US20220315721A1 - Resin surface hydrophilization method, plasma processing device, laminate body, and laminate body manufacturing method - Google Patents

Resin surface hydrophilization method, plasma processing device, laminate body, and laminate body manufacturing method Download PDF

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US20220315721A1
US20220315721A1 US17/625,272 US202017625272A US2022315721A1 US 20220315721 A1 US20220315721 A1 US 20220315721A1 US 202017625272 A US202017625272 A US 202017625272A US 2022315721 A1 US2022315721 A1 US 2022315721A1
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resin
plasma
chamber
processing device
metal
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Haruo HASHIGUCHI
Hiroyoshi Kubo
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Komiyama Electron Corp
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Komiyama Electron Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32366—Localised processing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • 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
    • 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
    • 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
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates
    • 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
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/568—Transferring the substrates through a series of coating stations
    • 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
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32733—Means for moving the material to be treated
    • H01J37/32743—Means for moving the material to be treated for introducing the material into processing chamber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32733—Means for moving the material to be treated
    • H01J37/32752—Means for moving the material to be treated for moving the material across the discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32899—Multiple chambers, e.g. cluster tools
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
    • H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/14—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using spraying techniques to apply the conductive material, e.g. vapour evaporation
    • H05K3/146—By vapour deposition
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H01J2237/336—Changing physical properties of treated surfaces
    • 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
    • H05K2203/09—Treatments involving charged particles
    • H05K2203/095—Plasma, e.g. for treating a substrate to improve adhesion with a conductor or for cleaning holes

Definitions

  • the present application relates to a resin surface hydrophilization method, a plasma processing device, a laminate body, and a laminate body manufacturing method, which are applicable to manufacturing a circuit substrate capable of handling millimeter waves or microwaves with a small transmission loss.
  • a low-dielectric liquid crystal polymer (LCP) or a low-dielectric fluororesin such as polytetrafluoroethylene (PTFE) has begun to be used instead of conventional polyimide.
  • LCP or PTFE has poor adhesion to copper used as a wire material.
  • the surface of the base member of the circuit substrate is chemically roughened, or unevenness is formed on the surface of copper foil which is to be brought into close contact with the substrate, thereby improving the degree of physical adhesion between the substrate and copper.
  • the contact angle of PTFE base member with water is about 50°.
  • the degree of adhesion between the PTFE base member and copper is about 0.4 N/mm. Therefore, in the process of producing a circuit pattern of copper on the PTFE base member, there is a fear that copper is peeled off from the PTFE base member.
  • the degree of adhesion between the PTFE base member and copper further decreases. Further, since the time during which the surface of PTFE base member is modified is about 24 hours, it is necessary to quickly bring copper into close contact with the surface of the PTFE base member, which has been a constraint on manufacturing circuit substrates.
  • Patent Document 1 the surface of a base member is cleaned with a high energy beam in a vacuum, and then, the surface of the base member is irradiated with ionized water vapor to adsorb a hydroxyl group on the surface of the base member.
  • the energy of the ionized water vapor is strong, the hydroxyl group once adsorbed is desorbed again from the surface of the base member when the surface of the base member is irradiated with ions of other water vapor. Therefore, the contact angle of the surface of the base member with water is about 40°.
  • a resin surface hydrophilization method of the present application includes a desorption step of desorbing at least a part of atoms constituting resin from a hydrophobic surface of the resin by irradiating the surface with plasma, and an introduction step of introducing a hydroxyl group on the surface of the resin subjected to the desorption step by irradiating the surface of the resin with hydroxyl radicals.
  • a laminate body manufacturing method of the present application includes a desorption step of desorbing at least a part of atoms constituting resin from a hydrophobic surface of the resin by irradiating the surface with plasma, an introduction step of introducing a hydroxyl group on the surface of the resin subjected to the desorption step by irradiating the surface of the resin with hydroxyl radicals, and a deposition step of depositing a metal film on a surface of the resin subjected to the introduction step.
