WO2005080073A1 - 薄膜複合材料、およびこれを用いた配線板用材料、配線板、電子部品用材料、電子部品、ならびにこれらの製造方法 - Google Patents
薄膜複合材料、およびこれを用いた配線板用材料、配線板、電子部品用材料、電子部品、ならびにこれらの製造方法 Download PDFInfo
- Publication number
- WO2005080073A1 WO2005080073A1 PCT/JP2004/013521 JP2004013521W WO2005080073A1 WO 2005080073 A1 WO2005080073 A1 WO 2005080073A1 JP 2004013521 W JP2004013521 W JP 2004013521W WO 2005080073 A1 WO2005080073 A1 WO 2005080073A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- thin film
- metal oxide
- film layer
- composite metal
- oxide thin
- Prior art date
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 316
- 239000002131 composite material Substances 0.000 title claims abstract description 307
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims description 39
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 229
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 229
- 229910052751 metal Inorganic materials 0.000 claims abstract description 89
- 239000002184 metal Substances 0.000 claims abstract description 89
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011889 copper foil Substances 0.000 claims abstract description 65
- 239000000470 constituent Substances 0.000 claims abstract description 56
- 239000003990 capacitor Substances 0.000 claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 20
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 18
- 229910052709 silver Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 27
- 229910052712 strontium Inorganic materials 0.000 claims description 25
- 239000004020 conductor Substances 0.000 claims description 18
- 239000011810 insulating material Substances 0.000 claims description 18
- 150000002739 metals Chemical class 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 7
- 239000010410 layer Substances 0.000 description 164
- 239000000243 solution Substances 0.000 description 47
- 239000010936 titanium Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000004544 sputter deposition Methods 0.000 description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 9
- 229910018104 Ni-P Inorganic materials 0.000 description 9
- 229910018536 Ni—P Inorganic materials 0.000 description 9
- 238000007747 plating Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 150000004703 alkoxides Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000000206 photolithography Methods 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- 238000007740 vapor deposition Methods 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 description 3
- -1 alkoxide compound Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WZIMSXIXZTUBSO-UHFFFAOYSA-N 2-[[bis(carboxymethyl)amino]methyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)CN(CC(O)=O)CC(O)=O WZIMSXIXZTUBSO-UHFFFAOYSA-N 0.000 description 2
- 229910000521 B alloy Inorganic materials 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/20—Dielectrics using combinations of dielectrics from more than one of groups H01G4/02 - H01G4/06
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0175—Inorganic, non-metallic layer, e.g. resist or dielectric for printed capacitor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0179—Thin film deposited insulating layer, e.g. inorganic layer for printed capacitor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0183—Dielectric layers
- H05K2201/0195—Dielectric or adhesive layers comprising a plurality of layers, e.g. in a multilayer structure
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
Definitions
- Thin film composite material wiring board material using the same, wiring board, electronic component material, electronic component, and method of manufacturing these
- the present invention relates to a thin film composite material suitably used for an electronic component such as a wiring board, a wiring board material using the same, a wiring board, a material for an electronic component, an electronic component, and a method of manufacturing these.
- Japanese Patent Laid-Open Publication No. 2001-160672 discloses a method in which a dielectric paste is attached to a flexible metal substrate, baked, and baked paste is used. It is described that the baked paste surface adheres to an organic layer whose surface is coated with an adhesive layer so as to be embedded in the adhesive.
- Japanese Patent Publication No. 2003-526880 discloses a metal foil substrate and a crystalline dielectric layer.
- a multi-layered thin film composite is described.
- a solution of an organic solvent of an alkoxide compound of a plurality of metals is applied to a substrate and heat-treated to form a crystalline dielectric layer of an oxide of a plurality of metals. It describes a method of forming a crystalline dielectric layer on a metal substrate by using a so-called sol-gel method, a sputter deposition method, or an organic metal chemical vapor deposition method.
- Japanese Patent Application Laid-Open No. 2001-160672 describes that barium titanate and titanium oxide paste are used.
- No. 63 uses oxides of metals selected from Groups IA, ⁇ , ⁇ , IVB and VB of the Periodic Table and metals selected from Groups IVA and VA of the Periodic Table.
