JP2014057074A - Condensation reaction product for filling polysiloxane-based trench and method for manufacturing trench filling film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a condensation reaction product for filling a trench, a solution of which having good storage stability, the solution being suitable for using for filling the trench formed in a substrate with silicon oxide, having high filling performance, permitting formation of a thick film, and having good crack resistance; and a method for manufacturing a trench filling film.SOLUTION: A condensation reaction product for filling a trench contains a condensation reaction product of a polysiloxane compound and silica particles, and a mixed solvent or an organic solvent (C), the mixed solvent comprising an organic solvent (A) having a vapor pressure of 530 Pa or above at 20°C and a boiling point of 80°C or above and below 130°C and an organic solvent (B) having a vapor pressure of below 530 Pa at 20°C and a boiling point of 130°C or above and 200°C or below, and the organic solvent (C) having a vapor pressure of 530 Pa or above at 20°C and a boiling point of 130°C or above and 200°C or below.

Description

  The present invention relates to a condensation reaction product for filling a trench for an insulating protective film in a trench formed in a semiconductor element, and a method for manufacturing a trench filling film.

  Shallow trench isolation technology (STI technology) as one of the technologies to electrically isolate circuit elements such as transistors, which are components of electronic devices such as DRAM (Dynamic Random Access Memory) Has been developed. 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 depth by the opening width of the trench) tends to increase.

As a material used for such trench filling, silicon oxide is widely and suitably used because high electrical insulation is required.
As a means for embedding silicon oxide in the trench, a method is known in which a fine groove of a trench is buried by a coating method and a silica film is formed by baking in an oxidizing atmosphere. For example, a silicone material is used as the silicon oxide precursor.
However, since the silicone material is accompanied by dehydration and dealcoholization condensation reactions during coating and baking, the resulting silica film is cracked or the seam in the buried portion (in the vicinity of the bottom of the trench, the buried material and the substrate material). Between the substrate and the substrate) and voids (a phenomenon in which a portion of the embedded material has a void), and peeling from the substrate.

  As a method for avoiding such a problem, a silicone material composed of silicon oxide particles and a silicon atom binder (see, for example, Patent Document 1 below), or a hydrogenated silicone compound having a reduced number of terminal silanol groups (for example, the following Patent Document: 2) has been proposed. These have been reported to show good embedding without generating seams or voids in fine trenches. However, with recent miniaturization of circuit elements, trenches tend to be finer and have a higher aspect ratio, and while maintaining a high-purity silica film, higher embedding in the trench and a thicker film are required. It has been. However, in the method of Patent Document 1, the obtained silica film contains a large amount of carbon components, and a high-purity silica film cannot be obtained. In the method of Patent Document 2, the concentration of the silicone compound in the solution is increased. If an attempt is made to increase the film thickness at the time of coating, there are problems such as poor embedding properties, poor storage stability of the silicone compound solution, and cracks after firing. Therefore, there is a demand for a high-purity silica film that simultaneously satisfies high trench embedding properties and thickening at the time of application, and that does not easily crack even after being fired.

JP 2006-310448 A JP 2008-101206 A

  The present invention has been made in view of the above problems, and its problem is that the storage stability of a solution suitable for use in embedding silicon oxide in a trench formed in a substrate is good, and the embedding property is improved. It is intended to provide a condensation reaction product for trench embedding that is high in thickness, can be thickened, and has good crack resistance, and a method for producing a trench embedding film.

As a result of intensive studies to solve the above problems, the present inventors have found the following condensation reaction product for trench filling and a method for producing a trench filling film, and have completed the present invention.
That is, the present invention is as follows.

  [1] Condensation reaction product of polysiloxane compound and silica particles, organic solvent (A) having a vapor pressure at 20 ° C. of 530 Pa or higher and a boiling point of 80 ° C. or higher and lower than 130 ° C., and vapor at 20 ° C. A mixed solvent comprising an organic solvent (B) having a pressure of less than 530 Pa and a boiling point of 130 ° C. or higher and 200 ° C. or lower, or a vapor pressure at 20 ° C. of 530 Pa or higher and a boiling point of 130 ° C. or higher and 200 ° C. A condensation reaction product for trench embedding comprising the following organic solvent (C):

[2] The polysiloxane compound has 40 mol% or more of at least one group selected from the group consisting of HSiO _3/2 group, MeHSiO group, and H ₂ SiO group, and the weight average molecular weight of the polysiloxane is 1, The condensation reaction product for trench embedding according to the above [1], wherein the silica particle has an average primary particle size of 1 nm or more and 100 nm or less.

  [3] In the above [1] or [2], the organic solvent (A) is at least one selected from the group consisting of alcohols, polyhydric alcohol derivatives, ketones, esters, ethers, and hydrocarbon solvents. The condensation reaction product for trench filling as described.