  • a plasma processing device of the present application includes a first processing device including a first chamber, a first holding unit which holds resin, a first gas introduction unit which introduces, into the first chamber, first gas for desorbing at least a part of atoms constituting the resin from a surface of the resin when turned into plasma, and a first plasma generation unit which turns the first gas into plasma; and a second processing device including a grounded second chamber, a second holding unit which holds the resin processed in the first chamber and to which a first DC voltage is applied, a second gas introduction unit which introduces, into the second chamber, second gas which generates hydroxyl radicals by being turned into plasma, and a second plasma generation unit which turns the second gas into plasma and to which a second DC voltage higher than the first DC voltage is applied.
  • a laminate body of the present application includes a resin base member in which a part of atoms present on a hydrophobic surface of resin is replaced with a hydroxyl group, and a metal deposition film formed on a surface of the resin base member.
  • a contact angle of the surface of the resin base member with water is equal to or smaller than 30°.
  • the resin surface hydrophilization method of the present application high hydrophilicity can be imparted to a hydrophobic surface of resin for a long period of time. Therefore, a metal film is easily formed on the surface of resin.
  • the laminate body manufacturing method of the present application a laminate body in which a resin base member and a metal deposition film are brought firmly close contact with each other can be obtained.
  • the resin surface hydrophilization method of the present application can be easily performed. In the laminate body of the present application, a resin base member and a metal deposition film are brought into firmly close contact with each other.
  • FIG. 1 is a flow of a laminate body manufacturing method.
  • FIG. 2 is a schematic cross-sectional view showing a basic configuration of a processing device.
  • FIG. 3 is a schematic cross-sectional view of a plasma processing device according to a first embodiment.
  • FIG. 4 is a schematic cross-sectional view of the plasma processing device according to a second embodiment.
  • FIG. 5 is a schematic cross-sectional view of the plasma processing device according to a third embodiment.
  • FIG. 6 is a schematic vertical cross-sectional view of the plasma processing device according to a fourth embodiment.
  • FIG. 7 is a schematic horizontal cross-sectional view of the plasma processing device according to the fourth embodiment.
  • FIGS. 8A to 8D show images when water was dropped on a surface of a substrate before and after processing of an example, and SEM images of the surface of the substrate.
  • FIG. 9 is a graph showing the measurement results of contact angles of the surface of the substrate after the processing of the embodiment with water.
  • FIG. 1 shows a flow of each step of a laminate body manufacturing method of the present application.
  • the first two steps correspond to a resin surface hydrophilization method.
  • the resin surface hydrophilization method of the embodiments of the present application includes a desorption step S 10 and an introduction step S 20 .
  • the desorption step S 10 a hydrophobic surface of resin is irradiated with plasma to desorb at least some of the atoms constituting the resin from the surface of the resin. That is, in the desorption step S 10 , the hydrophobic surface of the resin is cleaned with the plasma, in particular, with ions in the plasma to activate the surface of the resin.
  • the resin is not particularly limited as long as it has a hydrophobic surface, and examples thereof include fluororesin such as PTFE, polyimide, and LCP. It is preferable that the resin contains fluorine and carbon and that the atom desorbing from the hydrophobic surface of the resin is fluorine and carbon. This is because the hydrophobic surface of the resin is largely hydrophilized. In addition, the resin containing fluorine has a high insulating property and is excellent as an electronic substrate.
  • the resin may contain wholly aromatic polyester, and the atom desorbing from the hydrophobic surface of the resin may be oxygen. It is preferable that the plasma contains at least one of nitrogen and argon. This is because atoms constituting the resin are easily desorbed from the surface of the resin by ions of nitrogen or argon.
  • the surface of the resin subjected to the desorption step S 10 is irradiated with hydroxyl radicals to introduce a hydroxyl group (—OH) onto the surface of the resin.
  • the surface of the resin into which the hydroxyl group is introduced has high hydrophilicity.
  • water vapor is turned into plasma, and the surface of the resin subjected to the desorption step S 10 is irradiated with hydroxyl radicals in the plasma.
  • the desorption step S 10 and the introduction step S 20 are performed in a reduced pressure state, and that the introduction step S 20 is performed after the desorption step S 10 while the reduced pressure state is maintained.
  • a hydroxyl group can be introduced into the surface of the resin while maintaining a state in which the surface of the resin is activated in the desorption step S 10 .
  • the surface of the resin subjected to the introduction step S 20 maintains hydrophilicity over a long period of time, for example, one month or more. Therefore, there is no problem even when the resin is opened to the atmosphere after the introduction step S 20 .
