JP2008174392A - Method of manufacturing ceramic film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a ceramic film by which the film which is flat and smooth and has excellent characteristics is obtained in the manufacture of the ceramic film by a wet coating method using a ceramic fine particle. <P>SOLUTION: The method of manufacturing the ceramic film by which the ceramic film is formed by applying a coating liquid composition on a base material and heating and firing to carry out wet coating and firing includes a step for applying the coating liquid composition (A) obtained by dispersing ceramic particles in a dispersion medium on the base material, drying and firing and applying a coating liquid composition (B) obtained by dissolving an organic acid metal derivative on the resultant dried and fired based material as the outermost layer and firing. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a ceramic thin film on a substrate, and more particularly to a method for producing a ceramic film having improved smoothness and electrical characteristics by applying and firing a precursor composition by wet coating.

  Functional ceramic films such as conductors, superconductors, ferroelectrics, high dielectrics, dielectrics, piezoelectrics, pyroelectrics, etc. are being studied for various applications. In particular, it is used for electronic members of electronic parts such as high-dielectric capacitors, ferroelectric capacitors, gate insulating films, barrier films, capacitors, piezoelectric elements and the like that apply the characteristics of dielectric characteristics.

  Examples of the method for producing the film include a MOD method, a sol-gel method, a method in which a dispersion of ceramic particles is applied and then fired, a CVD method, an ALD method, and the like. For thin films with relatively low processing accuracy, wet coating methods such as the sol-gel method, MOD method, and the method of firing after applying a dispersion of ceramic particles are the preferred methods because of low production costs and easy film formation. As raw materials for the films used in these, metal alkoxide compounds, organic acid metal salts, and ceramic fine particles are used.

  For example, Patent Document 1 discloses a method for producing a ceramic thin film using a dispersion obtained by mixing an organometallic sol-gel solution and finely divided ceramic.

Further, Patent Document 2 discloses that a polycrystalline metal oxide is obtained by dispersing a fine powder particle of a metal oxide in a sol-gel liquid in which an organic metal compound, a metal alkoxide, or an organic acid salt and an organic solvent are mixed. A method of manufacturing a thin film is disclosed.

  Further, Patent Document 3 discloses a metal oxide ultrafine particle dispersion obtained by mixing a titanium composite metal oxide ultrafine particle dispersion solution obtained by hydrolysis in a microemulsion with a MOD solution for the same type of titanium composite metal oxide. A solution is disclosed, and as a MOD solution, a solution composed of n-barium butyrate, titanium isopropoxide, isoamyl butyrate, and 2,4-pentadione is disclosed.

Further, Patent Document 4 has a perovskite structure represented by ABO ₃ (A is Ba, Sr, Ca, Pb, Li, K, Na, B is Ti, Zr, Nb, Ta, Fe). Disclosed is a liquid composition in which ferroelectric oxide particles that are plate-like or needle-like crystals having a primary particle diameter of 100 nm or less are dispersed and a soluble metal compound that forms a ferroelectric oxide by heating is dissolved. As soluble metal compounds, inorganic salts such as nitrates, organic acid salts such as ethyl hexanoate, organometallic complexes such as acetylacetone complex, and metal alkoxides are disclosed.

  Patent Document 5 discloses an organic acid titanium compound represented by the general formula (I), which is stable in a coating pyrolysis method such as titanium oxide, P (L) ZT ferroelectric, and the like. It is disclosed that it is a material, and Patent Document 6 discloses a method for producing lead zirconate titanate mixed with an organic acid salt of titanium.

  However, those using ceramic particles in the wet coating method have insufficient smoothing of the resulting film, and may affect the next step of stacking layers. In addition, film characteristics such as electrical characteristics have a problem that the expected characteristics are not exhibited.

