WO2010093009A1 - 金属箔およびその製造方法，絶縁基板，配線基板 - Google Patents

金属箔およびその製造方法，絶縁基板，配線基板 Download PDF

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Publication number
WO2010093009A1
WO2010093009A1 PCT/JP2010/052056 JP2010052056W WO2010093009A1 WO 2010093009 A1 WO2010093009 A1 WO 2010093009A1 JP 2010052056 W JP2010052056 W JP 2010052056W WO 2010093009 A1 WO2010093009 A1 WO 2010093009A1
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Prior art keywords
plating
metal foil
roughened
copper
foil
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PCT/JP2010/052056
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English (en)
French (fr)
Japanese (ja)
Inventor
了一 小黒
宏途 沓名
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古河電気工業株式会社
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Application filed by 古河電気工業株式会社 filed Critical 古河電気工業株式会社
Priority to JP2010550555A priority Critical patent/JP5435505B2/ja
Priority to CN201080007921.0A priority patent/CN102317510B/zh
Priority to KR1020117013392A priority patent/KR101256086B1/ko
Publication of WO2010093009A1 publication Critical patent/WO2010093009A1/ja

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • 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
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/02—Single bars, rods, wires, or strips
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/381—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the substrate
    • 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
    • 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
    • H05K2203/03—Metal processing
    • H05K2203/0307—Providing micro- or nanometer scale roughness on a metal surface, e.g. by plating of nodules or dendrites
    • 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
    • H05K2203/0723—Electroplating, e.g. finish 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
    • H05K2203/1152—Replicating the surface structure of a sacrificial layer, e.g. for roughening

Definitions

  • the present invention relates to a metal foil and a manufacturing method thereof.
  • the present invention relates to a replica metal foil for forming a wiring with a thin film conductor layer on an insulating substrate, and a method for manufacturing the same.
  • the metal foil for replica is particularly suitable for manufacturing a wiring board for mounting a semiconductor element, an integrated circuit, an electronic component and the like.
  • the present invention also relates to an insulating substrate having a roughened surface formed using a metal foil, and a wiring substrate having a predetermined wiring pattern formed on the roughened surface of the insulating substrate.
  • wiring boards for mounting semiconductor elements, integrated circuits, electronic components, etc. are rapidly becoming more integrated, higher output, and faster in addition to being lighter, thinner and smaller. Therefore, for example, when forming a metal wiring such as copper on a semiconductor substrate, it is common to use sputtering film formation and electrolytic plating in combination.
  • process development for miniaturization of copper wiring is rapidly progressing with higher functions and higher speeds.
  • the electrical resistance of wiring materials causes signal delays, which hinders the increase in transmission speed. To do. For this reason, an ultrathin metal material having a small electric resistance is used as the wiring material.
  • a sputtering method and a CVD (chemical vapor deposition) method have been employed as a conventional technology for forming an ultrathin metal film on a wiring board.
  • a sputtering method that is advantageous from the viewpoint of mass productivity and stability of film formation is generally employed.
  • the wiring formed by the sputtering method has a problem that a disconnection accident easily occurs due to stress migration generated by electromigration or expansion / contraction of the wiring, and there is a problem in that the manufacturing yield of the wiring substrate is lowered.
  • the present invention provides a metal foil suitable for use in a so-called replica method in which a surface shape of a metal foil surface is transferred to an insulating substrate and a thin metal layer is formed on the transferred surface in the production of a wiring board. .
  • a wiring board for mounting semiconductor elements, integrated circuits, electronic components, etc. is an insulating substrate such as an epoxy resin or semi-cured resin coated imide resin, liquid crystal polymer resin film, etc. .
  • this wiring board is made by impregnating an insulating fiber such as an aramid resin or glass with an epoxy resin, and further, for example, an epoxy layer semi-cured state having a thickness of about 5 to 20 ⁇ m, that is, an insulating material such as a glass epoxy board formed by a B stage It is a substrate.
  • a metal foil is laminated on this insulating substrate.
  • a copper foil having a roughened surface is employed as the metal foil.
  • the roughened surface side of the metal foil is laminated on the surface of the insulating substrate by vacuum hot pressing.
  • the laminated metal foil is removed by etching.
