US20190003062A1 - Microetchant for copper and method for producing wiring board - Google Patents

Microetchant for copper and method for producing wiring board Download PDF

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Publication number
US20190003062A1
US20190003062A1 US16/067,665 US201716067665A US2019003062A1 US 20190003062 A1 US20190003062 A1 US 20190003062A1 US 201716067665 A US201716067665 A US 201716067665A US 2019003062 A1 US2019003062 A1 US 2019003062A1
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polymer
microetching agent
ion source
copper
microetching
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Keisuke Matsumoto
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MEC Co Ltd
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MEC Co Ltd
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Priority claimed from PCT/JP2017/004653 external-priority patent/WO2017141799A1/ja
Assigned to MEC COMPANY LTD. reassignment MEC COMPANY LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MATSUMOTO, KEISUKE
Publication of US20190003062A1 publication Critical patent/US20190003062A1/en
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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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • 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
    • H05K3/067—Etchants
    • 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
    • H05K3/383—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by microetching
    • 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
    • H05K2203/0756—Uses of liquids, e.g. rinsing, coating, dissolving
    • H05K2203/0776—Uses of liquids not otherwise provided for in H05K2203/0759 - H05K2203/0773
    • 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
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0789—Aqueous acid solution, e.g. for cleaning or etching

Definitions

  • the invention relates to a microetching agent for copper and a method for producing a wiring board.
  • a multilayer wiring board in general is produced by laminating an inner layer substrate, which includes a conductive layer composed of copper, copper alloy or the like, to another inner layer substrate or a copper foil with a prepreg held therebetween. Conductive layers are electrically connected with each other by a copper plated through-hole. In order to enhance the adhesion between the conductive layers and the resin such as a prepreg or solder, fine irregularities are formed on the surface of the conductive layers by using a microetching agent (roughening agent).
  • a microetching agent roughening agent
  • Organic acid-based microetching agents (See Patent Document 1), sulfuric acid-hydrogen peroxide-based microetching agents (See Patent Document 2), hydrochloric acid-based microetching agents (See Patent Document 3), and the like are known as the microetching agent for copper or copper alloy.
  • the microetching agent for copper or copper alloy.
  • For the purpose of adjusting roughened shape, etching rate etc., halogen, polymer, anticorrosive agent, surfactant, and the like are added to these microetching agents.
  • Patent Document 1 JP 9-41163 A
  • Patent Document 2 JP 2002-47583 A
  • Patent Document 3 WO2007/024312
  • a rolled copper foil and an electrolytic copper foil are mainly used as conductive layers of a printed wiring board.
  • rolled copper and electrolytic copper have different microscopic surface shapes.
  • crystal characteristics of the rolled copper and electrolytic copper are markedly different.
  • the roughened shape formed on the surface by the etching treatment may differ in some cases.
  • the rolled copper foil has large crystal grains and has a high uniformity of crystal plane orientation, so that formation of irregularities tends to be uneasy.
  • an object of the present invention is to provide a microetching agent that can form a roughened shape less affected by difference in the crystallinity of copper and with which a roughened shape excellent in terms of adhesion to resin or the like can be formed on each of rolled copper and electrolytic copper.
  • the present invention relates to a microetching agent for copper that is used for surface roughening of the copper.
  • the term “copper” in the present specification is meant to include copper and copper alloy.
  • the term “copper layer” is meant to include a copper wiring pattern layer as well.
  • the microetching agent is an acidic aqueous solution containing an inorganic acid, a cupric ion source, a halide ion source, a sulfate ion source, and a polymer.
  • the polymer contained in the microetching agent is a water-soluble polymer having a weight-average molecular weight of 1000 or more and having an amino group or a quaternary ammonium group in the side chain.
  • the polymer is preferably cationic.
  • the present invention relates to a method for producing a wiring board including a copper layer.
  • the production method of a wiring board includes a step of roughening the surface of a copper layer by bringing the aforementioned microetching agent into contact with the surface of the copper layer (roughening treatment step).
  • roughening treatment step it is preferable to add a replenishing liquid to the microetching agent in order to keep the composition of the microetching agent within a predetermined range.
  • a roughened shape excellent in adhesion to resin or the like can be formed uniformly even on rolled copper.
  • FIG. 1A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface that has not been subjected to an etching treatment.
  • FIG. 1B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic copper surface that has not been subjected to an etching treatment.
