EP0598763A1 - Bain acide de depot galvanique de cuivre et son utilisation. - Google Patents

Bain acide de depot galvanique de cuivre et son utilisation.

Info

Publication number
EP0598763A1
EP0598763A1 EP92916259A EP92916259A EP0598763A1 EP 0598763 A1 EP0598763 A1 EP 0598763A1 EP 92916259 A EP92916259 A EP 92916259A EP 92916259 A EP92916259 A EP 92916259A EP 0598763 A1 EP0598763 A1 EP 0598763A1
Authority
EP
European Patent Office
Prior art keywords
poly
bath according
aqueous acid
acid bath
methyl
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
EP92916259A
Other languages
German (de)
English (en)
Other versions
EP0598763B1 (fr
Inventor
Wolfgang Dahms
Horst Westphal
Michael Jonat
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
Atotech Deutschland GmbH and Co KG
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 Atotech Deutschland GmbH and Co KG filed Critical Atotech Deutschland GmbH and Co KG
Publication of EP0598763A1 publication Critical patent/EP0598763A1/fr
Application granted granted Critical
Publication of EP0598763B1 publication Critical patent/EP0598763B1/fr
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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • the invention relates to an acid bath for the galvanic deposition of shiny, ductile and leveled copper coatings and the use of this combination.
  • the bath according to the invention can be used both to reinforce the conductor tracks of printed circuits and in the decorative sector.
  • the prior art includes baths which contain a mixture of oxygen-containing high-molecular compounds with organic, in particular aromatic thio compounds (DE-AS 1521062).
  • DE-AS 1521062 organic, in particular aromatic thio compounds
  • DE-AS 2039831 describes an acidic copper bath which, in addition to a polymeric oxygen-containing compound and a thio compound with a water-soluble group, also contains at least one dye from the series of the polymeric phenazonium compound in solution. Further work describes the combination of organic thio compounds and polymeric oxygen-containing compounds with other dyes such as crystal violet (EP-PS 71512) or phthalocyanine derivatives with aposafranine (DE-PS 3420999) or a combination with amides (DE-PS 2746938).
  • the object of this invention is to avoid these disadvantages.
  • R 1 is a lower alkyl C- j to C_ j .
  • R 2 is an aliphatic chain or an aromatic radical and a either means 1 or 2.
  • the amount in which the polyalkylene glycol dialkyl ether can be added in order to achieve a significant improvement in the copper deposition is about 0.005 to 30 g / liter; preferably 0.02 to 8.0 g / liter.
  • the real molar mass can be between 500 and 35000 g / mol; preferably 800 to 4000 g / mol.
  • polyaclylene glycol dialkyl ethers are known per se or can be prepared by processes known per se by reacting polyalkylene glycols with an alkylating agent, such as, for example, dimethyl sulfate or tert. Bute " .
  • Table 1 shows examples of the polyalkylene glycol dialkyl ethers to be used according to the invention and their preferred uses. Turning concentration listed: Table 1
  • At least one thio compound with a water-solubilizing group can be added to the compound according to the invention.
  • Further additives, such as nitrogen-containing thio compounds, polymeric nitrogen compounds and / or polymeric phenazonium compounds, can also be added to the bath.
  • Table 2 lists some common thio compounds with water-soluble groups and their preferred application concentration:
  • Table 3 contains examples of nitrogen-containing thio compounds (so-called thiourea derivatives) and Table 4 for polymeric phenazonium compounds and Table 5 for polymeric nitrogen compounds.
  • N-acetylthiourea N-trifluoroacetythiourea N-ethylthiourea N-cyanoacetylthiourea N-allylthiourea o-tolylthiourea N, N'-butylene thiourea thiazolidinethiol (2) 4-thiazolinethiol (2)
  • Imidazolidinthiol (2) (N, • -ethylenethiourea) 4-methyl-2-pyrimidinthiol 2-thiouracil 1 Tables 3 to 5 may possibly be omitted.
  • composition of the bath according to the invention can vary within wide limits.
  • an aqueous solution of the following composition is used:
  • Copper sulfate (CuS0 4 * 5H 2 0) preferably
  • chloride ions Preferably chloride ions
  • copper sulfate instead of copper sulfate, other copper salts can also be used, at least in part.
  • the sulfuric acid can also be partially or completely replaced by fluoroboric acid, methanesulfonic acid or other acids.
  • the chloride ions are added as alkali chloride (eg sodium chloride) or in the form of hydrochloric acid pa.
  • alkali chloride eg sodium chloride
  • hydrochloric acid pa The addition of sodium chloride can be omitted in whole or in part if halogen ions are already present in the additives.
  • customary brighteners, levelers or wetting agents can also be present in the bathroom.
  • the working conditions of the bath are as follows:
  • the electrolyte movement takes place by blowing clean air in, so strongly that the electrolyte surface is in a strong flush.
  • Copper with a content of 0.02 to 0.067% phosphorus is used as the anode.
  • a well-leveled, shiny copper coating is obtained at an electrolyte temperature of 30 ° C. with a current density of 4 A / dm 2 and movement by blowing in air.
  • the electrolyte is now subjected to a permanent load of 500 Ah / 1, the gloss former consumed during the electrolysis being supplemented to set values, the electrolyte at the tub edge shows clear gelatinous polymer framing.
  • the electrolyte is now subjected to a permanent load of 500 Ah / 1, the gloss former consumed during the electrolysis being supplemented to set values, the electrolyte at the tub edge shows clear gelatinous polymer framing.
  • the compound according to the invention polypropylene glycol dimethyl ether
  • the electrolyte shows no polymer framing after aging.
  • the electrolyte is now subjected to a permanent load of 500 Ah / 1, the gloss former consumed during the electrolysis being supplemented to set values, the electrolyte at the tub edge shows clear gelatinous polymer framing.
  • the compound according to the invention octyl monomethyl polyalkyl glycol, is added to the electrolyte in the same amount, the electrolyte shows no polymer framing after aging.

