WO2021157373A1 - キャリア付金属箔 - Google Patents
キャリア付金属箔 Download PDFInfo
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- WO2021157373A1 WO2021157373A1 PCT/JP2021/002033 JP2021002033W WO2021157373A1 WO 2021157373 A1 WO2021157373 A1 WO 2021157373A1 JP 2021002033 W JP2021002033 W JP 2021002033W WO 2021157373 A1 WO2021157373 A1 WO 2021157373A1
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
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- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/225—Nitrides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3615—Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0005—Separation of the coating from the substrate
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0605—Carbon
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0676—Oxynitrides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
- C23C14/5853—Oxidation
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—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
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/281—Nitrides
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/155—Deposition methods from the vapour phase by sputtering by reactive sputtering
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
- C03C2218/322—Oxidation
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- 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
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0147—Carriers and holders
- H05K2203/0152—Temporary metallic carrier, e.g. for transferring material
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0147—Carriers and holders
- H05K2203/0156—Temporary polymeric carrier or foil, e.g. for processing or transferring
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/01—Tools for processing; Objects used during processing
- H05K2203/0147—Carriers and holders
- H05K2203/016—Temporary inorganic, non-metallic carrier, e.g. for processing or transferring
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/46—Manufacturing multilayer circuits
- H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
- H05K3/4682—Manufacture of core-less build-up multilayer circuits on a temporary carrier or on a metal foil
Definitions
- the present invention relates to a metal leaf with a carrier.
- multilayer printed wiring boards are used in many portable electronic devices for the purpose of weight reduction and miniaturization. Further, the multilayer printed wiring board is required to further reduce the thickness of the interlayer insulating layer and further reduce the weight of the wiring board.
- the coreless build-up method is a method in which insulating layers and wiring layers are alternately laminated (built-up) to form multiple layers without using a so-called core substrate.
- the coreless build-up method it has been proposed to use a metal foil with a carrier so that the support and the multilayer printed wiring board can be easily peeled off.
- Patent Document 1 Japanese Unexamined Patent Publication No.
- an insulating resin layer is attached to the carrier surface of a copper foil with a carrier to form a support, and a photoresist process is performed on the ultrathin copper layer side of the copper foil with a carrier.
- a build-up wiring layer is formed by laminating insulating materials and performing hot press processing, and the support substrate with carrier is peeled off.
- a method for manufacturing a package substrate for mounting a semiconductor element which includes removing an ultrathin copper layer, is disclosed.
- the metal foil with a carrier is heated at a high temperature for a long time because heat pressing is performed every time the insulating material is laminated. Further, since the heating temperature of this heat press working depends on the curing temperature of the insulating material to be laminated, the temperature varies depending on the type of the insulating material. In this respect, it is known that the higher the heating temperature of the hot press processing, the excessively the peel strength increases and the peelability is lost.
- Patent Document 2 International Publication No. 2019/131000 describes a carrier, an intermediate layer composed of a predetermined metal, a release layer containing a metal oxide layer and a carbon layer, an etching stopper layer provided as desired, and the like. And a copper foil with a carrier having an ultra-thin copper layer in order is disclosed.
- a predetermined release layer stable release property is maintained even after being heated at a high temperature of 350 ° C. or higher for a long time. It is said that it will be possible to do so.
- this document also describes that an intermediate layer, a carbon layer, an ultrathin copper layer, etc. are formed by sputtering in order to further reduce the thickness of the ultrathin copper layer, etc. in the copper foil with a carrier. ing.
- Patent Document 3 Japanese Unexamined Patent Publication No. 2017-88970
- a copper foil with a carrier having a carrier having a carrier, an intermediate layer containing nickel, and an ultrathin copper layer in this order, after the intermediate layer is formed and before the ultrathin copper layer is formed.
- an oxide layer NiO 2
- NiO 2 is formed on the surface of nickel by drying the intermediate layer under the condition of 30 to 100 ° C. for 1 to 300 seconds.
- Patent Document 3 it is said that the variation in peel strength after the ultra-thin copper layer side of the copper foil with a carrier is bonded onto an insulating substrate and pressure-bonded at 220 ° C. for 2 hours can be satisfactorily suppressed. ing.
- the metal foil with a carrier has heat resistance at a high temperature of, for example, 240 ° C. or higher. ..
- the metal leaf with a carrier provided with an intermediate layer containing Ni and NiO 2 disclosed in Patent Document 3 is stable at a hot press temperature of about 220 ° C. as described above, but has a low peel strength at 240 ° C. It does not correspond to the above-mentioned hot press working at a higher temperature.
- Patent Document 2 by using a metal foil with a carrier provided with a release layer containing a metal oxide layer and a carbon layer, stable release is performed even after being heated at a high temperature for a long time. Can retain sex.
- a carbon layer is formed as a release layer and a metal layer is formed on the carbon layer, foreign particles on the surface of the metal layer do not form the carbon layer (for example, when the metal layer is directly formed on the glass carrier). It turned out to increase in comparison. There is a concern that the foreign matter particles may affect the circuit formation in the subsequent process. Therefore, there is a demand for a metal foil with a carrier that can suppress the number of foreign matter particles while maintaining heat resistance.
- the present inventors have recently suppressed the number of foreign matter particles on the surface of the metal layer by interposing a peeling functional layer containing a predetermined metal oxynitride between the carrier of the metal foil with a carrier and the metal layer. It is possible to provide a metal foil with a carrier that can improve circuit formability and maintain stable peel strength even after being heated at a high temperature of 240 ° C. or higher (for example, 260 ° C.) for a long time. I got the knowledge.
- an object of the present invention is to suppress the number of foreign matter particles on the surface of the metal layer to improve circuit formability, and to be stable even after being heated at a high temperature of 240 ° C. or higher (for example, 260 ° C.) for a long time. It is an object of the present invention to provide a metal foil with a carrier capable of maintaining peelability.
- the carrier-attached metal foil 10 of the present invention includes a carrier 12, a peeling functional layer 14, and a metal layer 16 in this order.
- the peeling functional layer 14 is provided on the carrier 12 and is a layer containing a metal oxynitride.
- the metal layer 16 is a layer provided on the peeling function layer 14. In this way, by interposing the peeling functional layer 14 containing the metal oxynitride between the carrier 12 of the metal foil 10 with a carrier and the metal layer 16, the number of foreign particles on the surface of the metal layer 16 is suppressed and the circuit is performed. It is possible to provide a metal foil with a carrier which can improve formability and can maintain stable peeling strength even after being heated at a high temperature of 240 ° C. or higher (for example, 260 ° C.) for a long time. ..
- the metal leaf with a carrier provided with an intermediate layer containing Ni and NiO 2 as disclosed in Patent Document 3 is stable at a hot press temperature of about 220 ° C. at a low level of peel strength, but 240. It is not compatible with hot press working at high temperatures such as ° C or higher.
- Patent Document 2 by using a metal foil with a carrier provided with a release layer containing a metal oxide layer and a carbon layer, stable release is performed even after being heated at a high temperature for a long time. Can retain sex.
- the inclusion of the carbon layer in the release layer may affect the circuit formation in the subsequent process.
- FIG. 3 it is composed of a carrier 112 made of glass, an adhesion layer 114 made of Ti, a peeling auxiliary layer 116 made of Cu, a carbon layer 118 as a peeling layer, and Ti.
- the number of foreign matter particles (particle size of 5 ⁇ m or more) per square centimeter existing on the surface of the first metal layer 122 in the formed metal foil 110'with a carrier is shown in FIG.
