WO2010004856A1 - Liquide fournissant un catalyseur pour placage au palladium - Google Patents

Liquide fournissant un catalyseur pour placage au palladium Download PDF

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WO2010004856A1
WO2010004856A1 PCT/JP2009/061277 JP2009061277W WO2010004856A1 WO 2010004856 A1 WO2010004856 A1 WO 2010004856A1 JP 2009061277 W JP2009061277 W JP 2009061277W WO 2010004856 A1 WO2010004856 A1 WO 2010004856A1
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Prior art keywords
catalyst
copper
palladium
based metal
gold
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PCT/JP2009/061277
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English (en)
Japanese (ja)
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茂樹 清水
隆治 高崎
歓三 清原
健児 吉羽
良典 小暮
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日本高純度化学株式会社
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Priority to JP2010519714A priority Critical patent/JP5567478B2/ja
Publication of WO2010004856A1 publication Critical patent/WO2010004856A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0716—Metallic plating catalysts, e.g. for direct electroplating of through holes; Sensitising or activating metallic plating catalysts
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/072—Electroless plating, e.g. finish plating or initial plating

Definitions

  • the present invention relates to a catalyst application liquid for electroless reduction palladium plating, and more particularly to a catalyst application liquid having a specific composition used when electroless reduction palladium plating is performed on a copper-based metal.
  • solder joints of electronic materials in which conductor circuits are formed of copper-based metals are exposed, the copper-based metal surfaces are oxidized by heat treatment before solder joints, resulting in poor solder joints. Therefore, a surface treatment in which a nickel film of about 5 ⁇ m is formed on a metal surface of a copper-based conductor circuit and a gold film of about 0.05 ⁇ m is further formed on the metal surface by electroless plating has been widely put into practical use.
  • a surface treatment is performed by sequentially forming a palladium film by electroless palladium plating on a copper-based conductor circuit and then a gold film by electroless gold plating on the palladium film without forming a nickel film.
  • Patent Documents 1 and 2 the films formed by these known surface treatment methods have a problem that voids are generated in the solder near the joint when solder balls are joined. If voids are present in the solder joint, the conductor area as an electrical contact is reduced, so that a sufficient function as an electrical joint terminal could not be achieved.
  • the present invention has been made in view of the above-described background art, and the problem is that when performing electroless reduction palladium plating directly on a copper-based metal, there is no fine wiring bridge, and there is no film thickness unevenness. Electroless reduced palladium that can form a film that does not generate voids in solder when it is soldered onto a plated film that has been electrolessly plated with gold after electroless reduced palladium plating. It is in providing the catalyst provision liquid for plating.
  • Japanese Patent No. 2649750 discloses a method of activating with a catalyst application liquid containing a palladium compound.
  • Japanese Patent Application Laid-Open No. 2003-082468 discloses a method of activation with a catalyst-providing solution containing at least one compound selected from gold, silver, palladium, ruthenium, rhodium, platinum, and copper compounds. ing.
  • a catalyst-providing solution containing at least one compound selected from gold, silver, palladium, ruthenium, rhodium, platinum, and copper compounds.
  • these examples are provided with a catalyst using a water-soluble palladium compound, and a commercially available catalyst application solution for electroless reduction plating generally contains a water-soluble palladium compound.
  • the present inventor has conducted extensive studies on a catalyst-providing liquid that activates only a copper-based metal. As a result, at least (a) a water-soluble gold compound and (b) a nitrogen atom are present.
  • the catalyst imparting solution containing two or more 5-membered heterocyclic compounds and (c) a chelating agent having an iminodiacetic acid structure is used, the resulting electroless reduced palladium-plated film.
  • the film thickness is uniform, and the generation of voids is remarkably suppressed when soldered onto a plating film that has been subjected to electroless gold plating following electroless reduced palladium plating. As a result, the present invention has been completed.
  • the present invention is a catalyst-providing liquid for performing electroless reduction palladium plating on a copper-based metal, comprising a water-soluble gold compound and a five-membered ring structure having two or more nitrogen atoms as constituent components.
