WO2011162218A1 - Stratifié de couche d'isolation céramique et de couche métallique et procédé pour la production d'un stratifié - Google Patents

Stratifié de couche d'isolation céramique et de couche métallique et procédé pour la production d'un stratifié Download PDF

Info

Publication number
WO2011162218A1
WO2011162218A1 PCT/JP2011/064083 JP2011064083W WO2011162218A1 WO 2011162218 A1 WO2011162218 A1 WO 2011162218A1 JP 2011064083 W JP2011064083 W JP 2011064083W WO 2011162218 A1 WO2011162218 A1 WO 2011162218A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
insulating layer
ceramic insulating
metal layer
laminate
Prior art date
Application number
PCT/JP2011/064083
Other languages
English (en)
Japanese (ja)
Inventor
直彦 阿部
Original Assignee
三井金属鉱業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 三井金属鉱業株式会社 filed Critical 三井金属鉱業株式会社
Publication of WO2011162218A1 publication Critical patent/WO2011162218A1/fr

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/33—Thin- or thick-film capacitors 
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C04B37/025—Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of glass or ceramic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40—Capacitors
    • H01L28/60—Electrodes
    • H01L28/75—Electrodes comprising two or more layers, e.g. comprising a barrier layer and a metal layer
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • C04B2237/062—Oxidic interlayers based on silica or silicates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/08—Non-oxidic interlayers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/345—Refractory metal oxides
    • C04B2237/346—Titania or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/402—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/405—Iron metal group, e.g. Co or Ni
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40—Metallic
    • C04B2237/407—Copper
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/50—Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/70—Forming laminates or joined articles comprising layers of a specific, unusual thickness
    • C04B2237/708—Forming laminates or joined articles comprising layers of a specific, unusual thickness of one or more of the interlayers
    • 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
    • H05K1/0213—Electrical arrangements not otherwise provided for
    • H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
    • H05K1/023—Reduction of cross-talk, noise or electromagnetic interference using auxiliary mounted passive components or auxiliary substances
    • H05K1/0231—Capacitors or dielectric substances
    • 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
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors

Definitions

  • the laminated body of the ceramic insulating layer and the metal layer is an electronic circuit forming material for forming various electronic circuits including a capacitor circuit or a transistor circuit on a printed wiring board or a semiconductor substrate, or a capacitor or a transistor. It can be suitably used as an electronic component forming material for forming various electronic components.
  • electronic components such as capacitors and resistors are formed on the inner layer of a multilayer wiring board by a wiring pattern or the like at the manufacturing stage of the printed wiring board.
  • electronic components such as capacitors can be arranged directly under active elements such as ICs, and the wiring length between electronic components can be shortened to the limit and wiring can be simplified. It becomes possible. For this reason, increase in parasitic resistance can be suppressed, signals can be transmitted and received between components at higher speed, and generation of heat generation, unnecessary radiation, crosstalk, and the like can be suppressed.
  • the printed wiring board can be further reduced in thickness and thickness. Therefore, it is considered that the demand for such a printed wiring board with built-in electronic components will further increase in the future in the realization of portable electronic devices and the like that require further advanced processing.
  • Patent Document 1 and Patent Document 2 as one of the circuit forming materials, have an insulating layer or a dielectric layer on a metal foil as a conductive layer.
  • Capacitor circuit forming materials have been proposed that have a basic structure of laminated ceramic insulating layers.
  • the capacitance of the capacitor increases as the dielectric constant of the dielectric layer increases. Furthermore, when the electrode area is the same, the capacitance becomes larger as the distance between the electrodes is shorter. That is, in order to obtain a capacitor having a large capacitance, a laminate of a ceramic insulating layer and a metal layer in which a ceramic insulating layer and a metal layer having a high dielectric constant are stacked is required. Further, along with miniaturization of semiconductor integrated circuits, miniaturization of transistor circuits and thinning of gate insulating films are required. Therefore, it is required to form a ceramic insulating layer used as a dielectric layer or an insulating layer thin on a conductive layer and in a wide area.
  • sol-gel method electrophoretic electrodeposition, MOCVD method, sputtering deposition and the like have been adopted for forming the ceramic insulating layer.
  • sol-gel method a high temperature is applied to the metal layer as a base material during firing, and the metal layer is oxidized to cause deterioration of the base material, or the constituent metal of the metal layer diffuses into the ceramic insulating layer. As a result, the insulating property is lowered, and the reliability is sometimes lowered.
  • the metal material forming the conductive layer has low electrical resistivity and heat resistance. It was necessary to select a material that can withstand a high temperature process. In other words, from the viewpoint of electrical resistivity, there is a case where copper cannot be adopted when it is necessary to go through a high temperature process even though copper is superior.
  • the constituent material of the metal layer used as the base material can be selected as appropriate regardless of the method of forming the ceramic insulating layer. There has been a demand for improvement in production yield by preventing a decrease in insulating properties of the insulating layer.
  • the present inventors can appropriately select a metal material for forming a conductive layer regardless of a method for forming a ceramic insulating layer, and obtain a capacitor circuit having stable capacitor characteristics.
  • the present inventors have devised the following invention of a laminate of a ceramic insulating layer and a metal layer and a method of manufacturing the laminate, which can improve the production yield and obtain a highly reliable circuit forming material. .
  • a laminate of a ceramic insulating layer and a metal layer according to the present invention is a laminate of a ceramic insulating layer and a metal layer, and the metal layer has a surface on the side where the ceramic insulating layer is provided. Further, a protective layer made of a silicon compound having a layer thickness of 5 nm to 100 nm is provided.
  • the protective layer is preferably made of an amorphous silicon compound.
  • the method for producing a laminate of a ceramic insulating layer and a metal layer according to the present invention includes a protective layer forming step of forming a protective layer made of a silicon compound having a layer thickness of 5 nm to 100 nm on the upper surface of the metal layer, And a ceramic insulating layer forming step of forming the ceramic insulating layer on the surface of the protective layer.
  • a protective layer made of a silicon compound having a layer thickness of 5 nm to 100 nm is provided on the side of the metal layer on which the ceramic insulating layer is provided.
  • the ceramic insulating layer is formed on the upper surface of the metal layer through a high-temperature process such as firing in the course of manufacturing by various methods such as a sol-gel method, a sputtering method, a CVD method, and an electrophoretic electrodeposition method.
  • the oxidation of the metal layer can be extremely effectively prevented, the decrease in the conductivity of the metal layer as the conductive layer and the deterioration of the mechanical characteristics can be prevented. Adhesion with the system insulating layer is improved.
  • the protective layer acts as a barrier, preventing the metal constituting the metal layer from precipitating and diffusing into the ceramic insulating layer, thereby reducing the insulating properties of the ceramic insulating layer. And the deterioration of dielectric characteristics can be prevented, and the laminate can be provided as a highly reliable electronic circuit forming material or electronic circuit component forming material.
  • the metal material for forming the conductive layer can be appropriately selected regardless of the method for forming the ceramic insulating layer, and a capacitor circuit having stable capacitor characteristics can be obtained and produced. The yield can be improved and a highly reliable circuit forming material can be obtained.
  • the laminated body of the ceramic insulating layer and the metal layer according to the present invention can be used as, for example, a dielectric layer and a lower electrode forming layer of a capacitor, or a gate insulating film and a gate electrode of a transistor. It can be suitably used as an electronic circuit forming material for forming various electronic circuits on a substrate or a semiconductor substrate, or an electronic component forming material for forming various electronic components such as capacitors and transistors. .
  • 1. Laminated body of ceramic insulating layer and metal layer; The manufacturing method of the said laminated body is demonstrated in order.
  • a laminated body 100 according to the present invention is obtained by laminating a ceramic insulating layer 30 on the upper surface of a metal layer 10 with a protective layer 20 interposed therebetween.
  • the protective layer 20 is characterized by adopting a layer made of a silicon compound having a layer thickness of 5 nm to 100 nm.
  • the metal layer 10, the protective layer 20, and the ceramic insulating layer 30 will be described in this order.
  • the metal layer 10 has conductivity, and is a layer used as, for example, an electrode formation layer. Accordingly, various metals such as copper, aluminum, nickel, cobalt, gold, and platinum, or various metals that can be employed as the conductive layer such as an alloy thereof can be appropriately selected and used.
  • any of the above-listed materials can be suitably used, but it is preferable to use copper, aluminum, nickel, or an alloy thereof from the viewpoint of easy availability and low cost. Furthermore, copper or a copper alloy can be particularly preferably used because it has a low electrical resistivity and is excellent in workability during circuit formation by etching or the like.
  • a surface treatment layer using one or more selected from nickel, zinc, chromium, or an alloy thereof may be provided on the surface of the metal layer 10.
  • various surfaces according to the metal used for the surface treatment such as improvement of heat resistance and improvement of corrosion resistance of the metal layer 10.
  • a processing effect can be obtained. Therefore, even when copper or a copper alloy is selected as a constituent material of the metal layer 10, by providing the surface treatment layer between the metal layer 10 and the protective layer 20, a metal layer made of copper or a copper alloy.
  • the heat resistance, corrosion resistance, etc. of No. 10 can be improved and deterioration of the conductive layer, such as a decrease in conductivity and a decrease in mechanical properties, can be prevented.
  • the surface treatment layer has an arbitrary layer configuration, the illustration is omitted in FIG.
  • Silane coupling agent layer In the laminate 100 according to the present invention, a silane coupling agent layer may be provided between the metal layer 10 and the protective layer 20.
  • a silane coupling agent layer By providing the silane coupling agent layer, the wettability of the metal layer 10 can be improved and the adhesion between the metal layer 10 and the protective layer 20 can be improved. Since the silane coupling agent layer has an arbitrary layer configuration, the illustration thereof is omitted in FIG.
  • the metal layer 10 when a surface treatment layer and a silane coupling layer are provided between the metal layer 10 and the protective layer 20, only one of these layers may be provided, or both layers may be provided. Good.
  • both the surface treatment layer and the silane coupling agent layer are provided between the metal layer 10 and the protective layer 20, the metal layer 10, the surface treatment layer, the silane coupling agent layer, and the protective layer 20 are laminated in this order. It is preferable to provide as described above. This is because the surface treatment effect of the metal layer 10 by the surface treatment layer is obtained, and the adhesion between the protective layer 20 and the metal layer 10 is obtained by the silane coupling agent layer.
  • the protective layer 20 is a layer made of a silicon compound and having a thickness of 5 nm to 100 nm, and the ceramic insulating layer 30 is provided on the surface of the protective layer 20.
  • the protective layer 20 made of a silicon compound with a layer thickness of 5 nm to 100 nm, for example, when the ceramic insulating layer 30 is formed on the surface of the metal layer 10, Deterioration of the metal layer 10, that is, oxidation of the various metal materials constituting the metal layer 10 can be extremely effectively prevented, and deterioration of the metal layer 10 can be prevented.
  • the thickness of the protective layer 20 is more preferably in the range of 10 nm to 70 nm.
  • the thickness of the protective layer 20 is in the range of 10 nm to 70 nm, the deterioration of the metal layer 10 can be more effectively prevented even when a high temperature process is performed when the ceramic insulating layer 30 is formed. can do. Further, as described later, even when a BST (Barium Strontium Titanate) layer having a perovskite structure is employed as the ceramic insulating layer 30, it prevents the highly reactive BST layer from reacting with the metal layer 10. Further, it is possible to prevent the metal constituting the metal layer 10 from being precipitated and diffused in the ceramic insulating layer 30.
  • BST Barium Strontium Titanate