- the bar graph on the left side shows the number of foreign particles of the carrier-attached metal leaf 110'without the carbon layer 118
- the right bar graph shows the number of foreign matter particles of the carrier-attached metal foil 110 having the carbon layer 118. show.
- the carrier-attached metal foil 110 having the carbon layer 118 has three times or more foreign particles on the surface of the first metal layer 122 as compared with the carrier-attached metal foil 110'without the carbon layer 118. It turns out that it exists. Then, there is a concern that the foreign matter particles may affect the circuit formation in the subsequent process.
- the carrier-attached metal foil 10 of the present invention includes a peeling functional layer 14 containing a metal oxynitride instead of the carbon layer. Therefore, it is considered that the metal foil 10 with a carrier can effectively suppress an increase in the number of foreign matter particles on the surface of the metal layer 16, and as a result, the circuit formation in the subsequent process can be satisfactorily performed. Even so, the metal foil 10 with a carrier provided with the peeling functional layer 14 containing the metal oxynitride has stable peeling strength even after being heated at a high temperature of 240 ° C. or higher (for example, 260 ° C.) for a long time. Can be retained.
- the peeling functional layer 14 containing the metal oxynitride can suppress an excessive increase in the peeling strength due to heating.
- a specific index of peel strength after pressing at 260 ° C. for 2 hours at a pressure of 30 kgf / cm 2 , it is preferably 3 gf / cm or more and less than 50 gf / cm, and more preferably 3 gf / cm or more and 30 gf / cm. Is less than.
- the material of the carrier 12 may be any of glass, ceramics, silicon, resin, and metal.
- the carrier 12 is made of glass, silicon or ceramics.
- the form of the carrier 12 may be any of a sheet, a film and a plate. Further, the carrier 12 may be one in which these sheets, films, plates and the like are laminated.
- the carrier 12 may function as a rigid support such as a glass plate, a ceramic plate, a silicon wafer, a metal plate, or the like, or may have a non-rigid form such as a metal foil or a resin film. May be good.
- Preferred examples of the metal constituting the carrier 12 include copper, titanium, nickel, stainless steel, aluminum and the like.
- Preferred examples of the ceramics include alumina, zirconia, silicon nitride, aluminum nitride, and various other fine ceramics.
- Preferred examples of the resin include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide, polyimide, nylon, liquid crystal polymer, polyetheretherketone (PEEK®), polyamideimide, polyethersulfon, and the like. Examples thereof include polyphenylene sulfide, polytetrafluoroethylene (PTFE), and ethylene tetrafluoroethylene (ETFE).
- the coefficient of thermal expansion (CTE) is less than 25 ppm / K (typically 1.0 ppm / K or more and 23 ppm / K or less) from the viewpoint of preventing warpage of the coreless support due to heating when mounting the electronic element. ), and examples of such materials include various resins (particularly low thermal expansion resins such as polyimide and liquid crystal polymers), glass, silicon, and ceramics as described above.
- the carrier 12 preferably has a Vickers hardness of 100 HV or more, more preferably 150 HV or more and 2500 HV or less.
- the carrier 12 is preferably composed of glass, silicon or ceramics, more preferably glass or ceramics, and particularly preferably glass.
- the carrier 12 made of glass include a glass plate.
- the carrier 12 has surface flatness (coplanarity) which is advantageous for forming fine circuits, desmear in a wiring manufacturing process, and chemical resistance in various plating processes, and a carrier.
- a chemical separation method can be adopted when the carrier 12 is peeled from the attached metal foil 10.
- the glass constituting the carrier 12 include quartz glass, borosilicate glass, non-alkali glass, soda lime glass, aluminosilicate glass, and combinations thereof, and more preferably non-alkali glass, soda lime glass, and the like. And a combination thereof, particularly preferably non-alkali glass.
- Alkali-free glass is a glass containing silicon dioxide, aluminum oxide, boron oxide, and alkaline earth metal oxides such as calcium oxide and barium oxide as main components, and further containing boric acid, which is substantially free of alkali metals. That is.
- This non-alkali glass is stable with a low coefficient of thermal expansion in the range of 3 ppm / K or more and 5 ppm / K or less in a wide temperature range from 0 ° C to 350 ° C, so that warpage of the glass in a process involving heating is minimized. There is an advantage that it can be done.
- the thickness of the carrier 12 is preferably 100 ⁇ m or more and 2000 ⁇ m or less, more preferably 300 ⁇ m or more and 1800 ⁇ m or less, and further preferably 400 ⁇ m or more and 1100 ⁇ m or less. If the thickness is within such a range, it is possible to reduce the thickness of the wiring and the warpage that occurs when electronic components are mounted, while ensuring an appropriate strength that does not interfere with handling.
- the surface of the carrier 12 adjacent to the peeling functional layer 14 preferably has an arithmetic mean roughness Ra of 0.1 nm or more and 70 nm or less, which is measured according to JIS B 0601-2001 using a laser microscope. , More preferably 0.5 nm or more and 60 nm or less, further preferably 1.0 nm or more and 50 nm or less, particularly preferably 1.5 nm or more and 40 nm or less, and most preferably 2.0 nm or more and 30 nm or less.
- the line / space (L / S) is highly refined to the extent of 13 ⁇ m or less / 13 ⁇ m or less (for example, from 12 ⁇ m / 12 ⁇ m to 2 ⁇ m / 2 ⁇ m). It is suitable for forming a wiring pattern.
- the peeling functional layer 14 is a layer that is interposed between the carrier 12 and the metal layer 16 and contributes to stable peeling of the carrier 12.
- the peeling functional layer 14 is a layer containing a metal oxynitride, preferably TaON, from the viewpoint of maintaining stable peeling strength even after being heated at a high temperature of 240 ° C. or higher (for example, 260 ° C.) for a long time. It contains at least one metal oxynitride selected from the group consisting of NiON, TiON, NiWON and MoON, more preferably at least one selected from the group consisting of TaON, NiON, TiON and MoON, and even more preferably TaON.
- At least one selected from the group consisting of NiON and TiON particularly preferably at least one selected from the group consisting of TaON and TiON.
- the surface on the carrier 12 side is Cu, Ti, Ta, Cr, Ni, Al, Mo, Zn, W, TiN from the viewpoint of ensuring the adhesion between the carrier 12 and the metal layer 16.
- at least one selected from the group consisting of TaN more preferably at least one selected from the group consisting of Ti, Ta, Cr, Ni, Al, Mo, Zn, W, TiN and TaN.
- the content of the metal or metal nitride on the surface of the peeling functional layer 14 on the carrier 12 side is 30 atomic% or more, preferably 40 atomic% or more, more preferably 50 atomic% or more, still more preferably 60 atomic% or more. , Especially preferably 70 atomic% or more, and most preferably 80 atomic% or more.
- the upper limit of the content of the metal or the metal nitride is not particularly limited and may be 100 atomic%, but is typically 98 atomic% or less.
- the metal or metal nitride has good compatibility with the material of the carrier 12, and can ensure adhesion. By controlling the content in the above range, stable adhesion can be ensured even after being heated at a high temperature for a long time, which is preferable. These contents are values measured by analysis by X-ray photoelectron spectroscopy (XPS).
- the surface of the peeling functional layer 14 opposite to the carrier 12 is at least one metal selected from the group consisting of TaON, NiON, TiON, NiWON and MoON. It preferably contains an oxynitride, more preferably at least one selected from the group consisting of TaON, NiON, TiON and MoON, and even more preferably at least one selected from the group consisting of TaON, NiON and TiON. It preferably comprises at least one selected from the group consisting of TaON and TiON.
