WO2012108072A1 - Composition for forming silica-containing coating film for inkjet applications, method for forming silica-containing coating film, semiconductor device, and solar cell system - Google Patents

Abstract

The present invention relates to a composition for forming a silica-containing coating film for inkjet applications, which comprises a silicon compound produced by the hydrolysis/condensation of a compound represented by general formula (I), a solvent and a surface-controlling agent, wherein the solvent comprises a first solvent having a boiling point of 80-160˚C and a second solvent having a boiling point of 180-230˚C and the ratio of the content of the first solvent relative to the total content of the first and second solvents is 0.3-0.7 by mass. In the formula, R¹ represents an organic group having 1-20 carbon atoms; X represents a hydrolysable group; and n represents an integer of 0-2. R¹ _nSiX_4-n … (I)

Description

Silica-based film forming composition for inkjet, method for forming silica-based film, semiconductor device, and solar cell system

The present invention relates to a silica-based film forming composition for inkjet, a method for forming a silica film, a semiconductor device, and a solar cell system.

Silica-based coatings are applied in various fields because they are excellent in insulation, heat resistance, transparency, wear resistance, and the like. For example, in semiconductor devices, it is used as an insulation film between wires, element isolation films and mask materials from the viewpoint of insulation, heat resistance, and barrier properties. In liquid crystal devices, insulation, heat resistance, and transparency are used. From the viewpoint of performance, it is applied as a protective film of the element.

Conventionally, a gas phase growth method and a coating method are known as general methods for obtaining a silica-based film. In the semiconductor field, the gas layer growth method is widely applied and has a feature that a dense silica film can be obtained. However, there are problems such as the need for a special apparatus and an increase in apparatus cost associated with the recent increase in size of the processing substrate. On the other hand, the coating method has features such that film formation can be performed with a relatively simple apparatus and film formation on a large-sized substrate is relatively easy. Examples of the coating method include spin coating, spraying, dipping, roll coating, and screen printing.

By the way, as a method for forming a patterned silica-based film, a photolithography method has become the mainstream. However, patterning by the photolithography method has a drawback that the process is complicated and the cost is high. Therefore, in recent years, an inkjet method has been studied as a method for easily and inexpensively forming a pattern (Patent Document 1). Since the inkjet method can form a desired pattern at a desired position, it is not necessary to form a silica film on the entire surface of the substrate unlike the photolithography method, and the amount of material to be used can be greatly reduced. There is a big merit in terms of environment.

As a method for obtaining an ink jet-compatible silica-based film forming composition, a sol-gel method using alkoxysilane as a raw material is known (Patent Documents 2 and 3).

JP 2001-279134 A JP 2009-239983 A JP 2009-253127 A

However, as described in Patent Document 2, when ethanol or water is used as a solvent, or as described in Patent Document 3, a solvent at 100 ° C. or less may occupy 70 to 90% by weight of the entire composition. In such a case, if the non-ejection and ejection operations are repeated in ink jet drawing, nozzle clogging is likely to occur. In mass production, since such discharge and non-discharge are repeated, the conventional silica-based film-forming composition is not yet sufficient for practical use.

Furthermore, the silica-based film forming composition for ink jet is required to have a characteristic that the pattern at the time of drawing is difficult to bleed when the pattern is drawn using the composition. Here, in order to prevent clogging of the ink jet nozzles even when the operations of non-ejection and ejection are repeated, on the other hand, in order to make it difficult for the pattern during drawing to bleed, the nozzle tip of the silica-based film forming composition for ink jet It is necessary to satisfy both the non-drying property and the quick drying property at the time of pattern drawing. However, it is very difficult to satisfy these conflicting characteristics.

The present invention provides a silica-based film-forming composition for inkjet that can be ejected without causing clogging of inkjet nozzles even when the operations of non-ejection and ejection are repeated, and the pattern at the time of drawing is difficult to bleed, and the composition An object of the present invention is to provide a method for forming a silica-based film using a product, a semiconductor device, and a solar cell system.

In order to solve the above-mentioned problems, the present invention provides a silica-based film-forming composition for inkjet as described in the following (1) and (2), a method for forming a silica-based film as described in (3) below, (4) And the solar cell system described in the following (5).
(1) A silicon compound obtained by hydrolysis / polycondensation (hydrolysis condensation) of a compound represented by the following general formula (I), a solvent, and a surface conditioner, the solvent having a boiling point A mass ratio of the content of the first solvent to the total content of the first solvent and the second solvent, the first solvent having a temperature of 80 to 160 ° C. and the second solvent having a boiling point of 180 to 230 ° C. However, the silica-type film formation composition for inkjets which satisfies the relationship represented by the following conditions A, B, or C.
Condition A: When the boiling point of the first solvent is 80 to 100 ° C., the mass ratio is 0.3 to 0.5.
Condition B: When the boiling point of the first solvent is 100 to 130 ° C., the mass ratio is 0.4 to 0.6.
Condition C: When the boiling point of the first solvent is 130 to 160 ° C., the mass ratio is 0.5 to 0.7.
R ¹ _n SiX _4-n (I)
[Wherein R ¹ represents an organic group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and n represents an integer of 0 to 2. However, when n is 2, a plurality of R ¹ may be the same or different, and when n is 0 to 2, a plurality of X 1 may be the same or different. ]
(2) The composition according to (1), wherein the surface conditioner is a silicone-based surface conditioner.
(3) A process of forming a drawing pattern film by discharging the composition described in (1) or (2) onto a substrate by an inkjet method, and forming a drawing pattern film, and having a pattern by curing the drawing pattern film And a step of obtaining a silica-based film.
(4) A semiconductor device comprising a substrate and a silica-based coating film having a pattern formed on the substrate by the method described in (3).
(5) A solar cell system comprising the semiconductor device according to (4).

According to the present invention, a silica-based film-forming composition for inkjet that can be ejected without causing clogging of inkjet nozzles even when the operations of non-ejection and ejection are repeated, and the pattern at the time of drawing is difficult to bleed, and A method for forming a silica-based film using the composition, a semiconductor device, and a solar cell system are provided.

In addition, the present inventors guess as follows about the reason why the above-described effects are exhibited by the present invention.

