TW201922934A - Resin composition, cured film thereof, semiconductor device equipped with same, and method for producing semicondcutor device - Google Patents

Abstract

A siloxane resin composition that does not crack after high-temperature firing, the resin composition being characterized by being a resin composition including a filler and a polysiloxane and by including at least one selected from amine compounds, alkali metals, and alkaline earth metals and/or an organic compound that thermally decomposes at 500 DEG C or higher inside the filler.

Description

Resin composition, cured film thereof, semiconductor element provided with the cured film, and method for manufacturing semiconductor element

The present invention relates to a resin composition, a cured film thereof, a semiconductor element including the cured film, and a method of manufacturing a semiconductor element.

Generally, a protective film is formed on the surface of a substrate in order to protect the surface of the substrate. In particular, in the electrical and electronic industries, with the recent increase in the accumulation and multi-layering of semiconductor devices, the complexity of semiconductor devices and the unevenness on the surface of semiconductor devices have become noticeable. With the development of such semiconductors, for the purpose of protecting semiconductor devices from mechanical damage, chemical damage, electrostatic damage, ionic pollution, non-ionic pollution, and radiation pollution, or the purpose of flattening the unevenness of the surface of semiconductor devices, A passivation film or an interlayer insulation film for the purpose of insulating and planarizing wirings is formed on the surface of a semiconductor device along with the multilayering of circuits.

As a passivation film and an interlayer insulating film formed on the surface of a semiconductor device, a silicon oxide film is generally used. Examples of a method for forming a silicon oxide film on a surface of a semiconductor device include a chemical vapor deposition (CVD) method and a spin coating method. As a method of forming a silicon oxide film on the surface of a semiconductor device by a spin coating method, there is a method using an inorganic spin-on glass (SOG) and an organic SOG.

However, if the thickness of the silicon oxide film formed by the inorganic SOG exceeds 0.3 μm, cracks may occur. Therefore, recoating is required when a device substrate having unevenness of 1 μm or more is buried. However, the film itself has a lack of planarization capability. Therefore, after the film is formed, a planarization step using etch-back or chemical mechanical polishing (CMP) is required.

On the other hand, a silicon oxide film formed by organic SOG can be used to form a film with no cracks of 1 μm or more in a single coating. However, like inorganic SOG, the film itself has a lack of planarization ability. After the film is formed, a planarization step using etch-back is required. In addition, since a large amount of silanol groups and alkoxy groups remain in the silicon oxide film, the hygroscopicity is high, and the problem of carbon poisoning (carbon pollution) caused by the residual alkoxy groups occurs during the oxygen plasma treatment. The problem of poor electrical reliability of the interlayer insulator.

Therefore, as a method for improving the problem of the silicon oxide film formed by inorganic SOG and organic SOG, a composition including silicon dioxide particles and a polysiloxane compound is proposed (for example, refer to Patent Documents 1 to 3). ).
[Prior Art Literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2006-310448
[Patent Document 2] Japanese Patent Laid-Open No. 2013-122965
[Patent Document 3] Japanese Patent Laid-Open No. 5-263045

[Problems to be Solved by the Invention]
However, these silicone compositions still have problems such as insufficient crack resistance, and being unable to form a thick film with a thickness of 3 μm or more by a single high-temperature calcination.

This invention is made based on the said situation, and an object of this invention is to provide the siloxane resin composition which does not generate a crack after baking at high temperature.
[Means for solving problems]

The present invention is a resin composition comprising a filler and a polysiloxane. The resin composition is characterized in that the inside of the filler contains at least one selected from the group consisting of an amine compound, an alkali metal, and an alkaline earth metal, and / or Any of organic compounds that are thermally decomposed at 500 ° C or higher.

In addition, the present invention is a resin composition including a filler and a polysiloxane. The resin composition is characterized in that the filler is formed by using the resin composition at a temperature of 500 ° C to 1200 ° C. When the coating film is calcined, the filler has a shrinkage rate of an average particle diameter of 10% to 85%.
[Effect of the invention]

According to the present invention, a hardened film having a film thickness of 3 μm or more can be provided in a passivation film on the surface of a semiconductor device, or an insulating film between wirings with a multilayered circuit.

