JP5547890B2 - Reactant for filling polysiloxane trench - Google Patents

Description

  The present invention relates to a reactant for filling a trench for an insulating protective film in a trench formed in a semiconductor element and a method for producing a solution containing the reactant.

Shallow trench isolation technology (STI technology) has been developed as one of the technologies for electrically isolating circuit elements such as transistors, which are components of electronic devices such as DRAM (Dynamic R andom Access Memory). Has been. The STI technique is a technique for electrically isolating circuit elements by forming a trench in a position corresponding to a gap between circuit elements in a substrate and embedding an insulating material in the trench.
As device integration increases, the trench width in the STI technology becomes narrower, and therefore the trench aspect ratio (the value obtained by dividing the trench opening width by the trench depth) tends to increase.

As a material used for such trench filling, silicon oxide is widely used suitably because high electrical insulation is required.
As a means for embedding silicon oxide in the trench, conventionally, a silicon oxide film is formed on a silicon substrate having a trench by a sputtering method typified by a high-density plasma CVD method. However, with recent miniaturization of semiconductor elements, the trench width tends to be narrowed and the aspect ratio tends to be large. When silicon oxide is buried in a fine groove having a trench width of 0.2 μm or less and an aspect ratio of 2 or more by a CVD method, there is a problem that voids are easily generated in the fine groove.

As a method other than the sputtering method, a method of embedding a fine groove by a coating method and forming a silica film by baking in an oxidizing atmosphere is known, and a polysilazane material, a polysilane material, and a silicone material are known as materials. .
Polysilazane materials have been reported to have good trench embeddability and low cure shrinkage during conversion to silicon oxide films. (For example, Patent Document 1) However, the silicon oxide film obtained by baking by steam oxidation has a large amount of residual nitrogen, inferior electrical separation ability, and is dangerous because ammonia gas is generated during baking. was there.
The polysilane material has a problem that the applied polysilane compound is likely to evaporate and is easily broken when the coating amount is increased. (For example, Patent Document 2)

Silicone materials are accompanied by dehydration and dealcoholization condensation reactions during coating and firing, so the problem of voids and cracks occurring in the resulting silicon oxide film, when using silicone materials with organic groups, Silicon oxide has a large amount of residual carbon, resulting in poor electrical characteristics, large curing shrinkage when converting from silicone material to silicon oxide, and non-uniform density from the film surface to the bottom of the fine groove There was a problem.
As a method for avoiding the generation of voids and cracks using a silicone material, a composition comprising silicon oxide particles and a silicon atom binder has been proposed. (For example, Patent Document 3) However, since the silicon atom binder contains a large amount of organic groups, the curing shrinkage of the silicon oxide film during firing is large, and the HF etch rate of the silicon oxide after heating (1% in 1% HF aqueous solution after firing). Since the amount of film loss per unit time when immersed for a minute was high, there was a problem that the silicon oxide embedded in the trench in the HF cleaning process after CMP was greatly damaged.

As a method for obtaining a high-purity silicon oxide by reducing the amount of residual carbon, a hydrogenated silicone compound has been proposed in which terminal silanol groups are reduced. (For example, Patent Document 4) However, there is a problem that the crack resistance is poor.
JP 2001-308090 A JP 2003-31568 A JP 2006-310448 A JP 2008-101206 A

  The present invention has been made in view of the above circumstances, and the purpose thereof is a long pot life of a solution suitable for being used for embedding silicon oxide in a trench formed in a substrate, and the embedding property is high. An object of the present invention is to provide a trench filling condensation reaction product having a low cure shrinkage ratio and having HF resistance and crack resistance.

As a result of intensive studies to develop a method for achieving the above object, the present inventors have found the following trench filling composition and completed the present invention. That is, the present invention
[1] Condensation reaction product for trench embedding, wherein the condensation reaction product contains at least a condensation reaction product of a polysiloxane compound and silica particles, and the polysiloxane compound contains HSiO _3/2 group, MeHSiO group, and H _2. Having at least one group selected from SiO groups of 40 mol% or more, the weight average molecular weight of the polysiloxane is 1,000 or more and 200,000 or less, and the average primary particle size of the silica particles is 1 nm or more and 100 nm or less, Condensation reaction product for trench filling,

[2] The trench filling condensation product according to 1 above, wherein the condensation reaction product includes a reaction product obtained by condensation reaction of a polysiloxane compound and silica particles and a silane compound represented by the general formula (1). ,
R _n SiX _4-n Formula (1)
(In general formula (1), n is an integer of 1 to 3, R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, It is a group selected from an acetoxy group.)

[3] The 1 or above, wherein the polysiloxane compound includes a component derived from the silane compound represented by the general formula (2) to the general formula (6) and includes 30 mol% or more of the silane compound represented by the general formula (2). The condensation reaction product for trench filling according to 2,
HSiX ₃ general formula (2)
SiX ₄ general formula (3)
R ² SiX ₃ general formula (4)
R ₂ SiX ₂ general formula (5)
R ₃ SiX general formula (6)
(R in general formula (5) and general formula (6) is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and X in general formula (2) to general formula (6) is And R ² in the general formula (4) is a hydrocarbon group having 1 to 10 carbon atoms.)

[4] The above-described items 1 to 3, wherein the silica particles are 1% by mass or more and 80% by mass or less based on the total of the polysiloxane compound and the silica particles, or the polysiloxane compound, the silica particles, and the silane compound. The condensation reaction product for trench embedding according to any one of the above,
[5] The trench according to any one of 1 to 4, wherein the silane compound is greater than 0% by mass and less than or equal to 40% by mass with respect to the total of the polysiloxane compound, silica particles, and silane compound. Condensation reaction product for embedding,
[6] In the solution containing the condensation reaction product according to any one of 1 to 5 above, at least one kind selected from alcohols, ketones, esters, ethers, and hydrocarbon solvents having a boiling point of 100 ° C. or higher and 200 ° C. or lower. A reaction solution for trench filling, wherein the solvent is contained in an amount of 50% by mass or more based on the total amount of the solvent in the solution;

[7] In the production process of the polysiloxane, it reacts with 0.1 to 10 equivalents of water with respect to the total number of X contained in the silane compounds represented by the general formulas (2) to (6). The method for producing a condensation reaction product according to any one of 1 to 6, characterized by comprising a step of:
[8] The method for producing a condensation reaction product as described in 7 above, wherein the reaction of the polysiloxane compound and silica particles, or the polysiloxane compound, silica particles and a silane compound is performed in an acidic atmosphere.