Japanese Patent Laid-Open No. 11-502262 (especially claims 1, 4, 5) Japanese Patent Laying-Open No. 2005-213105 (particularly, claims 1, 5 and paragraphs [0018] [0021]) Japanese Patent Laying-Open No. 2005-247632 (particularly, claim 1, paragraph [0080]) Republished WO 2004/097854 (especially claim 1, page 5, lines 30-37) JP-A-5-230079 (in particular, claim 1, [0007]) JP-A-5-58636 (in particular, claim 1, [0012])

Accordingly, an object of the present invention is to provide a method for producing a ceramic film which can obtain a smooth and good film in the production of a ceramic film by a wet coating method using ceramic fine particles.

  As a result of repeated studies, the present inventors applied the coating solution composition obtained by dissolving the organic acid metal derivative in the uppermost layer of the film produced using the coating solution composition containing fine particles. The inventors have found that the problem can be solved, and have reached the present invention.

That is, the present invention is a wet coating method in which a coating liquid composition is applied onto a substrate and then heated and fired to form a ceramic film, and a method for producing a film by firing, in which ceramic particles are dispersed in a dispersion medium. Applying the coating composition (B) obtained by dissolving the organic acid metal derivative in the uppermost layer on the coated substrate obtained by coating the coating composition obtained by applying the coating composition (A) on the substrate and drying and / or firing. A method for producing a ceramic film by a firing step is provided.

  According to the present invention, it is possible to provide a ceramic thin film having a smooth surface, and in particular, it is possible to supply a film having good characteristics in a metal oxide.

The kind of ceramic formed by the method of the present invention is not particularly limited. Examples thereof include oxides, nitrides, carbides, oxynitrides, oxycarbides, and nitrides of one or more metal elements or metalloid elements. The present invention is suitable for forming a metal oxide film, indium oxide, tin-added indium oxide (ITO), tin oxide, titanium oxide, zirconium oxide, hafnium oxide, vanadium oxide, niobium oxide, tantalum oxide, titanium. Barium oxide (BTO), strontium titanate (STO), barium strontium titanate (BST), lead titanate (PT), lead zirconate (PZ), lead zirconate titanate (PZT), lead niobium titanate, Niobium-doped lead zirconate titanate (PNZT), lanthanum-doped lead zirconate titanate (PLZT), bismuth titanate (BTO), lanthanum-doped bismuth titanate (LBTO), neodymium-doped bismuth titanate, niobium-doped bismuth titanate, Silicon-hafnium oxide, aluminum-hafnium oxide, B-tantalum oxide, lithium niobate, potassium niobate, lithium lithium niobate, potassium sodium niobate, bismuth niobate, bismuth tantalate, bismuth strontium niobate, bismuth barium niobate, bismuth strontium tantalate, bismuth tantalate Barium, bismuth niobium tantalate, bismuth strontium niobium tantalate, bismuth barium niobium tantalate, bismuth strontium barium niobium tantalate, titanium-doped tantalum oxide, titanium-doped niobium oxide, yttrium-barium-copper oxide, yttrium-barium-copper oxide (Yttrium) -lanthanoid-barium-copper oxide, bismuth-strontium in which part or all of the yttrium site of the product is substituted with a lanthanoid element -Application to optical glass film, hard coating film, catalyst film, insulator, dielectric, high dielectric, ferroelectric, oxide superconductor, piezoelectric, pyroelectric, etc. using calcium-copper oxidation Is possible. Since the production method of the present invention has the characteristic that the smoothness of the obtained film is excellent, it is effective in applications where a further film needs to be formed on the obtained film. For example, it can be suitably used as a method for forming functional ceramics for electronic materials comprising an oxide film containing a Group 4 metal.