  • the desorption step S 10 is performed at a first pressure equal to or higher than 0.1 Pa and equal to or lower than 0.4 Pa, and the introduction step S 20 is performed at a second pressure equal to or higher than 30% and equal to or lower than 50% of the first pressure.
  • the introduction step S 20 is preferably performed at a temperature of the resin being equal to or higher than 150° C. and equal to or lower than 300° C. This is because the chemical reaction between the hydroxyl group and the surface of the resin is promoted, and the hydroxyl group is firmly introduced into the surface of the resin.
  • the laminate body manufacturing method of the present application includes the desorption step S 10 , the introduction step S 20 , and a deposition step S 30 .
  • the laminate body manufacturing method of the present application includes the deposition step S 30 after the resin surface hydrophilization method of the present application. Since the desorption step S 10 and the introduction step S 20 are the same as those in the resin surface hydrophilization method of the present application, the description of the desorption step S 10 and the introduction step S 20 is omitted.
  • a metal film is deposited on the surface of the resin subjected to the introduction step S 20 .
  • the deposition of the metal film is performed by, for example, a CVD method or a PVD method (sputtering).
  • Examples of the metal film include a copper film, a silver film, and a gold film.
  • the resin opened to the atmosphere after the introduction step S 20 may be used. However, in order to improve productivity and to suppress various contaminants from adhering to the resin, it is preferable to perform the introduction step S 20 and the deposition step S 30 while maintaining the reduced pressure state.
  • the laminate body manufacturing method of the present application may further include a coating step S 40 after the deposition step S 30 .
  • the coating step S 40 the surface of the deposited metal film is further coated with a metal layer formed of the same metal as the metal forming the metal film.
  • the method of coating the surface of the metal film with the metal layer include a method in which the metal film and the metal layer of the laminate body subjected to the deposition step S 30 are bonded together by thermocompression bonding, and a method in which the metal layer is formed on the metal film of the laminate body subjected to the deposition step S 30 by plating.
  • the laminate body of the embodiments of the present application includes the resin base member in which a part of atoms present on the hydrophobic surface of the resin is replaced with a hydroxyl group, and the metal deposition film formed on the surface of the resin base member. Then, the contact angle of the surface of the resin base member with water is equal to or smaller than 30°. Therefore, the surface of the resin base member and the metal deposition film are brought into firmly close contact with each other. More preferably, the contact angle of the surface of the resin base member with water is equal to or smaller than 10°.
  • the laminate body of the present application may further include, on the surface of the metal deposition film, the metal layer composed of the same metal as the metal forming the metal deposition film.
  • the resin may be polytetrafluoroethylene, and the atom replaced with a hydroxyl group may be fluorine. Further, the resin may be liquid crystal polymer containing wholly aromatic polyester.
  • FIG. 2 shows the basic configuration of a processing device 80 which can be used in the resin surface hydrophilization method of the present application.
  • the processing device 80 includes a vacuum chamber 2 , a fine plasma gun (FPG) 3 as the “plasma irradiation source”, a holding base 4 , a cover 5 , a first DC power source 9 , and a second DC power source 8 .
  • the vacuum chamber 2 is made of a metal such as aluminum alloy or stainless steel and is connected to the ground 10 .
  • the FPG 3 is arranged at the upper part in the vacuum chamber 2 .
  • the FPG 3 turns processing gas introduced into the vacuum chamber 2 from a gas introduction unit (not shown) into plasma.
  • the holding base 4 is installed below the FPG 3 to face the FPG 3 .
  • the holding base 4 is made of metal or an electrode, and holds a to-be-processed member 1 .
  • the cover 5 covers the upper surface of the holding base 4 .
  • the cover 5 is made of the same material as the to-be-processed member 1 so that the to-be-processed member 1 is uniformly irradiated with the plasma from the FPG 3 .
  • the first DC power source 9 is connected to the holding base 4 .
  • the second DC power source 8 is connected to the FPG 3 .
  • the processing gas such as nitrogen, argon, oxygen, and water vapor is introduced into the vacuum chamber 2 from the gas introduction unit while depressurizing the vacuum chamber 2 by an exhaust pump (not shown), thereby adjusting the pressure in the vacuum chamber 2 to a predetermined value, for example, 0.3 Pa being in a range between 0.1 Pa and 0.4 Pa both inclusive.
