EP3578693B1 - Wässrige zusammensetzung zur abscheidung einer zinn-silber-legierung und verfahren zur elektrolytischen abscheidung solch einer legierung - Google Patents

Wässrige zusammensetzung zur abscheidung einer zinn-silber-legierung und verfahren zur elektrolytischen abscheidung solch einer legierung Download PDF

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EP3578693B1
EP3578693B1 EP18176788.0A EP18176788A EP3578693B1 EP 3578693 B1 EP3578693 B1 EP 3578693B1 EP 18176788 A EP18176788 A EP 18176788A EP 3578693 B1 EP3578693 B1 EP 3578693B1
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Prior art keywords
tin
range
composition
aqueous composition
ions
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English (en)
French (fr)
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EP3578693A1 (de
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Himendra Jha
Ralf Schmidt
Christian Schwarz
Recep Kocer
Grigory VAZHENIN
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Atotech Deutschland GmbH and Co KG
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Atotech Deutschland GmbH and Co KG
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Priority to PT181767880T priority Critical patent/PT3578693T/pt
Priority to EP18176788.0A priority patent/EP3578693B1/de
Priority to PCT/EP2019/064621 priority patent/WO2019234088A1/en
Priority to TW108119427A priority patent/TWI715991B/zh
Publication of EP3578693A1 publication Critical patent/EP3578693A1/de
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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
    • 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
    • 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 aqueous composition for depositing a tin silver alloy, a method for electrolytically depositing such an alloy onto a substrate, and the use of said composition for electrolytically depositing tin silver alloy solder bumps or tin silver alloy solder caps onto pillars.
  • solder caps on copper pillars have turned out to be an interesting and promising alternative to conventional solder ball applications, in particular for Flip-Chip applications in microelectronic devices.
  • Solder caps on copper pillars typically consist of two elements: (i) a structural element made of copper forming the pillar, e.g. a cylinder and (ii) a solder cap on top of said pillar.
  • a large number of such capped copper pillars are typically arranged on a die, which is part of a wafer.
  • solder caps on copper pillars provide an improved thermal and electrical behaviour due to the comparatively large volume of copper in the capped pillar, which provides an excellent electrical connection and increased conductivity.
  • the solder cap provides an electrical as well as mechanical connection between the respective pillar and a corresponding feature, for example a pillar of another die.
  • solder caps on copper pillars is the slim shape of the pillars compared to ball-like conventional solder ball applications. This allows a reduced distance (also called pitch) between two neighbouring pillars, which is a key element for higher packaging.
  • the solder cap typically includes tin and in many cases is a tin silver alloy; typically being free of lead. Such an alloy usually provides an excellent solderability and is a suitable alternative to previously used lead-containing solder caps and solder balls, respectively.
  • JP 2006-265573 A discloses a tin silver alloy plating bath without cyanide, which improves solderability and appearance of an electrodeposition film obtained from the tin silver bath.
  • EP 0 854 206 B1 relates to an acidic tin silver alloy plating bath, which is substantially free of cyanide, and a method for electroplating tin silver alloy onto a substrate.
  • US 2014/0251818 A1 refers to a cyanide-free tin alloy plating solution having outstanding serial stability as well as a method of plating tin alloy onto an electroconductive object using the tin alloy plating solution.
  • the tin alloy plating solution contains tin ions and one or more additional metal ions of silver, copper, bismuth, indium, palladium, lead, zinc, or nickel, and peptides with cysteine residues.
  • WO 03/046260 A2 relates to an electrolysis bath for electrodepositing silver-tin alloys that, in addition to water serving as a solvent with a pH value of less than 1.5, contains a water-soluble silver compound, a water-soluble tin compound and an organic complexing agent.
  • an aliphatic complexing agent having a sulfide group and an amino group is used as a complexing agent, whereby said functional groups are bound to different carbon atoms.
  • EP 1 553 211 B1 relates to a tin-silver-copper plating solution comprising 30-90 wt% of water, a sulfonic acid, tin ions, copper ions and silver ions, wherein the concentration of the silver ions is 0.01 to 0.1 mol/L, the concentration of the tin ions is 0.21 to 2 mol/L, the concentration of the copper ions is 0.002 to 0.02 mol/L and the mole ratio of the silver-ions to the copper ions is in the range of 4.5 to 5.58.
  • US 6,607,653 B1 relates to a tin-copper alloy plating bath, tin-copper-bismuth alloy plating bath or tin-copper-silver alloy plating bath containing a soluble metal compound and a specific sulfur-containing compound.
  • EP 2 221 396 A1 relates to a composition
  • a composition comprising one or more sources of tin ions, one or more sources of alloying metal ions, the metal ions are selected from the group consisting of silver ions, copper ions and bismuth ions, one or more flavone compounds, and one or more compounds having a formula: HOR(R")SR'SR(R")OH wherein R, R' and R" are the same or different and are alkylene radicals having 1 to 20 carbon atoms.
  • an aqueous composition for depositing a tin silver alloy comprising
  • the additional objective is solved by a method for electrolytically depositing a tin silver alloy onto a substrate, the method comprising the steps
  • an aqueous composition according to the present invention for electrolytically depositing tin silver alloy solder bumps or tin silver alloy solder caps onto metal pillars, preferably for electrolytically depositing tin silver alloy solder caps onto copper pillars.
  • the term "at least one” denotes (and is exchangeable with) “one, two, three or more than three”.
  • the term "independently” denotes for example that in the at least one second compound of formula (II) X, R 1 , and R 2 in a first compound of formula (II) are selected independently from X, R 1 , and R 2 in a second and further compound of formula (II) in the aqueous composition of the present invention.
  • the at least one first compound is independently selected from a number of compound groups. This means that, if for example two first compounds are selected, each compound can be selected from a different compound group, for example one compound is a substituted bis(aminophenyl)disulfide, the other is a substituted dipyridyldisulfide. In other words, the selection of the first compound of said two first compounds is independent from the selection of the second first compound of said two first compounds.
  • the composition of the present invention is an aqueous composition, which means that water is the primary component.
  • aqueous composition which means that water is the primary component.
  • more than 50 wt-% of the aqueous composition is water, based on the total weight of the aqueous composition, preferably at least 60 wt-%, even more preferably at least 70 wt-%, most preferably 80 wt-% or more.
  • the aqueous composition is substantially free of organic solvents; more preferably does not contain organic solvents at all.
  • the aqueous composition is preferably an aqueous solution, i.e. is homogeneous and thus preferably does not contain any particles.
  • the term "at least” in combination with a particular value denotes (and is exchangeable with) this value or more than this value.
