EP3839092A1 - Verfahren zur aktivierung von mindestens einer oberfläche, aktivierungszusammensetzung und verwendung der aktivierungszusammensetzung zur aktivierung einer oberfläche zur stromlosen plattierung - Google Patents

Verfahren zur aktivierung von mindestens einer oberfläche, aktivierungszusammensetzung und verwendung der aktivierungszusammensetzung zur aktivierung einer oberfläche zur stromlosen plattierung Download PDF

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Publication number
EP3839092A1
EP3839092A1 EP19219076.7A EP19219076A EP3839092A1 EP 3839092 A1 EP3839092 A1 EP 3839092A1 EP 19219076 A EP19219076 A EP 19219076A EP 3839092 A1 EP3839092 A1 EP 3839092A1
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EP
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Prior art keywords
substituted
unsubstituted
group
substrate
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP19219076.7A
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English (en)
French (fr)
Inventor
Sebastian ZARWELL
Bexy Dosse
Michael MERSCHKY
Lutz Stamp
Regina Czezcka
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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 EP19219076.7A priority Critical patent/EP3839092A1/de
Publication of EP3839092A1 publication Critical patent/EP3839092A1/de
Pending legal-status Critical Current

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    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1889—Multistep pretreatment with use of metal first
    • 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
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
    • C23C18/206—Use of metal other than noble metals and tin, e.g. activation, sensitisation with 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/208—Multistep pretreatment with use of metal first
    • 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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
    • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
    • C23C18/2073—Multistep pretreatment
    • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first

Definitions

  • the present invention concerns a method for activating at least one surface of a substrate.
  • the present invention is directed at an activation composition for activating at least one surface of a substrate.
  • the present invention relates to a use of an activation composition for activating at least one surface of a substrate for subsequent electroless plating.
  • Electroless plating is the controlled autocatalytic deposition of a continuous film of metal without the assistance of an external supply of electrons. Contrary to that, electrolytic plating requires such an external supply of electrons.
  • the surfaces to be plated require a certain catalytic activity to allow a uniform and homogeneous metal deposition thereon. While metallic surfaces in many cases are catalytic enough for electroless plating, non-metallic surfaces are traditionally treated with palladium to make them receptive or catalytically active for subsequent metal deposition. This treatment is referred to as activation.
  • Palladium is however very expensive and only available in limited quantities. Electrical shorts are another issue known from palladium-based activation methods. These shorts are often caused by involuntary dissolution and re-deposition of palladium during subsequent steps such as during electroless plating. These shorts are highly undesired as they result in scrap production as the entire good becomes dysfunctional.
  • steps b) and c) In addition to steps b) and c), further steps are optionally included in between the named steps.
  • a method of the present invention is preferred, wherein the at least one surface obtained after step d) is contacted with the conditioning composition, preferably prior to step e). In some cases it is preferred that this is the only contacting with the conditioning composition. In other cases it is preferred that the contacting with the conditioning composition is carried out prior to step d) and after step d) (preferably prior to step e)).
  • no palladium ions or silver ions are required for the purpose of activating the at least one surface of the substrate.
  • a significant cost advantage can be achieved.
  • the activation composition is substantially free of, preferably does not comprise, palladium ions and/or palladium compounds.
  • the surface obtained after step e) provides an improved stability. This means that contacting the activated surface obtained after step e) with a subsequently used bath for metal or metal alloy plating, in particular for electroless copper plating, does not significantly contaminates the subsequently used plating bath. This in turn enhances the lifetime of subsequently used plating baths.
  • Activating a surface of a substrate means in the context of the present invention that said surface is rendered suitable, i.e. is being receptive, in particular for electroless metal or metal alloy deposition. Without limitation, the inventors believe that the method of the present invention results in a catalytically active surface ready for subsequent electroless plating.
  • the "copper coverage” is a possibility of assessing the effectiveness of a method for activating. After activation, an electroless metal plating step is performed on the activated surface and the surface coverage with the deposited metal/metal alloy layer is measured and compared to other activated surfaces with a deposited metal/metal layer thereon.
  • alkyl group comprises branched or unbranched alkyl groups, each comprising cyclic and/or non-cyclic structural elements, wherein cyclic structural elements of the alkyl groups naturally require at least three carbon atoms.
  • C1-CX-alkyl group denotes alkyl groups having 1 to X carbon atoms (X being an integer).
  • C1-C8-alkyl group for example includes, among others, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, and n-octyl.
  • Substituted alkyl groups are typically obtained by replacing at least one hydrogen by a substituent.
  • X is preferably 12, more preferably 10, even more preferably 8, most preferably 6, if not stated otherwise.