Hereinafter, preferred embodiments of the resin composition of the present invention, a cured film thereof, a semiconductor device including the cured film, and a method for manufacturing the same are described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with various changes according to the purpose or application.

The resin composition according to the embodiment of the present invention includes a filler and a polysiloxane.

(Polysiloxane)
The polysiloxane used in the present invention preferably contains at least one partial structure represented by any one of the following general formulas (1) to (3).

In the general formulae (1) to (3), R ¹ represents hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, a cycloalkyl group having 1 to 10 carbon atoms, and 2 to 10 carbon atoms. A plurality of R ¹ in the alkenyl group and the aryl group having 6 to 15 carbon atoms may be the same or different, respectively. The alkyl group, cycloalkyl group, alkenyl group, and aryl group may be any of an unsubstituted body and a substituted body. R ² represents any of hydrogen, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluorenyl group having 2 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Each R ² may be the same or different. These alkyl groups, fluorenyl groups, and aryl groups may be any of an unsubstituted body and a substituted body.

[Chemical 1]

The polysiloxane is preferably obtained by hydrolyzing and dehydrating one or more organic silanes selected from the group consisting of an organic silane represented by the following general formula (4) and an organic silane represented by the following general formula (5). Obtained polysiloxane.

[Chemical 2]

In the general formula (4), R ³ represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an aryl group having 6 to 20 carbon atoms. In the radical, a plurality of R ³ may be the same as or different from each other. The alkyl group, cycloalkyl group, alkenyl group, and aryl group may be any of an unsubstituted body and a substituted body, and may be selected according to the characteristics of the composition.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, n-hexyl, and n-decyl. Specific examples of cycloalkyl include cyclopentyl and cyclohexyl. Examples of the substituent include halogen, epoxy, glycidyl, oxetanyl, carboxyl, amine, mercapto, isocyanate, and succinic anhydride residues. Specific examples of the substituted alkyl group include trifluoromethyl, 3,3,3-trifluoropropyl, 3-glycidoxypropyl, and 2- (3,4-epoxycyclohexyl). ) Ethyl, [(3-ethyl-3-oxetanyl) methoxy] propyl, 1-carboxy-2-carboxypentyl, 3-aminopropyl, 3-mercaptopropyl, 3 -An isocyanatepropyl group, or a group having the following structure.

[Chemical 3]

Specific examples of the alkenyl group and its substituted include vinyl, allyl, 3-propenyloxypropyl, 3-methacryloxypropyl, and 2-methacryloxy Ethyl, 2-propenyloxyethyl and the like. Specific examples of the aryl group and its substituted body include phenyl, 4-tolyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-tert-butylphenyl, and 1-naphthalene. Base, 2-naphthyl, 4-styryl, 2-phenylethyl, 1- (4-hydroxyphenyl) ethyl, 2- (4-hydroxyphenyl) ethyl, 4-hydroxy-5- (4-hydroxyphenylcarbonyloxy) pentyl and the like. However, R ³ is not limited to these specific examples.

R ⁴ in the general formula (4) represents any of hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and a plurality of R ⁴ may be each The same or different. These alkyl groups, fluorenyl groups, and aryl groups may be any of an unsubstituted body and a substituted body, and may be selected according to the characteristics of the composition.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Specific examples of the fluorenyl group include ethenyl and the like. Specific examples of the aryl group include phenyl, 4-tolyl, 4-hydroxyphenyl, 4-methoxyphenyl, 4-thirdbutylphenyl, and 1-naphthyl. However, R ⁴ is not limited to these specific examples.

N in the general formula (4) represents an integer of 1 to 3. When n = 1, it is a trifunctional silane, when n = 2, it is a difunctional silane, and when n = 3, it is a monofunctional silane.