- Japanese Patent Publication No. 2003-526880 describes that PZT is used, and Japanese Patent Application Laid-Open No. 11 251185 describes that Pb, Zr, Ti, and Sr are used.
- the present invention provides a thin film composite material capable of forming a capacitor without processing at such a high temperature, a wiring board material using the same, a wiring board, a material for an electronic component, an electronic component, and the like. It is intended to provide a manufacturing method.
- the present invention provides a copper foil, formed on one surface of the copper foil, and at least one metal (Cr and Cr) selected from the group consisting of Cr, Ni, Au, Ag, and an alloy thereof.
- a first composite metal oxide thin film layer composed of an oxide, and formed on the surface of the first composite metal oxide thin film layer have Ba and Ba as constituent elements.
- / or a second composite metal oxide thin film layer containing at least a crystalline composite metal oxide containing Sr and Ti.
- the present invention also provides the above thin film composite material, wherein the thickness of the metal thin film layer is in the range of 50 nm to 1 m.
- the present invention also provides the above thin film composite material, wherein the thickness of the first composite metal oxide thin film layer is in the range of lOnm-200 nm.
- the sum of the thickness of the first composite metal oxide thin film layer and the thickness of the second composite metal oxide thin film layer is in the range of 30 nm to 2 m.
- the present invention provides the above-mentioned thin film composite material characterized by the following.
- the second composite metal oxide thin film layer preferably comprises,
- the present invention provides the above thin film composite material, further comprising an amorphous composite metal oxide containing Sr and Ti.
- an insulating material layer is formed on the other surface of the copper foil, and a conductor layer is formed on the surface of the second composite metal oxide thin film layer.
- a material for wiring boards characterized in that:
- the above-mentioned thin film composite material of the present invention wherein an insulating material layer is formed on the other surface of the copper foil, and a conductor pattern is formed on the surface of the second composite metal oxide thin film layer.
- the present invention also provides a material for an electronic component, wherein the conductor layer is formed on the surface of the second composite metal oxide thin film layer of the thin film composite material of the present invention.
- the present invention provides the above-mentioned thin film composite material of the present invention, wherein an insulating material layer is formed on the other surface of the copper foil, and a capacitor electrode is formed on the surface of the second composite metal oxide thin film layer.
- An electronic component characterized by being formed is provided.
- the present invention forms a metal thin film layer containing at least one metal selected from the group consisting of Cr, Ni, Au, Ag, and an alloy thereof on one surface of a copper foil.
- a first composite metal oxide thin film layer comprising an amorphous composite metal oxide containing Ba and / or Sr as constituent elements and Ti on the surface of the metal thin film layer; and Previous On the surface of the first composite metal oxide thin film layer, a second composite metal oxide thin film layer including at least a crystalline composite metal oxide containing Ba and Z or Sr as constituent elements and Ti.
- a heat treatment at 400 ° C. or less at least in the step of forming the first composite metal oxide thin film layer. I do.
- the present invention provides the method for producing a thin film composite material described above, wherein the thickness of the metal thin film layer is formed in a range of 50 nm to 1 ⁇ m.
- the present invention provides the method for producing a thin film composite material described above, wherein the thickness of the first composite metal oxide thin film layer is formed in a range of lOnm-200 nm.
- the total of the thickness of the first composite metal oxide thin film layer and the thickness of the second composite metal oxide thin film layer is in the range of 30 nm to 2 m.
- the present invention provides a method for producing the above-mentioned thin film composite material, wherein each is formed as follows.
- the second composite metal oxide thin film layer preferably comprises, as constituent elements:
- the present invention provides a step of forming an insulating material layer on the other surface of the copper foil of the thin film composite material produced by the production method of the present invention, and a step of forming the second composite metal oxide thin film layer. Forming a conductor layer on the surface; and a method for producing a wiring board material.
- the present invention provides a thin film composite material produced by the production method of the present invention, a step of forming an insulating material layer on the other surface of the copper foil, and a step of forming a second composite metal oxide thin film layer. Forming a conductive pattern on the surface of the wiring board.
- the present invention is characterized by including a step of forming a conductor layer on the surface of the second composite metal oxide thin film layer of the thin film composite material produced by the production method of the present invention.