  • FIG. 2A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 2B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 3A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 3B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 4 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 5 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 6 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 7 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 8 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 9 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 10 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 11 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 12A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 5000) of a rolled copper surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 12B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 5000) of an electrolytic surface subjected to a roughening treatment with a microetching agent of an Example.
  • FIG. 13A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 13B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 14A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 14B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 15A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 15B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 16 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 17 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 18 is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 19A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 19B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 20A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 20B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 21A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 21B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 22A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 22B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 23A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 23B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 24A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 24B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 25A is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of a rolled copper surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • FIG. 25B is a scanning electron microscope photograph (photographing angle: 45°, magnification: 3500) of an electrolytic surface subjected to a roughening treatment with a microetching agent of a Comparative Example.
  • the microetching agent of the present invention is used for forming a roughened shape on the surface of copper.
  • the microetching agent is an acidic aqueous solution containing an inorganic acid, a cupric ion source, a halide ion source, a sulfate ion source, and a polymer. Components contained in the microetching agent of the present invention will be described below.
  • a cupric ion source generates a cupric ion in an aqueous solution.
  • the cupric ion acts as an oxidant for oxidizing copper.
  • the cupric ion source include copper halides such as cupric chloride and cupric bromide; inorganic acid salts such as cupric sulfate and cupric nitrate; organic acid salts such as cupric formate and cupric acetate; cupric hydroxide; and cupric oxide.
  • Cupric halide can be used as a compound having both functions of halide ion source and the cupric ion source because the cupric halide generates a cupric ion and a halide ion in the aqueous solution.
  • Cupric sulfate can be used as used as a compound having both functions of the sulfate ion source and the cupric ion source because the cupric sulfate generates a cupric ion as well as a sulfate ion and a hydrogensulfate ion in the aqueous solution.
  • the cupric ion sources may be used in combination of two or more thereof.
  • Enhancing the concentration of the cupric ion source properly maintains the etching rate and can form a uniform roughened shape over the entire surface even on a copper layer, such as rolled copper, having large crystal grains of copper and having a high uniformity of crystal plane orientation.
  • the molar concentration of the cupric ion source is preferably 0.05 mol/L or more. It is to be noted that the molar concentration of the cupric ion source is a molar concentration of copper atoms contained in the cupric ion source and is equal to the concentration of the cupric ion in the etching agent.
  • the molar concentration of the cupric ion source is preferably 3 mol/L or less from the viewpoint of suppressing excessive etching and maintaining the solubility of the copper ion when the copper ion concentration rises in accordance with the progress of etching.
  • the molar concentration of the cupric ion source is more preferably 0.1 to 2 mol/L, further preferably 0.3 to 1.5 mol/L.
  • the inorganic acid has a function of dissolving copper oxidized by a cupric ion, as well as a function of adjusting pH. Lowering the pH of the microetching agent enhances the solubility of oxidized copper and tends to suppress deposition of other components when the copper ion concentration in the liquid rises in accordance with the progress of etching.
  • An inorganic acid is used as the acid from the viewpoint of keeping the pH of the microetching agent low.
  • a strong acid such as a hydrohalic acid such as hydrochloric acid or hydrobromic acid, sulfuric acid, or nitric acid is preferred.
  • the hydrohalic acid can be used as a compound having both functions of the halide ion source and the acid.
  • the sulfuric acid can be used as a compound having both functions of the sulfate ion source and the acid.
  • the microetching agent of the present invention preferably contains sulfuric acid and/or hydrohalic acid as the inorganic acid.
  • hydrohalic acids hydrochloric acid (aqueous solution of hydrogen chloride) is preferable.
  • the acids may be used in combination of two or more thereof, and an organic acid may be used in addition to an inorganic acid.
  • the pH of the microetching agent is preferably 3 or less, more preferably 2 or less, from the viewpoint of suppressing deposition of other components to enhance the stability of the etching agent when the cupric ion concentration rises.
  • the concentration of the inorganic acid of the microetching agent is preferably adjusted so that the pH may fall within the aforementioned range.
  • a halide ion source generates a halide ion in the aqueous solution.
  • the halide ion has a function of aiding dissolution of copper to form a copper layer surface excellent in adhesion.
  • Examples of the halide ion source may be ion sources of a chloride ion, a bromide ion and the like. Chloride ion is particularly preferred for uniformly forming a copper layer surface excellent in adhesion. Two or more kind of halide ion may be included in the microetching agent.