  The present invention provides a buried buried trench having high purity, low cure shrinkage, HF resistance and crack resistance suitable for use to bury silicon oxide in a trench formed in a substrate. An object of the present invention is to provide a resin composition.

Hereinafter, embodiments of the present invention will be described in detail.
Polystyrene having a polystyrene-reduced weight average molecular weight of 1,000 or more and 200,000 or less and containing at least one group of 40 mol% or more among groups selected from HSiO _3/2 group, MeHSiO group or H ₂ SiO group used in the present invention. In the siloxane compound, the silane compound represented by the general formula (2) to the general formula (6) is added to the total number of X contained in the silane compound represented by the general formula (2) to the general formula (6) in an acidic atmosphere. On the other hand, it is a condensation reaction product reacted with 0.1 to 10 equivalents of water.
HSiX ₃ general formula (2)
SiX ₄ general formula (3)
R ² SiX ₃ general formula (4)
R ₂ SiX ₂ general formula (5)
R ₃ SiX general formula (6)
R in the general formula (2), the general formula (5), and the general formula (6) is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the general formula (2) to the general formula (6) X is a group selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, and R and X may be the same or different. R and X may be the same or different. R ² in the general formula (4) is a hydrocarbon group having 1 to 10 carbon atoms.

  Specific examples of R in the above general formula (2), general formula (5), and general formula (6) of the silane compound used in producing the polysiloxane compound used in the present invention include a hydrogen atom, Methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, cyclopentyl, n-hexyl, i-hexyl, cyclohexyl, n-heptyl, i- Acyclic or cyclic aliphatic hydrocarbon groups such as heptyl, n-octyl, i-octyl, t-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, vinyl, propenyl, butenyl, Pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, styryl Acyclic and cyclic alkenyl groups, aralkyl groups such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, araalkenyl groups such as PhCH = CH- groups, phenyl groups, tolyl groups Or an aryl group like a xylyl group is mentioned. Among these, as a group having a small weight loss upon conversion to silicon oxide oxide upon firing and a small shrinkage rate, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen group is more preferable.

  Specific examples of X in the general formula (2) to the general formula (6) include, for example, halogen atoms such as chloride, bromide and iodide, methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, Examples thereof include an alkoxy group such as an n-butyloxy group, a t-butyloxy group, an n-hexyloxy group, and a cyclohexyloxy group, and an acetoxy group. Among these, halogen atoms such as chloride, bromide and iodide, alkoxy groups such as methoxy group and ethoxy group, and acetoxy groups are preferable because of high reactivity of the condensation reaction.

Specific examples of R ^{2 in} the general formula (4) include methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, cyclopentyl, n- Acyclic or ring such as hexyl, i-hexyl, cyclohexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, t-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl An aliphatic hydrocarbon group of formula, acyclic and cyclic alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, styryl, etc. Arals such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl An aryl group such as a kill group, an araalkenyl group such as a PhCH═CH— group, a phenyl group, a tolyl group, or a xylyl group. Among these groups, methyl and ethyl groups are preferable as the group having a small weight loss and a small shrinkage rate upon conversion to silicon oxide during firing.

The polysiloxane compound used in the present invention is a ratio of the hydrogenated silane compound represented by the general formula (2) and / or the hydrogenated silane compound represented by H ₂ SiX ₂ or MeHSiX ₂ in the general formula (5). However, it is preferably at least 40 mol%, more preferably at least 50 mol%, based on the total amount of silane compounds used in producing the polysiloxane compound. When the amount of the hydrogenated silane compound represented by the general formula (2) is within the above range, it is preferable because the shrinkage rate of the coating film is small during the conversion to silicon oxide during firing.
Moreover, among the hydrogenated silane compounds, the ratio of the hydrogenated silane compound represented by the general formula (2) is preferably 30% by mass or more in order to increase crack resistance.

The ratio of the silane compound represented by the general formula (3) used in the production of the polysiloxane compound used in the present invention is 30 mol with respect to the total of the silane compounds used in the production of the polysiloxane compound. % Or less, more preferably 20 mol% or less. Within the above range, the film forming property is good and the shrinkage rate is small, which is preferable.
The ratio of the silane compound represented by the general formula (4) used in the production of the polysiloxane compound used in the present invention is 30 mol with respect to the total of the silane compounds used in producing the polysiloxane compound. % Or less, more preferably 20 mol% or less. Within the above range, the film forming property is good and the shrinkage rate is small, which is preferable.

The ratio of the silane compound represented by the general formula (5) used in the production of the polysiloxane compound used in the present invention is 50 mol with respect to the total of the silane compounds used in the production of the polysiloxane compound. % Or less, more preferably 30 mol% or less. Within the above range, embeddability is good and crack resistance is high, which is preferable.
The ratio of the silane compound represented by the general formula (6) used in the production of the polysiloxane compound used in the present invention is 30 mol with respect to the total of the silane compounds used in producing the polysiloxane compound. % Or less, more preferably 20 mol% or less. Within the above range, embeddability is good and crack resistance is high, which is preferable.

  The polysiloxane compound used in the present invention is produced by a condensation reaction of the silane compounds represented by the general formulas (2) to (6) under an acidic atmosphere. When producing a polysiloxane compound, when X of the silane compound represented by the general formulas (2) to (6) contains a halogen atom or an acetoxy compound, Therefore, since the reaction system shows acidity by adding water, it may be added or not added with an acid catalyst in addition to the silane compound. Moreover, when all X of the silane compound represented by the general formulas (2) to (6) used in producing the polysiloxane compound is an alkoxy group, it is preferable to add an acid catalyst.

Examples of the acid catalyst include inorganic acids and organic acids.
Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and boric acid.
Examples of the organic acid include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, benzoic acid, and p-aminobenzoic acid. Examples include acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, tartaric acid, citraconic acid, malic acid, glutaric acid, and the like.

These compounds can be used alone or in combination of two or more. The amount of the acid catalyst used is preferably adjusted to a pH of 0.01 to 6.0 in the reaction system for producing the polysiloxane compound because the weight average molecular weight of the polysiloxane compound can be controlled.
When the polysiloxane compound used in the present invention is produced, it is produced in an organic solvent or a mixed solution system of water and an organic solvent. Examples of the organic solvent used in the condensation reaction include alcohols, esters, ketones, ethers, aliphatic hydrocarbons, aromatic hydrocarbon compounds, amide compounds, and the like.

