EP1285104B1 - Electrolyte et procede pour le depot de couches d'alliages etain-argent - Google Patents

Electrolyte et procede pour le depot de couches d'alliages etain-argent Download PDF

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Publication number
EP1285104B1
EP1285104B1 EP01936389A EP01936389A EP1285104B1 EP 1285104 B1 EP1285104 B1 EP 1285104B1 EP 01936389 A EP01936389 A EP 01936389A EP 01936389 A EP01936389 A EP 01936389A EP 1285104 B1 EP1285104 B1 EP 1285104B1
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EP
European Patent Office
Prior art keywords
silver
tin
electrolyte
salts
electrolyte according
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
EP01936389A
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German (de)
English (en)
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EP1285104A1 (fr
Inventor
Michael Dietterle
Manfred Jordan
Gernot Strube
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Dr Ing Max Schloetter GmbH and Co KG
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Dr Ing Max Schloetter GmbH and Co KG
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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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin

Definitions

  • the present invention relates to an acidic electrolyte for the deposition of tin-silver alloys, a process which uses this electrolyte by the process available coatings and the use of the Electrolytes for coating electronic components.
  • eutectic Lead tin solder is the tin-silver alloy.
  • the eutectic composition used as these are the lowering of the Processing temperatures to a minimum. Too high Processing temperatures may e.g. when soldering by PCBs and components of electronic assemblies too cause irreversible damage.
  • the eutectic Composition of the tin-silver alloy consists of 96.5 Wt.% Sn and 3.5 wt.% Ag.
  • the melting point of the eutectic is 221 ° C.
  • By alloying small amounts of Cu (about 1 Wt.%) Is a further lowering of the melting point 217 ° C possible.
  • the tin-silver solder SnAg3.5 is therefore also suitable as Alternative for the Bleizinnlot, because the former already as Lot is used for special applications and therefore already Practical experience available.
  • the Components for maintaining the solderability galvanic with Coatings of a tin-silver alloy are coated.
  • the main component of the solder is tin, would be one too Component coating with pure tin with the solder alloy compatible. Pure tin layers are but because of the already mentioned risk of whisker formation less desirable.
  • the silver content of the coating is on the one hand not desirable for economic reasons. on the other hand should the silver content of the tin-silver alloy advantageously ⁇ 10 wt.%, in order to reduce the solderability of the Coating at low temperatures, i. near the Eutectic of the tin-silver alloy, to enable.
  • the use of cyanide due to its high Toxicity can be avoided.
  • alkaline electrolytes are the following Disadvantages connected. Plants so far for the deposition used by tin-lead alloys of acidic electrolytes are not technically wastewater treatment cyanide electrolytes designed. Further use these conventional systems for the deposition of tin-lead alloys However, for economic reasons, it is also for the deposition of tin-silver alloys is desired.
  • the deposition rate is alkaline Electrolytes comparatively low. Since tin in the alkaline Milieu in tetravalent form, is the Deposition rate compared to a Sn (II) acidic electrolyte containing reduced by 50%.
  • the two separable metals contains, the potential difference of the two metals is large prefers the metal with the more positive standard potential deposited. That from a tin-silver electrolyte preferably silver deposited.
  • the reaction is recognizable by precipitation of finely divided black silver powder or the deposition of a silver level on the container wall.
  • the base materials to be coated have a more negative standard potential than silver.
  • the base material is often copper or a copper alloy.
  • the value for the standard potential Cu ⁇ Cu 2+ is + 0.35 V.
  • the difference to silver thus amounts to 0.45 V.
  • This potential difference causes silver to be deposited in the charge exchange on the copper surface. Such a reaction may impair the adhesion of the subsequently deposited layers.