  [4] The above-mentioned [1] to [3], wherein the organic solvent (B) is at least one selected from the group consisting of alcohols, polyhydric alcohol derivatives, ketones, esters, ethers, and hydrocarbon solvents. The condensation reaction product for trench filling according to any one of the above.

  [5] The above-mentioned [1] to [4], wherein the organic solvent (C) is at least one selected from the group consisting of alcohols, polyhydric alcohol derivatives, ketones, esters, ethers, and hydrocarbon solvents. The condensation reaction product for trench filling according to any one of the above.

  [6] The organic solvent (A) is 10% by mass or more and 50% by mass or less, and the organic solvent (B) is 50% by mass with respect to the total amount of the solvents contained in the trench filling condensation reaction product. The condensation reaction product for trench embedding according to any one of [1] to [5], which is 90% by mass or less or the organic solvent (C) is 60% by mass or more.

[7] In addition to the polysiloxane compound and the silica particles, the condensation reaction product further contains the following general formula (1):
R _n SiX _4-n
{Wherein, 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 an acetoxy group A plurality of R and X may be the same or different. } The condensation reaction product for trench embedding according to any one of [1] to [6], including a reaction product obtained by condensation reaction with a silane compound represented by

[8] The polysiloxane compound is represented by the following general formula (2):
HSiX ₃
{In the formula, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, and may be the same or different. } The condensation reaction product for trench embedding according to any one of the above [1] to [7], which is a condensation reaction product of a silane compound represented by:

[9] The polysiloxane compound is represented by the following general formula (2):
HSiX ₃
{In the formula, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, and may be the same or different. } And the following general formula (3):
SiX ₄
{In the formula, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, and may be the same or different. }, The following general formula (4):
R ² SiX ₃
{Wherein R ² is a hydrocarbon group having 1 to 10 carbon atoms, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group; May be the same or different. }, The following general formula (5):
R ₂ SiX ₂
{In the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group; The plurality of R and X may be the same or different. } Or a compound represented by the following general formula (6):
R ₃ SiX
{In the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group; R may be the same or different. } Is a condensation reaction product with at least one selected from silane compounds represented by the formula (2), and the proportion of the structure derived from the silane compound represented by the general formula (2) in the polysiloxane compound is 30 mol% or more The condensation reaction product for trench embedding according to any one of [1] to [8], wherein

  [10] 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 1] to [9].

  [11] The silane compound according to any one of [1] to [10], 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 the silane compound. Condensation reaction product for trench filling.

  Including a step of applying the condensation reaction product according to any one of [1] to [11] to a substrate having a trench by a spin coating method, wherein a rotation speed of at least a first stage in the spin coating method is 50 rpm to 700 rpm. A method for producing a trench buried film, wherein:

  According to the present invention, the storage stability of a solution suitable for use in embedding silicon oxide in a trench formed in a substrate is good, the embedding property is high, the film thickness can be increased, and the crack resistance is good. A condensation reaction product for trench filling and a method for producing a trench filling film are provided.

Hereinafter, embodiments of the present invention will be described in detail.
The polystyrene-equivalent weight average molecular weight used in the present invention is 1,000 to 200,000, and 40 mol% of at least one group selected from the group consisting of HSiO _3/2 group, MeHSiO group, and H ₂ SiO group. The above-mentioned polysiloxane compound contains at least one silane compound represented by the following general formula (2) alone or the general formula (2) and the following general formula (3) to general formula (6) in an acidic atmosphere. A condensation reaction product obtained by reacting 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):
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 , A group selected from the group consisting of an alkoxy group having 1 to 6 carbon atoms and an acetoxy group, and when present, a plurality of R and X may be the same or different from each other, and are represented by the general formula (4): R < ² > in it is a C1-C10 hydrocarbon group. }.

  Specific examples of R in the above 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, and 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 Acyclic or cyclic aliphatic hydrocarbon groups such as -octyl, t-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, Acyclic or ring such as cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, styryl An alkenyl group, an aralkyl group such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, an aralkenyl group such as a PhCH = CH- group, an aryl such as a phenyl group, a tolyl group, and a xylyl group Groups. 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 above general formula (2) to general formula (6) include 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, Acyclic such as n-hexyl, i-hexyl, cyclohexyl, n-heptyl, i-heptyl, n-octyl, i-octyl, t-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, etc. Or a cyclic aliphatic hydrocarbon group, acyclic or cyclic alkenyl such as vinyl, propenyl, butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, styryl Groups such as benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, etc. Examples include an aralkyl group, an araalkenyl group such as a PhCH═CH— group, an aryl group such as a phenyl group, a tolyl group, and 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. The amount of the hydrogenated silane compound represented by the general formula (2) is within the above range because the shrinkage rate of the coating film during the conversion to silicon oxide is reduced during firing. ,preferable. Further, 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 based on the total of the silane compounds used in producing the polysiloxane compound. It is preferable that it is 30 mol% or less, More preferably, it is 20 mol% or less. It is preferable to be within the above range since the film forming property is good and the shrinkage rate is small.