  Examples of the alcohols include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol, and ethylene glycol. Monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, B propylene glycol monopropyl ether, mono-ethers of polyhydric alcohols such as propylene glycol monobutyl ether.

Examples of the esters include methyl acetate, ethyl acetate, butyl acetate and the like. Examples of ketones include acetone, methyl ethyl ketone, methyl isoamyl ketone, and the like.
In addition to the above monoethers of polyhydric alcohols, for example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol Examples include polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of polyhydric alcohols such as dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane, anisole and the like.

Examples of the aliphatic hydrocarbon include hexane, heptane, octane, nonane, decane, and the like.
Examples of the aromatic hydrocarbon include aromatic hydrocarbon solvents such as benzene, toluene and xylene.
Examples of the amide compound include dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
Among these solvents, alcohol solvents such as methanol, ethanol, isopropanol and butanol, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether Ether solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferable because they are easily mixed with water and silica particles are easily dispersed.

These solvents may be used alone, or a plurality of solvents may be used in combination. Moreover, you may react in a bulk, without using the said solvent.
The polysiloxane compound used in the present invention is preferably produced by adding water to the silane compound represented by the general formulas (2) to (6). The amount of water added is 0.1 equivalent to 10 equivalents relative to the total number of moles of X of the silane compound represented by the general formulas (2) to (6) used in the production of the polysiloxane compound. It is preferably added in a range, more preferably in a range of 0.4 equivalents or more and 8 equivalents or less. When the amount of water added is 0.1 equivalent or more, the molecular weight of the polysiloxane compound is preferably increased, and the reaction with 10 equivalents or less increases the pot life of the trench filling reactant solution, This is preferable for improving crack resistance.

The reaction temperature for producing the polysiloxane compound used in the present invention is not particularly limited, but it is preferably in the range of −50 ° C. to 200 ° C., more preferably 0 ° C. to 150 ° C. By carrying out the reaction in the above range, the molecular weight when producing the polysiloxane compound can be controlled.
The weight average molecular weight in terms of polystyrene of the polysiloxane compound used when producing the trench filling reactant used in the present invention is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 150,000. 000 or less. When the weight average molecular weight of the polysiloxane compound is 1,000 or more, the film formability and crack resistance are good, and when the weight average molecular weight is 200,000 or less, the pot life of the reaction product is increased so as to fill the trench. . The polysiloxane compound used in the present invention may be reacted with silica particles as it is after being produced in the above organic solution, or after being produced in the above organic solution, concentrated or substituted with another organic solvent. Then, it may be reacted with silica particles.

Next, the silica particles used in the present invention will be described.
Examples of the silica particles used in the trench filling reactant of the present embodiment include fumed silica and colloidal silica.
The fumed silica can be obtained by reacting a compound containing a silicon atom with oxygen and hydrogen in a gas phase. Examples of the silicon compound used as a raw material include silicon halides (for example, silicon chloride).
Colloidal silica can be synthesized by a sol-gel method in which a raw material compound is hydrolyzed and condensed. Examples of the raw material compound for colloidal silica include alkoxy silicon (for example, tetraethoxysilane) and halogenated silane compounds (for example, diphenyldichlorosilane). Among these, colloidal silica obtained from alkoxysilicon is more preferable because it is required to have less impurities such as metal and halogen.

The average primary particle diameter of the silica particles is preferably 1 or more and 120 nm or less, and more preferably 1 or more and 40 nm or less. When the thickness is 120 nm or less, the embedding property in the trench is improved, and when the thickness is 1 nm or more, the crack resistance is improved.
The average secondary particle diameter of silica is preferably 2 nm or more and 250 nm or less, and more preferably 2 or more and 80 nm or less. When the thickness is 250 nm or less, the embedding property in the trench is improved, and when the thickness is 2 nm or more, the crack resistance is improved. In addition, the average secondary particle diameter of the silica particles is 0.1 to 3 times the minimum opening width of the trenches formed in the substrate within the above range. Is more preferable, and it is still more preferable that it is 0.1 to 2 times.

Silica particles are known to exhibit a so-called “reflow” phenomenon in which, when heated, the bonds are cleaved, recombined and rearranged. For this reason, even if the average secondary particle diameter of the silica particles is larger than the opening width of the trench, a reflow phenomenon occurs in the heating process described later, and a part of the finely divided silica particles reaches the inside of the trench. Become.
The shape of the silica particles can be spherical, rod-like, plate-like, fiber-like, or a shape in which some of them are combined, but preferably spherical. The term “spherical” as used herein includes not only true spheres but also cases where the shape is substantially spherical, such as a spheroid or oval.
The specific surface area of the silica particles is preferably 1000 m ² / g or less, more preferably 500 m ² / g or less, because the HF resistance is increased.
The silica particles are not limited as long as they meet the above requirements, and commercially available products can also be used.

  As such a commercial product, as colloidal silica, for example, LEVASIL series (manufactured by HC Starck Co., Ltd.), methanol silica sol IPA-ST, same MEK-ST, same NBA-ST, same XBA-ST, same DMAC-ST, ST-UP, ST-UPP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL ( As mentioned above, manufactured by Nissan Chemical Industries, Ltd.), Quateron PL series (manufactured by Fuso Chemical Co., Ltd.), etc .; As powdered silica particles, for example, Aerosil 130, 300, 380, TT600, OX50 (above, Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (above, manufactured by Asahi Glass Co., Ltd.), E220A E220 (above, Nippon Silica Kogyo (Ltd.)), SYLYSIA470 (manufactured by Fuji Silysia Chemical Co., Ltd.), the SG Flake (manufactured by Nippon Sheet Glass Co., Ltd.), and the like, can be mentioned, respectively.

  When making the said silica particle react with the polysiloxane compound of this invention, it can be made to react in the state disperse | distributed to the solvent. As a solvent to be used, water, an organic solvent, or a mixed solvent thereof can be used. The organic solvent used varies depending on the dispersion medium of the silica particles used. When the silica particle dispersion medium used is aqueous, water or an alcohol-based solvent may be added to the silica particle aqueous dispersion medium and then reacted with the polysiloxane compound, or the silica particle aqueous solution may be once alcoholized. You may react with a polysiloxane compound after substituting with a system solvent. Examples of the alcohol solvent that can be used include methanol, ethanol, n-propanol, 2-propanol, n-butanol, methoxyethanol, ethoxyethanol, and the like, which are preferable because they are easily mixed with water.