  • the present invention provides a catalyst-providing liquid characterized by containing a heterocyclic compound having a chelating agent having an iminodiacetic acid structure.
  • the present invention provides a method for producing a palladium plating film on a copper-based metal, characterized in that electroless reduction palladium plating is performed on the copper-based metal using the above-described catalyst imparting solution, Further, the present invention provides a palladium plating film on a copper-based metal obtained by performing electroless reduction palladium plating on a copper-based metal using the above catalyst-providing liquid.
  • the present invention also provides a palladium plating film on a copper-based metal, characterized in that it has gold of 3 ⁇ 10 ⁇ 5 g / cm 2 or less on a copper-based metal and is formed thereon.
  • the copper is characterized in that it is formed by depositing gold of 3 ⁇ 10 ⁇ 5 g / cm 2 or less on a copper-based metal using the above-described catalyst-providing liquid.
  • the present invention provides a palladium plating film on a base metal.
  • the present invention provides a palladium / gold plating on a copper-based metal, characterized by performing electroless reduction palladium plating on a copper-based metal and subsequently performing electroless gold plating using the above-described catalyst-providing solution.
  • the present invention provides a method for producing a film, and is obtained by performing electroless reduction palladium plating on a copper-based metal, followed by electroless gold plating, using the above-described catalyst imparting solution.
  • a palladium / gold plating film on a copper-based metal is provided.
  • the expression “palladium / gold” means that a gold film exists on the palladium film
  • the expression “copper / palladium / gold” means that the palladium film exists on the copper-based metal. , which means that a gold film exists on it.
  • the above-mentioned problems can be solved and the above-mentioned problems can be solved, and a uniform electroless reduced palladium plating film having no film thickness unevenness can be obtained on a copper-based metal. Even in this case, an electroless reduced palladium plating film having no bridge and no precipitation can be formed. Moreover, when electroless gold plating is performed on the palladium film and solder ball bonding is performed, generation of voids in the solder can be suppressed.
  • mapping analysis photograph (150 times) which shows the criterion judged as "defect” by the evaluation method of the bridge
  • SEM photograph (2000 times) which shows the judgment standard judged with "the absence” by the evaluation method of generation of a void, and is a SEM photograph (2000 times) of Example 4.
  • SEM photograph (2000 times) which shows the judgment standard judged with "it is” by the evaluation method of generation of a void, and is a SEM photograph (2000 times) of comparative example 1.
  • the present invention relates to a catalyst applying liquid for performing electroless reduction palladium plating on a copper-based metal.
  • the “copper-based metal” is used for ordinary conductor circuit formation and is not particularly limited as long as it contains copper, and includes copper alone or a copper alloy. Moreover, there is no limitation in particular as metals other than copper in a copper alloy, if the said effect of this invention is acquired.
  • the “copper-based metal” is preferably copper alone or a copper alloy containing 60% by mass or more of copper, and particularly preferably copper alone or a copper alloy containing 80% by mass or more of copper.
  • “electroless reduced palladium plating” refers to a plating step in which palladium alone or palladium alloy containing palladium is deposited by various reducing agents.
  • the element other than palladium constituting the palladium alloy is not particularly limited, and examples thereof include phosphorus (P), boron (B), carbon (C), sulfur (S), lead (Pb), and bismuth (Bi). .
  • One or more elements other than palladium are used to form a palladium alloy together with palladium.
  • the palladium plating layer in the present invention is preferably “palladium alone or a palladium alloy” containing preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of palladium. It is preferable because the effect can be obtained more.
  • the catalyst-providing liquid of the present invention contains at least (a) a water-soluble gold compound, (b) a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms, and (c) an iminodiacetic acid structure. It is essential to contain a chelating agent.