- the metal oxynitride contains O and N in arbitrary ratios with respect to the metal component (for example, Ta when the metal oxynitride is TaON) constituting the metal oxynitride.
- the metal oxide in the present invention has a general formula: MO x N y (in the formula, M is a metal component such as Ta, Ni, Ti, NiW, Mo, and x and y are 0 independently of each other. It can be represented by the basic composition (which is a real number that exceeds).
- the atomic ratio of O to the metal component constituting the metal oxynitride is preferably 4% or more (more preferably 5% or more and 120% or less).
- the atomic ratio of N to the metal component constituting the metal oxynitride is preferably 20% or more (more preferably 25% or more and 45% or less).
- the surface of the peeling functional layer 14 on the opposite side to the carrier 12 preferably has a metal component content of 20 atomic% or more and 80 atomic% or less, more preferably 25 atomic% or more and 75 atoms. % Or less, more preferably 30 atomic% or more and 70 atomic% or less, and particularly preferably 35 atomic% or more and 68 atomic% or less.
- the peeling functional layer 14 does not include a carbon layer (that is, a layer whose main component is composed of carbon) because the number of foreign matter particles on the surface of the metal layer 16 can be effectively suppressed.
- the peeling functional layer 14 may contain unavoidable impurities due to the raw material components, the film forming process, and the like.
- the carbon content of the peeling functional layer 14 may be less than or equal to the lower limit of detection value measured by XPS, but is typically 3 atomic% or less, and more typically 1 atom. % Or less.
- the carbon content of the outermost surface (depth 0 nm) measured by XPS tends to be high due to dirt or the like when exposed to the atmosphere. Therefore, the carbon content in the peeling functional layer 14 is the surface (that is, that is). The value is taken at a position (SiO 2 sputter rate conversion) at a depth of 2 nm from the surface of the peeling functional layer 14 opposite to the carrier 12.
- the peeling functional layer 14 may be manufactured by any method, but a layer formed by a magnetron sputtering method using a target is particularly preferable in that the uniformity of the film thickness distribution can be improved.
- the thickness of the peeling functional layer 14 is preferably 5 nm or more and 500 nm or less, more preferably 10 nm or more and 400 nm or less, further preferably 20 nm or more and 200 nm or less, and particularly preferably 30 nm or more and 100 nm or less. This thickness is a value measured by analyzing the layer cross section with an energy dispersive X-ray spectrophotometer (TEM-EDX) of a transmission electron microscope.
- TEM-EDX energy dispersive X-ray spectrophotometer
- the peeling functional layer 14 may have a one-layer structure as shown in FIG. 1, or may have a two-layer structure or more as shown in FIG.
- the peeling functional layer 14 includes an adhesion layer 14a and a peeling layer 14b as shown in FIG.
- the adhesion layer 14a has a function of causing stable peeling from the interface between the peeling function layer 14 and the metal layer 16 by relatively improving the adhesion at the interface between the carrier 12 and the peeling function layer 14.
- the adhesion layer 14a is preferably a layer containing at least one selected from the group consisting of Cu, Ti, Ta, Cr, Ni, Al, Mo, Zn, W, TiN and TaN, and more preferably Ti, At least one selected from the group consisting of Ta, Cr, Ni, Al, Mo, Zn, W, TiN and TaN, more preferably selected from the group consisting of Ti, Ni, Al, Mo, W, TiN and TaN.
- the adhesion layer 14a preferably has a content of the metal or metal nitride measured by X-ray photoelectron spectroscopy (XPS) of 30 atomic% or more, more preferably 40 atomic% or more, still more preferably 50 atoms. % Or more, more preferably 60 atomic% or more, particularly preferably 70 atomic% or more, and most preferably 80 atomic% or more.
- the upper limit of the content of the metal or the metal nitride in the adhesion layer 14a is not particularly limited and may be 100 atomic%, but 98 atomic% or less is realistic. Further, although not particularly limited, when the adhesion layer 14a is exposed to the atmosphere after being formed, the presence of oxygen mixed due to the film formation is allowed.
- the close contact layer 14a typically has an oxygen content of 0.1 atomic% or more and 10 atomic% or less, as measured by X-ray photoelectron spectroscopy (XPS), more typically 0.3 atomic%. It is 7 atomic% or more, and more typically 0.5 atomic% or more and 5 atomic% or less.
- the adhesion layer 14a may be produced by any method, but a layer formed by a magnetron sputtering method using a target is particularly preferable in that the uniformity of the film thickness distribution can be improved.
- the thickness T 1 of the adhesion layer 14a is preferably 5 nm or more and 400 nm or less, more preferably 10 nm or more and 300 nm or less, further preferably 50 nm or more and 200 nm or less, and particularly preferably 50 nm or more and 100 nm or less.
- This thickness is a value measured by analyzing the layer cross section with an energy dispersive X-ray spectrophotometer (TEM-EDX) of a transmission electron microscope.
- TEM-EDX energy dispersive X-ray spectrophotometer
- the release layer 14b is preferably a layer provided on the adhesion layer 14a and containing at least one metal oxynitride selected from the group consisting of TaON, NiON, TiON, NiWON and MoON, and more preferably TaON. , At least one selected from the group consisting of NiON, TiON and MoON, more preferably at least one selected from the group consisting of TaON, NiON and TiON, and particularly preferably at least one selected from the group consisting of TaON and TiON. It is a layer containing one kind.
- the release layer 14b has an atomic ratio of O to 4% or more (more preferably 5% or more and 120% or less) with respect to the metal component constituting the metal oxynitride, as measured by X-ray photoelectron spectroscopy (XPS).
- the atomic ratio of N to the metal component constituting the metal oxynitride is preferably 20% or more (more preferably 25% or more and 45% or less).
- the release layer 14b preferably has a content of metal components constituting the metal oxynitride of 20 atomic% or more and 80 atomic% or less, which is measured by X-ray photoelectron spectroscopy (XPS), more preferably.
- the release layer 14b may contain unavoidable impurities due to the raw material components, the film forming process, and the like.
- the release layer 14b may be produced by any method, but is formed by a reactive sputtering method in which a metal target or a metal nitride target is used and sputtering is performed in an atmosphere containing oxygen and / or nitrogen.
- a layer is preferable because the film thickness can be easily controlled by adjusting the film formation time.
- the release layer 14b may be formed by treating the surface of the adhesion layer 14a in oxygen plasma and / or nitrogen plasma using a commercially available plasma ashing device. Further, when the adhesion layer 14a contains a metal nitride (that is, TiN and / or TaN), the release layer 14b is produced by exposing the adhesion layer 14a formed in vacuum to an oxidizing atmosphere (for example, the atmosphere). You can also do it.
- a metal nitride that is, TiN and / or TaN
- the thickness T 2 of the release layer 14b is preferably 1 nm or more and 150 nm or less, more preferably 3 nm or more and 130 nm or less, further preferably 10 nm or more and 120 nm or less, and particularly preferably 50 nm or more and 100 nm or less.
- the release layer 14b can be formed thicker than the conventional release layer (carbon layer) made of carbon. In this respect, when the thickness T 2 of the release layer 14b is increased (for example, T 2 is 50 nm or more), the release layer 14b can also function as an etching stopper layer.