  When the dispersion medium of the silica particles used is a solvent such as alcohol, ketone, ester, or hydrocarbon, water or a solvent such as alcohol, ether, ketone, or ester can be used. Examples of alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol and the like. Examples of the ether solvent include dimethoxyethane. Examples of the ketone solvent include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, ethyl formate, propyl formate and the like.

  The reaction between the silica particles and the polysiloxane compound is preferably performed in an acidic atmosphere. The acid catalyst which can be used can use the same acid catalyst as when manufacturing a polysiloxane compound. If the acid catalyst is removed once when producing the polysiloxane compound, it is necessary to add the acid catalyst when reacting the silica particles with the polysiloxane compound, but the acid catalyst is not removed when producing the polysiloxane compound. When reacting as it is, the acid catalyst used when reacting the polysiloxane compound can be reacted with the polysiloxane compound and the silica particles without adding the acid catalyst, or the acid catalyst can be added again. I do not care.

The reaction temperature of the silica particles and the polysiloxane compound solution is not particularly limited, and it is carried out in the normal range of −50 ° C. to 200 ° C.
The ratio of the silica particles used is such that the silica particles are 1% by mass or more and 80% by mass or less based on the total of the polysiloxane compound and the silica particles, or the polysiloxane compound, the silica particles, and the silane compound. More preferably, it is 5 mass% or more and 70 mass% or less, More preferably, it is 10 mass% or more and 60 mass% or less. When it is 1% by mass or more, crack resistance is improved, and when it is 80% by mass or less, film quality is improved.

The polysiloxane trench filling reactant of the present invention may be reacted with a polysiloxane compound solution added to a dispersion medium of silica particles and then reacted with a silane compound represented by the general formula (1).
R _n SiX _4-n Formula (1)
N in the general formula (1) is an integer of 1 to 3. R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a group selected from a halogen atom, an alkoxy group having 1 to 6 carbon atoms and an acetoxy group, and R and X are the same or different. It doesn't matter. R and X in the general formula (1) are preferably selected from the same groups as in the general formulas (2), (5) and (6). Specific examples of R include a hydrogen atom, methyl, ethyl, n -Propyl, isopropyl, n-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, neopentyl, cyclopentyl, n-hexyl, i-hexyl, cyclohexyl, n-heptyl, i-heptyl, n-octyl , I-octyl, t-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl and the like acyclic or cyclic aliphatic hydrocarbon groups, vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclo Acyclic and cyclic alkenyl groups such as hexenyl, cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, styryl and the like; Aralkyl groups such as ru, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, aralkenyl groups such as PhCH = CH- groups, and aryl groups such as phenyl, tolyl or xylyl groups. It is done. Among these, as a group having a small weight loss upon conversion to silicon oxide oxide upon firing and a small shrinkage rate, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen group is more preferable.

Specific examples of X in the general formula (1) include halogen atoms such as chloride and bromide, methoxy group, ethoxy group, n-propyloxy group, i-propyloxy group, n-butyloxy group, and t-butyloxy. Group, an alkoxy group such as an n-hexyloxy group and a cyclohexyloxy group, and an acetoxy group. Among these, alkoxy groups such as a methoxy group and an ethoxy group and an acetoxy group are preferable because of high reactivity of the condensation reaction.
The silane compound represented by the general formula (1) to be added to the reactant for filling the trench according to the present invention may be one kind or a plurality of silane compounds. When adding a plurality of silane compounds, they may be added one by one or after mixing a plurality of silane compounds.

The addition amount of the silane compound represented by the general formula (1) is preferably in the range of more than 0% by mass and 40% by mass or less, more preferably 0% by mass with respect to the total of the polysiloxane compound, silica particles, and silane compound. Exceeding 30% by mass or less. The above range is preferable because the pot life of the trench-filling reaction product of the present invention is increased and crack resistance is increased.
The silane compound represented by the general formula (1) may be added neat, or may be added after once diluted with a solvent. As a solvent which can be diluted, any solvent may be used as long as the silane compound does not react. For example, ether type, hydrocarbon type, halogenated solvent and the like are used.

The concentration of the silane compound to be added is preferably in the range of 1 wt% to 100 wt%, more preferably 3 wt% to 50 wt%. It is preferable for it to be within the above range since the amount of solvent during production is reduced.
After adding a silane compound, it is preferable to make it react in the range of -50 degreeC or more and 200 degrees C or less for 1 minute or more and 100 hours. By controlling the reaction temperature and the reaction time, it is possible to control the viscosity at the time of film formation of the trench filling reactant of the present invention.

  The reactant for trench filling of the present invention is selected from alcohols, ketones, esters, ethers and hydrocarbon solvents having a boiling point of 100 ° C. or higher and 200 ° C. or lower after reacting with the silane compound represented by the general formula (1). It is preferable to use a dispersion or solution in which at least one kind of the solvent is contained in an amount of 50% by mass or more based on the total amount of the solvent in the polysiloxane-based trench embedding condensation reaction solution of the present invention. Alcohol, ketone, ester and ether solvents may be added in advance during the reaction between the polysiloxane compound and silica particles, or the reaction between the polysiloxane and silica particles and the silane compound. After the reaction between the compound and the silica particles, or the reaction between the polysiloxane compound and the silica particles and the silane compound, a solvent selected from the above may be further added. Further, after the reaction product is formed, the solvent once used in the reaction may be added after concentration by a method such as distillation.

  Specific examples of the alcohol, ketone, ester, ether, and hydrocarbon solvent include alcohols such as butanol, pentanol, hexanol, octanol, methoxyethanol, ethoxyethanol, propylene glycol monomethoxy ether, and propylene glycol monoethoxy ether. Solvents, methyl ethyl ketone, methyl isobutyl ketone, isoamyl ketone, ethyl hexyl ketone, cyclopentanone, cyclohexanone, γ-butyrolactone and other ketone solvents, butyl acetate, pentyl acetate, hexyl acetate, propyl propionate, butyl propionate, pentyl Ester solvents such as propionate, hexyl propionate, propylene glycol methyl ethyl acetate, ethyl lactate, butyl ethyl ether Examples include ether solvents such as butylpropyl ether, dibutyl ether, anisole, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol diethyl ether, and hydrocarbon solvents such as toluene and xylene. It is done. These solvent systems may be mixed with a solvent having a boiling point of 100 ° C. or lower as long as it is contained in an amount of 50% by mass or more in the solvent system included in the reactant for filling trenches of the present invention. A plurality of the above solvent systems may be used. By containing 50% by mass or more of alcohol, ketone, ester, ether, or hydrocarbon solvent having a boiling point of 100 ° C. or higher and 200 ° C. or lower, the pot life of the trench filling reactant can be increased. It is preferable for improving the film property.