  • the “water-soluble gold compound” in the present invention is particularly limited as long as it is a gold compound that is soluble in water so that the concentration in the catalyst-providing solution is suitable. Specific examples include gold cyanide, gold chloride, gold sulfite, gold thiosulfate, and the like. Preferred is a gold cyanide salt in view of the stability of the gold compound and the availability of chemicals, and particularly preferred is a first gold cyanide salt or a second gold cyanide salt.
  • the counter cation is not particularly limited, but an alkali metal salt is preferable as a catalyst-adding solution, and a potassium salt is particularly preferable.
  • the concentration of the “water-soluble gold compound” is not particularly limited, but is preferably 10 ppm or more and 2000 ppm or less, and particularly preferably 20 ppm or more and 1000 ppm or less, in terms of gold based on the total amount of the catalyst application liquid. If the concentration of the “water-soluble gold compound” is too high, the gold may precipitate in the catalyst-providing solution, resulting in instability as a catalyst-providing solution. If it is too small, the catalytic ability is incomplete. There is a case where non-deposition of electrolytic reduction palladium plating occurs.
  • the catalyst-providing liquid of the present invention does not substantially contain a water-soluble platinum group element compound.
  • the platinum group element include ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • voids may be generated in the solder when soldered as described above.
  • heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms includes elements other than carbon.
  • heterocycle having a 5-membered ring structure may be a heterocycle that is a condensed aromatic ring by condensing with an aromatic ring such as a benzene ring, a naphthalene ring, or another heterocycle.
  • the “other heterocycle” does not need to have two or more nitrogen atoms or a 5-membered ring.
  • heterocyclic ring of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms” there are no particular limitations on the heterocyclic ring of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms”.
  • imidazole ring, pyrazole ring, purine ring, 1,2,3-triazole ring, 1, Examples include 2,4-triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, benzimidazole ring, and benztriazole ring.
  • the substituent bonded to the heterocycle is not particularly limited, but an amino group, an alkyl group, an alkylamino group, and the like are preferable. Of these, amino groups are particularly preferred.
  • examples of the “heterocyclic compound having a 5-membered ring structure having two or more nitrogen atoms” include pyrazole, 3-aminopyrazole, 4-aminopyrazole, 5-aminopyrazole, imidazole, 2-aminoimidazole, 4 -Aminoimidazole, 5-aminoimidazole, purine, 2-aminopurine, 6-aminopurine, 1,2,3-triazole, 4-amino-1,2,3-triazole, 5-amino-1,2,3 -Triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, tetrazole, 5-aminotetrazole, 2-amino-1,3, 4-thiadiazole, 2-aminobenzimidazole, benztriazole or the like, or an alkyl-substituted product thereof is preferable And the like to. These are used alone or in combination.
  • imidazole 2-aminoimidazole, 4-aminoimidazole, 5-aminoimidazole, 1,2,4-triazole, 3-amino-1,2,4 are particularly preferable for obtaining the effects of the present invention.
  • -Triazole 5-aminotetrazole and the like.
  • the concentration of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms” is not particularly limited, but is preferably 10 ppm or more and 10,000 ppm or less, and particularly 50 ppm or more and 5000 ppm or less with respect to the entire catalyst-providing liquid. preferable. If the concentration is too high, precipitates may be generated. If the concentration is too low, voids may easily occur during solder ball bonding.
  • imino 2 capable of dissolving a copper-based metal constituting a copper-based conductor circuit or the like in a catalyst-providing solution. It preferably has an acetic acid structure.
  • a chelating agent having an iminodiacetic acid structure as an essential component, it is possible to promote uniform dissolution of the copper-based metal in the catalyst-providing liquid and to prevent the copper-based metal from reprecipitating, The application of catalyst nuclei can be performed uniformly and reliably, and the occurrence of bridging of the fine wiring due to metal adhesion to the insulator between the fine wirings can be prevented.
  • chelating agent having an iminodiacetic acid structure examples include, for example, ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and triethylenetetramine.
  • examples include 6-acetic acid, dicarboxymethyl glutamic acid, propanediamine tetraacetic acid, 1,3-diamino-2-hydroxylpropane tetraacetic acid, and the like, or water-soluble salts thereof.