- a method for producing electronic component materials is provided.
- the present invention also provides a step of forming a conductor layer on the surface of the second composite metal oxide thin film layer of the thin film composite material produced by the production method of the present invention, and the other surface of the copper foil.
- Perfect A method for manufacturing an electronic component comprising: a step of forming an edge material layer; and a step of forming a capacitor electrode by removing unnecessary portions of the conductor layer by etching.
- a thin film composite material capable of performing a heat treatment at a low temperature of 400 ° C. or less, forming a highly reliable and large capacitance capacitor on a copper foil. Can be provided. Further, by using the thin film composite material of the present invention, it is possible to provide a wiring board and an electronic component including a capacitor with high reliability and large capacitance.
- FIG. 1 is a cross-sectional view showing one embodiment of the thin film composite material of the present invention.
- FIG. 2 is a cross-sectional view showing another embodiment of the thin film composite material of the present invention.
- FIG. 3 is a sectional view showing still another embodiment of the thin film composite material of the present invention.
- FIG. 4 is a cross-sectional view showing one embodiment of a wiring board including a thin-film composite material of the present invention in its configuration.
- the thin film composite material of the present invention is a copper foil, formed on one surface of the copper foil, and at least one metal selected from the group consisting of Cr, Ni, Au, Ag, and an alloy thereof.
- a first composite metal oxide thin film layer formed on the surface of the metal thin film layer and containing Ba, Z or Sr as constituent elements, and Ti.
- a second composite metal oxide thin film formed on the surface of the first composite metal oxide thin film layer and containing at least a crystalline composite metal oxide containing Ba, Z or Sr, and Ti as constituent elements. Having a layer.
- a composite metal oxide containing Ba, Z or Sr, and Ti as constituent elements is particularly high in ceramics (for example, about 1500 for BaTiO and about 200 for SrTiO).
- a composite metal oxide to which other elements and metal oxides are added for example, Ba Properties were adjusted by adding CaTiO to BaTiO and composite metal oxides with improved electrical conductivity.
- a composite metal oxide can also be suitably used.
- the first composite metal oxide thin film layer is made of an amorphous composite metal oxide containing Ti as a constituent element and Ba or Z or Sr. Since the interface in contact with the metal thin film layer is amorphous, defects due to a mismatch between the lattice constant of the metal thin film layer and the lattice constant of the composite metal oxide are reduced, and insulation can be ensured. When the interface with the metal thin film layer is a crystalline region, thermal strain due to heat applied during the formation of the composite metal oxide thin film layer due to the mismatch between the lattice constant of the metal thin film layer and the lattice constant of the composite metal oxide film. Many defects occur at the interface with the metal thin film layer, and the insulating property is significantly reduced.
- the thickness of the first composite metal oxide thin film layer is preferably in the range of 10 nm to 200 nm, more preferably in the range of 20 ⁇ m to 150 nm. If the thickness of the first composite metal oxide thin film layer is less than 10 nm, the effect of providing the first composite metal oxide thin film layer to secure the insulation of the capacitor may be reduced, and the thickness may be 200 nm. If the dielectric constant exceeds the dielectric constant, the dielectric constant of the amorphous composite metal oxide is generally lower than the dielectric constant of the composite metal oxide composed of the crystalline region and the amorphous region, so that the capacitance of the capacitor may be reduced.
- the second composite metal oxide thin film layer contains at least a crystalline composite metal oxide containing Ba and Z or Sr as constituent elements and Ti, and preferably contains Z and Sr as constituent elements. And both the crystalline composite metal oxide containing Ba and Z or Sr as constituent elements and Ti as a constituent element, that is, a crystalline region and an amorphous region. When the whole is a crystalline region, the formation of the composite metal oxide thin film layer requires a high temperature, for example, 600 ° C or higher, so that oxidation of the copper foil proceeds easily and it is difficult to obtain a capacitor with high insulation properties. .
- the whole is an amorphous region, it is difficult to obtain a capacitor having a large capacitance because the dielectric constant of the composite metal oxide is low. Since the formation of the composite metal oxide thin film layer composed of the crystalline region and the amorphous region can be performed at a relatively low temperature, the oxidation of the copper foil can be suppressed, and at the same time, a thin film having a high dielectric constant can be obtained. .