  • halide ion source examples include hydrohalic acids such as hydrochloric acid and hydrobromic acid; and metal salts such as sodium chloride, calcium chloride, potassium chloride, ammonium chloride, potassium bromide, sodium bromide, copper chloride, copper bromide, zinc chloride, iron chloride and tin bromide.
  • the halide ion sources may be used in combination of two or more thereof.
  • the hydrohalic acid has functions of both the halide ion source and the acid
  • copper halide has functions of both the halide ion source and the cupric ion source.
  • the concentration of the halide ion in the microetching agent ie., the concentration of the halide ion that is ionized in the etching agent, is preferably 0.01 mol/L or more, more preferably 0.05 mol/L or more, and further preferably 0.1 mol/L or more.
  • the upper limit of the halide ion concentration is not particularly limited, the halide ion concentration is preferably 4 mol/L or less, more preferably 2 mol/L or less, from the viewpoint of solubility.
  • the molar concentration of the cupric ion source is preferably 0.2 times or more, more preferably 0.3 times or more, and further preferably 0.5 times or more, as large as the molar concentration of the halide ion source.
  • concentration ratio of the cupric ion and the halogen By adjusting the concentration ratio of the cupric ion and the halogen, a uniform roughened shape excellent in adhesion to resin or the like can be formed on each of the electrolytic copper and the rolled copper.
  • the molar concentration of the cupric ion source is preferably 10 times or less, more preferably 7 times or less, and further preferably 5 times or less, as large as the molar concentration of the halide ion source, from the viewpoint of obtaining compatibility between formation of the uniform roughened shape and solubility.
  • a sulfate ion source generates a sulfate ion (SO 4 2 ⁇ ) and/or a hydrogensulfate ion (HSO 4 ⁇ ) in the aqueous solution.
  • the sulfate ion source include sulfates such as potassium sulfate, sodium sulfate, calcium sulfate, magnesium sulfate, cupric sulfate, ferric sulfate, and ammonium sulfate, sulfuric acid, and sodium hydrogensulfate.
  • cupric sulfate has functions of both the sulfate ion source and the cupric ion source
  • sulfuric acid has functions of both the sulfate ion source and the acid.
  • the sulfate ion or hydrogensulfate ion in the microetching agent in addition to the cupric ion, halide ion, and polymer, irregularities having a fine shape suitable for adhesion to resin or the like can be formed on the surface of copper. Further, by presence of the sulfate ion and hydrogensulfate ion, the pH of the liquid can be kept low to enhance the stability of the aqueous solution.
  • the concentration of the sulfate ion source ie., a sum of the sulfate ion concentration and the hydrogensulfate ion concentration in the microetching agent, is preferably 0.02 mol/L or more.
  • the concentration of the sulfate ion source is more preferably 0.05 to 5 mol/L, and further preferably 0.1 to 3 mol/L.
  • the microetching agent of the present invention contains a water-soluble polymer having a weight-average molecular weight of 1000 or more and having an amino group or a quaternary ammonium group in a side chain. Together with the halide ion, the polymer has a function of forming a roughened shape having an excellent adhesion property. Fine irregularities can be formed uniformly on the surface of rolled copper by coexistence of the halide ion with the polymer having an amino group or a quaternary ammonium group in a side chain in the microetching agent.
  • the weight-average molecular weight of the polymer is preferable 2000 or more, more preferably 5000 or more, from the viewpoint of forming the uniform roughened shape.
  • the weight-average molecular weight of the polymer is preferably 5000000 or less, more preferably 2000000 or less, from the viewpoint of water solubility.
  • the weight-average molecular weight is a value obtained in terms of polyethylene glycol by gel permeation chromatography (GPC) analysis.
  • the polymer having a quaternary ammonium group in a side chain may be, for example, a polymer having a repeating unit represented by the following formula (I).
  • polymer having a repeating unit represented by the formula (I) examples include a quaternary ammonium salt-type styrene polymer and a quaternary ammonium salt-type aminoalkyl (meth)acrylate polymer.
  • the polymer having a quaternary ammonium group in a side chain may be one having a repeating unit in which the carbon atoms in the main chain and the quaternary ammonium group in the side chain form a cyclic structure, as represented by the following formula (II).
  • each of R 5 and R 6 is a chain or cyclic hydrocarbon group optionally having a substituent, where R 5 and R 6 may be bonded with each other to form a cyclic structure.