Specific examples of the organosilane represented by the general formula (4) include methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, and methyltriisopropyloxy. Silane, methyltri-n-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-n-propoxysilane, ethyltriisopropoxysilane, ethyltri-n-butoxysilane Silyl, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethyl Oxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacrylic acid Trimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-propenyloxypropyltrimethoxysilane, 3-propenyloxypropyltriethoxysilane, 3-propene Oxypropylmethyldimethoxysilane, 3-propenyloxypropylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 4-tolyltrimethoxy Silane, 4-hydroxyphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-thirdbutylphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyl Trimethoxysilane, 4-styryltrimethoxysilane, 2-phenylethyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 1- (4-hydroxyphenyl) ethyltrimethoxy Silane, 2- (4-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (4-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, trifluoromethyltrimethoxysilane, Trifluoromethyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxy Silane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, [(3-ethyl-3- Oxetanyl) methoxy] propyltrimethoxysilane, [(3-ethyl-3-oxetanyl ) Methoxy] propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-trimethoxy Trifunctional silanes such as methylsilylpropylsuccinic acid, 3-trimethoxysilylpropylsuccinic anhydride; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiethoxy Silane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, diisopropyldimethoxysilane, Diisopropyldiethoxysilane, di-n-butyldimethoxysilane, diphenyldimethoxysilane, (3-glycidyloxypropyl) methyldimethoxysilane, (3- Glycidyloxypropyl) methyldiethoxysilane, dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, methylvinyldimethoxysilane, divinyldiethyl Difunctional silanes such as oxysilane; trimethylmethoxysilane, tri-n-butylethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxy (Propyl) Monofunctional silanes such as dimethylethoxysilane. These organic silanes may be used alone or in combination of two or more. Among these organic silanes, a monofunctional silane or a difunctional silane is preferably used from the viewpoint of cracking resistance during firing, and a trifunctional silane is preferably used in terms of hardness.

The preferable content ratio of the organosilane unit represented by General formula (4) is as follows. The content ratio of the monofunctional silane unit to all the silane monomers in the polysiloxane is preferably 0 mol in terms of the molar ratio of the polysiloxane to the Si atom mol number of the Si atom derived from the organic silane. % To 10 mole%, more preferably 0 mole% to 5 mole%. When the content ratio of the monofunctional silane unit exceeds 10 mol%, the molecular weight of the polysiloxane may decrease. The content ratio of the difunctional silane unit to all silane monomers is preferably 0 mol% to 60 mol% based on the Si atom molar ratio of the polysiloxane as a whole to the Si atom derived from the organic silane. , More preferably 0 mol% to 40 mol%. When the content ratio of the difunctional silane unit exceeds 60 mol%, the shrinkage rate of the polysiloxane after firing becomes large, and shrinkage stress is generated, thereby easily causing cracks. The content ratio of the trifunctional silane unit to all silane monomers is preferably 50 mol% to 100 mol% based on the Si atom mole ratio of the entire polysiloxane to the Si atom originating from the organosilane. , More preferably 60 mol% to 100 mol%. If the content ratio of the trifunctional silane unit is less than 50 mol%, there is a possibility that the hardness after firing may decrease.

The content ratio of the organic silane unit represented by the general formula (4) can be determined by ¹ H-nuclear magnetic resonance (NMR), ¹³ C-NMR, ²⁹ Si-NMR, infrared (IR), and time-of-flight mass spectrometry. (Time of flight-mass spectrometry (TOF-MS), elemental analysis method, and ash measurement, etc.

In the general formula (5), R ⁵ to R ⁸ each independently represent a group selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms, and an aryl group having 6 to 15 carbon atoms. These alkyl groups, fluorenyl groups, and aryl groups may be any of an unsubstituted body and a substituted body, and may be selected according to the characteristics of the composition.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, and n-butyl. Specific examples of the fluorenyl group include ethenyl and the like. Specific examples of the aryl group include a phenyl group and the like. However, R ⁵ to R ⁸ are not limited to these specific examples. M in the general formula (5) represents an integer of 1 to 8.