- the crystalline and amorphous regions of the composite metal oxide thin film layer are Can be identified by observing dark-field images using a transmission electron microscope (TEM).
- the second composite metal oxide thin film layer has a force of at least two layers: a composite metal oxide thin film layer composed of the crystalline region and the amorphous region, and a composite metal oxide thin film layer composed entirely of the amorphous region. May be a laminated structure.
- the total thickness of the second composite metal oxide thin film layer and the first composite metal oxide thin film layer is preferably in the range of 30 nm—more preferably in the range of 50 nm—1.5 m. 100 ⁇ m—: The range of Lm is more preferable.
- the thickness of the second composite metal oxide thin film layer is less than 30 nm, the application potential of the capacitor in which the electric field strength of the composite metal oxide thin film layer is low may be limited, and the thickness may be reduced. If the value exceeds, a capacitor having a large capacitance may not be obtained.
- the metal thin film layer contains at least one metal selected from the group consisting of Cr, Ni, Au, Ag, and alloys thereof, and Cr and Z or Ni are more preferable in terms of cost.
- Ni is more preferred from the viewpoint of environmental pollution.
- Cr and Ni themselves form a stable oxide film, and Au and Ag themselves are difficult to oxidize. Suppresses the oxidization of the foil and contributes to securing the insulation of the capacitor.
- Other metals, such as SiO substrates, are often used to suppress oxidation
- the alloy is preferably one containing at least one or more components selected from Cr, Ni, Au and Ag forces in the alloy in an amount of 80% by weight or more.
- Such alloys include, for example, Ni—P alloy, Ni—B alloy, Ni P—B alloy, Ni—Co alloy, Ni—Cr alloy, Ni—Cr to Al alloy, Ni—Cr Si alloy, Ag—Nd There are alloys. If the content of at least one or a plurality of components selected from Cr, Ni, Au and Ag forces is less than 80% by weight, the effect of securing the insulation of the capacitor may be reduced. Ni-P alloy is more preferable in terms of cost and ease of formation.
- the thickness of the metal thin film layer is preferably in the range of 50 nm to 1 ⁇ m, more preferably in the range of 100 nm to 800 nm. If the thickness is less than 50 nm, the insulating property tends to decrease, and if the thickness is more than 1 m, cost is generally disadvantageous.
- the thickness of the metal thin film layer was measured by excavating the thin film layer with a focused ion beam processing device (FIB) and observing the obtained cross section with a scanning ion microscope (SIM). It can be measured by measuring the length.
- FIB focused ion beam processing device
- SIM scanning ion microscope
- a sol-gel method for example, a sol-gel method, a sputtering method, or a chemical vapor deposition method (CVD) is preferably used regardless of the second layer or the first layer.
- the sol-gel method is more preferable in that the composite metal oxide can be easily adjusted to a desired composition.
- the formation temperature is preferably 400 ° C or less, more preferably 350 ° C or less, in order to suppress the oxidation of the copper foil during the formation of the composite metal oxide thin film layer.
- the method for forming the metal thin film layer on the copper foil is not particularly limited, but, for example, a plating method, a vapor deposition method, a sputtering method, or the like can be suitably used.
- the copper foil is not particularly limited as long as it is a commonly used copper foil.
- a copper foil whose surface is treated with Zn or chromate for the purpose of heat resistance or protection is used for improving adhesion. Any of those having a roughened surface and those added with a small amount of another element, for example, Sn for the purpose of improving properties, can be suitably used.
- the thickness of the copper foil is not particularly limited, but is preferably from 10 ⁇ m to 100 ⁇ m from the viewpoint of handleability.
- the wiring board material of the present invention is the thin film composite material of the present invention, wherein an insulating material layer is formed on the other surface of the copper foil, and a conductor layer is formed on the surface of the second composite metal oxide thin film layer. It is characterized by having been formed.
- a known material for a wiring board can be used as the insulating material used for the insulating material layer.
- the conductor layer is formed by a known metal layer forming means such as a plating method, a vapor deposition method, and a sputtering method. It is possible to do.
