Composition for forming conductive film

Abstract

A composition is provided for forming a conductive film. The composition includes a metal compound, a reducing agent, an ionic compound and/or a polar compound, and a compound having at least one atom selected from a nitrogen atom, a sulfur atom and a phosphorus atom. The composition may be an ink composition for coating on an electronic device.

Claims

1. A composition for forming a conductive film, comprising a metal compound, a reducing agent, an ionic compound and/or a polar compound, and a compound having at least one atom selected from the group consisting of a nitrogen atom, a sulfur atom and a phosphorus atom, wherein a molecular weight of the ionic compound and/or polar compound is 1000 or more, and the ionic compound and/or polar compound comprises a constitutional unit represented by the following formula (XI): ##STR00045## wherein Ar.sup.2 represents a (n.sup.2+2)-valent aromatic group and the (n.sup.2+2)-valent aromatic group may have a substituent, R.sup.2 represents a direct bond or a (m.sup.2+1)-valent group, X.sup.2 represents a group comprising an ionic group or a polar group, and m.sup.2 and n.sup.2 represent each independently an integer of 1 or more, and when R.sup.2 is a direct bond, m.sup.2 is 1, and when there are a plurality of R.sup.2, they may be the same or different, and when there are a plurality of X.sup.2, they may be the same or different, and when there are a plurality of m.sup.2, they may be the same or different, wherein the compound having at least one atom selected from the group consisting of a nitrogen atom, a sulfur atom and a phosphorus atom is selected from the group consisting of an amine compound, a nitrogen-containing heterocyclic compound, a sulfide compound, a thiol compound, a sulfur-containing heterocyclic compound, a sulfoxide compound and a phosphine compound, wherein the amine compound is methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, 3,7-dimethyloctylamine, laurylamine, cyclopentylamine, dicyclopentylamine, cyclohexylamine, dicyclohexylamine, ditrifluoromethylamine, phenylamine, diphenylamine, alkoxyphenylamine in which the alkoxy group has 1 to 12 carbon atoms, di(alkoxyphenyl)amine in which the alkoxy groups have 1 to 12 carbon atoms, di(alkylphenyl)amine in which the alkyl groups have 1 to 12 carbon atoms, 1-naphthylamine, 2-naphthylamine, pentafluorophenylamine, pyridylamine, pyridazinylamine, pyrimidylamine, pyrazylamine, triazylamine, phenyl-alkylamine in which the alkyl group has 1 to 12 carbon atoms, alkoxyphenyl-alkylamine in which the alkoxy group and the alkyl group have 1 to 12 carbon atoms, alkylphenyl-alkylamine in which the alkyl groups have 1 to 12 carbon atoms, di(alkoxyphenyl-alkyl)amine in which the alkoxy groups and the alkyl groups have 1 to 12 carbon atoms, di(alkylphenyl-alkyl)amine in which the alkyl groups have 1 to 12 carbon atoms, 1-naphthyl-alkylamine in which the alkyl group has 1 to 12 carbon atoms, 2-naphthyl-alkylamine in which the alkyl group has 1 to 12 carbon atoms, ethanolamine, propanolamine, 1,2-ethylenediamine, tetraethylenediamine or phenylenediamine, and wherein the nitrogen-containing heterocyclic compound is pyridine, quinoline, 1,2-diazine, 1,3-diazine, 1,4-diazine, 1,3,5-triazine, pyrrole, pyrazole, imidazole, oxazole, thiazole, oxadiazole, thiadiazole or azadiazole.

2. The composition for forming a conductive film according to claim 1, wherein the metal constituting said metal compound is gold, silver or copper.

3. The composition for forming a conductive film according to claim 1, wherein said metal compound is a metal carboxylate.

4. The composition for forming a conductive film according to claim 1, wherein said reducing agent is an alcohol.

5. The composition for forming a conductive film according to claim 1, wherein an amount of said ionic compound and/or polar compound is 0.1 to 30 parts by weight with respect to 100 parts by weight of said metal compound.

6. The composition for forming a conductive film according to claim 1, wherein said ionic compound and/or polar compound is an ionic compound.

7. The composition for forming a conductive film according to claim 1, wherein said compound having a nitrogen atom is an amine compound.

8. The composition for forming a conductive film according to claim 1, wherein said compound having a sulfur atom is a sulfide compound.

9. The composition for forming a conductive film according to claim 1, wherein the composition is an ink composition.

10. The composition for forming a conductive film according to claim 6, wherein said compound having a nitrogen atom is an amine compound.

11. The composition for forming a conductive film according to claim 6, wherein said compound having a sulfur atom is a sulfide compound.

12. A method of producing a conductive film, comprising a step of coating the ink composition according to claim 9 on a substrate and a step of reducing said metal compound by heating the resultant coated film.

