CN111344435A - 复合铜箔 - Google Patents

复合铜箔 Download PDF

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Publication number
CN111344435A
CN111344435A CN201880073319.3A CN201880073319A CN111344435A CN 111344435 A CN111344435 A CN 111344435A CN 201880073319 A CN201880073319 A CN 201880073319A CN 111344435 A CN111344435 A CN 111344435A
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CN
China
Prior art keywords
copper foil
composite copper
composite
convex portion
plating
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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.)
Pending
Application number
CN201880073319.3A
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English (en)
Inventor
佐藤牧子
铃木理
小畠直贵
小锻冶快允
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Namics Corp
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Namics Corp
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Application filed by Namics Corp filed Critical Namics Corp
Publication of CN111344435A publication Critical patent/CN111344435A/zh
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/20—Other heavy 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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1637—Composition of the substrate metallic substrate
    • 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
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • 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
    • 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
    • C23C18/1837—Multistep pretreatment
    • 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
    • C23C18/1837—Multistep pretreatment
    • C23C18/1841—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
    • C23C18/31—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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/52—Treatment of copper or alloys based thereon
    • 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
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/63—Treatment of copper or alloys based thereon
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10—Other heavy metals
    • C23G1/103—Other heavy metals copper or alloys of copper
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
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    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • 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
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • 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
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • 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
    • H05K2203/0779—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
    • H05K2203/0793—Aqueous alkaline solution, e.g. for cleaning or etching
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/385—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by conversion of the surface of the metal, e.g. by oxidation, whether or not followed by reaction or removal of the converted layer

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
  • Chemically Coating (AREA)
  • Non-Insulated Conductors (AREA)

Abstract

本发明的目的在于提供一种新型的复合铜箔。用于解决课题的手段为一种复合铜箔，其为在铜箔的至少一部分的表面形成有铜以外的金属层的复合铜箔，在至少一部分的上述复合铜箔的表面具有凸部，在上述复合铜箔的截面，上述凸部的高度为10nm以上1000nm以下。

Description

复合铜箔
技术领域
本发明涉及一种复合铜箔。
背景技术
印刷电路板所使用的铜箔被要求具备与树脂的密合性。为了提高该密合性，采用通过蚀刻等对铜箔的表面进行粗面化处理从而提高物理的粘接力的方法。然而，伴随印刷电路板的高密度化，开始要求铜箔表面的平坦化。为了满足这样彼此相反的要求，开发了进行氧化工序和还原工序等的铜表面处理方法(WO2014/126193公开公报)。根据该方法，通过对铜箔进行预调理，浸渍于含有氧化剂的药液中，使铜箔表面氧化而形成氧化铜的凹凸，之后通过浸渍于含有还原剂的药液中，使氧化铜还原，从而调整表面的凹凸，调整表面的粗糙度。此外，作为利用氧化还原的铜箔的处理中的密合性的改善方法，开发了在氧化工序中添加表面活性分子的方法(日本特表2013－534054号公报)以及在还原工序后使用氨基噻唑系化合物等在铜箔的表面形成保护被膜的方法(日本特开平8－97559号公报)。另外，开发了如下方法，在使绝缘基板上的铜导体图案的表面粗化而形成了氧化铜层的表面上，形成具有离散分布的金属颗粒的镀敷膜的方法(日本特开2000－151096号公报)。
