WO2015137013A1 - Composition de formation de film de cuivre et procédé de fabrication de film de cuivre l'utilisant - Google Patents

Composition de formation de film de cuivre et procédé de fabrication de film de cuivre l'utilisant Download PDF

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Publication number
WO2015137013A1
WO2015137013A1 PCT/JP2015/053068 JP2015053068W WO2015137013A1 WO 2015137013 A1 WO2015137013 A1 WO 2015137013A1 JP 2015053068 W JP2015053068 W JP 2015053068W WO 2015137013 A1 WO2015137013 A1 WO 2015137013A1
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group
copper
copper film
composition
mol
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English (en)
Japanese (ja)
Inventor
阿部　徹司
和也 斎藤
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Adeka Corp
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Adeka Corp
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Priority to KR1020167023849A priority Critical patent/KR101779734B1/ko
Priority to CN201580007860.0A priority patent/CN105980599B/zh
Publication of WO2015137013A1 publication Critical patent/WO2015137013A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • 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
    • C23C18/08—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 metallic material
    • 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
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
    • 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
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/145—Radiation by charged particles, e.g. electron beams or ion irradiation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates to a copper film forming composition for forming a copper film on various substrates and a method for producing a copper film using the composition.
  • Patent Documents 1 to 4 a liquid mixture containing copper hydroxide or organic acid copper and a polyhydric alcohol as essential components is applied to various substrates and heated to a temperature of 165 ° C. or higher in a non-oxidizing atmosphere.
  • a series of characteristic methods for producing copper film-formed articles have been proposed.
  • copper formate is disclosed as an organic acid copper used in the liquid process
  • diethanolamine and triethanolamine are disclosed as polyhydric alcohols.
  • Patent Document 5 proposes a metal paste containing silver fine particles and an organic compound of copper, which can form a metal film having excellent solder heat resistance on a base electrode.
  • Copper formate is disclosed as an organic compound of copper used in the paste
  • diethanolamine is disclosed as an amino compound that is reacted with the paste to form a paste.
  • Patent Document 6 proposes a metal salt mixture for forming a metal pattern used in a circuit.
  • copper formate is disclosed as a metal salt
  • organic solvents such as diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and morpholine are disclosed as organic components.
  • Pyridine is disclosed as a ligand.
  • Patent Document 7 discloses a low temperature decomposable copper precursor containing copper formate that can be thermally decomposed at a low temperature after printing and a 3-dialkylaminopropane-1,2-diol compound, which is useful for the formation of wiring for electronics and the like. A composition is disclosed.
  • Patent Document 8 discloses a composition for forming a copper thin film containing copper formate and alkanolamine useful for the liquid process described above.
  • alkanolamines include monoethanolamine, diethanolamine, and triethanolamine.
  • Patent Document 9 discloses a method for producing a metal film by using a liquid composition containing an organometallic compound and irradiating the liquid composition with light using a flash lamp.
  • compositions for forming a copper film In order to produce a fine wiring or film at a low cost in a liquid process using a composition for forming a copper film, it is desirable to provide a composition that satisfies the following requirements. That is, it is a solution type that does not contain a solid phase such as fine particles, gives a copper film excellent in conductivity, can be converted to a copper film at low temperature and low energy, has good coating properties, and has storage stability. It is desired that the film thickness is good, that the film thickness obtained by one application can be easily controlled, and that the obtained film and the substrate have high adhesion.
  • a copper film manufacturing method by a flash lamp method using a xenon lamp is known.
  • PET polyethylene terephthalate
  • the conventional copper film forming composition is necessary for conversion to a copper film.
  • energy was high and the organic resin substrate was deteriorated. Therefore, there has been a strong demand for a composition for forming a copper film that can be converted into a copper film with low energy that does not deteriorate the organic resin substrate, and that can obtain a copper film having high adhesion to the substrate.
  • a composition for forming a copper film that sufficiently satisfies these requirements is not yet known.
  • an object of the present invention is to apply a copper film having sufficient conductivity and high adhesion to the substrate at low temperature and low energy by coating on the substrate and processing by a flash lamp method using a xenon lamp.
  • An object of the present invention is to provide a solution-like composition for forming a copper film that does not contain a solid phase such as fine particles.
