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ES2252673T3 - BATHROOM FOR GOLD ELECTROLYTIC DEPOSIT. - Google Patents

BATHROOM FOR GOLD ELECTROLYTIC DEPOSIT.

Info

Publication number
ES2252673T3
ES2252673T3 ES03729763T ES03729763T ES2252673T3 ES 2252673 T3 ES2252673 T3 ES 2252673T3 ES 03729763 T ES03729763 T ES 03729763T ES 03729763 T ES03729763 T ES 03729763T ES 2252673 T3 ES2252673 T3 ES 2252673T3
Authority
ES
Spain
Prior art keywords
gold
bismuth
bath
soluble
ammonium
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
ES03729763T
Other languages
Spanish (es)
Inventor
Pierre Laude
Pierre-Andre Aeby
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.)
Metalor Technologies International SA
Original Assignee
Metalor Technologies International SA
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 SA filed Critical Metalor Technologies International SA
Application granted granted Critical
Publication of ES2252673T3 publication Critical patent/ES2252673T3/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/48Electroplating: Baths therefor from solutions of gold

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

Abstract

A bath for the electrolytic deposition of gold comprises, in solution in water, a gold sulfite, a grain refiner, an inhibitor and a conducting salt. The grain refiner is chosen from soluble compounds of bismuth, tin, tellurium and selenium. Preferred Features: The soluble bismuth compound is a soluble complex of ammonium citrate and bismuth. The inhibitor contains a derivative of phosphonic acid. The conducting salt is ammonium sulfite. The bath may also contain 20-100 g/liter, preferably 50 g/liter, of amidosulphonic acid.

Description

Baño para depósito electrolítico de oro.Bath for gold electrolytic deposit.

La presente invención es relativa al campo de los baños para depósitos electrolíticos. Se refiere, más particularmente, a un baño de oro sulfítico del tipo de los empleados para depositar capas de oro a la vez dúctiles y espesas, es decir típicamente de más de 200 \mum. Estos depósitos están particularmente bien adaptados, especialmente, para la realización de protuberancias conductoras, conocidas bajo el nombre de "bumps", utilizadas para conectar microcircuitos electrónicos.The present invention is related to the field of baths for electrolytic deposits. It refers, more particularly, to a sulfite gold bath of the type of used to deposit layers of gold both ductile and thick, that is typically more than 200 µm. These deposits are particularly well adapted, especially for the realization of conductive protuberances, known under the name of "bumps", used to connect microcircuits electronic

Durante mucho tiempo, el oro ha estado presente en los baños electrolíticos bajo la forma de complejos cianurados, como (Au(CN)_{2}). Sin embargo, a pesar de la calidad de los depósitos obtenidos, la toxicidad de los cianuros ha conducido a la búsqueda de otros productos y disoluciones de complejos solubles de sulfitos de oro les han sustituido.For a long time, gold has been present in electrolytic baths in the form of cyanide complexes, as (Au (CN) 2). However, despite the quality of the deposits obtained, the toxicity of cyanides has led to the search for other products and solutions of soluble complexes of gold sulphites have replaced them.

Siendo la toxicidad una noción muy relativa, se definirá como tóxico una sustancia nociva en las cantidades utilizadas para la aplicación indicada y como no tóxico una sustancia que no represente nocividad para esta aplicación.Being toxicity a very relative notion, it define as toxic a harmful substance in the amounts used for the indicated application and as a non-toxic one Substance that does not represent harmfulness for this application.

Algunas utilizaciones de depósitos de oro, especialmente para la realización de bumps, necesitan que la capa de metal sea particularmente dúctil, regular, con granos finos y que presente una dureza muy baja.Some uses of gold deposits, especially for the realization of bumps, they need the layer metal is particularly ductile, regular, with fine grains and that present a very low hardness.

Ahora bien, los baños de oro sulfíticos conocidos actualmente suministran depósitos demasiado duros, lo que impone un tratamiento térmico suplementario para ablandarlos. Además, utilizan afinadores de granos tóxicos, que contienen arsénico o talio. Por otra parte, las disoluciones obtenidas son agresivas y atacan los sustratos, especialmente cuando se trata de fotoresistentes.Now the known sulfite gold baths they currently supply too hard deposits, which imposes a supplementary heat treatment to soften them. In addition, they use Toxic grain tuners, which contain arsenic or thallium. By On the other hand, the solutions obtained are aggressive and attack the substrates, especially when it comes to photoresists.

