present in electrolytic baths in the form of cyanide complexes, such as (Au (CN) 2 ) " . However, despite the quality of the deposits obtained, the toxicity of cyanides led to the search for other products and solutions of soluble complexes of gold sulfites have been substituted in. Toxicity being a very relative concept, we will define as toxic a harmful substance in the quantities used for the intended application and as non-toxic a substance not presenting no harmfulness for this application.
Certaines utilisations de dépôts d'or, notamment pour la réalisation de bumps, nécessitent que la couche de métal soit particulièrement ductile, régulière, à grains fins et présentant une très faible dureté.Certain uses of gold deposits, in particular for making bumps, require that the metal layer be particularly ductile, regular, with fine grains and having a very low hardness.
Or, les bains d'or sulfitiques connus actuellement fournissent des dépôts trop durs, ce qui impose un traitement thermique supplémentaire pour les ramollir. De plus, ils utilisent des affineurs de grains toxiques, contenant de l'arsenic ou du thallium. Par ailleurs, les solutions obtenues sont agressives et attaquent les substrats, notamment lorsqu'il s'agit de photorésistes.Now, the sulphite gold baths currently known provide deposits that are too hard, which requires additional heat treatment to soften them. In addition, they use toxic grain refiners, containing arsenic or thallium. Furthermore, the solutions obtained are aggressive and attack the substrates, especially when it comes to photoresists.
La présente invention a principalement pour but de fournir un bain d'or sulfitique exempt de composés toxiques et permettant de réaliser un dépôt particulièrement tendre, sans avoir recours à un traitement thermique ultérieur. Le pH du bain obtenu est neutre et la solution n'attaque pas les photorésistes couramment utilisés.The main object of the present invention is to provide a sulphite gold bath free of toxic compounds and making it possible to deposit particularly tender, without having to use a subsequent heat treatment. The pH of the bath obtained is neutral and the solution does not attack the photoresists commonly used.
De façon plus précise, le bain selon l'invention est du type comportant, en solution dans de l'eau, du sulfite d'or, un affineur de grain choisi parmi des composés solubles de bismuth, d'étain, de tellure et de sélénium, un complexant et un sel conducteur. Ce bain est caractérisé en ce qu'il comporte, en outre, de l'acide amidosulfonique.More specifically, the bath according to the invention is of the type comprising, in solution in water, gold sulfite, a grain refiner chosen from soluble compounds of bismuth, tin, tellurium and selenium, a complexing agent and a conductive salt. This bath is characterized in that it further comprises amidosulfonic acid.
D'autres caractéristiques de l'invention ressortiront de la description qui va suivre, non accompagnée de dessin.Other characteristics of the invention will emerge from the description which follows, not accompanied by a drawing.
De préférence, le bain pour dépôt électrolytique d'or selon l'invention comporte :Preferably, the bath for electrolytic deposition of gold according to the invention comprises:
- de 7 à 20 g/L d'or, sous la forme de sulfite d'or choisi parmi d'autres sels solubles d'or pour la qualité du dépôt obtenu,- from 7 to 20 g / L of gold, in the form of gold sulfite chosen from other soluble gold salts for the quality of the deposit obtained,
- de 5 à 50 mg/L de bismuth, sous la forme d'un sel soluble de citrate d'ammonium et de bismuth, utilisé comme affineur de grain non- toxique,- from 5 to 50 mg / L of bismuth, in the form of a soluble salt of ammonium citrate and bismuth, used as a non-toxic grain refiner,
- de 10 à 50 mL/L d'un dérivé d'acide phosphonique, par exemple, le produit connu sous le nom de Dequest 2010, utilisé comme complexant, - de 20 à 100 g/L de sulfite d'ammonium, utilisé comme sel conducteur pour l'électrodéposition, et- from 10 to 50 mL / L of a phosphonic acid derivative, for example, the product known as Dequest 2010, used as complexing agent, - from 20 to 100 g / L of ammonium sulfite, used as conductive salt for plating, and
- de 20 à 100 g/L d'acide amidosulfonique, également utilisé comme sel conducteur.- from 20 to 100 g / L of amidosulfonic acid, also used as a conductive salt.
Selon un mode de réalisation particulièrement avantageux, le bain comporte : - 10 g/L d'or, sous la forme de sulfite d'or,According to a particularly advantageous embodiment, the bath comprises: - 10 g / L of gold, in the form of gold sulfite,
- 15 mg/L de bismuth, sous la forme d'un sel soluble de citrate d'ammonium et de bismuth,- 15 mg / L of bismuth, in the form of a soluble salt of ammonium citrate and bismuth,
- 25 mL/L de Dequest 2010, - 50 g/L de sulfite d'ammonium, et- 25 mL / L of Dequest 2010, - 50 g / L of ammonium sulfite, and
- 50 g/L d'acide amidosulfonique.- 50 g / L of amidosulfonic acid.
Ainsi, le bain obtenu n'utilise ni de sel d'or toxique, ni d'affineur de grains toxique. De plus, il permet d'obtenir des dépôts tendres, présentant typiquement une dureté comprise entre 50 et 70 Vickers, sans qu'il soit nécessaire d'effectuer un quelconque traitement thermique. La solution obtenue n'attaque pas les substrats sur lesquelles des bumps sont couramment déposés et son pH est typiquement compris entre 6,7 et 7,5.Thus, the bath obtained uses neither toxic gold salt, nor toxic grain refiner. In addition, it makes it possible to obtain tender deposits, typically having a hardness of between 50 and 70 Vickers, without the need for any heat treatment. The solution obtained does not attack the substrates on which bumps are commonly deposited and its pH is typically between 6.7 and 7.5.
La description qui vient d'être faite n'est qu'un exemple particulier d'un bain pour dépôt d'or électrolytique selon l'invention. Il est aussi possible d'utiliser, comme affineur de grain, tout composé soluble d'étain, de tellure ou de sélénium. The description which has just been made is only a particular example of a bath for depositing electrolytic gold according to the invention. It is also possible to use, as grain refiner, any soluble compound of tin, tellurium or selenium.