  • the present inventors contain copper formate or a hydrate thereof, a diol compound having a specific structure, and a dye compound having a specific structure in a specific ratio.
  • the present inventors have found that a composition for forming a copper film satisfies the required performance, and have reached the present invention.
  • the present invention includes copper formate or a hydrate thereof 0.01 to 3.0 mol / kg, copper acetate or a hydrate thereof 0 to 3.0 mol / kg, represented by the following general formula (1). And at least one diol compound selected from the group consisting of a compound represented by the following general formula (1 ′), a compound represented by the following general formula (AI), a general formula (A -II), 0.001 to 20% by mass of at least one dye compound selected from the group consisting of a compound represented by thymol blue and quercetin, and an organic solvent that dissolves these components, When the total content of the copper formate or its hydrate and the content of the copper acetate or its hydrate is 1 mol / kg, the diol compound is added in an amount of 0.1 to 6.0 mol / kg. Provided is a composition for forming a copper film, contained in the range of kg.
  • X represents a hydrogen atom, a methyl group, an ethyl group, or a 3-aminopropyl group.
  • R 1 and R 2 are each independently Represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R 1 and R 2 may be bonded to each other to form a 5-membered ring or a 6-membered ring with an adjacent nitrogen atom)
  • Ar 1 and Ar 2 are each independently substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxy group, a halogen atom, a cyano group, or a vinyl group.
  • Ar 2 is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7.
  • R a and Ar 2 are bonded to each other to form a ring structure.
  • a plurality of R a may be different from each other, and in the general formula (A-II), Ar 3 to Ar 5 are each independently C 1-4 alkyl group, alkoxy group, carbo Shi group, a halogen atom, a cyano group, or a benzene ring or a naphthalene ring optionally substituted with a vinyl group
  • R b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group
  • q is When Ar 5 is a substituted or unsubstituted benzene ring, it represents an integer of 1 to 5, and when Ar 5 is a substituted or unsubstituted naphthalene ring, it represents an integer of 1 to 7.
  • R b and Ar 5 may be bonded to each other to form a ring structure, and when q is an
  • the present invention also provides a coating process for coating the copper film-forming composition on a substrate, and an irradiation film-forming process in which at least a part of the coated copper film-forming composition is irradiated with light using a xenon lamp. And a method for producing a copper film.
  • a copper film having sufficient conductivity and high adhesion to the substrate can be obtained at low temperature and with low energy by being coated on the substrate and processed by a flash lamp method using a xenon lamp.
  • a solution-like composition for forming a copper film that does not contain a solid phase such as fine particles is provided.
  • copper formate is used as a precursor (precursor) of the copper film.
  • the copper formate used in the composition for forming a copper film of the present invention may be a hydrate or a hydrate.
  • anhydrous copper formate (II), copper formate (II) dihydrate, copper formate (II) tetrahydrate and the like can be used.
  • copper formates may be mixed as they are, or may be mixed as an aqueous solution, an organic solvent solution, or an organic solvent suspension.
  • the content of copper formate in the composition for forming a copper film of the present invention is 0.01 to 3.0 mol / kg, preferably 1.0 to 2.5 mol / kg. If the content of copper formate is less than 0.01 mol / kg, a thin film may not be obtained. On the other hand, when the content of copper formate exceeds 3.0 mol / kg, the stability of the solution decreases.
  • “mol (mol) / kg” in the present invention represents “amount (mol) of solute dissolved in 1 kg of solution”.
  • the copper film forming composition of the present invention may contain copper acetate as a copper concentration control agent together with copper formate.
  • Copper acetate may be a hydrate or a hydrate.
  • anhydrous copper acetate (II), copper acetate (II) monohydrate and the like can be used.
  • these copper acetates may be mixed as they are, as in copper formate, or may be mixed as an aqueous solution, an organic solvent solution, or an organic solvent suspension.
  • the molecular weight of copper acetate (II) monohydrate is 199.65
  • 199.65 g of copper (II) acetate monohydrate is contained in 1 kg of the composition for forming a copper film of the present invention. In this case, the amount is 1.0 mol / kg.
  • the content of copper acetate in the composition for forming a copper film of the present invention is preferably 0 to 3.0 mol / kg, more preferably 0.01 to 2.5 mol / kg.
