JP6815219B2 - Composition for forming a nickel film and a method for producing a nickel film - Google Patents

Description

The present invention relates to a nickel film forming composition for forming a nickel film on various substrates , and a method for producing the same.

The nickel-containing thin film is mainly used for electronic component members such as resistance films and barrier films, recording media members such as magnetic films, and thin film solar cell members such as electrodes.

For example, Patent Document 1 discloses a nickel film-forming coating solution containing nickel formate and an amine-based solvent having a boiling point in the range of 180 ° C. or higher and lower than 300 ° C. as a main solvent. Further, Patent Document 2 contains nickel acetate, nickel formate, an alkanolamine solvent, and a glycol solvent as main components, and is a coating for forming a nickel film in which nickel acetate is 10 parts by mass or more with respect to 100 parts by mass of nickel acetate. The liquid is disclosed. Further, Patent Document 3 discloses a nickel compound-containing solution containing a nickel compound obtained by reacting N-substituted 2-aminoethanols with a nickel salt of an organic acid and using turpineol as a solvent.

International Publication No. 2006/135113 Japanese Unexamined Patent Publication No. 2008-153136 Japanese Unexamined Patent Publication No. 2005-336584

In order to inexpensively produce fine wirings and films in a liquid process using a nickel film-forming composition, 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, provides a nickel film with excellent conductivity, can be converted to a nickel film at low temperature and low energy, has good coatability, and has storage stability. It is desired that it is good and that the film thickness obtained by one application is easy to control. However, when a conventionally known nickel film-forming composition is used, it is necessary to bake the nickel film-forming composition at a temperature of 250 ° C. or higher in order to convert it into a nickel film.

Therefore, an object of the present invention is to obtain a nickel film having sufficient conductivity at a low temperature and with low energy by applying it on a substrate and heat-treating it at a temperature of less than 250 ° C. It is an object of the present invention to provide a phase-free solution-like nickel film forming composition.

As a result of repeated studies in view of the above circumstances, the present inventors have made a composition for forming a nickel film containing a nickel compound such as nickel formate, a specific compound, and an organic solvent for dissolving them in a specific ratio. We have found that the product satisfies the above-mentioned required performance, and have reached the present invention.

That is, the present invention comprises at least one nickel compound selected from nickel formate and its hydrate, a compound represented by the following general formula (I), and a compound represented by the following general formula (II). It contains an organic solvent that dissolves them, and the concentration of the nickel compound is 0.01 to 3.0 mol / kg, and the concentration of the compound represented by the general formula (I) is that of the nickel compound. It is 1.0 to 3.0 times the concentration, and the concentration of the compound represented by the general formula (II) is 0.5 to 3.0 times the concentration of the compound represented by the general formula (I). A composition for forming a nickel film, which is 0.7 times, is provided.

（前記一般式（Ｉ）中、Ｒ¹は、水素原子、メチル基、又はエチル基を表し、Ａは、炭素原子数１〜４のアルカンジイル基を表す）

(In the general formula (I), R ¹ represents a hydrogen atom, a methyl group, or an ethyl group, and A represents an alkanediyl group having 1 to 4 carbon atoms).

（前記一般式（ＩＩ）中、Ｒ²〜Ｒ⁹は、それぞれ独立に、水素原子又はメチル基を表す）

(In the general formula (II), R ^{2 to} R ⁹ independently represent a hydrogen atom or a methyl group).

Further, the present invention comprises a coating step of applying the nickel film forming composition on a substrate and a step of heating the applied nickel film forming composition at 150 to 225 ° C. Provide a manufacturing method.

According to the present invention, a solid phase of fine particles or the like capable of obtaining a nickel film having sufficient conductivity at a low temperature and low energy by applying it on a substrate and heat-treating it at a temperature of less than 250 ° C. A solution-free nickel film-forming composition is provided.

