WO2015012209A1 - Composition for copper film formation and copper film production method using same - Google Patents

Composition for copper film formation and copper film production method using same Download PDF

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Publication number
WO2015012209A1
WO2015012209A1 PCT/JP2014/069150 JP2014069150W WO2015012209A1 WO 2015012209 A1 WO2015012209 A1 WO 2015012209A1 JP 2014069150 W JP2014069150 W JP 2014069150W WO 2015012209 A1 WO2015012209 A1 WO 2015012209A1
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Prior art keywords
copper
copper film
composition
mol
forming
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PCT/JP2014/069150
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French (fr)
Japanese (ja)
Inventor
阿部　徹司
和也 斎藤
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株式会社Adeka
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Application filed by 株式会社Adeka filed Critical 株式会社Adeka
Priority to KR1020167002893A priority Critical patent/KR101734789B1/en
Priority to CN201480042051.9A priority patent/CN105408517B/en
Publication of WO2015012209A1 publication Critical patent/WO2015012209A1/en
Priority to PH12015502793A priority patent/PH12015502793A1/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
    • 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

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.
  • compositions for forming a copper film 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 into a copper film at low temperature, has good coating properties, and precipitates such as metallic copper It is desired that there is no generation, and that it is easy to control the film thickness obtained by one application, and it is particularly desirable that a copper film having excellent conductivity can be formed by heating at less than 200 ° C. Yes.
  • a composition for forming a copper film that sufficiently satisfies all of these requirements is not yet known.
  • an object of the present invention is to provide a composition for forming a copper film that sufficiently satisfies all of the above requirements. More specifically, it is possible to obtain a copper film having sufficient conductivity by coating on a substrate and heating at less than 200 ° C. Forming a solution-like copper film containing no solid phase such as fine particles It is to provide a composition for use.
  • the present inventors contain copper formate or a hydrate thereof, a diol compound having a specific structure, and a piperidine 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 relates to copper formate or a hydrate thereof 0.1 to 3.0 mol / kg, a diol compound represented by the following general formula (1), and a piperidine represented by the following general formula (2). And when the content of the copper formate or hydrate thereof is 1 mol / kg, the diol compound is contained in the range of 0.1 to 6.0 mol / kg, and the piperidine Provided is a composition for forming a copper film, which contains a compound in a range of 0.1 to 6.0 mol / kg.
  • R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group
  • R 3 represents a methyl group or an ethyl group, and m represents 0 or 1)
  • the present invention also includes a step of applying the copper film forming composition on a substrate and a step of heating the substrate coated with the copper film forming composition to below 200 ° C. to form a copper film. And providing a method for producing a copper film.
  • copper which is a solution containing no solid phase such as fine particles can be obtained by coating on a substrate and heating at a temperature of less than 200 ° C. to obtain a copper film having sufficient conductivity.
  • a film forming composition 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 may be appropriately adjusted according to the thickness of the copper film to be produced.
  • the content of copper formate is 0.1 to 3.0 mol / kg, preferably 1.0 to 2.5 mol / kg.
  • “mol (mol) / kg” in the present invention represents “amount (mol) of solute dissolved in 1 kg of solution”.
  • the molecular weight of copper (II) formate is 153.58, when 153.58 g of copper formate is contained in 1 kg of the composition for forming a copper film of the present invention, it is 1.0 mol / kg. .
  • the diol compound represented by the following general formula (1) which is a component constituting the composition for forming a copper film of the present invention, has an amino group.
  • the diol compound acts as a solubilizer for copper formate and copper formate hydrate.
  • the said diol compound showed the effect which suppresses generation
  • R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group
  • diol compound represented by the general formula (1) for example, the following compound No. 1-No. 6 is mentioned.
  • 2-amino-2-methyl-1,3-propanediol (No. 1) can be converted into a copper film at a low heating temperature, and a composition for forming a copper film. Since the electroconductivity of the copper film formed by is favorable, it is especially preferable.
  • the content of the diol compound in the composition for forming a copper film of the present invention is 0.1 to 6.0 mol / kg when the content of copper formate or a hydrate thereof is 1 mol / kg. It is a range. When the amount is less than 0.1 mol / kg with respect to 1 mol / kg of copper formate or a hydrate thereof, the conductivity of the obtained copper film becomes insufficient. On the other hand, if 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. A more preferable range is 0.5 to 2.0 mol / kg. Moreover, the said diol compound may be used independently and may be used in mixture of 2 or more types.
  • the composition for forming a copper film of the present invention contains a piperidine compound represented by the following general formula (2) as an essential component.
  • a piperidine compound represented by the following general formula (2) By containing this piperidine compound, the applicability of the copper film-forming composition can be improved, and the occurrence of precipitates such as metallic copper can be suppressed.
  • it by using in combination with copper formate or copper formate hydrate and the diol compound represented by the above general formula (1), it can be converted into a copper film by heating at less than 200 ° C. A composition can be obtained.
  • R 3 represents a methyl group or an ethyl group, and m represents 0 or 1)
  • 2-methylpiperidine (No. 8) is particularly preferable.
  • 2-methylpiperidine it is possible to obtain a composition for forming a copper film having particularly good coatability and an effect of suppressing the generation of precipitates such as metallic copper.
  • the content of the piperidine compound in the composition for forming a copper film of the present invention is 0.1 to 6.0 mol / kg when the content of copper formate or its hydrate is 1 mol / kg. It is a range. When the amount is less than 0.1 mol / kg with respect to 1 mol / kg of copper formate or its hydrate, the coatability deteriorates and a uniform copper film cannot be obtained. On the other hand, if it exceeds 6.0 mol / kg, the resulting copper film has insufficient conductivity. A more preferable range is 0.2 to 5.0 mol / kg. A more preferable range is 0.5 to 2.0 mol / kg. Moreover, the said piperidine compound may be used independently, and 2 or more types may be mixed and used for it.
  • the sum of the contents of the diol compound and the piperidine compound is 0.5 when the content of copper formate or a hydrate thereof is 1 mol / kg. It is preferably in the range of -2.0 mol / kg.
  • the coating property of the composition for forming a copper film, the conductivity of the obtained copper film, and the effect of suppressing the generation of precipitates such as metallic copper are improved, which is preferable.
  • it is less than 0.5 mol / kg a precipitate such as metallic copper may be generated.
  • the amount is more than 2.0 mol / kg, applicability may be deteriorated.
  • a more preferred range is 0.8 to 1.5 mol / kg.
  • 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%.
  • the range is preferably 5 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.
  • composition for forming a copper film of the present invention contains copper formate or a hydrate thereof, a specific diol compound, and a specific piperidine compound as essential components. However, you may contain arbitrary components other than these essential components in the range which does not inhibit the effect of this invention.
  • Optional components include: an organic solvent; an additive for increasing the film thickness of the obtained copper film; an additive for imparting stability to the composition for forming a copper film, such as an anti-gelling agent and a stabilizer;
  • additives for improving the coating property of the composition for forming a copper film such as an antifoaming agent, a thickener, a thixotropic agent, and a leveling agent; and film forming aids such as a combustion aid and a crosslinking aid.
  • the organic solvent may be any as long as it can stably dissolve the copper formate (or hydrate thereof), the diol compound, and the piperidine compound.
  • the organic solvent may be a single composition or a mixture.
  • Examples of organic solvents that can be used in the copper film forming composition of the present invention include alcohol solvents, diol solvents, ketone solvents, ester solvents, ether solvents, aliphatic or alicyclic hydrocarbons. Solvent, aromatic hydrocarbon solvent, hydrocarbon solvent 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, and tetralin.
