WO2014084077A1 - Tableau de connexions céramique métallisé au cuivre et procédé de fabrication associé - Google Patents

Tableau de connexions céramique métallisé au cuivre et procédé de fabrication associé Download PDF

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WO2014084077A1
WO2014084077A1 PCT/JP2013/081005 JP2013081005W WO2014084077A1 WO 2014084077 A1 WO2014084077 A1 WO 2014084077A1 JP 2013081005 W JP2013081005 W JP 2013081005W WO 2014084077 A1 WO2014084077 A1 WO 2014084077A1
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Prior art keywords
copper
zinc oxide
ceramic substrate
substrate
copper plating
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PCT/JP2013/081005
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English (en)
Japanese (ja)
Inventor
歩美 長瀬
寛 亀井
木谷　直樹
盟 青木
勉 品川
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ニッコー株式会社
地方独立行政法人大阪市立工業研究所
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Priority to JP2014550132A priority Critical patent/JP5947401B2/ja
Publication of WO2014084077A1 publication Critical patent/WO2014084077A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1279—Process of deposition of the inorganic material performed under reactive atmosphere, e.g. oxidising or reducing atmospheres
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/1648—Porous product
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/072—Electroless plating, e.g. finish plating or initial plating
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present invention relates to a wiring ceramic substrate that is copperized (copper metallized) by a wet method. More specifically, a method for producing a copper metallized wiring ceramic substrate, in which a zinc oxide layer is formed as an adhesion layer on a ceramic substrate by a wet method, and heat treatment is performed to improve adhesion, followed by copper plating is obtained by the method.
  • the present invention relates to a copper metallized wiring ceramic substrate and a power module wiring substrate using the substrate.
  • a metal circuit board made of copper or the like is bonded to a metallized metal layer deposited on a ceramic substrate through a brazing material such as a silver-copper alloy as a circuit board such as a power module board or a switching module board.
  • a ceramic circuit board produced by a so-called DBC (Direct Bond Bonder) method in which a copper plate is placed on a substrate or a ceramic substrate and heated to directly bond the ceramic substrate and the copper plate is used for example, JP-A-57-82181 (U.S. Pat. No. 4,505,418); Patent Document 1).
  • DBC Direct Bond Bonder
  • a thick film printing method in which a paste mixed with resin, copper powder and glass frit is printed on a substrate and fired at 800 to 900 ° C. in a reducing atmosphere.
  • a sputtering method in which a Cr or Ti thin film layer is provided on a substrate and copper is deposited thereon,
  • a direct plating method in which fine irregularities are formed on the ceramic surface and electroless plating or electrolytic plating is applied. According to these methods, fine wiring can be formed.
  • the thick film printing method has a high conductor resistance because the conductor is a sintered body, and the sputtering method makes it difficult to form a thick wiring layer.
  • the direct plating method can control the film thickness of the wiring layer by electrolytic plating, and a thick wiring layer corresponding to a large current and a fine wiring routing can coexist in the same substrate. If the adhesion strength can be obtained, the technique can greatly contribute to downsizing of the ceramic wiring substrate.
  • the substrate surface is coated with a SnCl 2 or PdCl 2 solution or the like. It is activated and forms a metal layer by electroless plating.
  • ceramic materials generally have high chemical stability, it is difficult to obtain a uniform etching effect, and in particular, it is difficult to obtain uniform adhesion in a microscopic region.
  • Patent Document 3 discloses that a zinc oxide layer is formed on a ceramic or glass substrate and is brought into contact with a solution in which a metal metal salt serving as a catalyst for electroless plating is dissolved. In parallel with the dissolution reaction, a metal layer is laminated on the surface of a ceramic or glass substrate by using the phenomenon that metal ions in the metal salt are taken into the surface and inside, and putting it in an electroless plating bath. A method of manufacturing a circuit board characterized by the above is described.
  • Patent Document 4 discloses that a metal complex of a metal constituting a metal oxide (ZnO, SnO 2 , TiO 2 , In 2 O 3, etc.) is formed in an alkaline aqueous solution. A metal oxide film was formed on the insulator substrate by contacting the insulator substrate with the solution containing the complex to thermally decompose the metal complex, and then palladium was applied on the metal oxide film in an alkaline catalyst solution. Subsequently, a metallization method with high adhesion is described in which a metal film (such as copper) is formed in an electroless plating solution and, if necessary, a metal film (such as copper) is formed by electroplating.