  • the concentration ratio of copper formate and copper acetate in the composition for forming a copper film of the present invention is not particularly limited, but 40% by mass or more of all copper in the composition for forming a copper film is due to the addition of copper formate. It is preferable that Moreover, it is especially preferable that the ratio of the concentration (mol / kg) of copper formate and copper acetate is about 1: 1 because a film having excellent electrical characteristics can be obtained.
  • a composition for forming a copper film having a low viscosity can be obtained as compared with a case where a composition for forming a copper film having the same copper concentration is prepared with only copper formate.
  • the coating property may be lowered if the viscosity is high. For this reason, by using copper acetate together with copper formate, the viscosity can be kept low even when the copper concentration is high, and the coatability can be maintained.
  • the copper concentration in the composition for forming a copper film greatly affects the thickness of the copper film formed by the coating method.
  • the composition for forming a copper film of the present invention is excellent in stability and coating property even if the copper concentration is high, and the film thickness of the obtained copper film can be easily controlled. it can.
  • a copper film which is a smooth conductive film having an appropriate film thickness within a wide range of several tens to 1,000 nm is formed by one coating. You can also.
  • the diol compound that is a component constituting the composition for forming a copper film of the present invention is selected from the group consisting of a compound represented by the following general formula (1) and a compound represented by the following general formula (1 ′). It is at least one, and has one or more amino groups in the molecule.
  • a diol compound exhibits an effect as a solubilizer for copper formate or copper formate hydrate.
  • membrane is shown.
  • X represents a hydrogen atom, a methyl group, an ethyl group, or a 3-aminopropyl group.
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 1 and R 2 may be bonded to each other to form a 5-membered ring or a 6-membered ring with the adjacent nitrogen atom.
  • alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group, a 2-propyl group, a butyl group, a 2-butyl group, an isobutyl group, and a tertiary butyl group.
  • Specific examples of the 5-membered or 6-membered ring formed by R 1 and R 2 being bonded together with the adjacent nitrogen atom include pyrrole, pyrrolidine, methylpyrrolidine, pyridine, 2-methylpyridine, 3-methylpyridine, Examples include 4-methylpyridine, 2,4-lutidine, 2,6-lutidine, piperidine, 2-methylpiperidine, 3-methylpiperidine, and 4-methylpiperidine.
  • Examples of the diol compound represented by the general formula (1) include the following compound No. 1-No. 4 can be mentioned.
  • diol compound represented by the general formula (1 ') for example, the following compound No. 5-No. 13 can be mentioned.
  • diethanolamine (Compound No. 1), N-methyldiethanolamine (Compound No. 2), N-ethyldiethanolamine (Compound No. 3), N-aminopropyl diethanolamine (Compound No. 4).
  • 3-dimethylamino-1,2-propanediol (Compound No. 8) are preferable because they give particularly good storage stability to the copper film-forming composition.
  • the resulting copper film has a conductive property. It is particularly preferable because of good properties.
  • the content of the diol compound in the composition for forming a copper film of the present invention is 1 mol / kg in total of the content of copper formate or its hydrate and the content of copper acetate or its hydrate.
  • the range is 0.1 to 6.0 mol / kg.
  • the amount is less than 0.1 mol / kg, the conductivity of the obtained copper film becomes insufficient.
  • it exceeds 6.0 mol / kg the coatability deteriorates and a uniform copper film cannot be obtained.
  • a more preferable range is 0.2 to 5.0 mol / kg.
  • the said diol compound may be used independently and may be used in mixture of 2 or more types.
  • the dye compound that is a component constituting the composition for forming a copper film of the present invention includes a compound represented by the following general formula (AI), a compound represented by the following general formula (A-II), thymol blue, And at least one selected from the group consisting of quercetin.
  • AI general formula
  • A-II general formula
  • thymol blue thymol blue
  • quercetin quercetin
  • Ar 1 and Ar 2 are each independently substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxy group, a halogen atom, a cyano group, or a vinyl group.
  • An benzene ring or a naphthalene ring which may be represented R a represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group, and p represents a case where Ar 2 is a substituted or unsubstituted benzene ring.
  • R a and Ar 2 may be bonded to each other to form a ring structure, and when p is an integer of 2 to 7, a plurality of R a may be different from each other.
