TWI457230B - Attached copper foil - Google Patents

Attached copper foil Download PDF

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Publication number
TWI457230B
TWI457230B TW101131657A TW101131657A TWI457230B TW I457230 B TWI457230 B TW I457230B TW 101131657 A TW101131657 A TW 101131657A TW 101131657 A TW101131657 A TW 101131657A TW I457230 B TWI457230 B TW I457230B
Authority
TW
Taiwan
Prior art keywords
layer
carrier
copper foil
copper
ultra
Prior art date
Application number
TW101131657A
Other languages
English (en)
Other versions
TW201323196A (zh
Inventor
Tomota Nagaura
Kazuhiko Sakaguchi
Original Assignee
Jx Nippon Mining & Metals Corp
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Publication date
Application filed by Jx Nippon Mining & Metals Corp filed Critical Jx Nippon Mining & Metals Corp
Publication of TW201323196A publication Critical patent/TW201323196A/zh
Application granted granted Critical
Publication of TWI457230B publication Critical patent/TWI457230B/zh

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • 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
    • 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
    • C23C28/02—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 only coatings only including layers of metallic material
    • C23C28/023—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 only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/04—Wires; Strips; Foils
    • 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
    • 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
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/38—Chromatising
    • 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
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • 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
    • C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
    • C25D3/16—Acetylenic compounds