The coating liquid composition (A) containing the ceramic particles according to the present invention will be described.
The coating liquid composition (A) contains ceramic particles as a constituent material of the film, and the ceramic particles are dispersed in a fluid dispersion medium such as water, an organic solvent, or a mixture of water and an organic solvent. It is a coating solution. The coating liquid composition (A) may contain one or more metal compounds that are soluble in the dispersion medium as a constituent material of the film, and may include thickeners, thixotropic agents, leveling agents, You may contain additives, such as a foaming agent and a dispersion stabilizer. The composition of the above components in the coating composition (A) according to the present invention is arbitrary and is selected depending on the coating property, production efficiency, and the like. A preferable composition is 100 to 10,000 parts by weight of the dispersion medium, 0 to 1000 parts by weight of the metal compound soluble in the dispersion medium, and 0 to 100 parts by weight of the additive with respect to 100 parts by weight of the ceramic particles.

  The composition of the ceramic particles may be the same as that of the ceramic film to be formed, or may constitute a part thereof. For example, when the ITO transparent conductive film is formed, the composition of the ceramic particles may be ITO or indium oxide. When indium oxide is used, the supply source to the tin film is a metal compound that may be contained in the coating liquid composition (A). However, unless there is a special reason, the ceramic particle composition having the same composition as the desired ceramic film is generally superior in both cost and performance. The ceramic particles may be surface-modified in order to maintain dispersibility.

  The average particle size of the ceramic particles according to the present invention is preferably 5 to 500 nm, and more preferably 10 to 100 nm, from the viewpoints of dispersibility and film productivity. When the average particle size becomes small, the film thickness obtained in a single coating process becomes small, and in the case of producing a film of the order of μm, the number of times of overcoating increases and the productivity is not good. When the average particle size is increased, the dispersion stability in the dispersion medium is deteriorated, and there is a tendency that problems such as precipitation occur.

  Examples of the organic solvent constituting the dispersion medium used in the coating liquid composition (A) include alcohol solvents, polyol solvents, ketone solvents, ester solvents, ether solvents, aliphatic or alicyclic hydrocarbons. Examples thereof include a solvent, an aromatic hydrocarbon solvent, a hydrocarbon solvent having a cyano group, and other solvents. These may be used alone or in combination of two or more.

  Examples of alcohol solvents include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, tertiary pentanol, Hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcycloheptanol, benzyl alcohol 2-methoxyethyl alcohol, 2-butoxyethyl alcohol, 2- (2-methoxyethoxy) ethanol, 2- (N, N-dimethylamino) ethanol, 3- (N, N- Methylamino) propanol.

  Examples of polyol solvents 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, 1, 4-cyclohexanedimethanol etc. are mentioned.

  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.

  Examples of ester solvents include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, 2 butyl acetate, 3 butyl acetate, amyl acetate, isoamyl acetate, 3 amyl acetate, and phenyl acetate , Methyl propionate, ethyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, 2 butyl propionate, 3 butyl propionate, amyl propionate, isoamyl propionate, 3 amyl propionate, phenyl propionate , Methyl lactate, ethyl lactate, methyl methoxypropionate, methyl ethoxypropionate, ethyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl Ether ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol mono second butyl ether acetate, ethylene glycol monoisobutyl ether acetate, ethylene glycol mono third Butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol mono secondary Tyl ether acetate, propylene glycol monoisobutyl ether acetate, propylene glycol mono tertiary 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-secondary butyl ether acetate, butylene glycol mono-isobutyl ether acetate, butylene glycol mono-tert-butyl ether acetate, methyl acetoacetate, ethyl acetoacetate, methyl oxobutanoate, ethyl oxobutanoate, γ-lactone, δ-lactone, etc. Can be mentioned.

  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, cymene, and tetralin.

  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-dicyanohexane. 1,4-dicyanocyclohexane, 1,4-dicyanobenzene and the like.

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

  The organic solvent may be selected from those that are easy to disperse ceramic particles and that exhibit sufficient solubility in a soluble metal compound described later and that are easy to use as a coating solvent. Among the above organic solvents, alcohol solvents exhibit good coating properties as coating solvents for various substrates such as silicon substrates, metal substrates, ceramic substrates, glass substrates, and resin substrates, and have good dispersibility of ceramic particles. Therefore, 1-butanol is more preferable. Moreover, when using a mixed solvent, the thing which has butanol as a main component is preferable, and what uses 50 mass% or more of 1-butanol is more preferable.