By using the organosilane represented by the general formula (5), a resin composition capable of forming a cured film with high mechanical strength, that is, a high elastic coefficient can be obtained.

The content ratio of the organosilane unit represented by the general formula (5) in the polysiloxane is preferably 30 mol in terms of the molar ratio of the entire polysiloxane to the Si atom mol number of the Si atom derived from the organosilane Ears% or less, more preferably 20 moles or less. When the content ratio is in the above-mentioned preferable range, the obtained cured film can obtain a high elastic coefficient. If the content ratio of the organosilane unit represented by the general formula (5) is more than 30 mol%, cracks may occur in the cured film. The content ratio of the organosilane unit represented by the general formula (5) can be determined by a combination of ¹ H-NMR, ¹³ C-NMR, ²⁹ Si-NMR, IR, TOF-MS, elemental analysis, and ash measurement.

Specific examples of the organosilane represented by the general formula (5) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, and tetra-n-butoxy Tetrafunctional silanes such as silane and tetraethoxysilane; "methyl silicate 51" (trade name, manufactured by Fuso Chemical Industry Co., Ltd.), "M silicate 51", "silicate 40", " Silicate 45 "(the above are the trade names, manufactured by Tama Chemical Industries, Ltd.)," methyl silicate 51 "," methyl silicate 53A "," ethyl silicate 40 "," ethyl Silicate compounds such as silicate 48 "(the above are trade names, manufactured by Colcoat). These organic silanes may be used alone or in combination of two or more.

From the viewpoint of improving crack resistance, it is preferred that the polysiloxane contains an acidic group or / and an aryl group having 6 to 20 carbon atoms.

The polysiloxane preferably has an acidic group. The acidic group is preferably a group exhibiting an acidity of less than pH 6, and specific examples thereof include a carboxyl group, an acid anhydride group, a sulfonic acid group, a phenolic hydroxyl group, a hydroxyimino group, a silanol group, and a mercapto group. Specific examples of the organic silane having an acidic group include, for example, 3-mercaptopropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic acid, 3-trimethoxysilylpropylsuccinic anhydride, 4 -Hydroxyphenyltrimethoxysilane, 4-methoxyphenyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 1- (4-hydroxyphenyl) ethyltrimethoxysilane, 2- ( 4-hydroxyphenyl) ethyltrimethoxysilane, 4-hydroxy-5- (4-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, and the like.

The content ratio of the organic silane unit having an acidic group in the polysiloxane is 0.1 mol% to 20 mol based on the Si atom mol ratio of the polysiloxane to the Si atom mol number derived from the organic silane. The ear% is preferably 1 mole% to 15 mole%, and further preferably 3 mole% to 12 mole%. If the content ratio is in the above-mentioned preferable range, crack resistance is improved, so it is preferable.

As described above, the introduction of the acidic group can be performed by using a silane monomer having an acidic group. In addition, it can also be introduced by reacting a reactive group in polysiloxane with a compound containing an acidic group and having a group that reacts with a reactive group in polysiloxane.

From the viewpoint of achieving both crack resistance and hardness, the polysiloxane preferably contains an aryl group having 6 to 20 carbon atoms. Examples of the silane-containing silane compound include phenyltrimethoxysilane, phenyltriethoxysilane, 4-tolyltrimethoxysilane, 4-hydroxyphenyltrimethoxysilane, and 4-methoxy Phenyltrimethoxysilane, 4-tert-butylphenyltrimethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 4-styryltrimethoxysilane, 2- Phenylethyltrimethoxysilane, 4-hydroxybenzyltrimethoxysilane, 1- (4-hydroxyphenyl) ethyltrimethoxysilane, 2- (4-hydroxyphenyl) ethyltrimethoxysilane , 4-hydroxy-5- (4-hydroxyphenylcarbonyloxy) pentyltrimethoxysilane, diphenyldimethoxysilane, and the like. Among these, from the viewpoint of further improving the crack resistance, a polycyclic aromatic group is preferable, and from the viewpoint of cost and performance, a naphthalene group-containing silane compound is preferably used. Furthermore, trifunctional silane is preferable. Specifically, 1-naphthyltrimethoxysilane and 2-naphthyltrimethoxysilane can be particularly preferably used. It is thought that three silanol groups are produced in the stage of hydrolysis of 1-naphthyltrimethoxysilane in the polymerization of polysiloxane, but in the next stage of dehydration condensation, due to the steric hindrance of 1-naphthyl The third of the three silanol groups reacts slowly. Therefore, it is considered that the polymer chain becomes linear at the initial stage of polymerization, and further becomes a ladder type when the condensation reaction progresses. It is speculated that in this way, a structured conformation is obtained, so that it is difficult to generate a film shrinkage stress in the coating film formation and calcination steps, the crack resistance is improved, and the hardness can be taken into account.