- the thin film composite material of the present invention has an insulating material layer formed on the other surface of the copper foil, and has a conductor pattern formed on the surface of the second composite metal oxide thin film layer.
- the conductive pattern can be formed by a known metal layer forming means and a known etching means such as a plating method, a vapor deposition method, and a sputtering method.
- the electronic component material of the present invention is characterized in that a conductor layer is formed on the surface of the second composite metal oxide thin film layer of the thin film composite material of the present invention. Things.
- an insulating material layer is formed on the other surface of the copper foil of the above-described thin film composite material of the present invention, and the surface of the second composite metal oxide thin film layer is formed on the second composite metal oxide thin film layer.
- Capacitor An electrode is formed.
- the insulating material used for the insulating material layer a known material for an electronic component can be used.
- the capacitor electrode can be formed, for example, by a known metal layer forming means and a known etching means such as a plating method, an evaporation method, and a sputtering method.
- the wiring board material, wiring board, electronic component material, and electronic component of the present invention may be bonded to another substrate using a known adhesive, an adhesive sheet, a pre-predader, or the like to form a multilayer.
- a multilayer wiring board or an electronic component having a capacitor function can be obtained.
- FIG. 1 is a cross-sectional view schematically showing one embodiment of the thin film composite material according to the present invention.
- the thin film composite material 1 includes a second composite metal oxide thin film layer 2 containing Ba and / or Sr as constituent elements and Ti as essential elements, Ba and / or Sr as constituent elements, and Ti
- a first composite metal oxide thin film layer 3 made of an amorphous composite metal oxide film containing: a metal thin film layer 4, and a copper foil 5.
- the second composite metal oxide thin film layer 2 includes a crystalline region 2a and an amorphous region 2b.
- FIG. 2 is a cross-sectional view schematically showing another embodiment of the thin film composite material according to the present invention.
- the second composite metal oxide thin film layer 6 essentially contains Ba and / or Sr and Ti as constituent elements, and includes a composite metal oxide thin film layer 6a including a crystalline region and an amorphous region, Another composite metal oxide thin film layer 6b composed of an amorphous composite metal oxide containing Ba and / or Sr and Ti is laminated.
- FIG. 3 is a cross-sectional view schematically showing still another embodiment of the thin film composite material according to the present invention.
- the second composite metal oxide thin film layer 7 includes Ba and / or Sr as constituent elements and Ti, and a composite metal oxide thin film layer 7a including a crystalline region and an amorphous region.
- 7a is composed of another composite metal oxide thin film layer 7b having different constituent elements and Z or composition
- 7a and 7b are composed of amorphous composite metal oxides having different constituent elements and Z or composition.
- another composite metal oxide thin film layer 7c is another composite metal oxide thin film layer 7c.
- FIG. 4 is a cross-sectional view schematically showing one embodiment of a wiring board including the thin film composite material according to the present invention in its configuration.
- the wiring board 8 is formed by laminating the thin film composite material 9 of the present invention and the substrate 10 with an adhesive sheet 11, and furthermore, on the second composite metal oxide thin film layer 9a of the thin film composite material 9 of the present invention.
- An electrode 12 formed by plating, vapor deposition, sputtering, etching, or a combination thereof, and a copper foil 9d included in the thin film composite material 9 of the present invention are processed by etching or the like.
- the unnecessary portions of the second composite metal oxide thin film layer 9a, the first composite metal oxide thin film layer 9b, and the metal thin film layer 9c are removed by etching or the like.
- Ba (OC H) and Ti (0— i C H) are mixed so that the molar ratio of Ba and Ti is 1: 1.
- a solution B was obtained by diluting a part of the solution A with 2-methoxyethanol so that the solution concentration became 0.2 M.
- water having a molar ratio to Ti of 1: 1 and ammonia of 1: 0.15 were added, and the mixture was stirred at 100 ° C. for 3 hours.
- Solution C containing crystalline metal oxide particles diluted with 2-methoxyethanol was obtained.
- the two solutions B and C prepared at 0.2 M were mixed at a volume ratio of 1: 1 to form a solution D (total sum of composite metal alkoxides Z crystalline metal oxides.
- Substance particles 50 mol% Z50 mol%).