  • hydrocarbon solvents having a cyano group examples include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane. 1,4-dicyanocyclohexane, 1,4-dicyanobenzene and the like.
  • solvents include N-methyl-2-pyrrolidone, dimethyl sulfoxide, and dimethylformamide.
  • alcohol-based solvents, diol-based solvents, and ester-based solvents are inexpensive and exhibit sufficient solubility in solutes, and further include silicon substrates, metal substrates, ceramic substrates, It is preferable because it exhibits good coating properties as a coating solvent for various substrates such as glass substrates and resin substrates.
  • alcohol solvents are particularly preferable because of their high solubility in solutes.
  • Content of said 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.
  • 0.01 mass of the organic solvent is used with respect to 100 mass parts of copper formate (even in the case of copper formate hydrate, converted to copper formate, the same shall apply hereinafter). Part to 5,000 parts by mass are preferably used.
  • 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 spin coating, 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. In the case of producing a copper film by screen printing, 0.01 to 20 parts by mass of an organic solvent is preferably used with respect to 100 parts by mass of copper formate.
  • copper acetate or a hydrate thereof can be used as an additive for increasing the thickness of the obtained copper film.
  • the copper concentration in the composition for forming a copper film can be increased, and a thick copper film can be obtained.
  • the content of copper acetate or the hydrate is not particularly limited, and depends on the thickness of the copper film to be formed. And adjust as appropriate.
  • the concentration ratio of copper formate or hydrate thereof and copper acetate or hydrate thereof is not particularly limited, but 40% by mass or more of all copper in the copper film forming composition is copper formate.
  • the content of copper acetate or a hydrate thereof is preferably in the range of 0.1 to 2.0 mol / kg when copper formate or a hydrate thereof is 1 mol / kg. More preferably, it is in the range of ⁇ 1.5 mol / kg. 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 copper film having excellent electrical characteristics can be obtained.
  • Additives for imparting stability to the copper film-forming composition include diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, alkanolamines typified by N-aminopropyldiethanolamine; 3-dimethylamino-1, Examples thereof include diol compounds having one or more amino groups represented by 2-propanediol.
  • N-methyldiethanolamine as a stabilizer is particularly preferred because the effect of suppressing the generation of precipitates such as metallic copper is enhanced.
  • the method for producing a copper film of the present invention comprises a step of applying the composition for forming a copper film of the present invention described above on a substrate (coating step), and a substrate coated with the composition for forming a copper film in 200 steps. And a step of forming a copper film by heating to less than ° C. (film formation step).
  • the substrate Before the film forming step, if necessary, the substrate may be kept at 50 ° C. or higher and lower than 150 ° C. to further dry a low boiling point component such as an organic solvent.
  • 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.
  • a plurality of processes from the above coating process to an arbitrary process can be repeated.
  • all the steps from the coating step to the film forming step may be repeated a plurality of times, or the coating step and the drying step may be repeated a plurality of times.
  • the atmosphere of the above drying process, film forming process, and annealing process is usually either a reducing gas atmosphere or an inert gas atmosphere.
  • a reducing gas atmosphere can provide a copper film with more excellent conductivity.
  • the reducing gas includes hydrogen
  • the inert gas includes helium, nitrogen, and argon.
  • the inert gas may be used as a diluent gas for the reducing gas.
  • composition for forming copper film [Examples 1 and 2] (no organic solvent)
  • the compounds shown in Table 1 were blended so as to have numerical values in parentheses (mol / kg, mass%) to obtain compositions 1 and 2 for forming a copper film.
  • concentration of each compound described in Table 1 is the quantity in 1 kg of the manufactured composition for copper film formation (hereinafter, the same).
  • Examples 3 to 9 (with organic solvent) The compounds shown in Table 2 were blended so that the numerical values in parentheses (mol / kg) were respectively obtained to obtain compositions 3 to 9 for forming a copper film. The remainder was ethanol.
  • Comparative compounds 1 to 4 were obtained by blending the compounds shown in Table 3 so that the concentration in parentheses was the numerical value (mol / kg). The remainder was ethanol.
  • a copper thin film was produced by a coating method using compositions 1 to 9 for forming a copper film, respectively. Specifically, first, each copper film forming composition was cast on a glass substrate for liquid crystal screen (Eagle XG (trade name): manufactured by Corning). Then, each copper film formation composition was apply
  • Example 12 for Example 12 using the composition 3 for forming a copper film, the operations from casting to main firing were carried out twice to form a copper thin film having a sufficient film thickness.
  • Comparative compositions 1 to 4 were used, respectively, to produce a copper thin film by a coating method. Specifically, first, each comparative composition was cast on a glass substrate for liquid crystal screen (Eagle XG (trade name): manufactured by Corning). Thereafter, 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
  • RTP-6 infrared heating furnace

Abstract

Provided is a composition for copper film formation that: contains 0.1-3.0 mol/kg of a copper formate or a hydrate thereof, a diol compound that is represented by formula (1), and a piperidine compound that is represented by formula (2); and that has a diol compound content in the range of 0.1-6.0 mol/kg and a piperidine compound content in the range of 0.1-6.0 mol/kg when the content of the copper formate or the hydrate thereof is 1 mol/kg. The composition for copper film formation is in a solution state that does not contain any solid phases such as fine particles, and makes it possible to obtain a copper film having sufficient conductivity by applying said composition on a substrate and heating at a temperature of less than 200 °C.

Description

銅膜形成用組成物及びそれを用いた銅膜の製造方法Composition for forming copper film and method for producing copper film using the same
　本発明は、種々の基体上に銅膜を形成するための銅膜形成用組成物、及びそれを用いた銅膜の製造方法に関する。 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.
　銅を電気導体とする導電層や配線を、液体プロセスである塗布熱分解法（ＭＯＤ法）や微粒子分散液塗布法によって形成する技術は、多数報告されている。 Many techniques have been reported for forming a conductive layer or wiring using copper as an electric conductor by a coating pyrolysis method (MOD method) or a fine particle dispersion coating method, which is a liquid process.
　例えば、特許文献１～４では、各種基体に水酸化銅又は有機酸銅と多価アルコールを必須成分とした混合液を塗布し、非酸化性雰囲気中で１６５℃以上の温度に加熱することを特徴とする一連の銅膜形成物品の製造方法が提案されている。そして、当該液体プロセスに使用する有機酸銅としてギ酸銅が開示されており、多価アルコールとして、ジエタノールアミン、トリエタノールアミンが開示されている。 For example, in 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. And copper formate is disclosed as an organic acid copper used in the liquid process, and diethanolamine and triethanolamine are disclosed as polyhydric alcohols.
　特許文献５では、半田耐熱性に優れる金属膜を下地電極上に形成することができる、銀微粒子と銅の有機化合物を含有する金属ペーストについて提案されている。当該ペーストに使用される銅の有機化合物としてギ酸銅が開示されており、これと反応させてペースト化させるアミノ化合物として、ジエタノールアミンが開示されている。 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, and diethanolamine is disclosed as an amino compound that is reacted with the paste to form a paste.
　特許文献６では、回路に用いる金属パターン形成用の金属塩混合物について提案されている。そして、当該混合物を構成する成分のうち、金属塩としてギ酸銅が開示されており、有機成分として、有機溶剤であるジエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、モルホリンが開示されており、金属配位子として、ピリジンが開示されている。 Patent Document 6 proposes a metal salt mixture for forming a metal pattern used in a circuit. Among the components constituting the mixture, copper formate is disclosed as a metal salt, and organic solvents such as diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, and morpholine are disclosed as organic components. Pyridine is disclosed as a ligand.