The silane-containing silane element in all the silane elements in the polymer is 40 mol% to 99 mol%, more preferably 70 mol% to 99 mol%, and further preferably 80 mol% to 98 mol. Ear%, particularly preferably 85 to 97 mole%.

Also preferred among aryl groups is naphthyl. All silane elements in the polymer have naphthyl silane elements in the range of 40 mol% to 99 mol%, more preferably 60 mol% to 98 mol%, and further preferably 85 mol% to 97 mol%. .

The content ratio of the organosilane unit having an aryl group in the polysiloxane can be used to determine the ²⁹ Si-NMR of the polysiloxane. Based on the peak area of Si bonded to the aryl group and the organic silane derived from the unbonded aryl group The ratio of the peak area of Si in the cell was obtained.

In addition, the weight average molecular weight (Mw) of the polysiloxane used in the present invention is not particularly limited, and it is preferably converted to polystyrene measured by gel permeation chromatography (GPC) It is preferably 500 to 100,000, more preferably 500 to 50,000. If it is the said preferable range, the coating film property of the obtained resin composition will be favorable.

When hydrolyzing and dehydrating and condensing an organosilane, a general method can be used. For example, a solvent, water, and an optional catalyst are added to a mixture containing an organic silane, and the mixture is heated and stirred at 50 ° C to 150 ° C, preferably 90 ° C to 130 ° C, for about 0.5 to 100 hours. In addition, during the stirring, if necessary, the hydrolysis by-products (alcohols such as methanol) or the condensation by-products (water) can be removed by distillation.

The solvent is not particularly limited, and generally, the same solvent as that described below can be used. The total amount of the organic silane and the amount of the inorganic particles that react with the organic silane is 100 parts by weight, and the amount of the solvent added is preferably 10 to 1,000 parts by weight. In addition, the amount of water used for the hydrolysis reaction is preferably 0.5 mol to 2 mol relative to 1 mol of the hydrolyzable group.

The catalyst added as necessary is not particularly limited, and an acid catalyst and an alkali catalyst can be preferably used. Specific examples of the acid catalyst include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, acetic acid, trifluoroacetic acid, formic acid, polycarboxylic acids, these anhydrides, and ion exchange resins. Specific examples of the alkali catalyst include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, diethylamine, and triethanolamine. , Diethanolamine, sodium hydroxide, potassium hydroxide, alkoxysilanes having an amine group, and ion exchange resins. The total amount of the organic silane and the amount of the inorganic particles that react with the organic silane is 100 parts by weight, and the added amount of the catalyst is preferably 0.01 to 10 parts by weight.

In addition, from the viewpoint of storage stability of the coating liquid of the resin composition, it is preferable that the catalyst is not contained in the polysiloxane solution after hydrolysis and dehydration condensation, and the catalyst can be removed if necessary. The method for removing the catalyst is not particularly limited. In terms of ease of operation and removability, water washing and / or treatment with an ion exchange resin is preferred. The water washing is a method of diluting a polysiloxane solution with an appropriate hydrophobic solvent, washing the water several times, and concentrating the obtained organic layer with an evaporator or the like. The treatment using an ion exchange resin is a method in which a polysiloxane solution is brought into contact with an appropriate ion exchange resin.

