TWI617700B - 無電極電鍍的方法 - Google Patents

無電極電鍍的方法 Download PDF

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Publication number
TWI617700B
TWI617700B TW105140926A TW105140926A TWI617700B TW I617700 B TWI617700 B TW I617700B TW 105140926 A TW105140926 A TW 105140926A TW 105140926 A TW105140926 A TW 105140926A TW I617700 B TWI617700 B TW I617700B
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TW
Taiwan
Prior art keywords
catalyst
copper
dextrin
metal
substrate
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TW105140926A
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English (en)
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TW201720958A (zh
Inventor
唐納德Ｅ 克里利
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羅門哈斯電子材料有限公司
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Publication of TW201720958A publication Critical patent/TW201720958A/zh
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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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1658—Process features with two steps starting with metal deposition followed by addition of reducing agent
    • 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
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/422—Plated through-holes or plated via connections characterised by electroless plating method; pretreatment therefor
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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    • 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
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    • 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
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    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
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    • 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
    • C23C18/1834—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • 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
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879—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
    • C23C18/18—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
    • C23C18/1875—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1882—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
    • 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
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    • 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
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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
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • C23C18/28—Sensitising or activating
    • C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • 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
    • C23C18/38—Coating with copper
    • 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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • 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
    • C23C18/48—Coating with alloys
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    • 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
    • C23C18/48—Coating with alloys
    • C23C18/50—Coating with alloys with alloys based on iron, cobalt or nickel
    • 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
    • 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
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
    • H05K3/181—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material by electroless plating
    • 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
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203—Fillers and particles
    • H05K2201/0242—Shape of an individual particle
    • H05K2201/0257—Nanoparticles
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    • 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
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H—ELECTRICITY
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    • 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
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Abstract

催化劑包含催化金屬奈米粒子及糊精作為穩定劑，其莫耳比能夠在存儲期間及在無電極金屬電鍍期間實現所述催化劑的穩定。所述催化劑為環保的且不含錫。所述催化劑良好黏附至包含通孔壁的印刷電路板的介電材料。

Description

用於印刷電路板和通孔的無電極金屬化的環保穩定催化劑
本發明涉及用於印刷電路板及通孔的無電極金屬化的環保穩定催化劑，其包含一定莫耳比的糊精穩定劑及催化金屬奈米粒子且不含錫。更具體而言，本發明涉及用於印刷電路板及通孔的無電極金屬化的環保穩定催化劑，其包含一定莫耳比的糊精穩定劑及催化金屬奈米粒子且不含錫以在存儲期間以及在無電極電鍍期間使催化劑穩定化，且所述催化劑良好黏附至印刷電路板的介電材料以使得光滑且均勻的金屬沈積在板表面上及通孔壁上。