  • the numeral m is an integer of 0 to 2.
  • X 2 and X 3 are each independently a single bond or a divalent linking group.
  • Specific examples of the polymer having a repeating unit represented by the formula (II) include a quaternary ammonium salt-type diallylamine polymer obtained by polymerization of a diallyldialkylammonium salt represented by the formula (IIa).
  • R 7 and R 8 are each independently a hydrogen atom or a chain or cyclic hydrocarbon group optionally having a substituent, and are preferably a hydrogen atom.
  • the quaternary ammonium group in the side chain may have a double bond between the nitrogen atom and the carbon atom, and may contain the nitrogen atom of the quaternary ammonium group as a constituent atom of the ring. Further, two polymer chains may be cross-linked by the quaternary ammonium group as in the repeating unit represented by the following formula (III).
  • X 4 to X 7 are each independently a single bond or a divalent linking group.
  • Examples of the counter anion Z ⁇ of the quaternary ammonium salt include Cl ⁇ , Br ⁇ , I ⁇ , ClO 4 ⁇ , BF 4 ⁇ , CH 3 COO ⁇ , PF 6 ⁇ , HSO 4 ⁇ , and C 2 H 5 SO 4 ⁇ .
  • X 1 to X 7 are a divalent linking group
  • specific examples thereof include methylene group, alkylene group having a carbon number of 2 to 10, arylene group, —CONH—R— group, and —COO—R— group (where R is a single bond, methylene group, alkylene group having a carbon number of 2 to 10, or an ether group (alkyloxyalkyl group) having a carbon number of 2 to 10).
  • the polymer having an amino group in a side chain may be, for example, a polymer having a repeating unit represented by the following formula (IV).
  • R 11 and R 12 are each independently a hydrogen atom or a chain or cyclic hydrocarbon group optionally having a substituent, where R 11 and R 12 may be bonded with each other to form a cyclic structure.
  • R 13 is a hydrogen atom or methyl group
  • X 11 is a single bond or a divalent linking group.
  • the amino group may be any of primary, secondary, and tertiary amino groups, and may form an ammonium salt.
  • the counter anion of the ammonium salt may be, for example, one that has been described above as the counter anion Z ⁇ of the quaternary ammonium salt.
  • R 14 is a hydrogen atom or a chain or cyclic hydrocarbon group optionally having a substituent.
  • the numeral m is an integer of 0 to 2.
  • X 12 and X 13 are each independently a single bond or a divalent linking group.
  • Specific examples of the polymer having a repeating unit represented by the formula (V) include a diallylamine polymer obtained by polymerization of diallylamine or a diallylamine salt.
  • the polymer having an amino group or a quaternary ammonium group in a side chain may be a copolymer.
  • the copolymer may include a repeating unit that contains an amino group or a quaternary ammonium group and a repeating unit that contains neither an amino group nor a quaternary ammonium group. Sequence of the repeating units in the copolymer is not particularly limited.
  • the copolymer may be any of an alternating copolymer, a block copolymer, and a random copolymer.
  • the ratio of the repeating units containing an amino group or a quaternary ammonium group relative to the monomer units of the whole polymer is preferably 20 mol % or more, more preferably 30 mol % or more, and further preferably 40 mol % or more.
  • the repeating unit contained in the copolymer may have neither an amino group nor a quaternary ammonium group.
  • Example of the repeating unit include structures derived from (meth)acrylic acid, alkyl (meth)acrylate, aminoalkyl (meth)acrylate, styrene derivatives, sulfur dioxide, and the like.
  • the polymer having a structure derived from a quaternary ammonium salt-type diallylamine represented by the above general formula (II) and the polymer having a structure derived from diallylamine represented by the above general formula (IV) preferably has a structure unit derived from sulfur dioxide represented by the following formula as a repeating unit of the copolymer.
  • the polymer may have both of an amino group and a quaternary ammonium group in a side chain.
  • the polymers may be used in combination of two or more thereof, where a polymer having an amino group in a side chain and a polymer having a quaternary ammonium group in a side chain may be used in combination.
  • the microetching agent of the present invention can be easily prepared by dissolving the aforementioned components in ion-exchanged water or the like.
  • the microetching agent may contain components other than those described above.
  • a nonionic surfactant as an antifoaming agent may be added and a complexing agent such as pyridine may be added for improving dissolving stability of copper.
  • various additives may be added as required. When these additives are added, the concentration of the additives in the microetching agent is about 0.0001 to 20% by weight.