  • the conductivity of the metal layer 10 is reduced and the ceramic insulating layer is provided. It is possible to prevent the decrease in the insulation property of 30 very effectively. For this reason, in the past, in consideration of the influence of heat applied when the ceramic insulating layer 30 is formed, copper or a copper alloy could not be actively employed as described above. As described above, copper or a copper alloy can be suitably used as a constituent material of the metal layer 10. Hereinafter, this point will be further described.
  • the ceramic insulating layer 30 As a method for forming the ceramic insulating layer 30, various methods such as a sol-gel method, an MOCVD method, a sputtering deposition method, and an electrophoretic electrodeposition method are generally employed. Conventionally, it has been necessary to appropriately select the metal constituting the conductive layer for forming the lower electrode in accordance with the method for forming the ceramic insulating layer 30. In other words, the heat applied when forming the ceramic insulating layer 30 may oxidize the metal material constituting the conductive layer and cause deterioration of the conductive layer. It was necessary to appropriately select a metal material constituting the conductive layer according to the method employed.
  • platinum or the like is used as a heat-resistant metal in order to prevent oxidation of the conductive layer when it is necessary to go through a high-temperature process such as a firing process in a sol-gel method or the like. It was.
  • a metal foil as the conductive layer
  • a nickel foil or a nickel alloy foil nickel-phosphorus alloy foil, nickel-cobalt alloy foil
  • a composite foil in which a nickel layer of, for example, about 1 ⁇ m to 5 ⁇ m is laminated on a copper layer Etc. have been adopted.
  • the metal material constituting the conductive layer for forming the lower electrode in the laminate 100 of the ceramic insulating layer and the metal layer is used when forming the ceramic insulating layer 30 used as a dielectric layer.
  • certain restrictions may be imposed on the type of metal that can be selected. For example, when copper and nickel are compared, the electrical resistivity of copper is about 1.68 ⁇ 10 ⁇ 8 ⁇ m, whereas the electrical resistivity of nickel is 6.99 ⁇ 10 ⁇ 8 ⁇ m. Copper is a nonmagnetic metal, whereas nickel is a magnetic metal.
  • the metal layer 10 is made of copper, which has a low electrical resistivity and is nonmagnetic. is there.
  • conventionally when a high temperature process exists when forming the ceramic insulating layer 30, copper or copper alloy is oxidized under this high temperature process, and the above-mentioned various problems occur, so copper or copper In some cases, the alloy could not be actively employed.
  • the present invention for example, a two-layer structure in which the metal layer 10 and the protective layer 20 are laminated as a conductive layer, and the ceramic insulating layer 30 is formed on the surface of the protective layer 20 using the conductive layer as a base material.
  • the metal layer 10 can be configured by appropriately selecting various metals including copper or a copper alloy regardless of the method of forming the ceramic insulating layer 30.
  • the protective layer 20 is preferably made of one kind selected from SiO 2 , SiN x —SiO 2 (x> 0) and SiN x (x> 0) as the silicon compound. Since the protective layer 20 made of these silicon compounds can be formed at a relatively low temperature, a heat load is not applied to the metal layer 10 when the protective layer 20 is formed, and the metal layer 10 is not oxidized. These silicon compounds are preferable because they have low reactivity with the metal layer 10 and do not react with the metal layer 10 to lower the conductivity of the metal layer 10. Further, since the protective layer 20 made of these silicon compounds is amorphous and excellent in flexibility, it is excellent in handling properties when the laminate 100 of the ceramic insulating layer and the metal layer is laminated on a substrate.
  • the ceramic insulating layer 30 is a layer that is used as an insulating layer or a dielectric layer when manufacturing various electronic components using the laminate 100, and is a layer made of an inorganic oxide. For example, considering the case where a capacitor circuit is formed by etching or the like using the multilayer body 100, it is preferable that the ceramic insulating layer 30 is thin.
  • the capacitance (C) of the capacitor can be obtained by the following equation, and is proportional to the dielectric constant and inversely proportional to the distance (d) between the electrodes, that is, the thickness of the ceramic insulating layer 30. Because.
  • C ⁇ 0 (A / d) (formula)
  • C is the capacitance of the capacitor
  • ⁇ is the dielectric constant of the ceramic insulating layer 30
  • ⁇ 0 is the vacuum dielectric constant
  • A is the surface area of the electrode
  • d is This is the distance between the upper electrode and the lower electrode.
  • Thickness of the ceramic insulating layer From the viewpoint of forming a capacitor having a large capacitance using the laminate 100 according to the present invention, or from the viewpoint of miniaturizing various electronic components such as transistors, the ceramic system according to the present invention
  • the insulating layer 30 is preferably thinner as described above. Specifically, the thickness is preferably in the range of 50 nm to 5.0 ⁇ m, and more preferably in the range of 50 nm to 2.0 ⁇ m. If the thickness of the ceramic insulating layer 30 is less than 50 nm, the layer thickness may be non-uniform, and the upper electrode and the lower portion when the capacitor circuit is formed due to the presence of gaps between the inorganic oxide particles.
  • the ceramic insulating layer 30 is composed of barium titanate, strontium titanate, barium strontium titanate, strontium zirconate, zirconic acid.
  • a perovskite ferroelectric thin layer having a basic composition such as bismuth is preferred.
  • the ceramic insulating layer 30 is a perovskite ferroelectric thin layer having a basic composition of any one of barium titanate, strontium titanate, and barium strontium titanate, the dielectric constant is high, This is particularly preferable from the viewpoint that a large capacity capacitor circuit can be obtained.
  • the ceramic insulating layer 30 is preferably impregnated with a resin component between particles or grain boundaries present in the ceramic insulating layer 30.
  • a resin component between particles or grain boundaries present in the ceramic insulating layer 30 is formed by the sol-gel method or the electrophoretic electrodeposition method. Therefore, by impregnating a resin component between particles or grain boundaries existing in the ceramic insulating layer 30, a structural defect serving as a leakage current channel can be filled.
  • the leakage current can be reduced, the deterioration of the insulating properties of the ceramic insulating layer 30 can be prevented, and it can function as a highly reliable insulating layer or dielectric layer, and the production yield can be improved. can do.
  • group insulating layer 30, or a grain boundary, the impregnation method, etc. are 2. This will be described later in the method for manufacturing the laminate 100 of the ceramic insulating layer and the metal layer.
  • the upper electrode formation layer 40 made of a metal material is provided on the upper surface of the ceramic insulating layer 30, and the metal layer 10 (including the protective layer 20) is provided.
  • the laminated body 100 may be configured as a capacitor circuit forming material (110) that uses the dielectric characteristics of the ceramic insulating layer.
  • the upper electrode formation layer 40 is preferably composed of any one of copper, copper alloy, nickel, nickel alloy, and aluminum.
  • the capacitor circuit forming material (110) thus configured can be suitably used, for example, when a capacitor circuit is formed on the inner layer of the printed wiring board by etching or the like.
  • the method for producing a laminate of a ceramic insulating layer and a metal layer according to the present invention includes a protective layer forming step of forming a protective layer 20 made of a silicon compound having a layer thickness of 5 nm to 100 nm on the metal layer 10; And a ceramic insulating layer forming step of forming the ceramic insulating layer 30 on the surface of the protective layer 20.
  • a protective layer forming step of forming a protective layer 20 made of a silicon compound having a layer thickness of 5 nm to 100 nm on the metal layer 10 and a ceramic insulating layer forming step of forming the ceramic insulating layer 30 on the surface of the protective layer 20.
  • the protective layer 20 made of the silicon compound having a thickness of 5 nm to 100 nm is formed on the metal layer 10.
  • the metal layer 10 can be made of various metals such as copper, nickel, cobalt, gold, and platinum, or metal foils of these alloys, etc.
  • copper or a copper alloy can be preferably used.
  • copper has the lowest electrical resistivity among the above-mentioned metals and is a non-magnetic material, so that it is suitable as a conductive layer and is easily available compared to other metals. This is because processing such as etching is easy and the manufacturing cost can be kept low because it is inexpensive.
  • the metal layer 10 can be formed using a metal foil made of the various metals described above.
  • a metal foil obtained by a rolling method or an electrolytic method can be used.
  • copper foil or copper alloy foil brass foil, Corson alloy foil
  • nickel foil or nickel alloy foil nickel-phosphorus alloy foil, nickel-cobalt alloy foil
  • the metal layer 10 may be a single composition metal layer from the viewpoint of satisfactorily forming a fine electrode pattern or wiring pattern in consideration of, for example, performing circuit formation by etching or the like. preferable. Moreover, you may provide the said surface treatment layer and / or a silane coupling agent layer on the surface of the metal layer 10 by a conventionally well-known method as needed.
  • the protective layer 20 is formed on the surface of the metal layer 10 so as to have a layer thickness of 5 nm to 100 nm. However, when the surface treatment layer and / or the silane coupling layer is provided on the surface of the metal layer 10, the protective layer 20 is provided on the surface of the outermost surface treatment layer or the silane coupling material layer. Form.
  • Polysilazane is applied within a range of 5 nm to 100 nm on the metal layer 10 provided with a surface treatment layer and / or a silane coupling agent layer as required. Apply to a thickness.
  • a coating method for example, a conventionally known coating method such as a spin coating method can be appropriately employed.
  • the polysilazane solution for example, SSL-SD500-HB manufactured by Exsia Co., Ltd. can be used.
  • it may be used after appropriately diluted with an organic solvent such as anhydrous dibutyl ether.
  • polysilazane is a polymer in which Si—N (silicon-nitrogen) bonds are repeated in the molecule, and is not particularly limited as long as it can be easily converted to silica (SiO 2 ).
  • Si—N silicon-nitrogen
  • perhydropolysilazane having a repeating structure of — (SiH 2 —NH) — in which two hydrogen atoms are bonded to Si atoms of Si—N bonds reacts with moisture in the atmosphere and is easily converted to silica. Therefore, it can be preferably used when forming the protective layer 20.
  • a dense and amorphous high-purity silica (amorphous SiO 2 ) layer can be obtained by using the organic solvent solution of perhydropolysilazane as a coating solution, drying in the air, and irradiating with UV.
  • the UV irradiation is performed in order to promote the reaction between polysilazane and moisture in the air to shorten the time required for conversion to silica and satisfy the productivity required for industrial production.
  • the drying is a process performed for the purpose of removing the solvent, preventing the flow of the coating film, and the like, and is generally performed in the range of 80 ° C to 130 ° C.
  • drying is performed for the purpose of removing the solvent, preventing the flow of the coating film, and the like. Therefore, it is not necessary to perform drying for a long time, and it may be appropriately performed within a range of about 10 seconds to 5 minutes.