  • the surface of the insulating substrate is vacuum-heat-pressed metal foil and the metal on the roughened surface of the metal foil that has penetrated into the insulating substrate.
  • the metal foil is a copper foil, it is generally used for the production of wiring boards. Etch away with an etchant such as iron chloride or copper chloride.
  • the metal on the roughened surface is removed from the surface of the insulating substrate by etching away the metal foil. For this reason, the uneven
  • the concave portion is formed not only with a large surface area but also with a shape in which there is a portion where the cross sectional area of the opening inside the concave portion is larger than the size of the cross sectional area of the opening on the concave surface. Therefore, the concave portion has an optimum shape for the anchor effect.
  • a metal having a low electrical resistivity for example, copper is thinly plated to a thickness of about 0.1 to 5 ⁇ m by electroless plating.
  • a plating mask is provided in a region other than the desired wiring pattern on the surface of the thinly plated plating layer.
  • the plating mask is formed, for example, by providing a photosensitive resin on the surface of the plating layer, and then exposing and developing with a light mask for forming a desired pattern.
  • a wiring is formed by electroplating a highly conductive metal, for example, copper, in a desired wiring pattern region where the photosensitive resin is not deposited.
  • etching is performed with an etching solution such as a hydrogen peroxide sulfate, a persulfate, or an ammonia complex, and the electroless plating layer that is not covered with the electroplating layer is removed. Since the electroless plating layer is thinner than the wiring of the electroplating metal layer, the etching rate is high. And the wiring of the electroplating layer of a desired pattern is hardly etched. For this reason, the electroless plating layer under the desired pattern by the electroplating layer is not etched because the wiring of the electroplating layer is protected using the mask. Finally, it is immersed in a mixed solution of potassium permanganate and sodium hydroxide. This removes the palladium that was deposited on the exposed surface of the insulating substrate and could not be etched with the etchant. (This method is disclosed in, for example, Patent Document 1.)
  • the roughened surface of the copper foil is plated on the surface of the copper foil by multiplying the current of electroplating several times as usual, that is, by utilizing an abnormal plating phenomenon (discoloration plating), The fine particles are grown by plating.
  • the overall rough shape such as the size, roughness, and granularity of the particles, is an important factor in the adhesion strength with the insulating substrate, and has been optimized by the copper foil manufacturer and is easily available. Although it is described as being, details thereof are not disclosed.
  • the present invention has been intensively studied on a replica metal foil suitable for manufacturing a wiring board for mounting a semiconductor element, an integrated circuit, an electronic component, etc., and a metal having a roughened surface having a preferable shape as a metal foil for replica use.
  • the present invention has succeeded in providing a wiring substrate having a wiring pattern that has excellent adhesion between the insulating substrate and the wiring pattern, and that has excellent etching straightness and thickness uniformity.
  • electrolytic copper foils on the market generally have a roughened shape for improving adhesion to the substrate, and the copper grains are generally closely attached at the roots.
  • the surface-treated metal foil mainly used for replicas according to the present invention is characterized in that fine columnar irregularities having a gap of 0.1 ⁇ m or more and 1.0 ⁇ m or less are formed on the roughened surface side.
  • the metal foil of the present invention is a metal foil having a roughened plating surface, and the roughened plating surface is subjected to roughening galvanization by burnt plating on at least one surface of the untreated metal foil.
  • the surface roughness of the surface is Rz value defined in JIS-B-0601 (hereinafter the same) is 1.0 ⁇ m to 2.5 ⁇ m, and the roughened bump formed by the roughened bump plating is The columnar shape has a gap of 0.1 ⁇ m or more and 1.0 ⁇ m or less between adjacent roughing bumps.
  • the metal foil of the present invention is a metal foil in which the roughened plating surface is subjected to rust prevention treatment.
  • the untreated metal foil is a rolled copper foil or an electrolytic copper foil, and the surface roughness of at least the plated roughened surface forming side of the untreated copper foil is from 1.0 ⁇ m to 2. It is a metal foil which is 2 ⁇ m.
  • the main use of the metal foil of the present invention is replica use.
  • the insulating substrate of the present invention is an insulating substrate having a roughened surface formed by transferring the uneven shape on the roughened plating surface of the metal foil.