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions 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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • H05K2201/0302—Properties and characteristics in general
    • H05K2201/0317—Thin film conductor layer; Thin film passive component
    • 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
    • H05K2201/032—Materials
    • 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
    • H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer or layered thin film adhesion layer
    • 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
    • H05K2203/03—Metal processing
    • H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
    • H05K3/025—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates by transfer of thin metal foil formed on a temporary carrier, e.g. peel-apart copper
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12431—Foil or filament smaller than 6 mils
    • Y10T428/12438—Composite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/125—Deflectable by temperature change [e.g., thermostat element]
    • Y10T428/12514—One component Cu-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/1266—O, S, or organic compound in metal component
    • Y10T428/12667—Oxide of transition metal or Al
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T428/12882—Cu-base component alternative to Ag-, Au-, or Ni-base component
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    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12903—Cu-base component
    • Y10T428/1291—Next to Co-, Cu-, or Ni-base component
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    • Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other
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    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12958—Next to Fe-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Description

附載體銅箔
本發明係關於一種附載體銅箔。更詳細而言，本發明係關於一種用作印刷配線板之材料之附載體銅箔。
通常，印刷配線板係於使絕緣基板接著於銅箔而製成覆銅積層板後，再經過藉由蝕刻而於銅箔面形成導體圖案等步驟而製造。伴隨著近年來電子機器之小型化、高性能化之需求增大，而發展搭載零件之高密度構裝化或信號之高頻化，對於印刷配線板要求導體圖案之微細化(細間距化)或高頻對應等。