  • the purpose of UV irradiation is to promote the reaction between polysilazane and moisture in the atmosphere.
  • the reaction promoting effect by UV irradiation is enhanced.
  • the temperature is lower than 150 ° C., the reaction promoting effect by heating cannot be sufficiently obtained, which is not preferable.
  • it exceeds 350 degreeC the heat load may be given with respect to the metal layer 10, and it is unpreferable.
  • the time required for UV irradiation is the time required for polysilazane to be converted to silica after the polysilazane solution is coated and the polysilazane coating layer is cured.
  • UV irradiation is performed in the above temperature range
  • the polysilazane coating layer that is, the protective layer 20 having a layer thickness of 5 nm to 100 nm is formed
  • it is converted to silica in the range of 1 minute to 180 minutes. Therefore, when the UV irradiation time is less than 1 minute, the reaction between polysilazane and moisture may not be completed.
  • the polysilazane layer has the above thickness, it is converted into a silica layer within 180 minutes. There is little need to irradiate UV beyond minutes.
  • CVD Method Chemical Vapor Phase Reaction Method
  • Physical Vapor Deposition Method In forming the protective layer 20, in addition to the method of applying a polysilazane coating solution, a conventionally known chemical vapor reaction method or physical vapor deposition method is used.
  • a SiO 2 layer, a SiNx (silicon nitride) -SiO 2 layer, or a SiNx layer may be formed.
  • the surface of the metal layer 10 is so-called glass coated, so that the oxidation effect of the metal layer 10 and the effect of preventing metal diffusion into the ceramic insulating layer 30 are achieved.
  • a sol-gel solution is applied to the surface of the metal layer 10 by a spin coating method or the like in the sol-gel method described below, the metal layer 10 is protected to prevent the metal layer 10 from being mechanically damaged. can do.
  • the ceramic insulating layer forming step is characterized in that the ceramic insulating layer 30 is formed on the surface of the protective layer 20 laminated on the metal layer 10 in the protective layer forming step.
  • the ceramic insulating layer 30 is formed on the surface of the protective layer 20, regardless of what method is adopted when forming the ceramic insulating layer 30, deterioration due to oxidation or the like of the metal layer 10 or the ceramic This is because diffusion of the base metal into the system insulating layer 30 can be prevented.
  • a sol-gel method As a method for forming the ceramic insulating layer 30, various methods such as a sol-gel method, an electrophoretic electrodeposition method, an MOCVD method, and a sputtering vapor deposition method can be employed.
  • a sol-gel method and an electrophoretic electrodeposition method which are particularly advantageous when the ceramic insulating layer 30 is formed thin over a wide area, will be described.
  • the sol-gel solution preparation step is a step for preparing a sol-gel solution for forming the ceramic insulating layer 30 having a desired composition.
  • the process is not particularly limited, and the sol-gel solution may be prepared by itself so as to be the ceramic insulating layer 30 having a desired composition, or a commercially available preparation solution may be used. .
  • a sol-gel solution capable of forming the ceramic insulating layer 30 having a desired composition for example, as the ceramic insulating layer 30, a BST layer having a perovskite structure as a crystal structure can be formed using 10 wt% BST (90/10/100) manufactured by Mitsubishi Materials.
  • 90/10/100 is the molar ratio of barium, strontium, and titanic acid.
  • (A-2) Coating process In the coating process, the sol-gel liquid prepared in the above-mentioned (A) sol-gel liquid preparation process is applied to the surface of the protective layer 20 of the metal layer 10, and the sol-gel liquid is dried to obtain the desired This is a step of obtaining a sol-gel solution coating layer having a layer thickness of.
  • a conventionally known method can be appropriately employed. However, in consideration of the uniformity of the layer thickness, the characteristics of the sol-gel solution, and the like, it is preferably performed by a spin coating method.
  • the coating method is characterized by adopting the following method. That is, applying a sol-gel solution to the surface of the protective layer 20 of the metal layer 10 and drying in an oxygen-containing atmosphere at a temperature range of 120 ° C. to 350 ° C. for 30 seconds to 10 minutes is repeated a plurality of times. It is preferable to adjust the layer thickness of the liquid coating layer. If the drying conditions are not met and the drying becomes insufficient, the final thickness of the ceramic insulating layer 30 may be reduced due to the flow of the coating film or re-dissolution during repeated application. Since it becomes uniform, it is not preferable.
  • the drying condition is out of the range and the drying becomes excessive, a heat load is applied to the metal layer 10 as a base material, and the metal layer 10 may be deteriorated. .
  • the sol-gel solution by repeatedly applying and drying the sol-gel solution, it is easy to adjust the layer thickness of the sol-gel solution coating layer, and the ceramic insulating layer 30 having a desired thickness can be obtained. Can do.
  • (A-3) Firing step The firing step is preferably performed at 400 to 800 ° C. for 5 to 120 minutes in an inert gas replacement (nitrogen gas atmosphere or the like; the same applies hereinafter) or a vacuum atmosphere. Through the firing step, the oxidation reaction of the precursor proceeds, and the ceramic insulating layer 30 according to the present invention can be obtained. The reason why the firing process is performed in an inert gas replacement or vacuum atmosphere is to prevent the metal layer 10 from being deteriorated.
  • the firing temperature is less than 400 ° C.
  • the above oxidation reaction is incomplete, excellent adhesion to the metal layer 10 as a base material, ceramic as a dielectric layer having an appropriate fineness and a crystal structure of an appropriate particle size It is difficult to obtain the system insulating layer 30.
  • the firing temperature exceeds 800 ° C.
  • firing is excessive, which is not preferable because the insulation of the ceramic insulating layer 30 is lowered, the physical strength of the metal layer 10 is lowered, and the conductivity is lowered.
  • the firing temperature and firing time can be appropriately changed to an appropriate temperature and time depending on the type of constituent metal of the metal layer 10 and the composition of the sol-gel solution used for forming the ceramic insulating layer 30. Of course.
  • the ceramic insulating layer 30 is obtained by firing the sol-gel solution coating layer in the above-mentioned temperature range in the firing step.
  • the protective layer 20 according to the present invention provided on the upper layer of the metal layer 10 as a base material, as described above the deterioration of the metal layer 10, that is, the oxidation of the metal material constituting the metal layer 10 Can be prevented very effectively, and the deterioration of the metal layer 10 can be prevented.
  • a highly reactive BST layer is formed using a BST solution or the like as a sol-gel solution when the ceramic insulating layer 30 is formed, the metal layer 10 and the BST layer are formed in the firing step or the like.
  • the reaction can be prevented and the metal constituting the metal layer 10 can be prevented from precipitating and diffusing in the ceramic insulating layer 30. Therefore, conventionally, when a temperature within the above range is applied to the metal layer 10 in the firing step, it has not been possible to positively adopt copper or a copper alloy in which an oxidation reaction easily proceeds. However, as described above, by providing the protective layer 20 on the upper layer of the metal layer 10, copper or a copper alloy can be suitably used as a constituent material of the metal layer 10.
  • the surface of the dielectric particles in the dielectric particle dispersion slurry prepared in the (b-1) slurry preparation step is charged positively or negatively.
  • the (b-2) electrodeposition step when a voltage is applied between the cathode electrode and the anode electrode arranged in the dielectric particle-dispersed slurry, the charged dielectric particles are electrophoresed. Adsorption and aggregation occur in the vicinity of one of the electrodes to form an electrodeposition layer made of dielectric particles on the electrode surface.
  • the metal layer 10 according to the present invention is used as an electrode on the film formation side where the electrodeposition layer is formed.
  • the ceramic insulating layer 30 according to the present invention is obtained by firing the electrodeposition layer by the firing step (b-3).
  • This electrophoretic electrodeposition method utilizes a so-called electrophoretic phenomenon, and has the advantages of high material use efficiency, high film formation speed, and excellent productivity. Therefore, when the ceramic insulating layer 30 is formed over a wide range on the surface of the metal layer 10 like the laminated body 100 of the ceramic insulating layer and the metal layer according to the present invention, the method can be suitably employed. it can. Hereinafter, each step will be further described.
  • the slurry preparation step is a step for obtaining a dielectric particle-dispersed slurry for forming the ceramic insulating layer 30 having a desired composition.
  • a dielectric particle-dispersed slurry in which dielectric particles are dispersed in a polar organic solvent such as acetone is prepared.
  • the dielectric particles it is preferable to use perovskite type dielectric particles.
  • the perovskite-type dielectric particles referred to here have a basic composition such as barium titanate, strontium titanate, barium strontium titanate, and bismuth zirconate.
  • those having a basic composition of any one of barium titanate, strontium titanate, and barium strontium titanate are particularly preferable. This is because dielectric particles having these compositions have stable electrophoretic deposition properties.
  • a commercially available dielectric particle dispersed slurry can also be used.
  • manganese, silicon, nickel, aluminum, lanthanum, niobium, magnesium, tin, or the like may be added as appropriate. These additive components are segregated at the grain boundaries, thereby blocking the leakage current flow path and preventing the short circuit.
  • Electrodeposition step In the electrodeposition step, as described above, the metal layer 10 is used as an electrode on the electrodeposition layer forming side.
  • the counter electrode of the metal layer 10 it is preferable to use a material composed of any component of stainless steel, titanium, or an insoluble anode material.
  • the metal layer 10 functions as a cathode electrode or an anode electrode in combination with the metal material constituting the metal layer 10 according to the present invention.
  • the distance between these electrodes is preferably about 1 cm to 20 cm, and the voltage applied between the electrodes is preferably 0.5 V to 200 V.
  • the distance between the electrodes is less than 1 cm, the inflow of the dielectric particle dispersed slurry is insufficient between the two electrodes, and stable electrophoretic deposition cannot be performed.
  • the distance between the electrodes exceeds 20 cm, the distance between the electrodes becomes too long, so that it is difficult to uniformly control the migration of the dielectric particles between the electrodes, and the layer thickness is uniform on the metal layer 10 side. It becomes difficult to form a simple electrodeposition layer.
  • the voltage applied between the electrodes is preferably 10V to 40V as described above.
  • the voltage applied between the two electrodes is less than 10 V, the migration speed of the dielectric particles is slow and the film formation speed is also lowered, so that the productivity required for industrial production is not satisfied.