印刷電路板(PCB)包含依賴於鑽探及電鍍通孔(PTH)的層壓不導電介電材料以形成板的相對側面與內層之間的連接。無電極電鍍為用於在表面上製備金屬塗層的熟知方法。介電表面的無電極電鍍需要預先將催化劑塗覆至待電鍍基板上。用以在無電極電鍍之前催化或活化層壓不導電介電基板區的最常使用的方法為用含水性錫-鈀膠體的酸性氯化物介質處理基板。膠體由被呈{SnCl3 -]錯合物外殼形式的錫 (II)離子穩定層包圍的鈀核心組成，所述錯合物充當表面穩定基團以避免膠體在懸浮液中凝聚。
在活化過程中，錫/鈀膠體催化劑吸附至介電基板，諸如含有環氧樹脂或聚醯亞胺的基板上以活化無電極金屬沈積。理論上，催化劑充當無電極金屬電鍍浴中自還原劑至金屬離子的電子轉移路徑中的載體。雖然無電極電鍍的效能受許多因素影響，諸如電鍍溶液的添加劑組合物，但活化步驟對於控制無電極電鍍的速率及機制而言才為關鍵的。
近年來，隨著電子裝置尺寸減小及所需效能提高，在電子包裝工業中對無缺陷電子電路的需求越來越高。雖然錫/鈀膠體在商業上已持續數十年用作無電極金屬電鍍的活化劑且一直提供可接受的服務，但其具有許多隨著對更高品質電子裝置的需求提高變得更加明顯的缺點。錫/鈀膠體的穩定性為主要問題。如上文所提及，錫/鈀膠體藉由錫(II)離子層穩定化且其抗衡陰離子可防止鈀凝聚。催化劑對空氣敏感且容易氧化成錫(IV)，因此膠體無法保持其膠態結構。此氧化進一步藉由在無電極電鍍期間提高溫度及攪動來促進。若錫(II)濃度下降至臨界水平，諸如接近零，則鈀金屬粒子的尺寸、附聚物及沈澱物生長，因此變得無催化活性。因此，對更穩定的催化劑的需求增加。另外，鈀的較高且波動的成本促進工業搜尋價格低廉的金屬。
已付出了相當多的努力來研發新型及改進的催化劑。因為鈀的高成本，已付出許多努力來研發無鈀催化劑，諸如膠態銀催化劑。另一研究方向為不含錫鈀催化劑，因為氯化亞錫成本較高且氧化錫需要單獨的加速步驟。除在總體 無電極方法中添加另一個步驟以外，加速步驟中所使用的材料通常自待電鍍基板剝去催化劑，在電鍍層中留下非所需空隙。此在印刷電路板製造中典型地使用的玻璃纖維基板上為尤其常見的。然而，此類不含錫催化劑已顯示為活性不夠且在印刷電路板製造中依賴於通孔電鍍。此外，此類催化劑典型地在存儲後活性逐漸降低，因此使得此類催化劑對於商業用途而言為不可靠及不可行的。
已研究錫錯合物的替代穩定部分，諸如聚乙烯吡咯啶酮(PVP)及樹枝狀聚合物。在文獻中，多個研究小組已報導穩定及均勻的PVP受保護奈米粒子。在文獻中亦已報導其它金屬膠體，諸如銀/鈀及銅/鈀，其中鈀經較便宜金屬部分置換；然而，到目前為止，仍不含錫/鈀膠態催化劑的商業上可接受的替代物。因此，仍然需要穩定且可靠的無電極金屬電鍍催化劑。
一種無電極電鍍方法，其包括：提供基板；將水性催化劑溶液塗覆至所述基板上，所述水性催化劑溶液包括一種或多種選自銀、金、鉑、鈀、銥、銅、鋁、鈷、鎳及鐵的金屬的奈米粒子；糊精；以及選自由葡萄糖、蔗糖、半乳糖、果糖、麥芽糖以及其混合物組成之群的還原劑，其中糊精與還原劑的重量比為100：1至1：5，所述水性催化劑溶液不含錫；使催化的基板與無電極金屬電鍍浴接觸；以及用無電極金屬電鍍浴使金屬無電極沈積於催化的基板上。
催化劑可用於使金屬無電極電鍍在基板上，包含具有金屬表面的基板及具有介電材料的彼等基板。本發明的 催化劑在存儲後以及在無電極金屬電鍍期間為穩定的。相比於習知錫/鈀催化劑，其並不易於氧化。另外，催化劑良好黏附至可為金屬、介電材料或其組合的基板表面及孔口壁。本發明的催化劑對基板的良好黏附性以及本發明的催化劑在基板上的穩定性使得無電極電鍍的金屬能夠在基板上形成均勻且平面的金屬沈積物。本發明的催化劑亦在孔口的壁及拐點上實現均勻、平面且保形的金屬電鍍。催化劑典型地用於在電解金屬電鍍，諸如銅電鍍之前在孔口的表面及壁上形成薄鍍層或觸擊層。用本發明的催化劑形成的觸擊層在電解金屬電鍍期間幫助實現均勻且基本上完整的孔口(諸如印刷電路板中的通孔)填充形成。
與催化劑的碳水化合物還原劑組合的糊精穩定劑不僅能夠使得催化劑良好黏附至基板，而且亦為生物可降解的，因此其並不存在環境危害。另外，本發明的催化劑不含錫且並不會引起習知錫/鈀催化劑的環境毒性處理問題。
如本說明書通篇所使用，除非上下文另外明確指示，否則以下縮寫將具有以下含義：A=安培；A/dm2=安培每平方分米；℃=攝氏度；g=公克；mg=毫克；ppm=百萬分率；ppm=mg/L；L=公升，nm=奈米；μm=微米(micron/micrometer)；mm=毫米；cm=公分；b.v.=按體積計；DI=去離子；mL=毫升；Mw=重量平均分子量；除非另外指出，否則所有量都為重量百分比。所有數值範圍為包含性的且可按任何次序組合，除非很明顯此等數值範圍被限制於總計為100%。
如在整個說明書中所使用，「特徵」為指基板上的幾何結構。「孔口」為指包含通孔及盲通道的凹陷特徵。如本說明書通篇所使用，除非另外指定，否則術語「電鍍」為指金屬無電極電鍍。術語「平面」為指具有均勻的表面構形的基本上平坦的表面。「沈積」及「電鍍」在本說明書通篇可互換使用。術語「印刷電路板」及「印刷佈線板」在本說明書通篇可互換使用。不定的冠詞「一個(種)(a及an)」表示單數及複數兩者。