- a copper foil having a size of 10 cm ⁇ 10 cm and a thickness of 70 m (for example, manufactured by Mitsui Kinzoku Mining Co., Ltd.)
- a 500 nm thick Ni thin film layer was formed on the glossy side of 3EC-VLP-70) by sputtering to obtain a copper foil with a Ni thin film layer.
- solution B was spin-coated on the Ni thin film layer side of the copper foil with the Ni thin film layer. After drying on a hot plate at 350 ° C for 4 minutes, solution B was spin-coated again and dried in the same manner to form a first composite metal oxide layer. Further, the operation of spin-coating the solution D on the first composite metal oxide layer and drying it in the same manner was repeated eight times to form a second composite metal oxide layer. Then, it was baked on a hot plate at 350 ° C for 2 hours to obtain a thin film composite material 1.
- a thin film composite material 2 was obtained in the same manner as in Example 1 except that the type of the metal thin film layer formed on the surface of the copper foil was changed from Ni to Pt.
- the solution B was spin-coated directly, and a thin film composite material 3 was obtained in the same manner as in Example 1 except for the above.
- a thin film composite material 4 was obtained in the same manner as in Example 1 except that the spin coating of the solution B was omitted.
- a thin film composite material 5 was obtained in the same manner as in Example 1, except that a Cr thin film was formed on the surface of the copper foil instead of the Ni thin film layer.
- the thin film composite material 6 was obtained in the same manner as in Example 1 except that the number of times of spin coating of the solution B was changed from 2 to 6.
- the thin film composite material 7 was obtained in the same manner as in Example 1 except that the number of times of spin coating of the solution D was changed from 8 to 24.
- a solution F was obtained by diluting a part of the solution E with 2-methoxyethanol so that the solution concentration became 0.2 M.
- water with a molar ratio of 1: 1 with Ti and ammonia with a ratio of 1: 0.15 are added, and the mixture is stirred at 100 ° C for 3 hours, and then becomes 0.2M.
- a solution G containing crystalline metal oxide particles diluted with 2-methoxyethanol was obtained.
- a 500-nm-thick Ni thin film layer was formed by sputtering on the glossy side of a 10-cm x 10-cm copper foil with a thickness of 70 m (for example, 3EC-VLP-70 manufactured by Mitsui Kinzoku Mining Co., Ltd.).
- a copper foil with a Ni thin film layer was obtained.
- solution F was spin-coated on the Ni thin film layer side of the copper foil with the Ni thin film layer. After drying on a hot plate at 350 ° C for 4 minutes, solution F was spin-coated again and dried in the same manner to form a first composite metal oxide layer. Furthermore, the operation of spin-coating the solution H on the first composite metal oxide layer and drying it in the same manner was repeated eight times to form a second composite metal oxide layer. Then, it was baked on a hot plate at 350 ° C. for 2 hours to obtain a thin film composite material 8.
- a solution J was obtained by diluting a part of the solution I with 2-methoxyethanol so that the solution concentration became 0.2M.
- a part of the solution I was mixed with water having a molar ratio of 1: 1 to Ti and ammonia having a molar ratio of 1: 0.15, and stirred at 100 ° C for 3 hours to obtain 0.2M.
- a solution K containing crystalline metal oxide particles diluted with 2-methoxyethanol was obtained.
- a 500 nm thick Ni thin film was formed on the glossy side of a 70 cm thick copper foil (for example, 3EC-VLP-70 manufactured by Mitsui Mining & Smelting Co., Ltd.) measuring 10 cm ⁇ 10 cm by sputtering. The layer was formed to obtain a copper foil with a Ni thin film layer.
- a 70 cm thick copper foil for example, 3EC-VLP-70 manufactured by Mitsui Mining & Smelting Co., Ltd.
- a bite was spin-coated on the Ni thin film layer side of the copper foil with the Ni thin film layer. After drying on a hot plate at 350 ° C for 4 minutes, the bite was spin-coated again and dried in the same manner to form the first composite metal oxide layer. Further, the operation of spin-coating the solution L on the first composite metal oxide layer and drying it in the same manner was repeated eight times to form a second composite metal oxide layer. Then, it was baked on a hot plate at 350 ° C. for 2 hours to obtain a thin film composite material 9.