  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 based on the total of the silane compounds used in producing the polysiloxane compound. It is preferable that it is 30 mol% or less, More preferably, it is 20 mol% or less. It is preferable to be within the above range because the film forming property is good and the shrinkage rate is small.

  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 based on the total of the silane compounds used in producing the polysiloxane compound. The amount is preferably 50 mol% or less, more preferably 30 mol% or less. Being within the above range is preferable because the embedding property is good and the crack resistance is high.

  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 based on the total of the silane compounds used in producing the polysiloxane compound. It is preferable that it is 30 mol% or less, More preferably, it is 20 mol% or less. Being within the above range is preferable because the embedding property is good and the crack resistance is high.

  When producing a polysiloxane compound, a halogen atom or an acetoxy compound is contained in X of at least one of the silane compounds represented by the general formulas (2) to (6). In this case, since the reaction system shows acidity by adding water for the condensation reaction, an acid catalyst may or may not be added in addition to the silane compound. In addition, when all of the silane compounds represented by the above general formulas (2) to (6) are all alkoxy groups, it is preferable to add an acid catalyst.

Examples of the acid catalyst include inorganic acids and organic acids.
Examples of inorganic acids 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. , 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. Regarding the amount of the acid catalyst used, adjusting the pH of the reaction system in the production of the polysiloxane compound to a range of 0.01 to 6.0 can control the weight average molecular weight of the polysiloxane compound. preferable.

  The polysiloxane compound used in the present invention 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.
Examples of the ethers include, in addition to the monoethers of the above 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 Examples include polyhydric alcohol ethers obtained by alkyl etherifying all hydroxyl groups of polyhydric alcohols such as glycol 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, butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Ether solvents such as ether, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferable because they are easy to mix with water and disperse silica particles easily.

These solvents may be used alone or in combination with a plurality of solvents. 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 reaction system. The amount of water added is, for example, 0.1 equivalents or more and 10 equivalents or less with respect to the total number of moles of X of the silane compounds represented by the general formulas (2) to (6). Preferably, it is the range of 0.4 equivalent or more and 8 equivalent 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 when it is 10 equivalents or less, the storage stability of the trench filling reactant solution is improved, Since crack resistance improves, it is preferable.

  Although there is no restriction | limiting in particular in the reaction temperature at the time of manufacturing the polysiloxane compound used by this invention, It is preferable to carry out in the range of -50 degreeC-200 degreeC, More preferably, in the range of 0 degreeC-150 degreeC. By carrying out the reaction in the above range, the molecular weight when producing the polysiloxane compound can be controlled.

  The polysiloxane compound used in the production of the trench filling condensation reaction product of the present invention, more typically a condensation reaction product of the silane compound represented by the general formula (2) or the general formula (2) The weight average molecular weight in terms of polystyrene of the condensation reaction product of the silane compound and at least one selected from the group consisting of the silane compounds represented by the general formulas (3) to (6) is 1,000 or more and 200, The range is preferably 2,000 or less, more preferably 2,000 or more and 150,000 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 storage stability of the trench filling reaction product becomes good. Therefore, it is preferable. The polysiloxane compound used in the present invention may be reacted with silica particles as it is after being produced in the above-mentioned organic solution, or after being produced in the above-mentioned 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 invention include fumed silica and colloidal silica.
The fumed silica can be obtained by reacting a compound containing silicon atoms with oxygen and hydrogen in the gas phase. Examples of the silicon compound used as a raw material include silicon halide (eg, 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). Especially, since it is preferable that there are few impurities, such as a metal and a halogen, the colloidal silica obtained from alkoxy silicon is more preferable.

The average primary particle diameter of the silica particles is preferably 1 nm or more and 120 nm or less, and more preferably 1 nm or more and 40 nm or less. When the average primary particle system is 1 nm or more, crack resistance is improved, and when the average primary particle system is 120 nm or less, the embedding property in the trench is improved.
The average secondary particle diameter of silica is preferably 2 nm or more and 250 nm or less, and more preferably 2 nm or more and 80 nm or less. When the average two-letter particle diameter is 2 nm or more, it is preferable because crack resistance is improved, and when it is 250 nm or less, embeddability in a trench is improved. In addition, the average secondary particle diameter of the silica particles is within the above range and 0.1 to 3 times the minimum opening width among the trenches formed in the substrate, the embedding property in the trenches is It is more preferable that it is 0.1 to 2 times the minimum opening width in terms of increase.