La presente invención tiene principalmente por objetivo suministrar un baño de oro sulfítico exento de compuestos tóxicos y que permita realizar un depósito particularmente blando, sin tener que recurrir a un tratamiento térmico posterior. El pH del baño obtenido es neutro y la disolución no ataca los fotoresistentes corrientemente utilizados.The present invention has mainly for aim to provide a sulfite gold bath free of compounds toxic and allowing a particularly soft deposit, without having to resort to a subsequent heat treatment. PH of the bath obtained is neutral and the solution does not attack the commonly used photoresists.

De forma más precisa, el baño según la invención es del tipo que comprende, en disolución en el agua, sulfito de oro, un afinador de grano elegido entre los compuestos solubles de bismuto, estaño, telurio y selenio, un complejante y una sal conductora. Este baño está caracterizado porque comprende, además, ácido amidosulfónico.More precisely, the bath according to the invention it is of the type that comprises, in solution in water, sulfite of gold, a grain tuner chosen among the soluble compounds of bismuth, tin, tellurium and selenium, a complexant and a salt conductive This bathroom is characterized in that it also includes amidosulfonic acid

Otras características de la invención resaltaran de la descripción que sigue, no acompañada de dibujo.Other features of the invention will highlight of the description that follows, not accompanied by drawing.

De preferencia, el baño para depósito electrolítico de oro según la invención comprende:Preferably, the bathroom for deposit Gold electrolytic according to the invention comprises:

--
de 7 a 20 g/L de oro, bajo la forma de sulfito de oro elegido entre otras sales solubles de oro por la calidad del depósito obtenido,from 7 to 20 g / L gold, in the form of gold sulphite chosen among others soluble gold salts by the quality of the deposit obtained,

--
de 5 a 50 mg/L de bismuto, bajo la forma de una sal soluble de citrato de amonio y de bismuto, utilizado como afinador de grano no tóxico,from 5 to 50 mg / L bismuth, in the form of a soluble citrate salt of ammonium and bismuth, used as a grain refiner not toxic,

--
de 10 a 50 mL/L de un derivado de ácido fosfónico, por ejemplo, el producto conocido bajo el nombre de Dequest 2010, utilizado como complejante,from 10 at 50 mL / L of a phosphonic acid derivative, for example, the product known under the name of Dequest 2010, used as complexing,

--
de 20 a 100 g/L de sulfito de amonio, utilizado como sal conductora para electrodeposición, yof 20 at 100 g / L of ammonium sulphite, used as a conductive salt for electrodeposition, and

--
de 20 a 100 g/L de ácido amidosulfónico, igualmente utilizado como sal conductora.of 20 at 100 g / L amidosulfonic acid, also used as salt conductive

Según un modo de realización particularmente ventajoso, el baño comprende:According to one embodiment particularly advantageous, the bathroom comprises:

--
10 g/L de oro, bajo la forma de sulfito de oro,10 g / L of gold, in the form of gold sulphite,

--
15 mg/L de bismuto, bajo la forma de una sal soluble de citrato de amonio y de bismuto,fifteen mg / L of bismuth, in the form of a soluble citrate salt of ammonium and bismuth,

--
25 mL/L de Dequest 2010,25 mL / L of Dequest 2010,

--
50 g/L de sulfito de amonio, y50 g / L of ammonium sulphite, and

--
50 g/l de ácido amidosulfónico.50 g / l of amidosulfonic acid.

Así, el baño obtenido no utiliza ni sal de oro tóxica, ni afinador de granos tóxico. Además, permite obtener depósitos blandos, que presentan típicamente una dureza comprendida entre 50 y 70 Vickers, sin que sea necesario efectuar cualquier tratamiento térmico. La disolución obtenida no ataca los sustratos sobre los cuales los bumps son corrientemente depositados y su pH está típicamente comprendido entre 6,7 y 7,5.Thus, the bath obtained does not use gold salt toxic, or toxic grain tuner. In addition, it allows to obtain soft deposits, which typically have a hardness comprised between 50 and 70 Vickers, without requiring any heat treatment. The solution obtained does not attack the substrates over which bumps are currently deposited and their pH It is typically between 6.7 and 7.5.

La descripción que acaba de hacerse no es más que un ejemplo particular de un baño para depósito de oro electrolítico según la invención. Es también posible utilizar, como afinador de grano, cualquier compuesto soluble de estaño, telurio o selenio.The description just made is nothing more than a particular example of a bath for electrolytic gold deposit according to the invention. It is also possible to use, as a tuner of grain, any soluble compound of tin, tellurium or selenium.