Solvent used in reaction of polysiloxane compound and silica particle, or reaction of polysiloxane compound, silica particle, silane compound, and reaction of polysiloxane compound and silica particle, or polysiloxane compound, silica particle and silane compound If the boiling point of water or alcohol produced during the reaction is lower than that of the alcohol, ketone, ester or ether solvent, distillation is performed during the reaction or after adding a solvent selected from the above after the reaction. It is preferable to remove the solvent having a low boiling point by a method such as the above because the pot life of the trench filling reaction product of the present invention becomes longer.
The trench filling reactant manufactured by such a method can be applied by a usual method. Examples thereof include spin coating, dip coating, roller blade coating, and spray coating. Among them, the spin coating method is preferable because the coating thickness at the time of film formation becomes uniform.

After coating by these methods, it is preferable to pre-cure at 50 to 200 ° C. in order to remove the residual solvent in the coating film.
An oxide can be obtained by oxidizing and heating and baking a film obtained by pre-curing.
General heating means such as a hot plate, an oven, and a furnace can be applied as the main curing oxidation and baking method. The heat treatment temperature is preferably 100 ° C to 1200 ° C, more preferably 200 ° C to 1000 ° C. More preferably, it is 300 to 900 degreeC. If it is in said range, since the film density after baking is high and the obtained film quality is good, it is preferable. Any of air, oxygen, or steam oxidation may be used as the atmosphere during the heating and firing. The oxidation and heating firing temperature is 200 to 850 ° C., and firing may be performed in an inert atmosphere such as N ₂ or Ar before and after oxidation.

There is no restriction | limiting in particular in the pressure at the time of an oxidation and a heat-firing process, It can implement by any pressure under pressure, a normal pressure, pressure reduction, or a vacuum.
Further, light treatment may be used in combination during oxidation and heat combustion. In this case, the light treatment may be performed before or after heating, or the light treatment may be performed simultaneously while heating. The temperature when heating and light treatment are performed simultaneously is preferably room temperature to 500 ° C., and the treatment time is about 0.1 to 120 minutes.
As light treatment, visible light, ultraviolet light, far ultraviolet light, etc. can be used, low pressure or high pressure mercury lamp, deuterium lamp, discharge light of rare gas such as argon, krypton, xenon, YAG laser, argon laser, An excimer laser such as a carbon dioxide laser, XeF, XeCl, XeBr, KrF, KrCl, ArF, or ArCl can be used as a light source. These light sources preferably have an output of 10 to 5,000 W. The wavelength of these lights may be as long as the composition in the coated film absorbs even a little, but it is preferably light having a wavelength of 170 nm to 600 nm, and the irradiation amount is from 0.1 to 1,000 J / cm ² , more preferably 1 to 100 J / cm ² . Ozone may be generated simultaneously with the light treatment. The light treatment within the above range is preferable because the oxidation reaction proceeds and the film quality after baking is improved.
The insulating film obtained by using the resin composition for filling a trench according to the present invention is suitable as an insulating film for a flash memory, for example.

Hereinafter, embodiments of the present invention will be described in detail with reference to Examples and Comparative Examples. The present invention is not limited to these.
(1) Molecular weight measurement of polysiloxane compound Using Tosoh's gel permeation chromatography (GPC), HLC-8220, the polysiloxane compound was measured in a 1% by mass solution in tetrahydrofuran (THF) solvent, and differential refraction was measured. The weight average molecular weight (Mw) in terms of polystyrene was determined by a rate meter (RI).
(2) Crack resistance Coating and baking are performed so that the film thickness after baking becomes 0.7 μm, the Si substrate after baking is observed with an optical microscope, and it is determined whether or not there are cracks with the optical microscope. And the case where there was no crack was marked as “good”.
(3) Shrinkage rate The film thickness before firing of the Si substrate and the film thickness after firing were measured with a spectroscopic ellipsometer UVISEL manufactured by HORIBA JOBINYVON, and the shrinkage rate was determined from the difference in film thickness before and after firing.

(4) HF resistance The fired Si substrate was immersed in an HF solution having a weight ratio of 1: 199 for 20 seconds, and the film thickness before and after the HF test was measured with a spectroscopic ellipsometer. The HF rate at which the film on the substrate was dissolved was 50 nm / If it is less than or equal to min, it was evaluated as ◯.
(5) Embeddability After cleaving a Si substrate having a trench and performing FIB processing, using a scanning electron microscope (SEM) S4700 manufactured by Hitachi, and measuring at an acceleration voltage of 5 kV, if the trench is buried ○.
(6) Crocodile spot life The produced polysiloxane-based trench filling reactant solution was allowed to stand at room temperature for 3 days, and it was evaluated as ◯ if it did not gel.
Production example of polysiloxane compound

[Production Example 1]
In a 1 L four-necked flask equipped with a distillation tower and a dropping funnel, 37.19 g (0.23 mol) of triethoxysilane and 200 g of isopropanol were placed, and a mixed solution of 36.68 g (2.04 mol) of water and 0.4 g of hydrochloric acid was added. It was dripped at room temperature. It stirred for 2 hours after completion | finish of dripping. 250 g of xylene was added, the temperature was raised, and isopropanol, water, hydrochloric acid and xylene were distilled off to obtain a 10% by mass xylene solution of the polysiloxane compound. The resulting xylene solution was neutral. When a part was sampled and GPC was measured, the weight average molecular weight was 12,000.

[Production Example 2]
Into a 1 L four-necked flask equipped with a distillation tower and a dropping funnel was placed 33.04 g (0.20 mol) of triethoxysilane, 4.65 g (0.022 mol) of tetraethoxysilane, and 200 g of isopropanol, and 37.41 g (2 0.08 mol) and 0.4 g of hydrochloric acid were added dropwise at room temperature. It stirred for 2 hours after completion | finish of dripping. 250 g of xylene was added, the temperature was raised, and isopropanol, water, hydrochloric acid and xylene were distilled off to obtain a 10% by mass polysiloxane compound xylene solution. The resulting xylene solution was neutral. When a part was sampled and GPC was measured, the weight average molecular weight was 65,000.

