EP3321396B1 - Trommelplattierung oder hochgeschwindigkeitsdrehplattierung mit einer neutralen zinnplattierungslösung - Google Patents

Trommelplattierung oder hochgeschwindigkeitsdrehplattierung mit einer neutralen zinnplattierungslösung Download PDF

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Publication number
EP3321396B1
EP3321396B1 EP17200630.6A EP17200630A EP3321396B1 EP 3321396 B1 EP3321396 B1 EP 3321396B1 EP 17200630 A EP17200630 A EP 17200630A EP 3321396 B1 EP3321396 B1 EP 3321396B1
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Prior art keywords
plating
acid
barrel
tin
plating solution
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English (en)
French (fr)
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EP3321396A1 (de
Inventor
Makoto Kondo
Yoko Mizuno
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Rohm and Haas Electronic Materials LLC
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Rohm and Haas Electronic Materials LLC
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    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • 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
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk
    • 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
    • C25D17/16—Apparatus for electrolytic coating of small objects in bulk
    • C25D17/18—Apparatus for electrolytic coating of small objects in bulk having closed containers
    • C25D17/20—Horizontal barrels
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors

Definitions

  • the present invention relates to a barrel plating or high-speed rotary plating method for electronic components using a neutral tin plating solution, and to the neutral tin plating solution used therein. More specifically, it relates to a barrel plating or high-speed rotary plating method, and to a neutral tin plating solution used therein, which is capable of improving the coverage of plating onto electronic components while preventing electronic components from coupling to each other when barrel plating or high-speed rotary plating is performed.
  • Tin plating is carried out broadly for the purpose of improving solderability of electronic components.
  • the method for tin plating electronic components can be selected from various different methods, such as barrel plating, rack plating, and the like, depending on the shape, the structure of the plating location, and the like.
  • Barrel plating is generally used as a method for plating small electronic components such as chip resistors, chip capacitors, and the like.
  • high-speed rotary plating has been carried out through flow-through platers, and the like, as a plating method for small electronic components.
  • Japanese Unexamined Patent Application Publication 2009-299123 discloses a tin electroplating solution for chip components with a pH of 1 or less, including stannous ions, oxygen, dipolyoxyalkylene alkyl amine or amine oxide, and a bonding inhibitor.
  • stannous ions oxygen, dipolyoxyalkylene alkyl amine or amine oxide
  • a bonding inhibitor a bonding inhibitor
  • Japanese Unexamined Patent Application Publication 2003-293186 discloses a neutral tin plating bath that includes a soluble stannous salt, an acid or salt, a complexing agent selected from an oxycarboxylic acid, or the like, and a quaternary amine polymer.
  • a neutral tin plating solution that uses a quaternary amine polymer is not adequately effective in preventing coupling between the objects to be plated, and further improvements are desired.
  • US2003/052014 discloses a method for plating electrodes of ceramic chip electronic components in a plating bath, wherein the bath contains tin (II) sulfamate, acting as a tin (II) salt; a complexing agent including at least one selected from the group consisting of citric acid, gluconic acid, pyrophosphoric acid, heptoic acid, malonic acid, malic acid, salts of these acids, and gluconic lactone; and a brightener including at least one surfactant having an HLB value of about 10 or more.
  • tin (II) sulfamate acting as a tin (II) salt
  • a complexing agent including at least one selected from the group consisting of citric acid, gluconic acid, pyrophosphoric acid, heptoic acid, malonic acid, malic acid, salts of these acids, and gluconic lactone
  • a brightener including at least one surfactant having an HLB value
  • EP1754805 discloses a tin electroplating solution devoid of harmful lead and having excellent solder wettability, and a method for depositing a tin film on electronic parts using such a tin electroplating solution, which includes organic acids, a naphtholsulfonic acid and, as needed, an antioxidant and a surfactant.
  • US2008/283406 discloses an additive obtained from the reaction product obtained by reacting glutaraldehyde and at least one type of compound selected from hydrocarbon compounds containing a hydroxyl group, and at least one type of compound selected from amine compounds, as well as a tin or tin alloy plating solution containing this additive.
  • EP2868775 discloses tin-containing electroplating baths having a combination of certain brightening agents provide tin-containing solder deposits having reduced void formation and smooth morphology.
  • JP2000-026991 discloses a method to improve the smoothness of a plated film, the aged stability of a bath and the stability of the composition of an electrodeposited material in the plating bath by incorporating a soluble salt composed of a tin salt or a mixture of the tin salt and other metallic salt, a monoamine type compound and a surfactant.
  • the object of the present invention is to enable suppression of coupling between the electronic components even when using barrel plating or high-speed rotary plating of electronic components that have been miniaturized in recent years, to provide an electronic component plating method, and a neutral tin plating solution used therein, wherein the foaming of the plating solution is extremely little when performing barrel plating or high-speed rotary plating.