  • potassium iodide As a complexing agent for silver is in the patent application EP 0 893 514 called potassium iodide, which is the standard potential of silver shifts by -870 mV. This gives you almost an approximation of the standard potential values for tin and Silver.
  • potassium iodide Disadvantageous for the use of potassium iodide is that it is in large excess of the amount of silver to be complexed must be used. There are concentrations of e.g. 300 g / l necessary. Since potassium iodide is an expensive compound, Such a process could not be economically viable become. In addition, a pH of 4 to 6 must be set become. In this area bivalent tin is only in Presence of complexing agents soluble. This effect in turn, a shift of the standard potential of tin and thus increase the potential difference between Tin and silver. Effective complexing agents for tin are e.g. Hydroxy carboxylic acids. These complicate the precipitation of Heavy metal compounds in wastewater treatment and are therefore undesirable.
  • weakly acidic electrolytes have only a low electrical conductivity.
  • Such electrolytes can be used only for the deposition of metal layers at low cathodic current densities (0.1 to 5 A / dm 2 ), ie in the so-called drum and frame technology with deposition rates of usually 0.05 to 2.5 microns / min. They are not suitable for high cathodic current densities (5 to 100 A / dm 2 ), which are present in the high-speed deposition (continuous plating), with which deposition rates of 2.5 to 50 microns / min are achieved. In summary, therefore, the method according to EP 0 893 514 is associated with a number of disadvantages.
  • EP 0 854 206 describes aromatic thiol compounds as Complexing agent. With such connections is a Displacement of the resting potential of silver by approx. -400 mV reachable. The values are thus sufficient to one to achieve common deposition of tin and silver and to get a stable electrolyte.
  • Aromatic compounds also often have one poor biodegradability and thus can too Lead to problems in biological wastewater treatment.
  • Toku-Gan H7-330437 be Thiourea or compounds derived therefrom Called complexing agent for silver. With these connections one also reaches a sufficient displacement of the Resting potential.
  • the disadvantage of thiourea and its Derivatives a not inconsistent health risk. Some of these compounds are particularly toxic to Aquatic organisms.
  • the object of the invention is therefore one against oxidation stable, acidic electrolytes for the deposition of tin-silver alloys to provide for the Use both at low cathodic current densities (Drum or frame technology) as well as at high cathodic current densities (continuous plating process) in Existing plants previously used for the separation of standard lead-tin layers are used is suitable and is not toxic, in particular the Wastewater treatment is not difficult, i. none Environmental degradation.
  • Alkylene groups having 2 to 5 carbon atoms are preferred, e.g. Ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene and tert-butylene groups.
  • the molar ratio of the organic sulfur compound to soluble silver (I) salt (molar amount of organic Sulfur compound: molar amount of soluble silver (I) salt) is preferably at least 1, more preferably 5: 1 to 1: 1, particularly preferably 3: 1.
  • the tin (II) may be present in the electrolyte as a salt of mineral, Alkyl sulfonic or alkanol sulfonic acids present.
  • salts of mineral acids are sulfates and Tetrafluoroborates.
  • Preferred salts of alkylsulfonic acids are e.g. Methanesulfonates, ethanesulfonates, n- and iso-propanesulfonates, Methanedisulfonates, ethanedisulfonates, 2,3-propanedisulfonates and 1,3-propanedisulfonates.
  • Alkanol sulfonates are 2-hydroxyethanesulfonates, 2-hydroxypropanesulfonates and 3-hydroxypropanesulfonates. Particularly preferred is tin (II) methanesulfonate.
  • the tin (II) salts are preferred in the electrolyte in one Amount of 5 to 200 g / l electrolyte, more preferably 10 to 100 g / l of electrolyte, calculated as tin (II), present.
  • the silver (I) is in the electrolyte preferably in the form of Salts of mineral, alkylsulfonic or alkanolsulfonic acids in front.
  • mineral, alkylsulfone or Alkanol sulfonic acid salts are as described above for Tin (II) salts mentioned compounds.
  • Particularly preferred Silver (I) methanesulfonate are as described above for Tin (II) salts mentioned compounds.
  • the electrolyte are preferably 0.05 to 50 g / l, especially preferably 0.1 to 20 g / l, silver (I) salts, calculated as Silver (I), present.