  Soluble metal compounds that may be contained in the coating liquid composition (A) according to the present invention include metal alkoxide compounds, organic acid metal derivatives, β-diketone complexes, β-ketoester complexes, nitrates, sulfates, and hydroxides. And metal atoms constituting these include group 1 elements such as lithium, sodium, potassium, rubidium and cesium, group 2 elements such as beryllium, magnesium, calcium, strontium and barium, scandium and yttrium. Lanthanoid elements (lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), group 3 elements such as actinoid elements, titanium, zirconium Group 4 elements of Um, Hafnium, Group 5 elements of vanadium, niobium, tantalum, Group 6 elements of chromium, molybdenum, tungsten, Group 7 elements of manganese, technetium, rhenium, Group 8 elements of iron, ruthenium, osmium, cobalt, Rhodium, iridium group 9 element, nickel, palladium, platinum group 10 element, copper, silver, gold group 11 element, zinc, cadmium, mercury group 12 element, aluminum, gallium, indium, thallium group 13 element, Germanium, tin, lead group 14 elements, arsenic, antimony, bismuth group 15 elements, and polonium group 16 elements.

  Examples of the alcohol constituting the metal alkoxide include methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, 2-butanol, tertiary butanol, pentanol, isopentanol, 2-pentanol, neopentanol, Tertiary pentanol, hexanol, 2-hexanol, heptanol, 2-heptanol, octanol, 2-ethylhexanol, 2-octanol, cyclopentanol, cyclohexanol, cycloheptanol, methylcyclopentanol, methylcyclohexanol, methylcyclo Heptanol, benzyl alcohol, 2-methoxyethyl alcohol, 2-butoxyethyl alcohol, 2- (2-methoxyethoxy) ethanol, 2- (N, N-dimethylamino) Examples of the organic acid that constitutes the organic acid metal derivative include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, caprylic acid, and the like, including butanol and 3- (N, N-dimethylamino) propanol. 2-ethylhexanoic acid, pelargonic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, linoleic acid, γ-linolenic acid, linolenic acid, Examples thereof include ricinoleic acid, lactic acid, 12-hydroxystearic acid, acrylic acid, methacrylic acid, cyclohexanecarboxylic acid, trifluoroacetic acid, pentafluoropropionic acid and the like. Β-diketone constituting the β-diketone complex includes acetylacetone and hexane. -2,4-dione, 5-methylhexane-2 4-dione, heptane-2,4-dione, 2-methylheptane-3,5-dione, 5-methylheptane-2,4-dione, 6-methylheptane-2,4-dione, 2,2-dimethyl Heptane-3,5-dione, 2,6-dimethylheptane-3,5-dione, 2,2,6-trimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3, 5-dione, octane-2,4-dione, 2,2,6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione, 2,2-dimethyl-6-ethyloctane -3,5-dione, 2,2,6,6-tetramethyloctane-3,5-dione, 2,9-dimethylnonane-4,6-dione, 2,2,6,6-tetramethyl-3 , 5-nonanedione, 2-methyl-6-e Alkyl-substituted β-diketones such as tildecane-3,5-dione, 2,2-dimethyl-6-ethyldecane-3,5-dione; 1,1,1-trifluoropentane-2,4-dione, 1, 1,1-trifluoro-5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 1,3-diperfluorohexyl Fluorine-substituted alkyl β-diketones such as propane-1,3-dione; 5-methoxypentane-2,4-dione, 2-methyl-6-methoxyheptane-3,5-dione, 1,1,5,5 -Tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, 2,2,6,6-tetramethyl-1- (2-methoxyethoxy) he Ethers such as Tan-3,5-dione substituted β- diketone. Examples of the β- ketoester include acetoacetic esters.