  • a metal film such as copper
  • Patent Document 5 discloses a first step of forming a copper oxide layer on a substrate, a second step of reducing the outer surface of the copper oxide layer to form metallic copper, and the metallic copper.
  • the first step of the copper metallization method comprising the third step of applying electrolytic copper plating to the surface, a zinc oxide film is formed on the substrate, electroless copper plating is applied on the zinc oxide film, and then in an oxygen atmosphere.
  • a copper metallization method for forming a copper oxide layer by heat treatment is disclosed.
  • Patent Document 6 a zinc oxide layer is formed on the entire surface of a substrate, and a permanent plating resist is formed on the zinc oxide layer without applying a catalytic metal.
  • the copper oxide layer is deposited in each opening on the substrate by reducing the deposited copper oxide layer in a predetermined aqueous solution to form a metal copper layer in each opening, and the substrate on which the metal copper layer is formed It is described that a copper wiring is formed on a metal copper layer in each opening by dipping in an electroless plating solution.
  • Patent Document 7 discloses that when an aqueous solution containing zinc ions, nitrate ions, and borane-amine complexes is used, a base material is contained in the aqueous solution without energization.
  • the zinc oxide film can be applied to both a conductive base material and a non-conductive base material at a relatively high film formation rate. It is described that the composition can be formed uniformly.
  • Patent Document 8 discloses a method for adjusting the concentrations of zinc ions and nitrate ions in a zinc oxide film forming composition containing zinc ions, nitrate ions and amine borane (DMAB) compounds, or There has been proposed a method capable of controlling the film structure of a zinc oxide film by controlling the orientation and precipitation state of the zinc oxide film by a method of adjusting the liquid temperature.
  • DMAB amine borane
  • Non-patent Document 1 Zinc oxide nanorods were formed on glass from zinc nitrate and DMAB aqueous solution, and the zinc oxide was C-axis oriented depending on the zinc nitrate concentration and time. It is disclosed to control the length and diameter of the nanorods.
  • Patent Document 9 discloses a method of performing electroless plating on a zinc oxide film on a ceramic substrate
  • Patent Document 10 discloses electrolytic plating.
  • a method of performing electrolytic copper plating using a copper plating solution having a composition containing copper acetate is disclosed.
  • none of these methods has sufficient adhesion strength when a thick wiring layer corresponding to a large current is formed on a ceramic substrate, and cannot be used as a substrate for a copper metallized wiring ceramic power module.
  • JP-A-57-82181 (US Pat. No. 4,505,418) JP-A-52-914 JP-A-6-61619 JP-A-8-144061 Japanese Patent No. 2990955 Japanese Patent No. 3486864 (US Pat. No. 6,607,981) Japanese Patent No. 3256676 JP 2005-47752 A JP 2007-126743 A JP 2009-24203 A
  • the present inventors have intensively studied. As a result, in order to firmly adhere the ceramic substrate and the wiring layer, the zinc oxide crystal formed on the ceramic substrate by a wet method has a specific shape and density. In addition, the present inventors have found that it is effective to heat-treat zinc oxide in an air atmosphere in the range of a constant temperature and have completed the present invention.
  • the present invention relates to the following method for producing a copper metallized wiring ceramic substrate and a copper metallized wiring ceramic substrate.
  • a process for producing a copper metallized wiring ceramic substrate comprising the step of forming [2] The method for producing a copper metallized wiring ceramic substrate according to item 1 above, wherein the needle-like zinc oxide crystal has a diameter of 40 to 80 nm, a length of 150 to 250 nm, and a heat treatment temperature of 700 ° C. or more and less than 900 ° C. .
  • a part of the substrate surface is shielded by a shielding plate during electrolytic copper plating, and a copper plating film having a copper plating wiring thickness of 50 to 100 ⁇ m and a portion of 5 to 10 ⁇ m is formed in the substrate 1 5.
  • [6] A copper metallized wiring ceramic substrate obtained by the method according to any one of 1 to 5 above.
  • [8] A power module wiring board using the copper metallized wiring ceramic substrate as described in 6 or 7 above.