- the metal oxynitride constituting the release layer 14b has a property of being difficult to dissolve in a flash etching solution (for example, Cu flash etching solution), and as a result, has excellent chemical resistance to the flash etching solution. Can exhibit sex. Therefore, the release layer 14b is a layer that is less likely to be etched by the flash etching solution than the metal layer 16 described later, and therefore can also function as an etching stopper layer.
- a flash etching solution for example, Cu flash etching solution
- the thickness T 2 of the release layer 14b shall be specified by performing elemental analysis in the depth direction of the metal leaf 10 with a carrier by X-ray photoelectron spectroscopy (XPS) according to various conditions described in Examples described later. Can be done. In the depth direction elemental analysis using XPS, even when the same etching conditions are used, the etching rate differs depending on the type of material, so it is not possible to obtain the numerical value of the thickness T 2 of the release layer 14b itself. Have difficulty. Therefore, for the thickness T 2 , the thickness converted to SiO 2 calculated from the time required for etching is used by utilizing the etching rate calculated from the SiO 2 film having a known film thickness. By doing so, the thickness can be uniquely determined, and quantitative evaluation becomes possible.
- XPS X-ray photoelectron spectroscopy
- T 1 / T 2 which is the ratio of the thickness T 1 of the adhesion layer 14a to the thickness T 2 of the release layer 14b, is preferably 0.03 or more and 400 or less, and more preferably 0. It is .07 or more and 300 or less, more preferably 0.1 or more and 200 or less, and particularly preferably 0.38 or more and 100 or less.
- each layer of the metal leaf 10 with a carrier during heating is formed. It is considered that this is due to a change in the diffusion behavior of the elements.
- the metal layer 16 is a layer made of metal.
- the metal layer 16 is composed of at least one metal or alloy selected from the group consisting of the transition elements of Group 4, Group 5, Group 6, Group 9, Group 10, and Group 11 and Al. At least one metal or alloy selected from the group consisting of Group 4 and Group 11 transition elements, Pt, Al, Nb, Co, Ni and Mo, more preferably the eleventh. At least one metal or alloy selected from the group consisting of group transition elements, Pt, Ti, Al and Mo, and even more preferably at least one selected from the group consisting of Cu, Au, Pt, Ti and Mo. Metals or alloys, particularly preferably at least one metal or alloy selected from the group consisting of Cu, Au and Pt, most preferably Cu.
- the metal constituting the metal layer 16 may be a pure metal or an alloy.
- the metal layer 16 preferably has a metal content of 60 atomic% or more, more preferably 70 atomic% or more, still more preferably 80 atomic% or more, particularly preferably 80 atomic% or more, as measured by X-ray photoelectron spectroscopy (XPS). It is preferably 90 atomic% or more.
- the upper limit of the metal content in the metal layer 16 is not particularly limited and may be 100 atomic%, but 98 atomic% or less is typical.
- the metal constituting the metal layer 16 may contain unavoidable impurities due to the raw material components, the film forming process, and the like.
- the metal layer 16 is preferably a layer formed by a vapor phase method such as sputtering.
- the metal layer 16 is preferably a non-roughened metal layer, but is subjected to preliminary roughening, soft etching treatment, cleaning treatment, and oxidation-reduction treatment as long as it does not interfere with the formation of a wiring pattern during the production of a printed wiring board. It may be one in which secondary roughening has occurred.
- the thickness T 3 of the metal layer 16 preferably has a thickness of 10 nm or more and 1000 nm or less, more preferably 20 nm or more and 900 nm or less, further preferably 30 nm or more and 700 nm or less, particularly preferably 50 nm or more and 600 nm or less, and particularly more preferably. It is 70 nm or more and 500 nm or less, most preferably 100 nm or more and 400 nm or less.
- This thickness is a value measured by analyzing the layer cross section with an energy dispersive X-ray spectrophotometer (TEM-EDX) of a transmission electron microscope.
- TEM-EDX energy dispersive X-ray spectrophotometer
- the production of the metal layer 16 having a thickness in such a range is preferably performed by a sputtering method from the viewpoint of in-plane uniformity of the film thickness and productivity in the form of a sheet or a roll.
- the surface of the metal layer 16 opposite to the peeling functional layer 14 (outer surface of the metal layer 16) has an arithmetic mean roughness Ra of 1.0 nm or more and 100 nm or less, which is measured in accordance with JIS B 0601-2001. It is more preferably 2.0 nm or more and 40 nm or less, further preferably 3.0 nm or more and 35 nm or less, particularly preferably 4.0 nm or more and 30 nm or less, and most preferably 5.0 nm or more and 15 nm or less.
- the metal layer 16 may have a one-layer structure or a two-layer or more structure. Further, as long as the carrier-attached metal foil 10 includes the carrier 12, the peeling function layer 14, and the metal layer 16 in this order, the other layers are provided as long as the original functions of the carrier-attached metal foil 10 are not impaired. It may be included. Examples of such other layers include an etching stopper layer as shown in Patent Document 2 (International Publication No. 2019/131000), and a metal (for example, Au or Pt) and a metal layer 16 constituting the metal layer 16.
- a barrier layer for example, Ti, Ta for suppressing the formation of an intermetal compound with a metal (for example, Cu) constituting a wiring layer that can be formed on the upper surface (that is, the surface of the metal foil 10 with a carrier on the side opposite to the carrier 12).
- a barrier layer for example, Ti, Ta
- a metal for example, Cu
- the metal leaf 10 with a carrier may be configured by sequentially providing the above-mentioned various layers on both sides of the carrier 12 so as to be vertically symmetrical.
- the thickness of the entire metal leaf 10 with a carrier is not particularly limited, but is preferably 500 ⁇ m or more and 3000 ⁇ m or less, more preferably 700 ⁇ m or more and 2500 ⁇ m or less, further preferably 900 ⁇ m or more and 2000 ⁇ m or less, and particularly preferably 1000 ⁇ m or more and 1700 ⁇ m or less.
- the shape and size of the metal leaf 10 with a carrier are not particularly limited, but are preferably a rectangular or square shape having a side of 10 cm or more, more preferably 20 cm or more, and further preferably 25 cm or more.
- the upper limit of the size when the metal foil 10 with a carrier is rectangular or square is not particularly limited, but one guideline for the upper limit is to set one side to 1000 cm. Further, the metal leaf 10 with a carrier is in a form that can be handled by itself before and after the formation of the wiring.
- the above-mentioned carrier 12 is prepared, and a peeling functional layer 14 (for example, an adhesive layer 14a and a peeling layer 14b) and a metal layer 16 are formed on the carrier 12. It can be manufactured by doing so.
- the formation of each of the peeling functional layer 14 and the metal layer 16 is preferably performed by the physical vapor deposition (PVD) method from the viewpoint that it is easy to cope with fine pitching due to ultrathinning.
- PVD physical vapor deposition
- Examples of the physical vapor deposition (PVD) method include a sputtering method, a vacuum deposition method, and an ion plating method, in which the film thickness can be controlled in a wide range from 0.05 nm to 5000 nm, and a wide width or area.
- the sputtering method is most preferable because it can ensure the uniformity of the film thickness.
- the film formation by the physical vapor deposition (PVD) method is not particularly limited as long as it is performed according to known conditions using a known vapor phase deposition apparatus.
- the sputtering method may be various known methods such as magnetron sputtering, bipolar sputtering method, and opposed target sputtering method.
- Magnetron sputtering has a high film forming speed and high productivity. It is preferable in terms of high point.
- Sputtering may be performed with either a DC (direct current) or RF (radio frequency) power source.
- a plate-type target whose target shape is widely known can be used, it is desirable to use a cylindrical target from the viewpoint of target utilization efficiency.