  As the above-mentioned soluble metal compound, there is no loss of metal components in the film due to volatility, the stability of the dissolved state is excellent, and the thickness of the film obtained by one coating can be increased. Derivatives are preferable, aliphatic organic acid metal derivatives having 2 to 18 carbon atoms are more preferable, and aliphatic organic acid metal derivatives having 6 to 12 carbon atoms are more preferable.

The organic acid metal derivative is generally represented by (RCOO) _n M (R is an organic group, M is a metal atom, and n is a valence of the metal atom M). A derivative does not necessarily have this structure and may have the following structure. For example, what is obtained from a monomeric metal compound such as tetrahalide, pentahalide, tetraalkoxide, or pentaalkoxide as a raw material usually has 1 to 6 metal atoms per molecule. Such a product is easy to produce and has good solubility in an organic solvent, and is preferable as an organic acid metal derivative of the coating solution composition of the present invention. The organic acid metal derivative that may be contained in the coating liquid composition (A) according to the present invention and the organic acid metal derivative that is contained in the coating liquid composition (B) described later are not limited to (RCOO) _n M. The following structures are also included.

(In the above chemical formula, M represents titanium, zirconium or hafnium, L represents an organic acid residue, a represents a number of 0 to 4, and b represents 1 or 2.)

(In the above chemical formula, X represents vanadium, niobium, and tantalum, L represents an organic acid residue, and c represents a number of 0 to 2.)

(In the above chemical formula, X represents vanadium, niobium, or tantalum, and L represents an organic acid residue.)

The coating liquid composition (B) according to the present invention will be described.
The coating liquid composition (B) is used for improving the smoothness of the formed ceramic film. The coating liquid composition (B) contains an organic acid metal derivative as a ceramic film precursor, and the organic acid metal derivative is dissolved in a solvent having fluidity such as an organic solvent or a mixture of water and an organic solvent. It is a coating solution. The coating liquid composition (B) may contain thickeners, thixotropic agents, leveling agents, antifoaming agents, and solubilizer additives. The composition of the above components in the coating composition (B) according to the present invention is arbitrary and is selected depending on the coating property, production efficiency, and the like. A preferable composition is 100 to 10000 parts by mass of the solvent and 0 to 100 parts by mass of the additive with respect to 100 parts by mass of the organic acid metal derivative.

  In the coating liquid composition (B), the composition of the organic acid metal derivative is blended so as to have the same composition as the ceramic film to be formed.

  Examples of the organic acid metal derivative contained in the coating liquid composition (B) include those exemplified as the dispersion medium-soluble metal compound of the coating liquid composition (A). As the organic acid metal derivative, an aliphatic organic acid metal derivative having 2 to 18 carbon atoms is preferable, and an aliphatic organic acid metal derivative having 6 to 12 carbon atoms is more preferable.

  In the method for producing a ceramic film of the present invention, a coating liquid composition (A) obtained by dispersing ceramic particles in a dispersion medium is coated on a substrate, dried and / or baked, and then on a coated substrate. This is a method for producing a ceramic film by applying and baking a coating liquid composition (B) in which an organic acid metal derivative is dissolved in the uppermost layer, and coating with the coating liquid composition (A) is repeated one or more times. The coating with the coating liquid composition (B) is repeated once or a plurality of times on the uppermost layer of the obtained film. The coating with the coating liquid composition (B) may be performed only once for the purpose of smoothing the ceramic film and improving the characteristics of the ceramic film. However, it may be performed several times to adjust the thickness of the film. Also good.

  As a coating method of the coating liquid composition, 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, screen printing method, inkjet method Method, brushing and the like.

  Drying in the method for producing a ceramic film of the present invention is a step of removing volatile components such as a dispersion medium and a solvent by heating and evaporating them from the coating film obtained by coating the coating liquid composition. Usually, it is performed at a temperature of 100 to 200 ° C. The baking process in the manufacturing method of this invention is a process of converting the coating film obtained by apply | coating a coating liquid composition into a ceramic film by heating, and is normally performed at the temperature of 350-800 degreeC. In the method for producing a ceramic film of the present invention, drying is not necessarily an essential step, but it is preferable to incorporate a drying step because the resulting ceramic film has good uniformity.