  • “at least 70 wt-%” denotes (and is exchangeable with) "70 wt-% or more than 70 wt-%”.
  • the term "substantially free" of a subject-matter independently denotes that said subject-matter is not present at all or is present only in (to) a very little and undisturbing amount (extent) without affecting the intended purpose of the invention.
  • a subject-matter e.g. a compound, a material, etc.
  • such a subject-matter might be added or utilized unintentionally, e.g. as unavoidable impurity.
  • Substantially free preferably denotes 0 (zero) ppm to 50 ppm, based on the total weight of the aqueous composition of the present invention, if defined for said aqueous composition, or based on the total weight of the tin silver alloy, if defined for said alloy; preferably 0 ppm to 25 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, most preferably 0 ppm to 1 ppm.
  • Zero ppm denotes that a respective subject-matter is not at all comprised.
  • aqueous composition of the present invention wherein the composition is acidic, preferably the composition has a pH in the range from -2 to +4, more preferably in the range from -1 to +2, most preferably in the range from -0.5 to +1.2.
  • acidic compositions in particular having a pH range as defined above, are typically free of cyanide, which is desired for environmental reasons.
  • the composition of the present invention is preferably free of cyanide.
  • pH ranges lead to an improved quality of the deposited tin silver alloy compared to a composition with a pH significantly higher than 4 or even being alkaline.
  • the stability is increased if the pH is in the above defined pH ranges.
  • the aqueous composition of the present invention is for depositing a tin silver alloy, preferably a tin silver alloy being substantially free of sulfur.
  • the aqueous composition of the present invention comprises (a) tin ions and (b) silver ions in order to deposit the tin silver alloy.
  • the tin ions are preferably tin (II) ions and the silver ions preferably silver (I) ions.
  • aqueous composition of the present invention wherein in the aqueous composition the tin ions are present in a total concentration in the range from 20 g/L to 200 g/L, based on the total volume of the aqueous composition, preferably in the range from 25 g/L to 150 g/L, more preferably in the range from 30 g/L to 120 g/L, even more preferably in the range from 35 g/L to 100 g/L, most preferably in the range from 40 g/L to 90 g/L.
  • a concentration significantly below 20 g/L often results in an undesired low deposition rate. If the concentration significantly exceeds 200 g/L problems with solubility are frequently observed. An optimal compromise of deposition rate and solubility is obtained in above defined preferred concentration ranges. Best results have been obtained with a concentration in the range from 35 g/L to 100 g/L and from 40 g/L to 90 g/L, respectively.
  • the tin ions are from a tin ion source.
  • the tin ion source of said tin ions is preferably at least one tin salt, more preferably at least one inorganic tin salt and/or at least one organic tin salt.
  • Preferred inorganic tin salts are selected from the group consisting of tin oxide, tin sulfate, and tin sulfide.
  • Preferred organic tin salts are selected from the group consisting of tin acetate, tin citrate, tin oxalate, and tin alkyl sulfonates.
  • tin ions are from at least one organic tin salt, preferably from at least one tin alkyl sulfonate.
  • tin methane sulfonate is preferred.
  • tin (II) is present as tin (II).
  • an aqueous composition of the present invention wherein in the aqueous composition the silver ions are present in a total concentration in the range from 0.1 g/L to 10 g/L, based on the total volume of the aqueous composition, preferably in the range from 0.2 g/L to 8 g/L, more preferably in the range from 0.3 g/L to 6 g/L, even more preferably in the range from 0.4 g/L to 4 g/L, most preferably in the range from 0.5 g/L to 2 g/L.
  • a concentration significantly below 0.1 g/L often results in an insufficient amount of silver in the tin silver alloy leading to undesired mechanical and electrical properties in respective solder caps and solder bumps.
  • the concentration significantly exceeds 10 g/L the composition is not sufficiently stable and plate out is sometimes observed.
  • too much silver is usually incorporated into the tin silver alloy, significantly increasing the melting point of a respective solder cap, which is undesired in subsequent reflow processes.
  • Optimal melting points are obtained in the above defined preferred concentration ranges, most preferably in the ranges from 0.4 g/L to 4 g/L and 0.5 g/L to 2 g/L, respectively.
  • the silver ions are from a silver ion source.
  • the silver ion source of said silver ions is preferably at least one silver salt, more preferably at least one inorganic silver salt and/or at least one organic silver salt.
  • Preferred inorganic silver salts are selected from the group consisting of silver oxide, silver sulfate, and silver nitrate.
  • Preferred organic silver salts are selected from the group consisting of silver acetate, silver citrate, silver oxalate, and silver alkyl sulfonates. More preferred is an aqueous composition of the present invention, wherein the silver ions are from at least one organic silver salt, preferably from at least one silver alkyl sulfonate. In the aqueous composition of the present invention most preferred is silver methane sulfonate.
  • silver is present as silver (I).
  • the silver ion source as well as the tin ion source comprise alkylsulfonates, more preferably are alkylsulfonates. This is in particular preferred if the pH in the aqueous composition of the present invention is (re)adjusted by means of alkylsulfonic acids. In this case only one type of organic acid anion is present in the composition of the present invention.
  • the molar ratio is as defined above, in particular in the range from 125:1 to 12:1 and from 100:1 to 15:1, respectively, an excellent uniform tin silver alloy is obtained and dendrites are very much suppressed in solder caped pillars.
  • composition of the present invention is substantially free of, preferably does not comprise, halide ions, most preferably chloride ions.
  • halide ions most preferably chloride ions.
  • silver chloride is very insoluble in an aqueous environment.
  • chloride ions although present in low amounts and not necessarily leading to immediate precipitation of insoluble chlorides, result in deposition defects in the tin silver alloy.
  • an aqueous composition of the present invention wherein the composition additionally comprises copper (II) ions, preferably in a total concentration from 0.06 g/L to 5 g/L, based on the total volume of the aqueous composition, more preferably in a total concentration from 0.3 g/L to 4 g/L, even more preferably in a total concentration from 0.8 g/L to 3 g/L.
  • Such a composition is for basically depositing a tin silver copper alloy.
  • an aqueous composition of the present invention wherein the composition comprises copper (II) ions in a total concentration from 0.06 g/L to 0.6 g/L, based on the total volume of the aqueous composition, preferably from 0.2 g/L to 0.5 g/L, more preferably from 0.3 g/L to 0.4 g/L.
  • copper is incorporated into the tin silver alloy only to a very limited extent.