- PVD physical vapor deposition
- the film formation of the adhesion layer 14a by the physical vapor deposition (PVD) method is selected from the group consisting of Cu, Ti, Ta, Cr, Ni, Al, Mo, Zn, W, TiN and TaN. It is preferable to use a target composed of at least one kind of metal or metal nitride and perform magneticetron sputtering in a non-oxidizing atmosphere because the film thickness distribution uniformity can be improved.
- the purity of the target is preferably 99.9 wt% or more.
- As the gas used for sputtering it is preferable to use an inert gas such as argon gas.
- the flow rate of argon gas or the like may be appropriately determined according to the sputtering chamber size and the film forming conditions, and is not particularly limited. Further, from the viewpoint of continuous film formation without operation failure such as abnormal discharge or plasma irradiation failure, the pressure at the time of film formation is preferably in the range of 0.1 Pa or more and 20 Pa or less. This pressure range may be set by adjusting the film forming power, the flow rate of argon gas, etc. according to the device structure, capacity, exhaust capacity of the vacuum pump, rated capacity of the film forming power source, and the like. Further, the sputtering power is film thickness uniformity of the film formation, in consideration of productivity and the like may be appropriately set within a range of 0.05 W / cm 2 or more 10.0 W / cm 2 or less per unit area of the target.
- the film thickness of the exfoliated layer 14b by the physical vapor deposition (PVD) method is at least one metal or metal selected from the group consisting of Ta, Ni, Ti, NiW, Mo, TiN and TaN. It is preferable that the target made of nitride is used and the film thickness is easily controlled by the reactive sputtering method in an atmosphere containing oxygen and / or nitrogen. The purity of the target is preferably 99.9% or more.
- the gas used for sputtering preferably contains, in addition to an inert gas (for example, argon gas), a gas for producing a metal oxynitride (for example, oxygen gas, nitric oxide gas, and nitrogen dioxide gas).
- the flow rates of these gases may be appropriately determined according to the sputtering chamber size and the film forming conditions, and are not particularly limited. Further, from the viewpoint of continuous film formation without operation failure such as abnormal discharge, the pressure at the time of film formation is preferably in the range of 0.1 Pa or more and 1.0 Pa or less. This pressure range may be set by adjusting the film forming power and the flow rate of the gas according to the device structure, capacity, exhaust capacity of the vacuum pump, rated capacity of the film forming power source, and the like. Further, the sputtering power is film thickness uniformity of the film formation, in consideration of productivity and the like may be appropriately set within a range of 0.05 W / cm 2 or more 15.0W / cm 2 or less per unit area of the target.
- the formation of the metal layer 16 by the physical vapor deposition (PVD) method (preferably the sputtering method) is performed on the transition elements of Group 4, Group 5, Group 6, Group 9, Group 10 and Group 11. Further, it is preferably carried out in an inert atmosphere such as argon using a target composed of at least one metal selected from the group consisting of Al.
- the target is preferably composed of a pure metal or alloy, but may contain unavoidable impurities.
- the purity of the target is preferably 99.9% or more, more preferably 99.99%, still more preferably 99.999% or more.
- a stage cooling mechanism may be provided during sputtering.
- the pressure at the time of film formation is preferably in the range of 0.1 Pa or more and 20 Pa or less.
- This pressure range may be set by adjusting the film forming power and the flow rate of argon gas according to the device structure, capacity, exhaust capacity of the vacuum pump, rated capacity of the film forming power source, and the like.
- the sputtering power is film thickness uniformity of the film formation, in consideration of productivity and the like may be appropriately set within a range of 0.05 W / cm 2 or more 10.0 W / cm 2 or less per unit area of the target.
- Example 1 As shown in FIG. 2, a release functional layer 14 (adhesion layer 14a and a release layer 14b) and a metal layer 16 are formed in this order on a glass sheet as a carrier 12 to prepare a metal foil 10 with a carrier. ..
- the specific procedure is as follows.
- -Ultimate vacuum less than 1 x 10 -4
- Example 2 As the peeling layer 14b, the metal foil 10 with a carrier was formed in the same manner as in Example 1 except that the TiON layer was formed by reactive sputtering as follows instead of performing the surface oxidation treatment of the adhesion layer 14a by exposure to the atmosphere. It was made.
- a TiON layer having a target thickness of about 100 nm was formed on the surface of the close contact layer 14a by reactive sputtering under the following equipment and conditions.
- -Equipment Single-wafer DC sputtering equipment (Canon Tokki Co., Ltd., MLS464)
- -Target 8 inch (203.2 mm) diameter TiN target (purity 99.95% or higher)
- -Ultimate vacuum less than 1 x 10 -4
- Pa-Gas Argon gas (flow rate: 90 sccm) and oxygen gas (flow rate: 10 sccm)
- -Sputtering pressure 0.35Pa -Sputtering power: 100W (0.3W / cm 2 )
- -Temperature during film formation 40 ° C
- Example 3 As the adhesion layer 14a, a Ti layer was formed instead of the TaN layer, and (ii) instead of subjecting the adhesion layer 14a to surface oxidation treatment by atmospheric exposure, the TaON layer was made reactive as follows.
- the metal leaf 10 with a carrier was produced in the same manner as in Example 1 except that it was formed by sputtering.
- a Ti layer having a thickness of 100 nm was formed on the carrier 12 as an adhesion layer 14a by a sputtering method. This sputtering was performed under the following conditions using the following equipment.
- -Equipment Single-wafer magnetron sputtering equipment (manufactured by Canon Tokki Co., Ltd., MLS464)
- -Target Ti target with a diameter of 8 inches (203.2 mm) (purity 99.999%)
- -Ultimate vacuum less than 1 x 10 -4
- Pa-Gas Argon gas (flow rate: 100 sccm) -Sputtering pressure: 0.35Pa -Sputtering power: 1000W (3.1W / cm 2 ) -Temperature during film formation: 40 ° C
- TaON layer having a target thickness of about 100 nm was formed on the surface of the close contact layer 14a by reactive sputtering under the following equipment and conditions.
- -Equipment Single-wafer DC sputtering equipment (Canon Tokki Co., Ltd., MLS464)
- -Target TaN target with a diameter of 8 inches (203.2 mm) (purity 99.98%)
- -Ultimate vacuum less than 1 x 10 -4
- Pa-Gas Argon gas (flow rate: 90 sccm) and oxygen gas (flow rate: 10 sccm)
- -Sputtering pressure 0.35Pa -Sputtering power: 100W (0.3W / cm 2 )
- -Temperature during film formation 40 ° C
- Example 4 A carrier-attached metal foil 10 was produced in the same manner as in Example 2 except that a Ti layer having a thickness of 100 nm was formed as the adhesion layer 14a under the same equipment and conditions as in Example 3.
- Example 5 The metal leaf 10 with a carrier was produced in the same manner as in Example 3 except that an Al layer was formed instead of the Ti layer as the adhesion layer 14a.
- Al layer having a thickness of 100 nm was formed on the carrier 12 as an adhesion layer 14a by a sputtering method. This sputtering was performed under the following conditions using the following equipment.
- -Equipment Single-wafer magnetron sputtering equipment (manufactured by Canon Tokki Co., Ltd., MLS464)
- -Target Al target with a diameter of 8 inches (203.2 mm) (purity 99.95% or more)
- -Ultimate vacuum less than 1 x 10 -4
- Pa-Gas Argon gas (flow rate: 100 sccm) -Sputtering pressure: 0.35Pa -Sputtering power: 1000W (3.1W / cm 2 ) -Temperature during film formation: 40 ° C
- Example 6 A carrier-attached metal foil 10 was produced in the same manner as in Example 2 except that an Al layer having a thickness of 100 nm was formed as the adhesion layer 14a under the same equipment and conditions as in Example 5.