In other words, in order to prevent clogging of the inkjet nozzles even when the non-ejection and ejection operations are repeated and to prevent the pattern at the time of drawing from bleeding, the non-drying property at the nozzle tip of the inkjet silica-based film forming composition And quick drying at the time of pattern drawing are required. In order to satisfy these contradictory characteristics, a mixed solvent containing a first solvent that is a low-boiling component and a second solvent that is a high-boiling component is used as the solvent for the silica-based film-forming composition for inkjet. This is very important. And in this mixed solvent, it is extremely possible to adjust each content so that the mass ratio of the content of the first solvent to the total content of the first solvent and the second solvent falls within a specific numerical range. is important. Thereby, it is considered that the non-drying property at the nozzle tip is achieved at a high level mainly by the action of the second solvent, and the quick drying property at the time of drawing is mainly achieved by the action of the first solvent. The solvent contained in the ink-jet silica-based film forming composition of the present invention is such that the mass ratio of the content of the first solvent to the total content of the first solvent and the second solvent is the above-mentioned conditions A to C. One of the above is satisfied. This is based on the knowledge of the present inventors that these conditions are suitable from the viewpoint of compatibility between non-drying at the nozzle tip of the silica-based film-forming composition for inkjet and quick drying at the time of pattern drawing. It is.

Furthermore, it is considered that the effect that the pattern at the time of drawing hardly bleeds is also due to the fact that the silica-based film-forming composition for inkjet contains a surface conditioner. Accordingly, it is considered that bleeding of the drawing pattern is suppressed by controlling the wettability to the substrate and the fluidity of the silica-based resin. More specifically, the bleeding of the drawing pattern is caused by a local increase in ink viscosity or surface due to non-uniform wetting (repelling, etc.) of the ink on the coated object or non-uniform evaporation of the solvent of the ink during ejection. It is thought to be caused by a change in tension. Therefore, the surface conditioner in the present invention is (1) a compound having the action of uniformizing the surface tension of the coating film in the drying process and improving the wettability to the coating object, and (2) evaporation of the solvent from the coating film surface. Is defined as at least one compound selected from compounds having the effect of homogenizing and reducing local viscosity increase and surface tension change.

Hereinafter, preferred embodiments of the present invention will be described in detail.

[Silica-based film-forming composition for inkjet]
The silica-based film-forming composition for inkjet according to this embodiment contains the following components (a) to (c).
(A) Silicon compound obtained by hydrolysis and polycondensation of a compound represented by the following general formula (I) R ¹ _n SiX _4-n (I)
[Wherein R ¹ represents an organic group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and n represents an integer of 0 to 2. However, when n is 2, a plurality of R ¹ may be the same or different, and when n is 0 to 2, a plurality of X 1 may be the same or different. ]
(B) a first solvent having a boiling point of 80 to 160 ° C. and a second solvent having a boiling point of 180 to 230 ° C., the first solvent with respect to the total content of the first solvent and the second solvent The solvent in which the mass ratio of the content satisfies the relationship represented by the following conditions A, B, or C.
Condition A: When the boiling point of the first solvent is 80 to 100 ° C., the mass ratio is 0.3 to 0.5.
Condition B: When the boiling point of the first solvent is 100 to 130 ° C., the mass ratio is 0.4 to 0.6.
Condition C: When the boiling point of the first solvent is 130 to 160 ° C., the mass ratio is 0.5 to 0.7.
(C) Surface conditioner.

Hereinafter, each of the component (a), the component (b), and the component (c) will be described in detail.

(A) Component: Silicon compound The silica-based film-forming composition for ink jet according to this embodiment has a silicon compound obtained by hydrolysis and polycondensation of the compound represented by the general formula (I) as an essential component. .

In the present specification, the “hydrolysis / polycondensation” means that the compound represented by the general formula (I) is hydrolyzed, condensed while dehydrating (H ₂ O), and polymerized. To do.

Examples of X in the general formula (I) include an alkoxy group, a halogen atom, an acetoxy group, an isocyanate group, and a hydroxyl group, and among these, an alkoxy group is preferable. By making X an alkoxy group, the liquid stability of the resulting silicon compound and the halogen concentration in the resulting composition can be suppressed.

When X is an alkoxy group, examples of the alkoxysilane include tetraalkoxysilane represented by the following general formula (I-1), trialkoxysilane represented by the following general formula (I-2), and the following general formula (I Dialkoxysilane represented by -3). An alkoxysilane may be used individually by 1 type, and may be used in combination of 2 or more type.
Si (OR ² ) ₄ (I-1)
[Wherein R ² may be the same or different and each independently represents an alkyl group. ]
R ³ Si (OR ⁴ ) ₃ (I-2)
[Wherein R ³ represents an alkyl group or a phenyl group, the phenyl group may have a substituent, and R ⁴ may be the same or different, and each independently represents an alkyl group. ]
R ⁵ ₂ Si (OR ⁶ ) ₂ (I-3)
[In the formula, R ⁵ may be the same or different, each independently represents an alkyl group or a phenyl group, the phenyl group may have a substituent, and R ⁶ may be the same or different, Each independently represents an alkyl group. ]

In the general formula (I-1), general formula (I-2) and general formula (I-3), the number of carbon atoms of the alkoxy group R (R ² , R ⁴ and R ⁶ ) is not particularly limited, Usually, it has 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms from the viewpoint of availability. Further, R (R ² , R ^4, and R ⁶ ) of the alkoxy group may be one in which a part of hydrogen atoms is substituted with fluorine.

Examples of the tetraalkoxysilane represented by the general formula (I-1) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, and tetrabutoxysilane. Of these, tetraethoxysilane is preferably used in terms of reactivity and reaction by-products.

Examples of trialkoxysilanes represented by the general formula (I-2) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, and ethyltriethoxysilane. , Ethyltri-n-propoxysilane, ethyltri-iso-propoxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltri-n-propoxysilane, propyltri-iso-propoxysilane, butyltrimethoxysilane, butyltriethoxysilane Butyltri-n-propoxysilane, butyltri-iso-propoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltri-n-propoxysilane, phenyltri iso- propoxysilane, and the like. Of these, methyltriethoxysilane, ethyltriethoxysilane, propyltriethoxysilane, and phenyltriethoxysilane are preferably used in terms of reactivity and reaction by-products.

Examples of dialkoxysilanes represented by the general formula (I-3) include dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propoxysilane, dimethyldi-iso-propoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, and diethyldiethoxysilane. -N-propoxysilane, diethyldi-iso-propoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-n-propyldi-n-propoxysilane, di-n-propyldi-iso-propoxy Silane, di-iso-propyldimethoxysilane, di-iso-propyldiethoxysilane, di-iso-propyldi-n-propoxysilane, di-iso-propyldi-iso-propoxysilane, di-n-butyldimethoxysilane, di n-butyldiethoxysilane, di-n-butyldi-n-propoxysilane, di-n-butyldi-iso-propoxysilane, di-sec-butyldimethoxysilane, di-sec-butyldiethoxysilane, di-sec- Butyldi-n-propoxysilane, di-sec-butyldi-iso-propoxysilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, di-tert-butyldi-n-propoxysilane, di-tert- Examples include butyldi-iso-propoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldi-n-propoxysilane, diphenyldi-iso-propoxysilane, and the like.