  • water-soluble salt Sodium salt, potassium salt, ammonium salt, etc. are mentioned. These are used alone or in combination of two or more.
  • acetic acid units in that the action of stably dissolving the copper-based metal is strong.
  • water-soluble salts are mentioned.
  • the “chelating agent having an iminodiacetic acid structure” in the present invention is preferably used in the range of 1 g / L to 100 g / L, more preferably 2 g / L to 60 g / L with respect to the entire catalyst-providing liquid. Particularly preferred is 3 g / L to 40 g / L.
  • concentration of the chelating agent is too large, it may be precipitated in the catalyst-providing liquid, and when it is too small, the catalyst activation on the copper-based metal surface may be insufficient.
  • the catalyst-imparting solution of the present invention can contain a pH buffering agent and the like as appropriate, if necessary.
  • the pH buffer is not particularly limited as long as it can alleviate fluctuations in pH without adversely affecting the properties of the catalyst-providing liquid. Regardless of whether it is an organic substance or an inorganic substance, an acid or a salt thereof may be added as appropriate. Specific examples include inorganic acids such as boric acid, phosphoric acid, and pyrophosphoric acid; organic acids such as citric acid, acetic acid, malic acid, succinic acid, and tartaric acid; or salts thereof.
  • the catalyst-providing liquid of the present invention is preferably pH 3 or more and pH 9 or less, particularly preferably pH 4 or more and pH 8 or less.
  • a commercially available catalyst-providing solution for electroless reduction plating containing palladium is in the vicinity of pH 1, which is significantly different from the preferred pH range of the catalyst-providing solution of the present invention. If the pH is too low, gold may be deposited, which may result in instability as a catalyst-imparting solution, and if the pH is too high, catalyst activity may be reduced and electroless reduced palladium plating may not proceed easily.
  • the treatment temperature of the catalyst imparting solution of the present invention is preferably 10 ° C. or more and 95 ° C. or less, and particularly preferably 20 ° C. or more and 90 ° C. or less. Further, the treatment time of the catalyst applying liquid of the present invention is preferably from 5 seconds to 15 minutes, particularly preferably from 10 seconds to 10 minutes.
  • the amount of catalyst core metal supported in the catalyst application liquid of the present invention is 0.05 to 3 mg / dm 2 (0.05 ⁇ 10 ⁇ 5 to 3 ⁇ 10 ⁇ 5). g / cm 2 ), preferably 0.1 to 2 mg / dm 2 (0.1 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 5 g / cm 2 ). Within this range, the effects of the present invention described above are easily obtained. That is, one embodiment of the present invention is “a copper-based metal having 3 mg / dm 2 or less (3 ⁇ 10 ⁇ 5 g / cm 2 or less) of gold on a copper-based metal and formed thereon.
  • “Palladium plating film on metal” is preferable because it has the above-mentioned effect. “Palladium plating film on copper-based metal having 3 ⁇ 10 ⁇ 5 g / cm 2 or less of gold on the copper-based metal and formed thereon” There is the effect of the present invention as long as this configuration is satisfied.
  • gold plating in order to be able to confirm the color tone of the deposited metal visually, that is, to say “gold plating”, about 6 mg / dm 2 (6 ⁇ 10 ⁇ 5 g / cm 2 , thickness 30 nm)
  • gold plating about 6 mg / dm 2 (6 ⁇ 10 ⁇ 5 g / cm 2 , thickness 30 nm)
  • the amount of precipitation described above is necessary, and normal displacement gold plating is deposited on the order of 12 mg / dm 2 (12 ⁇ 10 ⁇ 5 g / cm 2 , thickness 60 nm) or more. That is, the catalyst-providing liquid of the present invention deposits a significantly smaller amount of gold on a copper-based metal compared to substitutional electroless gold plating.
  • the catalyst application liquid of the present invention selectively activates a copper-based metal such as a copper-based conductor circuit formed on a printed circuit board, for example. It is used to selectively form only on a copper-based metal such as a conductor circuit.