  • a substituted or unsubstituted alkyl group is preferably selected from a substituted or unsubstituted C1-C8-alkyl group, more preferably from a substituted or unsubstituted C1-C4-alkyl group.
  • Such alkyl groups typically have an increased water-solubility.
  • above described groups are substituted with one or more than one substituent or unsubstituted.
  • the substituents are independently selected from the group consisting of hydroxy group (-OH) and carboxyl group (-CO 2 H) including its salts. Such substituents typically significantly increase water-solubility.
  • each of the groups is selected independently from each other unless stated otherwise hereinafter, meaning they can be selected to be the same members or different members of said group.
  • said surface is contacted with the respective composition, preferably by entirely or at least partially immersing said surface into the respective composition.
  • said surface is sprayed or wiped.
  • the substrate having the at least one surface is provided.
  • the at least one surface is preferably a non-conductive surface.
  • the beneficial effects of the present invention are particularly pronounced when using such a surface.
  • Preferred is a method of the present invention characterized in that the at least one surface is or comprises a non-metallic surface, preferably is or comprises an organic polymer and/or an oxide.
  • a preferred oxide is silica (i.e. silicon dioxide).
  • a preferred organic polymer is selected from the group consisting of plastic and silicones.
  • Preferred silicones are polysiloxanes.
  • said substrate is or comprises a material selected from the group consisting of glass, plastic, silicon, ceramic, and combinations of the aforementioned.
  • Glass preferably comprises one or more of silica glass (i.e. comprising amorphous silicon dioxide), soda-lime glass, float glass, fluoride glass (also referred to as fluorinated glass), aluminosilicates, phosphate glass, borate glass, quartz glass, borosilicate glass, chalcogenide glass, and aluminum oxide.
  • silica glass i.e. comprising amorphous silicon dioxide
  • soda-lime glass float glass
  • fluoride glass also referred to as fluorinated glass
  • aluminosilicates phosphate glass, borate glass, quartz glass, borosilicate glass, chalcogenide glass, and aluminum oxide.
  • Plastic preferably comprises one or more of epoxy-based resins, acrylonitrile-butadiene-styrene copolymer (ABS copolymer), polyamide (PA), polycarbonate (PC), polyimide (PI), polyethylene terephthalate (PET), liquid-crystal polymers (LCPs), and cyclic olefin copolymer (COC). More preferably, plastic comprises one or more of epoxy-based resins, polyimide (PI), liquid-crystal polymers (LCPs), cyclic olefin copolymer (COC), and polyethylene terephthalate (PET).
  • ABS copolymer acrylonitrile-butadiene-styrene copolymer
  • PA polyamide
  • PC polycarbonate
  • PI polyimide
  • PET polyethylene terephthalate
  • LCPs liquid-crystal polymers
  • COC cyclic olefin copolymer
  • plastic comprises one or more of epoxy-
  • a preferred epoxy-based resin is FR4.
  • Silicon preferably comprises one or more of polysilicon (preferably comprising doped polysilicon, most preferably comprising one or more of p-doped polysilicon and n-doped polysilicon), monocrystalline silicon, silica, silicon nitride, and silicon oxynitride.
  • polysilicon preferably comprising doped polysilicon, most preferably comprising one or more of p-doped polysilicon and n-doped polysilicon
  • monocrystalline silicon silica, silicon nitride, and silicon oxynitride.
  • Ceramics preferably comprise one or more of oxide-based ceramics, non-oxide based ceramics, and mixed oxide/non-oxide ceramics.
  • Preferred oxide-based ceramics comprise one or more of aluminum oxide, beryllium oxide, magnesium oxide, cerium oxides, yttrium oxides, titanium oxide, zirconium oxide, aluminum titanium oxide, and barium titanium oxide.
  • Preferred non-oxide based ceramics comprise one or more carbide (preferably silicon carbide), boride, nitride (preferably boron nitride and aluminum nitride), and silicides.
  • Preferred mixed oxide/non-oxide ceramics comprise one or more of silicon oxide nitride and silicon aluminum oxide nitride.
  • the substrate is selected from the group consisting of printed circuit boards, printed circuit foils, interposers, chip carriers, IC substrates, semiconductor wafers, circuit carriers, interconnect devices, copper clad laminates, and build-up films.
  • step b) of the method of the present invention the at least one surface of the substrate is pretreated with a pretreating composition.
  • the pretreating composition is aqueous.
  • more than one pretreating composition is applied (i.e. pretreating the at least one surface of the substrate with one or more than one pretreating composition) each having a different purpose (e.g. desmearing, cleaning, etching, reducing).