发明内容
发明要解决的技术问题
本发明的目的在于提供一种新型的复合铜箔。
用于解决技术问题的技术方案
本发明的一个实施方式为一种复合铜箔，其为在铜箔的至少一部分的表面形成有铜以外的金属层的复合铜箔，其中，在至少一部分的上述复合铜箔的表面具有凸部，在上述复合铜箔的截面，上述凸部的高度为10nm以上1000nm以下。可以在利用扫描电子显微镜得到的截面的摄影像中，以连接凸部两侧的凹部的极小点的线段的中点与凸部的极大点的距离，测定上述凸部的高度。另外，在深度6nm处，Cu相对于总金属量的比例可以为80％以下；在不含氧的深度，Cu相对于总金属量的比例可以为90％以上。上述凸部的高度可以为50nm以上500nm以下。另外，在上述复合铜箔的截面，高度为50nm以上的凸部在每3.8μm可以平均存在15个以上100个以下。上述金属层可以均匀且没有颗粒。Cu的比例为40atom％的深度处的Cu/O比可以在0.9以上。上述铜以外的金属可以为选自Sn、Ag、Zn、Al、Ti、Bi、CrvFe、Co、Ni、Pd、Au和Pt中的至少一种金属。
本发明的另一个实施方式为一种复合铜箔的制造方法，其包括：将铜箔表面进行氧化的第一工序；和对经氧化的上述铜表面进行镀敷处理的第二工序。可以在第一工序前，用碱性水溶液进行碱处理。在第一工序中，经氧化的上述铜箔表面可以被溶解剂溶解。在第二工序中，上述镀敷处理可以为使用催化剂的无电解镀敷。在第二工序中，上述镀敷处理可以为电解镀敷。
＝＝与关联文献的交叉参考＝＝
本发明基于2017年11月10日申请的日本国专利申请2017－217777和2018年3月30日申请的日本国专利申请2018－069608主张优先权，通过引用将该基础申请包含在本说明书中。
附图说明
图1为在本发明的实施例2～8、比较例1～2中示出复合铜箔的截面的扫描型电子显微镜(SEM)图像。
具体实施方式
以下，举出实施例对本发明的实施方式进行详细说明。其中，通过本说明书的记载，本发明的目的、特征、优点和其思想对于本领域技术人员而言是清楚的，本领域技术人员能够根据本说明书的记载容易地再现本发明。以下记载的发明的实施方式和具体的实施例等表示本发明的优选实施方式，为了例示或说明而示出，并不用来将本发明限定于此。本领域技术人员可以理解，在本说明书所公开的本发明的意图以及范围内，可以基于本说明书的记载进行各式各样的修饰。
＝＝复合铜箔＝＝
本发明的一个实施方式为在铜箔的至少一部分的表面形成有铜以外的金属层的复合铜箔。该复合铜箔中，在至少一部分的金属层的表面具有凸部。
该凸部的高度的平均优选为10nm以上、更优选为50nm以上、进一步优选为100nm以上，另外，优选为1000nm以下、更优选为500nm以下、进一步优选为200nm以下。该凸部的高度，例如可以为在利用聚焦离子束(FIB)制成的观察复合铜箔的截面的扫描型电子显微镜(SEM)像中，连接夹着凸部邻接的凹部的极小点而成的线段的中点与位于凹部之间的凸部的极大点的距离。
在物体的表面，高度为50nm以上的凸部在每3.8μm中优选平均存在15个以上、更优选为30个以上、进一步优选为50个以上。另外，优选为100个以下、更优选为80个以下、进一步优选为60个以下。关于凸部的个数，例如，可以通过在利用聚焦离子束(FIB)得到的观察复合铜箔的截面的扫描型电子显微镜(SEM)像中，计测高度为50nm以上的凸部在每3.8μm中的个数来计数。可以如上所述测定高度。
铜以外的金属的种类没有特别限定，优选为选自Sn、Ag、Zn、Al、Ti、Bi、Cr、Fe、Co、Ni、Pd、Au和Pt中的至少一种金属。
铜以外的金属层的厚度没有特别限定，优选为6nm以上、更优选为10nm以上、进一步优选为14nm以上。
铜以外的金属层中的金属的比例没有特别限定，在深度6nm处，Cu相对于总金属量的比例优选为80重量％以下、更优选为50重量％以下、更优选为30重量％以下。另外，在不含氧的深度，Cu相对于总金属量的比例优选为90重量％以上、更优选为95重量％以上、进一步优选为99重量％以上。另外，Cu的原子组成的比例为40％的深度处的Cu/O比优选在0.9以上、更优选在2以上、进一步优选在5以上。相对于规定深度的总金属量的Cu的比例，例如，可以采用离子溅射和X射线光电子分光法(XPS)测定。