  • Ar 3 to Ar 5 are each independently substituted with an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a carboxy group, a halogen atom, a cyano group, or a vinyl group.
  • R b represents a hydroxy group, an amino group, an alkylamino group, or a dialkylamino group
  • q represents a case where Ar 5 is a substituted or unsubstituted benzene ring.
  • R b and Ar 5 may be bonded to each other to form a ring structure, and when q is an integer of 2 to 7, a plurality of R b may be different from each other.
  • Examples of the dye compound represented by the general formula (AI) include the following compound No. 14-No. 17 can be mentioned.
  • examples of the dye compound represented by the general formula (A-II) include the following compound No. 18-No. 20 can be mentioned.
  • the content of the dye compound in the composition for forming a copper film of the present invention is 0.001 to 20% by mass, preferably 0.005 to 15% by mass, and 0.01 to 5% by mass. More preferably it is.
  • the amount is less than 0.001% by mass, the effect of blending the coloring compound is not recognized. On the other hand, when it exceeds 20 mass%, the effect by having mix
  • the said pigment compound may be used independently and may mix and use 2 or more types.
  • the organic solvent which comprises the composition for copper film formation of this invention can dissolve said copper formate (or its hydrate), a diol compound, a pigment
  • the organic solvent may be a single composition or a mixture.
  • Specific examples of the organic solvent used in the composition for forming a copper film of the present invention include alcohol solvents, diol solvents (excluding compounds represented by general formulas (1) and (1 ′)), Examples thereof include ketone solvents, ester solvents, ether solvents, aliphatic or alicyclic hydrocarbon solvents, aromatic hydrocarbon solvents, hydrocarbon solvents having a cyano group, and other solvents.
  • alcohol solvents examples include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, and third pen.
  • diol solvent examples include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol (3 -Methyl-1,3-butanediol), 1,2-hexanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, octanediol (2-ethyl- 1,3-hexanediol), 2-butyl-2-ethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, Examples include 1,4-cyclohexan
  • ketone solvent examples include acetone, ethyl methyl ketone, methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and methylcyclohexanone.
  • ester solvent examples include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, triamyl acetate, Phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, butyl propionate, tert-butyl propionate, amyl propionate, isoamyl propionate, 3 amyl propionate, propionate Acid phenyl, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhex
  • ether solvent examples include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, dioxane and the like.
  • Examples of the aliphatic or alicyclic hydrocarbon solvent include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decalin, and solvent naphtha.
  • aromatic hydrocarbon solvent examples include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, cymene, tetralin and the like.
  • hydrocarbon solvent having a cyano group examples include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6- Examples include dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene, and the like.
  • organic solvents examples include N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide and the like.
  • alcohol-based solvents, diol-based solvents and ester-based solvents are inexpensive and exhibit sufficient solubility in solutes.
  • silicon substrates, metal substrates, ceramic substrates, glass It is preferable because it exhibits good coating properties as a coating solvent for various substrates such as a substrate and a resin substrate.
  • a solvent having a hydroxyl group in the structure such as an alcohol solvent and a diol solvent is particularly preferable because of its high solubility in a solute.
  • the organic solvent in the composition for copper film formation of this invention is not specifically limited, If it adjusts suitably according to the thickness of the copper film to form and the manufacturing method of a copper film Good.
  • the organic solvent is added in an amount of 0.01 to 100 parts by mass of copper formate (even in the case of copper formate hydrate, converted to copper formate, the same shall apply hereinafter). It is preferable to use 5,000 parts by mass. When the amount of the organic solvent is less than 0.01 parts by mass, there may be a problem that the resulting copper film is cracked or has poor applicability.
  • the copper film obtained becomes thin, so that the ratio of an organic solvent increases, it is preferable not to exceed 5,000 mass parts from the surface of productivity. More specifically, when a copper film is produced by a spin coating method, it is preferable to use 20 to 1,000 parts by mass of an organic solvent with respect to 100 parts by mass of copper formate. When the copper film is produced by the screen printing method, it is preferable to use 0.01 to 20 parts by mass of an organic solvent with respect to 100 parts by mass of copper formate.
  • the composition for forming a copper film of the present invention may contain a piperidine compound represented by the following general formula (2).