  • Step b) is preferably carried out between steps a) and d) and is herein referred to as "pretreatment step".
  • the one or more than one pretreating composition is individually acidic or alkaline.
  • the one or more than one pretreating composition individually comprises one or more of an oxidizing agent, a surfactant, a reducing agent.
  • a preferred oxidizing agent is hydrogen peroxide.
  • a preferred reducing agent is NaBH 4 .
  • a method of the present invention is preferred, wherein between all method steps of the method of the present invention a pretreatment step is carried out.
  • the at least one surface of the substrate is conditioned with a conditioning composition.
  • the conditioning composition is an aqueous conditioning composition .
  • Step c) is preferably included in the method of the present invention after step a) and before step d). If optional step b) is also included, it is preferred to carry out optional step c) after step b). Step c) advantageously results in an improved metal or metal alloy coverage. Step c) is herein referred to as "conditioning step”.
  • the conditioning composition comprises one or more of a nitrogen containing polymer, preferably a nitrogen containing polymer having a high positive surface charge.
  • a preferred nitrogen containing polymer is selected from polyquaterniums.
  • the nitrogen containing polymer is different from the at least one unsubstituted or substituted N-heteroaromatic compound utilized in the activation composition.
  • the nitrogen containing polymer is selected from a group consisting of polyethylenimines and nitrogen containing polymers comprising one or more cationic building block.
  • Preferred polymers comprising one or more cationic building block are selected from the group consisting of nitrogen containing polymers comprising one or more quaternized amines, preferably selected from the group consisting of polyimidazole, polydial-lyldimethylammonium, and polyepichlorhydrin-dimethylamine and mixtures of the aforementioned.
  • the one or more cationic building block increases the positive surface charge of the respective polymers.
  • Preferred is a nitrogen containing polymer having a MW of 1000 g/mol or more, preferably determined by gel permeation chromatography (GPC).
  • the nitrogen containing polymer has a total concentration in a range from 0.01 wt.-% to 15 wt.-%, based on the total weight of the conditioning composition, more preferably from 0.1 wt.- % to 5 wt.-%, and even more preferably from 0.3 wt.-% to 2 wt.-%.
  • step c) is carried out at a temperature ranging from 25°C to 80°C, more preferably from 40°C to 75°C, and even more preferably from 45°C to 70 °C.
  • step c) is carried out for a time period ranging from 10 sec to 15 min, preferably from 30 sec to 10 min, and more preferably from 1 min to 5 min.
  • the pH of the conditioning composition is alkaline, preferably being in a range from 7.5 to 12, more preferably from 8 to 11, and even more preferably from 8.5 to 10.
  • step d) of the method of the present invention the at least one surface of the substrate is contacted with an activation composition (i.e. the activation composition of the present invention).
  • activation step This step is herein referred to as "activation step”.
  • the activation composition has a temperature in a range from 25°C to 70 °C, more preferably from 35°C to 60 °C, and even more preferably from 40°C to 60 °C.
  • step d) is carried out for a time period ranging from 30 sec to 25 min, preferably from 1 min to 15 min, and more preferably from 2 min to 10 min. Typically, shorter time periods were found not to be sufficient for activation, while longer time periods did not improve further the activation.
  • the activation composition comprises copper ions, preferably by utilizing at least one water-soluble copper salt or copper complex.
  • Preferred water-soluble copper salts and copper complexes are selected from the group consisting of copper sulfate, copper alkyl sulfonates (preferably copper methane sulfonate), copper aryl sulfonates (preferably copper p -toluene sulfonate and copper phenyl sulfonate), copper halides (preferably copper chloride), copper carboxylates (preferably copper acetate and copper citrate), copper fluoroborate, copper oxide, copper carbonate, hydrates and mixtures of the aforementioned. More preferably the water-soluble copper salts and copper complexes are selected from the group consisting of copper acetate, copper sulfate, copper alkyl sulfonates (preferably as defined above), and mixtures of the aforementioned.
  • the copper ions have a concentration ranging from 0.1 g/L to 30 g/L, more preferably from 0.5 g/L to 10 g/L, and even more preferably from 2 g/L to 7 g/L.
  • the activation composition comprises at least one unsubstituted or substituted N-heteroaromatic compound.
  • N-heteroaromatic compound denotes a compound comprising at least one aromatic ring with at least one ring nitrogen atom (i.e. at least one ring carbon atom is substituted with a nitrogen atom).
  • Preferred is a method of the present invention characterized in that the at least one unsubstituted or substituted N-heteroaromatic compound is a monocyclic compound.