  • the wiring board of the present invention is a wiring board in which a predetermined wiring pattern is formed on the roughened surface of the insulating substrate.
  • the metal foil manufacturing method of the present invention is added to an untreated metal foil having a surface roughness Rz value of 1.0 ⁇ m to 2.2 ⁇ m to a sulfuric acid-copper sulfate plating solution, a pyrophosphate copper plating solution or a copper carbonate plating solution.
  • Burn plating is performed in a plating bath to which a metal is added to form a roughened galvanized surface.
  • Capsule plating is applied to the roughened galvanized surface, and the surface roughness is 1.0 to 2.5 ⁇ m in terms of Rz value.
  • the additive metal added to the plating solution is iron, chromium, molybdenum, tungsten, and / or vanadium and antimony.
  • a rust prevention treatment is applied to the roughened plated surface.
  • the untreated metal foil is a rolled copper foil or an electrolytic copper foil.
  • the main use of the metal foil roughened by the metal foil manufacturing method of the present invention is a replica application.
  • the metal foil of the present invention is mainly excellent in the anchoring effect (anchor effect using the replica) in the replica application, it is possible to reduce the plating amount cost in the electroless plating which is a subsequent process. Moreover, since the metal foil of this invention is excellent in the adhesiveness of an insulated substrate and a wiring pattern, it is excellent in the etching straightness in the fine wire circuit etching process at the time of circuit manufacture. Therefore, the present invention has an excellent effect in the production of a wiring board for mounting a semiconductor element, an integrated circuit, an electronic component, and the like.
  • (A) is a photograph showing a standard (level) for judging the straightness of the circuit after etching.
  • (B) is a photograph showing a reference (level) for determining residual copper mapping by EPMA (X-ray microanalyzer; Electron Probe Micro-Analysis).
  • (C) is a photograph explaining the roughened bump gap.
  • the metal foil of the present invention may be a stainless steel foil, an aluminum foil, a copper foil or the like, and any metal foil that can be etched as a foil for replica use.
  • the present invention will be described in detail by taking, as an example, an electrolytic copper foil that is expected to be highly demanded as a metal foil.
  • an electrolytic copper foil before forming the roughened plating surface used in the present invention (hereinafter sometimes referred to as an untreated copper foil) has a unit thickness of 60 g / m 2 to 153 g / m 2 (nominal thickness of 9 to 18 ⁇ m).
  • the crystal structure in the thickness direction is fine grains (fine crystals).
  • “Nominal thickness” indicates the actually measured thickness.
  • Single heavy Mi of untreated copper foil in the range from 60 g / m 2 of 153 g / m 2, the untreated foils or roughened, handling properties at the time of laminating the roughening treatment foil on the insulating substrate Furthermore, it is because the characteristics such as the ease of the etching process when removing the foil by etching are excellent.
  • This untreated copper foil is burnt-plated.
  • a metal additive is added to a basic plating solution composition of any one of a sulfuric acid-copper sulfate plating solution, a pyrophosphate copper plating solution, and a copper carbonate plating solution in a plating bath for performing burnt plating.
  • a metal additive Fe (iron), Mo (molybdenum), Cr (chromium), W (tungsten), and V (vanadium) or Sb (antimony) or both are added.
  • the surface of the untreated copper foil is subjected to burnt plating in the vicinity of the limiting current density of the plating bath, thereby forming a bumpy columnar shape of fine crystals.
  • a predetermined amount of Fe (iron), Mo (molybdenum), Cr (chromium), and W (tungsten) is added to the burnt plating bath as shown below, so that a plurality of fine columnar shapes provide gaps. Formed. Further, by adding V (vanadium) or Sb (antimony), chemical resistance can be improved when a single-side treated foil is formed. Details of the plating method will be described later.
  • smooth plating so-called capsule plating
  • capsule plating is applied to roughen the surface of the roughened copper foil or replica so that the copper grains of the bumpy fine columnar shape on the surface of the roughened bumped surface formed by roughened bumped plating by burnt plating are not easily dropped.
  • Copper foil hereinafter, sometimes simply referred to as replica copper foil.
  • the capsule plating method will be described later.