  • a piperidine compound represented by the following general formula (2) By containing this piperidine compound, the coating property of the composition for forming a copper film can be improved, the storage stability can be improved, and the conductivity of the resulting copper film can be improved.
  • piperidine compound represented by the general formula (2) for example, the following compound No. 21-No. 27.
  • 2-methylpiperidine (Compound No. 22) is particularly preferably used.
  • 2-methylpiperidine By using 2-methylpiperidine, it is possible to obtain a composition for forming a copper film exhibiting particularly good coating properties and storage stability.
  • Content of the said piperidine compound in the composition for copper film formation of this invention is 1 mol / kg in total with content of copper formate or its hydrate, and content of copper acetate or its hydrate.
  • the range is preferably from 0.1 to 6.0 mol / kg, and more preferably from 0.2 to 5.0 mol / kg. If it is less than 0.1 mol / kg, the coatability is lowered and a uniform copper film may not be obtained. On the other hand, if it exceeds 6.0 mol / kg, the resulting copper film may have insufficient conductivity.
  • a more preferable range is 0.2 to 5.0 mol / kg.
  • the total content of the diol compound and the piperidine compound is the sum of the content of copper formate or a hydrate thereof and the content of copper acetate or a hydrate thereof. Is preferably in the range of 0.5 to 2.0 mol / kg, more preferably in the range of 1.0 to 1.5 mol / kg.
  • paintability and storage stability of the composition for copper film formation, and the electroconductivity of the copper film obtained become favorable, and it is preferable. If it is less than 0.5 mol / kg, a precipitate may be generated. On the other hand, applicability
  • the concentration ratio of the diol compound and the piperidine compound in the composition for forming a copper film of the present invention is not particularly limited, but when the diol compound is 1 mol / kg, the piperidine compound is 0.5 to 1.5. It is preferably in the range of mol / kg.
  • the case where the piperidine compound is 1 mol / kg (substantially equivalent to the diol compound) is particularly preferred because the solution has good stability and a copper film having excellent electrical characteristics can be obtained.
  • the composition for forming a copper film of the present invention may contain any component other than the essential components within a range that does not impair the effects of the present invention.
  • additives such as dyes, pigments, developers, sensitizers, anti-gelling agents, stabilizers and the like for imparting stability to the coating liquid composition; antifoaming agents, thickeners, Examples include additives for improving the coating properties of coating liquid compositions such as thixotropic agents and leveling agents; and film forming aids such as combustion aids and crosslinking aids.
  • the content in the case of using these optional components is a proportion of the total composition for forming a copper film, and is preferably 50% by mass or less, and more preferably 20% by mass or less.
  • the dye examples include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (2-phenyl-3-indolyl) phthalide, 3 -(P-dimethylaminophenyl) -3- (1,2-dimethyl-3-indolyl) phthalide, 3,3-bis (9-ethyl-3-carbazolyl) -5-dimethylaminophthalide, 3,3- Bis (2-phenyl-3-indolyl) -5-dimethylaminophthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2-methylindol-3-yl) phthalide, 3,3-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) vinyl] -4,5,6,7-tetrachlorophthalide and other triarylme
  • the pigment examples include iron oxide pigments, titanium pigments, blue and green inorganic pigments, carbon pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments.
  • iron oxide pigments include iron black, red pepper, and zinc ferrite pigments.
  • the titanium pigment examples include titanium oxide, nickel antimony titanium yellow, and chromium antimony titanium yellow.
  • blue and green inorganic pigments include ultramarine blue, cobalt blue, chromium oxide, and spinel green.
  • azo pigment examples include azo lake pigments such as Lake Red C, Watching Red, Brilliant Carmine 6B; Hosta Palm Yellow H4G, Nova Palm Yellow H2G, Nova Palm Red HFT, PV Fast Yellow HG, PV Fast Yellow H3R, PV Bordeaux Benzimidazolone pigments such as HF3R, PV Carmine HF4C, PV Red HF2B, PV Fast Maroon HMF01, and PV Fast Brown HFR; Yellow 8GN, chromophthal yellow 6G, chromophthal yellow 3G, chromophthal yellow GR, chromophthal orange 4R, chromophthal orange GP, chromophthalska
  • Chromophthal Red G Chromophthal Red G
  • chromophthal red BRN chromophthal red BG, chromophthal red 2B
  • a condensed azo pigments such as Chromophthal Brown 5R.