　特許文献７では、エレクトロニクス用配線の形成などに有用な、印刷後に低温で熱分解可能なギ酸銅と、３－ジアルキルアミノプロパン－１，２－ジオール化合物とを含有する低温分解性の銅前駆体組成物が開示されている。 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.
　特許文献８では、先述した液体プロセスに有用なギ酸銅とアルカノールアミンを含有する銅薄膜形成用組成物が開示されている。そして、アルカノールアミンとして、モノエタノールアミン、ジエタノールアミン、及びトリエタノールアミンが例示されている。 Patent Document 8 discloses a composition for forming a copper thin film containing copper formate and alkanolamine useful for the liquid process described above. Examples of alkanolamines include monoethanolamine, diethanolamine, and triethanolamine.
特開平１－１６８８６５号公報JP-A-1-168865 特開平１－１６８８６６号公報JP-A-1-168866 特開平１－１６８８６７号公報JP-A-1-168867 特開平１－１６８８６８号公報JP-A-1-168868 特開２００７－３５３５３号公報JP 2007-35353 A 特開２００８－２０５４３０号公報JP 2008-205430 A 特開２００９－２５６２１８号公報JP 2009-256218 A 特開２０１０－２４２１１８号公報JP 2010-242118 A
　ここで、銅膜形成用組成物を使用した液体プロセスにおいて微細な配線や膜を安価に製造するには、下記の要件を満足する組成物が提供されることが望まれる。すなわち、微粒子等の固相を含まない溶液タイプであること、導電性に優れた銅膜を与えること、低温で銅膜に転化できること、塗布性が良好であること、金属銅等の沈殿物の発生が無いこと、１回の塗布により得られる膜厚のコントロールが容易であること、が望まれ、特に２００℃未満で加熱することで導電性に優れた銅膜の形成ができることが望まれている。しかし、これらの要求の全てを十分に満たす銅膜形成用組成物は、未だ知られていない。 Here, in order to produce a fine wiring or film at a low cost in a liquid process using the composition for forming a copper film, it is desired 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 into a copper film at low temperature, has good coating properties, and precipitates such as metallic copper It is desired that there is no generation, and that it is easy to control the film thickness obtained by one application, and it is particularly desirable that a copper film having excellent conductivity can be formed by heating at less than 200 ° C. Yes. However, a composition for forming a copper film that sufficiently satisfies all of these requirements is not yet known.
　したがって、本発明の目的は、上記した要求の全てを十分に満たす銅膜形成用組成物を提供することにある。より具体的には、基体上に塗布し、２００℃未満で加熱することで、十分な導電性を有する銅膜を得ることが可能な、微粒子等の固相を含まない溶液状の銅膜形成用組成物を提供することにある。 Therefore, an object of the present invention is to provide a composition for forming a copper film that sufficiently satisfies all of the above requirements. More specifically, it is possible to obtain a copper film having sufficient conductivity by coating on a substrate and heating at less than 200 ° C. Forming a solution-like copper film containing no solid phase such as fine particles It is to provide a composition for use.
　本発明者等は、上記の実情に鑑み検討を重ねた結果、ギ酸銅又はその水和物と、特定の構造を有するジオール化合物と、特定の構造を有するピペリジン化合物とを特定の割合で含有する銅膜形成用組成物が上記要求性能を満たすことを見出し、本発明に到達した。 As a result of repeated studies in view of the above circumstances, the present inventors contain copper formate or a hydrate thereof, a diol compound having a specific structure, and a piperidine 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.
　すなわち、本発明は、ギ酸銅又はその水和物０．１～３．０モル／ｋｇと、下記一般式（１）で表されるジオール化合物と、下記一般式（２）で表されるピペリジン化合物と、を含有し、前記ギ酸銅又はその水和物の含有量を１モル／ｋｇとした場合に、前記ジオール化合物を０．１～６．０モル／ｋｇの範囲で含有し、前記ピペリジン化合物を０．１～６．０モル／ｋｇの範囲で含有することを特徴とする銅膜形成用組成物を提供する。 That is, the present invention relates to copper formate or a hydrate thereof 0.1 to 3.0 mol / kg, a diol compound represented by the following general formula (1), and a piperidine represented by the following general formula (2). And when the content of the copper formate or hydrate thereof is 1 mol / kg, the diol compound is contained in the range of 0.1 to 6.0 mol / kg, and the piperidine Provided is a composition for forming a copper film, which contains a compound in a range of 0.1 to 6.0 mol / kg.
Figure JPOXMLDOC01-appb-I000003
（前記一般式（１）中、Ｒ1及びＲ2は、各々独立に水素原子、メチル基、又はエチル基を表す）
Figure JPOXMLDOC01-appb-I000003
(In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group)
Figure JPOXMLDOC01-appb-I000004
（前記一般式（２）中、Ｒ3は、メチル基又はエチル基を表し、ｍは、０又は１を表す）
Figure JPOXMLDOC01-appb-I000004
(In the general formula (2), R 3 represents a methyl group or an ethyl group, and m represents 0 or 1)
　また、本発明は、上記の銅膜形成用組成物を基体上に塗布する工程と、前記銅膜形成用組成物が塗布された前記基体を２００℃未満に加熱して銅膜を形成する工程と、を有することを特徴とする銅膜の製造方法を提供する。 The present invention also includes a step of applying the copper film forming composition on a substrate and a step of heating the substrate coated with the copper film forming composition to below 200 ° C. to form a copper film. And providing a method for producing a copper film.
　本発明によれば、基体上に塗布し、２００℃未満の温度で加熱することで、十分な導電性を有する銅膜を得ることが可能な、微粒子等の固相を含まない溶液である銅膜形成用組成物が提供される。 According to the present invention, copper which is a solution containing no solid phase such as fine particles can be obtained by coating on a substrate and heating at a temperature of less than 200 ° C. to obtain a copper film having sufficient conductivity. A film forming composition is provided.
　本発明の銅膜形成用組成物の特徴の一つは、銅膜の前駆体（プレカーサ）としてギ酸銅を使用したことにある。本発明の銅膜形成用組成物に使用するギ酸銅は、無水和物でもよく、水和物でもよい。具体的には、無水ギ酸銅（II）、ギ酸銅（II）二水和物、ギ酸銅（II）四水和物などを用いることができる。これらのギ酸銅は、そのまま混合してもよく、水溶液、有機溶媒溶液、又は有機溶媒懸濁液として混合してもよい。 One of the features of the composition for forming a copper film of the present invention is that 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. Specifically, anhydrous copper formate (II), copper formate (II) dihydrate, copper formate (II) tetrahydrate and the like can be used. These 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.
　本発明の銅膜形成用組成物中のギ酸銅の含有量は、製造しようとする銅膜の厚さに応じて適宜に調整すればよい。ギ酸銅の含有量は０．１～３．０モル／ｋｇであり、１．０～２．５モル／ｋｇであることが好ましい。ここで、本発明における「モル（ｍｏｌ）／ｋｇ」は、「溶液１ｋｇに対して溶けている溶質の量（モル）」を表している。例えば、ギ酸銅（II）の分子量は１５３．５８であるので、本発明の銅膜形成用組成物１ｋｇ中にギ酸銅が１５３．５８ｇ含有されている場合には１．０モル／ｋｇとなる。 The content of copper formate in the composition for forming a copper film of the present invention may be appropriately adjusted according to the thickness of the copper film to be produced. The content of copper formate is 0.1 to 3.0 mol / kg, preferably 1.0 to 2.5 mol / kg. Here, “mol (mol) / kg” in the present invention represents “amount (mol) of solute dissolved in 1 kg of solution”. For example, since the molecular weight of copper (II) formate is 153.58, when 153.58 g of copper formate is contained in 1 kg of the composition for forming a copper film of the present invention, it is 1.0 mol / kg. .