  • FIG. 4 is a field emission scanning electron microscope (FE-SEM) photograph image ( ⁇ 50000) of the zinc oxide film formed in Example 1.
  • FIG. 6 is a field emission scanning electron microscope (FE-SEM) photograph image ( ⁇ 40000) of two types of zinc oxide films of different lengths formed in Example 4.
  • FIG. 6 is a field emission scanning electron microscope (FE-SEM) photograph image ( ⁇ 40000) of two types of zinc oxide films having different diameters formed in Example 5.
  • FIG. It is a field emission type scanning electron microscope (FE-SEM) photograph image (x50000) of the zinc oxide film formed in comparative example 2 (5).
  • 10 is a field emission scanning electron microscope (FE-SEM) photographic image ( ⁇ 50000) of the zinc oxide film formed in Comparative Example 3.
  • Step 2 of performing heat treatment at a temperature of less than 900 ° C. Step 3 of forming a copper plating film by performing electroless copper plating and electrolytic copper plating, and forming a wiring pattern by patterning the copper plating film with an etching resist
  • step 4 a copper metallized wiring ceramic substrate having a strong adhesion strength of a wiring layer that can also be applied to a power module substrate can be manufactured.
  • Step 1 Formation of acicular zinc oxide crystal film
  • a ceramic substrate selected from alumina, alumina zirconia, aluminum nitride, and silicon nitride substrate is used.
  • 99 mass% alumina, 96 mass% alumina, 92 mass% alumina, alumina zirconia, aluminum nitride, silicon nitride, etc. are mentioned.
  • an alumina zirconia substrate preferably used is composed of 94% by mass of alumina, 5% by mass of partially stabilized zirconia, and the remaining component is an auxiliary component containing one or more of magnesia, silica and calcia.
  • These substrates may be provided with through holes for through holes or vias.
  • the through hole indicates a state in which the wall surface of the hole is covered with a conductive metal film
  • the via indicates a state in which the inside of the hole is closely packed with a conductive metal.
  • These substrates are cleaned by, for example, UV (ultraviolet) ozone treatment to remove organic substances on the surface.
  • the means is not particularly limited as long as it can be cleaned.
  • the cleaning step may be omitted if there is no organic contamination such as when the substrate is immediately after baking.
  • Step 2 Formation of a film made of acicular zinc oxide crystals
  • a catalyst nucleus is applied on the substrate using a catalyst application liquid, and then the zinc oxide film is formed by a wet method in which the substrate is immersed in a zinc plating solution.
  • the catalyst application liquid is not limited as long as it can be immersed in a zinc plating solution to achieve the formation of a zinc oxide film, and a commercially available one can be used.
  • the wet method of forming a zinc oxide film zinc oxide crystals are formed by immersing in an aqueous solution of zinc nitrate and dimethylamine borane in Cryst. Growth Des., 2011, 11, 5533-5539 (Non-patent Document 1).
  • the diameter and generation rate of the zinc oxide crystals that are C-axis oriented and needle-shaped can be controlled by the zinc nitrate concentration.
  • a zinc oxide crystal is formed by dipping in a solution having a zinc nitrate concentration of 1.5 mM at 80 ° C. for 3 hours, a length of 967 nm and a diameter of 63 nm is obtained.
  • a zinc nitrate concentration is 50 mM
  • a needle having a length of 462 nm and a diameter of 125 nm is obtained. It is described that a zinc oxide crystal is obtained.
  • the composition of the zinc plating solution for forming the zinc oxide film is not limited to the one described in Non-Patent Document 1 as long as needle-shaped zinc oxide crystals having a target shape can be obtained.
  • aqueous solution containing 30 mM zinc nitrate and 5 mM dimethylamine borane it is immersed in this at 60 ° C. for 60 minutes, and a needle-like zinc oxide crystal film having a diameter of 60 nm, a length of 200 nm, and approximately 200 per 1 ⁇ m 2 is formed. can get.
  • Step 3 Heat treatment Next, the needle-like zinc oxide crystal film is formed at a temperature sufficient to cause mutual diffusion between the ceramic substrate and the needle-like zinc oxide crystal and to increase the adhesion between the ceramic substrate and the needle-like zinc oxide crystal.
  • the formed ceramic substrate is heat-treated.
  • the acicular zinc oxide crystal grows and loses its shape, adhesion due to the anchor effect with the copper plating film to be formed in the subsequent process can no longer be expected. There is.