  • the at least one unsubstituted or substituted N-heteroaromatic compound is selected from the group consisting of unsubstituted five-membered N-heteroaromatic compounds, substituted five-membered N-heteroaromatic compounds, unsubstituted six-membered N-heteroaromatic compounds, and substituted six-membered N-heteroaromatic compounds.
  • the at least one unsubstituted or substituted N-heteroaromatic compound is selected from the group consisting of unsubstituted and substituted pyrroles, unsubstituted and substituted pyrazoles, unsubstituted and substituted imidazoles, unsubstituted and substituted 1,2,3-triazoles, unsubstituted and substituted 1,2,4-triazoles, unsubstituted and substituted tetrazoles, unsubstituted and substituted oxazoles, unsubstituted and substituted isoxazoles, unsubstituted and substituted isothiazoles, unsubstituted and substituted thiazoles, unsubstituted and substituted 1,2,3-oxadiazoles, unsubstituted and substituted 1,2,5-oxadiazoles, unsubstituted and substituted 1,3,4-thiadiazoles
  • the at least one unsubstituted or substituted N-heteroaromatic compound is selected from the group consisting of unsubstituted and substituted pyrroles, unsubstituted and substituted pyrazoles, unsubstituted and substituted imidazoles, unsubstituted and substituted oxazoles, unsubstituted and substituted isoxazoles, unsubstituted and substituted isothiazoles, unsubstituted and substituted thiazoles, unsubstituted and substituted pyridines, unsubstituted and substituted pyridazines, unsubstituted and substituted pyrimidines, and unsubstituted and substituted pyrazines.
  • Preferred is a method of the present invention characterized in that the at least one unsubstituted or substituted N-heteroaromatic compound is represented by the following formula (A): wherein
  • X is selected as defined above in view of the bonding requirements present in the at least one unsubstituted or substituted N-heteroaromatic compound. If the sum of b and c is 4, preferably, X is not - N(R 1 )-. Thus, if the sum of b and c is 4, X is preferably selected from the group consisting of -N-, - O-, -S-, and -C(R 1 )-.
  • X is not -N-.
  • X is preferably selected from the group consisting of -N(R 1 )-, -O-, -S-, and -C(R 1 )-.
  • X may be bonded by single and/or double bonds depending on the necessities to fulfill the underlying Hückel requirement.
  • R is other than hydrogen.
  • the R being other than hydrogen is bonded to a carbon atom adjacent to the nitrogen atom in the N-heteroaromatic compound (i.e. adjacent to the N-atom in the ring).
  • each R is independently selected from the group consisting of hydrogen, unsubstituted and substituted alkyl group, hydroxy group, amino group, carboxyl group, oxycarbonyl group, and carbamoyl group, more preferably substituted alkyl group and carbamoyl group.
  • a preferred substituted alkyl group independently comprises an alkyl group substituted with one or more than one hydroxy group, an alkyl group substituted with one or more than one amino group, and/or an alkyl group substituted with one or more than one carboxyl group.
  • the unsubstituted and substituted amidoxime group is represented as: , wherein R A1 and R A2 are independently selected from the group consisting of hydrogen and alkyl group.
  • a substituted amidoxime group preferably comprises at least one of R A1 and R A2 not being hydrogen.
  • an unsubstituted amidoxime group preferably comprises R A1 and R A2 being hydrogen.
  • the unsubstituted or substituted N-heteroaromatic compound is a six-membered unsubstituted or substituted N-heteroaromatic compound.
  • the substituted N-heteroaromatic compound comprises at least a compound represented by the following formula (E): wherein
  • R E1 and R E2 are independently selected from the group consisting of hydrogen, alkyl group substituted with one or more (preferably one) hydroxy group, carboxyl group, and carbamoyl group (preferably as defined throughout the text).
  • a preferred alkyl group substituted with one or more hydroxy group is a methylol group (-CH 2 OH) and an ethylol group (-CH 2 -CH 2 OH).
  • the substituted N-heteroaromatic compound represented by formula (E) was found to be particularly effective (even compared to the compound represented by formula (L); see text below) in the method of the present invention, in particular by enhancing the copper coverage (see also examples below).
  • a method of the present invention is preferred, wherein the sum of b and c is 3.
  • a substituted five-membered N-heteroaromatic compound is very preferred.
  • a method of the present invention characterized in that the substituted N-heteroaromatic compound comprises at least a compound represented by the following formula (L): wherein R L is an alkyl group independently substituted with one or more than one substituent selected from the group consisting of amino group and carboxyl group.
  • R L is a C1-C4-alkyl group independently substituted with one or more than one substituent selected from the group consisting of amino group and carboxyl group.
