EP1717351A1 - Bain de galvanisation - Google Patents

Bain de galvanisation Download PDF

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Publication number
EP1717351A1
EP1717351A1 EP05009183A EP05009183A EP1717351A1 EP 1717351 A1 EP1717351 A1 EP 1717351A1 EP 05009183 A EP05009183 A EP 05009183A EP 05009183 A EP05009183 A EP 05009183A EP 1717351 A1 EP1717351 A1 EP 1717351A1
Authority
EP
European Patent Office
Prior art keywords
anode
bath according
electroplating bath
shield
electroplating
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Withdrawn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
EP05009183A
Other languages
German (de)
English (en)
Inventor
Ulrich Schmergel
Jean Dr. Rasmussen
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.)
MacDermid Enthone Inc
Original Assignee
Enthone 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 Enthone Inc filed Critical Enthone Inc
Priority to EP05009183A priority Critical patent/EP1717351A1/fr
Priority to CN2005101201051A priority patent/CN1854352B/zh
Priority to KR1020050122525A priority patent/KR100741198B1/ko
Priority to TW095107051A priority patent/TWI332533B/zh
Priority to JP2006121511A priority patent/JP4404871B2/ja
Priority to US11/380,559 priority patent/US20060272951A1/en
Publication of EP1717351A1 publication Critical patent/EP1717351A1/fr
Withdrawn legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/10—Electrodes, e.g. composition, counter electrode
    • C25D17/12—Shape or form
    • 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

Definitions

  • the invention relates to a galvanic bath, in particular an acidic electroplating bath, with an anode, a cathode and an electrolyte.
  • Electroplating baths of the aforementioned type are well known from the prior art, which is why it does not require a separate documentary proof at this point.
  • Galvanic processes such as copper plating, nickel plating, galvanizing or tinning, are operated by means of soluble or insoluble anodes.
  • soluble anodes also referred to as an active anode system
  • insoluble anodes also referred to as inert anode systems
  • the active layer As material for the active layer are usually electron-conducting materials, such as platinum, iridium or other precious metals, their mixed oxides or compounds of these elements are used.
  • the active layer can either be applied directly to the surface of the carrier material or can be located on a substrate arranged at a distance from the carrier material.
  • a substrate among others Also serve those materials that come into consideration as a substrate, so for example, stainless steel, titanium or the like.
  • additives to electroplating baths which, for example, act as brighteners, increase the hardness and / or increase the scattering.
  • organic compounds are preferably used as additives.
  • gases such as oxygen or chlorine are formed at the insoluble anode. These gases can cause the additives contained in the electroplating bath to oxidize, which can lead to partial or even complete degradation of these additives. This circumstance weighs double. On the one hand, the additives must be replaced continuously, on the other hand disrupt the degradation products of the additives, so that it is necessary to renew the plating baths more often or clean or regenerate, which is uneconomical and beyond also ecologically meaningful.
  • the WO 2004/038070 A2 discloses the use of pulse reverse currents in copper deposition from acid copper plating baths.
  • the electrolytes used here by way of example have a chloride content of between 10 and 500 mg / l, usually around 80 g / l.
  • Electrolytes are disclosed for the electrodeposition of copper, which may have a chloride content of 20 to 200 mg / l.
  • the electrolytes described herein may contain 1 to 300 g / l, preferably 150 to 250 g / l of an acid. HCl is also disclosed as a suitable acid. The chloride ion content described in the examples is 50 mg / l.
  • the invention proposes a galvanic bath, in particular an acidic electroplating bath, with an anode, a cathode and an electrolyte, wherein the anode is formed in two or more phases and wherein the electrolyte contains more than 70 mg / l chloride and above
  • the listed elements can be used in the form of anions or polyanions of their oxo acids, in strongly acidic solution as cations of their acid anhydrides or as heteropolyanions such as silicometallates.
  • the use of a two- or more-phase anode in combination with a high chloride content that is more than 70 mg / l chloride, leads to excellent coating results.
  • a high chloride content that is more than 70 mg / l chloride
  • the embodiment according to the invention is suitable because the high chloride content leads to a finer copper crystal structure and to a better layer thickness distribution.
  • a faster copper deposition is effected by higher applicable current densities.
  • the embodiment of the invention allows a cheaper copper oxide quality, which makes the inventive design particularly economical.
  • the electrolyte contains 90 mg / l to 5,000 mg / l, preferably 100 mg / l to 300 mg / l, more preferably 120 mg / l to 250 mg / l of chloride.
  • the term "two-phase or multi-phase" anode is to be understood as meaning an anode which consists of an anode base body on the one hand and a shield for the anode main body on the other hand.
  • the anode base body the first phase and the shield, the second phase.
  • the anode body in turn consists of a carrier material on the one hand and an active layer on the other.
  • the support material may consist of titanium, niobium, stainless steel or other inert metals.
  • the active layer may be formed as a coating and applied directly to the substrate. Iridium, platinum, other noble metals, their compounds and in particular their mixed oxide are particularly suitable as the active layer.
  • the shield of the anode is preferably arranged at a distance from the carrier material and consists of plastic or metal.
  • the shield may be formed as a fabric or grid or network.
  • the shield consists of a grid or mesh made of titanium.
  • the shield is formed by a polypropylene fabric.
  • Preferred is the use of a two-part shield, wherein the first part of the shield is formed of a mesh or mesh made of titanium, the second part of the shield being a fabric made of polypropylene. This is off Polypropylene existing fabric between the anode body on the one hand and the grid consisting of titanium or network on the other.
  • An anode with a two-part shield is three-phase.
  • the two-phase or multi-phase electrode system prevents too high a contamination of the electrolyte with oxygen and thus too high an additive consumption.
  • the galvanic bath according to the invention proves to be particularly economical.
  • the invention further proposes a method for electroplating in which a galvanic bath with the features described above is used.
  • the deposition is preferably carried out by means of direct current. In this way, a particularly fine crystal structure can be achieved, which leads to improved physical properties of the deposited layer.
  • the electroplating bath according to the invention can be used both in horizontal as well as in vertical systems.
  • the electroplating bath according to the invention is also suitable for metallization by means of pulse plating.
  • An advantage of the embodiment according to the invention is also the economic usability. Namely, when using inert anode systems, copper oxide or another copper compound can be used for the regeneration of the elaborated copper. In this case, the price of the copper oxide used depends very much on the chloride content, the copper oxide is the more expensive, the lower the chloride content. According to the invention, a particularly high chloride content is now used, which makes it possible to use particularly inexpensive copper oxide for regeneration purposes. For this reason too, the invention therefore proves to be particularly economical.
  • FIG. 1 shows a schematic side view of a multi-phase anode according to the invention.
  • Fig. 1 shows a schematic side view of an inventive multi-phase anode 1.
  • This anode 1 consists of an anode body 2 on the one hand and a shield 3 on the other.
  • FIG. 3 shows the graphic plot of the layer thickness distribution with constant chloride content as a function of the molybdenum concentration.
  • the anode main body 2 in turn consists of a carrier material 4 and a coating 5, that is to say an active layer.
  • the substrate 4 is preferably made of stainless steel, titanium or the like, whereas the coating 5 is preferably formed of iridium mixed oxide, platinum or the like.
  • the coating 5 can either be applied directly to the carrier material 4 or spaced therefrom. In the exemplary embodiment according to FIG. 1, the coating 5 is arranged at a distance from the carrier material 4, wherein the distance between carrier material 4 and coating 5 is marked with a. This distance a may be, for example, a few tenths of a millimeter.
  • the coating 7 is supported in the embodiment of FIG. 1 by a substrate which may consist of stainless steel, titanium or the like.
  • the shield 3 of the anode 1, as shown in FIG. 1 reveals, formed in two parts.
  • a first part of the shield 3 is formed by a fabric 6 made of a non-conductive material such as plastic (eg polypropylene), glass fiber, or mineral fiber or porous non-conductive diaphragms.
  • the second part of the shielding 3 consists of a grid or mesh 7 made of titanium.
  • the shielding 3 is formed at a distance from the anode base body 2, wherein the distance b between the anode base body 2 and the woven fabric 6 consisting of polypropylene can be 0.01 to 10 mm ,
  • the second part of the shielding 3, that is to say the grid or grid 7 made of titanium, is equally spaced from the first component of the shielding 3, that is to say the woven fabric 6 made of polypropylene, the distance c likewise amounting to 0.1 mm to 10 mm can.
  • Other dimensions are also conceivable here depending on the field of application of the electroplating bath. In this respect, the abovementioned distances are not to be considered limiting for the invention.