The alkoxysilanes represented by the general formula (I-1), general formula (I-2) and general formula (I-3) may be used alone or in combination of two or more. Also good. When the alkoxysilanes represented by the general formula (I-1), general formula (I-2) and general formula (I-3) are used in combination of two or more, the mixing ratio is not particularly limited. However, since it is easy to ensure the stability (viscosity stability) of the silica-based film forming composition for inkjet at room temperature and the crack resistance of the silica-based film obtained after inkjet is improved, the general formula (I -1) The molar amount M _{2 of the} trialkoxysilane represented by the general formula (I-2) and the dialkoxy represented by the general formula (I-3) relative to the molar amount M ₁ of the tetraalkoxysilane represented by -1) The ratio (M ₂ + M ₃ ) / M ₁ of the total amount of the silane molar amount M ₃ is preferably 0.1 or more, more preferably 0.5 or more, and 0.8 or more. Highly preferred. From the viewpoint of good wettability with the base substrate, (M ₂ + M ₃ ) / M ₁ is preferably 4.0 or less, more preferably 2.5 or less, and 1.5 or less. It is very preferable that

When the alkoxysilane is hydrolyzed and polycondensed, the component (b) may be used as a solvent, or a solvent other than the component (b) may be used. Solvents used for hydrolysis and polycondensation of alkoxysilane include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-iso-propyl ketone, methyl-n-butyl ketone, methyl-iso-butyl ketone, methyl-n- Pentyl ketone, methyl-n-hexyl ketone, diethyl ketone, dipropyl ketone, di-iso-butyl ketone, trimethylnonanone, cyclohexanone, cyclopentanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, γ-butyrolactone Ketone solvents such as γ-valerolactone;
Ether solvents such as diethyl ether, methyl ethyl ether, methyl propyl ether, di-iso-propyl ether, tetrahydrofuran, methyl tetrahydrofuran, dioxane, dimethyl dioxane;
Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol mono-n Alkylene glycol monoalkyl ether solvents such as butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether;
Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol di-n-propyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl mono-n-propyl ether, diethylene glycol methyl mono-n- Butyl ether, diethylene glycol di-n-propyl ether, diethylene glycol di-n-butyl ether, diethylene glycol methyl mono-n-hexyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol methyl ethyl ether, triethylene glycol Tyl mono-n-butyl ether, triethylene glycol di-n-butyl ether, triethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetradiethylene glycol methyl ethyl ether, tetraethylene glycol methyl mono-n -Butyl ether, diethylene glycol di-n-butyl ether, tetraethylene glycol methyl mono-n-hexyl ether, tetraethylene glycol di-n-butyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-n-propyl ether, propylene glycol Dibutyl ether, dipropylene glycol dimethyl ether Dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol methyl mono-n-butyl ether, dipropylene glycol di-n-propyl ether, dipropylene glycol di-n-butyl ether, dipropylene glycol methyl mono- n-hexyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, tripropylene glycol methyl ethyl ether, tripropylene glycol methyl mono-n-butyl ether, tripropylene glycol di-n-butyl ether, tripropylene glycol methyl mono-n- Hexyl ether, tetrapropylene glycol dimethyl ether, tetrapropylene glycol diethyl ether Alkylene glycol dialkyl ether solvents such as ter, tetradipropylene glycol methyl ethyl ether, tetrapropylene glycol methyl mono-n-butyl ether, tetrapropylene glycol methyl mono-n-hexyl ether, tetrapropylene glycol di-n-butyl ether;
Ethylene glycol methyl ether propionate, ethylene glycol ethyl ether propionate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol-n-butyl ether acetate, propylene glycol methyl ether acetate Alkylene glycol alkyl ether acetate solvents such as propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate;
Methyl acetate, ethyl acetate, propyl acetate, iso-propyl acetate, butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methyl pentyl acetate, 2-acetate Ethylbutyl, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, nonyl acetate, methyl acetoacetate, ethyl acetoacetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether, dipropylene acetate Glycol monomethyl ether, acetic acid dipropylene glycol monoethyl ether, diacetic acid glycol, methoxytriglycol acetate, ethyl propionate, propionate n-buty , Propionic acid iso- amyl, diethyl oxalate, oxalate, di -n- butyl, methyl lactate, ethyl lactate, n- butyl, ester solvents such as lactic acid n- amyl
Pyrrolidinone solvents such as N-methylpyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone;
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol (iso-butanol), 2-butanol (sec-butanol), 2-methyl-2-propanol (tert-butanol), 1 -Pentanol, 2-pentanol, 2-methylbutanol, 2-pentanol, 2-methyl-2-butanol (tert-pentanol), 3-methoxybutanol, 1-hexanol, 2-methylpentanol, 2- Hexanol, 2-ethylbutanol, 2-heptanol, 1-octanol, 2-ethylhexanol, 2-octanol, 1-nonyl alcohol, 1-decanol, 2-undecyl alcohol, trimethylnonyl alcohol, 2-tetradecyl alcohol, 2 -Heptade Alcohol, phenol, cyclohexanol, methylcyclohexanol, alcohol solvents such as benzyl alcohol;
Glycol solvents such as ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol;
Acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylsulfoxide and the like can be mentioned. These are used singly or in combination of two or more.

In addition, when a solvent other than the component (b) is used when hydrolyzing and polycondensing the alkoxysilane, the solvent is removed by distillation after the reaction, and the resulting siloxane resin is used as a silica-based film-forming composition for inkjet. It can be used for the preparation of products.

The amount of the solvent when the general formula (I-1), the general formula (I-2), and the general formulas to (I-3) are hydrolyzed and polycondensed using the above-mentioned solvent is determined depending on the uniformity of the reaction. Therefore, it is preferable that the SiO ₂ equivalent concentration be in the range of 5% by mass to 35% by mass, the lower limit being 10% by mass or more, and the upper limit being 30% by mass or less. .

In addition, when hydrolyzing and polycondensing alkoxysilane, a catalyst can be added to shorten the reaction time and make the reaction uniform. Examples of the catalyst include an acid catalyst, an alkali catalyst, a metal chelate compound, and the like, but it is preferable to use an acid catalyst from the viewpoint of ensuring the stability of the resulting silica-based film-forming composition for inkjet.

Examples of the acid catalyst include organic acids and inorganic acids. Examples of organic acids include formic acid, maleic acid, fumaric acid, phthalic acid, malonic acid, succinic acid, tartaric acid, malic acid, lactic acid, citric acid, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid , Octanoic acid, nonanoic acid, decanoic acid, oxalic acid, adipic acid, sebacic acid, butyric acid, oleic acid, stearic acid, linoleic acid, linolenic acid, salicylic acid, benzenesulfonic acid, benzoic acid, p-aminobenzoic acid, p- Examples include toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid and trifluoroethanesulfonic acid. Examples of inorganic acids include hydrochloric acid, phosphoric acid, nitric acid, boric acid, sulfuric acid, and hydrofluoric acid. Among these, it is particularly preferable to use maleic acid as the organic acid and nitric acid as the inorganic acid. These can be used alone or in combination of two or more.