  • an aqueous composition of the present invention wherein the composition comprises copper (II) ions in a total concentration from 0.7 g/L to 5 g/L, based on the total volume of the aqueous composition, preferably from 1 g/L to 4.2 g/L, more preferably from 1.3 g/L to 3.6 g/L, even more preferably from 2.1 g/L to 3.1 g/L.
  • copper is incorporated into the tin silver alloy to a more significant extent.
  • the obtained tin silver alloy is substantially free of, preferably does not comprise, copper.
  • an aqueous composition of the present invention is preferred, wherein the composition is substantially free of, preferably does not comprise, copper ions, preferably is substantially free of, preferably does not comprise, copper ions and bismuth ions.
  • an aqueous composition of the present invention being substantially free of, preferably not comprising, nickel ions, zinc ions, iron ions, lead ions, and aluminium ions.
  • said tin ions and said silver ions are the only depositable metal ions in the aqueous composition.
  • these metal ions are the only metal ions that are deposited in the tin silver alloy.
  • Group 3 to 15 refers to the 18 groups in the periodic table of elements.
  • the aqueous composition of the present invention comprises, besides (a) tin ions and (b) silver ions, (c) at least one (preferably one) first compound (as described throughout the present text) and additionally (d) at least one (preferably one) second compound of formula (II).
  • the at least one first compound is independently selected from the group consisting of unsubstituted bis(aminophenyl)disulfides, substituted bis(aminophenyl)disulfides, unsubstituted dipyridyldisulfides, and substituted dipyridyldisulfides, preferably is independently selected from the group consisting of unsubstituted bis(aminophenyl)disulfides, substituted bis(aminophenyl)disulfides, and unsubstituted dipyridyldisulfides, more preferably is independently selected from the group consisting of unsubstituted bis(aminophenyl)disulfides and substituted bis(aminophenyl)disulfides, most preferably is independently selected from the group consisting of unsubstituted bis(aminophenyl)disulfides.
  • unsubstituted denotes that no additional substitu
  • each phenyl moiety comprises a single amino group.
  • the unsubstituted bis(aminophenyl)disulfides are selected from the group consisting of 4,4'-diaminodiphenyl disulfide (also called 4,4'-dithiodianiline) and 2,2'-diaminodiphenyl disulfide (also called 2,2'-dithiodianiline). More preferred is an aqueous composition of the present invention, wherein the at least one first compound is 2,2'-diaminodiphenyl disulfide. Most preferred is an aqueous composition of the present invention, wherein 2,2'-diaminodiphenyl disulfide is the only first compound.
  • the unsubstituted dipyridyldisulfides are preferably selected from the group consisting of 4,4'-dipyridyldisulfide and 2,2'-dipyridyldisulfide.
  • an amino substituent denotes a second amino group in at least one of the two phenyl moieties.
  • an aqueous composition of the present invention wherein the substituted bis(aminophenyl)disulfides have at least one substituent independently selected from the group consisting of C1 to C4 alkyl, C1 to C4 alkoxy, hydroxyl, sulfhydryl, carboxyl, amino, nitro, and halide, preferably selected from the group consisting of C1 to C3 alkyl, C1 to C4 alkoxy, hydroxyl, and sulfhydryl, more preferably selected from the group consisting of C1 to C3 alkyl, C1 to C3 alkoxy, and hydroxyl.
  • substituent independently selected from the group consisting of C1 to C4 alkyl, C1 to C4 alkoxy, hydroxyl, sulfhydryl, carboxyl, amino, nitro, and halide, preferably selected from the group consisting of C1 to C3 alkyl, C1 to C4 alkoxy, hydroxyl, and sulfhydry
  • an aqueous composition of the present invention wherein the substituted dipyridyldisulfides have at least one substituent independently selected from the group consisting of C1 to C4 alkyl, C1 to C4 alkoxy, hydroxyl, sulfhydryl, carboxyl, amino, nitro, and halide, preferably selected from the group consisting of C1 to C3 alkyl, C1 to C4 alkoxy, hydroxyl, sulfhydryl, and amino, more preferably selected from the group consisting of C1 to C3 alkyl, C1 to C3 alkoxy, hydroxyl, and amino.
  • substituent independently selected from the group consisting of C1 to C4 alkyl, C1 to C4 alkoxy, hydroxyl, sulfhydryl, carboxyl, amino, nitro, and halide, preferably selected from the group consisting of C1 to C3 alkyl, C1 to C4 alkoxy, hydroxyl, sulfhydryl
  • aqueous composition of the present invention wherein the substituted dipyridyldisulfides have at least one substituent independently selected from the group consisting of methoxy, ethoxy, methyl, ethyl, hydroxyl, and amino.
  • substituted dipyridyldisulfides have at least one amino substituent.
  • aqueous composition of the present invention wherein the total concentration of all first compounds is in the range from 1 mmol/L to 100 mmol/L, based on the total volume of the aqueous composition, preferably from 5 mmol/L to 80 mmol/L, more preferably from 10 mmol/L to 60 mmol/L, even more preferably from 15 mmol/L to 50 mmol/L, most preferably from 20 mmol/L to 40 mmol/L.
  • the total concentration as defined above is formed by only one first compound, most preferably by 2,2'-diaminodiphenyl disulfide (2,2'-dithiodianiline). If the total concentration is significantly below 1 mmol/L or significantly above 100 mmol/L undesired variations in the tin silver alloy are frequently observed. Furthermore, in many cases issues with the bath stability were observed.
  • the at least one second compound of formula (II) comprises one or more than one, preferably one, sulfhydryl group (SH group) in residue X.
  • X denotes a C1 to C10 alkyl moiety comprising said one or more than one, preferably one, sulfhydryl group, preferably a C1 to C8 alkyl moiety, more preferably a C1 to C6 moiety, even more preferably a C1 to C5 alkyl moiety, most preferably a C1 to C4 alkyl moiety, each comprising said one or more than one, preferably one, sulfhydryl group.
  • X is a C1 alkyl moiety comprising one sulfhydryl group
  • X denotes -CH 2 -SH.
  • alkyl moieties with three or more than three carbon atoms are linear or branched, preferably linear.
  • Linear alkyl moieties are preferably covalently connected with the nitrogen atom in formula (II) via a terminal carbon atom in the linear alkyl moiety.
  • linear alkyl moieties are preferably n-alkyl moieties.
  • R 1 denotes hydrogen, methyl, ethyl, linear C3 to C5 alkyl, branched C3 to C5 alkyl, unsubstituted phenyl, substituted phenyl, unsubstituted benzyl, or substituted benzyl, preferably R 1 denotes hydrogen, methyl, ethyl, linear C3 to C5 alkyl, or branched C3 to C5 alkyl, more preferably R 1 denotes hydrogen, methyl, ethyl, or linear C3 to C5 alkyl, most preferably R 1 denotes methyl or ethyl.