  • the substituted N-heteroaromatic compound comprises one or more than one compound selected from the group consisting of pyridinedimethanol, picolinamide, picolinic acid, nicotinic acid, nicotineamide, histidine, and salts of the aforementioned, preferably selected from the group consisting of 2,6-pyridinedimethanol, 2-picolinamide, 2-picolinic acid, nicotinic acid, nicotineamide, histidine, and salts of the aforementioned, most preferably selected from the group consisting of 2,6-pyridinedimethanol, 2-picolinamide, 2-picolinic acid, and salts of the aforementioned.
  • Preferred salts are alkaline salts, earth alkaline salts, and ammonium salts.
  • the activation composition comprise further compounds.
  • the activation composition comprises iii) at least one enhancer compound different from ii) selected from the group consisting of sulfuric acid, sulfonic acids, carboxylic acids, polyols, salts and mixtures thereof.
  • Preferred salts are alkaline salts, earth alkaline salts, and ammonium salts.
  • the activation composition utilized in the method of the present invention provides an acceptable stability, stability is preferably further increased by utilizing said at least one enhancer compound.
  • sulfuric acid is added as a respective salt, i.e. as a sulfate salt.
  • Preferred salts comprise alkaline sulfates, earth alkaline sulfates, and sulfates of main group III metals of the period table of the elements (preferably aluminum sulfate).
  • Preferred sulfonic acids are selected from the group consisting of alkylsulfonic acids (preferably methanesulfonic acid and ethanesulfonic acid) and arylsulfonic acids (preferably phenylsulfonic acid, p -toluenesulfonic acid, and 5-sulfosalicylic acid (also known as 2-hydroxy-5-sulfobenzoic acid)).
  • alkylsulfonic acids preferably methanesulfonic acid and ethanesulfonic acid
  • arylsulfonic acids preferably phenylsulfonic acid, p -toluenesulfonic acid, and 5-sulfosalicylic acid (also known as 2-hydroxy-5-sulfobenzoic acid)
  • Very preferred sulfonic acids are arylsulfonic acid.
  • Preferred carboxylic acids are selected from the group consisting of aliphatic hydroxycarboxylic acids (preferably citric acid, tartaric acid, and malic acid), aliphatic aminocarboxylic acids (preferably glycine and alanine), and unsubstituted aliphatic carboxylic acids (preferably acetic acid and malonic acid).
  • Preferred carboxylic acids are aliphatic hydroxycarboxylic acids.
  • Preferred polyols are selected from the group consisting of glycols, sugar alcohols, and polyvinyl alcohols.
  • the polyols are aliphatic, even more preferably non-cyclic.
  • the polyols are preferably selected from the group consisting of C2-C10-polyols, more preferably from C2-C6-polyols.
  • Very preferred polyols are selected from the group consisting of ethane-1,2-diol (ethylene glycol), propane-1,2-diol (propylene glycol), propane-1,2,3-triol (glycerol) and (2 S ,3 R ,4 R ,5 R )-hexane-1,2,3,4,5,6-hexol (sorbitol).
  • the at least one enhancer compound different from ii) is selected from the group consisting of sulfuric acid, sulfonic acids, polyols, salts and mixtures thereof; even more preferably sulfonic acids and salts thereof, and yet even more preferably the at least one enhancer compound different from ii) is an arylsulfonic acid or a salt thereof, most preferably is sulfosalicylic acid or a salt thereof.
  • the at least one enhancer compound different from ii) (in its total concentration) and the copper ions are preferably present in a molar ratio ranging from 0.05:1 to 5:1, more preferably from 0.2:1 to 2:1, and even more preferably from 0.5:1 to 1.5:1.
  • the at least one enhancer compound does not only improves the stability of the activation composition but furthermore allows for improved metal or metal alloy coverage and furthermore synergistically works together with the at least one unsubstituted or substituted N-heteroaromatic compound (see examples below).
  • the enhancer compound alone i.e. without the at least one unsubstituted or substituted N-heteroaromatic compound does not allow for the benefits of the present invention to be obtained (see examples below).
  • Substantially free of preferably means a concentration of 50 mg/L or less, more preferably of 10 mg/L or less, even more preferably 1 mg/L or less.
  • the activation composition is a clear solution (i.e. without particles).
  • the pH of the activation composition is not particularly limited and is preferably adapted in such a way that the substrate having the at least one surface is not damaged in step d) of the method of the present invention.
  • Preferred is a method of the present invention, wherein the pH is at least 7, preferably the pH ranges from 8 to 14, more preferably from 8.5 to 12, and even more preferably from 9 to 10.
  • Said pH values are well suited for activating basically most of the substrates preferably used in electronics industry.