In the method for producing a ceramic film of the present invention, a calcination step of heating at a lower temperature than the firing step can be incorporated after the drying step of drying the solvent in the applied composition, and after the firing step. An annealing step may be incorporated. The temperature in the calcination step is preferably 150 ° C to 600 ° C, more preferably 200 ° C to 400 ° C. The temperature in the annealing step is preferably 450 ° C. to 1200 ° C., more preferably 600 ° C. to 1000 ° C.

  The calcination step and the firing step may be performed under various gas atmospheres for the purpose of promoting film formation and improving the surface state and electrical characteristics of the film. Examples of the gas include oxygen, ozone, water, carbon dioxide, hydrogen peroxide, nitrogen, helium, hydrogen, and argon. Further, energy other than heat, such as plasma or various radiations, may be applied or irradiated.

When the coating with the coating liquid composition (A) and the coating with the coating liquid composition (B) are performed a plurality of times, the above-described application to any step may be repeated a plurality of times. For example, all the steps from application to baking may be repeated a plurality of times, application and drying may be repeated a plurality of times, or application, drying, and calcination may be repeated a plurality of times. The same applies when coating the coating liquid composition (B) after coating with the coating liquid composition (A). After coating with the coating liquid composition (A), drying, calcining, and baking. Any of later may be sufficient.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following examples.
[Production Example] Production of 2-ethylhexanoic acid titanium derivative Under a dry argon gas atmosphere, a reaction flask was charged with 0.5 mol of tetrakis (isopropoxy) titanium and 250 ml of dry toluene, and 2 mol of 2-ethylhexanoic acid was added thereto. The mixture was refluxed for 4 hours. After toluene and low-boiling substances were distilled off from the reaction system at a bath temperature of 135 ° C., the system was further reduced in pressure to 3 to 1 torr to obtain 279 g of a yellow viscous liquid. The following measurement was performed on the obtained yellow liquid.

Elemental analysis (titanium content analysis: quantified as titanium dioxide by ashing method, carbon and hydrogen content: CHN elemental analysis)
Ti; 12.1% by mass, C; 54.9% by mass, H; 8.5% by mass
・ IR measurement and ¹ H-NMR
Confirmed that there is no isopropoxy group that binds to titanium.

[Example 1, Comparative Example 1]
The metal molar ratio of titanium, barium, and strontium in the 2-ethylhexanoate titanium derivative, barium 2-ethylhexanoate, and strontium 2-ethylhexanoate obtained in the above production example was 1: 0.6: 0.4. 1 part by mass of a composition dissolved in 1-butanol so that the titanium content in terms of conversion is 0.4 mol / kg, and the content of TiBa _0.6 Sr _0.4 O ₃ fine particles having an average particle diameter of 50 nm Was mixed with 7 parts by mass of a 1-butanol dispersion having a concentration of 0.4 mol / kg to obtain a coating liquid composition (a-1). In addition, the metal molar ratio of titanium, barium, and strontium in the 2-ethylhexanoic acid titanium derivative, barium 2-ethylhexanoate, and strontium 2-ethylhexanoate obtained in the above production example was 1: 0.6: 0.4. A composition in which 1-butanol was dissolved so that titanium was 0.4 mol / kg in terms of metal was used as a coating liquid composition (b-1).