  • branched C3 alkyl denotes its iso-form.
  • R 2 denotes methyl, ethyl, linear C3 to C5 alkyl, branched C3 to C5 alkyl, unsubstituted phenyl, substituted phenyl, unsubstituted benzyl, or substituted benzyl, preferably R 2 denotes methyl, ethyl, linear C3 to C5 alkyl, or branched C3 to C5 alkyl, more preferably R 2 denotes methyl, ethyl, or linear C3 to C5 alkyl, most preferably R 2 denotes methyl or ethyl.
  • Preferred substituents in said substituted phenyl and substituted benzyl are independently selected from the group consisting of hydroxyl, C1 to C3 alkyl, C1 to C3 alkoxy, amino, nitro, and carboxyl.
  • the at least one second compound of formula (II) serves as complexing agent in the aqueous composition of the present invention.
  • Preferred is an aqueous composition of the present invention, wherein compounds of formula (II) are the only complexing agents in the composition.
  • the aqueous composition of the present invention is substantially free of, preferably does not comprise, glycine, cysteine, and glutathione, more preferably is substantially free of, preferably does not comprise, amino acids with at least one sulfhydryl group and peptides with at last one sulfhydryl group, most preferably is substantially free of, preferably does not comprise, amino acids and peptides at all.
  • compounds of formula (II) surprisingly serve a second advantage.
  • compounds of the at least one first compound get reduced, which results in their monomerization.
  • This monomerization is basically desired.
  • compounds of formula (II) reduce compounds of the at least one first compound only to such an extent that unpleasant odors are largely prevented. Instead a progressive and self-regulated reducing is obtained such that the total amount of monomeric first compounds is kept very low but sufficiently high to ensure operational capabilities of the aqueous composition. This is advantageous for people working in close proximity to a respective composition.
  • linear C3 to C5 alkyl and branched C3 to C5 alkyl preferably and explicitly includes n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutan-2-yl, 2,2-dimethylpropyl, 3-methylbutyl, pentan-2-yl, pentan-3-yl, 3-methylbutan-2-yl, and 2-methylbutyl.
  • composition of the present invention wherein the at least one second compound of formula (II) is 2-(dimethylamino)ethanethiol.
  • compounds of formula (II) are preferably positively charged at the nitrogen atom due to the preferred highly acidic pH (for pH see details above in the text).
  • aqueous composition of the present invention wherein the total concentration of all said second compounds of formula (II) is in the range from 5 mmol/L to 100 mmol/L, based on the total volume of the aqueous composition, preferably from 8 mmol/L to 80 mmol/L, more preferably from 10 mmol/L to 60 mmol/L, even more preferably from 15 mmol/L to 50 mmol/L, most preferably from 20 mmol/L to 40 mmol/L.
  • the total concentration as defined above is formed by only one second compound, most preferably by only 2-(dimethylamino)ethanethiol. If the total concentration is significantly below 5 mmol/L, silver ions are not sufficiently complexed and undesired plate out is frequently observed.
  • aqueous composition of the present invention wherein the molar ratio of all first compounds to all second compounds is in the range from 10:1 to 1:10, preferably in the range from 7:1 to 1:7, more preferably in the range from 5:1 to 1:5, even more preferably in the range from 4:1 to 1:4, most preferably in the range from 3:1 to 1:3, even most preferably in the range from 2:1 to 1:2. If the molar ratio is significantly above 10:1 or significantly below 1:10 the stability of the aqueous composition is in some cases negatively affected. Furthermore, in some cases in the tin silver alloy the total amount of silver was negatively affected, leading to a tin silver alloy comprising too high or too little amounts of silver.
  • the aqueous composition of the present invention preferably comprises further compounds.
  • an aqueous composition of the present invention furthermore comprising (e) at least one organic acid anion, preferably an alkyl sulfonic acid anion, most preferably methane sulfonic acid anions.
  • Said at least one organic acid anion is preferably obtained from the source of tin ions and/or the source of silver ions.
  • said at least one organic acid anion is obtained from an organic acid, preferably from at least one alkyl sulfonic acid, most preferably from methane sulfonic acid.
  • said at least one organic acid anion is obtained from the source of tin ions, the source of silver ions, and an organic acid.
  • the aqueous composition of the present invention preferably contains only one type of organic acid anion, which is very preferred. Therefore, most preferred is an aqueous composition of the present invention, wherein in the composition alkyl sulfonate, preferably methane sulfonate, is the only organic acid anion.
  • Alkyl sulfonic acids are preferred acids because they serve as optimal pH adjuster and typically result in a very strong acidic pH. If other organic acid anions are utilized, preferably acetate, oxalate, and citrate, either as organic acid or in the source of tin ions and/or silver ions, an additional strong acid is usually needed to obtain the preferred strong acidic pH, for example strong inorganic acids, which include additional inorganic anions. This is less preferred, e.g. for the reasons stated above. Thus, preferred is an aqueous composition of the present invention, wherein the composition is substantially free of, preferably does not comprise, inorganic acids. Instead strong organic acids are preferred in the composition of the present invention.
  • aqueous composition of the present invention wherein in the aqueous composition the total concentration of all organic acid anions is in the range from 0.5 mol/L to 4.0 mol/L, based on the total volume of the aqueous composition, preferably from 0.6 mol/L to 2.5 mol/L, more preferably from 0.7 mol/L to 2 mol/L, even more preferably from 0.8 mol/L to 1.5 mol/L, most preferably from 0.9 mol/L to 1.3 mol/L.
  • the total concentration as defined above is formed by only one type of organic acid anions, more preferably by only alkyl sulfonates, most preferably by only methane sulfonate.
  • the composition is not sufficiently stable anymore. Furthermore, a too high total concentration creates severe issues or even damages on the substrate. If the total concentration is significantly below 0.5 mol/L an insufficient conductivity of the aqueous composition is usually obtained.
  • the aqueous composition of the present invention preferably comprises at least one surfactant.
  • the kind of surfactant is not particularly limited.
  • an aqueous composition of the present invention furthermore comprising (f) at least one surfactant, preferably selected from the group consisting of nonionic surfactants, amphoteric surfactants, cationic surfactants, and anionic surfactants, preferably nonionic surfactants and cationic surfactants, more preferably alkoxylated cationic surfactants and polyether nonionic surfactants, even more preferably alkylene oxide co-polymers and alkoxylated amines, most preferably ethylene oxide/propylene oxide co-polymers and ethoxylated amines.