The average primary particle system is a value obtained by calculation from the specific surface area of BET, and the average secondary particle system is a value measured by a dynamic light scattering photometer.
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-shaped, plate-shaped, fibrous, or a shape in which two or more of these are combined, but is 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 such that the BET specific surface area is 1,000 m ² / g or less, more preferably 500 m ² / g or less, from the viewpoint of good HF resistance. The BET specific surface area is a value measured by a method calculated from the pressure of N ₂ molecules and the amount of gas adsorption.

The silica particles are not limited as long as they meet the above requirements, and commercially available products can also be used.
As a commercially available 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, Same ST-UP, Same ST-OUP, Same ST-20, Same ST-40, Same ST-C, Same ST-N, Same ST-O, Same ST-50, Same ST-OL (Nissan Chemical Industries) (Manufactured by Co., Ltd.), Quateron PL series (manufactured by Fuso Chemical Co., Ltd.), OSCAL series (manufactured by Catalyst Kasei Kogyo Co., Ltd.), etc .; TT600, OX50 (above, Nippon Aerosil Co., Ltd.), Sildex H31, H32, H51, H52, H121, H122 (above, Asahi Glass Co., Ltd.) , E220A, E220 (or more, 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 cited.

  When the silica particles are reacted with the polysiloxane compound used in the present invention, the silica particles dispersed in a solvent can be reacted. As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. The type of organic solvent used varies depending on the dispersion medium of the silica particles used. When the silica particle dispersion medium used is water-based, the silica particles may be reacted with the polysiloxane compound after adding water or an alcohol-based solvent to the silica particle water-dispersion medium. After the substitution with an alcohol solvent, the silica particles may be reacted with the polysiloxane compound. Examples of the alcohol solvent that can be used include methanol, ethanol, n-propanol, 2-propanol, n-butanol, methoxyethanol, ethoxyethanol, and the like, and these are preferable because they are easily mixed with water.

  In the case where the dispersion medium of 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. Examples of the acid catalyst include the same acid catalyst as that used in the production of the polysiloxane compound. When removing the acid catalyst after the production of the polysiloxane compound, it is necessary to add the acid catalyst again when reacting the silica particles with the polysiloxane compound, but the silica particles are not removed after the production of the polysiloxane compound. In the case of reacting, the polysiloxane compound and the silica particles can be reacted with the acid catalyst used when the polysiloxane compound is reacted without adding the acid catalyst again. However, in this case, an acid catalyst may be added again during the reaction between the polysiloxane compound and the silica particles.

The reaction temperature between the silica particles and the polysiloxane compound solution is not particularly limited, and is performed in a normal range of −50 ° C. or more and 200 ° C. or less.
The ratio of the silica particles is preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 70% by mass with respect to the total of the polysiloxane compound and silica particles, or the polysiloxane compound, silica particles, and silane compound. % Or less, and more preferably 10% by mass or more and 60% by mass or less. The content of 1% by mass or more is preferable because crack resistance is increased, and the content of 80% by mass or less is preferable because the film quality is improved.

The reaction product for embedding a polysiloxane trench according to the present invention is prepared by adding a polysiloxane compound solution to a dispersion medium of silica particles and reacting the resultant, followed by the following general formula (1):
R _n SiX _4-n
{Wherein 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 acetoxy And a plurality of Rs and Xs may be the same or different from each other. } May be reacted.

  R and X in the general formula (1) are preferably selected from the same groups as those in the general formula (2), the general formula (5), or the general formula (6). 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, acyclic or cyclic aliphatic hydrocarbon groups such as i-heptyl, n-octyl, i-octyl, t-octyl, n-nonyl, i-nonyl, n-decyl, i-decyl, vinyl, propenyl, Non-rings such as butenyl, pentenyl, hexenyl, cyclohexenyl, cyclohexenylethyl, norbornenylethyl, heptenyl, octenyl, nonenyl, decenyl, styryl Or an aralkyl group such as a cyclic alkenyl group, benzyl, phenethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, an aralkenyl group such as a PhCH = CH- group, a phenyl group, a tolyl group, a xylyl group Such aryl groups are 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 (1) include halogen atoms such as chlorine and bromine, 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, an alkoxy group 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 plural kinds. When adding a plurality of types of silane compounds, they may be added one by one or after mixing a plurality of types of silane compounds.
The addition amount of the silane compound represented by the general formula (1) is within a range of 40% by mass or less of the total of the polysiloxane compound, the silica particles, and the silane compound represented by the general formula (1). More preferably, it is the range of 30 mass% or less. It is preferable that the addition amount of the silane compound represented by the general formula (1) is in the above range because the storage stability of the condensation reaction product for trench embedding of the present invention is improved and crack resistance is increased.