- Example 7 As the peeling functional layer 14, a metal foil with a carrier is formed in the same manner as in Example 1 except that only the Ta layer (adhesion layer 14a) is formed instead of the TaN layer (adhesion layer 14a) and the TaON layer (peeling layer 14b). 10 was prepared.
- Ta layer having a thickness of 100 nm was formed on the carrier 12 as an adhesion layer 14a by a sputtering method. This sputtering was performed under the following conditions using the following equipment.
- -Equipment Single-wafer magnetron sputtering equipment (manufactured by Canon Tokki Co., Ltd., MLS464)
- -Target Ta target with a diameter of 8 inches (203.2 mm) (purity 99.98%)
- Pa-Gas Argon gas (flow rate: 100 sccm) -Sputtering pressure: 0.35Pa -Sputtering power: 1000W (3.1W / cm 2 ) -Temperature during film formation: 40 ° C
- Example 8 (comparison) The metal leaf 10 with a carrier was produced in the same manner as in Example 2 except that a Ta layer was formed instead of the TiON layer as the release layer 14b.
- a Ta layer having a thickness of 100 nm as a peeling layer 14b was formed by reactive sputtering under the following equipment and conditions.
- -Equipment Single-wafer DC sputtering equipment (Canon Tokki Co., Ltd., MLS464)
- -Target Ta target with a diameter of 8 inches (203.2 mm) (purity 99.98%)
- -Ultimate vacuum less than 1 x 10 -4
- Pa-Gas Argon gas (flow rate: 100 sccm)
- -Temperature during film formation 40 ° C
- Example 9 (comparison) The metal leaf 10 with a carrier was produced in the same manner as in Example 1 except that the release layer 14b was not formed (that is, the surface oxidation treatment of the adhesion layer 14a was not performed).
- Example 10 (comparison) A carrier-attached metal foil 10 was produced in the same manner as in Example 2 except that a Ta / TaO x layer was formed instead of the TiON layer as the release layer 14b. Specifically, a Ta layer having a thickness of 100 nm was formed on the adhesion layer 14a under the same equipment and conditions as in Example 8. The sample on which the Ta layer was formed was taken out from the vacuum and exposed to the atmosphere for 1 minute to perform surface oxidation treatment (natural oxidation) of the Ta layer. By doing so, a Ta / TaO x layer was formed as the peeling layer 14b.
- Example 11 As shown in FIG. 3, a peeling functional layer (adhesion layer 114, a peeling auxiliary layer 116, and a carbon layer 118 as a peeling layer), a second metal layer 120, and a first metal layer 122 are placed on the carrier 112.
- a metal foil 110 with a carrier was produced by forming a film in this order. The specific procedure is as follows.
- -Target Ti target with a diameter of 8 inches (203.2 mm) (purity 99.999%)
- amorphous carbon layer having a thickness of 6 nm was formed as a carbon layer 118 on the peeling auxiliary layer by a sputtering method. This sputtering was performed under the following conditions using the following equipment.
- Second Metal Layer A Ti layer having a thickness of 100 nm was formed as the second metal layer 120 on the carbon layer by sputtering under the following equipment and conditions.
- -Equipment Single-wafer magnetron sputtering equipment (manufactured by Canon Tokki Co., Ltd., MLS464)
- -Target Ti target with a diameter of 8 inches (203.2 mm) (purity 99.999%)
- -Gas Argon gas (flow rate: 100 sccm)
- -Ultimate vacuum less than 1 x 10 -4
- Pa-Sputtering pressure 0.35 Pa -Sputtering power: 1000W (3.1W / cm 2 )
- the metal foils with carriers of Evaluation Examples 1 to 11 were evaluated in various ways as shown below. The evaluation results are as shown in Tables 1 and 2. Table 2 also shows the composition of the adhesion layer (including the peeling auxiliary layer in the case of Example 11) and the peeling layer as the peeling functional layer.
- Example 1 Semi-quantitative analysis of peeled layer>
- the depth direction analysis of the prepared metal leaf 10 with a carrier was performed by X-ray photoelectron spectroscopy (XPS) based on the following measurement conditions and analysis conditions. This analysis was performed by peeling the metal layer 16 from the carrier-attached metal foil 10 and then digging down from the exposed peeling functional layer 14 surface toward the depth direction by Ar ion etching under the following conditions.
- XPS X-ray photoelectron spectroscopy
- N 1s peak interferes with the Ta 4p3 peak
- the semi-quantitative value of N 1s was calculated from the N 1s peak area obtained by the waveform separation analysis.
- the energy ranges of the peak positions of N 1s and Ta 4p3 in the waveform separation analysis are as follows.
- the Gaussian function was used as the fitting function in the waveform separation analysis.
- -N 1s 395.9 to 398.2 eV -Ta 4p3 (metal): 399.5-400.5 eV -Ta 4p3 (oxide): 404.11 to 405.11 eV
- the results of the semi-quantitative values in the depth direction of the metal leaf 10 with a carrier of Example 1 are as shown in Table 1.
- the metal component (that is, Ta) constituting the TaON layer extends from the surface of the peeling functional layer 14 (spatter depth 0 nm) to a depth of 2.9 nm. It can be seen that there is a region in which the atomic ratio of O is 4% or more and the atomic ratio of N to the metal component constituting the metal oxynitride is 20% or more. Therefore, the thickness of the TaON layer (release layer 14b) in the carrier-attached metal leaf 10 of Example 1 is estimated to be about 3 nm in terms of SiO 2.
- peeling strength is 3gf / cm or more and less than 30gf / cm-Evaluation
- B Peeling strength is 30gf / cm or more and less than 50gf / cm-Evaluation
- Peeling strength is less than 3gf / cm or 50gf / cm or more (Including), or peeling occurs between the carrier-peeling function layers and cannot be evaluated.
- ⁇ Evaluation 3 Number of foreign particles> The number of foreign matter particles on the surface of the metal foils 10 and 110 with carriers on the metal layer 16 side or the surface on the first metal layer 122 side was measured as follows. First, a foreign matter inspection device (HS930, manufactured by Toray Engineering Co., Ltd.) was used to measure the total number of foreign matter particles (particle size of 5 ⁇ m or more) on the surface of the metal foil with a carrier having a predetermined area. Next, the total number was divided by the measurement area to calculate the number of foreign particles per unit area (1 square centimeter). The region from the end of the metal foil with a carrier to 10 mm was out of the measurement range.
- a foreign matter inspection device H930, manufactured by Toray Engineering Co., Ltd.
- the number of foreign matter particles of 5 ⁇ m or more per unit area thus obtained was rated and evaluated according to the following criteria. The results are as shown in Table 2.