One of the features of the nickel film forming composition of the present invention is that at least one nickel compound selected from nickel formate and its hydrate is used as a precursor (precursor) of the nickel film. The nickel compound used in the composition for forming a nickel film of the present invention may be an anhydrous product, a hydrate, or a combination of two or more types. Specifically, nickel (II) anhydride, nickel (II) formate dihydrate and the like can be used. These nickel compounds may be mixed as they are, or may be mixed as an aqueous solution, an organic solvent solution, or an organic solvent suspension.

The concentration of the nickel compound in the nickel film forming composition of the present invention is 0.01 to 3.0 mol / kg, preferably 1.0 to 2.5 mol / kg. If the concentration of the nickel compound is less than 0.01 mol / kg, a thin film may not be obtained. On the other hand, if the concentration of the nickel compound exceeds 3.0 mol / kg, the stability of the solution decreases. 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 nickel (II) formate is 148.73, 1.0 mol / mol / mol when 148.73 g of nickel (II) formate is contained in 1 kg of the nickel film-forming composition of the present invention. It becomes kg.

The compound represented by the following general formula (I), which is a component constituting the nickel film forming composition of the present invention, exhibits an effect as a solubilizer for nickel formate or nickel formate hydrate. In addition, it has the effect of improving the storage stability of the nickel film-forming composition and improving the conductivity when converted into a film.

（前記一般式（Ｉ）中、Ｒ¹は、水素原子、メチル基、又はエチル基を表し、Ａは、炭素原子数１〜４のアルカンジイル基を表す）

(In the general formula (I), R ¹ represents a hydrogen atom, a methyl group, or an ethyl group, and A represents an alkanediyl group having 1 to 4 carbon atoms).

The concentration of the compound represented by the general formula (I) in the nickel film forming composition of the present invention is 0.1 to 6.0 times the concentration of the nickel compound. For example, when the concentration of the nickel compound is 1 mol / kg, the concentration of the compound represented by the general formula (I) is in the range of 0.1 to 6.0 mol / kg. If the concentration of the compound represented by the general formula (I) is less than 0.1 times the concentration of the nickel compound, the conductivity of the obtained nickel film becomes insufficient. On the other hand, if it exceeds 6.0 times, the coatability deteriorates and a uniform nickel film cannot be obtained. The preferred range is 0.2 to 5.0 times, and 1.0 to 3.0 times is particularly preferable because the stability of the composition is particularly high.

In the general formula (I), examples of the alkanediyl group having 1 to 4 carbon atoms represented by A include methylene, ethylene, propane-1,3-diyl, propane-1,2-diyl, butylene and butane. Examples thereof include -1,3-diyl, butane-2,3-diyl, and butane-1,2-diyl.

Specific examples of the compound represented by the general formula (I) include aminoethanol, N-methylaminoethanol, N-ethylaminoethanol, 3-amino-1-propanol, 3-methylamino-1-propanol, 3-. Ethylamino-1-propanol, 1-amino-2-propanol, 1-methylamino-2-propanol, 1-ethylamino-2-propanol can be mentioned. Among them, it is preferable to use at least one compound selected from the group consisting of aminoethanol, N-methylaminoethanol, and 3-amino-1-propanol, and it is preferable to use N-methylaminoethanol and 3-amino-1-propanol. It is more preferable to use at least one of the above compounds, and it is particularly preferable to use N-methylaminoethanol.

The compound represented by the following general formula (II), which is a component constituting the nickel film forming composition of the present invention, exhibits an effect as a solubilizer for nickel formate or nickel formate hydrate. Further, when used in combination with the compound represented by the general formula (I), it has an effect of improving the storage stability of the nickel film-forming composition and improving the conductivity when converted into a film.

（前記一般式（ＩＩ）中、Ｒ²〜Ｒ⁹は、それぞれ独立に、水素原子又はメチル基を表す）

(In the general formula (II), R ^{2 to} R ⁹ independently represent a hydrogen atom or a methyl group).