　本発明の銅膜形成用組成物を構成する成分である下記一般式（１）で表されるジオール化合物は、アミノ基を有することを特徴とする。検討の結果、本発明者らは、当該ジオール化合物がギ酸銅及びギ酸銅水和物の可溶化剤として作用することを見出した。また、当該ジオール化合物が、銅膜形成用組成物中における金属銅等の沈殿物の発生を抑制し、さらには、形成される銅膜の導電性を向上させる効果を示すことを見出した。 The diol compound represented by the following general formula (1), which is a component constituting the composition for forming a copper film of the present invention, has an amino group. As a result of the study, the present inventors have found that the diol compound acts as a solubilizer for copper formate and copper formate hydrate. Moreover, it discovered that the said diol compound showed the effect which suppresses generation | occurrence | production of deposits, such as metallic copper, in the composition for copper film formation, and also improves the electroconductivity of the copper film formed.
Figure JPOXMLDOC01-appb-I000005
（前記一般式（１）中、Ｒ1及びＲ2は、各々独立に水素原子、メチル基、又はエチル基を表す）
Figure JPOXMLDOC01-appb-I000005
(In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group)
　上記一般式（１）で表されるジオール化合物としては、例えば、下記化合物Ｎｏ．１～Ｎｏ．６が挙げられる。 As the diol compound represented by the general formula (1), for example, the following compound No. 1-No. 6 is mentioned.
Figure JPOXMLDOC01-appb-I000006
Figure JPOXMLDOC01-appb-I000006
　以上列挙したジオール化合物の中でも、２－アミノ－２－メチル－１，３－プロパンジオール（Ｎｏ．１）は、低い加熱温度で銅膜への転化が可能になるとともに、銅膜形成用組成物によって形成される銅膜の導電性が良好であることから、特に好ましい。 Among the diol compounds listed above, 2-amino-2-methyl-1,3-propanediol (No. 1) can be converted into a copper film at a low heating temperature, and a composition for forming a copper film. Since the electroconductivity of the copper film formed by is favorable, it is especially preferable.
　本発明の銅膜形成用組成物中の上記ジオール化合物の含有量は、ギ酸銅又はその水和物の含有量を１モル／ｋｇとした場合に、０．１～６．０モル／ｋｇの範囲である。ギ酸銅又はその水和物１モル／ｋｇに対して０．１モル／ｋｇより少ないと、得られる銅膜の導電性が不十分となる。一方、６．０モル／ｋｇを超えると塗布性が悪化し、均一な銅膜が得られなくなる。より好ましい範囲は、０．２～５．０モル／ｋｇである。さらに好ましい範囲は、０．５～２．０モル／ｋｇである。また、上記ジオール化合物は、単独で使用してもよく、２種類以上を混合して使用してもよい。 The content of the diol compound in the composition for forming a copper film of the present invention is 0.1 to 6.0 mol / kg when the content of copper formate or a hydrate thereof is 1 mol / kg. It is a range. When the amount is less than 0.1 mol / kg with respect to 1 mol / kg of copper formate or a hydrate thereof, the conductivity of the obtained copper film becomes insufficient. On the other hand, if 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. A more preferable range is 0.5 to 2.0 mol / kg. Moreover, the said diol compound may be used independently and may be used in mixture of 2 or more types.
　本発明の銅膜形成用組成物は、下記一般式（２）で表されるピペリジン化合物を必須成分として含有する。このピペリジン化合物を含有させることで、銅膜形成用組成物の塗布性を良好にするとともに、金属銅等の沈殿物の発生を抑制することができる。さらに、ギ酸銅又はギ酸銅水和物、及び上記一般式（１）で表されるジオール化合物と組み合わせて用いることで、２００℃未満の加熱によって銅膜への転化することができる銅膜形成用組成物を得ることができる。 The composition for forming a copper film of the present invention contains a piperidine compound represented by the following general formula (2) as an essential component. By containing this piperidine compound, the applicability of the copper film-forming composition can be improved, and the occurrence of precipitates such as metallic copper can be suppressed. Furthermore, by using in combination with copper formate or copper formate hydrate and the diol compound represented by the above general formula (1), it can be converted into a copper film by heating at less than 200 ° C. A composition can be obtained.
Figure JPOXMLDOC01-appb-I000007
（前記一般式（２）中、Ｒ3は、メチル基又はエチル基を表し、ｍは、０又は１を表す）
Figure JPOXMLDOC01-appb-I000007
(In the general formula (2), R 3 represents a methyl group or an ethyl group, and m represents 0 or 1)
　上記一般式（２）で表されるピペリジン化合物としては、例えば、下記化合物Ｎｏ．７～Ｎｏ．１３が挙げられる。 As the piperidine compound represented by the general formula (2), for example, the following compound No. 7-No. 13 is mentioned.
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000008
Figure JPOXMLDOC01-appb-I000009
Figure JPOXMLDOC01-appb-I000009
　以上列挙したピペリジン化合物の中でも、特に２－メチルピペリジン（Ｎｏ．８）を用いることが好ましい。２－メチルピペリジンを用いることで、特に良好な塗布性と金属銅等の沈殿物の発生を抑制する効果を有する銅膜形成用組成物が得られる。 Among the piperidine compounds listed above, 2-methylpiperidine (No. 8) is particularly preferable. By using 2-methylpiperidine, it is possible to obtain a composition for forming a copper film having particularly good coatability and an effect of suppressing the generation of precipitates such as metallic copper.
　本発明の銅膜形成用組成物中の上記ピペリジン化合物の含有量は、ギ酸銅又はその水和物の含有量を１モル／ｋｇとした場合に、０．１～６．０モル／ｋｇの範囲である。ギ酸銅又はその水和物１モル／ｋｇに対して０．１モル／ｋｇより少ないと、塗布性が悪化し、均一な銅膜が得られなくなる。一方、６．０モル／ｋｇを超えると得られる銅膜の導電性が不十分となる。より好ましい範囲は、０．２～５．０モル／ｋｇである。さらに好ましい範囲は、０．５～２．０モル／ｋｇである。また、上記ピペリジン化合物は、単独で使用してもよく、２種類以上を混合して使用してもよい。 The content of the piperidine compound in the composition for forming a copper film of the present invention is 0.1 to 6.0 mol / kg when the content of copper formate or its hydrate is 1 mol / kg. It is a range. When the amount is less than 0.1 mol / kg with respect to 1 mol / kg of copper formate or its hydrate, the coatability deteriorates and a uniform copper film cannot be obtained. On the other hand, if it exceeds 6.0 mol / kg, the resulting copper film has insufficient conductivity. A more preferable range is 0.2 to 5.0 mol / kg. A more preferable range is 0.5 to 2.0 mol / kg. Moreover, the said piperidine compound may be used independently, and 2 or more types may be mixed and used for it.