  • a second DC voltage is applied to the FPG 3 from the second DC power source 8 , the plasma is generated from the processing gas in the FPG 3 .
  • the pressure in the vacuum chamber 2 is adjusted to, for example, a pressure equal to or higher than 0.1 Pa and equal to or lower than 0.4 Pa.
  • the desorption step S 10 is performed as the following procedure.
  • the to-be-processed member 1 made of resin is held by the holding base 4 , nitrogen and/or argon as the processing gas is introduced into the vacuum chamber 2 from the gas introduction unit, and the pressure in the vacuum chamber 2 is adjusted to 0.3 Pa being in a range between 0.1 Pa and 0.4 Pa both inclusive by the exhaust pump.
  • the second DC power source 8 is turned on while the first DC power source 9 is kept off, that is, while the holding base 4 is grounded.
  • the plasma is generated from the processing gas in the FPG 3 , and the to-be-processed member 1 is irradiated with the directional ions and radicals. Then, atoms are desorbed from the surface of the to-be-processed member 1 mainly by the impact of the ions. Since the ions and radicals are directional, atoms can be efficiently desorbed from the surface of the to-be-processed member 1 . Most of the desorbed atoms are discharged to the outside of the vacuum chamber 2 by the exhaust pump. Some of the desorbed atoms float in the vacuum chamber 2 or adhere to an inner wall of the vacuum chamber 2 or a component in the vacuum chamber 2 after floating. However, in the present embodiment, since the pressure in the vacuum chamber 2 is lower than that in a general glow discharge condition, there is almost no impurity floating in the vacuum chamber 2 . Therefore, contamination of the to-be-processed member 1 is suppressed.
  • the desorption step S 10 is performed using the processing device 80 , if the voltage of the second DC power source 8 is increased, a larger amount of the plasma is generated from the processing gas and the desorption of atoms from the surface of the to-be-processed member 1 is promoted.
  • the processing is performed at a high voltage at one time, the wrinkled wall shown in the photograph of FIG. 8B grows too much and the unevenness becomes large. Large unevenness is undesirable to cause increasing of the transmission loss of the electronic substrate.
  • the voltage of the second DC power source 8 is changed with time. Since the unevenness is not formed at the beginning of the desorption step S 10 , processing is performed at a high voltage to have an increased desorption amount.
  • contaminants adhering to the surface of the to-be-processed member 1 can also be preferably removed at once.
  • the voltage is lowered and mild processing is performed so that the surface roughness is not deteriorated.
  • residual stress is generated on the surface by the processing, the residual stress can be suppressed by mild processing in which the voltage is lowered in the latter half process.
  • the introduction step S 20 is performed as the following procedure.
  • the desorption step S 10 and the introduction step S 20 are preferably performed by separate processing devices 80 . This is because when the introduction step S 20 is performed in the same processing device 80 as the processing device 80 in which the desorption step S 10 has been performed, that is, when the introduction step S 20 is performed after the desorption step S 10 in the same processing device 80 , components desorbed from the surface of the to-be-processed member 1 in the desorption step S 10 may adhere to the inside of the vacuum chamber 2 , and in the subsequent introduction step S 20 , the adhering substances may float and adhere to the surface of the to-be-processed member 1 . If there is no influence of the floating substances derived from the desorption step S 10 , the desorption step S 10 and the introduction step S 20 may be performed in the same processing device 80
  • the to-be-processed member 1 subjected to the desorption step S 10 is held by the holding base 4 . It is preferable that the to-be-processed member 1 is moved from the processing device 80 in which the desorption step S 10 is performed to the processing device 80 in which the introduction step S 20 is to be performed without being opened to the atmosphere, for example, by providing a vacuum preliminary chamber between the two processing devices 80 .
  • the processing gas containing water and/or water vapor is introduced into the vacuum chamber 2 from the gas introduction unit. It is preferable that the processing gas is water vapor. This is because hydroxyl radicals are easily generated as the radicals 6 .
  • the pressure in the vacuum chamber 2 is adjusted by the exhaust pump so that the pressure in the vacuum chamber 2 becomes equal to or higher than 30% and equal to or lower than 50% of the pressure in the desorption step S 10 . Since the pressure in the introduction step S 20 is equal to or higher than 30% and equal to or lower than 50% of the pressure in the desorption step S 10 , a large amount of hydroxyl radicals are generated as the radicals 6 in the plasma from the processing gas.