  • aqueous composition of the present invention wherein the total concentration of all surfactants is in the range from 0.1 g/L to 20 g/L, based on the total volume of the aqueous composition, preferably from 0.4 g/L to 10 g/L, more preferably from 0.6 g/L to 8 g/L, most preferably from 1 g/L to 5 g/L. If the total concentration is significantly below 0.1 g/L in many cases the wettability is insufficient. If the total concentration is significantly exceeding 20 g/L it is often observed that undesired foam is formed.
  • the aqueous composition of the present invention furthermore preferably comprises, at least in many cases, at least one anti-foam agent.
  • the aqueous composition of the present invention preferably comprises tin (II) ions.
  • tin (II) ions are susceptible to oxidation, which results in tin (IV) ions. Such an oxidation is not desired because it promotes precipitation of tin (IV) species, such as tin (IV) oxide.
  • an anti-oxidizing agent is preferably utilized.
  • an aqueous composition of the present invention furthermore comprising (g) at least one anti-oxidizing agent, preferably selected from the group consisting of compounds comprising a hydroxylated ring moiety, most preferably selected from the group consisting of catechol, hydroquinone, resorcinol, phenolsulfonic acids, ascorbic acid, and naptholsulfonic acids.
  • at least one anti-oxidizing agent preferably selected from the group consisting of compounds comprising a hydroxylated ring moiety, most preferably selected from the group consisting of catechol, hydroquinone, resorcinol, phenolsulfonic acids, ascorbic acid, and naptholsulfonic acids.
  • Preferred hydroxylated ring moieties are hydroxylated aromatic compounds, more preferably benzene diols, even more preferably selected from the group consisting of catechol, hydroquinone, and resorcinol, most preferably selected from the group consisting of resorcinol and hydroquinone.
  • Most preferred is an aqueous composition of the present invention, wherein the at least one anti-oxidizing agent is resorcinol, more preferably resorcinol is the only anti-oxidizing agent in the aqueous composition of the present invention.
  • Anti-oxidizing agents as defined above are strong enough to avoid oxidation of tin (II) ions to tin (IV) ions without reducing tin (II) ions to metallic tin.
  • the aqueous composition of the present invention is preferably for electrolytically depositing a tin silver alloy and is preferably not for electroless deposition.
  • aqueous composition of the present invention wherein the total concentration of all anti-oxidizing agents is in the range from 1.0 mmol/L to 100 mmol/L, based on the total volume of the aqueous composition, preferably from 2.0 mmol/L to 70 mmol/L, more preferably from 4.0 mmol/L to 40 mmol/L, even more preferably from 5.0 mmol/L to 20 mmol/L, most preferably from 6.0 mmol/L to 15 mmol/L.
  • the total concentration as defined above is formed by only one type of anti-oxidizing agent, more preferably by only benzene diols, most preferably by only resorcinol.
  • the at least one anti-oxidizing agent is known as a typical anti-oxidizing agent, the amount of such a compound is preferably counted among the above mentioned total concentration of all anti-oxidizing agents.
  • the at least one anti-oxidizing agent is an organic acid and comprises a hydroxylated ring moiety, the amount of said compound is counted among above mentioned total concentration of all anti-oxidizing agents.
  • the present invention also refers to a method for electrolytically depositing a tin silver alloy onto a substrate, the method comprising the steps
  • the substrate is provided, preferably a conductive substrate.
  • the substrate is a semiconductor base substrate, preferably comprising a conductive or semi-conductive layer thereon.
  • a conductive or semi-conductive layer is also often referred to as seed layer.
  • the kind of seed layer is not particularly restricted.
  • a most preferred seed layer is a copper seed layer.
  • the substrate preferably is or comprises at least one metalloid and/or gallium, more preferably is or comprises at least one element selected from the group consisting of silicon, germanium, and gallium, most preferably is or comprises silicon. If the substrate is not in itself sufficiently conductive, it preferably comprises above mentioned conductive or semi-conductive layer.
  • the substrate is a wafer, preferably a wafer comprising a conductive or semi-conductive layer thereon, most preferably comprising a copper seed layer.
  • the substrate is a non-conductive substrate, preferably a substrate being or comprising glass or plastic.
  • the substrate preferably comprises already at least partly a conductive seed layer, or a conductive seed layer is deposited in a subsequent processing step.
  • the substrate (as defined before) comprises a plurality of individual structural features.
  • the substrate comprises a plurality of metal features, preferably a plurality of metal pillars and/or areas with at least one metal layer, more preferably a plurality of copper pillars and/or areas with at least one copper layer.
  • the metal features have an aspect ratio in the range from 1:40 to 15:1 (height:width), preferably in the range from 1:30 to 10:1, more preferably in the range from 1:20 to 7:1.
  • Metal pillars and copper pillars respectively, have a preferred aspect ratio in the range from 1:1 to 10:1, more preferably in the range from 1:1 to 7:1.
  • Metal bumps and copper bumps respectively, have a preferred aspect ratio in the range from 1:40 to 1:1, preferably in the range from 1:30 to 1:10.
  • individual structural features and metal features, respectively include individual geometrical forms such as pillars, spots and areas, which are accessible for tin silver alloy deposition by means of the method of the present invention.
  • said metal pillars and copper pillars, respectively have a cylindrical shape.
  • said metal pillars and copper pillars, respectively have a height in the range from 3 ⁇ m to 100 ⁇ m, preferably from 5 ⁇ m to 90 ⁇ m, more preferably from 9 ⁇ m to 80 ⁇ m, even more preferably from 15 ⁇ m to 70 ⁇ m, most preferably from 20 ⁇ m to 70 ⁇ m.
  • said metal pillars and copper pillars, respectively have a width in the range from 5 ⁇ m to 100 ⁇ m, preferably from 10 ⁇ m to 80 ⁇ m, more preferably from 10 ⁇ m to 30 ⁇ m.
  • said metal bumps and copper bumps can have any shape; preferably a cylindrical, polygonal, and/or rectangular shape.
  • the metal bumps and copper bumps respectively, have a height in the range from 0.5 ⁇ m to 50 ⁇ m, preferably from 1 ⁇ m to 30 ⁇ m, more preferably from 2 ⁇ m to 25 ⁇ m, even more preferably from 3 ⁇ m to 20 ⁇ m, most preferably from 4 ⁇ m to 15 ⁇ m.
  • bumps have a width of at least 50 ⁇ m, preferably of at least 80 ⁇ m, more preferably of at least 100 ⁇ m.