[Production Example 3]
A 200 mL eggplant flask is charged with 32.20 g (0.20 mol) of triethoxysilane, 2.62 g (0.022 mol) of dimethoxydimethylsilane and 50 g of isopropanol, and mixed with 11.37 g (0.063 mol) of water and 1.0 g of hydrochloric acid. The solution was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of a polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 6,800.

[Production Example 4]
A 200 mL eggplant flask is charged with 33.04 g (0.20 mol) of triethoxysilane, 2.37 g (0.022 mol) of dimethoxymethylsilane and 100 g of isopropanol, and mixed with 11.66 g (0.65 mol) of water and 1.0 g of hydrochloric acid. The solution was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of a polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 7,200.

[Production Example 5]
A 200 mL eggplant flask is charged with 32.20 g (0.20 mol) of triethoxysilane, 2.17 g (0.021 mol) of methoxytrimethylsilane and 50 g of isopropanol, and mixed with 10.96 g (0.61 mol) of water and 1.0 g of hydrochloric acid. The solution was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of a polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 5,400.

[Production Example 6]
In a 200 mL eggplant flask, 19.61 g (0.12 mol) of triethoxysilane, 4.41 g (0.037 mol) of dimethoxydimethylsilane, and 50 g of isopropanol were added, and 7.77 g (0.43 mol) of water and 1.0 g of hydrochloric acid were added. The mixed solution was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of a polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 4,800.

[Production Example 7]
In a 200 mL eggplant flask, 19.61 g (0.12 mol) of triethoxysilane, 4.10 g (0.040 mol) of dimethoxymethylsilane, and 100 g of isopropanol were added, and a mixed solution of 7.84 g of water and 1.0 g of hydrochloric acid was mixed at room temperature. It was dripped. After completion of dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of a polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 5,200.

[Production Example 8]
In a 500 mL four-necked flask equipped with a reflux tower and a dropping funnel, 19.61 g (0.12 mol) of triethoxysilane and 150 g of isopropanol were placed and cooled in a dry ice-ethanol bath. 16.48 g (0.041 mol) of 25% by mass of dichlorosilane in xylene was added dropwise with a syringe. After raising the temperature to 0 ° C., 7.91 g of water was added dropwise. After completion of the dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of the polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 7,500.

[Production Example 9]
In a 200 mL eggplant flask, 3.13 g (0.019 mol) of triethoxysilane, 13.05 g (0.109 mol) of dimethoxydimethylsilane, and 50 g of isopropanol were added, and 4.94 g (0.27 mol) of water and 1.0 g of hydrochloric acid were added. The mixed solution was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of a polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 3,700.

[Production Example 10]
A 200 mL eggplant flask is charged with 3.64 g (0.022 mol) of triethoxysilane, 12.87 g (0.12 mol) of methoxytrimethylsilane and 50 g of isopropanol, and mixed with 3.42 g (0.19 mol) of water and 1.0 g of hydrochloric acid. The solution was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 2 hours to obtain an isopropanol solution of a polysiloxane compound. When a part was sampled and GPC was measured, the weight average molecular weight was 850.
The above Production Examples 1 to 9 are summarized in Table 1.

[Example 1]
Into a 4 L 1 L flask having a distillation column and a dropping funnel, an isopropanol-dispersed silica particle having an average particle diameter of 7 nm and a concentration of 20% by mass manufactured by Catalyst Kasei Kogyo; AZ-1003, 15 g, 100 g of isopropanol and 1.0 g of hydrochloric acid are placed. Then, 120 g of a 10% by mass polysiloxane compound produced in Production Example 1 was dropped at room temperature. After the addition was completed, 250 g of xylene was further added, and then the temperature was raised to 100 ° C. in an oil bath and refluxed for 4 hours. After refluxing, the temperature of the oil bath was raised, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a xylene solution of a reaction product of a polysiloxane compound and silica particles. The xylene solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

2 mL of a xylene solution of the reaction product of the polysiloxane compound and silica particles was dropped on a 6-inch Si substrate, and spin coating was performed in two stages of a rotation speed of 500 rpm for 10 seconds and a rotation speed of 1000 rpm for 30 seconds. This substrate was pre-baked stepwise for 2 minutes on a hot plate at 50 ° C., 100 ° C., and 200 ° C. in air to remove the solvent. The obtained coating film was uniform with no repelling or foreign matter observed.
The obtained Si substrate was heated to 400 ° C. at 5 ° C./min in an oxygen atmosphere and baked for 30 minutes. The atmosphere was switched from oxygen to nitrogen, and after standing for 30 minutes, the temperature was raised to 700 ° C., fired for 1 hour, and lowered to room temperature at 2 ° C./min.

The evaluation shown in the above (2) to (4) was performed on the fired Si substrate, and the evaluation results are shown in Table 2.
Also, 1 mL of a xylene solution of a reaction product of the polysiloxane compound and silica particles was dropped on a Si chip having a trench with an opening degree of 100 nm and a depth of 0.3 μm, and spin coating, pre-baking, and baking were performed under the above conditions.
The obtained fired substrate was cleaved, and after FIB processing, SEM measurement was performed. As a result, local grooves, holes, cracks, and other voids were not observed, and no film formation abnormality was observed.

[Example 2]
Into a 4 L 1 L flask having a distillation column and a dropping funnel, an isopropanol-dispersed silica particle having an average particle diameter of 7 nm and a concentration of 20% by mass manufactured by Catalyst Kasei Kogyo; AZ-1003, 15 g, 100 g of isopropanol and 1.0 g of hydrochloric acid are placed. Then, 122 g of a 10 mass% polysiloxane compound xylene solution produced in Production Example 2 was added dropwise at room temperature. After the addition was completed, 250 g of xylene was further added, and then the temperature was raised to 100 ° C. in an oil bath and refluxed for 4 hours. After refluxing, the temperature of the oil bath was raised, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a xylene solution of a reaction product of a polysiloxane compound and silica particles. The xylene solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

A xylene solution of a reaction product of the polysiloxane compound and silica particles is applied to a 6-inch Si substrate and a Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 3]
Into a 4 L 1 L flask having a distillation tower and a dropping funnel, an isopropanol-dispersed silica particle having an average particle diameter of 7 nm and a concentration of 20% by mass; AZ-1003, 15 g, and 100 g of isopropanol manufactured by Catalyst Kasei Kogyo are put. 97 g of an isopropanol solution of the polysiloxane compound produced in (1) was added dropwise at room temperature. After the addition was completed, 250 g of xylene was further added, and then the temperature was raised to 100 ° C. in an oil bath and refluxed for 4 hours. After refluxing, the temperature of the oil bath was raised, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a xylene solution of a reaction product of a polysiloxane compound and silica particles. The xylene solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