  • the first DC power source 9 and the second DC power source 8 are turned on. The plasma is generated from the processing gas by a potential difference between the FPG 3 and the grounded vacuum chamber 2 .
  • the voltage from the first DC power source 9 is preferably smaller than the voltage from the second DC power source 8 , and is more preferably smaller than the voltage from the second DC power source 8 as being equal to or higher than 40% of the voltage from the second DC power source 8 .
  • the to-be-processed member 1 is irradiated with the hydroxyl radicals as the radicals 6 , which have no polarity in the remaining plasma.
  • the hydroxyl group is introduced into the surface of the to-be-processed member 1 .
  • the to-be-processed member 1 is hardly irradiated with the ions 7 , it is possible to suppress the hydroxyl group introduced into the surface of the to-be-processed member 1 by the impact of the ions from being desorbed again.
  • stable hydrophilicity is imparted to the surface of the to-be-processed member 1 .
  • the hydroxyl group is chemically bonded to the surface of the to-be-processed member 1 .
  • FIG. 3 schematically shows a plasma processing device 90 of the first embodiment of the present application.
  • the to-be-processed member is a sheet-like resin.
  • the plasma processing device 90 includes a first processing device 91 and a second processing device 92 .
  • the first processing device 91 for performing the desorption step S 10 includes a first chamber 25 , a supply roller 11 , first holding units 14 , 15 , a first gas introduction unit 17 , and FPGs 12 , 13 as a “first plasma generation unit” and a “plasma irradiation source.”
  • the supply roller 11 is wound with a sheet-like resin having a hydrophobic surface, and supplies the resin to the first holding units 14 , 15 while rotating.
  • the resin supplied from the supply roller 11 is held while being wound around a part of the cylindrical first holding units 14 , 15 .
  • the FPGs 12 are arranged so as to face the first holding unit 14 .
  • the FPGs 13 are arranged so as to face the first holding unit 15 .
  • the first gas introduction unit 17 introduces first gas to desorb, when turned into plasma, at least some of the atoms constituting the resin from the surface of the resin into the first chamber 25 .
  • first gas is nitrogen and/or argon.
  • a voltage is applied to each of the FPGs 12 , 13 from a power source (not shown) to cause the first gas to turn into plasma.
  • No voltage is applied to the first holding units 14 , 15 . That is, the first holding units 14 , 15 are grounded.
  • a plasma generating means in the first plasma generation unit is not particularly limited. The first plasma generation unit may generate plasma by being applied with an AC voltage.
  • the pressure in the first chamber 25 is about 0.3 Pa at which dark discharge can be maintained.
  • the desorption step S 10 if the voltage of the FPGs 12 , 13 is increased, a larger amount of the plasma is generated from the processing gas and the desorption of atoms from the surface of the to-be-processed member 1 is promoted.
  • the wrinkled wall shown in the photograph of FIG. 8B grows too much and the unevenness becomes large. Large unevenness is undesirable to cause increasing of the transmission loss of the electronic substrate.
  • the levels of the voltages to be applied to the respective FPGs 12 , 13 are set based on the order in which the sheet of the to-be-processed member 1 is irradiated with the plasma.
  • a difference is provided between the voltage to be applied to the FPG antecedently performing irradiation onto the sheet of the to-be-processed member 1 and the voltage to be applied to the FPG subsequently performing irradiation onto the sheet.
  • the levels of the voltages to be applied to the respective FPGs 12 , 13 are set based on the order in which the to-be-processed member 1 is irradiated with plasma.
  • the voltage to be applied thereto is set to a high voltage.
  • contaminants adhering to the surface can also be preferably removed at once.
  • a resin 16 a having passed through the first holding unit 14 has one surface processed. Thereafter, when the resin 16 a passes through the first holding unit 15 , a resin 16 b having both surfaces processed is obtained.
  • the resin 16 b having both surfaces processed is wound around a part of the guide roller 19 .
  • the resin is fluororesin such as PTFE
  • both surfaces of the resin 16 b are activated by desorption of fluorine and/or carbon.
  • both surfaces of the resin 16 b are activated by desorption of oxygen.