  • the “copper-based conductor circuit” is formed by forming a circuit with a copper-based metal on a base material that is an insulator such as glass epoxy, ceramic, or polyimide.
  • the method for forming a copper-based metal circuit is not particularly limited, and examples thereof include plating, vapor deposition, and lamination of a Cu plate.
  • the pretreatment step in the case of using the catalyst application liquid of the present invention is not particularly limited, and may be performed according to a pretreatment method before applying the catalyst application liquid, which is performed by normal electroless plating.
  • the electroless reduced palladium plating solution is not particularly limited and can be used. Examples thereof include those containing a water-soluble palladium compound, formic acid or a formic acid derivative, and a nitrogen-containing complexing agent. Other examples include water-soluble palladium compounds, amine compounds, organic compounds containing divalent sulfur, and compounds containing hypophosphorous acid compounds or borohydride compounds.
  • the palladium film formed using the catalyst-providing liquid of the present invention is preferably “palladium alone or a palladium alloy” containing 80% by mass or more of palladium, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. It is preferable for the effect of the present invention to be obtained more.
  • the film thickness of the palladium film is not particularly limited, but is preferably 0.03 ⁇ m to 1 ⁇ m, and particularly preferably 0.05 ⁇ m to 0.5 ⁇ m.
  • the plating conditions for electroless reduced palladium plating are not particularly limited and may be normal conditions.
  • the solder wettability after heat treatment may not be good.
  • electroless gold plating should be performed, and a gold plating film with good solder wettability should be applied. Forming on the outermost surface is preferable in that the effect of the present invention can be obtained more.
  • the thickness of the gold film is not particularly limited, but is preferably 0.03 ⁇ m to 0.3 ⁇ m, particularly preferably 0.05 ⁇ m to 0.1 ⁇ m.
  • the electroless gold plating conditions are not particularly limited and may be normal conditions.
  • Examples 1-6 Preparation of catalyst application liquid>
  • the water-soluble gold compound shown in Table 1 is 100 ppm in mass with respect to the entire catalyst-providing liquid in terms of metal gold, and (b) a hetero compound having a five-membered ring structure with two or more nitrogen atoms shown in Table 1.
  • the ring compound is 500 ppm by mass with respect to the entire catalyst-providing liquid
  • the chelating agent having (c) iminodiacetic acid structure shown in Table 1 is 20 g / L with respect to the entire catalyst-applying liquid. Dissolved.
  • each catalyst provision liquid was adjusted so that it might become pH 5.0.
  • a sodium hydroxide aqueous solution was used to raise the pH
  • hydrochloric acid was used to lower the pH.
  • Comparative Examples 1 and 2 As Comparative Example 1, a “catalyst-providing solution for electroless reduction nickel plating (KAT-450, manufactured by Uemura Kogyo Co., Ltd.)” containing commercially available palladium was used in a state of normal use. Further, as Comparative Example 2, a “catalyst imparting solution for electroless reduced nickel plating (ICP Axela, manufactured by Okuno Seiyaku Co., Ltd.)” containing commercially available palladium was used in a normal use state.
  • KAT-450 manufactured by Uemura Kogyo Co., Ltd.
  • ICP Axela manufactured by Okuno Seiyaku Co., Ltd.
  • Comparative Examples 3-20 The compound shown in the leftmost column of Table 1 is 100 ppm by mass with respect to the entire catalyst application liquid in terms of metal, and those specified to be contained in Table 1 include the heterocyclic compound shown in Table 1 in the entire catalyst application liquid.
  • the chelating agent shown in Table 1 was dissolved in pure water so as to be 20 g / L with respect to the entire catalyst application liquid.
  • each catalyst provision liquid was prepared by adjusting to pH shown in Table 1. For pH adjustment, an aqueous sodium hydroxide solution was used to raise the pH, and hydrochloric acid was used to lower the pH.