- -Evaluation A The number of foreign particles of 5 ⁇ m or more per square centimeter is less than 0.20-Evaluation
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Abstract
Description
キャリアと、
前記キャリア上に設けられ、金属酸窒化物を含む、剥離機能層と、
前記剥離機能層上に設けられる金属層と
を備えた、キャリア付金属箔が提供される。
本発明のキャリア付金属箔の一例が図1及び2に模式的に示される。図1及び2に示されるように、本発明のキャリア付金属箔10は、キャリア12と、剥離機能層14と、金属層16とをこの順に備えたものである。剥離機能層14はキャリア12上に設けられ、金属酸窒化物を含む層である。金属層16は剥離機能層14上に設けられる層である。このように、キャリア付金属箔10のキャリア12と金属層16との間に、金属酸窒化物を含む剥離機能層14を介在させることにより、金属層16表面の異物粒子数を抑制して回路形成性を向上し、かつ、240℃以上の高温(例えば260℃)で長時間加熱された後においても、安定した剥離強度を保持することが可能な、キャリア付金属箔を提供することができる。
本発明のキャリア付金属箔10は、上述したキャリア12を用意し、キャリア12上に、剥離機能層14(例えば密着層14a及び剥離層14b)及び金属層16を形成することにより製造することができる。剥離機能層14及び金属層16の各層の形成は、極薄化によるファインピッチ化に対応しやすい観点から、物理気相堆積(PVD)法により行われるのが好ましい。物理気相堆積(PVD)法の例としては、スパッタリング法、真空蒸着法、及びイオンプレーティング法が挙げられるが、0.05nmから5000nmまでといった幅広い範囲で膜厚制御できる点、広い幅ないし面積にわたって膜厚均一性を確保できる点等から、最も好ましくはスパッタリング法である。物理気相堆積(PVD)法による成膜は公知の気相成膜装置を用いて公知の条件に従って行えばよく特に限定されない。例えば、スパッタリング法を採用する場合、スパッタリング方式は、マグネトロンスパッタリング、2極スパッタリング法、対向ターゲットスパッタリング法等、公知の種々の方法であってよいが、マグネトロンスパッタリングが、成膜速度が速く生産性が高い点で好ましい。スパッタリングはDC(直流)及びRF(高周波)のいずれの電源で行ってもよい。また、ターゲット形状も広く知られているプレート型ターゲットを使用することができるが、ターゲット使用効率の観点から円筒形ターゲットを用いることが望ましい。以下、密着層14a、剥離層14b、及び金属層16の各層の物理気相堆積(PVD)法(好ましくはスパッタリング法)による成膜について説明する。
図2に示されるように、キャリア12としてのガラスシート上に、剥離機能層14(密着層14a及び剥離層14b)、及び金属層16をこの順に成膜してキャリア付金属箔10を作製した。具体的な手順は以下のとおりである。
厚さ1.1mmのガラスシート(材質:ソーダライムガラス、算術平均粗さRa:0.6nm)を用意した。
キャリア12上に密着層14aとして厚さ100nmのTaN層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTaNターゲット(純度99.95%以上)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
‐ 成膜時温度:40℃
密着層14aが形成された試料を真空中から取り出し、5分間大気暴露することで、密着層14aの表面酸化処理(自然酸化)を行った。この表面酸化処理により、剥離層14bとしてTaON層を形成した。
剥離層14b上に、金属層16として厚さ300nmのCu層を以下の装置及び条件でスパッタリングにより形成して、キャリア付金属箔10を得た。
‐ 装置:枚葉式DCスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のCuターゲット(純度99.98%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
‐ 成膜時温度:40℃
剥離層14bとして、大気暴露による密着層14aの表面酸化処理を行う代わりに、TiON層を以下のようにして反応性スパッタリングにより形成したこと以外は、例1と同様にしてキャリア付金属箔10の作製を行った。
密着層14aの表面に、狙いの厚さが約100nmのTiON層を以下の装置及び条件で反応性スパッタリングにより形成した。
‐ 装置:枚葉式DCスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTiNターゲット(純度99.95%以上)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:90sccm)及び酸素ガス(流量:10sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:100W(0.3W/cm2)
‐ 成膜時温度:40℃
(i)密着層14aとして、TaN層に代えて、Ti層を形成したこと、及び(ii)大気暴露による密着層14aの表面酸化処理を行う代わりに、TaON層を以下のようにして反応性スパッタリングにより形成したこと以外は、例1と同様にしてキャリア付金属箔10の作製を行った。
キャリア12上に密着層14aとして厚さ100nmのTi層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTiターゲット(純度99.999%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
‐ 成膜時温度:40℃
密着層14aの表面に、狙いの厚さが約100nmのTaON層を以下の装置及び条件で反応性スパッタリングにより形成した。
‐ 装置:枚葉式DCスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTaNターゲット(純度99.98%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:90sccm)及び酸素ガス(流量:10sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:100W(0.3W/cm2)
‐ 成膜時温度:40℃
密着層14aとして、TaN層に代えて、厚さ100nmのTi層を例3と同様の装置及び条件で形成したこと以外は、例2と同様にしてキャリア付金属箔10の作製を行った。
密着層14aとして、Ti層に代えて、Al層を形成したこと以外は、例3と同様にしてキャリア付金属箔10の作製を行った。
キャリア12上に密着層14aとして厚さ100nmのAl層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のAlターゲット(純度99.95%以上)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
‐ 成膜時温度:40℃
密着層14aとして、TaN層に代えて、厚さ100nmのAl層を例5と同様の装置及び条件で形成したこと以外は、例2と同様にしてキャリア付金属箔10の作製を行った。
剥離機能層14として、TaN層(密着層14a)及びTaON層(剥離層14b)に代えて、Ta層(密着層14a)のみを形成したこと以外は、例1と同様にしてキャリア付金属箔10の作製を行った。
キャリア12上に密着層14aとして厚さ100nmのTa層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTaターゲット(純度99.98%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
‐ 成膜時温度:40℃
剥離層14bとして、TiON層に代えて、Ta層を形成したこと以外は、例2と同様にしてキャリア付金属箔10の作製を行った。
密着層14a上に、剥離層14bとして厚さ100nmのTa層を以下の装置及び条件で反応性スパッタリングにより形成した。
‐ 装置:枚葉式DCスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTaターゲット(純度99.98%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:100W(0.3W/cm2)
‐ 成膜時温度:40℃
剥離層14bの形成を行わなかった(すなわち密着層14aの表面酸化処理を行わなかった)こと以外は、例1と同様にしてキャリア付金属箔10の作製を行った。
剥離層14bとして、TiON層に代えてTa/TaOx層を形成したこと以外は例2と同様にしてキャリア付金属箔10の作製を行った。具体的には、密着層14a上に厚さ100nmのTa層を例8と同様の装置及び条件で形成した。Ta層が形成された試料を真空中から取り出し、1分間大気暴露することで、Ta層の表面酸化処理(自然酸化)を行った。こうすることで、剥離層14bとしてTa/TaOx層を形成した。