The amount of catalyst used can be appropriately selected according to the type and amount of alkoxysilane, the type of catalyst, and the like. For example, a tetraalkoxysilane represented by the general formula (I-1), a trialkoxysilane represented by the general formula (I-2), and a dialkoxysilane represented by the general formula (I-3) are used in combination. When an acid catalyst is used as the catalyst, the molar ratio of the tetraalkoxysilane represented by the general formula (I-1) to the total number of moles of the alkoxysilane is represented by A and the trioxide represented by the general formula (I-2). When the molar ratio of alkoxysilane is B and the molar ratio of dialkoxysilane represented by the general formula (I-3) is C, the amount (molar ratio) of the acid catalyst used is [(4A + 3B + 2C) / 3000] to [ The range of (4A + 3B + 2C) / 10] is preferable, and the range of [(4A + 3B + 2C) / 3000] to [(4A + 3B + 2C) / 100] is more preferable. By making the usage-amount of an acid catalyst into the said range, reaction can fully advance and the phenomenon which gelatinizes because reaction advances too much can be suppressed.

In addition, when the alkoxysilane is hydrolyzed / polycondensed, the amount of water to be used can be appropriately selected according to the type and amount of the alkoxysilane used. For example, a tetraalkoxysilane represented by general formula (I-1), a trialkoxysilane represented by general formula (I-2), and a dialkoxysilane represented by general formula (I-3) are used in combination. In this case, the molar ratio of the tetraalkoxysilane represented by the general formula (I-1) to the total number of moles of alkoxysilane is A, the molar ratio of the trialkoxysilane represented by the general formula (I-2) is B, When the molar ratio of the dialkoxysilane represented by the formula (I-3) is C, the amount of water (molar ratio) is preferably in the range of [(4A + 3B + 2C) / 2] to [(4A + 3B + 2C) × 2] The range of [(4A + 3B + 2C) / 2] to [4A + 3B + 2C) × 1] is more preferable. By setting the amount of water within the above range, the reaction can be sufficiently advanced, and the phenomenon of gelation due to excessive progress of the reaction can be suppressed.

The weight average molecular weight (Mw) of the silicon compound as component (a) is preferably from 500 to 20000, more preferably from 500 to 10,000, from the viewpoints of solubility in a solvent and inkjet discharge properties. When the weight average molecular weight is within the above range, the film-formability of the silica-based film and the compatibility between the silicon compound and the solvent can be achieved at a high level. In the present specification, the weight average molecular weight is measured by gel permeation chromatography (hereinafter referred to as “GPC”) and converted using a standard polystyrene calibration curve.

<Measurement of weight average molecular weight>
The weight average molecular weight (Mw) can be measured, for example, by GPC under the following conditions.
(conditions)
Sample: 10 μL of silica-based film forming composition for inkjet
Standard polystyrene: Standard polystyrene manufactured by Tosoh Corporation (molecular weight: 190000, 17900, 9100, 2980, 578, 474, 370, 266)
Detector: manufactured by Hitachi, Ltd., RI-monitor, trade name “L-3000”
Integrator: Hitachi, Ltd., GPC integrator, product name “D-2200”
Pump: Hitachi, Ltd., trade name “L-6000”
Degassing device: Showa Denko Co., Ltd., trade name "Shodex DEGAS"
Column: manufactured by Hitachi Chemical Co., Ltd., trade names “GL-R440”, “GL-R430”, “GL-R420” are used in this order and are used Eluent: Tetrahydrofuran (THF)
Measurement temperature: 23 ° C
Flow rate: 1.75 mL / min Measurement time: 45 minutes

In this embodiment, the content of the component (a) in the silica-based film-forming composition for inkjet is preferably 5 to 35% by mass, and more preferably 5 to 30% by mass. If the content of the component (a) is 5% by mass or more, the film thickness of the silica-based film to be formed is not too thin and has an appropriate thickness. The possibility of being necessary can be reduced. Thereby, it becomes easy to suppress the increase in process time and the occurrence of bleeding of the drawing pattern due to the overlapping drawing. On the other hand, if content of (a) component is 35 mass% or less, there exists a tendency which can make the storage stability of the silica-type film forming composition for inkjets favorable.

(B) Component: Solvent The component (b) according to the present embodiment contains a first solvent having a boiling point of 80 to 160 ° C. and a second solvent having a boiling point of 180 to 230 ° C. content (hereinafter, _{"C 1"} hereinafter.) and the content of the second solvent (hereinafter, _{"C 2"} hereinafter.) the total amount of _(C 1 + _{C 2)} of the _{C 1} to the weight ratio _C 1 / (C ₁ + C ₂ ) is a mixed solvent that satisfies the relationship represented by the following conditions A, B, or C. In the present specification, “boiling point” means a boiling point at normal pressure.
Condition A: When the boiling point of the first solvent is 80 to 100 ° C., 0.3 ≦ C ₁ / (C ₁ + C ₂ ) ≦ 0.5.
Condition B: When the boiling point of the first solvent is 100 to 130 ° C., 0.4 ≦ C ₁ / (C ₁ + C ₂ ) ≦ 0.6.
Condition C: 0.5 ≦ C ₁ / (C ₁ + C ₂ ≦ 0.7 when the boiling point of the first solvent is 130 to 160 ° C.

The first solvent is not particularly limited as long as the boiling point is in the range of 80 to 160 ° C. Moreover, the 1st solvent contained in a composition may be 1 type, or 2 or more types.

Examples of the first solvent having a boiling point of 80 to 100 ° C. satisfying the condition (A) include 1-propanol, 2-propanol, 2-butanol and the like. Among these solvents, 2-propanol is preferably used because of compatibility with the resulting siloxane resin and the second solvent.

Examples of the first solvent having a boiling point of 100 to 130 ° C. satisfying the condition (B) include butyl acetate, isobutyl acetate, propylene glycol monomethyl ether and the like. The boiling point of the first solvent in the condition (B) is preferably 110 to 130 ° C. Among these solvents, isobutyl acetate is preferably used because of compatibility with the resulting siloxane resin and the second solvent.

Examples of the first solvent having a boiling point of 130 to 160 ° C. satisfying the condition (C) include propylene glycol monopropyl ether, ethyl lactate and cyclohexanone. The boiling point of the first solvent in the condition (C) is preferably 140 to 160 ° C. Among these solvents, it is preferable to use propylene glycol monopropyl ether because of compatibility with the resulting siloxane resin and the second solvent.