  • the method of the present invention comprises further between step d) and step e), step d1) rinsing the at least one surface of the substrate obtained after step d) with an alkaline aqueous rinsing composition.
  • Step d1) is herein referred to as "alkaline rinsing step".
  • the alkaline aqueous rinsing composition has a pH of 8 or more, preferably is in a range from 9 to 14, even more preferably from 10 to 13.5, and yet even more preferably from 11 to 13.
  • the pH is adjusted with one or more than one hydroxide, preferably one or more of NaOH, KOH, ammonia, and hydroxylamine.
  • Step d1) which is preferably optional, typically reduces the risk of drag-in of copper ions from the activation composition into a subsequently used compositions.
  • Such copper ions may for example reduce the lifetime of a subsequently used compositions such as of a reducing agent containing composition used in step e).
  • step e) of the method of the present invention the at least one surface of the substrate obtained after step d) (or preferably obtained after step d1)) is contacted with a reducing agent containing composition in order to chemically reduce the copper ions to metallic copper.
  • the reducing agent containing composition is an aqueous reducing agent containing composition, most preferably without particles.
  • Step e) By carrying out step e), the at least one surface of the substrate is finally activated.
  • Step e) is herein referred to as "reducing step".
  • the reducing agent containing composition preferably comprises at least one reducing agent.
  • the at least one reducing agent is selected from the group consisting of hypophosphoric acid, formaldehyde, paraformaldehyde, glyoxylic acid, sources of glyoxylic acid (preferably dihalo-acetic acid, dichloroacetic acid (which liberates glyoxylic acid in aqueous media)), amino boranes (preferably dimethylamino borane), borohydrides (preferably alkaline borohydrides, more preferably NaBH 4 and KBH 4 ), hydrazine, polysaccharides, sugars (preferably glucose), glycolic acid, formic acid, and salts and mixtures thereof.
  • Preferred salts are ammonium, alkaline and earth alkaline salts.
  • the at least one reducing agent is selected from the group consisting of boranes, preferably dimethylamino borane and borohydrides, preferably alkali borohydrides. Even more preferably, the at least one reducing agent is at least one borohydride, most preferably selected from the group consisting of sodium borohydride and potassium borohydride. The latter have been found to be particularly effective in the context of the present invention.
  • the at least one reducing agent has a total concentration ranging from 0.05 g/L to 20 g/L, based on the total volume of the reducing agent containing composition, preferably from 0.1 g/L to 15 g/L, and more preferably from 0.3 g/L to 15 g/L.
  • concentration of the at least one reducing agent preferably depends on the reducing strength of the particular reducing agent. While strong reducing agents such as sodium borohydride may be used in basically lower concentrations, weaker reducing agents such as dimethylamino borane are typically used in comparatively higher concentrations. The person skilled in the art can determine useful concentrations for that purpose by routine experiments.
  • step e) the reducing agent containing composition has a temperature in a range from 20°C to 60°C, more preferably from 30°C to 50 °C.
  • step e) is carried out for a time period ranging from 10 sec to 30 min, more preferably from 20 sec to 15 min.
  • step e the at least one surface of the substrate is activated.
  • the method of the present invention comprises further after step e), step f) contacting the at least one surface of the substrate obtained after step e) with an oxidation preventing rinsing composition.
  • Step f) is optional, but additionally improves the metal or metal alloy coverage.
  • Optional step f) is herein referred to as "anti-oxidative treatment step".
  • the oxidation preventing rinsing composition is preferably aqueous, most preferably an aqueous solution.
  • the oxidation preventing rinsing composition preferably comprises at least one anti-oxidative compounds, preferably selected from the group consisting of ascorbic acid, thiosulfate, hydrazine, hy-drazinecarbonat, carbohydrazide, methyleneglycolate, Ti(III) ions, formaldehyde, and borohydrides.
  • at least one anti-oxidative compounds preferably selected from the group consisting of ascorbic acid, thiosulfate, hydrazine, hy-drazinecarbonat, carbohydrazide, methyleneglycolate, Ti(III) ions, formaldehyde, and borohydrides.
  • the at least one anti-oxidative compound is ascorbic acid and/or a salt thereof.
  • a preferred salt is sodium ascorbate and potassium ascorbate.
  • the at least one anti-oxidative compound has a concentration ranging from 1 mg/L to 10 g/L, based on the total volume of the oxidation preventing rinsing composition, more preferably from 100 mg/L to 5 g/L, and even more preferably from 500 mg/L to 2 g/L.
  • the oxidation preventing rinsing composition has a temperature in a arrange from 10°C to 50°C, preferably from 15°C to 40°C, and more preferably from 20°C to 30°C.