  • the second feature of the present invention is that the acicular zinc oxide crystals formed in step 2 are heat-treated at 500 ° C. or higher and lower than 900 ° C., particularly preferably 700 ° C. or higher and lower than 900 ° C.
  • the heat treatment time is not particularly limited, but is preferably 15 minutes or longer and 3 hours or shorter. If it is shorter than this, the effect of heat treatment cannot be obtained, and if it is longer, it is not economical.
  • the firing furnace is not limited to a firing method such as a batch method or a belt method.
  • the firing atmosphere is a nitrogen atmosphere or a reducing atmosphere, the zinc oxide crystals are decomposed and the effect as an adhesive layer cannot be exhibited. Therefore, the firing is preferably performed in an oxidizing atmosphere such as an air atmosphere.
  • the above two characteristics are requirements for forming a needle-like crystal on the substrate, which is preferable for the zinc oxide form to exert the anchor effect to the maximum, and a temperature of 500 ° C. or higher and lower than 900 ° C., preferably 700 ° C. or higher.
  • Heat treatment at a temperature below 900 ° C. does not reach the temperature at which the zinc oxide crystal melts and loses its shape, and is effective for promoting interdiffusion between the ceramic substrate and zinc oxide and improving adhesion. .
  • Step 4 Formation of wiring pattern
  • an electrolytic copper plating film is formed in a desired thickness, and copper is etched with an etching resist.
  • the plating film is patterned to form a wiring pattern.
  • Catalyst application is performed using a catalyst application liquid as a pretreatment for electroless copper plating, but the catalyst application liquid is not particularly limited as long as it can achieve formation of an electroless copper plating film, and a commercially available one is used. It is done. Similarly, a commercially available electroless copper plating solution can be used.
  • electrolytic copper plating is performed by controlling the current density and time until a copper plating film having a desired thickness is obtained.
  • the copper plating bath is a common copper plating bath such as a copper sulfate plating bath or a copper pyrophosphate plating bath. Things can be used.
  • electrolytic copper sulfate plating is performed in order to increase the copper film thickness, the strength is generally lowered due to the strong acid of the plating solution.
  • the zinc oxide film is dissolved and peeled off.
  • the adhesion strength is greatly improved by the shape of the zinc oxide and the heat treatment conditions, and the strength is not impaired even if the copper film is thickened.
  • the through-holes for through holes formed in the substrate are formed with acicular zinc oxide crystal film and electroless copper plating film on the wall surface of the hole, similar to the substrate surface.
  • a copper metal film is formed by electrolytic copper plating to complete a through hole.
  • the same needle-like zinc oxide crystal film and electroless copper plating film as the substrate surface are formed on the wall surface of the hole like the through hole, and the copper metal film is formed on this by the electrolytic copper plating Subsequently, a film on the wall surface of the hole grows by copper plating, so that the entire hole is closely packed to complete the via.
  • a part of the substrate may be shielded by a shielding plate.
  • the shielding plate here is generally disposed between the object to be plated in the electrolytic plating solution and the anode, and a desired film thickness of the plating film is obtained by suppressing the flow of current.
  • the etching resist may be any as long as it can be etched, and a printing resist by screen printing or a photoresist that exposes a pattern with a photomask can be used.
  • the etching solution may be a commercially available general iron chloride etching solution, which is immersed and heated in a state heated to 60 ° C. to remove unnecessary portions of the copper film by etching.
  • the etching resist is stripped and removed with an alkaline aqueous solution or an organic solvent to obtain a copper wiring pattern.
  • the obtained copper wiring board may be heat-treated in the air or in a nitrogen atmosphere for the purpose of removing stress, if necessary.
  • the copper metallized wiring ceramic substrate obtained by the method of the present invention has strong adhesion with an average adhesion strength measured by the method described in Examples of 1.5 kgf / 2 mm ⁇ or more.
  • a lead wire is bent into an L shape on a land of a 2 mm square copper plating pattern, and soldered so that the lead wire stands vertically.
  • the lead wire was pulled in the vertical direction, and the strength (Kgf) at which the lead wire was peeled off from the soldered portion was measured with a push-pull gauge.
  • the measured value is an average value of 20 pieces. The higher the measured value, the greater the adhesion strength.