水性催化劑溶液包含選自銀、金、鉑、鈀、銥、銅、鋁、鈷、鎳及鐵的金屬奈米粒子；一種或多種穩定糊精；以及選自由以下組成之群的還原劑：葡萄糖、蔗糖、半乳糖、果糖、麥芽糖以及其混合物。較佳地，金屬選自銀、金及銅，更較佳地，金屬選自銀及銅，最佳地，金屬為銀。較佳地，糊精穩定化合物具有以下通式：
其中「n」為使得糊精的Mw為1000或更大，較佳10,000至1000,000的數字。
穩定糊精化合物及還原劑以足夠的量包含於水性催化劑中以提供所需穩定及無電極金屬電鍍。較佳地，穩定糊精化合物及還原劑處於其中糊精與還原劑為100：1至1：5，更佳60：1至1：2，且最佳30：1至1：1的重量比率下。可進行微量實驗以獲得使無電極金屬電鍍催化劑穩定化的特定 糊精穩定劑或糊精穩定劑與還原劑的組合的量。一般而言，一種或多種穩定化合物以50ppm至1000ppm的量包含於水性催化劑中。一般而言，以10ppm至250ppm的量包含還原劑。
視情況，一種或多種抗氧化劑包含於催化劑中。此類抗氧化劑包含(但不限於)有機酸，諸如單羧酸及聚羧酸。此類酸的實例包含苯甲酸及其衍生物、抗壞血酸、異抗壞血酸、蘋果酸、乙酸、酒石酸、羅謝爾(Rochelle)鹽及檸檬酸。以10ppm至200ppm，較佳20ppm至100ppm的量包含此類酸。
金屬來源包含此項技術及提供具有催化活性的金屬的文獻中已知的習知水可溶金屬鹽中的任一種。可使用兩種或更多種催化金屬的混合物。包含此類鹽以提供100ppm至2000ppm，較佳300ppm至1500ppm的量的金屬。銀鹽包含(但不限於)硝酸銀、乙酸銀、三氟乙酸銀、甲苯磺酸銀、三氟甲磺酸銀、氟化銀、氧化銀、硫代硫酸銀三鈉及氰化銀鉀。鈀鹽包含(但不限於)氯化鈀、乙酸鈀、氯化鈀鉀、氯化鈀鈉及硝酸鈀。金鹽包含(但不限於)氰化金、三氯化金、三溴化金、氯化鉀金、氰化鉀金、氯化鈉金及氰化鈉金。鉑鹽包含(但不限於)氯化鉑及硫酸鉑。銥鹽包含(但不限於)三溴化銥及氯化銥鉀。銅鹽包含(但不限於)硫酸銅及氯化銅。鎳鹽包含(但不限於)氯化鎳及硫酸鎳。鈷鹽包含(但不限於)乙酸鈷、氯化鈷、溴化鈷及硫酸鈷銨。鋁鹽包含(但不限於)硫酸鋁及硫酸鋁鈉。鐵鹽包含(但不限於)檸檬酸亞鐵銨、草酸亞鐵銨及硫酸亞鐵銨。較佳地，金屬鹽為銀、 銅及金。更較佳地，金屬鹽為銀及銅。最佳地，鹽為銀。
構成水性催化劑的組分可以任何次序組合。可使用此項技術及文獻中已知的任何適合的方法來製備水性催化劑。雖然組分的特定參數及量可能隨著方法而變化，但一般而言，首先使穩定化合物中的一種或多種溶解於足夠量的水中。視情況，可加熱水溶液以幫助溶解糊精穩定劑。在劇烈攪動下將作為水溶液的金屬的一種或多種來源與穩定劑溶液組合以形成均勻的混合物。隨後同樣在劇烈攪動下將含有一種或多種還原劑的水溶液與穩定劑及金屬鹽的混合物混合。儘管不受理論束縛，穩定劑可塗佈或包圍部分或大多數金屬以催化劑溶液穩定化。金屬及穩定劑的粒子直徑為至少1nm，典型地1nm至1000nm或如2nm至500nm。較佳地，粒子尺寸範圍為2nm至300nm，更佳2nm至100nm，且最佳2nm至10nm。
如此合成的催化劑的pH可在酸性至輕度鹼性範圍內。若催化劑為鹼性的，則在使用無電極金屬化催化劑之前使pH減小至低於7。可將一種或多種酸或其鹽添加至催化劑中以提供小於7，較佳1-6.5，更佳2-6的pH範圍。可使用足夠量的無機或有機酸或其鹽以使pH保持在所需範圍下。亦可使用無機及有機酸及鹽的混合物。無機酸的實例為鹽酸、硫酸及硝酸。有機酸包含單及聚羧酸，諸如二羧酸。有機酸的實例為苯甲酸、抗壞血酸、異抗壞血酸、蘋果酸、馬來酸、草酸、乙酸、檸檬酸及酒石酸。
可使用催化劑來無電極金屬電鍍各種基板。此類基板包含(但不限於)以下材料，包含無機物質，諸如金屬、 玻璃、陶瓷及瓷；以及有機物質，諸如樹脂、紙及布。金屬包覆及非包覆材料亦為可使用催化劑金屬電鍍的基板。
基板還包含印刷電路板。此類印刷電路板包含由熱固性樹脂、熱塑性樹脂以及其組合(包含纖維，諸如玻璃纖維，及前述浸透實施例)包覆及非包覆的金屬。
熱塑性樹脂包含(但不限於)縮醛樹脂、丙烯酸樹脂(諸如丙烯酸甲酯)、纖維素樹脂(諸如乙酸乙酯)、丙酸纖維素、乙酸丁酸纖維素及硝酸纖維素、聚醚、尼龍、聚乙烯、聚苯乙烯、苯乙烯摻合物(諸如丙烯腈苯乙烯及共聚物及丙烯腈-丁二烯苯乙烯共聚物)、聚碳酸酯、聚氯三氟乙烯及乙烯基聚合物及共聚物，諸如乙酸乙烯酯、乙烯醇、乙烯基縮丁醛、氯乙烯、氯乙烯-乙酸酯共聚物、偏二氯乙烯及乙烯基縮甲醛。
熱固性樹脂包含(但不限於)鄰苯二甲酸烯丙酯、呋喃、三聚氰胺-甲醛、酚-醛及酚-糠醛共聚物(單獨的或與丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物複合)、聚丙烯酸酯、矽酮、脲甲醛、環氧樹脂、烯丙基樹脂、鄰苯二甲酸甘油酯以及聚酯。
多孔材料包含(但不限於)紙、木材、玻璃纖維、布及纖維，諸如天然及合成纖維，諸如棉花纖維及聚酯纖維。