Claims (6)

1. Baño para depósito electrolítico de oro, que comprende, en disolución en el agua, sulfito de oro, un afinador de grano elegido entre los compuestos solubles de bismuto, estaño, telurio y selenio, un complejante y una sal conductora, caracterizado porque comprende, además, ácido amidosulfónico.1. Bath for gold electrolytic deposit, comprising, in solution in water, gold sulphite, a grain tuner chosen from the soluble compounds of bismuth, tin, tellurium and selenium, a complexing agent and a conductive salt, characterized in that it comprises In addition, amidosulfonic acid. 2. Baño según la reivindicación 1, caracterizado porque dicho compuesto de bismuto es un complejo soluble de citrato de amonio y de bismuto.2. Bath according to claim 1, characterized in that said bismuth compound is a soluble complex of ammonium citrate and bismuth. 3. Baño según una de las reivindicaciones 1 y 2, caracterizado porque dicho complejante contiene un derivado de ácido fosfónico.3. Bath according to one of claims 1 and 2, characterized in that said complexer contains a phosphonic acid derivative. 4. Baño según una de las reivindicaciones 1 a 3, caracterizado porque dicha sal conductora es sulfito de amonio.4. Bath according to one of claims 1 to 3, characterized in that said conductive salt is ammonium sulphite. 5. Baño según la reivindicación 4, caracterizado porque comprende:5. Bath according to claim 4, characterized in that it comprises:
--
de 7 a 20 g/L de oro,from 7 to 20 g / L gold,
--
de 5 a 50 mg/L de bismuto,from 5 to 50 mg / L bismuth,
--
de 10 a 50 mL/L de un derivado de ácido fosfónico, from 10 at 50 mL / L of a phosphonic acid derivative,
--
de 20 a 100 g/L de sulfito de amonio, yof 20 at 100 g / L of ammonium sulphite, and
--
de 20 a 100 g/L de ácido amidosulfónico. of 20 at 100 g / L amidosulfonic acid.
6. Baño según la reivindicación 5, caracterizado porque comprende:6. Bath according to claim 5, characterized in that it comprises:
--
10 g/L de oro,10 g / L of gold,
--
15 mg/L de bismuto,fifteen mg / L bismuth,
--
25 mL/L de un derivado de ácido fosfónico,25 mL / L of a phosphonic acid derivative,
--
50 g/L de sulfito de amonio, y50 g / L of ammonium sulphite, and
--
50 g/L de ácido amidosulfónico.50 g / L of amidosulfonic acid.
ES03729763T 2002-07-04 2003-06-20 BATHROOM FOR GOLD ELECTROLYTIC DEPOSIT. Expired - Lifetime ES2252673T3 (en)

Applications Claiming Priority (2)

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

Publications (1)

Publication Number Publication Date
ES2252673T3 true ES2252673T3 (en) 2006-05-16

Family

ID=29719808

Family Applications (1)

Application Number Title Priority Date Filing Date
ES03729763T Expired - Lifetime ES2252673T3 (en) 2002-07-04 2003-06-20 BATHROOM FOR GOLD ELECTROLYTIC DEPOSIT.

Country Status (6)

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

Families Citing this family (5)

* 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
CN103741181B (en) * 2014-01-10 2016-01-27 哈尔滨工业大学 A kind of many coordination agents cyanide-free gold electroplating plating solution and electrogilding technique
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

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE754151A (en) * 1969-08-08 1970-12-31 Sel Rex Corp AQUEOUS BATH FOR ELECTROLYTIC GOLD OR GOLD ALLOY PLATING ON A CONDUCTIVE ARTICLE, PROCESS FOR MANUFACTURING SUCH AQUEOUS BATH AND USE OF THE SAME
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
DE3805627A1 (en) * 1988-02-24 1989-09-07 Wieland Edelmetalle GOLD BATH
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
DE4425110C1 (en) * 1994-07-15 1995-10-26 Heraeus Gmbh W C Aq. plating bath for electrodeposition of palladium
US20040065225A1 (en) * 2001-02-28 2004-04-08 Susanne Ruebel Bath for the galvanic deposition of gold and gold alloys, and uses thereof

Also Published As

Publication number Publication date
DE60302074T2 (en) 2006-07-13
EP1378590A1 (en) 2004-01-07
EP1520063B1 (en) 2005-10-26
ATE307918T1 (en) 2005-11-15
AU2003240347A1 (en) 2004-01-23
WO2004005589A1 (en) 2004-01-15
DE60302074D1 (en) 2005-12-01
EP1520063A1 (en) 2005-04-06

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