A xylene solution of a reaction product of the polysiloxane compound and silica particles is applied to a 6-inch Si substrate and a Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 4]
Into a 4 L 1 L flask having a distillation tower and a dropping funnel, an isopropanol-dispersed silica particle having an average particle diameter of 7 nm and a concentration of 20% by mass; AZ-1003, 15 g, and 100 g of isopropanol manufactured by Catalyst Chemical Industry Co., Ltd. were placed. 148 g of an isopropanol solution of 10% by mass of the polysiloxane compound produced in (1) was added dropwise at room temperature. After the addition was completed, 250 g of xylene was further added, and then the temperature was raised to 100 ° C. in an oil bath and refluxed for 4 hours. After refluxing, the temperature of the oil bath was raised, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a xylene solution of a reaction product of a polysiloxane compound and silica particles. The xylene solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

A xylene solution of a reaction product of the polysiloxane compound and silica particles is applied to a 6-inch Si substrate and a Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 5]
Into a four-liter 1 L flask having a distillation column and a dropping funnel, an isopropanol-dispersed silica particle having an average particle diameter of 7 nm and a concentration of 20% by mass; 96 g of an isopropanol solution of 10% by mass of the polysiloxane compound produced in Example 3 was added dropwise at room temperature. After the addition was completed, 250 g of xylene was further added, and then the temperature was raised to 100 ° C. in an oil bath and refluxed for 4 hours. After refluxing, the temperature of the oil bath was raised, and isopropanol, hydrochloric acid, and water were distilled off from the distillation line to obtain a xylene solution of a reaction product of a polysiloxane compound and silica particles. The xylene solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

A xylene solution of a reaction product of the polysiloxane compound and silica particles is applied to a 6-inch Si substrate and a Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 6]
Into a four-necked 1 L flask having a distillation tower and a dropping funnel, put water-dispersed silica particles having an average particle size of 7 nm and a concentration of 6.3% by mass; PL-06, 47.62 g and 350 g of isopropanol, manufactured by Fuso Chemical Industry, 120 g of a 10% by mass polysiloxane compound xylene solution produced in Production Example 1 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 2.0 g (0.012 mol) of triethoxysilane and 10 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 200 g of propylene glycol methyl ethyl acetate (PGMEA) was added, the temperature of the oil bath was raised, isopropanol, hydrochloric acid, water and xylene were distilled off from the distillation line, and PGMEA as a reaction product of polysiloxane compound, silica particles and silane compound was removed. A solution was obtained. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 7]
Into a four-necked 1 L flask having a distillation tower and a dropping funnel, put water-dispersed silica particles having an average particle size of 7 nm and a concentration of 6.3% by mass; PL-06, 47.62 g and 350 g of isopropanol, manufactured by Fuso Chemical Industry, 113 g of a 10% by mass polysiloxane compound produced in Production Example 2 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 2.0 g (0.012 mol) of triethoxysilane and 10 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 200 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of polysiloxane compound, silica particles, and silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 8]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle size of 7 nm and a concentration of 6.3% by mass; PL-06, 47.62 g and 162 g of isopropanol, manufactured by Fuso Chemical Industry, 94 g of an isopropanol solution of the polysiloxane compound produced in Production Example 3 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 2.0 g (0.012 mol) of triethoxysilane and 34 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 200 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of polysiloxane compound, silica particles, and silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 9]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle diameter of 7 nm and a concentration of 6.3% by mass; PL-06, 71.43 g and 243 g of isopropanol, manufactured by Fuso Chemical Industry, 83 g of an isopropanol solution of the polysiloxane compound produced in Production Example 6 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 4.51 g (0.027 mol) of triethoxysilane and 88 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 200 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of polysiloxane compound, silica particles, and silane compound. The xylene solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 10]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle diameter of 7 nm and a concentration of 6.3% by mass; PL-06, 71.43 g and 243 g of isopropanol, manufactured by Fuso Chemical Industry, 133 g of an isopropanol solution of the polysiloxane compound produced in Production Example 7 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 4.51 g (0.027 mol) of triethoxysilane and 88 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 250 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of a polysiloxane compound, silica particles, and a silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 11]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle diameter of 7 nm and a concentration of 6.3% by mass; PL-06, 71.43 g and 243 g of isopropanol, manufactured by Fuso Chemical Industry, 183 g of an isopropanol solution of the polysiloxane compound produced in Production Example 8 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 4.51 g (0.027 mol) of triethoxysilane and 76 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 250 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of a polysiloxane compound, silica particles, and a silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 12]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle diameter of 7 nm and a concentration of 6.3% by mass; PL-06, 95.24 g and 324 g of isopropanol, manufactured by Fuso Chemical Industry, 78 g of an isopropanol solution of the polysiloxane compound produced in Production Example 3 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 6.01 g (0.037 mol) of triethoxysilane and 95 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 300 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of a polysiloxane compound, silica particles, and a silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Example 13]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle diameter of 7 nm and a concentration of 6.3% by mass; PL-06, 95.24 g and 324 g of isopropanol, manufactured by Fuso Chemical Industry, 76 g of an isopropanol solution of the polysiloxane compound produced in Production Example 6 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 6.01 g (0.037 mol) of triethoxysilane and 95 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 300 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of a polysiloxane compound, silica particles, and a silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
The other evaluation results are shown in Table 2.

[Comparative Example 1]
The 10% by mass polysiloxane compound xylene solution produced in Production Example 2 was concentrated to 20% by mass, and a 6-inch Si substrate was coated, pre-baked and fired under the same conditions as in Example 1. The obtained Si substrate was repelled and non-uniform.

[Comparative Example 2]
A 200 mL eggplant flask was charged with 10 mass% polysiloxane compound produced in the above Production Example 1 by placing water-dispersed silica particles having an average particle diameter of 7 nm and a concentration of 6.3 mass%; PL-06, 47.62 g, manufactured by Fuso Chemical Industries, Ltd. When 120 g of xylene solution was mixed without reacting, it was separated into two layers. When water was distilled off with an evaporator, gelation occurred.

[Comparative Example 3]
In a 200 mL eggplant flask, 20 mass% isopropanol-dispersed silica particles; 15-100 g of AZ-1003 were placed and mixed without reacting with 120 g of the 10 mass% polysiloxane compound xylene solution produced in Production Example 1 above. When isopropanol was distilled off with an evaporator, gelation occurred.