The concentration of the compound represented by the general formula (II) in the nickel film forming composition of the present invention is 0.4 to 0.9 times the concentration of the compound represented by the general formula (I). .. For example, when the concentration of the compound represented by the general formula (I) is 1 mol / kg, the concentration of the compound represented by the general formula (II) is in the range of 0.4 to 0.9 mol / kg. is there. It is obtained when the concentration of the compound represented by the general formula (II) is less than 0.4 times and more than 0.9 times the concentration of the compound represented by the general formula (I). The conductivity of the nickel film becomes insufficient. Since the obtained nickel film has good conductivity, it is preferably in the range of 0.5 to 0.7 times.

Specific examples of the compound represented by the general formula (II) include 4-amino-piperidine and 4-amino-2,2,6,6-tetramethylpiperidine. Of these, it is preferable to use 4-amino-2,2,6,6-tetramethylpiperidine.

The organic solvent constituting the nickel film forming composition of the present invention stably dissolves a nickel compound, a compound represented by the general formula (I), a compound represented by the general formula (II), and other components. Anything that can be done is sufficient. The organic solvent may be a single composition or a mixture. Specific examples of the organic solvent used in the composition for forming a nickel film of the present invention include alcohol-based solvents, diol-based solvents, ketone-based solvents, ester-based solvents, ether-based solvents, aliphatic or alicyclic hydrocarbon-based solvents. , Aromatic hydrocarbon solvents, hydrocarbon solvents having a cyano group, other solvents and the like.

Examples of the alcohol-based solvent include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, third 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, Diethyl 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 can be mentioned.

Examples of the diol-based solvent include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 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 thereof include 1,4-cyclohexanedimethanol.

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, methyl cyclohexanone and the like.

Examples of the ester solvent include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, secondary butyl acetate, tertiary butyl acetate, amyl acetate, isoamyl acetate, and tertiary amyl acetate. Phenyl acetate, methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, dibutyl propionate, tributyl propionate, amyl propionate, isoamyl propionate, triamyl propionate, propion Phenyl acid, methyl 2-ethylhexanoate, ethyl 2-ethylhexanoate, propyl 2-ethylhexanoate, isopropyl 2-ethylhexanoate, butyl 2-ethylhexanoate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethoxy Methyl propionate, 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 monobutyl ether Acetic acid, ethylene glycol monosecond butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol monothird butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether Acetic acid, propylene glycol monobutyl ether acetate, propylene glycol monosecond butyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol monothird 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 monosecond butyl ether acetate, butylene glycol monoisobutyl ether acetate, butylene glycol mono third Examples thereof include butyl ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutanoate, ethyl oxobutate, γ-lactone, and δ-lactone.

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.

Examples of the aliphatic or alicyclic hydrocarbon solvent include pentane, hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, decalin, and solvent naphtha.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, simene, tetraline and the like.

Examples of the hydrocarbon solvent having a cyano group include 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-. Examples thereof include dicyanohexane, 1,4-dicyanocyclohexane, and 1,4-dicyanobenzene.

Examples of other organic solvents include N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylformamide and the like.

In the present invention, among the above-mentioned organic solvents, alcohol-based solvents, diol-based solvents, and ester-based solvents are inexpensive, exhibit sufficient solubility in solutes, and further, a silicon substrate, a metal substrate, a ceramics substrate, and the like. It is preferable because it exhibits good coatability as a coating solvent for various substrates such as a glass substrate and a resin substrate. Among them, a solvent having a hydroxyl group in the structure such as an alcohol solvent and a diol solvent is particularly preferable because it has high solubility in a solute.