  • the roughened surface of the finished roughened plating surface has an Rz value specified by JIS-B-0601 (hereinafter the same) of 1.0 ⁇ m or more and 2.5 ⁇ m or less, and the copper particles are capsule plated. Even after being applied, the fine columnar shape (columnar shape) is maintained, and the columnar gaps between the columnar shapes are 0.1 ⁇ m or more and 1.0 ⁇ m or less.
  • the replica copper foil manufactured as described above is first laminated on an insulating substrate to be laminated, for example, an epoxy base material, a polyimide resin, or an organic film. Thereafter, the replica copper foil is completely dissolved and removed by etching to form a fine columnar replica having columnar gaps on the surface of the insulating substrate. That is, the uneven shape on the roughened plating surface of the replica copper foil (metal foil) is transferred to form a roughened surface on the insulating substrate. Then, after forming a metal film by plating on the roughened surface of the insulating substrate, wet etching is performed on the metal film, pattern processing is performed, and a predetermined wiring pattern is formed, thereby forming a wiring substrate. To do.
  • the copper foil of the present invention which is mainly used for replicas, has a fine columnar shape having a gap of 0.1 ⁇ m or more and 1.0 ⁇ m or less on the roughened surface side. For this reason, by using the copper foil, it is possible to easily form unevenness (replica) excellent in anchoring effect (anchor effect using a replica) with a uniform and concave spacing and shape on the surface of the insulating substrate. Can do. Therefore, the amount of plating during electroless plating, which is a subsequent process, can be saved to a minimum, and the straightness of etching in the fine line circuit etching process during subsequent circuit fabrication is excellent. Therefore, it is possible to provide a surface-treated copper foil having a roughened surface that is preferable as a replica copper foil suitable for manufacturing a wiring board for mounting a semiconductor element, an integrated circuit, an electronic component, or the like.
  • the fine columnar shape (roughening shape) applied to the copper foil surface is formed such that the surface roughness is 1.0 ⁇ m or more and 2.5 ⁇ m or less in terms of Rz value.
  • Rz corresponding to the depth of the replica
  • the roughening shape of the replica copper foil is particularly preferably 1.0 ⁇ m or more and 2.5 ⁇ m or less in terms of Rz value.
  • a fine columnar shape having a gap of 0.1 ⁇ m or more and 1.0 ⁇ m or less is formed on the roughened surface side of the replica copper foil.
  • the copper foil before the plating roughening treatment has a fine grain crystal structure.
  • the copper foil having a fine grain crystal structure is a glossy copper foil having a surface roughness Rz value of 1.0 ⁇ m or more and 2.2 ⁇ m or less before the roughening treatment.
  • a roughened shape having the gap can be provided by roughening a copper foil having a fine grain crystal structure. In other words, it is difficult to obtain the replica shape of the present invention by the roughing bump process using a general electrolytic copper foil base having columnar crystals.
  • the surface roughness of the untreated copper foil is defined as an Rz value of 1.0 ⁇ m or more.
  • the untreated copper foil having an Rz value of less than 1.0 ⁇ m has extremely low productivity in the foil-making process, and is industrial. It is because it is unsuitable as a material for use. If the Rz value exceeds 2.2 ⁇ m, the initial electrodeposited copper particles in the burnt plating process concentrate and adhere to the tip with high roughness (plating), resulting in dendritic extremely brittle roughening. In order to obtain a healthy state, it is necessary to excessively apply smooth plating in the next step.
  • the surface roughness of the untreated copper foil is defined as 2.2 ⁇ m or less in terms of Rz value.
  • the copper for replicas having the roughened bump plating of the present invention Rz (corresponding to the depth of the replica) of 1.0 ⁇ m or more and 2.5 ⁇ m or less, and the gap between the roughened bumps of 0.1 ⁇ m or more and 1.0 ⁇ m or less
  • the foil is laminated to the insulating substrate.
  • a cleaning process is performed by a permanganate process for removing the copper foil or the like to finish the insulating substrate surface without damaging the replica shape.
  • an ultra-thin copper film is formed on the surface of the insulating substrate by electroless plating, and the surface of the ultra-thin copper film is subjected to electrolytic copper plating.
  • the copper foil for replicas of the present invention uses a glossy copper foil having a surface roughness Rz value of 1.0 ⁇ m or more and 2.2 ⁇ m or less, and is subjected to a roughening bump process.