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)
  • Chemically Coating (AREA)

Abstract

Un bain acide aqueux sert à provoquer le dépôt galvanique de revêtements brillants, ductiles et nivelés en cuivre servant aussi bien à la décoration d'objets qu'au renforcement des pistes conductives de circuits imprimés. Ce bain se caractérise par le fait qu'il contient du dialkyléther de (poly)alkylèneglycol. Associés à des composés thiol contenant des groupes solubles dans l'eau, ces additifs permettent d'obtenir des électrolytes ayant une stabilité remarquable. On peut également y associer avec succès des composés supplémentaires de phénazonium, des composés polymères d'azote et/ou des composés thio azotés, selon les propriétés que l'on souhaite obtenir.
EP92916259A 1991-08-07 1992-07-22 Bain acide de depot galvanique de cuivre et son utilisation Expired - Lifetime EP0598763B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4126502A DE4126502C1 (fr) 1991-08-07 1991-08-07
DE4126502 1991-08-07
PCT/DE1992/000605 WO1993003204A1 (fr) 1991-08-07 1992-07-22 Bain acide de depot galvanique de cuivre et son utilisation

Publications (2)

Publication Number Publication Date
EP0598763A1 true EP0598763A1 (fr) 1994-06-01
EP0598763B1 EP0598763B1 (fr) 1995-12-13

Family

ID=6438067

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92916259A Expired - Lifetime EP0598763B1 (fr) 1991-08-07 1992-07-22 Bain acide de depot galvanique de cuivre et son utilisation

Country Status (8)

Country Link
US (1) US5433840A (fr)
EP (1) EP0598763B1 (fr)
JP (1) JP3121346B2 (fr)
AT (1) ATE131546T1 (fr)
CA (1) CA2115062C (fr)
DE (2) DE4126502C1 (fr)
ES (1) ES2082486T3 (fr)
WO (1) WO1993003204A1 (fr)