The second solvent has a boiling point of 180 ° C. to 230 ° C., preferably 180 ° C. to 200 ° C. There is no particular limitation as long as the boiling point is within such a range. As the second solvent, γ-butyrolactone, ethers and glycols can be used, and examples thereof include dipropylene glycol monomethyl ether and propylene glycol. The second solvent contained in the composition may be one type or two or more types.

In the composition according to the present embodiment, the mass ratio C ₁ / (C ₁ + C ₂ ) satisfies the relationship represented by the above condition A, condition B, or condition C according to the boiling point of the first solvent. Therefore, it is possible to achieve both non-drying at the nozzle tip when discharging the composition and quick drying at the time of pattern drawing, and the ink jet nozzles will not be clogged even when non-discharge and discharge operations are repeated, and at the time of drawing The pattern can be hard to spread.

(C) Component: Surface Conditioner Component (c) according to this embodiment is a surface conditioner. When the composition contains a surface conditioner, it is possible to control the wettability of the ink to the substrate surface and the cross-sectional shape of the pattern, which is effective in preventing the pattern from bleeding. As the component (c), a commercially available compound as a surface conditioner can be used without particular limitation. Specifically, a fluorine-based surface conditioner, a silicone-based surface conditioner, a nonionic surface conditioner, and the like can be used. Can be used. Of these, the use of a silicone-based surface conditioner is particularly effective in suppressing pattern bleeding.

The content of the component (c) is preferably 0.1% by mass or more and more preferably 0.2% by mass or more with respect to the component (a). Moreover, 1.0 mass% or less is preferable with respect to (a) component, and, as for content of (c) component, 0.8 mass% or less is more preferable. In addition, (c) component may be used individually by 1 type or in combination of 2 or more types.

[Method of forming silica-based film]
The method for forming a silica-based film according to the present embodiment includes a step of forming a drawing pattern film by discharging the composition onto a substrate by an inkjet method to form a drawing pattern film, and a step of precuring the drawing pattern film. And a step of curing the drawing pattern film to obtain a silica-based film having a pattern.

<Process for forming drawing pattern film>
Pattern drawing by the inkjet method can be performed using an inkjet apparatus. Ink jet devices are generally roughly classified into two types, a continuous type (continuous discharge type) and an on-demand type. In this embodiment, it is preferable to use an on-demand type. The continuous type is a system in which ink is always ejected continuously even when a pattern is not drawn on a substrate. On-demand type, on the other hand, is a method of drawing a pattern on a substrate by ejecting ink in a necessary amount when necessary.

The on-demand type includes an inkjet apparatus using a piezoelectric element that deforms when a voltage is applied, and a thermal inkjet apparatus that discharges using bubbles generated by heating. The silica-based film-forming composition for inkjet according to the present embodiment may basically use either method, but it is preferable to use an inkjet device using a piezo element from the viewpoint of suppressing ink composition change. .

When the pattern is drawn by the inkjet method, the substrate on which the pattern is drawn may be drawn while being heated in the range of 50 to 100 ° C. By heating the substrate, the quick drying property of the ink on the substrate can be further improved, and the disorder of the drawing pattern can be prevented.

<Step of precuring the drawing pattern film>
In the present embodiment, a step of precuring the drawing pattern film may be provided before the step of curing the drawing pattern film. When pre-curing, the polycondensation reaction of the siloxane resin in the drawing pattern film is accelerated and the organic solvent is heated with a hot plate or the like at the first stage baking: 80 to 140 ° C. and the second stage baking: 180 to 250 ° C. You may perform drying in steps. Further, the first stage and the second stage bake may be further multistaged. By the multi-stage baking, the siloxane resin is uniformly cured, and it is possible to prevent the drawing pattern from being disturbed due to the thermal convection when the solvent is removed.

<Step of curing drawing pattern film>
In this step, the final curing is performed, for example, by baking the drawing pattern film (which may not be precured) at a heating temperature of 350 to 1000 ° C. If the heating temperature for final curing is 350 ° C. or higher, sufficient curing is easily achieved, and if it is 1000 ° C. or lower, the substrate is unlikely to be adversely affected.

The heating time for the final curing is preferably 2 to 60 minutes, more preferably 2 to 30 minutes. If this heating time is 60 minutes or less, the amount of heat input will not increase excessively, and thus the deterioration of the substrate will be suppressed gradually. Further, as the heating device, a heat treatment device such as a quartz tube furnace, other furnaces, a hot plate, rapid thermal annealing (RTA), UV irradiation annealing, EB irradiation annealing, or the like can be used.

The atmosphere of the gas at the time of final curing may be either an inert gas atmosphere such as nitrogen, argon or helium, or an active gas atmosphere such as oxygen or ozone, as long as the substrate is not adversely affected.

The use of the silica-based film forming composition for inkjet according to the present embodiment and the method for forming the silica-based film is not particularly limited, but for example, it can be used for a device including an insulating film such as a semiconductor device (element) or a multilayer wiring board. Can be mentioned. More specifically, in a semiconductor device, it can be used as a surface protective film (passivation film), a buffer coat film, an interlayer insulating film, a diffusion prevention film, and the like. On the other hand, in a multilayer wiring board, it can be suitably used as an interlayer insulating film.

[Semiconductor devices]
The semiconductor device of this embodiment includes a substrate and a silica-based film having a predetermined pattern formed on the substrate by the method for forming a silica-based film. Such semiconductor devices include, for example, individual semiconductors such as diodes, transistors, compound semiconductors, thermistors, varistors, thyristors, DRAMs (Dynamic Random Access Memory), SRAMs (Static Random Access Memory), EPROMs. (Eraseable Programmable Read Only Memory), Mask ROM (Mask Read Only Memory), EEPROM (Electrically Erasable Programmable Read Only Memory), Flash Memory and Other Memory Elements, Microprocessor, DSP , Theoretical circuit elements such as ASIC, integrated circuit elements such as compound semiconductors represented by MMIC (monolithic microwave integrated circuit), hybrid integrated circuits (hybrid IC) , Light emitting diodes, and a photoelectric conversion element such as a charge coupled device.

Also, examples of the multilayer wiring board include a high-density wiring board such as MCM.

[Solar cell system]
The solar cell system of this embodiment includes the semiconductor device. Among the semiconductor devices described above, the photoelectric conversion element is a semiconductor device used in a solar cell system, and has been actively developed due to the influence of recent environmental problems. A typical photoelectric conversion element includes a semiconductor Si wafer in which an impurity called a dopant is diffused to form a pn junction. In such a photoelectric conversion element, there is a case where an element in which a non-diffusion region and a diffusion region of a dopant are mixed on one Si wafer is sometimes produced in order to increase the efficiency of the solar cell. In such a case, it is necessary to form a diffusion prevention mask in the non-diffusion region. Up to now, a diffusion prevention mask has been obtained by patterning a silica-based film formed by CVD or the like by a photolithography method. However, if the silica-based film forming composition for inkjet according to the present embodiment is used, a silica-based film patterned by inkjet can be obtained, which is useful because the number of steps and the necessary materials can be reduced.