  • the present inventors arrived at the present invention through discovering that it is possible to improve manufacturability in barrel plating or high-speed rotary plating through preventing the objects being plated from coupling together, and through having little foaming in the plating solution, through the addition, to the neutral tin plating solution, of a diamine that has a polyoxyalkylene chain.
  • one aspect of the present invention provides an electronic component barrel plating or high-speed rotary plating method that includes a step that carries out barrel plating or high-speed rotary plating on electronic components having a ceramic portion using a tin plating solution that includes (A) stannous ions from a tin salt of alkane sulfonic acids or alkanol sulfonic acids, (B) at least one selected from alkane sulfonic acids, alkanol sulfonic acids and salts thereof, (C) a complexing agent selected from gluconic acid, citric acid, malonic acid, succinic acid, tartaric acid, or a salt thereof, and (D) a diamine that includes a polyoxyalkylene chain, and wherein the pH is in a range between 4 and 8.
  • one aspect of the present invention provides a tin plating solution for barrel plating or high-speed rotary plating that includes (A) stannous ions, (B) an acid or a salt, (C) a complexing agent, and (D) a diamine that includes a polyoxyalkylene chain, and wherein the pH is in a range between 4 and 8.
  • the barrel plating or high-speed rotary plating method for electronic components according to the present invention has, as a distinctive feature, the use of a plating solution that includes (A) stannous ions, (B) an acid or a salt, (C) a complexing agent, and (D) a diamine that includes a polyoxyalkylene chain, and wherein the pH is in a range between 4 and 8.
  • a plating solution that includes (A) stannous ions, (B) an acid or a salt, (C) a complexing agent, and (D) a diamine that includes a polyoxyalkylene chain, and wherein the pH is in a range between 4 and 8.
  • the stannous ions are included as a required structural requirement.
  • Stannous ions are double-oxidized tin ions.
  • an arbitrary compound may be used insofar as it is a compound that is able to supply stannous ions.
  • stannous salts of substituted or non-substituted alkane sulfonic acids and alkanol sulfonic acids such as, for example, methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, 2-hydroxy ethane-1-sulfonic acid, 2-hydroxy propane-1-sulfonic acid, and 1-hydroxy propane-2-sulfonic acid are used. These compounds able to supply these ions may be used singly or in mixtures of two or more thereof.
  • the inclusion proportion of the stannous ions within the plating solution may be, for example, between 5 g/L and 30 g/L, as tin ions, or, preferably, between 8 g/L and 25 g/L, or more preferably, between 10 g/L and 20 g/L.
  • the plating solution used in the present invention comprises methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, 2-hydroxy ethane-1-sulfonic acid, 2-hydroxy propane-1-sulfonic acid, or 1-hydroxy propane-2 sulfonic acid.
  • Methane sulfonic acid is preferred.
  • an arbitrary salt may be used, such as an alkaline metal salt, an alkaline earth metal salt, an ammonium salt, an amine salt, or the like.
  • the acids and salts may be used singly or in combinations of two or more.
  • the plating solution that is used in the present invention will be a neutral plating solution
  • an acid as described above
  • any of a variety of bases may be added, as a pH adjusting agent, to the plating solution to adjust the pH into a range of between 4 and 8.
  • the inclusion proportion of the acid or salt in the plating solution is, for example, between 30 g/L and 300 g/L, and preferably between 50 g/L and 200 g/L, and more preferably between 80 g/L and 150 g/L.
  • the plating solution used in the present invention includes a complexing agent as a required structural condition.
  • a complexing agent as a required structural condition.
  • a double-ionized tin ion in a tin plating solution is stable in a strong acid, but becomes unstable when near neutral, and tends to segregate out as a tin metal, so the plating solution tends to decompose.
  • a complexing agent must be included.
  • the complexing agent is selected from, gluconic acid, citric acid, malonic acid, succinic acid, tartaric acid, or a salt thereof. Of these, gluconic acid or a salt thereof is preferred, and sodium gluconate is most preferred.
  • the inclusion proportion of the complexing agent in the plating solution is, for example, between 80 g/L and 250 g/L, and preferably between 100 g/L and 200 g/L, and more preferably between 125 g/L and 175 g/L.
  • the plating solution used in the present invention includes, as a required structural condition, a diamene that has a polyoxyalkylene chain.
  • a diamene that has a polyoxyalkylene chain prevents the objects being plated from coupling together, enabling an improvement in manufacturability in barrel plating.
  • the diamene that includes a polyoxyalkylene alkylene chain is a compound described by the following chemical formula:
  • R 1 is a straight-chain or branched-chain alkylene group with a carbon number between 1 and 6, and more preferably is a straight-chain or branched-chain alkylene group with a carbon number between 1 and 4.
  • R 2 through R 5 is, independently, a branched-chain alkylene group with a carbon number between 1 and 6, and more preferably is a branched-chain alkylene group with a carbon number between 1 and 4.
  • n, m, o, and p is an integer between 1 and 8. Note that the total of n, m, o, and p is between 1 and 60, and preferably between 2 and 30, and more preferably between 4 and 25.