催化劑可用於電鍍低及高Tg樹脂兩者。低Tg樹脂的Tg低於160℃且高Tg樹脂的Tg為160℃及更高。典型地，高Tg樹脂的Tg為160℃至280℃或如170℃至240℃。高Tg聚合物樹脂包含(但不限於)聚四氟乙烯(PTFE)及聚四氟乙烯摻合物。此類摻合物包含例如具有聚苯醚及氰酸酯的 PTFE。其它類型的包含具有高Tg的樹脂的聚合物樹脂包含(但不限於)環氧樹脂，諸如雙官能及多官能環氧樹脂、雙馬來醯亞胺/三嗪及環氧樹脂(BT環氧樹脂)、環氧樹脂/聚苯醚樹脂、丙烯腈丁二烯苯乙烯、聚碳酸酯(PC)、聚苯醚(PPO)、聚亞苯基醚(PPE)、聚苯硫醚(PPS)、聚碸(PS)、聚醯胺、聚酯(諸如聚對苯二甲酸乙二酯(PET)及聚對苯二甲酸丁二酯(PBT))、聚醚酮(PEEK)、液晶聚合物、聚胺基甲酸酯、聚醚醯亞胺、環氧樹脂以及其複合物。
催化劑可用於將金屬沈積於印刷電路板的通孔或通道的壁上。可在製造印刷電路板的水平及垂直方法兩者中使用催化劑。
水性催化劑可與習知無電極金屬電鍍浴一起使用。雖然設想催化劑可用於無電極沈積可經無電極電鍍的任何金屬，但典型地，所述金屬選自銅、銅合金、鎳或鎳合金。更典型地，金屬選自銅及銅合金，最典型地，使用銅。可商購無電極銅電鍍浴的一個實例為CIRCUPOSITTM 880無電極銅浴(可購自馬薩諸塞州馬波羅的陶氏電子材料有限責任公司(Dow Electronic Materials,LLC,Marlborough,MA))。
典型地，銅離子源包含(但不限於)水溶性鹵化物、硝酸鹽、乙酸鹽、硫酸鹽及銅的其它有機及無機鹽。可使用此類銅鹽中的一種或多種的混合物提供銅離子。實例包含硫酸銅(諸如五水合硫酸銅)、氯化銅、硝酸銅、氫氧化銅及胺基磺酸銅。組合物中可使用習知量的銅鹽。一般而言，組合物中的銅離子濃度可在0.5g/L至30g/L範圍內。
一種或多種合金金屬亦可包含於無電極組合物 中。此類合金金屬包含(但不限於)鎳及錫。銅合金的實例包含銅/鎳及銅/錫。典型地，銅合金為銅/鎳。
鎳及鎳合金無電極浴的鎳離子源可包含鎳的一種或多種習知水可溶鹽。鎳離子源包含(但不限於)硫酸鎳及鹵化鎳。鎳離子源可習知量包含於無電極合金組合物中。典型地，以0.5g/L至10g/L的量包含鎳離子源。
使基板金屬化中所使用的方法步驟可取決於待電鍍表面為否為金屬或介電的而變化。特定步驟及步驟順序亦可隨著方法而變化。用於無電極金屬電鍍基板的習知步驟可與催化劑一起使用；然而，水性穩定化金屬催化劑並不需要如許多習知無電極電鍍方法中的加速步驟。因此，當使用催化劑時，較佳排除加速步驟。一般而言，將催化劑塗覆至准備用金屬無電極電鍍的基板表面，繼而塗敷金屬電鍍浴。無電極金屬電鍍參數，諸如溫度及時間可為習知的。可使用習知基板製備方法，諸如清潔或使基板表面脫脂，使表面粗糙化或微粗糙化，蝕刻或微蝕刻表面，溶劑膨脹應用，除膠渣通孔及各種沖洗及抗變色處理。此類方法及調配物在此項技術中為熟知的且揭示於文獻中。
典型地，當待金屬電鍍的基板為介電材料，諸如在印刷電路板表面上或通孔壁上時，用水沖洗板且清潔，且繼而使通孔壁除膠渣。典型地，預備或軟化通孔的介電表面或膠渣為以應用溶劑膨脹開始。
可使用任何習知溶劑膨脹劑。特定類型可取決於介電材料的類型而變化。上文揭示介電質的實例。可進行微量實驗以測定哪種溶劑膨脹劑適用於特定介電材料。介電質 的Tg通常決定所使用的溶劑膨脹劑的類型。溶劑膨脹劑包含(但不限於)二醇醚及其相關醚乙酸酯。可使用習知量的二醇醚及其相關醚乙酸酯。可商購的溶劑膨脹劑的實例為CIRCUPOSITTM Hole Prep 211A、CIRCUPOSITTM Hole Prep 3303及CIRCUPOSITTM Hole Prep 4120(可購自陶氏電子材料公司)。
視情況，基板及通孔用水沖洗。隨後施加促進劑。可使用習知促進劑。此類促進劑包含硫酸、鉻酸、鹼性高錳酸或等離子蝕刻。典型地，使用鹼性高錳酸作為促進劑。可商購促進劑的一個實例為CIRCUPOSITTM促進劑4130及CIRCUPOSITTM MLB促進劑3308(可購自羅門哈斯電子材料公司(Rohm and Haas Electronic Materials))。
視情況，基板及通孔再次用水沖洗。隨後施用中和劑以中和促進劑殘留的任何殘餘物。可使用習知中和劑。典型地，中和劑為含有一種或多種胺的水性酸性溶液或3wt%過氧化物及3wt%硫酸的溶液。可商購的中和劑的實例為CIRCUPOSITTM MLB中和劑216-5。基板及通孔用水沖洗且可保持濕潤或乾燥。
在除膠渣之後，施用酸或鹼性調節劑。可使用習知調節劑。此類調節劑可包含一種或多種陽離子性界面活性劑、非離子性界面活性劑、錯合劑及pH調節劑或緩衝劑。可商購的酸調節劑的實例為CIRCUPOSITTM調節劑3320A及CIRCUPOSITTM調節劑3327(可購自陶氏電子材料公司)。適合的鹼性調節劑包含(但不限於)含有一種或多種四級胺及多元胺的水性鹼性界面活性劑溶液。可商購的鹼性界面活性 劑的實例為CIRCUPOSITTM調節劑231、3325、813及860。在調節之後，基板及通孔用水沖洗。