The silica-based coating according to this embodiment can be used for applications such as liquid crystal parts, optical waveguides, and photoresists, but the usage is not limited to this.

Hereinafter, the present invention will be described more specifically based on experimental examples, but the present invention is not limited to the following experimental examples.

(Preparation of silicon compound A)
Water 36 in which 0.4 g of maleic acid was dissolved in a solution in which 66.2 g of tetraethoxysilane and 76.1 g of phenyltriethoxysilane were dissolved in 21.3 g of dipropylene glycol monomethyl ether (boiling point 188 ° C.) 0.0 g was added dropwise over 10 minutes under stirring and reacted for 10 hours to obtain 200 g of a silicon compound solution. At this time, the ratio M ₂ / M ₁ of the molar amount M ₂ of phenyltriethoxysilane to the molar amount M ₁ of tetraethoxysilane was 1.0. Then, it distilled off under reduced pressure using the evaporator until the said silicon compound solution whole quantity became 95 g or less. Thereafter, dipropylene glycol monomethyl ether was added until the total amount of the silicon compound solution reached 100 g to obtain silicon compound A. The siloxane resin solid content concentration of the silicon compound A at this time was 60% by mass.

(Preparation of silicon compound B)
Water in which 0.4 g of maleic acid is dissolved in a solution in which 66.2 g of tetraethoxysilane and 76.1 g of phenyltriethoxysilane are dissolved in 21.3 g of triethylene glycol dimethyl ether (boiling point 216 ° C.) 36. 0 g was added dropwise over 10 minutes under stirring and reacted for 10 hours to obtain 200 g of a silicon compound solution. At this time, the ratio M ₂ / M ₁ of the molar amount M ₂ of phenyltriethoxysilane to the molar amount M ₁ of tetraethoxysilane was 1.0. Then, it distilled off under reduced pressure using the evaporator until the said silicon compound solution whole quantity became 95 g or less. Thereafter, triethylene glycol dimethyl ether was added until the total amount of the silicon compound solution reached 100 g to obtain silicon compound B. The siloxane resin solid content concentration of the silicon compound B at this time was 60% by mass.

(Preparation of silicon compound C)
Water in which 0.4 g of maleic acid was dissolved in a solution in which 66.2 g of tetraethoxysilane and 76.1 g of phenyltriethoxysilane were dissolved in 21.3 g of tetraethylene glycol dimethyl ether (boiling point 273 ° C.) 0 g was added dropwise over 10 minutes under stirring and reacted for 10 hours to obtain 200 g of a silicon compound solution. At this time, the ratio M ₂ / M ₁ of the molar amount M ₂ of phenyltriethoxysilane to the molar amount M ₁ of tetraethoxysilane was 1.0. Then, it distilled off under reduced pressure using the evaporator until the said silicon compound solution whole quantity became 95 g or less. Thereafter, silicon compound C was obtained by adding tetraethylene glycol dimethyl ether until the total amount of the silicon compound solution reached 100 g. At this time, the siloxane resin solid content concentration of the silicon compound C was 60% by mass.

[Experimental Example 1]
To the silicon compound A, 0.3 g of Dispalon 1711 (trade name, manufactured by Enomoto Kasei Co., Ltd., registered trade name) is added and stirred to the silicon compound A, and 2-propanol (boiling point 82 ° C.) is added to 17. 2g was added. At this time, the mass ratio of the 2-propanol content to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.3. Moreover, the siloxane resin solid content concentration at this time was 51%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.3 is added until the solid content concentration of the siloxane resin is 20%. Silica-based film-forming composition A-1 was produced.

[Experiment 2]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 26.7 g of 2-propanol (boiling point 82 ° C.) was added. At this time, the mass ratio of the content of 2-propanol to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.4. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition A-2 was prepared.

[Experiment 3]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 40.0 g of 2-propanol (boiling point 82 ° C.) was added. At this point, the mass ratio of the 2-propanol content to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.5. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition A-3 was produced.

[Experimental Example 4]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 17.2 g of 1-propanol (boiling point 97 ° C.) was added. At this time, the mass ratio of the content of 1-propanol to the total content of 1-propanol (boiling point 97 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.3. Moreover, the siloxane resin solid content concentration at this time was 51%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.3 is added until the solid content concentration of the siloxane resin is 20%. Silica-based film forming composition A-4 was prepared.

[Experimental Example 5]
To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 17.2 g of 2-propanol (boiling point 82 ° C.) was added. At this point, the mass ratio of the 2-propanol content to the total content of 2-propanol (boiling point 82 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.3. Moreover, the siloxane resin solid content concentration at this time was 51%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.3 is added until the solid content concentration of the siloxane resin is 20%. Silica-based film forming composition A-5 was produced.

[Experimental Example 6]
To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 40.0 g of 2-propanol (boiling point 82 ° C.) was added. At this time, the mass ratio of the content of 2-propanol to the total content of 2-propanol (boiling point 82 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.5. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition A-6 was produced.

[Experimental Example 7]
To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 17.2 g of 1-propanol (boiling point 97 ° C.) was added. At this time, the mass ratio of the content of 1-propanol to the total content of 1-propanol (boiling point 97 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.3. Moreover, the siloxane resin solid content concentration at this time was 51%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.3 is added until the solid content concentration of the siloxane resin is 20%. Silica-based film forming composition A-7 was produced.

[Experimental Example 8]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 10.0 g of 2-propanol (boiling point 82 ° C.) was added. At this point, the mass ratio of the 2-propanol content to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.2. Moreover, the siloxane resin solid content concentration at this time was 55%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.2 until the siloxane resin solid content concentration becomes 20% is added to the inkjet. A silica-based film-forming composition a-1 was produced.

[Experimental Example 9]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 60.0 g of 2-propanol (boiling point 82 ° C.) was added. At this time, the mass ratio of the content of 2-propanol to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.6. At this time, the siloxane resin solid content concentration was 38%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.6 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition a-2 was prepared.

[Experimental Example 10]
To the silicon compound A, 26.7 g of 2-propanol (boiling point 82 ° C.) was added. At this point, the mass ratio of the content of 2-propanol to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.4. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition a-3 was prepared.

[Experimental Example 11]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 17.2 g of isobutyl acetate (boiling point 118 ° C.) was added. At this time, the mass ratio of the content of isobutyl acetate to the total content of isobutyl acetate (boiling point 118 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.3. Moreover, the siloxane resin solid content concentration at this time was 51%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.3 is added until the solid content concentration of the siloxane resin is 20%. Silica-based film forming composition a-4 was prepared.