  • the discoloration plating bath composition for roughening the copper foil is as follows.
  • burnt plating is performed under the following plating conditions.
  • Bath temperature 20-30 ° C., preferably 23.5-25.5 ° C.
  • Current density 25 to 35 A / dm 2 by DC rectification, preferably 28 ⁇ 1.5 A / dm 2
  • the surface of the copper foil subjected to burnt plating has a surface roughness of either the surface peeled off from the surface of the cathode drum of the electrolytic plating foil (glossy surface) or the liquid surface (matte surface). If the Rz value is 1.0 ⁇ m or more and 2.2 ⁇ m or less, there is no problem.
  • the glossy surface side In the case of an electrolytic copper foil manufactured with a general columnar crystal structure, it is preferable to use the glossy surface side. However, in the case of copper foils made of fine crystals and smooth on both sides (for example, WS foil which is an electrolytic copper foil made by Furukawa Electric Co., Ltd.), the matte side is smoother than the glossy side. Rich.
  • the rough matting treatment is performed by subjecting the smooth mat surface side to burnt plating and then the capsule plating treatment, the Rz value is 2.5 ⁇ m or less, and the roughening is performed.
  • a rough surface having a shape in which the gap between the bumps is 0.1 ⁇ m or more and 1.0 ⁇ m or less can be formed.
  • smooth capsule plating is performed on the surface of the roughened bump-formed shape formed by the above-mentioned burn plating under the following conditions.
  • the copper foil is subjected to organic rust prevention treatment, chromate treatment, nickel treatment or zinc treatment as rust prevention treatment to obtain a roughened copper foil for replica.
  • the organic rust inhibitor is preferably benzotriazole (1.2.3-Benzotriazole [nominal: BTA]), but may be a commercially available derivative.
  • the amount of treatment may be soaked to the extent that the surface does not discolor copper oxide for up to 24 hours under the salt spray test (salt water concentration: 5% -NaCl, temperature 35 ° C.) specified in JIS-Z-2371.
  • the amount quantitatively analyzed as adhering Ni metal may be 0.06 to 0.12 mg-Ni / dm 2 (analyzed value per 10 cm).
  • the roughened surface side exceeds 0.12 mg / dm 2 , the possibility of occurrence of a migration failure is increased, which is not preferable. Further, if it is less than 0.06 mg-Ni / dm 2 , a sufficient rust prevention effect cannot be obtained.
  • the amount quantitatively analyzed as deposited Zn metal may be 0.15 to 0.35 mg-Zn / dm 2 (analyzed value per 10 cm). Even if the roughened surface side exceeds 0.35 mg / dm 2 , there is no particular problem if the surface is only brassed by the diffusion effect, but an appropriate upper limit is preferably 0.35 mg-Zn / dm 2 . On the other hand, if it is less than 0.15 mg-Zn / dm 2 , the occurrence of discoloration defects occurs empirically, which is not preferable. In addition, it can select arbitrarily whether roughening processing is carried out on one side of copper foil, or roughening processing is carried out on both surfaces.
  • the obtained copper foil for replica for example, copper foil for roughening with a nominal thickness of 9 ⁇ m
  • BGA All-Grid-Array
  • replica for example, the roughening surface side Bond to the target substrate.
  • all of this copper foil is etched away efficiently, and it cleans with a permanganate processing liquid.
  • the permanganic acid treatment liquid has an effect of dissolving metal residues other than copper taken in at the time of burn plating. For this reason, the permanganic acid treatment liquid is an optimal chemical as a pretreatment agent that can achieve the means for wiping out migration concerns and the subsequent electroless copper plating process.
  • electroless copper plating may be applied to the replica surface of the base material in accordance with an electroless copper plating chemical process. Moreover, depending on the case, thickness can be added by electroplating on electroless copper plating, and it can also lead to cost reduction.
  • L / S Line / Space
  • the electrolytic copper foil is described as an example of the untreated metal foil.
  • an untreated metal foil it can apply similarly to rolled copper foil, aluminum foil, stainless steel foil, etc. besides electrolytic copper foil.