對應於細間距化，最近要求厚度9μm以下、甚至是厚度5μm以下之銅箔，但此種極薄之銅箔機械強度較低，於製造印刷配線板時易於破損或產生褶皺，因此，出現一種將具有一定厚度之金屬箔用作載體並於其介隔剝離層而電鍍有極薄銅層的附載體銅箔。附載體銅箔之通常之使用方法為：使極薄銅層之表面貼合於絕緣基板並進行熱壓接後，經由剝離層而剝離載體。
已知，先前作為剝離層，係由Cr、Ni、Co、Fe、Mo、Ti、W、P、或該等之合金、或該等之水合物形成。進而，亦記載有下述情況：於謀求加熱壓製等高溫使用環境之剝離性之穩定化方面，若於剝離層之基底設置Ni、Fe或該等之合金層，則較為有效。(日本特開2010-006071號公報、日本特開2007-007937號公報)
該等文獻中存在下述情況：對剝離層上之鍍敷係因其剝離性而非常難以進行均勻之鍍敷，因此，根據鍍敷條件之不同，於所形成之極薄銅箔上針孔之數量變多。因此，亦記載有下述情況：首先於剝離層上進行預鍍銅，進而於預鍍層上鍍銅，藉此可於剝離層上實施均勻之鍍敷，從而可明顯地減少極薄銅箔之針孔數。
[專利文獻1]日本特開2010-006071號公報
[專利文獻2]日本特開2007-007937號公報
於附載體銅箔中，必需避免於對絕緣基板進行積層步驟前極薄銅層自載體剝離，另一方面，於對絕緣基板進行積層步驟後極薄銅層必需可自載體剝離。又，於附載體銅箔中，於極薄銅層側之表面存在針孔之情況會導致印刷配線板之性能不良而欠佳。
關於該等方面，於先前技術中尚未進行充分研究，仍留有改善空間。因此，本發明之課題在於提供一種於對絕緣基板進形積層步驟前極薄銅層不會自載體剝離而另一方面於對絕緣基板進行積層步驟後可剝離的附載體銅箔。進而，本發明之課題亦在於提供一種於極薄銅層側表面之針孔的產生受到抑制的附載體銅箔。
為了達成上述目的，本發明人等反覆進行潛心研究，結果發現下述情況極為有效：使用銅箔作為載體，並使由Ni層及極薄之Cr層此2層構成之中間層形成於極薄銅層與載體之間。
本發明係基於上述認知而完成者，於一種態樣中為一種附載體銅箔，其具備有銅箔載體、積層於銅箔載體上之中間層、及積層於中間層上之極薄銅層，中間層由與銅箔載體之界面連接的Ni層及與極薄銅層之界面連接的Cr層構成，Ni層存在1000~40000μg/dm2 之Ni，Cr層存在10~100μg/dm2 之Cr。
於本發明之附載體銅箔之一實施形態中，Ni量為1000~10000μg/dm2 ，Cr量為10~50μg/dm2 。
於本發明之附載體銅箔之另一實施形態中，將Cr相對於Ni之質量比擴大1000倍之值處於0.5~10之範圍。
於本發明之附載體銅箔之又一實施形態中，Cr係藉由電解鉻酸鹽而附著。
本發明之附載體銅箔於對絕緣基板進行積層步驟前，於載體與極薄銅層之間獲得必要之密合性，另一方面，於對絕緣基板進行積層步驟後，極薄銅層可容易地自載體剝離。又，本發明之附載體銅箔中針孔之產生受到抑制，因此可穩定地提供高品質之極薄銅層。
<1.載體>
使用銅箔作為可使用於本發明中之載體。載體於典型情況下係以壓延銅箔或電解銅箔之形態來提供。通常，電解銅箔係使銅自硫酸銅鍍浴電解析出於鈦或不鏽鋼之滾筒上而製造，壓延銅箔係反覆進行利用壓延輥之塑性加工與熱處理而製造。銅箔之材料，除精銅或無氧銅等高純度銅 外，亦可使用例如摻有Sn之銅、摻有Ag之銅、添加有Cr、Zr或Mg等之銅合金、添加有Ni及Si等之卡遜系銅合金等銅合金。再者，於本說明書中，單獨使用「銅箔」一詞時認為亦包括銅合金箔。
關於可使用於本發明中之載體之厚度亦無特別限制，只要適當調節為適於發揮作為載體之作用之厚度即可，例如可設為12μm以上。然而，若過厚，則生產成本變高，因此通常較佳為設為70μm以下。因此，載體之厚度於典型情況下為12~70μm，更典型情況下為18~35μm。
<2.中間層>
於銅箔載體之單面或兩面上設置由Ni及Cr此2層構成之中間層。以Ni層連接於與銅箔載體之界面、Cr層連接於與極薄銅層之界面的方式進行積層。下述所述，Ni與Cu之接著力高於Cr與Cu之接著力，因此於剝離極薄銅層時，係於極薄銅層與Cr層之界面上進行剝離。中間層中，期待Ni層具有防止Cu成分逐漸自載體向極薄銅箔擴散之阻障效果。於僅於單面設置中間層之情形時，較佳為於銅箔載體之相反面設置鍍Ni層等防銹層。又，於使用電解銅箔作為載體之情形時，就減少針孔之觀點而言，較佳為於光潤面設置中間層。
構成中間層之Ni層例如可藉由電鍍、非電解鍍敷及浸漬鍍敷等濕式鍍敷、或者濺鍍、CVD及PVD等乾式鍍敷而獲得。就成本之觀點而言，較佳為電鍍。