[Experimental example 12]
To the silicon compound C, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 40.0 g of 2-propanol (boiling point 82 ° C.) was added. At this time, the mass ratio of the content of 2-propanol to the total content of 2-propanol (boiling point 82 ° C.) and tetraethylene glycol dimethyl ether (boiling point 273 ° C.) was 0.5. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition a-5 was produced.

[Experimental Example 13]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 26.7 g of isobutyl acetate (boiling point 118 ° C.) was added. At this time, the mass ratio of the content of isobutyl acetate to the total content of the content of isobutyl acetate (boiling point 118 ° C.) and the content of dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.4. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling point solvent to the total content of the high-boiling point component and the low-boiling point component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition B-1 was produced.

[Experimental Example 14]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 40.0 g of isobutyl acetate (boiling point 118 ° C.) was added. At this time, the mass ratio of the content of isobutyl acetate to the total content of the content of isobutyl acetate (boiling point 118 ° C.) and the content of dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.5. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition B-2 was prepared.

[Experimental Example 15]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 60.0 g of isobutyl acetate (boiling point 118 ° C.) was added. At this point, the mass ratio of the content of isobutyl acetate to the total content of isobutyl acetate (boiling point 118 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.6. At this time, the siloxane resin solid content concentration was 38%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.6 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition B-3 was prepared.

[Experimental Example 16]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 26.7 g of butyl acetate (boiling point 126 ° C.) was added. At this time, the mass ratio of the content of butyl acetate to the total content of butyl acetate (boiling point 126 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.4. At this time, the siloxane resin solid content concentration was 47%. Therefore, until the siloxane resin solid content concentration reaches 20%, a mixed solvent in which the mass ratio of the content of the low boiling point component to the total content of the high boiling point component and the low boiling point component is 0.4 is added, and the silica for inkjet A system film-forming composition B-4 was prepared.

[Experimental Example 17]
To the silicon compound B, 0.3 g of Dispalon 1711 (Tsubakimoto Kasei), a silicone-based surface conditioner, was added and stirred, and 26.7 g of isobutyl acetate (boiling point 118 ° C.) was added. At this point, the mass ratio of the isobutyl acetate content to the total content of isobutyl acetate (boiling point 118 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.4. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition B-5 was produced.

[Experiment 18]
To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 60.0 g of isobutyl acetate (boiling point 118 ° C.) was added. At this time, the mass ratio of the content of isobutyl acetate to the total content of isobutyl acetate (boiling point 118 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.6. At this time, the siloxane resin solid content concentration was 38%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.6 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition B-6 was produced.

[Experimental Example 19]
To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 26.7 g of butyl acetate (boiling point 126 ° C.) was added. At this time, the mass ratio of the content of butyl acetate to the total content of butyl acetate (boiling point 126 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.4. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition B-7 was produced.

[Experiment 20]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 17.2 g of isobutyl acetate (boiling point 118 ° C.) was added. At this time, the mass ratio of the content of isobutyl acetate to the total content of isobutyl acetate (boiling point 118 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.3. Moreover, the siloxane resin solid content concentration at this time was 51%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.3 is added until the solid content concentration of the siloxane resin is 20%. A silica-based film-forming composition b-1 was produced.

[Experiment 21]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 93.5 g of isobutyl acetate (boiling point 118 ° C.) was added. At this time, the mass ratio of the content of isobutyl acetate to the total content of the content of isobutyl acetate (boiling point 118 ° C.) and the content of dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.7. Moreover, the siloxane resin solid content concentration at this time was 31%. Therefore, this mixed solvent in which the mass ratio of the content of the low boiling point component to the total content of the high boiling point component and the low boiling point component is 0.7 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film forming composition b-2 was produced.

[Experimental example 22]
40.0 g of isobutyl acetate (boiling point 118 ° C.) was added to the silicon compound A. At this time, the mass ratio of the content of isobutyl acetate to the total content of the content of isobutyl acetate (boiling point 118 ° C.) and the content of dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.5. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film-forming composition b-3 was produced.

[Experimental example 23]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 60.0 g of 2-propanol (boiling point 82 ° C.) was added. At this time, the mass ratio of the content of 2-propanol to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.6. At this time, the siloxane resin solid content concentration was 38%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.6 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film-forming composition b-4 was produced.

[Experimental example 24]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 26.7 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this point, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) is 0.4. Met. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film-forming composition b-5 was produced.

[Experiment 25]
To the silicon compound C, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 60.0 g of isobutyl acetate (boiling point 118 ° C.) was added. At this point, the mass ratio of the isobutyl acetate content to the total content of isobutyl acetate (boiling point 118 ° C.) content and tetraethylene glycol dimethyl ether (boiling point 273 ° C.) content was 0.6. At this time, the siloxane resin solid content concentration was 38%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.6 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film-forming composition b-6 was produced.

[Experiment 26]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 40.0 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this time, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) is 0.5. Met. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 until the siloxane resin solid content concentration becomes 20% is added, and the silica for inkjet A system film-forming composition C-1 was produced.

[Experiment 27]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 60.0 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this time, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) is 0.6. Met. At this time, the siloxane resin solid content concentration was 38%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.6 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film-forming composition C-2 was produced.

[Experiment 28]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 93.5 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this point, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) is 0.7. Met. Moreover, the siloxane resin solid content concentration at this time was 31%. Therefore, this mixed solvent in which the mass ratio of the content of the low boiling point component to the total content of the high boiling point component and the low boiling point component is 0.7 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition C-3 was prepared.

[Experimental example 29]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 40.0 g of cyclohexanone (boiling point 156 ° C.) was added. At this time, the mass ratio of the content of cyclohexanone to the total content of cyclohexanone (boiling point 156 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.5. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition C-4 was produced.

[Experiment 30]
To the silicon compound B, 0.3 g of Dispalon 1711 (Tsubakimoto Kasei) which is a silicone surface conditioner was added and stirred, and 40.0 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this time, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.5. It was. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition C-5 was produced.

[Experimental example 31]
To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 93.5 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this time, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.7. . Moreover, the siloxane resin solid content concentration at this time was 31%. Therefore, this mixed solvent in which the mass ratio of the content of the low boiling point component to the total content of the high boiling point component and the low boiling point component is 0.7 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition C-6 was produced.

[Experiment 32]
To the silicon compound B, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 40.0 g of cyclohexanone (boiling point 156 ° C.) was added. At this time, the mass ratio of the content of cyclohexanone to the total content of cyclohexanone (boiling point 156 ° C.) and dimethyltriglycol (boiling point 216 ° C.) was 0.5. Moreover, the siloxane resin solid content concentration at this time was 43%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.5 is added until the solid content concentration of the siloxane resin reaches 20%. Silica-based film forming composition C-7 was produced.