  • Example 1 On the surface side of the untreated electrolytic copper foil having fine crystal grains with a unit thickness of 107 g / m 2 (corresponding to a nominal thickness of 12 ⁇ m), the surface roughness is 1.5 ⁇ m in terms of Rz value, Under the conditions, burnt plating was used to form a roughened bump. Electrolytic treatment (discoloration plating) was performed with the following bath composition and plating conditions.
  • capsule plating was performed with the following bath composition and plating conditions in order to obtain a strong and sound roughened bump-shaped shape that does not fall off by performing smooth plating on the rough surface of the burnt plating.
  • ⁇ Sulfuric acid concentration 100 g / l
  • Copper concentration from copper sulfate 50g-Cu / l
  • Bath temperature 55 °C
  • Current density 22 A / dm 2 by DC rectification
  • the copper foil manufactured in Example 1 was laminated on a commercially available high-frequency insulating substrate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) under the conditions of 220 ° C., 30 kgf / cm 2 and 100 min. Thereafter, all the copper foils laminated on the surface were completely dissolved and removed with a cupric chloride etching solution (specific gravity: 1.265; bath temperature: 45 ° C.), and washed thoroughly with water. Next, so-called permanganic acid etching was performed on the replica portion using desmear process liquid (Mc. Dicer 9204, 9275, 9276, 9279) manufactured by McDermit Japan Co., Ltd., and sufficient washing with water was performed. Then, a copper film having a thickness of about 3.0 ⁇ m was formed on the surface according to a known electroless copper plating process for thickening (Hitachi, Ltd. AP2 process).
  • a cupric chloride etching solution specific gravity: 1.265; bath temperature:
  • the adhesion strength (kN / m) is measured by plating the surface of the copper film of the substrate with an electroless copper film to a thickness of 35 ⁇ m using a known sulfuric acid-copper sulfate bath, and 0.1 m / m width on the plated surface.
  • the pattern was printed with a UV ink that was cured by UV irradiation and a screen, and the pattern obtained by etching was measured according to JIS-C-6481. Furthermore, regarding the interval between roughing bumps on the treated surface and the presence or absence thereof, the interval between the outermost contours of the roughing bumps taken at a magnification of a stereomicroscope (see FIG. 1C) passed the JIS standard.
  • a plurality of columnar shapes are formed at intervals by copper particles being dispersed and adhering to the treatment surface and electrodeposition-grown in a dendritic shape.
  • the plurality of columnar shapes are formed so that the width decreases as the distance from the processing surface increases. For this reason, the interval between the bottoms of the columnar shape was measured as described above.
  • the measurement results are also shown in Table 1.
  • Determination of the straightness of the circuit after etching shown in Table 1 is based on the observation result of an optical microscope.
  • the judgment criteria are ⁇ when the etched surface is almost straight in the micrograph, and ⁇ when the linearity is slightly difficult but practically unquestionable.
  • the case where it was judged that there was a problem in practicality was rated as x.
  • FIG. 1 (B) the observation of mapping by copper residue is ⁇ when the copper residue cannot be completely confirmed by EPMA observation, ⁇ when the copper residue is almost unidentifiable, or slightly residual, but practically ⁇ indicates that there is no problem.
  • the interval between the rough edges of the roughened bumps on the surface of the treated surface passed the JIS standard, as shown in Fig. 1 (C).
  • the distance between the intervals was obtained by actual measurement using a commercially available micro caliper and converting according to the magnification.
  • Example 2 The single weight thickness of the untreated copper foil having fine crystal grains used in Example 1 is 63 g / m 2 (the nominal thickness is equivalent to 7 ⁇ m). Except for this point, each treatment was carried out in exactly the same manner as in Example 1 with the discoloration plating conditions, capsule plating conditions, and rust prevention treatment conditions, and the evaluation measurement results are also shown in Table 1.
  • Example 3 It is a unit thickness of 153 g / m 2 (corresponding to a nominal thickness of 18 ⁇ m) of the untreated copper foil having fine crystal grains used in Example 1. Except for this point, each treatment was carried out in exactly the same manner as in Example 1 with the discoloration plating conditions, capsule plating conditions, and rust prevention treatment conditions, and the evaluation measurement results are also shown in Table 1.