可在調節之後進行微蝕刻。可使用習知微蝕刻組合物。微蝕刻被設計以在暴露的金屬上提供微粗糙化金屬表面(例如內層及表面蝕刻)，以便增強後續沈積的無電極及稍後電鍍物的黏附性。微蝕刻劑包含(但不限於)10g/L至200g/L過硫酸鈉或氧代單過硫酸鈉或氧代單過硫酸鉀及硫酸(1-5%)混合物，或一般硫酸/過氧化氫。可商購的微蝕刻組合物的實例為CIRCUPOSITTM微蝕刻劑3330及PREPOSITTM 748。視情況，基板用水沖洗。
視情況，可隨後對微蝕刻基板及通孔進行預浸漬。可使用足夠量的無機或有機酸或其鹽。亦可使用無機及有機酸及鹽的混合物。無機酸的實例為鹽酸、硫酸及硝酸。有機酸包含單及聚羧酸，諸如二羧酸。有機酸的實例為苯甲酸、抗壞血酸、異抗壞血酸、蘋果酸、馬來酸、草酸、乙酸、檸檬酸及酒石酸。
隨後將糊精穩定化催化劑塗覆至基板及通孔上。在催化劑中的停留時間可在1-15分鐘，典型地2-8分鐘範圍內變化。溫度可在室溫至80℃或如30℃至60℃範圍內。在施用催化劑之後，基板及通孔用水沖洗。
基板及通孔的壁隨後用金屬，諸如銅、銅合金、鎳或鎳合金與無電極浴電鍍。典型地，將銅電鍍在基板表面及通孔壁上。鍍敷時間及溫度可為習知的。典型地，在20℃至80℃，更典型地30℃至60℃的溫度下進行金屬沈積。基板可浸沒於無電極電鍍浴中或無電極可經由流體泵送或將條噴 射至基板上。典型地，沈積可進行5秒至30分鐘；然而，電鍍時間可取決於基板上的金屬的厚度變化。
視情況，可對金屬施用抗變色劑。可使用習知抗變色組合物。抗變色劑的一個實例為ANTI TARNISHTM 7130(可獲自陶氏電子材料公司)。基板可視情況沖洗且隨後可將板乾燥。
進一步加工可包含藉由光成像及在基板上的進一步金屬沈積(如銅、銅合金、錫及錫合金的電解金屬沈積)而進行的習知加工。
催化劑可用於將金屬無電極電鍍在基板上，包含介電材料的基板且在存儲後及在無電極金屬電鍍期間為穩定的。催化劑為生物可降解的，因此其並不存在環境危害。糊精穩定化金屬催化劑實現無加速步驟的無電極金屬電鍍且實現基板，甚至印刷電路板的通孔的壁的金屬電鍍。
以下實例並不意圖限制本發明的範圍，而為進一步說明本發明。
實例1 糊精/銀催化劑合成，其中葡萄糖作為還原劑
藉由在室溫下在含有900mL DI水的燒杯中使3克糊精溶解製備糊精/銀催化劑。將472mg硝酸銀添加至50mL DI水中且劇烈攪拌混合物直至其完全溶解為止。將硝酸銀混合物添加至糊精溶液中且劇烈攪拌，同時連續地加熱。將pH調節至9-13且在極劇烈攪動下將100mg溶解於20mL DI水中的葡萄糖添加至溶液混合物中。溶液迅速自無色改變為紅棕色，指示銀離子還原成銀金屬。隨後將最終體積調節 至一公升。用無機或有機酸再調節溶液pH且如此合成的催化劑具有5至10的pH，如使用ACCUMET AB15 pH計所量測。將含有水性催化劑溶液的燒杯放置於50℃水浴中持續約12小時以測試其穩定性。在約12小時之後，無可觀測到的沈澱物，指示催化劑仍為穩定的。
實例2 無電極銅電鍍
實例1中製備的催化劑溶液用作儲備溶液且2份等分試樣用DI水稀釋至250ppm的奈米粒子濃度。用抗壞血酸將等分試樣的pH調節至3或5。糊精與還原劑的重量比為約30：1。
尺寸為10cm×5cm的兩個裸露的層壓物試片用3% b.v.CIRCUPOSITTM調節劑231調節且在室溫下用自來水沖洗。隨後使每個試片浸沒於兩個含有糊精/銀催化劑的等分試樣中的一個中約5分鐘以用催化劑預塗佈每個試片。在催化作用期間，在約40℃的溫度下加熱具有試片的水性催化劑浴。隨後在36℃下將催化的試片浸沒在CIRCUPOSITTM 880無電極銅電鍍浴中約15分鐘。無電極銅電鍍浴的pH為約12。
自無電極銅浴中移出試片且在室溫下用去離子水沖洗。兩個試片似乎完全被銅電鍍。在試片的整個表面上銅沈積物似乎為光滑、均勻且平面的。根據ASTM D3359，使用3M 250膠帶測試來測試銅沈積物的黏附性。將膠帶施加至每個試片的一個表面且自試片拉出膠帶。在膠帶上未觀測到銅沈積物，指示每個試片的良好銅黏附性。
實例3 通孔電鍍
提供具有多個通孔的六種不同層壓物：NP-175、370 HR、TUC-752、SY-1141、SY-1000-2及FR-408。NP-175來自南亞公司(Nan Ya)。370 HR及FR4-408來自伊索拉(Isola)。TUC-752來自臺灣聯合技術公司(Taiwan Union Technology)且SY-1141及SY-1000-2來自生益(Shengyi)。層壓物的Tg值在140℃至180℃範圍內。每個層壓物為5cm×12cm。每個層壓物的通孔處理如下：1.每個層壓物的通孔用CIRCUPOSITTM MLB調節劑211在78℃下除膠渣7分鐘；2.每個層壓物的通孔隨後用流動的自來水沖洗4分鐘；3.通孔隨後在13的pH下在78℃下用CIRCUPOSITTM MLB促進劑213水性高錳酸溶液處理10分鐘；4.通孔隨後在流動的自來水中沖洗4分鐘；5.通孔隨後在46℃下用CIRCUPOSITTM MLB中和劑216-5溶液處理5分鐘；6.每個層壓物的通孔隨後用流動的自來水沖洗4分鐘；7.通孔隨後在含有3% CIRCUPOSITTM調節劑231鹼性調節劑的水性浴中在40℃下處理5分鐘；8.每個層壓物的通孔隨後用流動的自來水沖洗4分鐘；9.通孔隨後在室溫下用PREPOSTTM 748處理2分鐘；10.每個層壓物的通孔隨後用流動的自來水沖洗4分鐘；11.六個層壓物的通孔隨後在40℃下用來自經200ppm糊精穩定化的硝酸銀的300ppm銀催化劑預塗佈5分鐘，其中催化劑粒徑在7-10nm範圍內。還原劑為200ppm葡萄糖。 用抗壞血酸將催化劑的pH調節至約3；12.通孔隨後用流動的自來水沖洗4分鐘；13.層壓物隨後在40℃下且在約13的pH下浸沒在CIRCUPOSITTM 880無電極銅電鍍浴中且使銅沈積於通孔壁上持續15分鐘；14.銅電鍍層壓物隨後用冷水沖洗4分鐘；15.隨後用壓縮空氣乾燥每個銅電鍍層壓物；且16.使用下文所描述的背光方法檢測層壓物的通孔壁的銅電鍍覆蓋度。