図3に示されるように、キャリア112上に、剥離機能層(密着層114、剥離補助層116、及び剥離層としての炭素層118)、第2金属層120、及び第1金属層122をこの順に成膜してキャリア付金属箔110を作製した。具体的な手順は以下のとおりである。
厚さ1.1mmのガラスシート(材質:ソーダライムガラス、算術平均粗さRa:0.6nm)を用意した。
キャリア112上に、密着層114として厚さ100nmのTi層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTiターゲット(純度99.999%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
‐ 成膜時温度:40℃
密着層114上に、剥離補助層116として厚さ100nmのCu層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)の銅ターゲット(純度99.98%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(6.2W/cm2)
‐ 成膜時温度:40℃
剥離補助層上に、炭素層118として厚み6nmのアモルファスカーボン層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)の炭素ターゲット(純度99.999%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:250W(0.7W/cm2)
‐ 成膜時温度:40℃
炭素層上に、第2金属層120として厚さ100nmのTi層を以下の装置及び条件でスパッタリングにより形成した。
‐ 装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のTiターゲット(純度99.999%)
‐ ガス:アルゴンガス(流量:100sccm)
‐ 到達真空度:1×10-4Pa未満
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
第2金属層上に、第1金属層122として厚さ300nmのCu層をスパッタリング法により形成した。このスパッタリングは以下の装置を用いて以下の条件で行った。
・装置:枚葉式マグネトロンスパッタリング装置(キヤノントッキ株式会社製、MLS464)
‐ ターゲット:直径8インチ(203.2mm)のCuターゲット(純度99.99%)
‐ 到達真空度:1×10-4Pa未満
‐ ガス:アルゴンガス(流量:100sccm)
‐ スパッタリング圧:0.35Pa
‐ スパッタリング電力:1000W(3.1W/cm2)
‐ 成膜時温度:40℃
例1~11のキャリア付金属箔について、以下に示されるとおり、各種評価を行った。評価結果は表1及び2に示されるとおりであった。また、表2には剥離機能層としての密着層(例11の場合は剥離補助層を含む)及び剥離層の組成も併せて示してある。
例1につき、作製したキャリア付金属箔10の深さ方向分析を以下の測定条件及び解析条件に基づきX線光電子分光法(XPS)により行った。この分析は、キャリア付金属箔10から金属層16を剥離した後、露出した剥離機能層14表面から深さ方向に向かって、以下の条件でArイオンエッチングによって掘り下げながら行った。
‐ 加速電圧:500V
‐ エッチングエリア:2mm×2mm
‐ エッチング速度:SiO2換算で4.4nm/min
‐ 装置:X線光電子分光装置(アルバック・ファイ株式会社製、Versa ProbeIII)
‐ 励起X線:単色化Al-Kα線(1486.6eV)
‐ 出力:50W
‐ 加速電圧:15kV
‐ X線照射径:200μmφ
‐ 測定面積:200μmφ
‐ パスエネルギー:26.0eV
‐ エネルギーステップ:0.1eV
‐ 中和銃:有
‐ 測定元素及び軌道:(sweep数:Ratio:Cycle数)
C 1s:(3:6:1)
N 1s:(30:6:1)
O 1s:(5:6:1)
Cu 2p3:(2:6:1)
Ta 4d: (30:6:1)
データ解析ソフト(アルバック・ファイ株式会社製「マルチパックVer9.4.0.7」)を用いてXPSデータの解析を行った。スムージングは15点で行い、バックグラウンドモードはShirleyを使用した。なお、半定量算出における各元素のバックグラウンド範囲は以下のとおりである。
‐ C 1s:280.0~292.0eV
‐ N 1s(Ta 4p3を含む):392.0~410.0eV
‐ O 1s:528.0~540.0eV
‐ Cu 2p3:927.0~939.0eV
‐ Ta 4d:212.0~250.0eV
‐ N 1s:395.9~398.2eV
‐ Ta 4p3(金属):399.5~400.5eV
‐ Ta 4p3(酸化物):404.11~405.11eV
キャリア付金属箔10、110における熱履歴としての真空熱プレスを行った後の剥離強度の測定を以下のように行った。キャリア付金属箔10、110の金属層16側又は第1金属層122側に、厚さ18μmのパネル電解銅めっきを施した後、熱履歴として260℃で2時間30kgf/cm2の圧力でプレスした。得られた銅張積層板に対して、JIS C 6481-1996に準拠して、金属層16又は第1金属層122と一体となった電気銅めっき層を剥離した時の剥離強度(gf/cm)を測定した。このとき、測定幅は50mmとし、測定長さは20mmとした。こうして得られた剥離強度(平均値)を以下の基準で格付け評価した。結果は表2に示されるとおりであった。
‐ 評価A:剥離強度が3gf/cm以上30gf/cm未満
‐ 評価B:剥離強度が30gf/cm以上50gf/cm未満
‐ 評価C:剥離強度が3gf/cm未満若しくは50gf/cm以上(剥離不可を含む)、又はキャリア-剥離機能層間で剥離が起こり評価不能
キャリア付金属箔10、110の金属層16側表面又は第1金属層122側表面の異物粒子数の測定を以下のように行った。まず、異物検査装置(東レエンジニアリング株式会社製、HS930)を使用し、所定の面積のキャリア付金属箔表面における異物粒子(粒子サイズ5μm以上)の合計数を測定した。次に、上記合計数を測定面積で割り、単位面積(1平方センチメートル)あたりの異物粒子数を算出した。なお、キャリア付金属箔の端部から10mmまでの領域は測定範囲外とした。こうして得られた単位面積あたりの5μm以上の異物粒子数を以下の基準で格付け評価した。結果は表2に示されるとおりであった。
‐ 評価A:1平方センチメートルあたりの5μm以上の異物粒子数が0.20未満
‐ 評価B:1平方センチメートルあたりの5μm以上の異物粒子数が0.20以上0.50未満
‐ 評価C:1平方センチメートルあたりの5μm以上の異物粒子数が0.50以上
評価2及び3の評価結果に基づいて総合評価を決定した。すなわち、評価2の評価結果が評価A又はBであり、かつ、評価3の評価結果が評価A又はBである場合を合格、それ以外の場合を不合格と判定した。結果は表2に示されるとおりであった。
Claims (11)
- キャリアと、
前記キャリア上に設けられ、金属酸窒化物を含む、剥離機能層と、
前記剥離機能層上に設けられる金属層と
を備えた、キャリア付金属箔。 - 前記金属酸窒化物が、TaON、NiON、TiON、NiWON及びMoONからなる群から選択される少なくとも1種を含む、請求項1に記載のキャリア付金属箔。
- 前記剥離機能層が、
前記キャリア上に設けられ、Cu、Ti、Ta、Cr、Ni、Al、Mo、Zn、W、TiN及びTaNからなる群から選択される少なくとも1種を含む密着層と、
前記密着層上に設けられ、TaON、NiON、TiON、NiWON及びMoONからなる群から選択される少なくとも1種の金属酸窒化物を含む剥離層と、
を含む、請求項1又は2に記載のキャリア付金属箔。 - 前記密着層が、Cu、Ti、Ta、Cr、Ni、Al、Mo、Zn、W、TiN及びTaNからなる群から選択される少なくとも1種を30原子%以上含む、請求項3に記載のキャリア付金属箔。
- 前記密着層の厚さT1が5nm以上400nm以下である、請求項3又は4に記載のキャリア付金属箔。
- 前記剥離層は、X線光電子分光法(XPS)により測定される、前記金属酸窒化物を構成する金属成分に対するOの原子比率が4%以上であり、かつ、前記金属酸窒化物を構成する金属成分に対するNの原子比率が20%以上である、請求項3~5のいずれか一項に記載のキャリア付金属箔。
- 前記剥離層の厚さT2が1nm以上150nm以下である、請求項3~6のいずれか一項に記載のキャリア付金属箔。
- 前記剥離層の厚さT2に対する前記密着層の厚さT1の比であるT1/T2が0.03以上400以下である、請求項3~7のいずれか一項に記載のキャリア付金属箔。
- 前記キャリアが、ガラス、シリコン、又はセラミックスで構成される、請求項1~8のいずれか一項に記載のキャリア付金属箔。
- 前記金属層がCu、Au及びPtからなる群から選択される少なくとも1種の金属又は合金で構成される、請求項1~9のいずれか一項に記載のキャリア付金属箔。
- 前記金属層の厚さT3が10nm以上1000nm以下である、請求項1~10のいずれか一項に記載のキャリア付金属箔。
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