  • phthalocyanine pigment examples include phthalocyanine blue and phthalocyanine green.
  • condensed polycyclic pigment examples include quinacridone pigments such as PV Fast Pink E, Shinkasha Red B and Shinkasha Red Y; isoindolinone pigments such as Irgazine Yellow 2GLT, Irgazine Yellow 3RLTN and Chromophthal Orange 2G Perylene pigments such as perylene red, perylene maroon and perylene scarlet; perinone pigments such as perinone orange; dioxazine pigments such as dioxazine violet; Quinophthalone pigments such as Paliotol Yellow L0960HG.
  • these pigments can be used individually by 1 type or in combination of 2 or more types.
  • the addition amount of the dye and the pigment is preferably 0.02 to 20% by mass, more preferably 0.1 to 15% by mass, based on the amount of copper in the copper film forming composition.
  • the method for producing a copper film of the present invention includes a coating step of applying the composition for forming a copper film of the present invention described above onto a substrate, and a xenon lamp on at least a part of the applied composition for forming a copper film. And an irradiation film forming step of irradiating with light. If necessary, it may further include a drying step of keeping the substrate at 50 to 200 ° C. and volatilizing a low boiling point component such as an organic solvent before the irradiation film forming step. Further, after the irradiation film forming step, an annealing step for improving the conductivity of the copper film by holding the substrate at 200 to 500 ° C. may be further included.
  • spin coating method dip method, spray coating method, mist coating method, flow coating method, curtain coating method, roll coating method, knife coating method, bar coating method, slit coating method, screen Examples thereof include a printing method, a gravure printing method, an offset printing method, an ink jet method, and a brush coating.
  • the irradiation conditions in the irradiation film forming step are not particularly limited.
  • irradiation conditions such as irradiation time of 0.1 to 100 milliseconds, voltage of 400 to 4,000 V, irradiation energy of 0.1 to 10 J / cm 2 are used. Can be mentioned.
  • a plurality of processes from the above coating process to an arbitrary process can be repeated.
  • all the processes from the coating process to the irradiation film forming process may be repeated a plurality of times, and the coating process and the drying process may be repeated a plurality of times.
  • the atmosphere of the drying step and the irradiation film forming step is usually any of air, a reducing gas, and an inert gas, and it is economical when it is in the air.
  • the atmosphere of the annealing process is usually either a reducing gas or an inert gas. It is preferable to anneal in a reducing gas atmosphere because a copper film with better conductivity can be obtained.
  • An example of the reducing gas is hydrogen.
  • helium, nitrogen, and argon can be mentioned as an inert gas.
  • the inert gas may be used as a diluent gas for the reducing gas.
  • plasma; discharge lamp such as laser; energy other than heat such as various radiations may be applied or irradiated.
  • Comparative compounds 1 to 3 were obtained by blending the compounds shown in Table 2 so as to obtain numerical values in parentheses (mol / kg), respectively. The remainder was ethanol. Moreover, the density
  • Comparative copper films 1-12 Comparative copper films 1-12 were each cast on a PET substrate (50 mm ⁇ 50 mm, thickness 0.1 mm). Each comparative composition was applied by spin coating under conditions of 500 rpm for 5 seconds and 2,000 rpm for 20 seconds. Subsequently, it dried in air
  • the xenon flash lamp apparatus trade name “SUS686”, manufactured by USHIO INC.
  • Preparation 2 of copper film forming composition > [Examples 21 to 24] As shown below, predetermined compounds were blended so as to have numerical values in parentheses (mol / kg, mass%) to obtain compositions 21 to 24 for forming copper films. The remainder is all ethanol. Further, the concentration (mol / kg) of each compound shown below is an amount in 1 kg of the produced composition.