  • the soluble silver salts can be generated upon preparation of the electrolyte by adding silver compounds which dissolve in the acidic range to form salts.
  • silver compounds which dissolve in the acidic range to form salts are silver oxide (Ag 2 O) or silver carbonate (Ag 2 CO 3 ).
  • the electrolyte may also contain various additives, the usually in acidic electrolytes for the separation of Tin alloys are used, e.g. grain refining Additives, wetting agents and / or brighteners included.
  • the grain refining additive is preferably in an amount from 0.1 to 50 g / l of electrolyte, preferably 1 to 10 g / l Electrolyte, before.
  • the wetting agent may be used in an amount of 0.1 to 50 g / l Electrolyte, preferably 0.5 to 10 g / l electrolyte present.
  • the alkyl sulfonic acid and the alkanol sulfonic acid have preferably 1 to 10, more preferably 1 to 5, Carbon atoms on.
  • the alkylsulfonic acids e.g. Methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, iso-propane sulfonic acid, methanedisulfonic acid, Ethanedisulfonic acid, 2,3-propanedisulfonic acid or 1,3-propanedisulfonic acid available.
  • usable Alkanol sulfonic acids are e.g. 2-hydroxyethanesulfonic acid, 2-hydroxypropanesulfonic acid and 3-hydroxypropanesulfonic acid.
  • the alkyl and / or alkanol sulfonic acid is in the electrolyte preferably in a concentration of 50 to 300 g / l Electrolyte, more preferably 100-200 g / l electrolyte.
  • the pH of the acidic electrolyte is preferably 0 to ⁇ 1.
  • the present invention further provides a method for the electrolytic coating of substrates with tin-silver alloys, in which using the Electrolyte according to the invention, an anode of metallic Tin and a cathode of the substrate to be coated the Coating applied by passing direct current becomes made available.
  • tin-silver alloys can silver in a proportion of 0.1 to 99.9 wt.% Contained.
  • a silver content of 0.5 to 10 wt.%, more preferably 2 to 5% by weight, on.
  • the silver content may e.g. by Variation of the concentration ratios of tin and Silver salts in the electrolyte, the electrolyte temperature and the Flow rate of the electrolyte, based on the coating material, to be adjusted.
  • the current density can be 0.1 A / dm 2 (drum or rack technology) up to 100 A / dm 2 (high-speed systems).
  • the temperature of the electrolyte is preferably in the range from 0 to 70 ° C, more preferably in the range of 20 to 50 ° C.
  • a substrate to be coated e.g. copper surfaces or surfaces of copper-containing alloys.
  • the electrolyte according to the invention can be used for the coating of electronic components are used.
  • a tin-silver electrolyte was prepared as follows: 150 g / l 70% aqueous methanesulfonic acid 20 g / l Tin (II), as Zinnmethansulfonat 1 g / l Silver (I) as silver methanesulfonate 2 g / l 3.6 dithiaoctanediol-1.8 4 g / l Nonylphenol ethoxylate with 14 EO groups (Lutensol AP-14 from BASF)
  • tin-silver electrolyte 150 g / l 70% aqueous methanesulfonic acid 40 g / l Tin (II), as Zinnmethansulfonat 1.5 g / l Silver (I) as silver methanesulfonate 4 g / l 3.6 dithiaoctanediol-1.8 4 g / l ethoxylated bisphenol A (Lutron HF-3 from BASF)
  • the deposition of the tin-silver coating from this electrolyte on a copper sheet was carried out at 40 ⁇ 2 ° C in a high-speed system in the current density range of 5 to 20 A / dm 2 .
  • the electrolyte was stirred vigorously (magnetic stirrer, 40 mm stirring bar, stirring speed 700 rpm). Light gray, semi-matt deposits were achieved.
  • the determination of the alloy composition by means of X-ray fluorescence measurement gave the following values: Deposition at 5 A / dm 2 5.7% by weight Ag Deposition at 10 A / dm 2 4.6% by weight Ag Deposition at 15 A / dm 2 4.1% by weight Ag Deposition at 20 A / dm 2 4.4% by weight Ag
  • tin-silver electrolyte 150 g / l 70% aqueous methanesulfonic acid 20 g / l Tin (II), as Zinnmethansulfonat 0.5 g / l Silver (I) as silver methanesulfonate 2 g / l 3.6 dithiaoctanediol-1.8 4 g / l Nonylphenol ethoxylate with 14 EO groups (Lutensol AP-14 from BASF)
  • Example 2 The deposition was carried out as indicated in Example 1. A uniform light gray-smooth deposit was obtained. The silver content at 2 A / dm 2 was 2 wt.%.
  • Example 4 The experiment carried out in Example 4 was repeated except that the 3,6-dithiaoctanediol-1,8 was replaced by the aromatic sulfur compound 2-mercaptoaniline (2.5 g / l). Table 2 shows the test results. Time [d] Resting potential shift [mV] 0 -380 1 -350 3 -80 6 -20