  • the metal layer 10 having the protective layer 20 laminated is used as the electrode on the film formation side, so that particles are deposited on the surface of the protective layer 20. If it does so, the said particle
  • the ceramic insulating layer 30 having a desired thickness can be formed by controlling the value of the voltage applied between the two electrodes and the energization time.
  • (B-3) Firing step In the electrophoretic electrodeposition method, the firing step can be performed basically under the same conditions as in the sol-gel method, and thus description thereof is omitted here.
  • a) the sol-gel method and b) electrophoretic electrodeposition method have been described as the ceramic insulating layer forming step.
  • Various methods such as MOCVD and sputtering deposition can be employed.
  • a resin component impregnation step is provided after the ceramic insulating layer 30 is formed by these methods. The impregnation step of the resin component is performed, for example, in (a) sol-gel method and (b) electrophoretic electrodeposition method after finishing the (a-3) and (b-3) firing steps, respectively.
  • the resin component impregnation step is a step for filling a structural defect serving as a leakage current flow path by impregnating a resin component between particles or grain boundaries present in the ceramic insulating layer 30. is there.
  • a resin component impregnated in the particles or grain boundaries present in the ceramic insulating layer 30 it is preferable to use a resin composition using an epoxy resin as a main component.
  • the epoxy resin contains 40 wt% to 70 wt% of the epoxy resin, 20 wt% to 50 wt% of the polyvinyl acetal resin, and 0.1 wt% to 20 wt% of the melamine resin or urethane resin with respect to the total resin component. It is preferable to use a resin composition in which 5 wt% to 80 wt% of the resin is a rubber-modified epoxy resin.
  • any epoxy resin can be used without particular limitation as long as it is commercially available for molding laminated plates and electronic parts.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, novolac type epoxy resin, o-cresol novolac type epoxy resin, triglycidyl isocyanurate, N, N-diglycidylaniline and other glycidylamine compounds
  • examples thereof include glycidyl ester compounds such as tetrahydrophthalic acid diglycidyl ester and brominated epoxy resins such as tetrabromobisphenol A diglycidyl ether.
  • These epoxy resins are preferably used alone or in combination.
  • the polymerization degree and epoxy equivalent as an epoxy resin are not specifically limited.
  • epoxy resin curing agents examples include dicyandiamide, organic hydrazides, imidazoles, amines of aromatic amines, phenols such as bisphenol A and brominated bisphenol A, novolaks such as phenol novolac resins and cresol novolacs, An acid anhydride such as phthalic anhydride can be used.
  • curing agent may be used individually by 1 type, and 2 or more types may be mixed and used for it. The addition amount of the curing agent with respect to the epoxy resin can be appropriately determined according to each epoxy equivalent.
  • curing agent for example, a tertiary amine, an imidazole-based, a urea-based curing accelerator, or the like can be used.
  • the epoxy resin is preferably 40% by weight to 70% by weight of the total resin component as described above.
  • the compounding quantity of an epoxy resin is less than 40 weight%, the insulation and heat resistance of the ceramic type
  • the compounding amount of the epoxy resin exceeds 70% by weight, when the resin component is cured, the so-called resin flow becomes too large, and the resin is uniformly distributed between particles in the ceramic insulating layer 30 or between grain boundaries. The resin component cannot be impregnated and the resin component tends to be unevenly distributed in the ceramic insulating layer 30, which is not preferable.
  • a rubber-modified epoxy resin as a part of the epoxy resin composition.
  • the rubber-modified epoxy resin products marketed for adhesives or paints can be used without particular limitation. Specifically, “EPICLON® TSR-960” (trade name, manufactured by Dainippon Ink, Inc.), “EPOTOTOTO® YR-102” (trade name, manufactured by Toto Kasei), “Sumiepoxy® ESC-500” (trade name, Sumitomo Chemical) And “EPOMIK VSR 3531” (trade name, manufactured by Mitsui Petrochemical Co., Ltd.) can be used. These rubber-modified epoxy resins may be used alone or in combination of two or more.
  • the blending amount of the rubber-modified epoxy resin is preferably 5 to 80% by weight of the total amount of the epoxy resin.
  • the rubber-modified epoxy resin By using the rubber-modified epoxy resin, fixing of the resin component in the ceramic insulating layer 30 can be promoted. Therefore, when the amount of the rubber-modified epoxy resin is less than 5% by weight, the effect of promoting fixing in the ceramic insulating layer 30 cannot be obtained. On the other hand, if the blending amount of the rubber-modified epoxy resin exceeds 80% by weight, the heat resistance as a cured resin may be reduced.
  • the polyvinyl acetal resin is synthesized by a reaction between polyvinyl alcohol and aldehydes.
  • the polyvinyl acetal resin those commercially available for paints and adhesives can be used without any particular limitation.
  • the degree of polymerization of the raw material polyvinyl alcohol, the type of raw aldehydes and the degree of acetalization are not particularly limited, but the degree of polymerization is considered in consideration of heat resistance as a cured resin and solubility in a solvent. It is desirable to use products synthesized from 2000-3500 polyvinyl alcohol.
  • a modified polyvinyl acetal resin having a carboxyl group or the like introduced in the molecule is also commercially available, but can be used without particular limitation as long as there is no problem in compatibility with the combined epoxy resin.
  • the blending amount of the polyvinyl acetal resin blended in the insulating layer is 20% by weight to 50% by weight of the total amount of the resin composition. If the blending amount is less than 20% by weight, the effect of improving the fluidity as a resin cannot be obtained. On the other hand, if the blending amount exceeds 50% by weight, the water absorption rate of the insulating layer after curing becomes high, which is extremely undesirable as a constituent material of the ceramic insulating layer 30.
  • the resin composition used in the present invention preferably contains a melamine resin or a urethane resin as a crosslinking agent for the polyvinyl acetal resin in addition to the above components.
  • alkylated melamine resin commercially available for coating can be used.
  • alkylated melamine resins include methylated melamine resins, n-butylated melamine resins, iso-butylated melamine resins, and mixed alkylated melamine resins.
  • the molecular weight and alkylation degree as a melamine resin are not particularly limited.
  • the urethane resin a resin containing an isocyanate group in a molecule marketed for an adhesive or a paint can be used.
  • the urethane resin include a reaction product of a polyisocyanate compound such as tolylene diisocyanate, diphenylmethane diisocyanate, and polymethylene polyphenyl polyisocyanate and a polyol such as trimethylolpropane, polyether polyol, and polyester polyol. Since these compounds are highly reactive as resins and may be polymerized by moisture in the atmosphere, in the present invention, these resins are blocked with phenols or oximes so as not to cause this problem. It is preferable to use a urethane resin called isocyanate.
  • the blending amount of the melamine resin or the urethane resin added to the resin composition in the present invention is 0.1% by weight to 20% by weight of the total amount of the resin composition.
  • the blending amount is less than 0.1% by weight, the crosslinking effect of the polyvinyl acetal resin is insufficient, the heat resistance of the insulating layer is lowered, and when the blending amount exceeds 20% by weight, the fixability in the ceramic insulating layer 30 is achieved. Deteriorates.
  • additives such as inorganic fillers, antifoaming agents, leveling agents, coupling agents and the like can be used for this resin composition as desired. These improve the permeability of the resin component to the ceramic insulating layer 30 and are effective in improving flame retardancy and reducing costs.
  • the above resin composition is present in the ceramic insulating layer 30 by applying it to the surface of the ceramic insulating layer 30 by a spin coating method or the like after the firing step and heating it using a hot plate, an oven or the like.
  • the resin component can be impregnated between particles or between grain boundaries.
  • Upper electrode layer forming step As described above, when the multilayer body 100 according to the present invention is used as a capacitor circuit forming material (110 (see FIG. 1)), an upper electrode made of a metal material is formed on the upper surface of the ceramic insulating layer 30.
  • An upper electrode layer forming step for forming the layer 40 may be provided.
  • the upper electrode formation layer 40 may be formed by bonding a metal foil of any one of copper foil, copper alloy foil, nickel foil and nickel alloy foil to the upper surface of the ceramic insulating layer 30,
  • the upper electrode forming layer 40 may be formed by a plating method using any one of copper, a copper alloy, nickel, a nickel alloy, and aluminum, or a method such as sputtering deposition.
  • Example 1 describes an example in which a laminated body 100 of a ceramic insulating layer and a metal layer according to the present invention is manufactured by using a sol-gel method when the ceramic insulating layer 30 is formed.
  • the metal layer 10 obtained by laminating a 20 nm SiO 2 layer as the protective layer 20 on the surface of the 18 ⁇ m smooth copper foil as the metal layer 10 was obtained.
  • SEM manufactured by JEOL; JSM-700IF
  • JSM-700IF magnification 100,000 times
  • Sol-gel solution preparation step In the sol-gel solution preparation step, a commercially available sol-gel solution (10 wt% BST (90/10/100) solution manufactured by Mitsubishi Materials Corporation) was used.
  • (A-2) Coating process In the coating process, the above sol-gel solution is applied to the surface of the protective layer 20 of the metal layer 10 by a spin coating method, and then air is applied at 190 ° C. for 1 minute using a hot plate. Dried in. With this step as one unit step, the one unit step was repeated 6 times to form a sol-gel liquid coating layer.
  • (A-3) Firing step Then, the metal layer 10 provided with the sol-gel liquid coating layer is subjected to a nitrogen atmosphere (atmosphere in which saturated water vapor containing 25 ° C. is blown; the same applies to the firing step hereinafter). Using a tube furnace, firing was performed under firing conditions of 600 ° C. ⁇ 60 minutes.
  • (A-4) Resin impregnation step Thereafter, 100 parts by weight of an epoxy resin (Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.) and 1 part by weight of an imidazole compound (Curesol 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.) as an epoxy resin curing agent
  • an epoxy resin Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.
  • an imidazole compound Curesol 2E4MZ manufactured by Shikoku Kasei Kogyo Co., Ltd.
  • methyl ethyl ketone (reagent) was used as a solvent to prepare an epoxy resin varnish having a total amount of epoxy resin and an epoxy resin curing agent of 0.22 wt% as a solid content.
  • the epoxy resin varnish as a coating solution by spin coating, it is applied to the surface of the sol-gel solution coating layer after baking, and heated in the atmosphere at 190 ° C. for 90 minutes using a hot plate, and the resin is ceramic. Impregnation was carried out between particles or grain boundaries existing in the system insulating layer 30. Thus, a laminate 100 of the ceramic insulating layer and the metal layer of Example 1 according to the present invention was manufactured.