  • a plating solution that includes the compounds set forth above is able to reduce coupling of electronic components when performing barrel plating or high-speed rotary plating, and enables plating operations to be performed stably with little production of bubbles that would be a problem when performing plating.
  • the weight-average molecular weight of the diamene that has the polyoxyalkylene chain is preferably between 200 and 1100, and more preferably between 300 and 600.
  • the weight-average molecular weight is a value that is measured using the GPC method.
  • the diamene with the polyoxyalkylene chain may use that which is commercially available, and, for example, may use Adeka Polyether EDP-450, Adeka Polyether BM-54 (manufactured by Adeka Co., Ltd.), or the like.
  • the inclusion proportion of the diamene with a polyoxyalkylene chain in the plating solution is, for example, between 0.1 g/L and 30 g/L, and preferably between 0.5 g/L and 20 g/L, and more preferably between 1 g/L and 5 g/L.
  • the pH of the neutral tin plating solution used in the present invention is in a range between 4 and 8, and preferably between 5 and 7.
  • a base or an acid may be added to the plating solution to adjust the pH into this range.
  • Acids that may be used include, for example, methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid, hydrochloric acid, sulfuric acid, and the like.
  • bases that can be used there are, for example, sodium hydroxide, potassium hydroxide, and aqueous ammonia.
  • the neutral tin plating solution used in the present invention may include, as other arbitrary components, components that are typically added to plating solutions.
  • oxidation inhibiting agents, brightening agents, smoothing agents, conductive salts, anode solvents, corrosion inhibiting agents, wetting agents, and the like may be used.
  • an oxidation inhibiting agent may be used as appropriate.
  • the oxidation inhibiting agent is used to prevent the tin ions from being oxidized from 2+ to 4+, where, for example, hydroquinone, catechol, resorcin, phloroglucin, pyrogallol, hydroquinone, sulfonic acid, a salt thereof, or the like, may be used.
  • the oxidation inhibiting agent may be used suitably in a concentration, in the plating bath, of, for example, between 100 mg/L and 50 g/L, or preferably between 200 mg/L and 20 g/L, and more preferably, between 0.5 g/L and 5 g/L.
  • capacitors, inductors, thermistors, and varistors have ceramic portions within the components, meaning that strong acid plating solutions cannot be used, and thus plating using the neutral plating bath of the present invention is preferred.
  • the barrel plating method according to the present invention includes the case of placing, into the barrel, only the objects to be plated, without addition of the dummy balls.
  • the barrel plating method may use an arbitrary apparatus, such as of a horizontal or an inclined rotating barrel type, a pivoting barrel type, a vibrating barrel type, or the like.
  • the barrel plating may be carried out with the temperature of the plating solution between, for example, 10 and 50 °C, and preferably between 20 and 40 °C.
  • the cathode current density may be selected as appropriate in a range that is, for example, between 0.01 and 10 A/dm 2 , and preferably between 0.05 and 5 A/dm 2 , and more preferably between 0.1 and 0.5 A/dm 2 .
  • a method may be selected wherein, for example, the plating bath is not stirred during the plating process, or, for example, may be stirred using a stirrer, or the method may have a fluid flow using a pump.
  • the plating may be carried out using, for example, a flow-through plater, or the like, under conditions of between 10 and 50 °C, with a cathode current density between 0.01 and 10 A/dm 2 , with small electronic components, which are the objects to be plated, being plated during high-speed rotation.
  • the coupling proportions (the proportion by weight of the adhered chips, relative to the total chip weight), and the clumping proportions (the proportion by weight of the dummy balls that were clumped together, relative to the total weight of dummy balls) were calculated, and, similarly, are given in Table 1.
  • Hull cell testing was carried out using the plating solutions of the electrolytic baths that were prepared, and the external appearances of the plating coatings that were produced were observed with the naked eye, and the plating grain sizes were measured using SEM (at 2000x).
  • An electrolytic bath of a tin plating solution was prepared with the same composition as in the first embodiment, except for the use of 2 g/L of lauryl dimethylaminoacetate betaine (Amphitol 20BS, manufactured by Kao Corp.) instead of the (D) Adeka Polyether EDP-450 in the first embodiment.
  • the foamability of the plating solution was high, and thus unsuitable for barrel plating.
  • An electrolytic bath of a tin plating solution was prepared with the same composition as in the first embodiment, except for the use of 2 g/L of a quaternary ammonium salt polymer (Papiogen P-113 (Comparative Example 2)), SenkaFix 401 (Comparative Example 3), and a quaternary ammonium salt (Eretat M-65 (Comparative Example 4)), respectively, instead of the (D) Adeka Polyether EDP-450 in the first embodiment.
  • the plating solution produced in Comparative Example 4 had high foamability, so was not suitable for barrel plating.
  • the same procedures were performed for each as in the first embodiment.
  • the external appearance of the plating coating obtained in the Hull cell testing for the plating solution produced in Comparative Example 2 was white, with an excellent result, but in the barrel plating test the coupling rate was high, at 81.3%.
  • the external appearance of the plating coating produced in the Hull cell testing was grayish-black, which was undesirable.