  • an evaluation substrate was prepared separately from the evaluation, and in addition to the above-described catalyst applying solution and electroless reduced palladium plating solution, a known electroless displacement gold plating solution (IM- GOLDPC (manufactured by Nippon High Purity Chemical Co., Ltd.) was used, and electroless reduced palladium and then electroless displacement gold plating were performed in the steps shown in Table 3. The evaluation method was evaluated.
  • IM- GOLDPC manufactured by Nippon High Purity Chemical Co., Ltd.
  • Evaluation board 1 An evaluation substrate having the configuration shown in FIGS. 1 and 2 was produced. Circular copper pads with a diameter of 0.76 mm are arranged in a grid pattern on a polyimide resin substrate 40 mm long x 40 mm wide x 1.0 mm thick, and each copper pad is surrounded by a photo solder resist. The one coated with is used. Each copper pad is formed of copper having a thickness of 12 ⁇ m, the thickness of the photo solder resist is 20 ⁇ m, and the diameter of the opening of the solder ball pad is 0.62 mm.
  • Evaluation board 2 The evaluation board
  • the film thickness of the electroless reduced palladium film formed on the copper of the solder ball pad of the evaluation board 1 was measured at 10 points using a fluorescent X-ray film thickness meter (SEA5120, manufactured by Seiko Instruments Inc.), and the average film
  • the deposition uniformity of electroless reduced palladium plating was evaluated by comparing the thickness, maximum film thickness, and minimum film thickness. A sample having a very small minimum film thickness was evaluated as “precipitation unevenness”. All the measured values were 0.00 ⁇ m and evaluated as “no precipitation”. The results are shown in Table 4.
  • the copper wiring of the evaluation board 2 is scanned with a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.) (hereinafter abbreviated as “SEM”) and an energy dispersive X-ray analyzer (EMAX EX-220, manufactured by HORIBA).
  • SEM scanning electron microscope
  • EMAX EX-220 an energy dispersive X-ray analyzer
  • the evaluation substrate 1 to which the solder balls are fused is cut into a size of about 15 mm ⁇ 15 mm so that the operation is easy, and is placed in a mold for cold embedding resin. (No. 105, manufactured by Marumoto Struers) and its curing agent were poured and cured. The cured sample was polished using a SiC polishing paper and a polishing machine, and the cross section was exposed so that the cross section of the joint between the solder ball and the ball pad could be seen.
  • a water-soluble gold compound of the present invention (b) a heterocyclic compound in which the nitrogen atom has two or more five-membered ring structures, and (c) an iminodiacetic acid structure.
  • the catalyst application liquid containing a chelating agent as an essential component has sufficient catalytic action for electroless reduction palladium plating on a copper-based conductor circuit, and does not have a fine wiring bridge and forms a uniform palladium plating film. Furthermore, it was found that the film formed by electroless gold plating after electroless reduced palladium plating was free of voids in the solder when solder balls were bonded onto the film. (Examples 1 to 6).
  • Comparative Examples 1 to 10 which do not contain a water-soluble gold compound
  • Comparative Examples 1 to 5 having a low pH of 1.0 have no fine wiring bridge and form a uniform palladium plating film. Although it was possible, extremely large voids were generated during soldering. In Comparative Examples 6 to 10 having a pH of 5.0 close to the neutral pH range, the catalyst could not be activated uniformly, and deposition unevenness of the palladium plating film occurred.
  • the catalyst-providing liquid for electroless reduced palladium plating of the present invention can provide an electroless reduced palladium plated film having no film thickness unevenness and no bridge on a copper-based metal, and solder ball bonding Since generation of voids at the time can also be suppressed, it is widely used in all fields where solder joints of copper-based conductor circuits are used.