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US5849171A (en) * 1990-10-13 1998-12-15 Atotech Deutschland Gmbh Acid bath for copper plating and process with the use of this combination
JP3313277B2 (ja) * 1995-09-22 2002-08-12 古河サーキットフォイル株式会社 ファインパターン用電解銅箔とその製造方法
US6460548B1 (en) * 1997-02-14 2002-10-08 The Procter & Gamble Company Liquid hard-surface cleaning compositions based on specific dicapped polyalkylene glycols
WO1998036042A1 (fr) * 1997-02-14 1998-08-20 The Procter & Gamble Company Compositions liquides de nettoyage de surfaces dures a base de glycols de polyalkylene specifiques presentant un double coiffage
US5863410A (en) * 1997-06-23 1999-01-26 Circuit Foil Usa, Inc. Process for the manufacture of high quality very low profile copper foil and copper foil produced thereby
US7033463B1 (en) * 1998-08-11 2006-04-25 Ebara Corporation Substrate plating method and apparatus
KR100656581B1 (ko) * 1998-09-03 2006-12-12 가부시키가이샤 에바라 세이사꾸쇼 기판의 도금방법 및 장치
US6444110B2 (en) * 1999-05-17 2002-09-03 Shipley Company, L.L.C. Electrolytic copper plating method
JP2001073182A (ja) * 1999-07-15 2001-03-21 Boc Group Inc:The 改良された酸性銅電気メッキ用溶液
EP2111087B1 (fr) 1999-08-06 2011-01-19 Ibiden Co., Ltd. Carte de circuit imprimé multicouche
LU90532B1 (en) * 2000-02-24 2001-08-27 Circuit Foil Luxembourg Trading Sarl Comosite copper foil and manufacturing method thereof
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US6361673B1 (en) 2000-06-27 2002-03-26 Ga-Tek Inc. Electroforming cell
US6679983B2 (en) * 2000-10-13 2004-01-20 Shipley Company, L.L.C. Method of electrodepositing copper
DE10058896C1 (de) * 2000-10-19 2002-06-13 Atotech Deutschland Gmbh Elektrolytisches Kupferbad, dessen Verwendung und Verfahren zur Abscheidung einer matten Kupferschicht
US7074315B2 (en) 2000-10-19 2006-07-11 Atotech Deutschland Gmbh Copper bath and methods of depositing a matt copper coating
US6797146B2 (en) * 2000-11-02 2004-09-28 Shipley Company, L.L.C. Seed layer repair
US20020195351A1 (en) * 2001-04-12 2002-12-26 Chang Chun Plastics Co., Ltd. Copper electroplating composition for integrated circuit interconnection
JP2003105584A (ja) * 2001-07-26 2003-04-09 Electroplating Eng Of Japan Co 微細配線埋め込み用銅メッキ液及びそれを用いた銅メッキ方法
US6911068B2 (en) * 2001-10-02 2005-06-28 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
US6652731B2 (en) 2001-10-02 2003-11-25 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
US6736954B2 (en) * 2001-10-02 2004-05-18 Shipley Company, L.L.C. Plating bath and method for depositing a metal layer on a substrate
EP1310582A1 (fr) * 2001-11-07 2003-05-14 Shipley Company LLC Procédé de placage électrolytique de cuivre
US6676823B1 (en) * 2002-03-18 2004-01-13 Taskem, Inc. High speed acid copper plating
EP1475463B2 (fr) * 2002-12-20 2017-03-01 Shipley Company, L.L.C. Méthode pour placage électrolytique utilisant du courant pulsé inversé
DE10261852B3 (de) * 2002-12-20 2004-06-03 Atotech Deutschland Gmbh Gemisch oligomerer Phenaziniumverbindungen und dessen Herstellungsverfahren, saures Bad zur elektrolytischen Abscheidung eines Kupferniederschlages, enthaltend die oligomeren Phenaziniumverbindungen, sowie Verfahren zum elektrolytischen Abscheiden eines Kupferniederschlages mit einem das Gemisch enthaltenden Bad
US6851200B2 (en) * 2003-03-14 2005-02-08 Hopkins Manufacturing Corporation Reflecting lighted level
DE102004045451B4 (de) 2004-09-20 2007-05-03 Atotech Deutschland Gmbh Galvanisches Verfahren zum Füllen von Durchgangslöchern mit Metallen, insbesondere von Leiterplatten mit Kupfer
TWI400365B (zh) * 2004-11-12 2013-07-01 Enthone 微電子裝置上的銅電沈積
US20070158199A1 (en) * 2005-12-30 2007-07-12 Haight Scott M Method to modulate the surface roughness of a plated deposit and create fine-grained flat bumps
US20070178697A1 (en) * 2006-02-02 2007-08-02 Enthone Inc. Copper electrodeposition in microelectronics
CN101416569B (zh) 2006-03-30 2011-04-06 埃托特克德国有限公司 用金属填充孔和凹处的电解方法
JP2007327127A (ja) * 2006-06-09 2007-12-20 Daiwa Fine Chemicals Co Ltd (Laboratory) 銀めっき方法
US7905994B2 (en) 2007-10-03 2011-03-15 Moses Lake Industries, Inc. Substrate holder and electroplating system
US8262894B2 (en) 2009-04-30 2012-09-11 Moses Lake Industries, Inc. High speed copper plating bath
EP2547731B1 (fr) * 2010-03-18 2014-07-30 Basf Se Composition pour l'électrodéposition de métaux comprenant un agent de nivellement
US8691987B2 (en) 2010-09-24 2014-04-08 Andrew M. Krol Method of producing polymeric phenazonium compounds
US8735580B2 (en) 2010-09-24 2014-05-27 Andrew M. Krol Method of producing polymeric phenazonium compounds
CN103422079B (zh) * 2012-05-22 2016-04-13 比亚迪股份有限公司 一种化学镀铜液及其制备方法
EP2735627A1 (fr) * 2012-11-26 2014-05-28 ATOTECH Deutschland GmbH Composition de bain de placage de cuivre
JP2017503929A (ja) * 2013-11-25 2017-02-02 エンソン インコーポレイテッド 銅の電析
DE102014208733A1 (de) * 2014-05-09 2015-11-12 Dr. Hesse Gmbh & Cie Kg Verfahren zum elektrolytischen Abscheiden von Kupfer aus Wasser basierenden Elektrolyten
JP6733314B2 (ja) * 2015-09-29 2020-07-29 三菱マテリアル株式会社 高純度銅電解精錬用添加剤と高純度銅製造方法
KR20210094558A (ko) * 2018-11-07 2021-07-29 코벤트야 인크. 새틴 구리조 및 새틴 구리층 침착 방법
JP7374556B2 (ja) 2019-11-29 2023-11-07 ダイハツ工業株式会社 変速機

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Also Published As

Publication number Publication date
EP0598763B1 (fr) 1995-12-13
JP3121346B2 (ja) 2000-12-25
ES2082486T3 (es) 1996-03-16
CA2115062A1 (fr) 1993-02-18
DE4126502C1 (fr) 1993-02-11
ATE131546T1 (de) 1995-12-15
JPH07505187A (ja) 1995-06-08
DE59204703D1 (de) 1996-01-25
CA2115062C (fr) 2005-11-22
US5433840A (en) 1995-07-18
WO1993003204A1 (fr) 1993-02-18

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