The content of the above-mentioned organic solvent in the composition for forming a nickel film of the present invention is not particularly limited, and may be appropriately adjusted according to the thickness of the nickel film to be formed and the method for producing the nickel film. Good. For example, when a nickel film is produced by a coating method, 0.01 to 0.01 to 100 parts by mass of nickel formate (converted to nickel formate even in the case of nickel formate hydrate, the same applies hereinafter). It is preferable to use 5,000 parts by mass. If the amount of the organic solvent is less than 0.01 parts by mass, problems such as cracks in the obtained nickel film or deterioration of coatability may occur. Further, as the proportion of the organic solvent increases, the obtained nickel film becomes thinner, so that it is preferable that the amount does not exceed 5,000 parts by mass from the viewpoint of productivity. More specifically, when a nickel film is produced by the 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 nickel formate. When a nickel film is produced by a 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 nickel formate.

The nickel film-forming composition of the present invention may contain any component other than the essential component as long as the effect of the present invention is not impaired. Optional components include additives for imparting stability to the coating liquid composition such as dyes, pigments, color formers, sensitizers, antigelling agents, stabilizers; defoamers, thickeners, etc. Additives for improving the coatability of the coating liquid composition such as a rocking agent and a leveling agent; a film forming aid such as a combustion aid and a cross-linking aid can be mentioned. When these arbitrary components are used, the content thereof is preferably 50% by mass or less, more preferably 20% by mass or less, as a percentage of the entire composition for forming a nickel film.

Examples of the dye include 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3- (p-dimethylaminophenyl) -3- (2-phenyl-3-indrill) phthalide, and 3 -(P-Dimethylaminophenyl) -3- (1,2-dimethyl-3-indrill) 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-Triarylmethane compounds such as tetrachlorophthalide; 4,4-bis (dimethylamino) ) Diphenylmethane-based compounds such as benzhydrinbenzyl ether, N-2,4,5-trichlorophenyl leukooramine; (3) Rhodamine-β-anilinolactam, 3- (N-methyl-N-cyclohexylamino)- 6-Methyl-7-anilinofluorane, 3-diethylamino-7-octylaminofluorane, 3-diethylamino-7- (2-chloroanilino) fluorane, 3-diethylamino-7- (2-fluoroanilino) fluorane, 3-Diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (2,4-dimethylanilino) fluorane, 3-diethylamino-7-dibenzylaminofluorane, 3- Diethylamino-6-chloro-7- (β-ethoxyethylamino) fluorane, 3-diethylamino-6-chloro-7- (γ-chloropropylamino) fluorane, 3- (N-ethyl-N-isoamylamino) -6 -Methyl-7-anilinofluorane, 3- (N-ethyl-N-ethoxyethylamino) -6-methyl-7-anilinofluorane, 3- (N-ethyl-N-tetrahydrofurfurylamino)- 6-Methyl-7-anilinofluorane, 3-dibutylamino-7- (2-chloroanilino) fluorane, 3- (N-ethyl-N-tolylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3-piperidino-6-methyl-7-anilinofluorane , 3- (4- (4- Anilino) Xanthene compounds such as anilino-6-methyl-7-chlorofluorane; thiazine compounds such as benzoyl leucomethylene blue and p-nitrobenzoyl leucomethylene blue; 3-methylspirodinaphthopyrane, 3-ethylspirinaftopyrane , 3-benzylspirodinaphthopyrane, 3-methylnaphtho- (3-methoxybenzo) spiropyran and other spiro-based compounds; others 3,5', 6-tris (dimethylamino) -spiro [9H-fluoren-9,1' -(3'H) -isobenzofuran] -3'-one, 1,1-bis [2- (4-dimethylaminophenyl) -2- (4-methoxyphenyl) ethenyl] -4,5,6,7 −Tetrachloro (3H) isobenzofuran-3-one, 3- (4-diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, 3-( 4-diethylamino-2-methylphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide and the like can be mentioned. These dyes can be used alone or in combination of two or more.