中間層中Cr層係較薄地存在於極薄銅層之界面，該情 況於獲得下述特性方面極其重要：於對絕緣基板進行積層步驟前極薄銅層不自載體剝離，另一方面於對絕緣基板進行積層步驟後極薄銅層可自載體剝離。於不設置Ni層而使Cr層存在於載體與極薄銅層之邊界之情形時，剝離性幾乎未提高，於無Cr層而直接積層Ni層與極薄銅層之情形時，根據Ni層中之Ni量，剝離強度會過強或過弱，而無法獲得適當之剝離強度。再者，亦可於Cr層中混入Zn。
又，若Cr層存在於載體與Ni層之邊界，則於極薄銅層之剝離時中間層亦隨之剝離，即於載體與中間層之間產生剝離，因此欠佳。此種狀況不僅可於在與載體之界面設置有Cr層之情形時產生，即便於與極薄銅層之界面設置有Cr層，若Cr量過多則亦可產生。一般認為其原因在於：Cu與Ni易固溶，因此若該等接觸，則因相互擴散而接著力變高難以剝離，另一方面，Cr與Cu難以固溶而難以產生相互擴散，因此於Cr與Cu之界面上接著力較弱而易於剝離。又，於中間層之Ni量不足之情形時，於載體與極薄銅層之間僅存在微量之Cr，因此兩者密合而難以剝離。
為了使Cr層存在於極薄銅層之界面，可藉由下述方式而實現：於形成Ni層後，藉由例如電解鉻酸鹽、電鍍、非電解鍍敷及浸漬鍍敷等濕式鍍敷、或者濺鍍、CVD及PVD等乾式鍍敷而使微量之Cr附著，並於其上形成極薄銅層。就以低成本使微量之Cr附著之觀點而言，較佳為電解鉻酸鹽。
於本發明中，Ni量係以濃度20質量%之硝酸溶解樣品 並利用ICP發光分析進行測定，Cr量係藉由以濃度7質量%之鹽酸溶解樣品並利用原子吸光法進行定量分析而測定。再者，於對極薄銅層之表面進行了含有Ni或Cr之鍍敷等表面處理之情形時，自附載體銅箔剝離極薄銅層，並對剩餘之載體進行上述Ni量與Cr量之測定即可。
就上述觀點而言，於本發明中，將中間層之Cr的附著量設為10~100μg/dm2 ，將Ni的附著量設為1000~40000μg/dm2 。又，存在伴隨Ni量增加而針孔量變多之傾向，但若處於該範圍內，則亦可抑制針孔數量。就無不均而均勻地剝離極薄銅層之觀點、及抑制針孔之觀點而言，Cr附著量較佳設為10~50μg/dm2 ，更佳設為10~40μg/dm2 ，Ni附著量較佳設為1000~10000μg/dm2 ，更佳設為1500~9000μg/dm2 。
又，較佳為，將Cr相對於Ni之質量比擴大1000倍之值(=(Cr之附著量(μg/dm2 ))/(Ni之附著量(μg/dm2 ))×1000)處於0.5~10之範圍，更佳為處於1~9之範圍。其原因在於：藉由使Cr相對於Ni之量為該範圍，以抑制針孔及提高極薄銅箔之剝離特性。
<3.極薄銅層>
於中間層上設置極薄銅層。極薄銅層可藉由利用硫酸銅、焦磷酸銅、胺基磺酸銅、氰化銅等之電解浴的電鍍而形成，就用於一般之電解銅箔中、且可於高電流密度形成銅箔方面而言，較佳為硫酸銅浴。極薄銅層之厚度並無特別限制，但通常比載體薄，例如為12μm以下。典型情況 下為0.5~12μm，更典型情況下為2~5μm。
<4.粗化處理>
例如為了使極薄銅層之表面與絕緣基板之密合性變良好等，亦可於該表面藉由實施粗化處理而設置粗化處理層。粗化處理例如可藉由以銅或銅合金形成粗化粒子而進行。粗化處理亦可微細。粗化處理層亦可為由選自由銅、鎳、磷、鎢、砷、鉬、鉻、鈷及鋅所組成之群中之任一單體、或包含任意1種以上之合金構成的層等。又，亦可於進行粗化處理後、或不進行粗化處理而由鎳、鈷、銅、鋅之單體或合金等形成二次粒子或三次粒子及/或防銹層，並進而對其表面實施鉻酸鹽處理、矽烷偶合劑處理等處理。即，可於粗化處理層之表面形成選自由防銹層、鉻酸鹽處理層及矽烷偶合劑處理層組成之群中之1種以上之層，亦可於極薄銅層之表面形成選自由防銹層、鉻酸鹽處理層及矽烷偶合劑處理層組成之群中之1種以上之層。
<5.附載體銅箔>
以此方式，而製造具備有銅箔載體、於銅箔載體上依序積層有Ni層及Cr層之中間層、及積層於中間層上之極薄銅層的附載體銅箔。附載體銅箔本身之使用方法係業者周知，例如可於使極薄銅層之表面貼合於紙基材酚樹脂、紙基材環氧樹脂、合成纖維布基材環氧樹脂、玻璃布/紙複合基材環氧樹脂、玻璃布/玻璃不織布複合基材環氧樹脂及玻璃布基材環氧樹脂、聚酯膜、聚醯亞胺膜等絕緣基板並進行熱壓接後剝離載體，將接著於絕緣基板之極薄銅 層蝕刻成目標之導體圖案，而最終製造印刷配線板。於本發明之附載體銅箔之情形時，剝離部位主要為Cr層與極薄銅層之界面。
[實施例]
以下，藉由本發明之實施例而進一步詳細地說明本發明，但本發明不受該等實施例任何限定。
1.附載體銅箔之製造
<No.1>
準備厚度35μm之長條電解銅箔(JX日鑛日石金屬公司製造，JTC)作為銅箔載體。以下述條件於繞捲型連續鍍敷線對該銅箔之光潤面進行電鍍，藉此形成4000μg/dm2 之附著量之Ni層。
‧Ni層
硫酸鎳：250~300g/L