  • Example 4 On the surface where the surface roughness on the liquid surface side of the untreated electrolytic copper foil with fine crystal grains is Rz value of 1.5 ⁇ m with a thickness of 107 g / m 2 (corresponding to a nominal thickness of 12 ⁇ m), the following bath composition And burnt plating was applied to form rough and rough bumps under the plating conditions.
  • pH was adjusted to 1.2 with industrial concentrated sulfuric acid, and the copper pyrophosphate electrolytic plating bath was formed.
  • Example 5 The surface roughness on the liquid surface side of the untreated electrolytic copper foil having fine crystal grains with a unit thickness of 107 g / m 2 (equivalent to a nominal thickness of 12 ⁇ m) is 1.5 ⁇ m in terms of Rz value under the following conditions. Burn plating to form a roughened bump was applied. Here, with respect to the following basic bath, each compound was added so that it might become the following density
  • Example 6 instead of the untreated metal foil, an industrial general-purpose rolled aluminum foil having a single weight of 68 g / m 2 (nominal thickness corresponding to 25 ⁇ m) was used. Further, before the burnt plating, the surface was degreased and washed with a 25 g / l sodium hydroxide solution (bath temperature: 85 ° C.). Then, the surface to be burnt plated with a solution obtained by dissolving 50 g / l of zinc oxide in an acetic acid acid bath was subjected to a zinc plating pretreatment of 0.35 mg-Zn / dm 2 so that sound burnt plating could be performed. Except for these points, the burn treatment conditions, capsule plating conditions, and rust prevention treatment conditions were the same as in Example 1, and the evaluation measurement results are also shown in Table 1.
  • Example 1 When the burn plating treatment for forming the roughened bumps of Example 1 was performed, molybdenum, iron, chromium, tungsten, vanadium, and chlorine were not used as additive metals and additives in the bath. Except for these points, the same capsule plating and rust prevention treatment as in Example 1 were performed, the same evaluation measurement was performed, and the results are also shown in Table 1.
  • Example 2 instead of the untreated copper foil having fine crystal grains used in Example 1, a commercially available single-side roughened electrolytic copper foil having a nominal columnar crystal with a nominal thickness of 12 ⁇ m (GTS-MP- manufactured by Furukawa Electric Co., Ltd.) 12 ⁇ m foil) was used. Except for this point, each treatment was carried out in the same manner as in Example 1 for the discoloration plating conditions, capsule plating conditions, and rust prevention treatment conditions, and the evaluation measurement results are also shown in Table 1.
  • the circuit etching straightness is superior to those of the comparative examples, there is no fear of migration between circuits, and the member also uses adhesion strength.
  • a metal wiring film having sufficient strength required for the above-mentioned and improved in quality as compared with an ultrathin copper film obtained by a conventional method can be formed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Parts Printed On Printed Circuit Boards (AREA)
PCT/JP2010/052056 2009-02-13 2010-02-12 金属箔およびその製造方法，絶縁基板，配線基板 WO2010093009A1 (ja)