Claims

REVENDICATIONS
1. Bain pour dépôt électrolytique d'or, comportant, en solution dans de l'eau, du sulfite d'or, un affineur de grain choisi parmi des composés solubles de bismuth, d'étain, de tellure et de sélénium, un complexant et un sel conducteur, caractérisé en ce qu'il comporte, en outre, de l'acide amidosulfonique.1. Bath for electrolytic deposition of gold, comprising, in solution in water, gold sulfite, a grain refiner chosen from soluble compounds of bismuth, tin, tellurium and selenium, a complexing agent and a conductive salt, characterized in that it also comprises amidosulfonic acid.
2. Bain selon la revendication 1 , caractérisé en ce que ledit composé de bismuth est un complexe soluble de citrate d'ammonium et de bismuth.2. Bath according to claim 1, characterized in that said bismuth compound is a soluble complex of ammonium citrate and bismuth.
3. Bain selon l'une des revendications 1 et 2, caractérisé en ce que ledit complexant contient un dérivé d'acide phosphonique.3. Bath according to one of claims 1 and 2, characterized in that said complexing agent contains a derivative of phosphonic acid.
4. Bain selon l'une des revendications 1 à 3, caractérisé en ce que ledit sel conducteur est du sulfite d'ammonium.4. Bath according to one of claims 1 to 3, characterized in that said conductive salt is ammonium sulfite.
5. Bain selon la revendication 4, caractérisé en ce qu'il comporte:5. Bath according to claim 4, characterized in that it comprises:
- de 7 à 20 g/L d'or, - de 5 à 50 mg/L de bismuth,- from 7 to 20 g / L of gold, - from 5 to 50 mg / L of bismuth,
- de 10 à 50 mL/L d'un dérivé d'acide phosphonique,- from 10 to 50 mL / L of a phosphonic acid derivative,
- de 20 à 100 g/L de sulfite d'ammonium,- from 20 to 100 g / L of ammonium sulfite,
- de 20 à 100 g/L d'acide amidosulfonique.- from 20 to 100 g / L of amidosulfonic acid.
6. Bain selon la revendication 5, caractérisé en ce qu'il comporte : - 10 g/L d'or,6. Bath according to claim 5, characterized in that it comprises: - 10 g / L of gold,
- 15 mg/L de bismuth,- 15 mg / L of bismuth,
- 25 mL/L d'un dérivé d'acide phosphonique,- 25 mL / L of a phosphonic acid derivative,
- 50 g/L de sulfite d'ammonium, et- 50 g / L of ammonium sulfite, and
- 50 g/L d'acide amidosulfonique. - 50 g / L of amidosulfonic acid.
PCT/CH2003/000400 2002-07-04 2003-06-20 Bath for gold electrodeposition WO2004005589A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP03729763A EP1520063B1 (en) 2002-07-04 2003-06-20 Bath for gold electrodeposition
AT03729763T ATE307918T1 (en) 2002-07-04 2003-06-20 BATH FOR GALVANIC GOLD DEPOSITION
AU2003240347A AU2003240347A1 (en) 2002-07-04 2003-06-20 Bath for gold electrodeposition
DE60302074T DE60302074T2 (en) 2002-07-04 2003-06-20 BATHROOM FOR GALVANIC GOLD BUST