Examples of the pigment include iron oxide pigments, titanium pigments, blue and green inorganic pigments, carbon pigments, azo pigments, phthalocyanine pigments, condensed polycyclic pigments and the like. Examples of iron oxide-based pigments include iron black, red iron oxide, and zinc ferrite pigments. Examples of the titanium-based pigment include titanium oxide, nickel antimony titanium yellow, chromium antimony titanium yellow and the like. Examples of blue and green inorganic pigments include ultramarine blue, cobalt blue, chromium oxide, spinel green and the like. Examples of azo pigments include azo lake pigments such as Lake Red C, Watching Red, and Brilliant Carmine 6B; Hosta Palm Yellow H4G, Nova Palm Yellow H2G, Nova Palm Red HFT, PV Fast Yellow HG, PV Fast Yellow H3R, and PV Bordeaux. Benz imidazolone pigments such as HF3R, PV Carmine HF4C, PV Red HF2B, PV Fast Maroon HMF01, PV Fast Brown HFR; Diarilide pigments such as Diarilide Yellow, Diarilide Orange, Pyrazolone Red, PV Fast Yellow HR; Yellow 8GN, Chromophthal Yellow 6G, Chromophthal Yellow 3G, Chromophthal Yellow GR, Chromophthal Orange 4R, Chromophthal Orange GP, Chromophthal Scarlet RN, Chromophthal Red G, Chromophthal Red BRN, Chromophthal Red BG, Chromophthal Red Condensed azo pigments such as Red 2B and Chromophthal Brown 5R can be mentioned. Examples of the phthalocyanine pigment include phthalocyanine blue and phthalocyanine green. Examples of the condensed polycyclic pigment 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 Chromophtal Orange 2G. Perylene pigments such as perylene red, perylene maroon, perylene carlet; perinone pigments such as perinone orange; dioxazine pigments such as dioxazine violet; anthraquinone pigments such as Philesta Yellow RN, chromoftal red A3B, and slene blue Examples thereof include quinophthalone pigments such as Paliotor Yellow L0960HG. In addition, these pigments can be used alone or in combination of two or more. The amount of the dye and the pigment added is preferably 0.02 to 20% by mass, more preferably 0.1 to 15% by mass, based on the amount of nickel in the nickel film forming composition.

Next, the method for producing the nickel film of the present invention will be described. The method for producing a nickel film of the present invention comprises a coating step of applying the nickel film-forming composition of the present invention described above onto a substrate, and heating the applied nickel film-forming composition to form a nickel film. It has a film forming step of forming. The heating temperature in the film forming step is preferably 150 to 225 ° C. because a nickel thin film having good conductivity can be obtained, and particularly preferably 200 to 225 ° C. If necessary, before the film forming step, a drying step of holding the substrate or the substrate coated with the nickel film forming composition at 50 to 150 ° C. and volatilizing low boiling point components such as an organic solvent is further provided. You may.

The coating methods in the above coating process include 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, and screen. Examples thereof include a printing method, a gravure printing method, an offset printing method, an inkjet method, and brush coating.

Further, in order to obtain the required film thickness, a plurality of steps from the above coating step to an arbitrary step 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.

The atmosphere of the drying step and the film forming step is usually a reducing gas atmosphere or an inert gas atmosphere. A reducing gas atmosphere is preferable because a nickel film having more excellent conductivity can be obtained. Hydrogen can be mentioned as the reducing gas. In addition, examples of the inert gas include helium, nitrogen, and argon. The inert gas may be used as a diluting gas for the reducing gas. Further, in each step, plasma; laser; discharge lamp such as xenon lamp, mercury lamp, mercury xenon lamp, xenon flash lamp, argon flash lamp, deuterium lamp; even if energy other than heat such as various radiations is applied or irradiated. Good.

The nickel film of the present invention can be produced by the above production method. That is, the nickel film of the present invention is a heating product of the above-mentioned composition for forming a nickel film. Applications of the nickel film of the present invention include electrode film, barrier film, resistance film, magnetic film, barrier metal film for liquid crystal, member for thin film solar cell, member for semiconductor device, nanostructure, hydrogen storage alloy, and microelectricity. Mechanical actuators and the like can be mentioned.

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 and the like.