The coating liquid composition (a-1) was cast on a Si / SiO2 / Ti / Pt laminated substrate and applied by spin coating at 500 rpm for 10 seconds, followed by a drying process at 120 ° C. for 10 minutes, and at 400 ° C. for 15 minutes. The calcination step, a formation step by a baking step at 700 ° C. for 30 minutes, was performed and cooled to room temperature. The coating liquid composition (b-1) is cast on this, spin-coated at 500 rpm for 10 seconds and 2000 rpm for 15 seconds, a drying process at 120 ° C. for 10 minutes, a calcining process at 400 ° C. for 15 minutes, and a baking process at 700 ° C. for 30 minutes. The formation process by a process was performed and the barium strontium titanate film | membrane was obtained. This was designated Example 1.
Also, the coating liquid composition (a-1) was cast on a Si / SiO2 / Ti / Pt laminated substrate and applied by spin coating at 500 rpm for 10 seconds, followed by a drying step at 120 ° C. for 10 minutes at 400 ° C. The formation process by the calcination process for 15 minutes and the baking process for 30 minutes at 700 degreeC was performed, and the barium strontium titanate film | membrane was obtained. This was designated as Comparative Example 1.

About the obtained film, surface crack evaluation by visual observation and optical microscope, film thickness measurement by cross-sectional SEM image, smoothness evaluation of film surface by SEM image, composition analysis by X-ray diffraction and sputtering of Pt electrode on top of thin film, Was used as the upper electrode, and the relative dielectric constant and leakage current were measured by aixACCT TFA 1000 (aixACCT Systems Gmbh). The results are shown in Table 1.

The composition BST in the above table is barium strontium titanate, and so on.

  From Table 1 above, it was confirmed that Example 1 in which the uppermost layer of the film was coated with the coating composition (b-1) was also excellent in smoothness and electrical characteristics.

[Examples 2 and 3]
A 2-ethylhexanoic acid titanium derivative obtained in the above production example was added to a 1-butanol dispersion having an average particle diameter of 50 nm of TiBa _0.6 Sr _0.4 O ₃ fine particles of 0.8 mol / kg, 2- A coating liquid composition in which barium ethylhexanoate and strontium 2-ethylhexanoate were added at a molar ratio of 1: 0.6: 0.4 so that the titanium content was 1.0 mol / kg (a- After applying 2) to the Si / SiO2 / Ti / Pt laminated substrate by bar coater (red: 12 μm standard) or spin coating (500 rpm, 10 seconds), drying step at 120 ° C. for 10 minutes, calcining at 400 ° C. for 15 minutes The process, the baking process for 30 minutes at 700 degreeC, was cooled to room temperature, and the barium strontium titanate film | membrane was formed on Pt layer. The coating liquid composition (b-1) is cast on this, spin-coated at 500 rpm for 10 seconds and 2000 rpm for 15 seconds, a drying process at 120 ° C. for 10 minutes, a calcining process at 400 ° C. for 15 minutes, and a baking process at 700 ° C. for 30 minutes. The formation process by the process was performed to form a barium strontium titanate film. The obtained film was subjected to surface crack evaluation, film thickness measurement, smoothness evaluation, and composition analysis in the same manner as in Example 1. The results are shown in Table 2.

From Table 2 above, barium strontium titanate having a smoothness of the order of 800 to 1000 nm was obtained by the method of the present invention.

Claims (6)

A method for producing a film by applying a coating liquid composition on a substrate and heating and baking to form a ceramic film and a film by baking, wherein the coating liquid composition (A) is obtained by dispersing ceramic particles in a dispersion medium. A ceramic film formed by applying and baking a coating liquid composition (B) obtained by dissolving an organic acid metal derivative on the uppermost layer on a coated substrate obtained by coating on a substrate and drying and / or firing. Production method. The method for producing a ceramic film according to claim 1, wherein the average particle diameter of the ceramic particles in the coating liquid composition (A) is in the range of 10 to 100 nm. The method for producing a ceramic film according to claim 1 or 2, wherein the coating liquid composition (A) contains a metal compound soluble in the dispersion medium. The method for producing a ceramic film according to any one of claims 1 to 3, wherein the organic acid metal derivative contained in the coating liquid composition (B) is an aliphatic organic acid salt derivative having 6 to 12 carbon atoms. The method for producing a ceramic film according to claim 1, wherein the produced ceramic film is a metal oxide film. The method for producing a ceramic film according to any one of claims 1 to 5, wherein the produced ceramic film contains a Group 4 metal oxide film.