金属层优选为没有颗粒的均匀的层。其中，所谓均匀，意指在95％以上的面、优选在98％以上的面、更优选在99％以上的面，该层的厚度不超过层的平均厚度的5倍、优选不超过3倍、更优选不超过2倍的情况。通过形成没有颗粒的均匀的金属层，能够提高热处理后的密合性。
该复合铜箔能够用作印刷电路板中使用的铜箔。即，通过将复合铜箔和树脂以层状粘接而制作叠层板，从而能够用于制造印刷电路板。另外，该复合铜箔能够用作二次电池中使用的集电体。即，通过将含有石墨等活性物质和聚偏氟乙烯等粘结剂树脂的浆料涂布于复合铜箔，并使其干燥来制作电极，从而能够用于制造二次电池。
如上所述的复合铜箔具有低粗糙化并且具备良好的密合性、耐热性的优点。
＝＝复合铜箔的制造方法＝＝
本发明的一个实施方式为复合铜箔的制造方法，该复合铜箔的制造方法包括：将铜箔表面进行氧化的第一工序；和对经氧化的铜表面进行镀敷处理的第二工序。
首先，在第一工序中，用氧化剂将铜表面进行氧化，形成氧化铜的层，同时在表面形成凹凸部。在该氧化工序以前，虽然不需要进行蚀刻等粗面化处理工序，但是也可以进行粗面化处理工序。还可以进行脱脂清洗或用于防止将酸带入氧化工序的碱处理。碱处理的方法没有特别限定，利用优选为0.1～10g/L、更优选为1～2g/L的碱性水溶液、例如氢氧化钠水溶液在30～50℃处理0.5～2分钟左右即可。
氧化剂没有特别限定，例如，可以使用亚氯酸钠、次氯酸钠、氯酸钾、高氯酸钾等的水溶液。氧化剂中，可以添加各种添加剂(例如，如磷酸三钠十二水和物的磷酸盐)、表面活性分子。作为表面活性分子，可以例示卟啉、卟啉大环、扩展卟啉(Expanded Porphyrin)、环缩小卟啉、直链卟啉聚合物、卟啉夹心配合物、卟啉排列、硅烷、四有机-硅烷、氨基乙基-氨基丙基－三甲氧基硅烷、(3-氨基丙基)三甲氧基硅烷、(1-[3-(三甲氧基甲硅烷基)丙基]脲)((l－[3－(Trimethoxysilyl)propyl]urea))、(3-氨基丙基)三乙氧基硅烷、((3-环氧丙基氧丙基)三甲氧基硅烷)、(3-氯丙基)三甲氧基硅烷、(3-环氧丙基氧丙基)三甲氧基硅烷、二甲基二氯硅烷、3-(三甲氧基甲硅烷基)丙基甲基丙烯酸酯、乙基三乙酰氧基硅烷、三乙氧基(异丁基)硅烷、三乙氧基(辛基)硅烷、三(2-甲氧基乙氧基)(乙烯基)硅烷、氯三甲基硅烷、甲基三氯硅烷、四氯化硅、四乙氧基硅烷、苯基三甲氧基硅烷、氯三乙氧基硅烷、乙烯-三甲氧基硅烷、胺、糖等。
氧化反应条件没有特别限定，氧化剂的液温优选为40～95℃、更优选为45～80℃。反应时间优选为0.5～30分钟、更优选1～10分钟。
在第一工序中，可以用溶解剂将经氧化的铜箔表面溶解，调整经氧化的铜箔表面的凹凸部。
本工序中使用的溶解剂没有特别限定，优选为螯合剂、特别优选生物降解性螯合剂，可以例示乙二胺四乙酸、二乙醇甘氨酸、L－谷氨酸二乙酸·四钠、乙二胺－N,N’－二琥珀酸、3－羟基－2、2’－亚胺基二琥珀酸钠、甲基甘氨酸2乙酸3钠、天冬氨酸二乙酸4钠、N－(2－羟基乙基)亚胺基二乙酸二钠、葡萄糖酸钠等。
溶解剂的pH没有特别限定，优选为碱性、更优选为pH8～10.5、进一步优选为pH9.0～10.5、进一步优选为pH9.8～10.2。
在该工序中，对铜表面进行处理，直至氧化铜的溶解率成为35～99％、优选成为77～99％并且CuO的厚度成为4～150nm、优选成为8～50nm。在该条件下，与预成型坯(prepreg)的剥离强度变高，处理偏差降低。
接下来，在第二工序中，通过用铜以外的金属对氧化铜的层进行镀敷处理，制造复合铜箔。镀敷处理方法可以使用公知的技术，例如，作为铜以外的金属，可以使用Sn、Ag、Zn、Al、Ti、Bi、Cr、Fe、Co、Ni、Pd、Au、Pt或者各种合金。镀敷工序也没有特别限定，可以通过电解镀敷、无电解镀敷、真空蒸镀、化成处理等进行镀敷。
在无电解镍镀敷的情况下，优选进行使用催化剂的处理。作为催化剂，优选使用铁、钴、镍、钌、铑、钯、锇、铱和它们的盐。通过进行使用催化剂的处理，能够得到均匀且颗粒不零散存在的金属层。由此，复合铜箔的耐热性提高。在无电解镍镀敷的情况下，作为还原剂，优选使用铜和氧化铜不具有催化剂活性的还原剂。作为铜和氧化铜不具有催化剂活性的还原剂，可以列举次磷酸钠等次磷酸盐。