　また、本発明の銅膜形成用組成物における、上記ジオール化合物と上記ピペリジン化合物の含有量の和は、ギ酸銅又はその水和物の含有量を１モル／ｋｇとした場合に、０．５～２．０モル／ｋｇの範囲であることが好ましい。これにより、銅膜形成用組成物の塗布性、得られる銅膜の導電性、及び金属銅等の沈殿物の発生を抑制する効果が良好となるので好ましい。０．５モル／ｋｇより少ないと、金属銅等の沈殿物が発生する場合がある。一方、２．０モル／ｋｇよりも多いと塗布性が悪化する場合がある。より好ましい範囲は、０．８～１．５モル／ｋｇの範囲である。 In the composition for forming a copper film of the present invention, the sum of the contents of the diol compound and the piperidine compound is 0.5 when the content of copper formate or a hydrate thereof is 1 mol / kg. It is preferably in the range of -2.0 mol / kg. Thereby, the coating property of the composition for forming a copper film, the conductivity of the obtained copper film, and the effect of suppressing the generation of precipitates such as metallic copper are improved, which is preferable. When it is less than 0.5 mol / kg, a precipitate such as metallic copper may be generated. On the other hand, when the amount is more than 2.0 mol / kg, applicability may be deteriorated. A more preferred range is 0.8 to 1.5 mol / kg.
　また、本発明の銅膜形成用組成物中におけるジオール化合物とピペリジン化合物の濃度比率は特に限定されるものではないが、ジオール化合物１モル／ｋｇとした場合に、ピペリジン化合物が０．５～１．５モル／ｋｇの範囲であることが好ましい。ピペリジン化合物が１モル／ｋｇ（ジオール化合物とほぼ等量）である場合が、溶液の安定性がよく、電気特性に優れた銅膜が得られるため、特に好ましい。 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%. The range is preferably 5 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.
　本発明の銅膜形成用組成物は、ギ酸銅又はその水和物、特定のジオール化合物、及び特定のピペリジン化合物を必須成分として含有する。ただし、これらの必須成分以外の任意の成分を、本発明の効果を阻害しない範囲で含有してもよい。任意の成分としては、有機溶剤；得られる銅膜の膜厚を厚くするための添加剤；ゲル化防止剤、安定剤等の銅膜形成用組成物に安定性を付与するための添加剤；消泡剤、増粘剤、揺変剤、レベリング剤等の銅膜形成用組成物の塗布性を改善するための添加剤；燃焼助剤、架橋助剤等の成膜助剤が挙げられる。 The composition for forming a copper film of the present invention contains copper formate or a hydrate thereof, a specific diol compound, and a specific piperidine compound as essential components. However, you may contain arbitrary components other than these essential components in the range which does not inhibit the effect of this invention. Optional components include: an organic solvent; an additive for increasing the film thickness of the obtained copper film; an additive for imparting stability to the composition for forming a copper film, such as an anti-gelling agent and a stabilizer; Examples include additives for improving the coating property of the composition for forming a copper film such as an antifoaming agent, a thickener, a thixotropic agent, and a leveling agent; and film forming aids such as a combustion aid and a crosslinking aid.
　上記有機溶剤は、上記のギ酸銅（又はその水和物）、ジオール化合物、及びピペリジン化合物を安定に溶解することができれば、いずれのものでもよい。当該有機溶剤は、単一組成でも混合物でもよい。本発明の銅膜形成用組成物に使用することができる有機溶剤の例としては、アルコール系溶剤、ジオール系溶剤、ケトン系溶剤、エステル系溶剤、エーテル系溶剤、脂肪族又は脂環族炭化水素系溶剤、芳香族炭化水素系溶剤、シアノ基を有する炭化水素溶剤、その他の溶剤等が挙げられる。 The organic solvent may be any as long as it can stably dissolve the copper formate (or hydrate thereof), the diol compound, and the piperidine compound. The organic solvent may be a single composition or a mixture. Examples of organic solvents that can be used in the copper film forming composition of the present invention include alcohol solvents, diol solvents, ketone solvents, ester solvents, ether solvents, aliphatic or alicyclic hydrocarbons. Solvent, aromatic hydrocarbon solvent, hydrocarbon solvent having a cyano group, and other solvents.
　アルコール系溶剤としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、１－ブタノール、イソブタノール、２－ブタノール、第３ブタノール、ペンタノール、イソペンタノール、２－ペンタノール、ネオペンタノール、第３ペンタノール、ヘキサノール、２－ヘキサノール、ヘプタノール、２－ヘプタノール、オクタノール、２－エチルヘキサノール、２－オクタノール、シクロペンタノール、シクロヘキサノール、シクロヘプタノール、メチルシクロペンタノール、メチルシクロヘキサノール、メチルシクロヘプタノール、ベンジルアルコール、エチレングリコールモノアセタート、エチレングリコールモノエチルエーテル、エチレングリコールモノフェニルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノブチルエーテル、２－（２－メトキシエトキシ）エタノール、２－（Ｎ，Ｎ－ジメチルアミノ）エタノール、３－（Ｎ，Ｎ－ジメチルアミノ）プロパノール等が挙げられる。 Examples of alcohol solvents include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, and third pen. Tanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, Benzyl alcohol, ethylene glycol monoacetate, ethylene glycol monoethyl ether, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether , Ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, 2- (2- Methoxyethoxy) ethanol, 2- (N, N-dimethylamino) ethanol, 3- (N, N-dimethylamino) propanol and the like.
　ジオール系溶剤としては、例えば、エチレングリコール、プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、イソプレングリコール（３－メチル－１，３－ブタンジオール）、１，２－ヘキサンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、１，２－オクタンジオール、オクタンジオール（２－エチル－１，３－ヘキサンジオール）、２－ブチル－２－エチル－１，３－プロパンジオール、２，５－ジメチル－２，５－ヘキサンジオール、１，２－シクロヘキサンジオール、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール等が挙げられる。 Examples of the diol solvent 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-cyclohexanedimethanol.
　ケトン系溶剤としては、例えば、アセトン、エチルメチルケトン、メチルブチルケトン、メチルイソブチルケトン、エチルブチルケトン、ジプロピルケトン、ジイソブチルケトン、メチルアミルケトン、シクロヘキサノン、メチルシクロヘキサノン等が挙げられる。 Examples of the ketone solvent include acetone, ethyl methyl ketone, methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and methylcyclohexanone.
　エステル系溶剤としては、例えば、ギ酸メチル、ギ酸エチル、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸第２ブチル、酢酸第３ブチル、酢酸アミル、酢酸イソアミル、酢酸第３アミル、酢酸フェニル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸イソプロピル、プロピオン酸ブチル、プロピオン酸イソブチル、プロピオン酸第２ブチル、プロピオン酸第３ブチル、プロピオン酸アミル、プロピオン酸イソアミル、プロピオン酸第３アミル、プロピオン酸フェニル、２－エチルヘキサン酸メチル、２－エチルヘキサン酸エチル、２－エチルヘキサン酸プロピル、２－エチルヘキサン酸イソプロピル、２－エチルヘキサン酸ブチル、乳酸メチル、乳酸エチル、メトキシプロピオン酸メチル、エトキシプロピオン酸メチル、メトキシプロピオン酸エチル、エトキシプロピオン酸エチル、エチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノプロピルエーテルアセテート、エチレングリコールモノイソプロピルエーテルアセテート、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノ第２ブチルエーテルアセテート、エチレングリコールモノイソブチルエーテルアセテート、エチレングリコールモノ第３ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノイソプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、プロピレングリコールモノ第２ブチルエーテルアセテート、プロピレングリコールモノイソブチルエーテルアセテート、プロピレングリコールモノ第３ブチルエーテルアセテート、ブチレングリコールモノメチルエーテルアセテート、ブチレングリコールモノエチルエーテルアセテート、ブチレングリコールモノプロピルエーテルアセテート、ブチレングリコールモノイソプロピルエーテルアセテート、ブチレングリコールモノブチルエーテルアセテート、ブチレングリコールモノ第２ブチルエーテルアセテート、ブチレングリコールモノイソブチルエーテルアセテート、ブチレングリコールモノ第３ブチルエーテルアセテート、アセト酢酸メチル、アセト酢酸エチル、オキソブタン酸メチル、オキソブタン酸エチル、γ－ラクトン、δ－ラクトン等が挙げられる。 Examples of the ester solvent 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-ethylhexanoate, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate, Methyl toxipropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol mono Butyl ether acetate, ethylene glycol mono sec-butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol mono tertiary butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopro Ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol mono sec-butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono-tert-butyl ether acetate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether Acetate, Butylene glycol monopropyl ether acetate, Butylene glycol monoisopropyl ether acetate, Butylene glycol monobutyl ether acetate, Butylene glycol mono sec-butyl ether acetate, Butylene glycol monoisobutyl ether acetate, Butylene glycol mono Examples include 3-butyl ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutanoate, ethyl oxobutanoate, γ-lactone, and δ-lactone.
　エーテル系溶剤としては、例えば、テトラヒドロフラン、テトラヒドロピラン、モルホリン、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、ジブチルエーテル、ジエチルエーテル、ジオキサン等が挙げられる。 Examples of the ether solvent include tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, diethyl ether, dioxane and the like.
　脂肪族又は脂環族炭化水素系溶剤としては、ペンタン、ヘキサン、シクロヘキサン、メチルシクロヘキサン、ジメチルシクロヘキサン、エチルシクロヘキサン、ヘプタン、オクタン、デカリン、ソルベントナフサ等が挙げられる。 Examples of the aliphatic or alicyclic hydrocarbon solvent include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decalin, and solvent naphtha.
　芳香族炭化水素系溶剤としては、ベンゼン、トルエン、エチルベンゼン、キシレン、メシチレン、ジエチルベンゼン、クメン、イソブチルベンゼン、シメン、テトラリンが挙げられる。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, cymene, and tetralin.
　シアノ基を有する炭化水素溶剤としては、１－シアノプロパン、１－シアノブタン、１－シアノヘキサン、シアノシクロヘキサン、シアノベンゼン、１，３－ジシアノプロパン、１，４－ジシアノブタン、１，６－ジシアノヘキサン、１，４－ジシアノシクロヘキサン、１，４－ジシアノベンゼン等が挙げられる。 Examples of hydrocarbon solvents having a cyano group include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane. 1,4-dicyanocyclohexane, 1,4-dicyanobenzene and the like.
　その他の溶剤としては、Ｎ－メチル－２－ピロリドン、ジメチルスルホキシド、ジメチルホルムアミドが挙げられる。 Other solvents include N-methyl-2-pyrrolidone, dimethyl sulfoxide, and dimethylformamide.
　本発明においては、上記の有機溶剤の中でも、アルコール系溶剤、ジオール系溶剤、及びエステル系溶剤が安価であり、しかも溶質に対する十分な溶解性を示し、さらに、シリコン基体、金属基体、セラミックス基体、ガラス基体、樹脂基体等の様々な基体に対する塗布溶媒として良好な塗布性を示すので、好ましい。中でも、アルコール系溶剤が、溶質に対する溶解性が高く、特に好ましい。 In the present invention, among the above organic solvents, alcohol-based solvents, diol-based solvents, and ester-based solvents are inexpensive and exhibit sufficient solubility in solutes, and further include silicon substrates, metal substrates, ceramic substrates, It is preferable because it exhibits good coating properties as a coating solvent for various substrates such as glass substrates and resin substrates. Among these, alcohol solvents are particularly preferable because of their high solubility in solutes.
　本発明の銅膜形成用組成物中の上記の有機溶剤の含有量は、特に限定されるものではなく、形成しようとする銅膜の厚さや、銅膜の製造方法に応じて適宜調節すればよい。例えば、塗布法によって銅膜を製造する場合には、ギ酸銅（ギ酸銅水和物の場合であってもギ酸銅で換算、以下同様）１００質量部に対して、有機溶剤を０．０１質量部～５，０００質量部使用することが好ましい。有機溶剤の量が０．０１質量部より少ないと、得られる銅膜にクラックが発生する、或いは塗布性が悪化する等の不具合が生ずる場合がある。また、有機溶剤の割合が増すほど得られる銅膜が薄くなるので、生産性の面から５，０００質量部を超えないことが好ましい。より具体的には、スピンコート法によって銅膜を製造する場合には、ギ酸銅１００質量部に対して、有機溶剤を２０質量部～１，０００質量部使用することが好ましい。また、スクリーン印刷法によって銅膜を製造する場合には、ギ酸銅１００質量部に対して、有機溶剤を０．０１質量部～２０質量部使用することが好ましい。 Content of said 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. For example, when a copper film is produced by a coating method, 0.01 mass of the organic solvent is used with respect to 100 mass parts of copper formate (even in the case of copper formate hydrate, converted to copper formate, the same shall apply hereinafter). Part to 5,000 parts by mass are preferably used. 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. Moreover, since 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 spin coating, 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. In the case of producing a copper film by screen printing, 0.01 to 20 parts by mass of an organic solvent is preferably used with respect to 100 parts by mass of copper formate.
　得られる銅膜の膜厚を厚くするための添加剤としては、例えば酢酸銅又はその水和物を使用することができる。このような添加剤を添加することにより、銅膜形成用組成物中の銅濃度を濃くすることができ、膜厚の厚い銅膜を得ることができる。例えば、当該添加剤として酢酸銅又はその水和物を使用する場合における、酢酸銅又はその水和物の含有量は、特に限定されるものではなく、形成しようとする銅膜の厚さに応じて適宜に調整すればよい。ギ酸銅又はその水和物と、酢酸銅又はその水和物との濃度比率は、特に限定されるものではないが、銅膜形成用組成物中のすべての銅の４０質量％以上がギ酸銅の添加によるものであることが好ましい。酢酸銅又はその水和物の含有量は、ギ酸銅又はその水和物を１モル／ｋｇとした場合に、０．１～２．０モル／ｋｇの範囲であることが好ましく、０．５～１．５モル／ｋｇの範囲であることがさらに好ましい。また、ギ酸銅と酢酸銅の濃度（モル／ｋｇ）の比が、約１：１であることが、電気特性に優れた銅膜が得られるため、特に好ましい。 As an additive for increasing the thickness of the obtained copper film, for example, copper acetate or a hydrate thereof can be used. By adding such an additive, the copper concentration in the composition for forming a copper film can be increased, and a thick copper film can be obtained. For example, when copper acetate or a hydrate thereof is used as the additive, the content of copper acetate or the hydrate is not particularly limited, and depends on the thickness of the copper film to be formed. And adjust as appropriate. The concentration ratio of copper formate or hydrate thereof and copper acetate or hydrate thereof is not particularly limited, but 40% by mass or more of all copper in the copper film forming composition is copper formate. It is preferable to be due to the addition of The content of copper acetate or a hydrate thereof is preferably in the range of 0.1 to 2.0 mol / kg when copper formate or a hydrate thereof is 1 mol / kg. More preferably, it is in the range of ˜1.5 mol / kg. 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 copper film having excellent electrical characteristics can be obtained.
　銅膜形成用組成物に安定性を付与するための添加剤としては、ジエタノールアミン、Ｎ－メチルジエタノールアミン、Ｎ－エチルジエタノールアミン、Ｎ－アミノプロピルジエタノールアミンに代表されるアルカノールアミン；３－ジメチルアミノ－１，２－プロパンジオールに代表される１つ以上のアミノ基を有するジオール化合物が挙げられる。Ｎ－メチルジエタノールアミンを安定剤として添加した場合は、金属銅等の沈殿物の発生を抑制する効果が高くなることから特に好ましい。 Additives for imparting stability to the copper film-forming composition include diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, alkanolamines typified by N-aminopropyldiethanolamine; 3-dimethylamino-1, Examples thereof include diol compounds having one or more amino groups represented by 2-propanediol. The addition of N-methyldiethanolamine as a stabilizer is particularly preferred because the effect of suppressing the generation of precipitates such as metallic copper is enhanced.
　次に、本発明の銅膜の製造方法について説明する。本発明の銅膜の製造方法は、これまでに説明した本発明の銅膜形成用組成物を基体上に塗布する工程（塗布工程）と、銅膜形成用組成物が塗布された基体を２００℃未満に加熱して銅膜を形成する工程（成膜工程）とを有する。必要に応じて成膜工程の前に、基体を５０℃以上１５０℃未満に保持し、有機溶剤等の低沸点成分を揮発させる乾燥工程をさらに有してもよい。また、成膜工程の後に、基体を１００℃以上２００℃未満に保持して銅膜の導電性を向上させるアニール工程をさらに有してもよい。 Next, a method for producing the copper film of the present invention will be described. The method for producing a copper film of the present invention comprises a step of applying the composition for forming a copper film of the present invention described above on a substrate (coating step), and a substrate coated with the composition for forming a copper film in 200 steps. And a step of forming a copper film by heating to less than ° C. (film formation step). Before the film forming step, if necessary, the substrate may be kept at 50 ° C. or higher and lower than 150 ° C. to further dry a low boiling point component such as an organic solvent. Moreover, you may further have the annealing process which hold | maintains a base | substrate at 100 degreeC or more and less than 200 degreeC after a film-forming process, and improves the electroconductivity of a copper film.
　上記の塗布工程における塗布方法としては、スピンコート法、ディップ法、スプレーコート法、ミストコート法、フローコート法、カーテンコート法、ロールコート法、ナイフコート法、バーコート法、スリットコート法、スクリーン印刷法、グラビア印刷法、オフセット印刷法、インクジェット法、刷毛塗り等が挙げられる。 As the coating method in the above coating process, 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.
　また、必要な膜厚を得るために、上記の塗布工程から任意の工程までを複数繰り返すことができる。例えば、塗布工程から成膜工程の全ての工程を複数回繰り返してもよく、塗布工程と乾燥工程を複数回繰り返してもよい。 In addition, in order to obtain a required film thickness, a plurality of processes from the above coating process to an arbitrary process can be repeated. For example, all the steps from the coating step to the film forming step may be repeated a plurality of times, or the coating step and the drying step may be repeated a plurality of times.
　上記の乾燥工程、成膜工程、及びアニール工程の雰囲気は、通常、還元性ガス雰囲気と不活性ガス雰囲気のいずれかである。還元性ガス雰囲気のほうが、より導電性に優れた銅膜を得ることができる。還元性ガスとしては水素が挙げられ、不活性ガスとしては、ヘリウム、窒素、及びアルゴンが挙げられる。不活性ガスは、還元性ガスの希釈ガスとして使用してもよい。また、各工程においてプラズマ；レーザー；キセノンランプ、水銀ランプ、水銀キセノンランプ、キセノンフラッシュランプ、アルゴンフラッシュランプ、重水素ランプ等の放電ランプ；各種放射線等の熱以外のエネルギーを印加又は照射してもよい。 The atmosphere of the above drying process, film forming process, and annealing process is usually either a reducing gas atmosphere or an inert gas atmosphere. A reducing gas atmosphere can provide a copper film with more excellent conductivity. The reducing gas includes hydrogen, and the inert gas includes helium, nitrogen, and argon. The inert gas may be used as a diluent gas for the reducing gas. In each step, plasma; laser; discharge lamp such as xenon lamp, mercury lamp, mercury xenon lamp, xenon flash lamp, argon flash lamp, deuterium lamp, etc .; Good.
　以下、実施例をもって本発明をさらに詳細に説明する。しかしながら、本発明は以下の実施例等によって何ら制限を受けるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.
＜銅膜形成用組成物＞
［実施例１及び２］（有機溶媒無し）
　表１に記載の化合物をそれぞれカッコ内の数値の濃度（ｍｏｌ／ｋｇ、質量％）となるように配合して銅膜形成用組成物１及び２を得た。なお、表１に記載した各化合物の濃度は、製造した銅膜形成用組成物１ｋｇ中の量である（以下、同様）。 <Composition for forming copper film>
[Examples 1 and 2] (no organic solvent)
The compounds shown in Table 1 were blended so as to have numerical values in parentheses (mol / kg, mass%) to obtain compositions 1 and 2 for forming a copper film. In addition, the density | concentration of each compound described in Table 1 is the quantity in 1 kg of the manufactured composition for copper film formation (hereinafter, the same).
Figure JPOXMLDOC01-appb-I000010
Figure JPOXMLDOC01-appb-I000010
［実施例３～９］（有機溶媒有り）
　表２に記載の化合物をそれぞれカッコ内の数値の濃度（ｍｏｌ／ｋｇ）となるように配合して銅膜形成用組成物３～９を得た。なお、残分は全てエタノールとした。 [Examples 3 to 9] (with organic solvent)
The compounds shown in Table 2 were blended so that the numerical values in parentheses (mol / kg) were respectively obtained to obtain compositions 3 to 9 for forming a copper film. The remainder was ethanol.
Figure JPOXMLDOC01-appb-I000011
Figure JPOXMLDOC01-appb-I000011
［比較例１～４］（有機溶媒有り）
　表３に記載の化合物をそれぞれカッコ内の数値の濃度（ｍｏｌ／ｋｇ）となるように配合して比較組成物１～４を得た。なお、残分は全てエタノールとした。 [Comparative Examples 1 to 4] (with organic solvent)
Comparative compounds 1 to 4 were obtained by blending the compounds shown in Table 3 so that the concentration in parentheses was the numerical value (mol / kg). The remainder was ethanol.
Figure JPOXMLDOC01-appb-I000012
Figure JPOXMLDOC01-appb-I000012
＜銅膜の製造＞
［実施例１０～１８］
　銅膜形成用組成物１～９をそれぞれ使用し、塗布法により銅薄膜を製造した。具体的には、まず、各銅膜形成用組成物を液晶画面用のガラス基板（Ｅａｇｌｅ　ＸＧ（商品名）：コーニング社製）上にキャストした。その後、５００ｒｐｍで５秒及び２，０００ｒｐｍで２０秒の条件にてスピンコート法によって各銅膜形成用組成物を塗布した。次いで、ホットプレートを用いて大気中、１００℃で３０秒間乾燥した。乾燥後のガラス基板を、赤外線加熱炉（ＲＴＰ－６（商品名）：アルバック理工社製）を用いてアルゴン雰囲気下、１６０℃で２０分間加熱して本焼成し、銅薄膜を得た。なお、本焼成時のアルゴンのフロー条件は３００ｍＬ／ｍｉｎとし、昇温速度は１６０℃／３０秒とした。なお、銅膜形成用組成物３は銅濃度が低いため、キャスト～本焼成までの操作を１回行うだけでは得られる銅薄膜が薄く、後述する表面抵抗値を測定するために必要な膜厚を十分に確保することができない。そこで、銅膜形成用組成物３を用いた実施例１２については、キャスト～本焼成までの操作を２回実施し、十分な膜厚を有する銅薄膜を形成した。 <Manufacture of copper film>
[Examples 10 to 18]
A copper thin film was produced by a coating method using compositions 1 to 9 for forming a copper film, respectively. Specifically, first, each copper film forming composition was cast on a glass substrate for liquid crystal screen (Eagle XG (trade name): manufactured by Corning). Then, each copper film formation composition was apply | coated by the spin coat method on the conditions of 500 second for 5 seconds, and 2,000 rpm for 20 seconds. Subsequently, it dried in air | atmosphere for 30 second at 100 degreeC using the hotplate. The glass substrate after drying was subjected to main baking by heating at 160 ° C. for 20 minutes in an argon atmosphere using an infrared heating furnace (RTP-6 (trade name) manufactured by ULVAC-RIKO) to obtain a copper thin film. In addition, the flow conditions of argon at the time of this baking were 300 mL / min, and the temperature increase rate was 160 degreeC / 30 second. In addition, since the copper film-forming composition 3 has a low copper concentration, the copper thin film obtained is thin only by performing the operations from casting to main firing once, and the film thickness necessary for measuring the surface resistance value described later. Cannot be secured sufficiently. Therefore, for Example 12 using the composition 3 for forming a copper film, the operations from casting to main firing were carried out twice to form a copper thin film having a sufficient film thickness.
［比較例５～８］
　比較組成物１～４をそれぞれ使用し、塗布法により銅薄膜を製造した。具体的には、まず、各比較組成物を液晶画面用のガラス基板（Ｅａｇｌｅ　ＸＧ（商品名）：コーニング社製）上にキャストした。その後、５００ｒｐｍで５秒及び２，０００ｒｐｍで２０秒の条件にてスピンコート法によって各比較組成物を塗布した。次いで、ホットプレートを用いて大気中、１００℃で６０秒間乾燥した。乾燥後のガラス基板を、赤外線加熱炉（ＲＴＰ－６（商品名）：アルバック理工社製）を用いてアルゴン雰囲気下、２１０℃で２０分間加熱して本焼成し、銅薄膜を得た。なお、本焼成時のアルゴンのフロー条件は３００ｍＬ／ｍｉｎとし、昇温速度は２１０℃／３０秒とした。 [Comparative Examples 5 to 8]
Comparative compositions 1 to 4 were used, respectively, to produce a copper thin film by a coating method. Specifically, first, each comparative composition was cast on a glass substrate for liquid crystal screen (Eagle XG (trade name): manufactured by Corning). Thereafter, 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 | atmosphere at 100 degreeC for 60 second using the hotplate. The dried glass substrate was baked by heating at 210 ° C. for 20 minutes in an argon atmosphere using an infrared heating furnace (RTP-6 (trade name) manufactured by ULVAC-RIKO) to obtain a copper thin film. In addition, the flow conditions of argon at the time of this baking were 300 mL / min, and the temperature increase rate was 210 degreeC / 30 second.
＜評価＞
［表面抵抗値の測定］
　抵抗率計（ロレスタＧＰ（商品名）：三菱化学アナリテック社製）を使用し、実施例１０～１８及び比較例５～８で製造したガラス基板上の各銅薄膜の表面抵抗値を測定した。測定した表面抵抗値を表４に示す。 <Evaluation>
[Measurement of surface resistance]
Using a resistivity meter (Loresta GP (trade name): manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the surface resistance value of each copper thin film on the glass substrate produced in Examples 10 to 18 and Comparative Examples 5 to 8 was measured. . Table 4 shows the measured surface resistance values.
Figure JPOXMLDOC01-appb-I000013
Figure JPOXMLDOC01-appb-I000013
　表４に示すように、比較例５～８では２１０℃で焼成したが、導電性を示す銅薄膜を形成することができなかった。これに対して、実施例１０～１８では、１６０℃で焼成しても電気特性の良好な銅薄膜が形成されたことが確認できた。以上より、実施例１～９の銅膜形成用組成物を用いれば、２００℃未満の低温で焼成した場合であっても電気特性の良好な銅膜を形成可能であることが確認された。 As shown in Table 4, in Comparative Examples 5 to 8, firing was performed at 210 ° C., but a copper thin film exhibiting conductivity could not be formed. On the other hand, in Examples 10 to 18, it was confirmed that a copper thin film with good electrical characteristics was formed even when baked at 160 ° C. From the above, it was confirmed that if the compositions for forming a copper film of Examples 1 to 9 were used, it was possible to form a copper film with good electrical characteristics even when fired at a low temperature of less than 200 ° C.

Claims (4)

  1. 　ギ酸銅又はその水和物０．１～３．０モル／ｋｇと、下記一般式（１）で表されるジオール化合物と、下記一般式（２）で表されるピペリジン化合物と、を含有し、
    　前記ギ酸銅又はその水和物の含有量を１モル／ｋｇとした場合に、前記ジオール化合物を０．１～６．０モル／ｋｇの範囲で含有し、前記ピペリジン化合物を０．１～６．０モル／ｋｇの範囲で含有することを特徴とする銅膜形成用組成物。
    Figure JPOXMLDOC01-appb-I000001
    （前記一般式（１）中、Ｒ1及びＲ2は、各々独立に水素原子、メチル基、又はエチル基を表す）
    Figure JPOXMLDOC01-appb-I000002
    （前記一般式（２）中、Ｒ3は、メチル基又はエチル基を表し、ｍは、０又は１を表す）     Copper formate or a hydrate thereof 0.1 to 3.0 mol / kg, a diol compound represented by the following general formula (1), and a piperidine compound represented by the following general formula (2) ,
    When the content of the copper formate or its hydrate is 1 mol / kg, the diol compound is contained in the range of 0.1 to 6.0 mol / kg, and the piperidine compound is contained in the amount of 0.1 to 6 A composition for forming a copper film, which is contained in a range of 0.0 mol / kg.
    Figure JPOXMLDOC01-appb-I000001
    (In the general formula (1), R 1 and R 2 each independently represents a hydrogen atom, a methyl group, or an ethyl group)
    Figure JPOXMLDOC01-appb-I000002
    (In the general formula (2), R 3 represents a methyl group or an ethyl group, m represents 0 or 1)
  2. 　前記ジオール化合物が、２－アミノ－２－メチル－１，３－プロパンジオールである請求項１に記載の銅膜形成用組成物。 The composition for forming a copper film according to claim 1, wherein the diol compound is 2-amino-2-methyl-1,3-propanediol.
  3. 　前記ピペリジン化合物が、２－メチルピペリジンである請求項１又は２に記載の銅膜形成用組成物。 The composition for forming a copper film according to claim 1 or 2, wherein the piperidine compound is 2-methylpiperidine.
  4. 　請求項１～３のいずれか１項に記載の銅膜形成用組成物を基体上に塗布する工程と、
    　前記銅膜形成用組成物が塗布された前記基体を２００℃未満に加熱して銅膜を形成する工程と、を有することを特徴とする銅膜の製造方法。     Applying a copper film-forming composition according to any one of claims 1 to 3 on a substrate;
    And heating the substrate coated with the composition for forming a copper film to below 200 ° C. to form a copper film.
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