  • Example 1 Alumina zirconia with a composition containing 94% by mass of alumina, 5% by mass of partially stabilized zirconia and one or more of magnesia, silica, and calcia as auxiliary components, and through-holes for through holes (diameter 130 ⁇ m)
  • a substrate provided with was prepared.
  • the substrate surface was subjected to UV ozone treatment for 10 minutes to remove organic substances.
  • a commercially available catalyst application liquid (Okuno Pharmaceutical Co., Ltd., Technoclear SN, AG, PD) was used, and Sn—Ag—Pd catalyst nuclei were applied to the substrate surface.
  • a commercially available catalyst application liquid (Okuno Pharmaceutical Co., Ltd., Techno Clear BPD) was used to apply a palladium catalyst. Thereafter, plating was performed with a commercially available electroless copper plating solution (Sulcup PGT manufactured by Uemura Kogyo Co., Ltd.) at 36 ° C. for 20 minutes to obtain an electroless copper plating film of about 0.3 ⁇ m.
  • the electrolytic copper plating for obtaining a predetermined copper thickness may be a general one, for example, copper sulfate pentahydrate 220 g / L, concentrated sulfuric acid 55 g / L, a commercially available brightener (ACB, manufactured by World Metal Co., Ltd.).
  • a plating solution containing ⁇ 90 M, 10 ml / L) was prepared and energized for 60 minutes at room temperature and a cathode current density of 6 A / dm 2 to obtain a copper plating film having a thickness of 70 ⁇ m.
  • the coating was etched with an iron chloride etchant and patterned.
  • the obtained copper pattern had an average adhesion strength of 6.31 Kgf / 2 mm ⁇ , and was very excellent in adhesion.
  • Example 2 A substrate having a through hole having a diameter of 100 ⁇ m was prepared for vias, which was alumina having a composition containing 96% by mass of alumina and one or more of magnesia, silica, and calcia as auxiliary components.
  • a zinc oxide layer was formed after UV ozone treatment, and heat treatment was performed in a belt furnace for 15 minutes at 800 ° C. in an air atmosphere. Thereafter, an electroless copper plating film was formed. In the electrolytic copper plating, a current was passed for 45 minutes at room temperature and a cathode current density of 6 A / dm 2 to obtain a copper plating film having a thickness of 50 ⁇ m.
  • the via was filled with copper by the growth of the electrolytic copper film from the side surface of the through hole.
  • a part of the substrate surface was shielded with a shielding plate during electrolytic plating.
  • the shielding plate was disposed between the object to be plated in the electrolytic plating solution and the anode, and a portion having a copper thickness of 10 ⁇ m was simultaneously formed in the substrate by suppressing the flow of current.
  • the film was covered with an etching resist to cover the non-etched portion, and then etched with an iron chloride etchant to form a power module substrate wiring pattern.
  • the obtained copper pattern became very excellent in adhesiveness.
  • Example 3 A silicon nitride substrate which is a nitride was prepared. A heat treatment was performed at 800 ° C. for 60 minutes in an air atmosphere in a batch furnace to form a thin oxide film layer on the nitride substrate surface. Thereafter, a zinc oxide layer was formed after UV ozone treatment in the same manner as in Example 1, and heat treatment was performed at 800 ° C. in the atmosphere. An electroless copper plating film was formed and energized for 45 minutes by electrolytic copper plating to obtain a 50 ⁇ m thick copper plating film. The film was coated with an etching resist on the non-etched portion, and then etched and patterned with an iron chloride etchant. The obtained copper pattern was very excellent in adhesion.
  • Example 4 94% by mass of alumina, 5% by mass of partially stabilized zirconia, and alumina zirconia having a composition containing one or more of magnesia, silica, and calcia as auxiliary components, and provided with through holes for through holes.
  • a plurality of substrates were prepared. Each substrate surface was subjected to UV ozone treatment for 10 minutes in the same manner as in Example 1 to remove organic substances.
  • a commercially available catalyst application solution (Okuno Pharmaceutical Co., Ltd., Technoclear SN, AG, PD) was used to apply Sn-Ag-Pd catalyst nuclei to the substrate surface.