这样，通过对铜箔进行第一工序和第二工序，能够制造表面具有凸部的复合铜箔。凸部的Ra没有特别限定，优选为0.02μm以上、更优选为0.04μm以上，另外，优选为0.20μm以下、更优选为0.05μm以下。对于本领域技术人员而言，容易设定能够得到这样的氧化铜的方式的温度、时间等的条件。
对通过这些工序制造的铜箔，可以进行使用硅烷偶联剂等的偶联处理、使用苯并三唑类等的防锈处理。
另外，可以在通过这些工序制造的铜箔与预成型坯之间设置粘接层。粘接层的形成方法没有特别限定，例如可以叠层粘接性树脂膜，也可以通过涂布树脂清漆来形成。
实施例
在实施例和比较例1中，作为铜箔使用DR－WS(古河电工株式会社制、厚度：18μm)，对光亮(shiny)面(光泽面。与相反面比较时更平坦的面。)进行镀敷处理。对于比较例2，采用电解铜箔F2－WS(古河电工株式会社制、厚度：18μm)的哑光(matt)面。以下，对其工序的详细进行说明。
(1)碱处理
用1.2g/L的氢氧化钠水溶液在40℃进行1分钟预调理。这是为了以减轻氧化处理的不均匀为目的的脱脂清洗。需要说明的是，对比较例2不进行碱处理。
(2)氧化处理
对进行碱处理后的铜箔，用氧化处理用水溶液(NaClO2 130g/L-NaOH 12g/L)在45℃进行1分钟氧化处理。需要说明的是，对比较例2不进行氧化处理。这些处理后，对铜箔进行水洗。
(3)镀敷处理
关于进行氧化处理后的铜箔，对实施例1～3，使用镀镍用电解液(氨基磺酸镍470g/L－硼酸40g/L)实施电解镀敷。
对实施例5，使用镀铬用电解液(無水铬酸100g/L－硫酸1g/L)实施电解镀敷。对实施例6，使用镀锌用电解液(氧化锌10g/L－氢氧化钠115g/L－9500A 5ml/L(日本表面化学株式会社制)-9500B 0.5ml/L(日本表面化学株式会社制)－Hyper Soft 10ml/L(日本表面化学株式会社制))实施电解镀敷。温度、时间、电流密度等的条件如表1所记载。对比较例1，不进行任何镀敷处理的工序。对实施例4，使用感光溶液(1.0g/L氯化锡、0.5～3.0mL/L盐酸)在30℃进行1分钟处理、使用活化溶液(100mg/L氯化钯、0.1mL/L盐酸)在30℃进行1分钟处理，之后使用Ni－P镀敷溶液(BLUE SUMER、Japan Kanigen Co.,Ltd.)在90℃进行5秒钟无电解镀敷。
在实施例7中，使用对在实施例2得到的铜箔在硅烷偶联剂(Shin-Etsu Silicone制KBM－803)1wt％水溶液中以室温浸渍1分钟后、在70℃的干燥机内干燥1分钟而制成的铜箔。
[表1]
Figure BDA0002489016730000071
(4)凸部的高度和个数、以及表面粗糙度的测定
测定实施例1～6和比较例1～2所得到的复合铜箔的凸部的高度和个数、以及表面粗糙度。具体而言，利用共聚焦扫描电子显微镜控制器MC－1000A(Lasertec Corporation制)进行测定。在扫描型电子显微镜(SEM)图像中，将连接夹着凸部邻接的凹部的极小点而成的线段的中点与位于凹部之间的凸部的极大点的距离作为凸部的高度。利用5个独立位置的SEM图像，对1个图像测定3处，计算其平均值，作为凸部的平均高度。接下来，在5个SEM图像中，计数每3.8μm中的高度为50nm以上的凸部的个数，计算5个平均值。以算术平均粗糙度(Ra)计算表面粗糙度。将扫描电子显微镜的观察结果示于图1，将各测定结果示于表2。其中，Ra的值越低，表示铜箔表面的表面粗糙度越小。
(5)Cu以外的金属量的测定
对实施镀敷后的实施例1～6的铜箔，测定Cu以外的金属量。具体而言，将实施了镀敷的铜箔和没有实施镀敷的铜箔以3cm见方切断，分别溶解于12％硝酸水溶液中，利用高频感应耦合等离子体(ICP)分析法测定铜箔每单面的金属量，将其差作为Cu以外的金属量。将其结果示于表2。
(6)密合性的测定I剥离强度的测定