  • the resin 16 b is supplied via the guide roller 19 into a second chamber 27 of the second processing device 92 which performs the introduction step S 20 in a state in which both surfaces thereof are activated.
  • a connection portion 26 provided with differential exhaust is arranged between the first chamber 25 and the second chamber 27 .
  • the differential exhaust separates the first chamber 25 and the second chamber 27 and the pressure in the first chamber 25 and the pressure in the second chamber 27 can be set different. As described above, since the desorption step S 10 and the introduction step S 20 are continuously performed by separately using the first processing device 91 and the second processing device 92 , high productivity can be ensured.
  • the second processing device 92 for performing the introduction step S 20 includes the second chamber 27 , second holding units 22 , 23 , a second gas introduction unit 18 , and FPGs 20 , 21 as the “second plasma generating unit” and the “plasma irradiation source.”
  • the second chamber 27 is grounded.
  • the second holding units 22 , 23 hold the resin 16 b processed in the first chamber 25 , and a first DC voltage is applied from a power source (not shown).
  • Each of the second holding units 22 , 23 include a heater 28 serving as a heating unit.
  • the temperature of the second holding units 22 , 23 is preferably maintained at a temperature equal to or higher than 150° C. and equal to or lower than 300° C. by the heaters 28 . This is because a hydroxyl group can be efficiently introduced into the surface of the resin 16 b.
  • the second gas introduction unit 18 introduces, into the second chamber 27 , a second gas which is turned into plasma to generate hydroxyl radicals.
  • the second gas is water vapor.
  • the FPGs 20 , 21 turn the second gas into plasma, and a second DC voltage higher than the first DC voltage is applied from a power source (not shown).
  • the first DC voltage is equal to or larger than 40% and equal to or lower than 99% of the second DC voltage.
  • the resin 16 b supplied from the first chamber 25 is held while being wound around a part of the cylindrical second holding units 22 , 23 .
  • the FPGs 20 are arranged so as to face the second holding unit 22 .
  • the FPGs 21 are arranged so as to face the second holding unit 23 .
  • the introduction step S 20 can be performed on both surfaces of the resin in the second processing device 92 . Further, since two FPGs are arranged for one second holding unit, the introduction step S 20 can be efficiently performed.
  • the pressure in the second chamber 27 is preferably equal to or higher than 30% and equal to or lower than 50% of the pressure in the first chamber 25 .
  • a resin 16 c having passed through the second holding unit 22 is hydrophilized on one surface thereof.
  • a resin 16 d having passed through the second holding unit 23 is hydrophilized on both surfaces thereof.
  • the resin 16 d is wound to a winding roller 24 . After the surfaces of all the resin are hydrophilized, the second chamber 27 is opened to the atmosphere and the resin 16 d is taken out.
  • FIG. 4 schematically shows a plasma processing device 95 of a second embodiment of the present application.
  • the plasma processing device 95 includes a first processing device (not shown), a second processing device 93 , and a third processing device 96 which performs the deposition step S 30 .
  • the second processing device 93 is substantially the same as the second processing device 92 .
  • the third processing device 96 includes a third chamber 65 , third holding units 68 , 71 , and metal deposition units 97 98 .
  • the third holding units 68 , 71 hold the resin 16 d processed in the second chamber 27 .
  • the metal deposition unit 97 includes an FPG 67 as the “plasma irradiation source” and a copper target 66 serving as a metal target. That is, an ion beam emitted from the FPG 67 collides with the copper target 66 , and copper ejected from the copper target 66 is deposited on one surface of the resin 16 d to form a copper deposition film.
  • the thickness of the copper deposition film is equal to or larger than 10 nm and equal to or smaller than 400 nm.
  • the metal deposition unit 98 includes an FPG 70 as the “plasma irradiation source” and a copper target 69 .
  • the resin 16 d subjected to the introduction step S 20 in the second chamber 27 is supplied into the third chamber 65 via the guide roller 63 .
  • a connection portion 64 provided with differential exhaust is arranged between the second chamber 27 and the third chamber 65 .
  • the resin 16 d supplied into the third chamber 65 is held while being wound around a part of the cylindrical third holding units 68 , 71 .
  • a laminate body 62 b in which the copper deposition film is formed on one surface of the resin 16 d is obtained.