[Experimental Example 33]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 26.7 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this point, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) is 0.4. Met. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film forming composition c-1 was prepared.

[Experimental example 34]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 160.0 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this time, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) is 0.8. Met. Moreover, the siloxane resin solid content concentration at this time was 23%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.8 is added until the solid content of the siloxane resin reaches 20%. A silica-based film forming composition c-2 was prepared.

[Experimental Example 35]
To the silicon compound A, 26.7 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this point, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) is 0.4. Met. At this time, the siloxane resin solid content concentration was 47%. Therefore, this mixed solvent in which the mass ratio of the content of the low-boiling component to the total content of the high-boiling component and the low-boiling component is 0.4 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film forming composition c-3 was produced.

[Experimental Example 36]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 93.5 g of 2-propanol (boiling point 82 ° C.) was added. At this point, the mass ratio of the 2-propanol content to the total content of 2-propanol (boiling point 82 ° C.) and dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.7. Moreover, the siloxane resin solid content concentration at this time was 31%. Therefore, this mixed solvent in which the mass ratio of the content of the low boiling point component to the total content of the high boiling point component and the low boiling point component is 0.7 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film forming composition c-4 was prepared.

[Experiment 37]
To the silicon compound A, 0.3 g of Dispalon 1711 which is a silicone surface conditioner was added and stirred, and 93.5 g of isobutyl acetate (boiling point 118 ° C.) was added. At this time, the mass ratio of the content of isobutyl acetate to the total content of the content of isobutyl acetate (boiling point 118 ° C.) and the content of dipropylene glycol monomethyl ether (boiling point 188 ° C.) was 0.7. Moreover, the siloxane resin solid content concentration at this time was 31%. Therefore, this mixed solvent in which the mass ratio of the content of the low boiling point component to the total content of the high boiling point component and the low boiling point component is 0.7 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film-forming composition c-5 was produced.

[Experiment 38]
To the silicon compound C, 0.3 g of Dispalon 1711 which is a silicone-based surface conditioner was added and stirred, and 93.5 g of propylene glycol monopropyl ether (boiling point 150 ° C.) was added. At this time, the mass ratio of the content of propylene glycol monopropyl ether to the total content of propylene glycol monopropyl ether (boiling point 150 ° C.) and tetraethylene glycol dimethyl ether (boiling point 273 ° C.) is 0.7. there were. Moreover, the siloxane resin solid content concentration at this time was 31%. Therefore, this mixed solvent in which the mass ratio of the content of the low boiling point component to the total content of the high boiling point component and the low boiling point component is 0.7 is added until the solid content concentration of the siloxane resin reaches 20%. A silica-based film forming composition c-6 was prepared.

The following evaluations were carried out on the silica-based film-forming compositions for ink jets of Experimental Examples 1 to 38 thus obtained.

[Evaluation of nozzle clogging during re-discharge]
For evaluation of nozzle clogging at the time of re-discharge, a NanoPrinter-1100 Standard inkjet discharge machine manufactured by Microjet Co., Ltd. was used.
<Clogging evaluation A>
Discharge at room temperature (23 ° C) (3 minutes), non-discharge (20 minutes), discharge (30 seconds), non-discharge (20 minutes), discharge (30 seconds) It was determined whether or not the ink was discharged without clogging the nozzles when the discharge and non-discharge of the composition were repeated.
<Clogging evaluation B>
Ink (silica-based film formation for each inkjet) in the order of discharge (3 minutes), non-discharge (10 minutes), discharge (30 seconds), non-discharge (10 minutes), discharge (30 seconds) at room temperature (23 ° C.) It was determined whether or not the ink was discharged without clogging the nozzles when the discharge and non-discharge of the composition were repeated.
<Clogging evaluation C>
At room temperature (23 ° C), discharge (3 minutes), non-discharge (5 minutes), discharge (30 seconds), non-discharge (5 minutes), discharge (30 seconds) in the order of ink (silica-based film formation for each inkjet) It was determined whether or not the ink was discharged without clogging the nozzles when the discharge and non-discharge of the composition were repeated.

[Evaluation of bleeding of drawing pattern]
The bleeding of the drawing pattern was evaluated as follows. First, using a NanoPrinter-1100 Standard inkjet ejector, ink (each silica-based film-forming composition for inkjet) was ejected, and a predetermined pattern was drawn on a mirror-Si wafer heated to 70 ° C. At this time, the drawing conditions of the apparatus were set to “width 800 μm, length 20000 μm, film thickness 1.2 μm”. Then, when the drawn pattern actual dimension width is 960 μm or less, which is 120% of the 800 μm, A evaluation, B evaluation when the drawn pattern actual dimension width is 1000 μm or less which is 125% of the 800 μm, 1040 μm which is 130% of the 800 μm Bleeding was evaluated by C evaluation for the following cases and D evaluation for cases exceeding 1040 μm.

Tables 1 to 6 show the compositions of the ink-jet silica-based film forming compositions of Experimental Examples 1 to 38 and the evaluation results.

Claims (5)

1. Containing a silicon compound obtained by hydrolytic condensation of a compound represented by the following general formula (I), a solvent, and a surface conditioner,
   The solvent includes a first solvent having a boiling point of 80 to 160 ° C. and a second solvent having a boiling point of 180 to 230 ° C.,
   A silica-based coating film for inkjet, wherein the mass ratio of the content of the first solvent to the total content of the first solvent and the second solvent satisfies the relationship represented by the following conditions A, B, or C: Forming composition.
   Condition A: When the boiling point of the first solvent is 80 to 100 ° C., the mass ratio is 0.3 to 0.5.
   Condition B: When the boiling point of the first solvent is 100 to 130 ° C., the mass ratio is 0.4 to 0.6.
   Condition C: When the boiling point of the first solvent is 130 to 160 ° C., the mass ratio is 0.5 to 0.7.
   R ¹ _n SiX _4-n (I)
   [Wherein R ¹ represents an organic group having 1 to 20 carbon atoms, X represents a hydrolyzable group, and n represents an integer of 0 to 2. However, when n is 2, a plurality of R ¹ may be the same or different, and when n is 0 to 2, a plurality of X 1 may be the same or different. ]
2. The composition according to claim 1, wherein the surface conditioner is a silicone-based surface conditioner.
3. A step of ejecting the composition according to claim 1 or 2 onto a substrate by an ink jet method to perform pattern drawing to form a drawing pattern film; and
   Curing the drawing pattern film to obtain a silica-based film having a pattern;
   A method for forming a silica-based film.
4. A semiconductor device comprising: a substrate; and a silica-based film having a pattern formed on the substrate by the method according to claim 3.
5. A solar cell system comprising the semiconductor device according to claim 4.