  • the microetching agent free from hydrogen peroxide has advantages such that the concentration control of the solution and the effluent disposal are simplified. For this reason, the concentration of hydrogen peroxide in the microetching agent is most preferably zero. On the other hand, a trace amount of hydrogen peroxide that may be contained in the raw material etc. is permissible.
  • the concentration of hydrogen peroxide in the microetching agent is preferably 0.1% by weight or less, more preferably 0.01% by weight or less.
  • the microetching agent of the present invention can be widely used for roughening a copper layer surface, and so on. Irregularities are formed uniformly on the treated copper surface, leading to satisfactory adhesion to resins of a prepreg, a plating resist, an etching resist, a solder resist, an electrodeposition resist, a coverlay and the like.
  • the microetching agent also provides a surface excellent in solderability, and is therefore particularly useful for production of various wiring boards including those for pin grid array (PGA) and those for ball grid array (BGA). It is also useful for surface treatment of a lead frame.
  • microetching agent of the present invention difference in the roughened shape caused by difference in the crystallinity of copper is small, so that a roughened shape excellent in adhesion to resin or the like can be formed both on the electrolytic copper and on the rolled copper. For this reason, even when a copper foil serving as an object of treatment is different, there is no need to change the etching agent, and the same etching agent can be repetitively used.
  • the aforementioned microetching agent is brought into contact with the surface of a copper layer to roughen the surface thereof.
  • one layer among the plurality of copper layers may be treated with the aforementioned microetching agent, or alternatively, two or more of the copper layers may be treated with the aforementioned microetching agent.
  • a conventional microetching agent is used mainly for surface roughening of electrolytic copper foil
  • the aforementioned microetching agent can form a roughened shape uniformly on the surface of each of electrolytic copper and rolled copper.
  • the microetching agent of the present invention can be suitably used also for roughening of the copper layer in which the surface to be treated (surface that is brought into contact with the microetching agent) is made of rolled copper.
  • the method for bringing the microetching agent into contact with the surface of the copper layer is not particularly limited, and examples thereof include a method in which a microetching agent is sprayed to the surface of a copper layer to be treated and a method in which a copper layer to be treated is dipped in a microetching agent.
  • a microetching agent temperature 10 to 40° C.
  • a spray pressure 0.03 to 0.3 MPa for 5 to 120 seconds.
  • the copper layer is dipped, it is preferred to perform etching at a microetching agent temperature of 10 to 40° C. for 5 to 120 seconds.
  • the copper layer is dipped in a microetching agent, it is preferred to blow air into the microetching agent by bubbling or the like so that a cuprous ion generated in the microetching agent by etching of copper is oxidized to a cupric ion.
  • the microetching agent is substantially free from hydrogen peroxide, an effluent disposal of the microetching agent after use is easy, and the disposal treatment can be performed by a general simple method using, for example, a neutralizer, a polymer coagulant or the like.
  • the etching amount in the roughening treatment is not particularly limited. From the viewpoint of forming the irregularities uniformly on copper surface irrespective of the crystallinity of copper, the etching amount is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more. When the etching amount is excessively large, an inconvenience such as electrical disconnection caused by complete etching of the copper layer or increase in the electrical resistance caused by decrease in the wiring cross-sectional area may be generated. For this reason, the etching amount is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less.
  • the “etching amount” refers to an average etching amount (dissolved amount) in the depth direction, and is calculated from a weight and a specific gravity of copper dissolved by a microetching agent, and a front projection area of the copper surface.
  • an acidic aqueous solution for removing generated smut after the roughening treatment.
  • an acidic aqueous solution to be used for washing hydrochloric acid, an aqueous sulfuric solution, a nitric acid aqueous solution and the like can be used.
  • Hydrochloric acid is preferred because it has less influence on a roughened shape and has high smut removing performance.
  • the acid concentration of the acidic aqueous solution is preferably 0.3 to 35% by weight, more preferably 1 to 10% by weight.
  • the washing method is not particularly limited, and examples thereof include a method in which an acidic aqueous solution is sprayed to a roughened copper layer surface and a method in which a roughened copper layer is dipped in an acidic aqueous solution.
  • the acidic aqueous solution it is preferred to perform washing at an acidic aqueous solution temperature of 15 to 35° C. and a spray pressure of 0.03 to 0.3 MPa for 3 to 30 seconds.