  • step f) is carried out for a time period ranging from 5 sec to 5 min, more preferably from 20 sec to 1 min.
  • step f) the oxidation preventing rinsing composition is kept an inert atmosphere while step f) is carried out, preferably under nitrogen and/or argon.
  • the oxidation preventing rinsing composition has a pH in a range from 4 to 7, more preferably from 5 to 6.5, most preferably if the oxidation preventing rinsing composition is kept under an inert atmosphere, or 7 to 13, more preferably from 8 to 12, most preferably if the oxidation preventing rinsing composition comprises formaldehyde.
  • the method of the present invention comprises further after step e) or after step f), step g) contacting the at least one surface of the substrate with at least one electroless metal or metal alloy plating bath.
  • a metal or metal alloy layer is deposited on the activated at least one surface of the substrate.
  • a preferred metal or metal alloy, respectively, to be deposited in step g) is selected from the group consisting of copper, copper alloy, nickel, nickel alloy, cobalt and cobalt alloy, most preferred being coper and copper alloy.
  • a copper and copper alloy is of paramount interest in the electronics industry and therefore particularly preferred in the context of the present invention.
  • Suitable electroless metal or metal alloy plating baths are generally known in the art and commercially available.
  • the method of the present invention preferably comprises further steps, most preferably drying and/or rinsing steps.
  • the present invention also refers to an activation composition for activating at least one surface of a substrate, preferably an activation composition as defined above and utilized in the method of the present invention (most preferably as defined as being preferred).
  • the activation composition is preferably for activating a non-metallic surface.
  • the activation composition of the present invention is prepared by dissolving all components in a solvent, preferably water.
  • the present invention relates to a use of an activation composition according to the present invention for activating at least one surface of a substrate for subsequent electroless plating.
  • kits-of-parts suitable to formulate the activation composition of the present invention preferably utilized in the method of the present invention.
  • the kit-of-parts of the present invention comprises at least the following individual parts:
  • the kit-of parts comprises further individual part: C) an aqueous solution comprising at least one enhancer compound different from ii) selected from the group consisting of sulfuric acid, sulfonic acids, carboxylic acids, polyols, salts and mixtures thereof.
  • individual part C) is comprised in part B) (i.e. in the aqueous solution comprising at least one unsubstituted or substituted N-heteroaromatic compound).
  • kit-of-parts as defined above easily facilitates the preparation of the activation composition of the present invention as the individual parts can be mixed easily and, if necessary, diluted further with a solvent, preferably water. Additional components as described throughout the text for the activation composition are preferably added as further individual parts (of the kit-of-parts, preferably as aqueous solutions thereof) or already included in one or more of parts A), B), and C). When using the kit-of-parts, no solids have to be handled which is advantageous from environmental and occupational health and safety aspects.
  • the present invention is particularly well suited to be used in the electronics and semiconductor industry, for example in the manufacturing of printed circuit boards, IC substrates and the like.
  • the copper coverage of the activated surface was evaluated by measuring the copper concentration in the activation composition before and after the activation was carried out.
  • the determined concentration difference corresponds to the amount of metallic copper formed on the surface.
  • the coverage of such a layer in recessed structures is typically evaluated using an industry standard Backlight Test. For that, the substrate is sectioned, so as to allow areas of incomplete coverage to be detected as bright spots when viewed over a strong light source [see for further information US 2008/0038450 A1 , incorporated herein by reference in its entirety].
  • the coverage of the copper or copper alloy layer is correlated to the amount of light that is observed under a conventional optical microscope.
  • results of the backlight test are given on a scale from D1 to D10, wherein D1 means the worst result (very low coverage) and D10 the best result (high coverage). Reference samples showing results from D1 to D10 are shown in Fig. 3 of WO 2013/050332 A1 .
  • the substrates were amorphous silica substrates.
  • aqueous activation compositions were prepared by dissolving in deionized water (for further details see Table 1):
  • each activation composition was adjusted to the pH value given in Table 1.
  • the copper coverage increased significantly when the activation composition comprised a substituted N-heteroaromatic compound.
  • the copper coverage was increased by more than 80% compared to comparative example #a, which did not use any N-heteroaromatic compound in the activation composition.
  • the N-heteroaromatic compounds utilized in #c to #j showed an even improved copper coverage compared to #b.
  • activation compositions containing additives being different from ii) i.e. being not an unsubstituted or substituted N-heteroaromatic compound as defined for the present invention, were tested on silica substrates too.