(filler)
The resin composition of the present invention contains a filler. By including the filler, it is possible to maintain the crack resistance of the cured film and suppress voids.

From the viewpoint of suppressing voids, the average particle diameter of the filler is preferably 1,000 nm or less, more preferably 500 nm or less, still more preferably 200 nm or less, still more preferably 100 nm or less, and particularly preferably 70 nm or less. From the viewpoint of crack resistance, the average particle diameter of the filler is preferably 1 nm or more, more preferably 7 nm or more, and even more preferably 10 nm or more.

The average particle diameter of the filler can be measured by observation with a scanning electron microscope (SEM). In the SEM photograph in which the surface or cross section of the pre-baked film or the calcined film of the resin composition is enlarged to 10,000 times, the maximum diameter of 10 particles observed in an arbitrary 200 nm square is measured and divided by The measured number of particles is the average particle diameter.

The term "containing filler" includes both of the following: the resin composition contains only a filler, and the resin composition is selected from the group consisting of an organic silane represented by the general formula (4) and an organic silane represented by the general formula (5). The filler obtained by the reaction of one or more of the organosilanes and the filler, and the polysiloxane is grafted from the surface of the filler as a form of the filler used in the resin composition.

The so-called organic silane is reacted with a filler, and the organosilane is hydrolyzed and dehydrated and condensed in the presence of the filler to obtain a filler-containing polysiloxane. The filler can also be pre-treated with a silane coupling agent in advance.

Hereinafter, a polysiloxane obtained by reacting an organosilane with a filler is referred to as a filler-containing polysiloxane. When the filler is silica particles, it is referred to as a polysiloxane containing silica particles. In addition, a polysiloxane obtained without reacting a filler is referred to as a polysiloxane containing no filler.

From the viewpoint of the denseness of the cured film, the resin composition is preferably a filler containing polysiloxane and grafted from the surface of the filler.

It is preferable that the filler contained in this resin composition contains an inorganic particle from the point which can withstand baking at 500 degreeC or more. The inorganic particles are particles containing a metal compound or a semiconductor compound. Examples of the metal compound or the semiconductor compound include elements selected from the group consisting of silicon, lithium, sodium, aluminum, magnesium, potassium, calcium, zirconia, titanium, tin, tungsten, and barium. The metal compound or semiconductor compound is a halide, oxide, nitride, hydroxide, carbonate, sulfate, nitrate, metasilicate, or the like of the metal or semiconductor.

Specific examples of the inorganic particles include silicon dioxide particles, lithium fluoride particles, lithium chloride particles, lithium bromide particles, lithium oxide particles, lithium carbonate particles, lithium sulfate particles, lithium nitrate particles, lithium metasilicate particles, Lithium hydroxide particles, sodium fluoride particles, sodium chloride particles, sodium bromide particles, sodium carbonate particles, sodium bicarbonate particles, sodium sulfate particles, sodium nitrate particles, sodium metasilicate particles, sodium hydroxide particles, fluoride Magnesium particles, magnesium chloride particles, magnesium bromide particles, magnesium oxide particles, magnesium carbonate particles, magnesium sulfate particles, magnesium nitrate particles, magnesium hydroxide particles, potassium fluoride particles, potassium chloride particles, potassium bromide particles, potassium carbonate particles , Potassium sulfate particles, potassium nitrate particles, calcium fluoride particles, calcium chloride particles, calcium bromide particles, calcium oxide particles, calcium carbonate particles, calcium sulfate particles, calcium nitrate particles, calcium hydroxide particles, strontium fluoride particles, Barium fluoride particles, lanthanum fluoride particles, and the like.

Among these, from the viewpoint of compatibility with polysiloxane, silicon dioxide particles are preferred. Since it is applied to a wet lift-off process in a semiconductor process, from the viewpoint of silicon compound particles that are soluble in hydrofluoric acid, silicon dioxide particles are more preferred.

From the viewpoint of application to a silicon semiconductor, a compound containing Si as a main component is more preferable. Examples of the compound containing Si as a main component include silicon oxide and silicon nitride.