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Abstract

L'invention porte sur un liquide fournissant un catalyseur. Lorsqu'un placage au palladium à réduction non électrolytique est effectué directement sur un matériau de circuit conducteur à base de cuivre, le liquide fournissant un catalyseur permet de déposer un film de revêtement régulier exempt d'irrégularité d'épaisseur sans ponter de fines lignes de câblage. Lorsque le placage au palladium à réduction non électrolytique est suivi par un placage à l'or non électrolytique, puis par une soudure au dépôt résultant, un film de revêtement ne comportant pas de vide peut être formé. Le liquide fournissant un catalyseur est utilisé pour effectuer un placage au palladium à réduction non électrolytique sur un métal à base de cuivre. Le liquide fournissant un catalyseur est caractérisé en ce qu'il contient, comme ingrédients constitutifs, un composé d'or soluble dans l'eau, un composé hétérocyclique ayant une structure cyclique à cinq chaînons comprenant deux ou plusieurs atomes d'azote, et un agent chélatant ayant une structure d'acide iminodiacétique. L'invention porte également sur un procédé pour produire un dépôt de palladium sur un métal à base de cuivre, caractérisé par l'utilisation de liquide fournissant un catalyseur pour effectuer un placage au palladium à réduction non électrolytique sur le métal à base de cuivre ; et sur un dépôt de palladium produit sur un métal à base de cuivre par le procédé.
PCT/JP2009/061277 2008-07-08 2009-06-22 Liquide fournissant un catalyseur pour placage au palladium WO2010004856A1 (fr)

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US9968353B2 (en) 2001-06-04 2018-05-15 Medtronic Vascular, Inc. Catheter based fastener implantation apparatus and methods
US9320503B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Devices, system, and methods for guiding an operative tool into an interior body region
US10098770B2 (en) 2001-11-28 2018-10-16 Medtronic Vascular, Inc. Endovascular aneurysm devices, systems, and methods
US9808250B2 (en) 2001-11-28 2017-11-07 Medtronic Vascular, Inc. Systems and methods for attaching a prosthesis within a body lumen or hollow organ
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US10595867B2 (en) 2001-11-28 2020-03-24 Medtronic Vascular, Inc. Systems and methods for attaching a prosthesis within a body lumen or hollow organ
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US10299791B2 (en) 2001-11-28 2019-05-28 Medtronic Vascular, Inc. Endovascular aneurysm repair system
US9320589B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Endovascular aneurysm repair system
US9320591B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Devices, systems, and methods for prosthesis delivery and implantation, including the use of a fastener tool
US8231639B2 (en) 2001-11-28 2012-07-31 Aptus Endosystems, Inc. Systems and methods for attaching a prosthesis within a body lumen or hollow organ
US10194905B2 (en) 2001-11-28 2019-02-05 Medtronic Vascular, Inc. Devices, systems, and methods for endovascular staple and/or prosthesis delivery and implantation
US8591636B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method
US20140083860A1 (en) * 2010-12-14 2014-03-27 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US8591637B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US9234282B2 (en) * 2010-12-14 2016-01-12 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US8961669B2 (en) * 2010-12-14 2015-02-24 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US20140087062A1 (en) * 2010-12-14 2014-03-27 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US10444996B2 (en) 2011-09-28 2019-10-15 International Business Machines Corporation Automated selection of functions to reduce storage capacity based on performance requirements
US10444995B2 (en) 2011-09-28 2019-10-15 International Business Machines Corporation Automated selection of functions to reduce storage capacity based on performance requirements
JP2013108180A (ja) * 2011-11-22 2013-06-06 Samsung Electro-Mechanics Co Ltd 基板及びその製造方法
US10941493B2 (en) 2016-06-13 2021-03-09 C. Uyemura & Co., Ltd. Film formation method
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CN109563624A (zh) * 2016-10-05 2019-04-02 小岛化学药品株式会社 无电解镀钯金工艺
JP2018059154A (ja) * 2016-10-05 2018-04-12 小島化学薬品株式会社 無電解パラジウム／金めっきプロセス

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KR101639084B1 (ko) 2016-07-12
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TW201009114A (en) 2010-03-01
JPWO2010004856A1 (ja) 2011-12-22
KR20110028312A (ko) 2011-03-17

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