The silane compound represented by the general formula (1) may be added neat (that is, as it is without being diluted with a solvent), or may be added after being diluted with a solvent once. As a solvent for dilution, 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 can be used. The concentration when the silane compound represented by the general formula (1) is added is preferably in the range of 1% by mass to 100% by mass, and more preferably 3% by mass to 50% by mass. It is preferable that the concentration is within the above range in that the amount of solvent can be reduced.
The silane compound represented by the general formula (1) is preferably reacted in the range of −50 ° C. to 200 ° C. for 1 minute to 100 hours after addition. By controlling the reaction temperature and the reaction time, it is possible to control the viscosity when the trench embedding reactant of the present invention is formed.

  The trench filling condensation reaction product of the present invention is reacted with the silane compound represented by the above general formula (1) and then has a vapor pressure at 20 ° C. of 530 Pa or higher and a boiling point of 80 ° C. or higher and lower than 130 ° C. An organic solvent (A) and a mixed solvent consisting of an organic solvent (B) having a vapor pressure of less than 530 Pa at 20 ° C. and a boiling point of 130 ° C. or higher and 200 ° C. or lower, or a vapor pressure at 20 ° C. of 530 Pa The solution is preferably in the form of a solution containing the organic solvent (C) having a boiling point of 130 ° C. or higher and 200 ° C. or lower.

  The solid content concentration of the dispersion or solution is 5 mass from the viewpoint of improving the storage stability and satisfying the embedding in a fine trench having a narrow trench width and a large aspect ratio and a thick film at the same time. % To 40% by mass, more preferably 10% to 30% by mass. The organic solvent (A), (B) or (C) is a reaction between a polysiloxane compound and silica particles, or a reaction product between a polysiloxane and silica particles and a silane compound represented by the general formula (1). In this case, it may be added in advance, or after the reaction between the polysiloxane compound and the silica particles, or the reaction between the polysiloxane compound and the silica particles and the silane compound represented by the general formula (1), A solvent selected from the above may be further added. In addition, after the reaction product is formed, the organic solvent may be added after the solvent once used in the reaction is distilled and concentrated by a method such as distillation.

  As the organic solvent (A) having a vapor pressure at 20 ° C. of 530 Pa or higher and a boiling point of 80 ° C. or higher and lower than 130 ° C., an alcohol, a polyhydric alcohol derivative, a ketone, an ester, an ether, or a hydrocarbon solvent is preferable. A vapor pressure at 20 ° C. of 530 Pa or higher and a boiling point of 80 ° C. or higher is preferable because the film can be thickened at the time of application while maintaining storage stability. When the boiling point is lower than 130 ° C., the film formability is improved. This is preferable. Moreover, it is preferable that 10 to 50 mass% of the said organic solvent (A) is contained with respect to the sum total of the solvent which occupies for the said solution. This is preferably 10% by mass or more because the film thickness can be increased at the time of coating while maintaining storage stability, and it is preferably 50% by mass or less because the film formability is improved.

  Specific examples of the organic solvent (A) include, for example, t-amyl alcohol, isopropyl alcohol, neopentyl alcohol, butanol, propargyl alcohol, 1-propanol, 3-methyl-2-butanol, and 3-methyl-1-butyne-3. Alcohol solvents such as ol, polyhydric alcohol derivative solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diisopropyl ketone, diethyl ketone, methyl oxide, methyl isobutyl ketone, methyl Ketone solvents such as n-butyl ketone and methyl-n-propyl ketone, butyl formate, allyl acetate, isobutyl acetate, isopropyl acetate, butyl acetate, propyl acetate, dicarbonate Chill, diethyl carbonate, ethyl propionate, ester solvents methyl butyrate, cyclohexane, toluene, heptane, and a hydrocarbon-based solvents such as benzene. Among these, 1-propanol, ethylene glycol diethyl ether, diisopropyl ketone, methyl-n-butyl ketone, butyl acetate, dimethyl carbonate, and diethyl carbonate are more preferable because the film formability is improved.

  The organic solvent (B) having a vapor pressure at 20 ° C. of less than 530 Pa and a boiling point of 130 ° C. or higher and 200 ° C. or lower is preferably an alcohol, a polyhydric alcohol derivative, a ketone, an ester, an ether, or a hydrocarbon solvent. When the vapor pressure at 20 ° C. is less than 530 Pa and the boiling point is 130 ° C. or higher, storage stability is improved, and when it is 200 ° C. or lower, the solvent easily evaporates during precuring. Moreover, it is preferable that 50 to 90 mass% of the said organic solvent (B) is contained with respect to the sum total of the solvent which occupies for the said solution. When it is 50% by mass or more, the film formability is improved, and when it is 90% by mass or less, it is preferable because the film can be thickened by coating once during coating while maintaining storage stability.