  • Table 2 Activation compositions (comparative) and copper coverage # additive c (additive) [mmol/L] c (Cu 2+ ) [mmol/L] pH change in copper coverage relative to #a a none 0 1.8 3-4 0 k citric acid 0.96 0.9 11.0 -2.0% 1 citric acid 1.91 1.8 11.7 -12.4% m citric acid 1.20 0.9 11.4 0.2% n 1,2-diaminocyclohexane * * No copper deposition on the substrates was detectable but significant reduction of copper ions in the activation composition was observed due to copper precipitation.
  • Comparative examples #k to #n did not show any increased copper coverage compared to comparative example #a, and are therefore ineffective.
  • Respective aqueous activation compositions were prepared by dissolving in deionized water:
  • Each activation composition was adjusted to a pH value of 10.
  • FR-4 substrates Isola IS 410
  • ABS substrates respectively, were subjected to the following steps to activate them: First, after providing the respective substrates, they were pretreated with a pretreating composition (Securiganth Cleaner 902, Atotech) at neutral pH in order to clean the at least one surface.
  • a pretreating composition Tinth Cleaner 902, Atotech
  • the obtained substrates were conditioned with a conditioning composition (Nano cleaner V, Atotech) with subsequent rinsing.
  • the pretreated and conditioned substrates were contacted with the respective activation composition at 50°C for 5 minutes. Subsequently, the substrates were rinsed with an alkaline solution under an inert atmosphere.
  • the obtained substrates were contacted with a reducing agent containing composition (Neoganth Reducer WA, Atotech) at 35°C for 20 seconds. Afterwards an anti-oxidative post-treatment composition was applied under an inert atmosphere.
  • a reducing agent containing composition Neoganth Reducer WA, Atotech
  • the substrates were fully covered with copper after the electroless copper plating step.
  • the thickness of the copper layer on the surface of the substrate was 1 ⁇ m on FR-4, and 0.6 ⁇ m on ABS, respectively, determined by measuring 5 points on each substrate with XRF using the XRF instrument Fischerscope XDV-SDD (Helmut Fischer GmbH, Germany).
  • the backlight test for FR-4 was D8.
  • the activation composition according to the present invention i.e. comprising copper ions, at least one unsubstituted or substituted N-heteroaromatic compound, and an enhancer compound
  • the activation composition according to the present invention was considerably more stable compared to activation compositions according to the present invention but without an enhancer compound. It was observed that the tendency of forming agglomerates and even precipitates is significantly reduced in the presence of the enhancer compound.

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EP19219076.7A 2019-12-20 2019-12-20 Verfahren zur aktivierung von mindestens einer oberfläche, aktivierungszusammensetzung und verwendung der aktivierungszusammensetzung zur aktivierung einer oberfläche zur stromlosen plattierung Pending EP3839092A1 (de)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113445031A (zh) * 2021-06-24 2021-09-28 广东硕成科技有限公司 一种金属活性剂及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248632A (en) * 1971-03-30 1981-02-03 Schering Aktiengesellschaft Solution and process for the activation of surfaces for metallization
EP0381873A2 (de) * 1989-02-03 1990-08-16 Kemifar S.P.A. Aktivierungszusammensetzung zum Beschichten von elektrisch isolierfähigen Substraten und Verfahren zum Beschichten solcher Substrate unter Verwendung der Zusammensetzung
US20080038450A1 (en) 2006-07-07 2008-02-14 Rohm And Haas Electronic Materials Llc Environmentally friendly electroless copper compositions
WO2013050332A2 (en) 2011-10-05 2013-04-11 Atotech Deutschland Gmbh Formaldehyde-free electroless copper plating solution
EP3287465A1 (de) * 2016-08-24 2018-02-28 LCY Chemical Corp. Metallkatalysator, herstellungsverfahren und anwendung davon

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4248632A (en) * 1971-03-30 1981-02-03 Schering Aktiengesellschaft Solution and process for the activation of surfaces for metallization
EP0381873A2 (de) * 1989-02-03 1990-08-16 Kemifar S.P.A. Aktivierungszusammensetzung zum Beschichten von elektrisch isolierfähigen Substraten und Verfahren zum Beschichten solcher Substrate unter Verwendung der Zusammensetzung
US20080038450A1 (en) 2006-07-07 2008-02-14 Rohm And Haas Electronic Materials Llc Environmentally friendly electroless copper compositions
WO2013050332A2 (en) 2011-10-05 2013-04-11 Atotech Deutschland Gmbh Formaldehyde-free electroless copper plating solution
EP3287465A1 (de) * 2016-08-24 2018-02-28 LCY Chemical Corp. Metallkatalysator, herstellungsverfahren und anwendung davon

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113445031A (zh) * 2021-06-24 2021-09-28 广东硕成科技有限公司 一种金属活性剂及其制备方法

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