  • step (B) an aqueous composition of the present invention, preferably as described throughout the text as being preferred, is provided, typically in a tank for electrolytic metal deposition.
  • step (C) of the method of the present invention the tin silver alloy is electrolytically deposited onto the substrate.
  • Step (C) requires that the substrate is sufficiently conductive in order to electrolytically deposit the tin silver alloy.
  • the substrate provided in step (A) is already sufficiently conductive or the substrate provided in step (A) is processed in subsequent steps such that it is sufficiently conductive prior to step (C).
  • the substrate in step (C) preferably comprises at least one conductive or semi-conductive layer such that the tin silver alloy is electrolytically deposited thereon.
  • the at least one conductive or semi-conductive layer is a conductive metallic, conductive semi-metallic, or conductive non-metallic layer. Most preferably it is a conductive metallic layer, preferably a metallic copper layer, typically a copper seed layer.
  • step (C) the tin silver alloy is deposited as solder caps on pillars and/or as solder bumps.
  • the substrate is operated as a cathode in order to deposit the tin silver alloy in step (C).
  • the electrical current is a direct current, preferably with a cathodic current density in the range from 1 A/dm 2 to 100 A/dm 2 , more preferably with a cathodic current density in the range from 3 A/dm 2 to 70 A/dm 2 , most preferably with a cathodic current density in the range from 5 A/dm 2 to 50 A/dm 2 .
  • the direct current in step (C) is not supplemented by current pulses. This means that preferably in step (C) the direct current is the only electrical current.
  • the method of the present invention gives excellent results. This means that at such current densities excellent and very uniform tin silver alloys are deposited and additionally the number of dendrites is impressively low. This is in particular the case compared to compositions comprising amino acids with at least one sulfhydryl group, e.g. cysteine (see examples below). Therefore, particular preferred is a method of the present invention, wherein the electrical current comprises a direct current with a cathodic current density in the range from 10 A/dm 2 to 40 A/dm 2 , more preferably in the range from 12 A/dm 2 to 35 A/dm 2 .
  • step (C) the contacting and supplying of electrical current is carried out for 3 seconds to 400 min, preferably for 5 seconds to 200 min, most preferably for 6 seconds to 100 min. If the contacting is carried out for significantly less than 3 seconds typically an incomplete tin silver alloy is deposited and the uniformity of the solder caps is insufficient.
  • step (C) of the method of the present invention preferably a tin silver alloy layer is deposited, preferably with a layer thickness in the range from 1 ⁇ m to 150 ⁇ m, more preferably in the range from 4 ⁇ m to 100 ⁇ m, even more preferably in the range from 7 ⁇ m to 90 ⁇ m, most preferably in the range from 10 ⁇ m to 80 ⁇ m.
  • the silver content in the electrolytically deposited tin silver alloy is in the range from 0.1 wt-% to 10 wt-%, based on the total weight of the electrolytically deposited tin silver alloy, preferably is in the range from 0.5 wt-% to 5 wt-%, most preferably is in the range from 1.5 wt-% to 3.5 wt-%. Most preferably the rest of the tin silver alloy is tin. Thus, the major metal in the tin silver alloy is tin.
  • a method of the present invention is preferred, wherein the tin content in the electrolytically deposited tin silver alloy is at least 60 wt-%, based on the total weight of the electrolytically deposited tin silver alloy, preferably at least 70 wt-%, more preferably at least 80 wt-%, even more preferably at least 90 wt-% or at least 95 wt.-%, most preferably at least 96.5 wt-%, and even most preferably at least 98.5 wt-% or at least 99.5 wt.-%.
  • a tin silver alloy as described above is very much desired and suitable for solder caps on pillars and as solder bumps because of its excellent solderability.
  • the tin silver alloy comprises copper.
  • the tin silver alloy obtained with the method of the present invention is not a ternary alloy, more preferably not a tin silver copper alloy.
  • the tin silver alloy is substantially free of, preferably does not comprise, one, more than one or all elements of the group consisting of zinc, nickel, iron, copper, bismuth, aluminium, and lead.
  • the tin silver alloy obtained with the method of the present invention is substantially free of, preferably does not comprise, lead.
  • step (C) the aqueous composition has a temperature in the range from 5°C to 90°C, preferably in the range from 15°C to 60°C, more preferably in the range from 20°C to 50°C, most preferably in the range from 22 °C to 40°C. If the temperature is significantly below 5°C no adequate deposition speed is obtained. If the temperature is significantly above 90°C undesired evaporation and bath instability occurs.
  • the present invention also refers to a use of the aqueous composition of the present invention for electrolytically depositing tin silver alloy solder bumps or tin silver alloy solder caps onto metal pillars, preferably for electrolytically depositing tin silver alloy solder caps onto copper pillars.
  • silicon-based wafer coupons rendered conductive by means of an approximately 500 nm copper seed layer, each comprising nine dies with a plurality of cylindrical copper pillars (height: 10 ⁇ m) were provided.
  • the copper pillars were formed within a respective photoresist.
  • tin silver alloys were deposited on top of the copper pillars to form respective solder caps.
  • solder caps were obtained.
  • the respective substrates were immersed into the respective composition for varying contact times according to the supplied current density such that in each case an approximately 15 ⁇ m tin silver solder cap was deposited (immersion for 60 seconds to 120 seconds depending on applied current density).
  • the temperature of each composition was 25°C and stirring was set to 300 rpm.
  • the number and average area of dendrites as well as the uniformity of the solder caps were determined. The parameters for each deposition experiment and the respective results are summarized in Table 1.
  • Table 1 shows that in a deposition experiment utilizing the aqueous composition E-1 the number of dendrites is insignificant, even at comparatively high current densities such as 30 A/dm 2 . This is also observed for the average area of dendrites, which is significantly higher in comparative aqueous composition C-1.
  • the number of dendrites and the average area of dendrites were determined by a light microscope (Olympus LEXT OLS4000) using software "Olympus Stream Enterprise Desktop 2.2".
  • Fig. 1 shows the result utilizing aqueous composition E-1 and Fig. 2 the result of comparative aqueous composition C-1, both at 30 A/dm 2 .
  • Fig. 1 almost no dendrites are present, wherein in Fig. 2 significantly more dendrites can be seen.
  • copper pillars with solder caps obtained with aqueous composition E-1 exhibit a higher uniformity compared to respective capped copper pillars obtained with comparative aqueous composition C-1, in particular at a current density of 30 A/dm 2 .
  • WIP and WID parameters well known in this technical field.