  • Example 2 As the laminated body 100 of the ceramic insulating layer and the metal layer of Example 2, it was carried out except that (a-3) the firing step was performed at 500 ° C. in the ii) ceramic insulating layer forming step of Example 1 above.
  • a laminate 100 of a ceramic insulating layer and a metal layer of Example 2 according to the present invention was manufactured by the same method as Example 1.
  • the ceramic insulating layer 30 was formed by electrophoretic deposition as the laminate 100 of the ceramic insulating layer and the metal layer of Example 3.
  • Protective layer forming step In the protective layer forming step, as in Example 1 and Example 2 above, surface smooth copper having a laminated surface of Rz ⁇ 1.0 ⁇ m and a layer thickness of 18 ⁇ m manufactured by Mitsui Mining & Smelting Co., Ltd. A foil (NA-DFF, 18 ⁇ m) was used as the metal layer 10. Then, using a polysilazane silica coating agent (SSL-SD500-HB) manufactured by Exsia Co., Ltd. without dilution, it was dried in the atmosphere at 150 ° C. for 1 minute using a hot plate, and then in the atmosphere at 250 ° C.
  • SSL-SD500-HB polysilazane silica coating agent
  • a protective layer 20 having a thickness of about 60 nm was formed on the upper surface of the metal layer 10 in the same manner as in Example 1 and Example 2 except that UV irradiation was performed while heating using a hot plate.
  • the thickness of the protective layer 20 was measured using SEM (manufactured by JEOL; JSM-700IF) (magnification 100,000 times) in the same manner as in Example 1 and Example 2.
  • Ceramic insulating layer forming step In the ceramic insulating layer forming step, the ceramic insulating layer 30 was formed on the surface of the protective layer 20 of the metal layer 10 by electrophoretic deposition.
  • the average particle diameter of dielectric particles refers to the arithmetic average value when the major axis of 100 particles is laterally extended using the SEM.
  • Electrodeposition step In the electrodeposition step, the metal layer 10 is used as a cathode electrode, a stainless steel plate is used as an anode electrode, and the two electrodes are separated from each other by 20 mm in the dielectric particle dispersion slurry prepared above. Arranged. Then, a BST electrodeposition layer having a thickness of about 1.5 ⁇ m was formed on the metal layer 10 as a cathode electrode by applying a voltage of 30 V between both electrodes and applying a direct current for 20 seconds.
  • (B-3) Firing step The metal layer 10 on which the BST electrodeposition layer was formed was fired using a tube furnace at 600 ° C. for 60 minutes in a nitrogen atmosphere.
  • (B-4) Resin impregnation step Next, the resin component is impregnated between particles or grain boundaries existing in the BST electrodeposition layer after firing by the same method as in Example 1 and Example 2, A ceramic insulating layer 30 according to the invention was formed, and a laminate 100 of the ceramic insulating layer 30 and the metal layer 10 of Example 3 according to the present invention was manufactured.
  • Comparative Example 3 In order to compare with the laminate 100 obtained in Example 3, i) a ceramic insulating layer formed by electrophoretic deposition in the same manner as in Example 3 except that the protective layer 20 was not provided in the protective layer forming step. 30 to form a laminate of the ceramic insulating layer and the metal layer of Comparative Example 3. However, in Comparative Example 3, since the protective layer 20 made of SiO 2 which is an insulating material is not provided on the surface of the metal layer 10, the ceramic insulating layer having substantially the same thickness as the ceramic insulating layer 30 of Example 3. In order to form 30, the voltage applied between both electrodes is set to 20 V in the electrodeposition process.
  • FIG. 2A is a SEM photograph showing the surface of the ceramic insulating layer 30 formed in Example 1
  • FIG. 4 is a SEM photograph showing the surface of the formed ceramic insulating layer 30.
  • 2C is an SEM photograph showing the surface of the ceramic insulating layer 30 formed in Comparative Example 1
  • FIG. 2D shows the surface of the ceramic insulating layer 30 formed in Comparative Example 2. It is a SEM photograph. However, each SEM photograph was obtained by photographing the surface of the ceramic insulating layer 30 at a magnification of 30,000 using a SEM (JSM-700IF) manufactured by JEOL.
  • JSM-700IF SEM
  • Example 1 and Comparative Example 1 the firing temperature when forming the ceramic insulating layer 30 was 600 ° C.
  • the firing temperature was 500 ° C.
  • FIG. 2C copper crystals can be observed on the surface of the ceramic insulating layer 30 of Comparative Example 1 fired at 600 ° C.
  • FIG. 2D no copper crystals are observed on the surface of the ceramic insulating layer 30 of Comparative Example 2 fired at 500.degree.
  • FIG. 2 (d) as indicated by an arrow A, portions that are visually recognized as white on the surface of the ceramic insulating layer 30 are observed. The part visually recognized as white is a part swollen by firing (see FIG. 3C).
  • Example 1 and Example 2 in Example 1 and Example 2 according to the present invention, the protective layer 20 made of SiO 2 is formed on the surface of the copper foil as the metal layer 10 and then the ceramic.
  • the laminated body 100 (refer FIG. 1) in which the system insulation layer 30 was formed is obtained.
  • Example 1 a laminated body of the metal layer 10 and the ceramic insulating layer 30 was formed in the same manner as in Comparative Example 1 except that the protective layer 20 was provided. See FIG. 2A. Then, it can be seen that copper crystals are not recognized and copper diffusion into the ceramic insulating layer 30 is prevented. Further, in FIGS.
  • the protective layer 20 is formed on the metal layer 10
  • the ceramic insulating layer 30 is formed on the surface of the protective layer 20, thereby diffusing the constituent metals of the metal layer 10 into the ceramic insulating layer 30. It was confirmed that there was an effect to suppress, a change in shape due to oxidation of the metal layer 10 was prevented, and a smooth ceramic insulating layer 30 could be formed.
  • FIGS. 3A and 3B show SEM photographs in which a cross section of the laminate 100 (see FIG. 1) of the metal layer 10 and the ceramic insulating layer 30 formed in Example 1 is shown.
  • 3C and 3D show SEM photographs in which a cross section of the laminate 100 of the metal layer 10 and the ceramic insulating layer 30 formed in Comparative Example 1 is photographed.
  • 3 (a) and 3 (c) are taken at a magnification of 5,000 times
  • FIGS. 3 (b) and 3 (d) are taken at a magnification of 50,000 times.
  • the laminate 100 formed in Example 1 was formed in a thin film between the copper foil as the metal layer 10 and the ceramic insulating layer 30. A protective layer 20 is observed. And the surface of the ceramic type
  • FIGS. 3C and 3D in the laminate formed in Comparative Example 1, countless copper crystals diffused on the surface of the ceramic insulating layer 30 are recognized.
  • FIGS. 4A and 4B show cross-sectional SEM photographs of the laminate 100 formed in Example 2.
  • 4A and 4C are taken at a magnification of 5,000 times
  • FIGS. 4B and 4D are taken at a magnification of 50,000 times.
  • Example 2 and Comparative Example 2 since the firing temperature is 500 ° C., no copper crystal diffused on the surface of the ceramic insulating layer 30 is observed. However, as shown in FIGS. 4C and 4D, in the laminated body of Comparative Example 2, innumerable swelling was observed on the surface of the ceramic insulating layer 30, and the surface of the ceramic insulating layer 30 was wavy. I understand that As described above, when unevenness is generated on the surface of the ceramic insulating layer 30 due to the shape change accompanying the oxidation of the metal layer 10, the insulating characteristic or the dielectric characteristic becomes uneven depending on the location, and the lamination of the ceramic insulating layer and the metal layer is performed. The yield as a body cannot be improved.
  • group insulating layer 30 is shown. Is recognized. Further, it can be seen that no swelling of the surface of the ceramic insulating layer 30 formed on the surface of the protective layer 20 is observed, and the ceramic insulating layer 30 having a uniform layer thickness is obtained.
  • the ceramic insulating layer 30 having a uniform layer thickness can be formed on the upper surface of the metal layer 10 via the protective layer 20, and copper diffusion to the ceramic insulating layer 30 can be prevented. It was confirmed that this could be prevented. Therefore, according to the present invention, it is possible to prevent deterioration of the insulating property and dielectric property of the ceramic insulating layer 30 due to metal diffusion, and to manufacture the laminate 100 of the ceramic insulating layer and the metal layer with high production yield. it can.
  • Oxidation of metal layer (1) Next, in order to evaluate the oxidation state of copper as the metal layer 10, the ceramic system formed in Example 1 and Example 2 using X'Pert PRO manufactured by Panalical Co., Ltd. X-ray diffraction of the surface of the insulating layer 30 was performed.
  • FIG. 5 shows the result. In FIG. 5, the horizontal axis indicates the incident angle (2 ⁇ ), and the vertical axis indicates the intensity (au).
  • FIG. 6 shows the X-ray diffraction results of the ceramic insulating layer 30 formed in Comparative Example 1 and Comparative Example 2.
  • FIG. 6 shows the ceramic insulation formed under the same conditions as in Comparative Example 1 and Comparative Example 2 together with the X-ray diffraction results of each ceramic insulating layer 30 in (a) Comparative Example 1 and (b) Comparative Example 2.
  • the X-ray diffraction result (c) before firing of the layer 30 is also shown.
  • diffraction peaks indicating the BaTiO 3 is confirmed by performing firing. From this, it can be seen that the oxidation reaction of the BaTiO 3 precursor progressed by firing, and the ceramic insulating layer 30 was formed.
  • the diffraction peak indicating Cu 2 O by performing firing appears, copper constituting the metal layer 10 by firing is observed to have oxidized.
  • FIG. 5 shows (a) the firing of the ceramic insulating layer 30 formed under the same conditions as in the first and second embodiments, together with the X-ray diffraction results of the respective ceramic insulating layers 30 in the first and second embodiments.
  • the previous X-ray diffraction result (c) is also shown.
  • FIGS. 5A and 5B for the ceramic insulating layer 30 formed in Example 1 and Example 2, although a diffraction peak indicating BaTiO 3 appears, a diffraction peak indicating Cu 2 O appears. Has not appeared. Therefore, from the result, by forming the protective layer 20 on the metal layer 10, it is possible to effectively prevent oxidation of the copper constituting the metal layer 10 in the firing step when forming the ceramic insulating layer 30. It was confirmed that it was possible.
  • FIG. 7 and FIG. 8 are electron beam microanalyzer photographs in the cross section of the laminate of the metal layer 10 and the ceramic insulating layer 30 formed in Example 1 and Comparative Example 1, respectively. Show. However, for taking the sectional analysis photograph, an energy dispersive X-ray analyzer INCA Energy PentaFETx3. It was performed using.
  • FIG. 7 no diffusion of copper on the surface of the ceramic insulating layer 30 is observed in FIG. Further, referring to FIG. 7C, the distribution of oxygen atoms remains only in the ceramic insulating layer 30, and the oxidation reaction of the precursor of BiTO 3 proceeds by firing, but the oxidation reaction of copper does not occur. This is also confirmed from this figure. Further, as shown in FIG. 7E, the distribution of silicon atoms (Si) is recognized between the metal layer 10 and the ceramic insulating layer 30, and the protective layer 20 made of SiO 2 is formed in a thin film shape. Can be confirmed.
  • Table 1 shows the results of evaluating the capacity density, dielectric loss tangent, and production yield in the laminate 100 of the ceramic insulating layer and the metal layer formed in Example 1 and Example 2.