  • the copper layer is dipped, it is preferred to perform washing at an acidic aqueous solution temperature of 15 to 35° C. for 3 to 30 seconds.
  • the concentrations of the components in the microetching agent during the treatment can be properly maintained by performing the roughening treatment while adding the replenishing liquid into the microetching agent.
  • the replenishing liquid is an aqueous solution containing an inorganic acid, a cupric ion source, a halide ion source, a sulfate ion source, and the aforementioned polymer.
  • the adding amount of the replenishing liquid and the timing of adding the replenishing liquid can be appropriately set according to the concentration control range of each component or the like.
  • the components in the replenishing liquid are similar to the components contained in the microetching agent described above.
  • the concentrations of the components in the replenishing liquid are appropriately adjusted according to the initial concentration of the microetching agent to be used for treatment, or the like.
  • a treatment with an aqueous solution of azoles or an alcohol solution may be performed in order to further improve adhesion to a resin.
  • an oxidation treatment called a brown oxide treatment or a black oxide treatment may be performed.
  • a substrate having a rolled copper foil (HA foil manufactured by JX Nippon Mining & Metals Corporation) was used as a test board.
  • the microetching agent (25° C.) shown in Table 1 was sprayed onto the copper foil of the above test board under the conditions with a spray pressure of 0.1 MPa, and etching was performed with the etching time adjusted such that an etching amount of the copper is set to 0.5 ⁇ m. Then, the test board was washed with water, and the etched surface was dipped in hydrochloric acid at a temperature of 25° C. (hydrogen chloride concentration: 3.5% by weight) for 15 seconds, and then washed with water and dried.
  • test board was prepared by forming 18 ⁇ m-thick copper plating on a glass fiber fabric epoxy resin-impregnated copper-clad laminate in which an electrolytic copper foil having a thickness of 35 ⁇ m had been laminated on both surfaces of an insulating substrate (manufactured by Hitachi Chemical Company, Ltd., trade name: MCL-E-67, 10 cm ⁇ 10 cm, thickness of 0.2 mm).
  • etching, acid pickling, washing with water, and drying were performed in the same manner as described above with use of the etching agents of Examples 1, 2, 11 and Comparative Examples 3, 4.
  • Polymer A alternating copolymer of diallyldialkylammonium (quaternary ammonium) and hydrochloride.sulfur dioxide having a repeating unit shown below and having a weight-average molecular weight of about 5000.
  • Polymer B alternating copolymer of diallylamine (secondary amine) hydrochloride and sulfur dioxide having a repeating unit shown below and having a weight-average molecular weight of about 5000.
  • Polymer C alternating copolymer of diallylamine (secondary amine) acetate and sulfur dioxide having a repeating unit shown below and having a weight-average molecular weight of about 5000
  • Polymer D random copolymer of vinylpyrrolidone and N,N-dimethyl aminoethylmethacrylamide diethylsulfate having a structure shown below and weight-average molecular weight of about 800000.
  • Polymer E dicyandiamide.formaldehyde condensation polymer having a structure shown below
  • FIG. 8 Cupric sulfate pentahydrate 138 Polymer B 0.120 Example 8 35% Hydrochloric acid 63 0.55 0.60 0.55 5 FIG. 9 Cupric sulfate pentahydrate 138 Polymer C 0.100 Example 9 35% Hydrochloric acid 63 0.55 0.60 0.55 5 FIG. 10 Cupric sulfate pentahydrate 138 Polymer D 0.040 Example 10 35% Hydrochloric acid 63 0.55 0.60 0.55 4 FIG. 11 Cupric sulfate pentahydrate 138 Polymer E 0.010 Example 11 62.5% Sulfuric acid 50 0.55 0.42 0.66 5 FIG. 12A FIG.
  • FIG. 12B Cupric sulfate pentahydrate 85 Cupric chloride dihydrate 36 Polymer A 0.048 Comparative 35% Hydrochloric acid 63 0.55 0.60 0.55 2 FIG. 13A FIG. 13B Example 1 Cupric sulfate pentahydrate 138 Comparative Acetic acid 60 0.23 1.32 0.00 2 FIG. 14A FIG. 14B Example 2 Cupric chloride dihydrate 40 Ammonium acetate 80 Sodium chloride 50 Polymer D 0.003 Comparative 62.5% Sulfuric acid 188 0.54 0.00 1.74 2 FIG. 15A FIG.