  Specific examples of the organic solvent (B) include alcohol solvents such as isoamyl alcohol, 2-ethylbutanol, hexanol, heptanol, octanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene, and the like. Polyhydric alcohol derivative solvents such as glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol methyl ethyl acetate, cyclohexanone, methylcyclohexanone, methyl-n-hexyl ketone, methyl-n-heptyl ketone Ketone solvents such as ethyl acetoacetate, hexyl formate, amyl acetate, ethyl lactate, lactic acid Chill, methyl lactate, isoamyl propionate, ester solvents, anisole, ethylbenzyl ether and butyl propionate, ether solvents such as diisoamyl ether, dipentene, and a hydrocarbon solvent decalin. Among these, diethylene glycol dimethyl ether, propylene glycol methyl ethyl acetate, dipentene, and decalin are more preferable because of better storage stability.

  As said organic solvent (C) whose vapor pressure in 20 degreeC is 530 Pa or more and whose boiling point is 130 to 200 degreeC, alcohol, a polyhydric alcohol derivative, a ketone, ester, ether, and a hydrocarbon type solvent are preferable. A vapor pressure at 20 ° C. of 530 Pa or higher and a boiling point of 130 ° C. or higher is preferable because a thick film can be formed at the time of application while maintaining storage stability, and the boiling point is 200 ° C. or lower. This is preferable because the solvent is easily evaporated during the preliminary curing. Moreover, it is preferable that 60 mass% or more of the said organic solvent (C) is contained with respect to the sum total of the solvent which occupies for the said solution. This is preferable because the storage stability is improved, the film thickness can be increased even when the solid content concentration is low, and the film formability is improved.

  Specific examples of the organic solvent (C) include, for example, alcohol solvents such as 4-methyl-2-pentanol, polyhydric alcohol derivative solvents such as propylene glycol monoethyl ether, acetylacetone, ethyl-n-butyl ketone, Examples thereof include ketone solvents such as di-n-propyl ketone, ester solvents such as isoamyl acetate, diethyl malonate, and butyl butyrate, and hydrocarbon solvents such as isopropylbenzene, ethylbenzene, and xylene. Among these, isopropylbenzene, ethylbenzene, and xylene are more preferable because of better storage stability.

  The organic solvent (A) is 10% by mass or more and 50% by mass or less with respect to the total solvent in the solution, and the organic solvent (B) is 50% by mass or more with respect to the total solvent in the solution. If it is a mixed solvent contained in 90% by mass or less, or if the organic solvent (C) is contained in an amount of 60% by mass or more based on the total amount of the solvent in the solution, other solvents are contained in these solvents. It may be mixed. Further, a plurality of the organic solvents (A), (B) or (C) may be used.

  The trench filling reactant of the present invention produced by such a method can be applied onto a substrate by a usual method. Examples of the coating method include spin coating, dip coating, roller blade coating, and spray coating. Of these, the spin coating method is particularly preferable from the viewpoint of uniformity of the coated surface. When applying by a spin coating method, it may be applied at a single rotation speed or a combination of multiple rotation speeds, but at least the first rotation speed is 50 rpm to 700 rpm. It is preferable. This is because the condensation reaction product for filling the trench is spread over the entire surface of the silicon substrate by rotating at a low speed in the first stage, and the organic solvent (A) is evaporated, so that the solid content concentration of the condensation reaction product for filling the trench is low. This is because it is possible to increase the film thickness. In addition, the number of times of applying the trench filling condensation reaction product may be one or more, but it is more preferable to apply it once from the viewpoint of improving film formability and manufacturing cost.

  After applying the trench filling condensate by these methods, it is preferably pre-cured at 50 to 200 ° C. to remove the residual solvent in the coating film. Thereafter, a silicon oxide can be obtained by oxidizing and heating and baking the film obtained by pre-curing.

As a method of oxidation and heating and firing, general heating means such as a hot plate, an oven, and a furnace can be applied. The heat treatment temperature is preferably 100 ° C to 1,200 ° C, more preferably 200 ° C to 1,000 ° C, and still more preferably 300 ° C to 900 ° C. It is preferable that the heat treatment temperature be within the above range because the film density after firing is high and the film quality obtained is good. As an atmosphere at the time of heating and baking, any of air, oxygen, or steam oxidation atmosphere may be used. The temperature of oxidation and heating and firing is in the range of 200 to 850 ° C., and firing may be performed in an inert atmosphere such as N ₂ or Ar before and after oxidation. The pressure during the oxidation / heating and firing step is not particularly limited, and can be performed under pressure, normal pressure, reduced pressure, or 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 or higher and 500 ° C. or lower, and the processing time is about 0.1 minutes or longer and 120 minutes or shorter.