13. The method of producing a conductive film according to claim 12, wherein the temperature of heating said coated film is 200° C. or lower.

14. A conductive film formed by the method of producing a conductive film according to claim 12, and comprising an ionic compound and/or a polar compound.

15. An electronic device, equipped with the conductive film according to claim 14.

16. The electronic device according to claim 15, wherein said conductive film is a cathode and/or an anode.

Description

EXAMPLES

(1) The present invention will be illustrated specifically by examples and comparative examples below, but the present invention is not limited to them.

(2) The surface resistance (Ω/□) of the conductive film was measured using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, Loresta GP MCP-T610 type).

Synthesis Example 1

Synthesis of Ionic Compound P-1

(3) 2,7-dibromo-9-fluorenone (52.5 g), ethyl salicylate (154.8 g) and mercaptoacetic acid (1.4 g) were added into a 300 mL flask, the gas in the flask was purged with a nitrogen gas. To this was added methanesulfonic acid (630 mL), and the mixture was stirred at 75° C. overnight. The resultant mixture was left to cool, and added into ice water and stirred for 1 hour. The resultant solid was separated by filtration, and washed with heated acetonitrile. The washed solid was dissolved in acetone, a solid was re-crystallized from the resultant acetone solution, and separated by filtration.

(4) The solid obtained above (62.7 g), 2-[2-(2-methoxyethoxyl)ethoxy]-p-toluenesulfonate (86.3 g), potassium carbonate (62.6 g) and 1,4,7,10,13,16-hexaoxacyclooctadecane (referred to also as “18-crown-6” in some cases) (7.2 g) were dissolved in N, N-dimethylformamide (referred to as “DMF” in some cases) (670 mL), the resultant solution was transferred into a flask and stirred at 105° C. overnight. The resultant mixture was left to cool to room temperature, and added into ice water and stirred for 1 hour.

(5) To the resultant reaction solution was added chloroform (300 mL) and liquid separation and extraction were performed, and the resultant organic phase was concentrated, to obtain 2,7-dibromo-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxyl)ethoxy]ethoxy]phenyl]-fluorene (compound D) (51.2 g).

(6) ##STR00041##

(7) A nitrogen gas atmosphere was prepared in a flask, then, the compound D (15 g), bis(pinacolato)diboron (8.9 g), [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) dichloromethane complex (0.8 g), 1,1′-bis(diphenylphosphino)ferrocene (0.5 g), potassium acetate (9.4 g) and dioxane (400 mL) were added, heated at 110° C., and refluxed with heating for 10 hours. After left to cool, the resultant reaction solution was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was washed with methanol three times, dissolved in toluene, to the resultant solution was added activated carbon and the mixture was stirred. Thereafter, filtration was performed, and the resultant filtrate was concentrated under reduced pressure, to obtain 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-bis[3-ethoxycarbonyl-4-[2-[2-(2-methoxyethoxyl)ethoxy]ethoxy]phenyl]-fluorene (compound E) (11.7 g).

(8) ##STR00042##

(9) An inert gas atmosphere was prepared in a flask, then, the compound D (0.55 g), the compound E (0.61 g), triphenylphosphinepalladium (0.01 g), methyl trioctyl ammonium chloride (manufactured by Sigma Aldrich, trade name Aliquat336 (registered trademark)) (0.20 g) and toluene (10 mL) were added, and heated at 105° C. Into the resultant reaction solution, a 2M sodium carbonate aqueous solution (6 mL) was dropped, and the mixture was refluxed for 8 hours. To the resultant reaction solution was added 4-tert-butylphenylboronic acid (0.01 g) and the mixture was refluxed for 6 hours. Thereafter, to this was added a sodium diethyldithiacarbamate aqueous solution (10 mL, concentration: 0.05 g/mL) and the mixture was stirred for 2 hours. The resultant mixed solution was dropped into methanol (300 mL) and the mixture was stirred for 1 hour, then, the deposited precipitate was filtrated, dried under reduced pressure for 2 hours, and dissolved in tetrahydrofuran (20 mL). The resultant solution was dropped into a mixed solvent of methanol (120 mL) and a 3 wt % acetic acid aqueous solution (50 mL) and the mixture was stirred for 1 hour, then, the deposited precipitate was filtrated, and dissolved in tetrahydrofuran (20 mL). The resultant solution was dropped into methanol (200 mL) and the mixture was stirred for 30 minutes, then, the deposited precipitate was filtrated, to obtain a solid.

(10) The resultant solid was dissolved in tetrahydrofuran, and purified by passing through an alumina column and a silica gel column. The tetrahydrofuran solution recovered from the column was concentrated, then, dropped into methanol (200 mL), and the deposited solid was filtrated, and dried. The yield of the resultant poly[9,9-bis[3-ethoxycarbonyl-4-bis[2-[2-(2-methoxyethoxyl)ethoxy]ethoxy]phenyl]-fluorene] (compound F) was 520 mg.