- a Ni-P thin film with a Ni content of 93% by weight is applied to the copper foil surface by a plating method (for example, electroless plating using ICP Nicolon U manufactured by Okuno Pharmaceutical Co., Ltd.).
- a thin film composite material 10 was obtained in the same manner as in Example 6, except that the thickness was formed to 600 nm.
- An upper electrode having a size of 1 mm ⁇ lmm was formed on the surface of the thin film composite material 110 obtained as described above on the side of each composite metal oxide thin film layer by vapor deposition of Au.
- the composite metal oxide thin film layer and the metal thin film layer near the upper electrode were scraped with a diamond pen to expose the copper foil, which was used as the lower electrode.
- the capacitance between the upper electrode and the lower electrode was regarded as the capacitance of the capacitor, and the capacitance was measured.
- the capacitance was measured at 25 ° C at a frequency of 1 MHz using a 4285A Precision 'LCR meter manufactured by Agilent Technologies.
- a set of 30 upper and lower electrodes was prepared and measured.
- Each of the thin film composite materials 110 was excavated using a focused ion beam processing apparatus (FIB), and the exposed cross section was observed with a scanning ion microscope, and the composite metal oxide in the thin film composite material was observed. The thicknesses of the thin film layer and the metal thin film layer were measured. The dark-field image of the cross section of the composite metal oxide thin film layer was observed using a transmission electron microscope (TEM), and the The presence or absence of a crystalline region was observed.
- TEM transmission electron microscope
- the term “yield” indicates the number of capacitors for which the measurement of the capacitance was possible, among the 30 capacitors each formed.
- the capacitance indicates the average value of the capacitors that could be measured.
- a wiring board was manufactured using the thin film composite material 1 of Example 1.
- the copper foil side of thin film composite material 1 and the copper-clad laminate (MCL-BE-67G ( ⁇ ) manufactured by Hitachi Chemical Co., Ltd.) are bonded using an adhesive sheet (GF-3600 manufactured by Hitachi Chemical Co., Ltd.)
- a multilayer board ⁇ was obtained.
- Adhesion conditions are high Crimping was performed in a hot vacuum press at a temperature of 175 ° C and a pressure of IMPa for 1 hour.
- a Ni-P thin film layer having a thickness of 0.5 m was formed on the surface of the multilayer board M on the side of the second composite metal oxide thin film layer of the thin film composite material 1 by electroless Ni-P plating.
- a Cu thick film was formed to a thickness of 20 m by electric Cu plating.
- an alkali developing resist H-9040, manufactured by Hitachi Chemical Co., Ltd.
- H-9040 was formed by photolithography, and the Cu thick film and the Ni-P thin film layer were etched with a 10% by weight aqueous ferric chloride solution.
- an upper electrode of the capacitor was formed.
- an alkali-developable resist was formed again by photolithography, and 0.1 M ethylenediaminetetraacetic acid disodium salt (EDTA'2Na) was added.
- the first and second composite metal oxide thin film layers were etched with 30% by weight aqueous hydrogen peroxide.
- an alkali developing type resist was formed again by photolithography, and the Ni thin film layer and the copper foil were etched with a 10% by weight aqueous solution of ferric chloride.
- the lower electrode and wiring layer of the capacitor were formed.
- the resist was stripped with a 5% by weight aqueous solution of sodium hydroxide to obtain a multilayer wiring board having a capacitor.
- the capacitance of this capacitor was measured at a frequency of 1 MHz at 25 ° C using a 4285A Precision 'LCR meter manufactured by Agilent Technologies. All of the 30 capacitors could be measured, with an average of 720 pF.
- a wiring board was manufactured using the thin film composite material 9 of Example 6 above.
- a Ni—P thin film layer is formed on the surface of the thin film composite material 9 on the side of the second composite metal oxide thin film layer by electroless Ni—P plating to a thickness of 0.1.
- a thick Cu film was formed to a thickness of 20 IX m.
- the copper foil side of the thin film composite material 9 and a copper-clad laminate (MCL-BE-67G (H) manufactured by Hitachi Chemical Co., Ltd.) were bonded using an adhesive sheet (GF-3600 manufactured by Hitachi Chemical Co., Ltd.).