对实施例1～7和比较例1～2的各铜箔，测定叠层后的剥离强度和热处理后的剥离强度。首先，对各铜箔，叠层预成型坯(R5670KJ(松下株式会社制)，使用真空高压压制机在真空中以210℃保持30分钟，由此得到测定试样(Initial)。为了测试对热的耐性，在177℃的炉中投入10天，得到测定试样(耐热试验)。对这些测定试样通过90°剥离试验(日本工业规格(JIS)C5016)求出剥离强度(kgf/cm)。另外，在实施例8中，对在实施例2得到的铜箔，在箔与预成型坯之间作为粘接树脂层夹入以苯醚低聚物和弹性体为主成分的粘接膜(NAMICSCORPORATION制、NC0207)，利用真空高压压制机在真空中以210℃保持30分钟，由此得到测定试样(初始状态，Initial)，进而在同样的条件测定热处理后的剥离强度。剥离强度越大，表示预成型坯与铜箔的密合性越高。将其结果示于表3。
此外，耐热劣化率用以下的式子计算。
耐热劣化率(％)＝100－((耐热试验后的剥离强度/初始状态的剥离强度)×100)
(7)密合性的测定II渗出的判定
对实施例1～6和比较例1～2的各铜箔，为了测试对酸的耐性，将叠层后的铜箔在HCl水溶液(4N)中在60℃浸渍90分钟，得到测定试样，进行90°剥离试验(日本工业规格(JIS)C5016)。这时，在铜箔侧的粘接面，检查是否因渗出而发生颜色变化。将其结果示于表3。
(8)结果
[表2]
Figure BDA0002489016730000081
[表3]
Figure BDA0002489016730000091
关于没有进行氧化处理和镀敷处理的比较例2，凸部的高度极度高，表面粗糙度也显著粗糙。关于仅进行氧化处理、而未进行镀敷处理的比较例1，虽然表面粗糙度和剥离强度均为没有问题的水平，但发生耐酸试验后的渗出，并且耐热劣化率高。
另一方面，进行了氧化处理和适当的强度的镀敷处理的实施例1～6中，与镀敷处理的方法和被覆金属的种类无关地，任一因子均为没有问题的值。可以认为镀敷处理提高密合性。其中，实施例1中，虽然如表2记载未观察到凹凸，但如表3所记载，性能没有问题。
另外，即使如实施例7那样对所制造的铜箔进行偶联处理，或者如实施例8那样在所制造的铜箔与预成型坯之间设置粘接层，也如表3所记载，铜箔的性能没有问题。
如此，通过在利用氧化处理的表面粗化后进行镀敷处理，能够制作剥离强度、耐酸试验后的渗出、耐热劣化率优异的铜箔，该复合铜箔能够很好地用于印刷电路板。
产业上的可利用性
根据本发明，能够提供新型的复合铜箔。

Claims (13)

1.一种复合铜箔，其特征在于：
其为在铜箔的至少一部分的表面形成有铜以外的金属层的复合铜箔，
在至少一部分的所述复合铜箔的表面具有凸部，
在所述复合铜箔的截面，所述凸部的高度为10nm以上1000nm以下。
2.如权利要求1所述的复合铜箔，其特征在于：
在深度6nm处，Cu相对于该处总金属量的比例为80％以下；
在不含氧的深度，Cu相对于该处总金属量的比例为90％以上。
3.如权利要求1或2所述的复合铜箔，其特征在于：
所述凸部的高度为50nm以上500nm以下。
4.如权利要求1～3中任一项所述的复合铜箔，其特征在于：
在所述复合铜箔的截面，高度为50nm以上的凸部在每3.8μm中平均存在15个以上100个以下。
5.如权利要求1～4中任一项所述的物体，其特征在于：
在利用扫描电子显微镜得到的截面的摄影像中，以连接凸部两侧的凹部的极小点的线段的中点与凸部的极大点的距离，测定所述凸部的高度。
6.如权利要求1～5中任一项所述的复合铜箔，其特征在于：
所述金属层均匀且没有颗粒。
7.如权利要求1～6中任一项所述的复合铜箔，其特征在于：
Cu的比例为40atom％的深度处的Cu/O比在0.9以上。
8.如权利要求1～7中任一项所述的复合铜箔，其特征在于：
所述铜以外的金属为选自Sn、Ag、Zn、Al、Ti、Bi、Cr、Fe、Co、Ni、Pd、Au和Pt中的至少一种金属。
9.一种复合铜箔的制造方法，其特征在于，包括：
将铜箔表面氧化的第一工序；和
对经氧化的所述铜表面进行镀敷处理的第二工序。
10.如权利要求9所述的制造方法，其特征在于：
在第一工序前，用碱性水溶液进行碱处理。
11.如权利要求9或10所述的复合铜箔的制造方法，其特征在于：
在第一工序中，经氧化的所述铜箔表面被溶解剂溶解。
12.如权利要求9～11中任一项所述的复合铜箔的制造方法，其特征在于：
在第二工序中，所述镀敷处理为使用催化剂的无电解镀敷。
13.如权利要求9～12中任一项所述的复合铜箔的制造方法，其特征在于：
在第二工序中，所述镀敷处理为电解镀敷。
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