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JP2011219789A (ja) * 2010-04-06 2011-11-04 Fukuda Metal Foil & Powder Co Ltd 銅張積層板用処理銅箔及び該処理銅箔を絶縁性樹脂基材に接着してなる銅張積層板並びに該銅張積層板を用いたプリント配線板。
WO2012043182A1 (ja) * 2010-09-27 2012-04-05 Jx日鉱日石金属株式会社 プリント配線板用銅箔、その製造方法、プリント配線板用樹脂基板及びプリント配線板
JP2015042765A (ja) * 2013-07-23 2015-03-05 Jx日鉱日石金属株式会社 表面処理銅箔、キャリア付銅箔、基材、プリント配線板、プリント回路板、銅張積層板及びプリント配線板の製造方法
JP2015147978A (ja) * 2014-02-06 2015-08-20 古河電気工業株式会社 高周波回路用銅箔、銅張積層板及びプリント配線板
JP2017133105A (ja) * 2017-03-06 2017-08-03 Ｊｘ金属株式会社 キャリア付銅箔、プリント配線板、プリント回路板、銅張積層板及びプリント配線板の製造方法
US9955583B2 (en) 2013-07-23 2018-04-24 Jx Nippon Mining & Metals Corporation Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed wiring board, copper clad laminate and method for producing printed wiring board
WO2019177319A1 (ko) * 2018-03-14 2019-09-19 주식회사 엘지화학 매립형 투명 전극 기판 및 이의 제조방법
US11840602B2 (en) 2019-12-23 2023-12-12 Chang Chun Plastics Co., Ltd. Laminate, circuit board, and liquid crystal polymer film applied to the same

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KR20170018342A (ko) 2014-06-06 2017-02-17 가부시키가이샤 유에이씨제이 집전체용 금속박, 집전체 및 집전체용 금속박의 제조 방법
KR102647658B1 (ko) * 2018-03-27 2024-03-15 미쓰이금속광업주식회사 조화 처리 구리박, 캐리어를 구비한 구리박, 동장 적층판 및 프린트 배선판

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JP4354271B2 (ja) * 2003-12-26 2009-10-28 三井金属鉱業株式会社 褐色化表面処理銅箔及びその製造方法並びにその褐色化表面処理銅箔を用いたプラズマディスプレイの前面パネル用の電磁波遮蔽導電性メッシュ
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JP2011219789A (ja) * 2010-04-06 2011-11-04 Fukuda Metal Foil & Powder Co Ltd 銅張積層板用処理銅箔及び該処理銅箔を絶縁性樹脂基材に接着してなる銅張積層板並びに該銅張積層板を用いたプリント配線板。
KR101871029B1 (ko) 2010-09-27 2018-06-25 제이엑스금속주식회사 프린트 배선판용 구리박, 그 제조 방법, 프린트 배선판용 수지 기판 및 프린트 배선판
WO2012043182A1 (ja) * 2010-09-27 2012-04-05 Jx日鉱日石金属株式会社 プリント配線板用銅箔、その製造方法、プリント配線板用樹脂基板及びプリント配線板
US9028972B2 (en) 2010-09-27 2015-05-12 Jx Nippon Mining & Metals Corporation Copper foil for printed wiring board, method for producing said copper foil, resin substrate for printed wiring board and printed wiring board
JP5781525B2 (ja) * 2010-09-27 2015-09-24 Jx日鉱日石金属株式会社 プリント配線板用銅箔、その製造方法、プリント配線板用樹脂基板及びプリント配線板
JP2016208041A (ja) * 2010-09-27 2016-12-08 Ｊｘ金属株式会社 プリント配線板用樹脂基板及びその製造方法、プリント配線板及びその製造方法、半導体パッケージ基板及びその製造方法、並びに、プリント配線板用銅箔の製造方法
JP2015042765A (ja) * 2013-07-23 2015-03-05 Jx日鉱日石金属株式会社 表面処理銅箔、キャリア付銅箔、基材、プリント配線板、プリント回路板、銅張積層板及びプリント配線板の製造方法
JP2017075406A (ja) * 2013-07-23 2017-04-20 Ｊｘ金属株式会社 表面処理銅箔、キャリア付銅箔、基材の製造方法、プリント配線板の製造方法、プリント回路板の製造方法、銅張積層板の製造方法
US9955583B2 (en) 2013-07-23 2018-04-24 Jx Nippon Mining & Metals Corporation Surface-treated copper foil, copper foil with carrier, substrate, resin substrate, printed wiring board, copper clad laminate and method for producing printed wiring board
JP2015147978A (ja) * 2014-02-06 2015-08-20 古河電気工業株式会社 高周波回路用銅箔、銅張積層板及びプリント配線板
JP2017133105A (ja) * 2017-03-06 2017-08-03 Ｊｘ金属株式会社 キャリア付銅箔、プリント配線板、プリント回路板、銅張積層板及びプリント配線板の製造方法
WO2019177319A1 (ko) * 2018-03-14 2019-09-19 주식회사 엘지화학 매립형 투명 전극 기판 및 이의 제조방법
US11259417B2 (en) 2018-03-14 2022-02-22 Lg Chem, Ltd. Embedded-type transparent electrode substrate and method for manufacturing same
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US11926698B2 (en) 2019-12-23 2024-03-12 Chang Chun Plastics Co., Ltd. Liquid crystal polymer film and laminate comprising the same
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TWI432615B (zh) 2014-04-01
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