  • the evaluation was performed for the case where resin impregnation was performed on the ceramic insulating layer 30 and the case where it was not performed. Table 1 shows both of these evaluation results.
  • the capacitance density and dielectric loss tangent were measured using an LCR high tester 3532-50 manufactured by HIOKI.
  • 16 laminated bodies 100 of ceramic insulating layers and metal layers are manufactured for each condition, and the quality of each laminated body 100 of ceramic insulating layers and metal layers is set to capacity density and dielectric.
  • Each item of tangent and leakage current was evaluated and evaluated based on the proportion of non-defective products.
  • Comparative Examples 1 and 2 in terms of capacity density. Smaller than. However, the high capacity density of the laminate of the ceramic insulating layer and the metal layer obtained in Comparative Example 1 and Comparative Example 2 is considered to be caused by an increase in leakage current due to a short circuit. As a result, in Comparative Example 1 and Comparative Example 2, the production yields were as low as 18.8% and 68.8%, respectively, and it was difficult to obtain good products with good yields.
  • Example 1 and Example 2 as described above, the diffusion of copper in the ceramic insulating layer 30 is prevented, and the layer thickness of the ceramic insulating layer 30 is also configured uniformly. As a result, the occurrence of short circuits is small and the value of leakage current is small. In addition, Example 1 and Example 2 have lower dielectric loss tangent values than Comparative Example 1 and Comparative Example 2, respectively. As a result, the production yield was 81.3% in Example 1 and 100% in Example 2.
  • the capacity density is reduced as compared with the case where the resin impregnation is not performed.
  • the tangent value was 1/10 or less, and it was confirmed that a good product having a small dielectric tangent value can be obtained.
  • the resin impregnation can fill the structural defect of the ceramic insulating layer 30 serving as a flow path for the leakage current, so that a short circuit can be prevented and the leakage current can be further reduced. As a result, the production yield was 81.3% when the resin impregnation was not performed, but it could be improved to 93.8% by performing the resin impregnation.
  • the leakage current density is evaluated with reference to FIG. 9 and FIG.
  • a copper layer (upper part) was formed on the surface of the ceramic insulating layer of each laminated body by a sputtering vapor deposition method. Electrode forming layer) was formed. Then, using this copper layer as the upper electrode and the metal layer 10 as the lower electrode, a voltage was applied between these two electrodes, and the leakage current density with respect to the voltage value was measured.
  • the leakage current density in the presence or absence of resin impregnation of the ceramic insulating layer 30 was also evaluated.
  • FIG. 9A shows the measurement result for Example 1 when the resin impregnation of the ceramic resin layer 30 is performed
  • FIG. 9B shows the measurement result for Example 1 when the resin impregnation is not performed.
  • C has shown the measurement result about the comparative example 1.
  • FIG. 10A shows the measurement result for Example 2 when the resin impregnation of the ceramic resin layer 30 is performed
  • FIG. 10B shows the measurement result for Example 2 when the resin impregnation is not performed.
  • the measurement results are shown, and (c) shows the measurement results for Comparative Example 2.
  • Example 1 and Comparative Example 1 are evaluated.
  • the laminate 100 of the layer and the metal layer has a leakage current density value reduced to 1/1000 or less.
  • FIG. 9 shows that when the resin-impregnated ceramic insulating layer 30 in Example 1 (a) is compared with the resin-impregnated (b) (b), the resin-impregnated one leaks. It can be seen that the current density is low.
  • Example 2 and Comparative Example 2 are evaluated. Regarding Example 2 and Comparative Example 2, the same tendency as in Example 1 and Comparative Example 1 was observed. That is, referring to FIG. 10, the ceramic of Example 2 according to the present invention shown in (a) and (b) of the laminate of the ceramic insulating layer and metal layer of Comparative Example 2 shown in (c). It can be seen that the laminate 100 of the system insulating layer 30 and the metal layer 10 has a leakage current density value reduced to 1/1000 or less. From FIG. 10, in Example 2, when the resin-impregnated ceramic insulating layer 30 (a) and the resin-impregnated (b) were compared, the ceramic insulating layer 30 was compared. It can be seen that the value of the leakage current density is lower when the resin is impregnated.
  • FIG. 11A is a SEM photograph showing a cross section of the laminate 100 formed in Example 3, and FIG. 11B is a SEM photograph showing a cross section of the laminate formed in Comparative Example 3.
  • FIG. 11A in the laminate 100 of Example 3, the protective layer 20 made of thin SiO 2 between the copper foil as the metal layer 10 and the ceramic insulating layer 30 can be confirmed. .
  • FIG. 11B it can be seen that a copper oxide layer formed by oxidizing copper is formed between the copper foil layer and the ceramic insulating layer 30 instead of the protective layer 20.
  • the protective layer 20 made of a silicon compound on the surface of the metal layer 10 it is possible to prevent oxidation of the metal constituting the metal layer 10, that is, copper, and to prevent deterioration of the metal layer 10. Can do.
  • the laminate 100 (a) of the ceramic insulating layer and the metal layer of Example 3 according to the present invention is the laminate (b) of the ceramic insulating layer and the metal layer of Comparative Example 3. It can be seen that the value of the leakage current density is small as compared with the above, and a short circuit between the upper electrode and the lower electrode is prevented. Moreover, when the voltage applied between both electrodes is 20 V or more, the value of the leakage current density in the laminate 100 of the ceramic insulating layer and the metal layer of Example 3 is the same as that of the ceramic insulating layer of Comparative Example 3. Although it is about 1/10 of the value of the leakage current density in the laminate with the metal layer, the difference increases when the voltage applied between the two electrodes is less than 20V.
  • the ceramic insulating layer as the insulating layer or the dielectric layer in the laminated body 100 of the ceramic insulating layer and the metal layer according to the present invention has high reliability, and operates at a lower voltage using the laminated body 100. It can be said that the effect of reducing leakage current is great when forming an electronic circuit (including a semiconductor circuit).
  • Table 2 shows the evaluation results of the capacity density, dielectric loss tangent, production yield, and layer thickness of the ceramic insulating layer in the laminate 100 of the ceramic insulating layer and the metal layer obtained in Example 3 and Comparative Example 3. Show.
  • Example 3 As shown in Table 2, in Example 3, a voltage of 30 V was applied for 20 seconds in the electrodeposition process, and in Comparative Example 3, a voltage of 20 V was applied for 20 seconds in the electrodeposition process.
  • the finally obtained ceramic insulating layers 30 had substantially the same thickness, which were 1.6 ⁇ m and 1.5 ⁇ m, respectively.
  • the protective layer 20 made of SiO 2 which is an insulating material is provided on the surface of the metal layer 10 formed in Example 3, so that the protective layer 20 is not provided with the metal layer 10 of the comparative example. In comparison, it is conceivable that the electrical characteristics during electrodeposition are degraded. However, as shown in FIG.
  • the ceramic insulating layer 30 having a desired layer thickness is formed through the protective layer 20 by changing the voltage, energizing time, etc. as appropriate, and adjusting the amount of deposited particles deposited on the electrode surface on the film formation side. 10 upper layers can be laminated.
  • the capacity density of the laminate 100 of the ceramic insulating layer and the metal layer of Example 3 is lower than that of the laminate of the ceramic insulating layer and the metal layer of Comparative Example 3.
  • the dielectric loss tangent value of the laminated body 100 of the ceramic insulating layer and the metal layer of Example 3 is lower than the laminated body of the ceramic insulating layer and the metal layer of Comparative Example 3, and the production yield is also implemented.
  • Example 3 is higher.
  • the thickness of the ceramic insulating layer 30 is increased by about 1.5 times, even if the protective layer 20 is not provided, the insulating property of the ceramic insulating layer 30 is improved and the capacity density is reduced, but the leakage current density is also reduced. . However, no improvement in the value of dielectric loss tangent is observed.
  • the reference shown in Table 3 is the ceramic insulating layer when the electrodeposition process is performed at 30 V when the laminate of the ceramic insulating layer and the metal layer of Comparative Example 3 is manufactured. It is an evaluation result about a laminated body with a metal layer. As shown for reference, the thickness of the ceramic insulating layer 30 was increased about 1.5 times by performing the electrodeposition step at 30V.
  • FIG. 12C shows the measurement result of the leakage current density for the laminate shown as this reference example. 12A and 12C are compared, the value of the leakage current density is obtained by increasing the layer thickness of the ceramic insulating layer 30 in Comparative Example 3 by about 1.5 times. A value similar to 3 is shown.
  • the laminated body 100 according to the present invention can effectively prevent the occurrence of a leakage current as compared with the conventional case even when the ceramic insulating layer 30 is thinned, and the reliability. It is possible to form an electronic circuit or electronic component circuit having a high height.
  • the protective layer 20 was formed so that the thickness of the protective layer 20 was 20 nm when the laminate 100 of the ceramic insulating layer and the metal layer of Example 3 was formed. .
  • the thickness of the protective layer 20 is reduced, the leakage current density can be reduced as compared with the case where the protective layer 20 is not provided, and various values such as a decrease in the dielectric loss tangent value can be obtained. The effect of was recognized.
  • the metal layer 10 Oxidation can be prevented very effectively, and a decrease in the conductivity of the metal layer 10 can be prevented.
  • the protective layer 20 on the metal layer 10 the metal constituting the metal layer 10 is prevented from diffusing into the ceramic insulating layer 30, and the insulating property of the ceramic insulating layer 30 is lowered. Alternatively, it is possible to prevent a decrease in dielectric characteristics.
  • the laminate 100 of the ceramic insulating layer and the metal layer according to the present invention it becomes possible to form an electronic circuit or electronic component having higher reliability than the conventional one, and the ceramic system.
  • the production yield of the laminated body 100 of an insulating layer and a metal layer can be improved.
  • the laminate of the ceramic insulating layer and the metal layer according to the present invention can be used very effectively as a forming material for reducing the leakage current of the insulating layer and forming a highly reliable electronic circuit or electronic component. . Furthermore, by laminating the protective layer on the surface of the copper foil layer, oxidation or the like of the copper foil layer under a high temperature process can be prevented. For this reason, since there is a high temperature process in the past, there is an excellent effect that it is possible to employ copper foil as various constituent materials even when copper foil cannot be employed. Can expand the industrial applicability of copper foil.