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02405558A EP1378590A1 (en) 2002-07-04 2002-07-04 Bath for gold electro deposition
EP02405558.4 2002-07-04

Publications (1)

Publication Number Publication Date
WO2004005589A1 true WO2004005589A1 (en) 2004-01-15

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PCT/CH2003/000400 WO2004005589A1 (en) 2002-07-04 2003-06-20 Bath for gold electrodeposition

Country Status (6)

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EP (2) EP1378590A1 (en)
AT (1) ATE307918T1 (en)
AU (1) AU2003240347A1 (en)
DE (1) DE60302074T2 (en)
ES (1) ES2252673T3 (en)
WO (1) WO2004005589A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103741181A (en) * 2014-01-10 2014-04-23 哈尔滨工业大学 Multi-coordination-agent cyanide-free electrogilding liquid and electrogilding process
CN107299366A (en) * 2017-08-24 2017-10-27 重庆立道表面技术有限公司 Non-cyanide plating solution for copper-plating used

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005036133C5 (en) 2005-07-26 2017-07-13 Ivoclar Vivadent Ag Bath for the electrodeposition of gold and gold alloys and additive mixture for such a bath
KR101464343B1 (en) * 2013-04-02 2014-11-28 한밭대학교 산학협력단 Non cyanide gold plating bath for bump and preparation method of bump
CN103741180B (en) * 2014-01-10 2015-11-25 哈尔滨工业大学 Non-cyanide bright electrogilding additive and application thereof

Citations (3)

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Publication number Priority date Publication date Assignee Title
CH506628A (en) * 1969-08-08 1971-04-30 Sel Rex Corp Aqueous bath for electroplating gold or gold alloy on a conductive article, method of making said aqueous bath and use thereof
DE3805627A1 (en) * 1988-02-24 1989-09-07 Wieland Edelmetalle GOLD BATH
DE4425110C1 (en) * 1994-07-15 1995-10-26 Heraeus Gmbh W C Aq. plating bath for electrodeposition of palladium

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CH530473A (en) * 1969-08-19 1972-11-15 Sel Rex Corp Process for the electrolytic deposition of brilliant gold and electrolytic bath for the implementation of this process
DD245787A3 (en) * 1984-10-25 1987-05-20 Mikroelektronik Friedrich Enge BATHROOM FOR THE HIGH-SPEED DEPOSITION OF GOLD
US4795534A (en) * 1986-09-25 1989-01-03 Vanguard Research Associates, Inc. Electrolyte solution and process for gold electroplating
DE3905705A1 (en) * 1989-02-24 1990-08-30 Degussa BATHROOM FOR GALVANIC DEPOSITION OF FINE GOLD COATINGS
DE4226167C2 (en) * 1992-08-07 1996-10-24 Sel Alcatel Ag Method for electrically conductive connection using flip-chip technology
CN100392155C (en) * 2001-02-28 2008-06-04 威兰牙科技术有限责任两合公司 Bath for galvanic deposition of gold and gold alloys, and use thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH506628A (en) * 1969-08-08 1971-04-30 Sel Rex Corp Aqueous bath for electroplating gold or gold alloy on a conductive article, method of making said aqueous bath and use thereof
DE3805627A1 (en) * 1988-02-24 1989-09-07 Wieland Edelmetalle GOLD BATH
DE4425110C1 (en) * 1994-07-15 1995-10-26 Heraeus Gmbh W C Aq. plating bath for electrodeposition of palladium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103741181A (en) * 2014-01-10 2014-04-23 哈尔滨工业大学 Multi-coordination-agent cyanide-free electrogilding liquid and electrogilding process
CN107299366A (en) * 2017-08-24 2017-10-27 重庆立道表面技术有限公司 Non-cyanide plating solution for copper-plating used

Also Published As

Publication number Publication date
AU2003240347A1 (en) 2004-01-23
DE60302074D1 (en) 2005-12-01
EP1520063A1 (en) 2005-04-06
EP1520063B1 (en) 2005-10-26
DE60302074T2 (en) 2006-07-13
ATE307918T1 (en) 2005-11-15
EP1378590A1 (en) 2004-01-07
ES2252673T3 (en) 2006-05-16

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