Claims (8)

  1. Électrolyte aqueux acide pour la déposition d'alliages étain-argent, comprenant :
    un ou plusieurs acides alkylsulfoniques et/ou acides alkanolsulfoniques,
    un ou plusieurs sels solubles d'étain (II),
    un ou plusieurs sels solubles d'argent (I), et
    une ou plusieurs combinaisons soufrées organiques,
    caractérisé en ce que les combinaisons soufrées organiques présentent la formule générale suivante : X-R1-[Z-R2]n-Z-R3-Y dans laquelle Z représente respectivement un atome de soufre, ou un atome d'oxygène, et les résidus Z étant identiques ou différents, R1, R2 et R3 représentant indépendamment de chaque autre un groupe alkylène, présentant de 2 à 10 atomes de carbone, n = 1 à 20, X et Y, indépendamment de chaque autre, sont respectivement -OH, -SH ou -H et, pour le cas dans lequel seul un Z représente un atome de soufre, X et/ou Y est -SH et, pour le cas dans lequel Z est exclusivement un atome d'oxygène, X et Y sont chacun -SH.
  2. Électrolyte selon la revendication 1, caractérisé en ce que le rapport molaire de la combinaison soufrée organique par rapport au sel soluble d'argent (I) (quantité molaire de la combinaison soufrée organique : quantité molaire de sel soluble d'argent (I)) est d'au moins 1.
  3. Électrolyte selon la revendication 1 ou 2, caractérisé en ce que les sels d'étain (II) sont les sels d'acides minéraux, d'acides alkylsulfoniques ou alkanolsulfoniques.
  4. Électrolyte selon l'une ou plusieurs des revendications 1 à 3, caractérisé en ce que les sels d'argent (I) sont les sels séparés d'acides minéraux, d'acides alkylsulfoniques ou alkanolsulfoniques.
  5. Électrolyte selon l'une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'un additif, ayant comme but d'affiner les grains, est intégré.
  6. Électrolyte selon la revendication 5, caractérisé en ce que l'on prévoit, comme additif d'affinage des grains, des tensio-actifs non ionogènes, de formule générale RO-(CH2CH2-O)n-H, dans laquelle R est un groupe alkyle, aryle, alkaryle ou aralkyle et n = 1 à 20.
  7. Procédé de revêtement électrolytique de substrats par des alliages étain-argent, caractérisé en ce que le revêtement est effectué avec passage de courant continu, avec utilisation d'un électrolyte selon l'une des revendications 1 à 6, d'une anode réalisée en étain métallique et d'une cathode formée du substrat à revêtir.
  8. Utilisation de l'électrolyte selon l'une des revendications 1 à 6, pour le revêtement de composants électroniques.
EP01936389A 2000-05-30 2001-05-22 Electrolyte et procede pour le depot de couches d'alliages etain-argent Expired - Lifetime EP1285104B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10026680A DE10026680C1 (de) 2000-05-30 2000-05-30 Elektrolyt und Verfahren zur Abscheidung von Zinn-Silber-Legierungsschichten und Verwendung des Elektrolyten
DE10026680 2000-05-30
PCT/EP2001/005901 WO2001092606A1 (fr) 2000-05-30 2001-05-22 Electrolyte et procede pour le depot de couches d'alliages etain-argent

Publications (2)

Publication Number Publication Date
EP1285104A1 EP1285104A1 (fr) 2003-02-26
EP1285104B1 true EP1285104B1 (fr) 2003-11-19

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EP01936389A Expired - Lifetime EP1285104B1 (fr) 2000-05-30 2001-05-22 Electrolyte et procede pour le depot de couches d'alliages etain-argent

Country Status (7)

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US (1) US6998036B2 (fr)
EP (1) EP1285104B1 (fr)
JP (1) JP4446040B2 (fr)
CN (1) CN1190523C (fr)
AU (1) AU2001262313A1 (fr)
DE (2) DE10026680C1 (fr)
WO (1) WO2001092606A1 (fr)