  • An electroless copper plating film was formed in the same manner as in Example 1 and energized for 45 minutes by electrolytic copper plating to obtain a copper plating film having a thickness of 50 ⁇ m. After coating the non-etched portion with an etching resist, the film was patterned by etching with an iron chloride etchant. The obtained copper patterns had average adhesion strengths of 3.18 kgf / 2 mm ⁇ and 2.57 kgf / 2 mm ⁇ , respectively. Thus, the adhesiveness was slightly inferior to that of Example 1, but it could withstand practical use (see FIG. 6).
  • Example 5 94% by mass of alumina, 5% by mass of partially stabilized zirconia, and alumina zirconia having a composition containing one or more of magnesia, silica, and calcia as auxiliary components, with through holes for through holes
  • a plurality of substrates were prepared. Similarly to Example 1, each substrate surface was subjected to UV ozone treatment for 10 minutes to remove organic substances.
  • a commercially available catalyst application solution (Okuno Pharmaceutical Co., Ltd., Technoclear SN, AG, PD) was used to apply Sn—Ag—Pd catalyst nuclei to the substrate surface.
  • the zinc nitrate concentration was changed to 10 mM and 50 mM, respectively, and an aqueous solution containing 5 mM dimethylamine borane was prepared.
  • aqueous solution containing 5 mM dimethylamine borane was prepared.
  • a film made of approximately 200 needle-like zinc oxide crystals is formed on the ceramic substrate, each having a diameter of 20 nm and 100 nm, a length of 200 nm, and 1 ⁇ m 2. It confirmed (refer FIG. 3 (A) and (B)).
  • An electroless copper plating film was formed in the same manner as in Example 1 and energized for 45 minutes by electrolytic copper plating to obtain a copper plating film having a thickness of 50 ⁇ m. After coating the non-etched portion with an etching resist, the film was patterned by etching with an iron chloride etchant. The obtained copper patterns had an average adhesion strength of 3.06 kgf / 2 mm ⁇ and 1.77 kgf / 2 mm, respectively. ⁇ and adhesion was slightly inferior to Example 1, but it was able to withstand practical use (see FIG. 6).
  • Comparative Example 1 Substrate with through-holes for through-holes, which is composed of 94% by mass of alumina, 5% by mass of partially stabilized zirconia, and one or more of magnesia, silica, and calcia as auxiliary components. Prepared. A zinc oxide layer was formed after UV ozone treatment as in Example 1, but no heat treatment was performed. Thereafter, an electroless copper plating film was formed, and in the electrolytic copper plating, current was passed for 45 minutes at room temperature and a cathode current density of 6 A / dm 2 , but the zinc oxide layer was not sufficiently adhered, and the substrate and the copper plating film were separated. (See FIG. 7).
  • Comparative Example 2 Substrate with through-holes for through-holes, which is composed of 94% by mass of alumina, 5% by mass of partially stabilized zirconia, and one or more of magnesia, silica, and calcia as auxiliary components. Prepared. In the same manner as in Example 1, the substrate surface was subjected to UV ozone treatment, a zinc oxide layer was formed, and baked in a batch furnace in an air atmosphere at a processing temperature of 900 ° C. for 1 hour. By observing the FE-SEM image of the substrate surface, it was confirmed that the zinc oxide crystals on the ceramic substrate were melted and deformed (see FIG. 4).
  • electrolysis copper plating was carried out at room temperature at a cathode current density of 6 A / dm 2 for 45 minutes.
  • the adhesion strength of the copper plating was 1.12 kgf / 2 mm ⁇ , the adhesion was insufficient, and the substrate and the copper plating film were separated.
  • Examples 6-8 Substrate with through-holes for through-holes, which is composed of 94% by mass of alumina, 5% by mass of partially stabilized zirconia, and one or more of magnesia, silica, and calcia as auxiliary components. 4 were prepared, and after the UV ozone treatment as in Comparative Example 2 (Example 1), after forming the zinc oxide layer, in order to see the effect of the heat treatment temperature, 500 ° C. (Example 6), 600 ° C. ( Example 7) and 700 ° C. (Example 8) were changed in temperature, and heat treatment was performed in a batch furnace for 1 hour in an air atmosphere.
  • each substrate was subjected to electroless copper plating and electrolytic copper plating in the same manner as in Comparative Example 2 to form a copper film.
  • the adhesion strength of copper plating is shown in Table 1 and FIG. 7 together with the adhesion strength of Example 1 and Comparative Examples 1 and 2.