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)
  • Electroplating Methods And Accessories (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
EP05009183A 2005-04-27 2005-04-27 Bain de galvanisation Withdrawn EP1717351A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP05009183A EP1717351A1 (fr) 2005-04-27 2005-04-27 Bain de galvanisation
CN2005101201051A CN1854352B (zh) 2005-04-27 2005-11-02 电镀浴
KR1020050122525A KR100741198B1 (ko) 2005-04-27 2005-12-13 전기 도금 배스
TW095107051A TWI332533B (en) 2005-04-27 2006-03-02 Electroplating bath
JP2006121511A JP4404871B2 (ja) 2005-04-27 2006-04-26 電気めっき槽
US11/380,559 US20060272951A1 (en) 2005-04-27 2006-04-27 Electroplating process and composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP05009183A EP1717351A1 (fr) 2005-04-27 2005-04-27 Bain de galvanisation

Publications (1)

Publication Number Publication Date
EP1717351A1 true EP1717351A1 (fr) 2006-11-02

Family

ID=34935798

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05009183A Withdrawn EP1717351A1 (fr) 2005-04-27 2005-04-27 Bain de galvanisation

Country Status (6)

Country Link
US (1) US20060272951A1 (fr)
EP (1) EP1717351A1 (fr)
JP (1) JP4404871B2 (fr)
KR (1) KR100741198B1 (fr)
CN (1) CN1854352B (fr)
TW (1) TWI332533B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1803837A1 (fr) 2005-11-25 2007-07-04 Enthone, Inc. Procédé et appareillage pour le nettoyage de solutions de traitement