Abstract

L'invention porte sur un stratifié d'une couche d'isolation céramique et d'une couche métallique, et également sur un procédé pour produire ce stratifié, avec lesquels il est possible de sélectionner de façon appropriée des matériaux structurels pour la couche métallique, qui sert de matériau de base, quel que soit le procédé utilisé pour former la couche d'isolation céramique, avec lesquels une détérioration du matériau de base et une réduction des performances d'isolation de la couche d'isolation pendant le processus de production de la couche d'isolation céramique peuvent être empêchées, et avec lesquels un rendement de production amélioré peut être obtenu. Un stratifié (100) d'une couche d'isolation céramique (30) et d'une couche métallique (10), une couche protectrice (20) étant disposée sur la surface du côté de la couche métallique (10) sur laquelle est formée la couche d'isolation céramique (30), et la couche protectrice (20) étant formée à partir d'un composé de silicium ayant une épaisseur de couche de 5 nm à 100 nm.
PCT/JP2011/064083 2010-06-21 2011-06-20 Stratifié de couche d'isolation céramique et de couche métallique et procédé pour la production d'un stratifié WO2011162218A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010140830A JP2012000947A (ja) 2010-06-21 2010-06-21 セラミック系絶縁層と金属層との積層体及び当該積層体の製造方法
JP2010-140830 2010-06-21

Publications (1)

Publication Number Publication Date
WO2011162218A1 true WO2011162218A1 (fr) 2011-12-29

Family

ID=45371401

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/064083 WO2011162218A1 (fr) 2010-06-21 2011-06-20 Stratifié de couche d'isolation céramique et de couche métallique et procédé pour la production d'un stratifié

Country Status (3)

Country Link
JP (1) JP2012000947A (fr)
TW (1) TW201210809A (fr)
WO (1) WO2011162218A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107731524A (zh) * 2016-08-10 2018-02-23 钰邦电子（无锡）有限公司 薄膜电容器及其制作方法
CN110970327A (zh) * 2018-09-28 2020-04-07 日本碍子株式会社 半导体制造装置用部件

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04209767A (ja) * 1990-11-30 1992-07-31 Ibiden Co Ltd 窒化アルミニウム基板の製造方法
JP2001284774A (ja) * 2000-03-28 2001-10-12 Kyocera Corp 金属箔付きフィルムおよびセラミック配線基板の製造方法
JP2005262506A (ja) * 2004-03-16 2005-09-29 Mitsui Mining & Smelting Co Ltd 絶縁層形成用の樹脂層を備えたキャリア箔付電解銅箔、銅張積層板、プリント配線板、多層銅張積層板の製造方法及びプリント配線板の製造方法
JP2007035975A (ja) * 2005-07-27 2007-02-08 Mitsui Mining & Smelting Co Ltd 支持基板付キャパシタ層形成材及びキャパシタ層形成材並びにこれらの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04209767A (ja) * 1990-11-30 1992-07-31 Ibiden Co Ltd 窒化アルミニウム基板の製造方法
JP2001284774A (ja) * 2000-03-28 2001-10-12 Kyocera Corp 金属箔付きフィルムおよびセラミック配線基板の製造方法
JP2005262506A (ja) * 2004-03-16 2005-09-29 Mitsui Mining & Smelting Co Ltd 絶縁層形成用の樹脂層を備えたキャリア箔付電解銅箔、銅張積層板、プリント配線板、多層銅張積層板の製造方法及びプリント配線板の製造方法
JP2007035975A (ja) * 2005-07-27 2007-02-08 Mitsui Mining & Smelting Co Ltd 支持基板付キャパシタ層形成材及びキャパシタ層形成材並びにこれらの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107731524A (zh) * 2016-08-10 2018-02-23 钰邦电子（无锡）有限公司 薄膜电容器及其制作方法
CN110970327A (zh) * 2018-09-28 2020-04-07 日本碍子株式会社 半导体制造装置用部件

Also Published As

Publication number Publication date
JP2012000947A (ja) 2012-01-05
TW201210809A (en) 2012-03-16

Similar Documents

Publication Publication Date Title
JP3841814B1 (ja) キャパシタ層形成材及びそのキャパシタ層形成材の製造方法
JP6254306B2 (ja) 表面処理銅箔、キャリア付銅箔、基材の製造方法、プリント配線板の製造方法、プリント回路板の製造方法、銅張積層板の製造方法
EP1387367B1 (fr) Particule composite pour dielectriques, particule de resine composite ultra-microparticulaire, composition pour realiser des dielectriques et leur utilisation
US9779880B2 (en) Resin composition and dielectric layer and capacitor produced therefrom
JP5864299B2 (ja) 樹脂組成物
KR100674848B1 (ko) 고유전율 금속-세라믹-폴리머 복합 유전체 및 이를 이용한임베디드 커패시터의 제조 방법
KR100685273B1 (ko) 절연재료, 필름, 회로기판 및 이들의 제조방법
JP4171725B2 (ja) 誘電体形成用組成物、キャパシタ層並びに印刷回路基板
JP5544444B1 (ja) 樹脂基材、プリント配線板、プリント回路板、銅張積層板及びプリント配線板の製造方法
JP5176290B2 (ja) ペースト組成物、誘電体組成物、誘電体シート、およびこれらを用いたキャパシタ内蔵回路基板
TWI787442B (zh) 樹脂組成物、附樹脂銅箔、介電體層、貼銅層合板、電容器元件及內裝電容器之印刷電路板
KR101926808B1 (ko) 작업성이 우수한 수지 조성물, 절연필름 및 프리프레그
WO2011162218A1 (fr) Stratifié de couche d'isolation céramique et de couche métallique et procédé pour la production d'un stratifié
TWI665254B (zh) 樹脂組成物、附樹脂銅箔、介電體層、貼銅層合板、電容器元件及內裝電容器之印刷配線板
JPWO2008044573A1 (ja) キャパシタ層形成材及びキャパシタ層形成材の製造方法並びにそのキャパシタ層形成材を用いて得られる内蔵キャパシタを備えるプリント配線板
WO2004081952A1 (fr) Materiau polymere composite a constante dielectrique elevee, carte de circuits imprimes multicouche et carte de module
JP3876679B2 (ja) 樹脂組成物とその利用
JP3820668B2 (ja) 金属ベース基板及びその製造方法
US20120141777A1 (en) Laminate composed of ceramic insulating layer and metal layer, and method for producing the same
US11890853B2 (en) Resin layered product, dielectric layer, metal foil with resin, capacitor element, and printed wiring board with built-in capacitor
JP2006123232A (ja) 誘電体フィラー含有樹脂層付銅箔及びその誘電体フィラー含有樹脂層付銅箔を用いて得られたプリント配線板
JP2020113848A (ja) 積層アンテナ及び積層アンテナの製造方法
KR20040042315A (ko) 절연층의 두께 편차가 감소된 절연필름, 그 제조방법 및이를 이용한 다층 인쇄회로기판

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11798102

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11798102

Country of ref document: EP

Kind code of ref document: A1