氯化鎳：35~45g/L
乙酸鎳：10~20g/L
檸檬酸三鈉：15~30g/L
光澤劑：糖精、丁炔二醇等
十二烷基硫酸鈉：30~100ppm
pH值：4~6
浴溫：50~70℃
電流密度：3~15A/dm2
於水洗及酸洗後，繼而於繞捲型連續鍍敷線上，以下述條件進行電解鉻酸鹽，藉此而使11μg/dm2 之附著量之 Cr層附著於Ni層上。
‧電解鉻酸鹽處理
液組成：重鉻酸鉀1~10g/L、鋅0~5g/L
pH值：3~4
液溫：50~60℃
電流密度：0.1~2.6A/dm2
庫侖量：0.5~30As/dm2
繼而，於繞捲型連續鍍敷線上，以下述條件進行電鍍，藉此而於Cr層上形成厚度5~10μm之極薄銅層，從而製造附載體銅箔。
‧極薄銅層
銅濃度：30~120g/L
H2 SO4 濃度：20~120g/L
電解液溫度：20~80℃
電流密度：10~100A/dm2
<No.2~23>
相對於No.1，藉由調整線速度，而製作Ni附著量及Cr附著量如表1所記載般發生多種變更之No.2~23之附載體銅箔。Ni附著量或Cr附著量為0之例係未實施鍍Ni或電解鉻酸鹽處理。
又，對於No.1、7、14、18，對極薄銅層表面依次進行以下之粗化處理、防銹處理、鉻酸鹽處理、及矽烷偶合劑處理。
‧粗化處理
Cu：10~20g/L
Co：1~10g/L
Ni：1~10g/L
pH值：1~4
液溫：40~50℃
電流密度Dk：20~30A/dm2
時間：1~5秒
Cu附著量：15~40mg/dm2
Co附著量：100~3000μg/dm2
Ni附著量：100~1000μg/dm2
‧防銹處理
Zn：超過0~20g/L
Ni：超過0~5g/L
pH值：2.5~4.5
液溫：30~50℃
電流密度Dk：超過0~1.7A/dm2
時間：1秒
Zn附著量：5~250μg/dm2
Ni附著量：5~300μg/dm2
‧鉻酸鹽處理
K2 Cr2 O7
(Na2 Cr2 O7 或者CrO3 )：2~10g/L
NaOH或者KOH：10~50g/L
ZnO或者ZnSO4 ‧7H2 O：0.05~10g/L
pH值：7~13
浴溫：20~80℃
電流密度：0.05~5A/dm2
時間：5~30秒
Cr附著量：10~150μg/dm2
‧矽烷偶合劑處理
乙烯基三乙氧基矽烷水溶液
(乙烯基三乙氧基矽烷濃度：0.1~1.4wt%)
pH值：4~5
浴溫：25~60℃
浸漬時間：5~30秒
又，對於No.4、5、19、20、21，對極薄銅層表面依次進行以下之粗化處理1、粗化處理2、防銹處理、鉻酸鹽處理、及矽烷偶合劑處理。
‧粗化處理1
(液組成1)
Cu：10~30g/L
H2 SO4 ：10~150g/L
W：0~50mg/L
十二烷基硫酸鈉：0~50mg/L
As：0~200mg/L
(電鍍條件1)
溫度：30~70℃
電流密度：25~110A/dm2
粗化庫侖量：50~500As/dm2
鍍敷時間：0.5~20秒
‧粗化處理2
(液組成2)
Cu：20~80g/L
H2 SO4 ：50~200g/L
(電鍍條件2)
溫度：30~70℃
電流密度：5~50A/dm2
粗化庫侖量：50~300As/dm2
鍍敷時間：1~60秒
‧防銹處理
(液組成)
NaOH：40~200g/L
NaCN：70~250g/L
CuCN：50~200g/L
Zn(CN)2 ：2~100g/L
As2 O3 ：0.01~1g/L
(液溫)
40~90℃
(電流條件)
電流密度：1~50A/dm2
鍍敷時間：1~20秒
‧鉻酸鹽處理
K2 Cr2 O7 (Na2 Cr2 O7 或者CrO3 )：2~10g/L
NaOH或KOH：10~50g/L
ZnOH或ZnSO4 ‧7H2 O：0.05~10g/L
pH值：7~13
浴溫：20~80℃
電流密度：0.05~5A/dm2
時間：5~30秒
‧矽烷偶合劑處理
於噴塗0.1vol%~0.3vol%之3-縮水甘油氧丙基三甲氧基矽烷水溶液後，於100~200℃之空氣中進行0.1~10秒鐘之乾燥/加熱。
又，對於No.2、6、8、22、23，對極薄銅層表面依次進行以下之粗化處理1、粗化處理2、防銹處理、鉻酸鹽處理、及矽烷偶合劑處理。
‧粗化處理1
液組成：銅10~20g/L、硫酸50~100g/L
液溫：25~50℃
電流密度：1~58A/dm2
庫侖量：4~81As/dm2
‧粗化處理2
液組成：銅10~20g/L、鎳5~15g/L、鈷5~15g/L
pH值：2~3
液溫：30~50℃
電流密度：24~50A/dm2
庫侖量：34~48As/dm2
‧防銹處理
液組成：鎳5~20g/L、鈷1~8g/L
pH值：2~3
液溫：40~60℃