  • Copper film forming composition 21 Copper formate tetrahydrate (1.0 mol / kg) Compound No. 2 (1.0 mol / kg) Compound No. 14 (5% by mass) Compound No. 22 (1.0 mol / kg)
  • Copper film forming composition 22 Copper formate tetrahydrate (1.0 mol / kg) Compound No. 2 (1.0 mol / kg) Thymol blue (5% by mass) Compound No. 22 (1.0 mol / kg)
  • Copper film forming composition 23 Copper formate tetrahydrate (1.0 mol / kg) Compound No. 2 (1.0 mol / kg) Quercetin (5% by mass) Compound No. 22 (1.0 mol / kg)
  • Copper film forming composition 24 Copper formate tetrahydrate (0.5 mol / kg) Copper acetate tetrahydrate (0.5 mol / kg) Compound No. 2 (1.0 mol / kg) Compound No. 14 (5% by mass) Compound No. 22 (1.0 mol / kg) Thymol blue (5% by mass) Compound No. 18 (5% by mass)
  • Comparative Compound 4 was obtained by blending predetermined compounds so as to have numerical values in parentheses (mol / kg and mass%). The remainder is all ethanol. Moreover, the concentration (mol / kg) of each compound shown below is the amount in 1 kg of the produced composition.
  • Each of the copper film forming compositions 21 to 24 was cast on a PET substrate (50 mm ⁇ 50 mm, thickness 0.1 mm). Each composition for forming a copper film was applied by spin coating under conditions of 500 rpm for 5 seconds and 2,000 rpm for 20 seconds. Subsequently, it dried in air
  • Comparative copper film 13 Comparative copper film 13 was cast on a PET substrate (50 mm ⁇ 50 mm, thickness 0.1 mm). Comparative composition 4 was applied by spin coating under conditions of 500 rpm for 5 seconds and 2,000 rpm for 20 seconds. Subsequently, it dried in air
  • the evaluation copper films 23 to 26 were all films having very good conductivity, but the comparative copper film 13 was a film having no conductivity. Further, considering the results shown in Table 4 together with the results shown in Table 3, the copper films for evaluation 23 to 26 have a lower surface resistance than the evaluation copper films 1 to 22 and are more excellent in conductivity. It turns out that it is a copper film.
  • the evaluation copper films 1 to 26 are all films having high adhesion.
  • the comparative copper film 1 is a film having low adhesion.

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Abstract

La présente invention concerne une composition de formation de film de cuivre qui est sous forme d'une solution qui est exempte de matières solides, telles que des particules fines, et qui, lorsqu'elle est appliquée sur un substrat et traitée par un procédé par lampe flash à l'aide d'une lampe au xénon, peut former, à basse température et à basse énergie, un film de cuivre qui présente une conductivité suffisante et une adhérence élevée au substrat. L'invention concerne une composition de formation de film de cuivre qui comprend du formiate de cuivre ou un hydrate correspondant, au moins un composé diol choisi dans le groupe constitué de composés représentés par la formule générale (1) et de composés représentés par la formule générale (1'), un composé colorant spécifique et un solvant organique qui peut dissoudre ces composants et dans laquelle le composé diol est contenu en une quantité de 0,1 à 6 moles/kg pour chaque mole/kg de la somme de la teneur en formiate de cuivre ou en un hydrate correspondant et de la teneur en acétate de cuivre ou en un hydrate correspondant.
PCT/JP2015/053068 2014-03-12 2015-02-04 Composition de formation de film de cuivre et procédé de fabrication de film de cuivre l'utilisant Ceased WO2015137013A1 (fr)

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CN111630119A (zh) * 2017-12-22 2020-09-04 加拿大国家研究委员会 用于高电导率精细印刷的铜油墨
EP3662027A4 (fr) * 2017-08-01 2021-04-14 National Research Council of Canada Encre de cuivre

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JP6387280B2 (ja) * 2014-10-03 2018-09-05 株式会社Adeka 銅膜形成用組成物及びそれを用いた銅膜の製造方法

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JP2000328252A (ja) * 1999-05-24 2000-11-28 Hyper Photon System:Kk 金属パターン形成方法
JP2009256218A (ja) * 2008-04-14 2009-11-05 Toray Ind Inc 銅前駆体組成物およびそれを用いた銅膜の製造方法。
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EP3662027A4 (fr) * 2017-08-01 2021-04-14 National Research Council of Canada Encre de cuivre
US11505712B2 (en) 2017-08-01 2022-11-22 National Research Council Of Canada Copper ink
CN111630119A (zh) * 2017-12-22 2020-09-04 加拿大国家研究委员会 用于高电导率精细印刷的铜油墨

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