[Comparative Example 4]
In a 500 mL four-necked flask equipped with a distillation column and a dropping funnel, 20% by mass isopropanol-dispersed silica particles; AZ-1003, 15 g, 27.57 g (0.17 mol) of triethoxysilane, 9.19 g of tetraethoxysilane (0.1. 044 mol), and a mixed solution of 24.48 g of water and 1.0 g of hydrochloric acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 2 hours, 250 g of xylene was added, and the temperature was raised to remove isopropanol, water and hydrochloric acid. The resulting xylene solution was neutral. This xylene solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.
A xylene solution of the reaction product of the silane compound and silica particles is applied to a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, pre-baking, and baking. went. The obtained Si substrate had cracks of 0.6 μm. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, generation of voids and cracks was observed.

[Comparative Example 5]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle diameter of 7 nm and a concentration of 6.3% by mass; PL-06, 71.43 g and 243 g of isopropanol, manufactured by Fuso Chemical Industry, 72 g of an isopropanol solution of the polysiloxane compound produced in Production Example 9 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 4.51 g (0.027 mol) of triethoxysilane and 56 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 200 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of polysiloxane compound, silica particles, and silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The obtained Si substrate was uniform with no repelling or foreign matter observed. When the Si substrate having a trench was cleaved and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and no film formation abnormality was observed.
When the HF test of the obtained 6-inch Si substrate was performed, the Si substrate became cloudy. An attempt was made to measure the film thickness after the HF test with an ellipsometer, but the film thickness could not be measured.

[Comparative Example 6]
Into a four-necked 1 L flask having a distillation column and a dropping funnel, put water-dispersed silica particles having an average particle size of 7 nm and a concentration of 6.3% by mass; PL-06, 47.62 g and 162 g of isopropanol, manufactured by Fuso Chemical Industry, 71 g of an isopropanol solution of the polysiloxane compound produced in Production Example 10 was added dropwise at room temperature. After completion of dropping, the mixture was stirred for 30 minutes, and a solution diluted with 2.0 g (0.012 mol) of triethoxysilane and 34 g of xylene was dropped. The mixture was refluxed at 100 ° C. for 4 hours. After refluxing, 200 g of PGMEA was added, the oil bath was heated, and isopropanol, hydrochloric acid, water, and xylene were distilled off from the distillation line to obtain a PGMEA solution of a reaction product of polysiloxane compound, silica particles, and silane compound. The PGMEA solution of the reaction product of the obtained polysiloxane compound and silica particles was neutral. The PGMEA solution was concentrated to 20% by mass and allowed to stand at room temperature for 3 days, but the varnish did not gel.

The PGMEA solution of the reaction product of the polysiloxane compound and silica particles is coated on a 6-inch Si substrate and an Si substrate having a trench with an opening degree of 100 nm and a depth of 0.3 μm under the same conditions as in Example 1, prebaking, and baking. Went. The film thickness of the obtained Si substrate was 0.6 μm, and generation of cracks was observed. When the Si substrate having a trench was cut and subjected to SEM measurement after FIB processing, local cracks were observed.
The above results are shown in Table 2.

  From Table 2, the reaction product of polysiloxane compound and silica particles or polysiloxane compound, silica particles and silane compound has a long pot life as a varnish, and has excellent film-forming properties, crack resistance, HF resistance, and embedding properties. I understand.

  The composition of the present invention can be suitably used in the field of trench filling reactants for insulating protective films in trenches formed in semiconductor devices.

Claims (8)

A condensation reaction product for trench filling, wherein the condensation reaction product contains at least a condensation reaction product of a polysiloxane compound and silica particles, and the polysiloxane compound is composed of an HSiO _3/2 group, a MeHSiO group, and an H ₂ SiO group. Trench embedding characterized by having at least one selected group of 40 mol% or more, the polysiloxane having a weight average molecular weight of 1,000 or more and 200,000 or less, and an average primary particle size of the silica particles of 1 nm or more and 100 nm or less Condensation reaction product. The condensation reaction product is added to the condensation reaction product of the polysiloxane compound and the silica particles, and the condensation reaction product is represented by the following general formula (1):
R _n SiX _4-n Formula (1)
{In the general formula (1), n is an integer of 1 to 3, R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, X is a halogen atom, an alkoxy group having 1 to 6 carbon atoms, And a group selected from the group consisting of acetoxy groups. } Containing silane compound represented by the further reaction product obtained by condensation reaction, condensation reaction for embedding trench according to claim 1. Formula wherein the polysiloxane compound from the following general formula (2) (6):
HSiX ₃ general formula (2)
SiX ₄ general formula (3)
R ² SiX ₃ general formula (4)
R ₂ SiX ₂ general formula (5)
R ₃ SiX general formula (6)
{R in General Formula (5) and General Formula (6) is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms , and X in General Formula (2) to General Formula (6) is a halogen atom, It is a group selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and an acetoxy group, and R ² in the general formula (4) is a hydrocarbon group having 1 to 10 carbon atoms. It comprises components derived from the silane compound represented by}, and, the general formula (2) silane compounds represented by containing more than 30 mol%, claim 1 or trench burying condensation reaction product according to 2. The total of said silica particles and said polysiloxane compound silica particles, or the polysiloxane compound and the silica particles and the silane compound, is below 80 wt% or more 1 wt%, one of the claims 1 to 3, The condensation reaction product for trench filling according to claim 1. The total of the silane compound the polysiloxane compound and silica particles and the silane compound, is below 0 wt% excess 40 wt%, the trench burying condensation reaction product according to any one of claims 2-4 . In the solution containing the condensation reaction product according to any one of claims 1 to 5, at least selected from the group consisting of alcohols, ketones, esters, ethers, and hydrocarbon solvents having a boiling point of 100 ° C or higher and 200 ° C or lower. A trench filling reaction solution, wherein one kind of solvent is contained in an amount of 50% by mass or more based on the total amount of solvents in the solution. Oite the preparation of the polysiloxane compound, the formula (2) to the total number of moles of X contained in the silane compound represented by (6), 0.1 equivalents more than 10 equivalents or less of water The method for producing a condensation reaction product for trench embedding according to any one of claims 3 to 5 , comprising a reaction step. The reaction of the polysiloxane compound and the silica particles, or the reaction is carried out between the polysiloxane compound and the silica particles and the silane compound in an acidic atmosphere, The method of claim 7.