每個板側向地切割以暴露通孔的電鍍有銅的壁。自每個板獲取約1mm厚的十個側向孔洞以測定通孔壁覆蓋度。使用普遍可接受的背光定級標度。每個板的1mm截面放置在50X放大率的習知光學顯微鏡下。藉由在顯微鏡下觀測到的光量測定銅沈積物的品質。若未觀測到光，則截面完全為黑色且在背光標度上評定為5，指示通孔壁的完全銅覆蓋。若光穿過整個截面而無任何黑暗區域，則此表明器壁上存在極少至無銅金屬沈積且截面評定為0。若截面具有一些黑暗區域以及明亮區域，則其被評定為0與5之間。
除NP-175板外，糊精/銀催化劑的平均背光值為4.5及更大。典型地，4.5及更大的背光值指示在電鍍工業中商業上可接受的催化劑。
實例4 糊精/銀催化劑合成，其中蔗糖作為還原劑
藉由在50℃至55℃下加熱的情況下在含有1000mL DI水的燒杯中使3克糊精溶解製備糊精/銀催化劑。將472 mg硝酸銀添加至50mL DI水中且混合直至其完全溶解為止。將混合物添加至溶液中且劇烈攪拌，同時連續地加熱。將pH自9調節至13且使100mg蔗糖溶解於20mL中。在極劇烈攪動下將DI水添加至溶液混合物中。溶液迅速自無色改變為紅棕色，指示銀離子還原成銀金屬。隨後將最終體積調節至一公升。用有機酸再調節溶液pH且如此合成的催化劑具有約5至10的pH，如使用ACCUMET AB15 pH計所量測。將含有水性催化劑溶液的燒杯放置於50℃水浴中持續約12小時以測試其穩定性。在約12小時之後，無可觀測到的沈澱物，指示催化劑仍為穩定的。
實例5 無電極銅電鍍
實例1中製備的催化劑溶液用作儲備溶液且2份等分試樣用DI水稀釋至250ppm的奈米粒子濃度。用抗壞血酸將等分試樣的pH調節至3或5。糊精與還原劑的重量比為約30：1。
尺寸為10cm×5cm的兩個裸露的層壓物試片用3% b.v.CIRCUPOSITTM調節劑231調節且在室溫下用自來水沖洗。隨後使每個試片浸沒於兩個含有糊精/銀催化劑的等分試樣中的一個中約5分鐘以用催化劑預塗佈每個試片。在催化作用期間，在約40℃的溫度下加熱具有試片的水性催化劑浴。隨後在36℃下將催化的試片浸沒在CIRCUPOSITTM 880無電極銅電鍍浴中約15分鐘。無電極銅電鍍浴的pH為約12。
自無電極銅浴中移出試片且在室溫下用去離子水沖洗。兩個試片似乎完全被銅電鍍。在試片的整個表面上 銅沈積物似乎為光滑、均勻且平面的。根據ASTM D3359，使用3M 250膠帶測試來測試銅沈積物的黏附性。將膠帶施加至每個試片的一個表面且自試片拉出膠帶。在膠帶上未觀測到銅沈積物，指示每個試片的良好銅黏附性。
實例6 糊精/銀催化劑合成，其中半乳糖作為還原劑
藉由在50℃至55℃下加熱的情況下在含有1000mL DI水的燒杯中使3克糊精溶解製備糊精/銀催化劑。將472mg硝酸銀添加至50mL DI水中且混合直至其完全溶解為止。將混合物添加至溶液中且劇烈攪拌，同時連續地加熱。將pH調節至9-13且使100mg半乳糖溶解於20mL中。在極劇烈攪動下將DI水添加至溶液混合物中。溶液迅速自無色改變為紅棕色，指示銀離子還原成銀金屬。隨後將最終體積調節至一公升。用有機酸再調節溶液pH且如此合成的催化劑具有約5至10的pH，如使用ACCUMET AB15 pH計所量測。將含有水性催化劑溶液的燒杯放置於50℃水浴中持續約12小時以測試其穩定性。在約12小時之後，無可觀測到的沈澱物，指示催化劑仍為穩定的。
實例7 無電極銅電鍍
實例1中製備的催化劑溶液用作儲備溶液且2份等分試樣用DI水稀釋至250ppm的奈米粒子濃度。用抗壞血酸將等分試樣的pH調節至3或5。糊精與還原劑的重量比為約30：1。
尺寸為10cm×5cm的兩個裸露的層壓物試片用 3% b.v.CIRCUPOSITTM調節劑231調節且在室溫下用自來水沖洗。隨後使每個試片浸沒於兩個含有糊精/銀催化劑的等分試樣中的一個中約5分鐘以用催化劑預塗佈每個試片。在催化作用期間，在約40℃的溫度下加熱具有試片的水性催化劑浴。隨後在36℃下將催化的試片浸沒在CIRCUPOSITTM 880無電極銅電鍍浴中約15分鐘。無電極銅電鍍浴的pH為約12。
自無電極銅浴中移出試片且在室溫下用去離子水沖洗。兩個試片似乎完全被銅電鍍。在試片的整個表面上銅沈積物似乎為光滑、均勻且平面的。根據ASTM D3359，使用3M 250膠帶測試來測試銅沈積物的黏附性。將膠帶施加至每個試片的一個表面且自試片拉出膠帶。在膠帶上未觀測到銅沈積物，指示每個試片的良好銅黏附性。