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1712660A1 (fr) * 2005-04-12 2006-10-18 Enthone Inc. Anode insoluble
EP1961842A1 (fr) * 2007-02-22 2008-08-27 Atotech Deutschland Gmbh Dispositif et procédé pour le placage électrolytique d'un métal
EP2009147A1 (fr) * 2007-06-20 2008-12-31 METAKEM Gesellschaft für Schichtchemie der Metalle GmbH Ensemble anode pour placage électrolytique
US8940158B2 (en) * 2009-02-13 2015-01-27 Chlorking, Inc. System and method for chlorine generation and distribution
US8221600B2 (en) 2010-09-23 2012-07-17 Sunpower Corporation Sealed substrate carrier for electroplating
US8221601B2 (en) 2010-09-23 2012-07-17 Sunpower Corporation Maintainable substrate carrier for electroplating
JP5792820B2 (ja) * 2010-09-23 2015-10-14 サンパワー コーポレイション 電気メッキ用の非浸透性基板キャリア
US8317987B2 (en) 2010-09-23 2012-11-27 Sunpower Corporation Non-permeable substrate carrier for electroplating
US9006147B2 (en) 2012-07-11 2015-04-14 Faraday Technology, Inc. Electrochemical system and method for electropolishing superconductive radio frequency cavities
CN104073862A (zh) * 2014-07-11 2014-10-01 张钰 一种用于碱性锌镍合金电镀的不溶性阳极装置
CN105887144B (zh) * 2016-06-21 2018-09-21 广东光华科技股份有限公司 电镀铜镀液及其电镀铜工艺
DE102019202899B3 (de) * 2019-03-04 2019-11-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Wässrige Formulierung zum Herstellen einer Schicht aus Gold und Silber

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US3857683A (en) 1973-07-27 1974-12-31 Mica Corp Printed circuit board material incorporating binary alloys
EP0625593A2 (fr) 1993-05-19 1994-11-23 LeaRonal, Inc. Procédé pour réduire l'accumulation de bone dans les bains d'étamage acide
US6129830A (en) * 1996-12-13 2000-10-10 Atotech Deutschland Gmbh Process for the electrolytic deposition of copper layers
EP1310582A1 (fr) 2001-11-07 2003-05-14 Shipley Company LLC Procédé de placage électrolytique de cuivre
US20040060728A1 (en) 2001-01-04 2004-04-01 Philippe Steiert Method for producing electroconductive structures
WO2004059045A2 (fr) 2002-12-23 2004-07-15 METAKEM Gesellschaft für Schichtchemie der Metalle mbH Anode pour electrodeposition

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US3832296A (en) * 1972-08-07 1974-08-27 Kennecott Copper Corp Electrowinning cell and method with provision for electrolyte circulation
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DE19545231A1 (de) * 1995-11-21 1997-05-22 Atotech Deutschland Gmbh Verfahren zur elektrolytischen Abscheidung von Metallschichten
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DE19834353C2 (de) * 1998-07-30 2000-08-17 Hillebrand Walter Gmbh & Co Kg Alkalisches Zink-Nickelbad
KR100366631B1 (ko) * 2000-09-27 2003-01-09 삼성전자 주식회사 폴리비닐피롤리돈을 포함하는 구리도금 전해액 및 이를이용한 반도체 소자의 구리배선용 전기도금방법
US6610192B1 (en) * 2000-11-02 2003-08-26 Shipley Company, L.L.C. Copper electroplating
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
US20040217005A1 (en) * 2002-07-24 2004-11-04 Aron Rosenfeld Method for electroplating bath chemistry control
EP1712660A1 (fr) * 2005-04-12 2006-10-18 Enthone Inc. Anode insoluble

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3857683A (en) 1973-07-27 1974-12-31 Mica Corp Printed circuit board material incorporating binary alloys
EP0625593A2 (fr) 1993-05-19 1994-11-23 LeaRonal, Inc. Procédé pour réduire l'accumulation de bone dans les bains d'étamage acide
US6129830A (en) * 1996-12-13 2000-10-10 Atotech Deutschland Gmbh Process for the electrolytic deposition of copper layers
US20040060728A1 (en) 2001-01-04 2004-04-01 Philippe Steiert Method for producing electroconductive structures
EP1310582A1 (fr) 2001-11-07 2003-05-14 Shipley Company LLC Procédé de placage électrolytique de cuivre
WO2004059045A2 (fr) 2002-12-23 2004-07-15 METAKEM Gesellschaft für Schichtchemie der Metalle mbH Anode pour electrodeposition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1803837A1 (fr) 2005-11-25 2007-07-04 Enthone, Inc. Procédé et appareillage pour le nettoyage de solutions de traitement

Also Published As

Publication number Publication date
CN1854352B (zh) 2010-09-22
TW200704831A (en) 2007-02-01
US20060272951A1 (en) 2006-12-07
KR20060113344A (ko) 2006-11-02
CN1854352A (zh) 2006-11-01
TWI332533B (en) 2010-11-01
JP2006307344A (ja) 2006-11-09
KR100741198B1 (ko) 2007-07-19
JP4404871B2 (ja) 2010-01-27

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