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WO2012001132A1 (fr) 2010-06-30 2012-01-05 Schauenburg Ruhrkunststoff Gmbh Couches de métal noble/métal pouvant subir des contraintes tribologiques

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US6805786B2 (en) * 2002-09-24 2004-10-19 Northrop Grumman Corporation Precious alloyed metal solder plating process
JP4434669B2 (ja) 2003-09-11 2010-03-17 Ｎｅｃエレクトロニクス株式会社 電子部品
US7713859B2 (en) * 2005-08-15 2010-05-11 Enthone Inc. Tin-silver solder bumping in electronics manufacture
EP1918426A1 (fr) 2006-10-09 2008-05-07 Enthone, Inc. Composition d'électrolytes et procédé de placage d'argent or d'alliage d'argent sur des substrats
EP2097254B1 (fr) * 2006-12-19 2011-10-05 Mahle International GmbH Palier coulissant
WO2009140524A2 (fr) * 2008-05-15 2009-11-19 Interplex Industries, Inc. Revêtement en composé d'étain-argent sur cartes à circuits imprimés
EP2221396A1 (fr) * 2008-12-31 2010-08-25 Rohm and Haas Electronic Materials LLC Compositions de dépôt électrique à l'alliage d'étain sans plomb et procédés
JP5313773B2 (ja) * 2009-06-04 2013-10-09 三菱伸銅株式会社 めっき付き銅条材及びその製造方法
US8440065B1 (en) 2009-06-07 2013-05-14 Technic, Inc. Electrolyte composition, method, and improved apparatus for high speed tin-silver electroplating
US9175400B2 (en) * 2009-10-28 2015-11-03 Enthone Inc. Immersion tin silver plating in electronics manufacture
JP5854727B2 (ja) 2010-09-21 2016-02-09 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ シアン化物を含まない銀電気めっき液
JP5854726B2 (ja) 2010-09-21 2016-02-09 ローム アンド ハース エレクトロニック マテリアルズ エルエルシーＲｏｈｍ ａｎｄ Ｈａａｓ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＬＬＣ ニッケル上に銀ストライクを電気めっきする方法
BR112013006922A2 (pt) * 2010-09-24 2016-07-12 Det Norske Veritas As método e aparelho para a redução eletroquímica de dióxido de carbono
US8888984B2 (en) 2012-02-09 2014-11-18 Rohm And Haas Electronic Materials Llc Plating bath and method
US8980077B2 (en) 2012-03-30 2015-03-17 Rohm And Haas Electronic Materials Llc Plating bath and method
US9512529B2 (en) * 2013-06-04 2016-12-06 Rohm And Haas Electronic Materials Llc Electroplating baths of silver and tin alloys
JP6834070B2 (ja) * 2016-06-13 2021-02-24 石原ケミカル株式会社 電気スズ及びスズ合金メッキ浴、当該メッキ浴を用いて電着物を形成した電子部品の製造方法
JP2019052355A (ja) * 2017-09-15 2019-04-04 上村工業株式会社 電解Ｓｎ又はＳｎ合金めっき液及びＳｎ又はＳｎ合金めっき物の製造方法
KR102552655B1 (ko) * 2018-08-10 2023-07-06 쑤저우 레킨 세미컨덕터 컴퍼니 리미티드 발광소자 패키지 및 광원 모듈
CN115029745A (zh) * 2022-07-08 2022-09-09 云南锡业集团（控股）有限责任公司研发中心 一种可减少元件镀层工艺步骤并提升焊点可靠性的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012001132A1 (fr) 2010-06-30 2012-01-05 Schauenburg Ruhrkunststoff Gmbh Couches de métal noble/métal pouvant subir des contraintes tribologiques

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WO2001092606A1 (fr) 2001-12-06
DE50101007D1 (de) 2003-12-24
EP1285104A1 (fr) 2003-02-26
AU2001262313A1 (en) 2001-12-11
DE10026680C1 (de) 2002-02-21
CN1190523C (zh) 2005-02-23
JP2003535222A (ja) 2003-11-25
US6998036B2 (en) 2006-02-14
US20050029112A1 (en) 2005-02-10
JP4446040B2 (ja) 2010-04-07
CN1432074A (zh) 2003-07-23

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