  • titrations were performed as follows: In a first step an aqueous stock solution (concentration of complexing compound: 50 g/L) comprising the respective compound(s) for silver ions was prepared.
  • a second step portions from the stock solution were added stepwise to a titration solution comprising silver methanesulfonate (concentration corresponding to 1 g/L Ag (I) ions) and a silver rotating disk electrode (RDE) (1000 rpm).
  • the change in overpotential upon adding portions from the stock solution was determined in reference to a reference electrode.
  • the temperature of the titration solution was 25°C.
  • Fig. 3 shows that the complexing properties vary significantly among the tested compounds.
  • compound D alone (glutathione) shows significant complexing properties and a similar maximum overpotential of approximately -250 mV.
  • compound D is less strongly forming respective complexes. This can be seen in the higher concentration of compound D which is required in order to obtain an overpotential especially in the range from -50 mV to -200 mV. This means that compound D is less effective than compound B at lower concentrations.
  • glutathione in some cases suffers the disadvantage that it is not sufficiently stable over time in respective aqueous compositions (shelf-life).
  • Compound C alone also shows significant complexing properties towards silver ions and is a typical complexing compound in known compositions (compare JP 2006-265573 A ).
  • Fig. 3 shows that compound C is a very capable complexing compound. A maximum of approximately -250 mV is already obtained at comparatively low concentrations of less than 2 g/L. Generally, if complex formation takes place at already very low concentrations the working concentration in a respective aqueous composition is typically also low. Under such circumstances maintaining this low working concentration is challenging and requires very sensitive analytical tools, which is usually not desired.
  • Compound E also shows a maximum overpotential of approximately -250 mV, and, thus, in this regard is very similar compared to compound B, C, and D. In contrast, compound E very quickly forms strong complexes. This is seen in the fact that at already 1 g/L almost the maximum overpotential is obtained. Although compound D is very capable in forming complexes the working concentration is typically too low and maintaining it in a respective aqueous composition is demanding.
  • the combinations of A and B as well as of A and C are the only means to obtain very strong complexes. In each case a maximum overpotential of approximately -400 mV is obtained. Such strong complex formation is desired in order to avoid undesired plate out of silver. Plate out typically occurs if silver ions are insufficiently complexed such that either insoluble silver species precipitate in the aqueous composition or silver is deposited too quickly on a respective substrate even in the absence of an electrical current.
  • the combination A and B additionally shows a desired working concentration range to obtain an overpotential in the range from -250 mV to -400 mV.
  • the combination A and C suffers the disadvantage that respective solder caps are more susceptible to dendrite formation (compare item 2 above).
  • compound A was present in an approximately equimolar amount compared to 50 g/L of compound B and C, respectively.
  • the total concentration of compound A in the stock solution is identical to the concentration of compound A for combinations A and B and A and C, respectively.

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Claims (15)

  1. Eine wässrige Zusammensetzung zum Abscheiden einer Zinn-Silber-Legierung, wobei die Zusammensetzung Folgendes umfasst:
    (a) Zinnionen,
    (b) Silberionen,
    (c) mindestens eine erste Verbindung, die unabhängig aus der Gruppe bestehend aus unsubstituierten Bis(aminophenyl)disulfiden, substituierten Bis(aminophenyl)disulfiden, unsubstituierten Dipyridyldisulfiden und substituierten Dipyridyldisulfiden ausgewählt ist, und
    (d) mindestens eine zweite Verbindung der Formel (II)
    Figure imgb0006
     wobei jeweils unabhängig
    X eine C1- bis C10-Alkylgruppe bedeutet umfassend eine oder mehr als eine Sulfhydrylgruppe,
    R1 Wasserstoff, Methyl, Ethyl, lineares C3- bis C5-Alkyl, verzweigtes C3- bis C5-Alkyl, unsubstituiertes Phenyl, substituiertes Phenyl, unsubstituiertes Benzyl oder substituiertes Benzyl bedeutet und
    R2 Methyl, Ethyl, lineares C3- bis C5-Alkyl, verzweigtes C3- bis C5-Alkyl, unsubstituiertes Phenyl, substituiertes Phenyl, unsubstituiertes Benzyl oder substituiertes Benzyl bedeutet.
  2. Die Zusammensetzung nach Anspruch 1, wobei es sich bei der mindestens einen zweiten Verbindung der Formel (II) um eine Verbindung der Formel (IIa)
    Figure imgb0007
     wobei unabhängig
    R1 Wasserstoff, Methyl, Ethyl, lineares C3- bis C5-Alkyl, verzweigtes C3- bis C5-Alkyl, unsubstituiertes Phenyl, substituiertes Phenyl, unsubstituiertes Benzyl oder substituiertes Benzyl bedeutet,
    R2 Methyl, Ethyl, lineares C3- bis C5-Alkyl, verzweigtes C3- bis C5-Alkyl, unsubstituiertes Phenyl, substituiertes Phenyl, unsubstituiertes Benzyl oder substituiertes Benzyl bedeutet und
    n 1, 2, 3 oder 4 bedeutet.
  3. Die Zusammensetzung nach Anspruch 1 oder 2, wobei die substituierten Bis(aminophenyl)disulfide und substituierten Dipyridyldisulfide mindestens einen Substituenten aufweisen, der unabhängig aus der Gruppe bestehend aus C1- bis C4-Alkyl, C1- bis C4-Alkoxy, Hydroxyl, Sulfhydryl, Carboxyl, Amino, Nitro und Halogenid ausgewählt ist.
  4. Die Zusammensetzung nach einem der vorherigen Ansprüche, wobei die Zusammensetzung sauer ist, wobei die Zusammensetzung vorzugsweise einen pH-Wert im Bereich von -2 bis +4, weiter bevorzugt im Bereich von -1 bis +2, ganz besonders bevorzugt im Bereich von -0,5 bis +1,2 aufweist.
  5. Die Zusammensetzung nach einem der vorherigen Ansprüche, wobei das Molverhältnis aller ersten Verbindungen zu allen zweiten Verbindungen im Bereich von 10:1 bis 1:10, vorzugsweise im Bereich von 7:1 bis 1:7, weiter bevorzugt im Bereich von 5:1 bis 1:5, noch weiter bevorzugt im Bereich von 4:1 bis 1:4, ganz besonders bevorzugt im Bereich von 3:1 bis 1:3, am meisten bevorzugt im Bereich von 2:1 bis 1:2 liegt.