  • a laminate body 62 c in which the copper deposition films are formed on both sides of the resin 16 d is obtained.
  • the laminate body 62 c is wound to the winding roller 24 .
  • the third chamber 65 is opened to the atmosphere and the laminate body 62 c is taken out. It is preferable that the processes from the desorption step S 10 to the deposition step S 30 are continuously performed under reduced pressure.
  • the metal deposited by the third processing apparatus is the same as at least a part of the inner wall of the second chamber 27 , the FPGs 20 , 21 , and the components installed in the second chamber 27 , so as not to be defective even when the metal floating from the inner wall of the second chamber 27 , the FPGs 20 , 21 , and the components installed in the second chamber 27 adheres to the resins 16 b , 16 c , 16 d.
  • sheets 50 , 51 made of the same metal as the metal to be deposited by the third processing device may be arranged as a shielding portion for covering at least a part of the inner wall of the second chamber 27 of the second processing device 101 and the components installed in the second chamber 27 , for example, the FPGs 20 , 21 . Since the metal deposited by the third processing device is the same as the metal forming the sheets 50 , 51 , it is prevented from being defective even when the metal floating from the sheets 50 , 51 adheres to the resins 16 b , 16 c , 16 d.
  • FIGS. 6 and 7 schematically show a plasma processing device 110 of a fourth embodiment of the present application.
  • the to-be-processed member is a resin 30 a in the form of a sheet-like piece.
  • the plasma processing device 110 includes vacuum preliminary chambers 38 , 41 , a first processing chamber 111 for performing the desorption step S 10 , a second processing chamber 112 for performing the introduction step S 20 , and gate valves 33 , 34 , 35 , 36 , 37 .
  • the first processing chamber 111 includes a first chamber 39 .
  • the second processing chamber 112 includes second chambers 40 a , 40 b.
  • a movable portion 31 for holding the resin 30 a at the end thereof and a raceway portion 32 a for mounting and conveying the movable portion 31 are arranged in the vacuum preliminary chamber 38 .
  • a raceway portion 32 b for conveying the movable portion 31 holding the resin 30 b is arranged in the first chamber 39 .
  • a raceway portion 32 c for conveying the movable portion 31 holding the resin 30 c is arranged in the second chamber 40 a .
  • a raceway portion 32 d for conveying the movable portion 31 holding the resin 30 d is arranged in the second chamber 40 b .
  • a raceway portion 32 e for conveying the movable portion 31 holding the resin 30 e is arranged in the vacuum preliminary chamber 41 .
  • a linear guide, a rack-and-pinion, or the like can be adopted as a conveying method for the resins 30 a , 30 b , 30 c , 30 d , 30 e.
  • the plasma processing device 110 is operated as follows.
  • the gate valve 33 is opened, and the movable portion 31 holding the end part of the resin 30 a is mounted on the raceway portion 32 a in the vacuum preliminary chamber 38 .
  • the gate valve 33 is closed to reduce the pressure in the vacuum preliminary chamber 38 .
  • the gate valve 34 is opened.
  • the movable portion 31 is moved into the first chamber 39 and the gate valve 34 is closed.
  • the desorption step S 10 is performed on the resin 30 b in the first chamber 39 to obtain the resin 30 c having both surfaces thereof activated.
  • the resin 30 b can be efficiently and homogeneously processed while using two pairs of the FPGs 42 , 43 .
  • the resin 30 c that is, the movable portion 31 moves to the position in front of the gate valve 35 .
  • the gate valve 35 is opened to move the movable portion 31 into the second chamber 40 a and the gate valve 35 is closed.
  • the introduction step S 20 is performed on the upper surface of the resin 30 c to obtain the resin 30 d .
  • the resin 30 d that is, the movable portion 31 moves to the position in front of the second chamber 40 b .
  • the introduction step S 20 is performed on the lower surface of the resin 30 d to obtain the resin 30 e .
  • the voltage applied to an electrode plate 45 a is larger than the voltage of the grounded second chamber 40 a and smaller than the voltage applied to the FPG 44 a as the “plasma radiation source.”
  • the voltage applied to an electrode plate 45 b is larger than the voltage of the grounded second chamber 40 b and smaller than the voltage applied to the FPG 44 b as the “plasma radiation source.”