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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)
  • Electroplating Methods And Accessories (AREA)

Claims (5)

  1. Zinnplattierungslösung für Trommelplattierung oder Hochgeschwindigkeits-Rotationsplattierung, umfassend:
    (A) Zinn(II)-Ionen, ausgewählt aus einem Zinnsalz von Alkansulfonsäuren oder Alkanolsulfonsäuren;
    (B) eine Säure oder ein Salz, ausgewählt aus Methansulfonsäure, Ethansulfonsäure, Propansulfonsäure, 2-Hydroxyethan-1-sulfonsäure, 2-Hydroxypropan-1-sulfonsäure und 1-Hydroxypropan-2-sulfonsäure;
    (C) ein Komplexierungsmittel, ausgewählt aus Gluconsäure, Zitronensäure, Malonsäure, Bernsteinsäure, Weinsäure oder einem Salz davon; und
    (D) ein Diamin mit einer Polyoxyalkylenkette, beschrieben durch die nachstehende chemische Formel:
    Figure imgb0004
    wobei R1 eine geradkettige oder verzweigtkettige Alkylengruppe mit einer Kohlenstoffzahl zwischen 1 und 6 ist, jedes von R2 bis R5 unabhängig eine verzweigtkettige Alkylengruppe mit einer Kohlenstoffzahl zwischen 1 und 6 ist, jedes von n, m, o und p eine ganze Zahl zwischen 1 und 8 ist, wobei ein pH-Wert in einem Bereich zwischen 4 und 8 liegt.
  2. Zinnplattierungslösung für Trommelplattierung oder Hochgeschwindigkeits-Rotationsplattierung nach Anspruch 1, wobei das Diamin mit der Polyoxyalkylenkette ein Molekulargewicht zwischen 200 und 1100 aufweist
  3. Zinnplattierungslösung für Trommelplattierung oder Hochgeschwindigkeits-Rotationsplattierung nach Anspruch 1, wobei das Komplexierungsmittel Natriumgluconat ist.
  4. Trommelplattierungs- oder Hochgeschwindigkeits-Rotationsplattierungsverfahren für elektronische Komponenten, ausgewählt aus Kondensatoren, Induktoren, Thermistoren und Varistoren mit einem Keramikteil, einschließend einen Schritt für Trommelplattierung oder Hochgeschwindigkeits-Rotationsplattierung einer elektronischen Komponente unter Verwendung einer Zinnplattierungslösung nach einem der Ansprüche 1 bis 3
  5. Verfahren nach Anspruch 4, wobei die Trommelplattierung mit einer Stromdichte zwischen 0,05 A/dm2 und 0,5 A/dm2 ausgeführt wird.
EP17200630.6A 2016-11-11 2017-11-08 Trommelplattierung oder hochgeschwindigkeitsdrehplattierung mit einer neutralen zinnplattierungslösung Active EP3321396B1 (de)

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CN111918998A (zh) 2018-04-12 2020-11-10 东丽株式会社 片状物及其制造方法
CN109338420A (zh) * 2018-12-14 2019-02-15 江苏艾森半导体材料股份有限公司 一种环保中性电镀锡电解液
JP2022059731A (ja) * 2020-10-02 2022-04-14 メルテックス株式会社 バレルめっき用スズめっき液
CN113930812B (zh) * 2021-11-15 2023-10-31 广东羚光新材料股份有限公司 片式电子元器件镀锡液和锡电镀方法
CN114351232A (zh) * 2022-01-14 2022-04-15 张家港扬子江冷轧板有限公司 一种电镀锡预电镀漂洗水循环系统及循环方法

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CN108070885A (zh) 2018-05-25
JP2018076570A (ja) 2018-05-17
EP3321396A1 (de) 2018-05-16
CN108070885B (zh) 2020-09-15
TWI659130B (zh) 2019-05-11
KR20180053229A (ko) 2018-05-21
TW201817921A (zh) 2018-05-16
JP6818520B2 (ja) 2021-01-20
KR102097996B1 (ko) 2020-04-07
US20180135195A1 (en) 2018-05-17

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