(11) The compound F had a polystyrene-equivalent number-average molecular weight of 5.2×10.sup.4. The compound F is composed of a constitutional unit represented by the following formula, according to the result of NMR.

(12) ##STR00043##

(13) The compound F (200 mg) was placed in a 100 mL flask, and the gas in the flask was purged with a nitrogen gas. Thereafter, to this were added tetrahydrofuran (20 mL) and ethanol (20 mL), and the resultant mixture was heated up to 55° C. Thereafter, an aqueous solution prepared by dissolving cesium hydroxide (200 mg) in water (2 mL) was added to this, and the mixture was stirred at 55° C. for 6 hours. The resultant mixture was cooled down to room temperature, then, the reaction solvent was distilled off under reduced pressure. The resultant solid was washed with water, and dried under reduced pressure, to obtain a pale yellow solid (150 mg, cesium salt of compound F, hereinafter, referred to as “ionic compound P-1”). It was confirmed according to the NMR spectrum that a signal derived from an ethyl group at an ethyl ester portion in the compound F disappeared completely. The ionic compound P-1 is composed of a constitutional unit represented by the following formula.

(14) ##STR00044##

(15) The polystyrene-equivalent number-average molecular weight of the ionic compound P-1 was identical to that of the compound F.

Example 1

Fabrication of Conductive Film F-1

(16) With respect to 1.0 part by weight of silver acetate, 0.1 part by weight of the ionic compound P-1 (namely, 10 parts by weight with respect to 100 parts by weight of silver compound), 0.5 parts by weight of ethylene glycol (corresponding to reducing agent), 1.0 part by weight of 1,2-ethylenediamine (EDA) and 10.0 parts by weight of 1-butanol were mixed, to prepare an ink composition for forming a conductive film.

(17) The resultant ink composition was spin-coated on a glass substrate. The resultant glass substrate was heated at 200° C. in air for 10 minutes to evaporate the solvent, then, cooled down to room temperature, to obtain a conductive film F-1 having a thickness of about 200 nm.

Comparative Example 1

Fabrication of Conductive Film FS-1

(18) A conductive film FS-1 was obtained in the same manner as in Example 1 excepting that the ionic compound P-1 was not used in Example 1.

Example 2

Fabrication of Conductive Film F-2

(19) A conductive film F-2 was obtained in the same manner as in Example 1 excepting that methanol was used instead of 1-butanol in Example 1.

Example 3

Fabrication of Conductive Film F-3

(20) A conductive film F-3 was obtained in the same manner as in Example 2 excepting that tetrahydrothiophene (THT) was used instead of 1,2-ethylenediamine in Example 2.

Comparative Example 2

Fabrication of Conductive Film FS-2

(21) The same operation as in Example 3 was conducted excepting that the ionic compound P-1 was not used in Example 3, to obtain no conductive film FS-2.

Example 4

Fabrication of Conductive Film F-4

(22) A conductive film F-4 was obtained in the same manner as in Example 2 excepting that 1.0 part by weight of 1,2-ethylenediamine and 1.0 part by weight of tetrahydrothiophene were used instead of 1.0 part by weight of 1,2-ethylenediamine in Example 2.

(23) [Evaluation of Conductive Film]

(24) The surface resistances of the conductive films F1 to 4 and the conductive films FS 1 to 2 obtained above were measured. The results are shown in Table 1.

(25) TABLE-US-00001 TABLE 1 Ionic Surface Conductive compound Other resistance film P-1 components (Ω/□) Example 1 F-1 use EDA 14 Comparative FS-1 nonuse EDA 122 Example 1 Example 2 F-2 use EDA 15 Example 3 F-3 use THT 2.5 Comparative FS-2 nonuse THT Film Example 2 formation is impossible Example 4 F-4 use EDA and 27 THT

(26) As apparent from Table 1, the conductive films formed from the compositions for forming a conductive film of the present invention are excellent in electric conductivity because of small surface resistance. The composition for forming a conductive film containing the ionic compound P-1 is excellent also in film-formability. From these results, the conductive films formed from the compositions for forming a conductive film of the present invention are useful for formation of a conductive film such as an electrode and the like in an electronic device.

INDUSTRIAL APPLICABILITY

(27) According to the present invention, a composition for forming a conductive film, which is useful for formation of a conductive film excellent in electric conductivity can be provided. According to a preferable embodiment of the present invention, a composition for forming a conductive film excellent in film-formability can be provided. Further, according to the present invention, a method of producing a conductive film using the composition and a conductive film produced by this production method can be provided. The conductive film formed from the composition for forming a conductive film of the present invention can be used particularly suitably as a conductive film in an electronic device because of inclusion of an ionic compound and/or a polar compound.