  • Comparative Example 3 A plurality of substrates having through-holes for through-holes were prepared, which were alumina zirconia having a composition of 94% by mass of alumina and 5% by mass of partially stabilized zirconia. Similarly to Example 1, each substrate surface was subjected to UV ozone treatment for 10 minutes to remove organic substances. In the pretreatment for forming the zinc oxide layer, a commercially available catalyst application solution (Okuno Pharmaceutical Co., Ltd., Technoclear SN, AG, PD) was used to apply Sn-Ag-Pd catalyst nuclei to the substrate surface.
  • a commercially available catalyst application solution (Okuno Pharmaceutical Co., Ltd., Technoclear SN, AG, PD) was used to apply Sn-Ag-Pd catalyst nuclei to the substrate surface.
  • the zinc nitrate concentration was changed to 100 mM, an aqueous solution containing 5 mM dimethylamine borane was prepared, and a zinc oxide film was formed at 65 ° C. Observation of an FE-SEM image of the substrate surface after firing confirmed that film-like zinc oxide crystals were formed on the ceramic substrate (see FIG. 5).
  • An electroless copper plating film was formed in the same manner as in Example 1 and energized for 45 minutes by electrolytic copper plating to obtain a copper plating film having a thickness of 50 ⁇ m.
  • the film was patterned by etching with an iron chloride etchant, but the obtained copper pattern had insufficient adhesion of the zinc oxide layer, and between the zinc oxide and the copper plating film. I peeled it off.

Abstract

La présente invention concerne un procédé pour la production d'un tableau de connexions céramique métallisé au cuivre. Ledit procédé consiste : à former un film qui comprend 150 à 250 cristaux en aiguilles d'oxyde de zinc par μm2 sur un matériau de base céramique par un procédé par voie humide d'immersion du matériau de base céramique dans un liquide de placage au zinc, lesdits cristaux en aiguilles d'oxyde de zinc présentant un diamètre de 20 à 100 nm et une longueur de 120 à 280 nm ; à traiter thermiquement le matériau de base céramique obtenu dans l'atmosphère à une température de 500 à moins de 900 º ; à former un dépôt de cuivre par dépôt autocatalytique de cuivre ou électroplacage au cuivre ; et à soumettre le dépôt de cuivre à une formation de motifs avec une substance de réserve pour former un schéma de câblage. Selon le procédé, un tableau de connexions céramique métallisé au cuivre présentant une excellente adhérence et pouvant être utilisé en tant que tableau de connexions pour un module de puissance peut ainsi être obtenu.
PCT/JP2013/081005 2012-11-28 2013-11-18 Tableau de connexions céramique métallisé au cuivre et procédé de fabrication associé WO2014084077A1 (fr)

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JP2017141189A (ja) * 2016-02-10 2017-08-17 学校法人同志社 抗菌性を有する酸化亜鉛粉体の製造方法
CN111868301A (zh) * 2018-03-28 2020-10-30 大日本印刷株式会社 布线基板以及制造布线基板的方法
CN113079646A (zh) * 2021-03-23 2021-07-06 江苏富乐德半导体科技有限公司 一种dpc覆铜陶瓷基板表面金属化方法

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JP2003051463A (ja) * 2001-05-29 2003-02-21 Sharp Corp 金属配線の製造方法およびその方法を用いた金属配線基板

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JP2002141639A (ja) * 2000-10-31 2002-05-17 Mitsuboshi Belting Ltd セラミックス基板のメタライズ方法、セラミックス回路基板の製造方法及びセラミックス回路基板
JP2007126743A (ja) * 2005-10-04 2007-05-24 Okuno Chem Ind Co Ltd 無電解めっき用前処理方法及び無電解めっき皮膜の形成方法

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Publication number Priority date Publication date Assignee Title
JP2017141189A (ja) * 2016-02-10 2017-08-17 学校法人同志社 抗菌性を有する酸化亜鉛粉体の製造方法
CN111868301A (zh) * 2018-03-28 2020-10-30 大日本印刷株式会社 布线基板以及制造布线基板的方法
CN113079646A (zh) * 2021-03-23 2021-07-06 江苏富乐德半导体科技有限公司 一种dpc覆铜陶瓷基板表面金属化方法

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