For light treatment, visible light, ultraviolet light, far ultraviolet light, etc. can be used, as well as low-pressure or high-pressure mercury lamp, deuterium lamp, discharge light of rare gas such as argon, krypton, xenon, YAG laser, argon laser, carbon dioxide gas An excimer laser such as laser, XeF, XeCl, XeBr, KrF, KrCl, ArF, ArCl, or the like 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 is not limited as long as the composition for burying trenches in the applied film has any absorption, but is preferably light having a wavelength of 170 nm to 600 nm. a 000J / cm ^2, more preferably 1~100J / cm ^2. During the light treatment, ozone may be generated at the same time. For example, by performing the light treatment under the above conditions, the oxidation reaction proceeds, and the film quality after baking can be improved.

  The insulating film obtained by using the condensation reaction product for trench embedding according to the present invention is suitable as an insulating film for 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) Film formability When a trench filling composition is applied on a Si substrate and the solvent is removed by pre-baking, the Si substrate is observed with an optical microscope, and no cracks, repellency, or foreign matter is observed. ○, when at least one of these was observed was marked as x.

(3) Crack resistance The trench embedding condensation reaction product is applied and fired on the Si substrate so that the film thickness after firing becomes 1 μm, and the fired Si substrate is observed with an optical microscope. It was determined whether or not a crack was present, and a case where no crack was present was marked as ◯, and a case where a crack was present as x.

(4) Shrinkage rate In a film coated on a 6-inch Si substrate, the film thickness t ₀ after preheating and the film thickness t ₁ after firing were measured with a spectroscopic ellipsometer UVISE made by HORIBA JOBINYVON, and (curing) shrinkage rate Was (t ₀ -t ₁ ) / t ₀ * 100.

(5) Embedding property After cutting and applying a Si substrate having a trench after coating / firing in a direction perpendicular to the longitudinal direction of the trench and performing FIB processing, a scanning electron microscope (SEM) S4700 manufactured by Hitachi, Ltd. was used. , Measured at an acceleration voltage of 5 kV, ○ when the inside of the trench is filled with a condensation reaction product for burying the trench, and no voids such as grooves, holes, cracks, etc. are observed, and × when such a void is observed .

(6) Storage stability (pot life)
The produced polysiloxane-based trench filling reactant solution was allowed to stand at room temperature for 3 days.

Production Example of Polysiloxane Compound [Production Example]
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. A part was sampled and the molecular weight was measured using GPC. As a result, the weight average molecular weight was 12,000.

[Example 1]
Into a 4 L 1 L flask having a distillation tower and a dropping funnel, put water-dispersed silica particles having an average particle size of 6 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 the above production example 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. After concentrating the PGMEA solution to 30% by mass, 1-Propanol was added to obtain a 20% by mass varnish. The varnish was allowed to stand at room temperature for 3 days, but the varnish did not gel.

  2 mL of the above varnish was dropped on a 6-inch Si substrate, and spin coating was performed in two stages of a rotation speed of 300 rpm for 60 seconds and a rotation speed of 1000 rpm for 30 seconds. This substrate was pre-baked stepwise for 2 minutes in this order 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 cracks, cissing or foreign matter observed.

The Si substrate on which the coating film was formed 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./minute.
The fired Si substrate was evaluated for crack resistance and shrinkage. The evaluation results are shown in Table 1 below.

  Further, 1 mL of the varnish was dropped onto a Si chip having a trench with an opening width of 50 nm and a depth of 0.5 μm, and spin coating, pre-baking, and baking were similarly performed under the above conditions. The obtained fired substrate was cleaved in a direction perpendicular to the longitudinal direction of the trench, and after SEM measurement after FIB processing, local voids such as grooves, holes and cracks were not observed, and embeddability Was very good.

[Example 2]
Into a 4 L 1 L flask having a distillation tower and a dropping funnel, put water-dispersed silica particles having an average particle size of 6 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, 250 g of xylene was further added, the oil bath was heated, and isopropanol, hydrochloric acid, water and xylene were distilled off from the distillation line to obtain a xylene 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. 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 varnish was coated, pre-baked and fired under the same conditions as in Example 1 on a Si chip having a 6-inch Si substrate and a trench having an opening width of 50 nm and a depth of 0.5 μm. The obtained Si substrate was a uniform one in which cracks, cissing and foreign matters were not observed. When the obtained Si substrate having a trench was cleaved in a direction perpendicular to the longitudinal direction of the trench and subjected to SEM measurement after FIB processing, voids such as local grooves, holes and cracks were not observed, and embedded. The sex was very good. The other evaluation results are shown in Table 1 below.