  6. Die Zusammensetzung nach einem der vorherigen Ansprüche, wobei das Molverhältnis der Zinnionen zu den Silberionen im Bereich von 200:1 bis 5:1, vorzugsweise im Bereich von 150:1 bis 10:1, weiter bevorzugt im Bereich von 125:1 bis 12:1, ganz besonders bevorzugt im Bereich von 100:1 bis 15:1 liegt.
  7. Die Zusammensetzung nach einem der vorherigen Ansprüche, ferner umfassend
    (e) mindestens ein Anion einer organischen Säure, vorzugsweise ein Alkylsulfonsäure-Anion, ganz besonders bevorzugt Methansulfonsäure-Anionen.
  8. Die Zusammensetzung nach einem der vorherigen Ansprüche, ferner umfassend
    (f) mindestens ein Tensid, das vorzugsweise aus der Gruppe bestehend aus nichtionischen Tensiden, amphoteren Tensiden, kationischen Tensiden und anionischen Tensiden, vorzugsweise nichtionischen Tensiden und kationischen Tensiden, weiter bevorzugt alkoxylierten kationischen Tensiden und nichtionischen Polyethertensiden, noch weiter bevorzugt Alkylenoxid-Copolymeren und alkoxylierten Aminen, ganz besonders bevorzugt Ethylenoxid/Propylenoxid-Copolymeren und ethoxylierten Aminen, ausgewählt ist.
  9. Die Zusammensetzung nach einem der vorherigen Ansprüche, ferner umfassend
    (g) mindestens ein Antioxidans, das vorzugsweise aus der Gruppe bestehend aus Verbindungen mit einer hydroxylierten Ringeinheit ausgewählt ist und ganz besonders bevorzugt aus der Gruppe bestehend aus Catechol, Hydrochinon, Resorcin, Phenolsulfonsäuren, Ascorbinsäure und Naphtholsulfonsäuren ausgewählt ist.
  10. Die Zusammensetzung nach einem der vorherigen Ansprüche, wobei die Zusammensetzung keine Kupferionen umfasst, vorzugsweise keine Kupferionen und keine Bismutionen umfasst.
  11. Die Zusammensetzung nach einem der vorherigen Ansprüche, wobei das Gesamtgewicht der Zinnionen und der Silberionen 80 Gew.-% bis 100 Gew.-% aller Metallkationen aus Gruppe 3 bis Gruppe 15 in der wässrigen Zusammensetzung ausmacht, bezogen auf das Gesamtgewicht aller Metallkationen aus Gruppe 3 bis Gruppe 15 in der wässrigen Zusammensetzung, vorzugsweise mindestens 90 Gew.-%, weiter bevorzugt mindestens 95 Gew.-%, noch weiter bevorzugt mindestens 98 Gew.-%, ganz besonders bevorzugt mindestens 99 Gew.-%.
  12. Ein Verfahren zum elektrolytischen Abscheiden einer Zinn-Silber-Legierung auf einem Substrat, wobei das Verfahren die folgenden Schritte umfasst:
    (A)Bereitstellen des Substrats,
    (B)Bereitstellen einer wässrigen Zusammensetzung nach einem der Ansprüche 1 bis 11,
    (C)Inkontaktbringen des Substrats mit der wässrigen Zusammensetzung und Zuführen eines elektrischen Stroms derart, dass die Zinn-Silber-Legierung elektrolytisch auf dem Substrat abgeschieden wird.
  13. Das Verfahren nach Anspruch 12, wobei der Silbergehalt in der elektrolytisch abgeschiedenen Zinn-Silber-Legierung im Bereich von 0,1 Gew.-% bis 10 Gew.-%, bezogen auf das Gesamtgewicht der elektrolytisch abgeschiedenen Zinn-Silber-Legierung, liegt, vorzugsweise im Bereich von 0,5 Gew.-% bis 5 Gew.-% liegt, ganz besonders bevorzugt im Bereich von 1,5 Gew.-% bis 3,5 Gew.-% liegt.
  14. Das Verfahren nach Anspruch 12 oder 13, wobei das Substrat mehrere Metallmerkmale, vorzugsweise mehrere Metallsäulen und/oder Bereiche mit mindestens einer Metallschicht, weiter bevorzugt mehrere Kupfersäulen und/oder Bereiche mit mindestens einer Kupferschicht, umfasst.
  15. Verwendung einer wässrigen Zusammensetzung nach einem der Ansprüche 1 bis 11 zum elektrolytischen Abscheiden von Lötperlen aus Zinn-SilberLegierungen oder von Lötkappen aus Zinn-SilberLegierungen auf Metallsäulen, vorzugsweise zum elektrolytischen Abscheiden von Lötkappen aus Zinn-Silber-Legierungen auf Kupfersäulen.
EP18176788.0A 2018-06-08 2018-06-08 Wässrige zusammensetzung zur abscheidung einer zinn-silber-legierung und verfahren zur elektrolytischen abscheidung solch einer legierung Active EP3578693B1 (de)

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EP18176788.0A EP3578693B1 (de) 2018-06-08 2018-06-08 Wässrige zusammensetzung zur abscheidung einer zinn-silber-legierung und verfahren zur elektrolytischen abscheidung solch einer legierung
PCT/EP2019/064621 WO2019234088A1 (en) 2018-06-08 2019-06-05 Aqueous composition for depositing a tin silver alloy and method for electrolytically depositing such an alloy
TW108119427A TWI715991B (zh) 2018-06-08 2019-06-05 用於沉積錫銀合金之水性組合物及用以電解沉積該合金之方法

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JP3301707B2 (ja) 1997-01-20 2002-07-15 ディップソール株式会社 錫−銀合金酸性電気めっき浴
JP3433291B2 (ja) * 1999-09-27 2003-08-04 石原薬品株式会社 スズ−銅含有合金メッキ浴、スズ−銅含有合金メッキ方法及びスズ−銅含有合金メッキ皮膜が形成された物品
DE10158227A1 (de) 2001-11-15 2003-06-05 Siemens Ag Elektrolysebad zum galvanischen Abscheiden von Silber-Zinn-Legierungen
AU2003252677A1 (en) * 2002-07-25 2004-02-16 Shinryo Electronics Co., Ltd. Tin-silver-copper plating solution, plating film containing the same, and method for forming the plating film
JP4756887B2 (ja) 2005-03-22 2011-08-24 石原薬品株式会社 非シアン系のスズ−銀合金電気メッキ浴
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JP6088295B2 (ja) 2013-03-07 2017-03-01 ローム・アンド・ハース電子材料株式会社 スズ合金めっき液
JP6210148B2 (ja) * 2015-12-28 2017-10-11 三菱マテリアル株式会社 ＳｎＡｇ合金めっき液
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