<Preparation of composition for nickel film formation>
[Examples 1 to 3]
The compounds shown in Table 1 were blended so as to have a concentration (mol / kg) of a numerical value in parentheses, and heated to 80 ° C. to obtain nickel film forming compositions 1 to 3. The balance is all ethylene glycol monobutyl ether. The concentration (mol / kg) of each compound shown in Table 1 is the amount in 1 kg of the produced composition.

[Comparative Examples 1 to 9]
The compounds shown in Table 2 were blended so as to have a numerical value (mol / kg) in parentheses, and heated to 80 ° C. to obtain Comparative Compositions 1 to 9. The balance is all ethylene glycol monobutyl ether. The concentration (mol / kg) of each compound shown in Table 2 is the amount in 1 kg of the produced composition.

<Manufacturing of nickel film>
[Examples 4 to 6: Nickel films for evaluation 1 to 3]
Nickel thin films were produced by a coating method using the nickel film forming compositions 1 to 3 respectively. Specifically, first, each nickel film-forming composition was cast on a glass substrate (trade name "Eagle XG", manufactured by Corning Inc.). Then, each nickel film forming composition was applied by a spin coating method under the conditions of 500 rpm for 5 seconds and 2,000 rpm for 20 seconds. It was then dried in the air at 80 ° C. for 30 seconds using a hot plate. The dried glass substrate is heated at 220 ° C. for 30 minutes in an argon atmosphere using an infrared heating furnace (trade name “RTP-6”, manufactured by Advance Riko Co., Ltd.) and fired to form a nickel thin film (nickel film for evaluation). 1-3) were obtained. The flow condition of argon at the time of the main firing was 300 mL / min, and the heating rate was 40 ° C./min.

[Comparative Examples 10 to 18: Comparative Nickel Films 1 to 9]
Nickel thin films (comparative nickel films 1 to 9) were obtained in the same manner as in Examples 4 to 6 described above except that the comparative compositions 1 to 9 were used.

<Evaluation>
[Measurement of surface resistance value]
Each thin film (evaluation nickel film 1-3) on a glass substrate manufactured in Examples 4 to 6 and Comparative Examples 10 to 18 using a resistivity meter (trade name "Loresta GP", manufactured by Mitsubishi Chemical Analytech Co., Ltd.). , The surface resistivity values of the comparative nickel films 1 to 9) were measured. The measured surface resistance values are shown in Table 3.

As shown in Table 3, the evaluation nickel films 1 to 3 were all films having good conductivity, but the comparative nickel films 1 to 9 were all non-conductive films. Among them, the nickel film 2 for evaluation was found to exhibit particularly excellent conductivity.

Claims (4)

At least one nickel compound selected from nickel formate and its hydrate, a compound represented by the following general formula (I), a compound represented by the following general formula (II), and an organic solvent for dissolving them. And, containing,
The concentration of the nickel compound is 0.01 to 3.0 mol / kg.
The concentration of the compound represented by the general formula (I) is 1.0 to 3.0 times the concentration of the nickel compound.
A composition for forming a nickel film, wherein the concentration of the compound represented by the general formula (II) is 0.5 to 0.7 times the concentration of the compound represented by the general formula (I).

(In the general formula (I), R ¹ represents a hydrogen atom, a methyl group, or an ethyl group, and A represents an alkanediyl group having 1 to 4 carbon atoms).

(In the general formula (II), R ^{2 to} R ⁹ independently represent a hydrogen atom or a methyl group). The composition for forming a nickel film according to claim 1, wherein the compound represented by the general formula (I) is at least one of N-methylaminoethanol and 3-amino-1-propanol. The composition for forming a nickel film according to claim 1 or 2, wherein the compound represented by the general formula (II) is 4-amino-2,2,6,6-tetramethylpiperidine. A coating step of applying the nickel film forming composition according to any one of claims 1 to 3 onto a substrate, and
A method for producing a nickel film, comprising a step of heating the applied composition for forming a nickel film at 150 to 225 ° C.