- GF-3600 manufactured by Hitachi Chemical Co., Ltd.
- the bonding conditions were as follows: high-temperature vacuum press, temperature 175 ° C, pressure IMPa for 1 hour.
- an alkali developable resist (H-9040, manufactured by Hitachi Chemical Co., Ltd.) is formed by photolithography, and the Cu thick film and the Ni—P thin film layer are etched with a 10% by weight aqueous solution of ferric chloride.
- the upper electrode of the capacitor was formed.
- alkali developing again by photolithography A type resist was formed, and the first and second composite metal oxide thin film layers were etched with a 30% by weight aqueous hydrogen peroxide solution containing 0.1 M ethylenediaminetetraacetic acid'disodium salt (EDTA'2Na).
- an alkali-developable resist was formed again by photolithography, and the Ni thin film layer and copper foil were etched with a 10% by weight aqueous ferric chloride solution to form a capacitor. A lower electrode and a wiring layer were formed.
- the resist was stripped with a 5% by weight aqueous solution of sodium hydroxide to obtain a multilayer wiring board having a capacitor.
- the capacitance of this capacitor was measured at a frequency of 1 MHz at 25 ° C. using a 4285A Precision 'LCR meter manufactured by Agilent Technologies, Inc. 29 of the 30 capacitors were measured, with an average of 895 pF.
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
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JP2006510155A JP4148293B2 (ja) | 2004-02-19 | 2004-09-16 | 薄膜複合材料、およびこれを用いた配線板用材料、配線板、電子部品用材料、電子部品、ならびにこれらの製造方法 |
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JP2004042749 | 2004-02-19 | ||
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Cited By (1)
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CN110767450A (zh) * | 2018-07-27 | 2020-02-07 | 浙江清华柔性电子技术研究院 | 薄膜电容器 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0831951A (ja) * | 1994-07-12 | 1996-02-02 | Texas Instr Inc <Ti> | 強誘電体薄膜キャパシタ及びその製造方法 |
JPH0897532A (ja) * | 1995-09-11 | 1996-04-12 | Hitachi Ltd | 薄膜コンデンサ |
JPH08161933A (ja) * | 1994-12-06 | 1996-06-21 | Sharp Corp | 強誘電体薄膜及び強誘電体薄膜被覆基板並びに強誘電体薄膜の製造方法 |
JPH08245263A (ja) * | 1994-11-24 | 1996-09-24 | Fuji Xerox Co Ltd | 酸化物薄膜およびその作製方法 |
WO2003002782A1 (en) * | 2001-06-28 | 2003-01-09 | Energenius, Inc. | Method of making a nickel-coated copper substrate and thin film composite containing the same |
-
2004
- 2004-09-16 JP JP2006510155A patent/JP4148293B2/ja not_active Expired - Fee Related
- 2004-09-16 WO PCT/JP2004/013521 patent/WO2005080073A1/ja active Application Filing
- 2004-09-16 TW TW093128029A patent/TW200529251A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0831951A (ja) * | 1994-07-12 | 1996-02-02 | Texas Instr Inc <Ti> | 強誘電体薄膜キャパシタ及びその製造方法 |
JPH08245263A (ja) * | 1994-11-24 | 1996-09-24 | Fuji Xerox Co Ltd | 酸化物薄膜およびその作製方法 |
JPH08161933A (ja) * | 1994-12-06 | 1996-06-21 | Sharp Corp | 強誘電体薄膜及び強誘電体薄膜被覆基板並びに強誘電体薄膜の製造方法 |
JPH0897532A (ja) * | 1995-09-11 | 1996-04-12 | Hitachi Ltd | 薄膜コンデンサ |
WO2003002782A1 (en) * | 2001-06-28 | 2003-01-09 | Energenius, Inc. | Method of making a nickel-coated copper substrate and thin film composite containing the same |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110767450A (zh) * | 2018-07-27 | 2020-02-07 | 浙江清华柔性电子技术研究院 | 薄膜电容器 |
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JP4148293B2 (ja) | 2008-09-10 |
JPWO2005080073A1 (ja) | 2008-01-10 |
TW200529251A (en) | 2005-09-01 |
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