[Comparative Example 1]
A 500 mL four-necked flask equipped with a distillation tower and a dropping funnel is used. Catalyst 100K, average particle size 7 nm, 20% by mass isopropanol-dispersed silica particles; AD-1003, 15 g and triethoxysilane 27.57 g (0.17 mol) Then, 9.19 g (0.044 mol) of tetraethoxysilane was added, 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 dropping, the mixture was stirred for 2 hours, 250 g of PGMEA was added, the oil bath was heated, and isopropanol, xylene, water and hydrochloric acid were removed from the distillation line. The obtained PGMEA solution 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 varnish was applied to a Si chip having a 6-inch Si substrate and a trench having an opening width of 50 nm and a depth of 0.5 μm under the same conditions as in Example 1, coating, prebaking, and baking. The obtained Si substrate had cracks of 0.6 μm. When the Si substrate having the obtained trench was cleaved in a direction perpendicular to the longitudinal direction of the trench and subjected to SEM measurement after FIB processing, generation of voids and cracks was observed, and the trench burying property was poor. .

  The insulating film obtained by using the condensation reaction product for trench embedding according to the present invention is suitably used as an insulating film for flash memory, for example.

Claims (11)

  A condensation reaction product of a polysiloxane compound and silica particles, an organic solvent (A) having a vapor pressure at 20 ° C. of 530 Pa or more and a boiling point of 80 ° C. or more and less than 130 ° C., and a vapor pressure at 20 ° C. of 530 Pa A trench-filling condensation reaction product comprising a mixed solvent comprising an organic solvent (B) having a boiling point of 130 ° C. or higher and 200 ° C. or lower. The polysiloxane compound has 40 mol% or more of at least one group selected from the group consisting of HSiO _3/2 group, MeHSiO group, and H ₂ SiO group, and the weight average molecular weight of the polysiloxane is 1,000 or more and 200 2. The condensation reaction product for trench embedding according to claim 1, wherein the average primary particle diameter of the silica particles is 1 nm or more and 100 nm or less.   The condensation for trench embedding according to claim 1 or 2, wherein the organic solvent (A) is at least one selected from the group consisting of alcohols, polyhydric alcohol derivatives, ketones, esters, ethers, and hydrocarbon solvents. Reactant.   The said organic solvent (B) is at least 1 sort (s) chosen from the group which consists of alcohol, a polyhydric alcohol derivative, a ketone, ester, ether, and a hydrocarbon-type solvent, The any one of Claims 1-3. Condensation reaction product for trench filling.   The organic solvent (A) is 10% by mass or more and 50% by mass or less, and the organic solvent (B) is 50% by mass or more and 90% by mass with respect to the total of the solvents contained in the trench filling condensation reaction product. The condensation reaction product for trench embedding according to any one of claims 1 to 4, wherein the condensation reaction product is at most%. In addition to the polysiloxane compound and the silica particles, the condensation reaction product further contains the following general formula (1):
R _n SiX _4-n
{Wherein, 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 an acetoxy group A plurality of R and X may be the same or different. } The condensation reaction product for trench embedding according to any one of claims 1 to 5, comprising a reaction product subjected to a condensation reaction with a silane compound represented by: The polysiloxane compound has the following general formula (2):
HSiX ₃
{In the formula, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, and may be the same or different. } The condensation reaction product for trench embedding according to any one of claims 1 to 6, which is a condensation reaction product of a silane compound represented by: The polysiloxane compound has the following general formula (2):
HSiX ₃
{In the formula, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, and may be the same or different. } And the following general formula (3):
SiX ₄
{In the formula, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group, and may be the same or different. }, The following general formula (4):
R ² SiX ₃
{Wherein R ² is a hydrocarbon group having 1 to 10 carbon atoms, X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group; May be the same or different. }, The following general formula (5):
R ₂ SiX ₂
{In the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group; The plurality of R and X may be the same or different. } Or a compound represented by the following general formula (6):
R ₃ SiX
{In the formula, R is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; X is a group selected from the group consisting of a halogen atom, an alkoxy group having 1 to 6 carbon atoms, and an acetoxy group; R may be the same or different. } Is a condensation reaction product with at least one selected from silane compounds represented by the formula (2), and the proportion of the structure derived from the silane compound represented by the general formula (2) in the polysiloxane compound is 30 mol% or more The condensation reaction product for trench filling according to any one of claims 1 to 7, wherein   The said silica particle is 1 mass% or more and 80 mass% or less with respect to the sum total of the said polysiloxane compound and the said silica particle, or the said polysiloxane compound, the said silica particle, and the said silane compound. The condensation reaction product for trench filling according to any one of the above.   The condensation for trench embedding according to any one of claims 1 to 9, wherein the silane compound is greater than 0 mass% and not more than 40 mass% with respect to the total of the polysiloxane compound, silica particles, and the silane compound. Reactant.   A step of applying the condensation reaction product according to any one of claims 1 to 10 to a substrate having a trench by a spin coating method, wherein a rotation speed of at least a first stage in the spin coating method is 50 rpm to 700 rpm. A method for producing a trench buried film, characterized in that: