Classifications

• • 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

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• 2013
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