實例8 糊精/銀催化劑合成，其中果糖作為還原劑
藉由在50℃至55℃下加熱的情況下在含有1000mL DI水的燒杯中使3克糊精溶解製備糊精/銀催化劑。將472mg硝酸銀添加至50mL DI水中且混合直至其完全溶解為止。將混合物添加至溶液中且劇烈攪拌，同時連續地加熱。將pH調節至9-13且使100mg果糖溶解於20mL中。在極劇烈攪動下將DI水添加至溶液混合物中。溶液迅速自無色改變為紅棕色，指示銀離子還原成銀金屬。隨後將最終體積調節至一公升。用有機酸再調節溶液pH且如此合成的催化劑具有約5至10的pH，如使用ACCUMET AB15 pH計所量測。將含有水性催化劑溶液的燒杯放置於50℃水浴中持續約12小時以測試其穩定性。在約12小時之後，無可觀測到的沈澱物， 指示催化劑仍為穩定的。
實例9 無電極銅電鍍
實例1中製備的催化劑溶液用作儲備溶液且2份等分試樣用DI水稀釋至250ppm的奈米粒子濃度。用抗壞血酸將等分試樣的pH調節至3或5。糊精與還原劑的重量比為約30：1。
尺寸為10cm×5cm的兩個裸露的層壓物試片用3% b.v.CIRCUPOSITTM調節劑231調節且在室溫下用自來水沖洗。隨後使每個試片浸沒於兩個含有糊精/銀催化劑的等分試樣中的一個中約5分鐘以用催化劑預塗佈每個試片。在催化作用期間，在約40℃的溫度下加熱具有試片的水性催化劑浴。隨後在36℃下將催化的試片浸沒在CIRCUPOSITTM 880無電極銅電鍍浴中約15分鐘。無電極銅電鍍浴的pH為約12。
自無電極銅浴中移出試片且在室溫下用去離子水沖洗。兩個試片似乎完全被銅電鍍。在試片的整個表面上銅沈積物似乎為光滑、均勻且平面的。根據ASTM D3359，使用3M 250膠帶測試來測試銅沈積物的黏附性。將膠帶施加至每個試片的一個表面且自試片拉出膠帶。在膠帶上未觀測到銅沈積物，指示每個試片的良好銅黏附性。
實例10 糊精/銀催化劑合成，其中麥芽糖作為還原劑
藉由在50℃至55℃下加熱的情況下在含有1000mL DI水的燒杯中使3克糊精溶解製備糊精/銀催化劑。將472mg硝酸銀添加至50mL DI水中且混合直至其完全溶解為 止。將混合物添加至溶液中且劇烈攪拌，同時連續地加熱。將pH調節至9-13且使100mg麥芽糖溶解於20mL中。在極劇烈攪動下將DI水添加至溶液混合物中。溶液迅速自無色改變為紅棕色，指示銀離子還原成銀金屬。隨後將最終體積調節至一公升。用有機酸再調節溶液pH且如此合成的催化劑具有約5至10的pH，如使用ACCUMET AB15 pH計所量測。將含有水性催化劑溶液的燒杯放置於50℃水浴中持續約12小時以測試其穩定性。在約12小時之後，無可觀測到的沈澱物，指示催化劑仍為穩定的。
實例11 無電極銅電鍍
實例1中製備的催化劑溶液用作儲備溶液且2份等分試樣用DI水稀釋至250ppm的奈米粒子濃度。用抗壞血酸將等分試樣的pH調節至3或5。糊精與還原劑的重量比為約30：1。
尺寸為10cm×5cm的兩個裸露的層壓物試片用3% b.v.CIRCUPOSITTM調節劑231調節且在室溫下用自來水沖洗。隨後使每個試片浸沒於兩個含有糊精/銀催化劑的等分試樣中的一個中約5分鐘以用催化劑預塗佈每個試片。在催化作用期間，在約40℃的溫度下加熱具有試片的水性催化劑浴。隨後在36℃下將催化的試片浸沒在CIRCUPOSITTM 880無電極銅電鍍浴中約15分鐘。無電極銅電鍍浴的pH為約12。
自無電極銅浴中移出試片且在室溫下用DI水沖洗。試片似乎完全被銅電鍍。銅沈積物似乎使光滑、均勻且平面的。

Claims (10)

  1. 一種無電極電鍍的方法，其包括：a)提供基板；b)將水性催化劑溶液塗覆至所述基板上，所述水性催化劑溶液包括一種或多種選自銀、金、鉑、鈀、銥、銅、鋁、鈷、鎳及鐵的金屬的奈米粒子；糊精；以及選自由葡萄糖、蔗糖、半乳糖、果糖、麥芽糖以及其混合物組成之群的還原劑，其中所述糊精與還原劑的莫耳比為100：1至1：5，所述水性催化劑溶液不含錫；c)使催化的基板與無電極金屬電鍍浴接觸；以及d)用所述無電極金屬電鍍浴使金屬無電極沈積於所述催化的基板上。
  2. 如申請專利範圍第1項所述的方法，其中所述糊精與所述還原劑的莫耳比為60：1至1：2。
  3. 如申請專利範圍第2項所述的方法，其中所述糊精與所述還原劑的莫耳比為30：1至1：1。
  4. 如申請專利範圍第1項所述的方法，其中所述水性催化劑溶液進一步包括一種或多種抗氧化劑。
  5. 如申請專利範圍第1項所述的方法，其中所述基板包括多個孔口。
  6. 如申請專利範圍第1項所述的方法，其中無電極沈積的金屬為銅、銅合金、鎳或鎳合金。
  7. 如申請專利範圍第1項所述的方法，其中所述奈米粒子直徑至少為1nm。
  8. 如申請專利範圍第1項所述的方法，其中一種或多種糊精化合物的量為50ppm至1000ppm。
  9. 如申請專利範圍第1項所述的方法，其中所述基板包括多個通孔。
  10. 如申請專利範圍第1項所述的方法，其進一步包括將調節劑塗覆至所述基板上。
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