電流密度：5~20A/dm2
庫侖量：10~20As/dm2
‧鉻酸鹽處理
液組成：重鉻酸鉀1~10g/L、鋅0~5g/L
pH值：3~4
液溫：50~60℃
電流密度：0~2A/dm2 (由於為浸漬鉻酸鹽處理，故亦可於無電解情況下實施)
庫侖量：0~2As/dm2 (由於為浸漬鉻酸鹽處理，故亦可於無電解情況下實施)
‧矽烷偶合劑處理
二胺基矽烷水溶液之塗佈(二胺基矽烷濃度：0.1~0.5wt%)
2.附載體銅箔之特性評價
對以上述方式獲得之附載體銅箔以下述方法實施特性評價。將結果示於表1。再者，對於No.1~8、14、18~23，亦對未對極薄銅層表面進行表面處理之情形、以及進行表面處理之情形進行特性評價。表1之結果係未對極薄銅層 表面進行表面處理之情形時的結果。對極薄銅層表面進行表面處理之情形時特性評價之結果與未對極薄銅層表面進行表面處理之情形時之特性評價的結果相同。
<針孔>
以民用之照片用背光為光源，並以目視測定針孔之數量。評價係依據以下基準進行。
×：針孔超過10,000個/dm2
△：局部地存在超過10,000個/dm2 之部位
○：針孔為100~10,000個/dm2
◎：針孔未達100個/dm2
<剝離強度(BT壓製後)>
將附載體銅箔之極薄銅層側與BT基板貼合，以195℃壓製2h，利用測力計剝離載體箔側，藉此測定剝離強度。

Claims (20)

  1. 一種附載體銅箔，其具備有銅箔載體、積層於銅箔載體上之中間層、及積層於中間層上之極薄銅層；中間層由與銅箔載體之界面連接的Ni層及與極薄銅層之界面連接的含Cr層構成，Ni層存在1000~40000μg/dm2 之Ni，含Cr層存在10~100μg/dm2 之Cr。
  2. 如申請專利範圍第1項之附載體銅箔，其中，含Cr層係藉由電解鉻酸鹽、溼式鍍敷或乾式鍍敷來形成。
  3. 如申請專利範圍第1項之附載體銅箔，其中，Ni之附著量為1000~10000μg/dm2 ，Cr之附著量為10~50μg/dm2 。
  4. 如申請專利範圍第1項之附載體銅箔，其中，將Cr相對於Ni之質量比擴大1000倍之值處於0.5~10的範圍。
  5. 如申請專利範圍第1項之附載體銅箔，其中，Cr係藉由電解鉻酸鹽而附著。
  6. 如申請專利範圍第1項之附載體銅箔，其中，於該極薄銅層表面具有粗化處理層。
  7. 如申請專利範圍第6項之附載體銅箔，其中，該粗化處理層係由選自由銅、鎳、磷、鎢、砷、鉬、鉻、鈷及鋅所組成之群中之任一單體、或包含任意1種以上之合金構成的層。
  8. 如申請專利範圍第6項之附載體銅箔，其中，該粗化處理層之表面具有選自由防銹層、鉻酸鹽處理層及矽烷偶合劑處理層組成之群中之1種以上之層。
  9. 如申請專利範圍第1項之附載體銅箔，其中，該極薄銅層之表面具有選自由防銹層、鉻酸鹽處理層及矽烷偶合劑處理層組成之群中之1種以上之層。
  10. 一種附載體銅箔，其具備有銅箔載體、積層於銅箔載體上之中間層、及積層於中間層上之極薄銅層；中間層由與銅箔載體之界面連接的Ni層及與極薄銅層之界面連接的鍍鉻酸鹽或鍍Cr層構成，Ni層存在1000~40000μg/dm2 之Ni，鍍鉻酸鹽或鍍Cr層存在10~100μg/dm2 之Cr。
  11. 如申請專利範圍第10項之附載體銅箔，其中，Ni之附著量為1000~10000μg/dm2 ，Cr之附著量為10~50μg/dm2 。
  12. 如申請專利範圍第10項之附載體銅箔，其中，將Cr相對於Ni之質量比擴大1000倍之值處於0.5~10的範圍。
  13. 如申請專利範圍第10項之附載體銅箔，其中，Cr係藉由電解鉻酸鹽而附著。
  14. 如申請專利範圍第10項之附載體銅箔，其中，於該極薄銅層表面具有粗化處理層。
  15. 如申請專利範圍第14項之附載體銅箔，其中，該粗化處理層係由選自由銅、鎳、磷、鎢、砷、鉬、鉻、鈷及鋅所組成之群中之任一單體、或包含任意1種以上之合金構成的層。
  16. 如申請專利範圍第14項之附載體銅箔，其中，該粗化處理層之表面具有選自由防銹層、鉻酸鹽處理層及矽烷 偶合劑處理層組成之群中之1種以上之層。
  17. 如申請專利範圍第10項之附載體銅箔，其中，該極薄銅層之表面具有選自由防銹層、鉻酸鹽處理層及矽烷偶合劑處理層組成之群中之1種以上之層。
  18. 一種印刷配線板，其係使用申請專利範圍第1至17項中任一項之附載體銅箔製造而成者。
  19. 一種覆銅積層板，其係使用申請專利範圍第1至17項中任一項之附載體銅箔製造而成者。
  20. 一種電子機器，使用有申請專利範圍第18項之印刷配線板。
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