  • the resins 30 c , 30 d are irradiated with the remaining hydroxyl radicals in the plasma.
  • the resin 30 e that is, the movable portion 31 moves to the position in front of the gate valve 36 .
  • the gate valve 36 is opened, the movable portion 31 is moved into the vacuum preliminary chamber 41 , and the gate valve 36 is closed. After the pressure in the vacuum preliminary chamber 41 is made atmospheric, the gate valve 37 is opened to take out the resin 30 e.
  • fine plasma guns (linear type ion beam source FPG-L040S manufactured by Finesolution Co., Ltd.) (the same applies hereinafter) were used to perform the desorption step on a commercially available A4-grade fluororesin substrate under the conditions that the pressure in the chamber was 0.3 Pa, the electric power supplied to the FPG was 300 W, and the processing gas was nitrogen or argon.
  • FPG linear type ion beam source FPG-L040S manufactured by Finesolution Co., Ltd.
  • fine plasma guns were used to perform the introduction step on the substrate subjected to the desorption step while the voltage applied to the holding base holding the substrate was set lower than the voltage applied to the FPG under the conditions that the pressure in the chamber was 0.15 Pa in the chamber, the electric power supplied to the FPG was 300 W, and the processing gas was water vapor.
  • FIG. 8A shows an image obtained by measuring the contact angle of the surface of the substrate with water without performing the desorption step and the introduction step, that is, before the processing.
  • the water dropped on the surface of the substrate before the processing was rounded. In other words, the surface of the substrate before the processing exhibited high water repellency.
  • the contact angle of the surface of the substrate before the processing with water was larger than 90°.
  • FIG. 8B shows an image obtained by measuring the contact angle of the surface of the substrate with water after performing the desorption step and the introduction step, that is, after the processing. As shown in FIG. 8B , the water dropped on the surface of the substrate after the processing spread. In other words, the surface of the substrate after the processing exhibited high water hydrophilicity.
  • FIG. 8C shows a scanning electron microscope (SEM) image of the surface of the substrate before the processing. Scratches and holes generated when the fluororesin block was peeled off into a sheet shape were observed.
  • FIG. 8D shows an SEM image of the surface of the substrate after the processing. The scratches and holes observed on the surface of the substrate before the processing disappeared, and elongated unevenness was observed. The unevenness is considered to be caused by the irradiation of the substrate with ions in the desorption step. As described above, although the surface morphology of the substrate changed greatly before and after the processing, the surface roughness of the substrate hardly changed before and after the processing.
  • FIG. 9 shows the measurement result of the contact angle of the surface of the fluororesin sheet after the processing with water.
  • the short side of the fluororesin sheet was taken as an X axis
  • the long side was taken as a Y axis
  • the center of the fluororesin sheet was taken as a coordinate (0,0).
  • the contact angle with water was measured at a total of 15 points including 5 points in the short side direction and 3 points in the long side direction. One point was measured twice and the mean value was plotted.
  • the variation in the Y-axis direction was 0.3° to 1.9° at any X-axis point. Further, the variation in the X-axis direction was 1.6° to 1.9°.
  • the contact angle was smaller than 6° at all measurement points.
  • the degree of adhesion between the substrate and the copper was about 0.8 N/mm, indicating strong adhesion between the substrate and the copper.
  • the resin surface hydrophilization method, the plasma processing device, the laminate body, and the laminate body manufacturing method of the present application are used for a circuit substrate used in a mobile phone for communicating high-speed and large-capacity information. Since the relative dielectric constant of the fluororesin is lower than that of air, the fluororesin substrate is particularly suitable for a material of a high-frequency substrate. Compared with circuit substrates using other general materials, a circuit substrate using fluororesin has a low relative dielectric constant and small dielectric loss tangent even when a high frequency current flows, and has a small dielectric loss.
  • the hydrophilicity of the substrate is improved, the adhesion with copper wiring can be improved, and a circuit substrate which can withstand use in a high frequency band can be provided.
  • the technology applicable to the use in the high frequency band can be applied not only to the main body of the mobile phone but also to a substrate used for a base station of the mobile phone, a substrate for communication dedicated to a home, a factory, or an area, or a substrate for a millimeter wave radar used for automatic driving of an automobile, a drone, or the like, and has a wide application range.

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