  • Example 3 35% Hydrogen peroxide 15 Cupric sulfate pentahydrate 134 NaOH 0.65 5-nitrobenzotriazole 0.40 Cresolsulfonic acid 0.57 Comparative 62.5% Sulfuric acid 188 0.54 0.00 1.74 1
  • Example 4 35% Hydrogen peroxide 15 Cupric sulfate pentahydrate 134 Polymer A 0.048 Comparative 62.5% Sulfuric acid 47 0.55 0.00 0.55 1
  • Example 5 Cupric sulfate pentahydrate 63 Copper oxide 24 Polymer A 0.048
  • Comparative Example 2 in which an organic acid-based microetching agent was used, a roughened shape was formed uniformly on the surface of electrolytic copper ( FIG. 14B ); however, the surface of rolled copper was not roughened ( FIG. 14A ).
  • Comparative Example 3 in which a sulfuric acid-hydrogen peroxide-based microetching agent was used, a roughened shape was formed uniformly on the surface of electrolytic copper ( FIG. 15B ); however, the surface of rolled copper was not roughened ( FIG. 15A ).
  • Example 1 in which a microetching agent containing hydrochloric acid, copper sulfate, and a polymer was used, a roughened shape excellent in adhesion to resin was formed uniformly on the surface of each of rolled copper ( FIG. 2A ) and electrolytic copper ( FIG. 2B ).
  • Example 2 in Example 2 as well, a roughened shape excellent in adhesion to resin was formed uniformly on the surfaces of both of rolled copper ( FIG. 3A ) and electrolytic copper ( FIG. 3B ).
  • Examples 3 to 6 in which the blending amount of hydrochloric acid, copper sulfate, and the polymer was changed, a roughened shaped was formed uniformly on the surface of rolled copper.
  • Example 11 in which a microetching agent containing sulfuric acid, copper sulfate, copper chloride, and a polymer was used, a roughened shape was formed uniformly on the surfaces of both of rolled copper ( FIG. 12A ) and electrolytic copper ( FIG. 12B ) in the same manner as in Examples 1, 2.
  • Polymer F poly(oxyethyleneoxypropylene(5E.O., 5P.O.))glycol monoether (number-average molecular weight of about 510)
  • Polymer G polyethyleneimine (weight-average molecular weight of about 70000)
  • Polymer H polyethyleneimine (weight-average molecular weight of about 300)
  • Polymer I polyoxyethylene-polyoxypropylene block polymer adduct of ethylenediamine represented by the following formula
  • Example 9 Cupric sulfate pentahydrate 138 Polymer G 0.200 Comparative 35% Hydrochloric acid 63 2 FIG. 22A FIG. 22B
  • Example 10 Cupric sulfate pentahydrate 138 Polymer H 0.010 Comparative 35% Hydrochloric acid 63 1 FIG. 23A FIG. 23B
  • Example 11 Cupric sulfate pentahydrate 138 Polymer H 0.050 Comparative 35% Hydrochloric acid 63 2 FIG. 24A FIG. 24B
  • Example 12 Cupric sulfate pentahydrate 138 Polymer I 0.010 Comparative 62.5% Sulfuric acid 47 1 FIG. 25A FIG. 25B
  • Example 13 Cupric sulfate pentahydrate 63 Polymer I 0.500
  • an aqueous solution containing an inorganic acid, a cupric ion, a halide ion, a sulfate ion, and a polymer having a quaternary ammonium group or an amino group in a side chain can specifically form fine irregularities uniformly on the surface of rolled copper as well as electrolytic copper.

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KR102598530B1 (ko) * 2018-01-05 2023-11-06 가부시키가이샤 아데카 조성물 및 에칭 방법
CN109679775B (zh) * 2019-02-21 2021-03-23 深圳市天熙科技开发有限公司 用于线路板孔金属化工艺的酸性整孔剂、及线路板的制备方法
KR102404620B1 (ko) 2020-06-02 2022-06-15 멕크 가부시키가이샤 마이크로 에칭제 및 배선 기판의 제조 방법
JP6799347B1 (ja) * 2020-06-02 2020-12-16 メック株式会社 マイクロエッチング剤および配線基板の製造方法
CN115989314A (zh) * 2020-08-24 2023-04-18 富士胶片株式会社 处理液、基板的处理方法
JP2023075794A (ja) * 2021-11-19 2023-05-31 株式会社Ｓｃｒｅｅｎホールディングス 基板処理方法
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