As for the content of the filler, if the content of the filler is small, the crack resistance is insufficient, and when the content of the filler is large, the filterability is lacking. From the viewpoint of crack resistance and filterability, the filler content is preferably 40% to 80% by weight, and more preferably 45% to 75% by weight, relative to the total amount of the filler and the polysiloxane. It is more preferably 50% by weight to 70% by weight.

One embodiment of the filler used in the present invention includes at least one selected from the group consisting of an amine compound, an alkali metal, and an alkaline earth metal, and / or any organic compound that is thermally decomposed at 500 ° C or higher.

Among amine compounds, alkali metals and alkaline earth metals, amine compounds are particularly preferred. Among the amine compounds, alkanolamine compounds are particularly preferred.

Specific examples of the amine compound include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-octylamine, n-decylamine, and n-cetylamine , Cyclopentylamine, cyclohexylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dicyclohexylamine, trimethylamine, triethylamine, dicyclohexylmethylamine, tetramethylenediamine, Hexamethylene diamine, monoethanolamine, monopropanolamine, monobutanolamine, monopentanolamine, tetramethylammonium hydroxide, alkanolamines such as N, N-dimethylpropanolamine, benzylamine, Aniline, 1-naphthylamine, 2-naphthylamine, dibenzylamine, diphenylamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4 -Toluenediamine, 2,6-toluenediamine, 4,4'-diaminodiphenylmethane, hydrazine, hexamethylenetetramine, 1,4-diazabicyclo [2.2.2] octane , 1,5-diazabicyclo [4.3.0] -5-nonane, 1,8-diazabicyclo [5.4.0] -7-undecene, piperidine, piperazine, morpholine, imidazole Aromatic amines, such as pyrazole, ammonia, etc.

The term "thermal decomposition at 500 ° C or higher" refers to the time taken for the temperature to rise to 500 ° C at 10 ° C / min by thermogravimetric analysis (TGA) when the weight at room temperature is 100 parts by weight. The remaining weight parts of dots are 1 weight part or less. The organic compound that undergoes thermal decomposition at 500 ° C or higher is not particularly limited, and a compound containing an alkanediol structure is preferred from the viewpoint of easy thermal decomposition.

From the viewpoint of thermal decomposability and affinity with a filler, the compound having an alkanediol structure is preferably a compound having an ethylene glycol structure or a propylene glycol structure. Examples of the compound having an ethylene glycol structure or a propylene glycol structure include polyethylene glycol, polypropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, and ethylene glycol mono-n-butyl ether. Ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether N-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and the like.

The residue after thermal decomposition is preferably 1% or less. It is more preferably 0.5% or less, and still more preferably 0.1% or less.

Another embodiment of the filler used in the present invention is one having the following properties with respect to the shrinkage of the particle diameter. The shrinkage ratio of the filler average particle diameter when the coating film formed using the resin composition of the present invention is fired at a temperature of at least one point of 500 ° C. to 1200 ° C. is 10% to 85%.

The shrinkage of the filler average particle diameter is defined as follows. When the average particle diameter of the filler before calcination (pre-baking film) is set to a and the average particle diameter of the filler after calcination is set to b, the shrinkage ratio is expressed as ((ab) / a) × 100 (%) .

When the polysiloxane containing a filler is calcined at 500 ° C to 1200 ° C, the filler usually does not shrink, but the shrinkage of the polysiloxane as a binder is generally 20% to 90%, so it cannot be used. Fully resistant to self-shrinking and cracking.

If the average particle diameter of the filler when firing is performed at a temperature of at least 500 ° C to 1200 ° C, the shrinkage ratio between the calcination (pre-baking film) and the calcination after the calcination is 10% to 85%. The shrinkage rate of the polysiloxane of the agent is similar. Therefore, it is presumed that the filler contained in the calcination also shrinks, thereby reducing the stress caused by the self-shrinking of the siloxane film, which is a close adhesive, and improving the crack resistance. The lower limit of the shrinkage ratio is more preferably 20% or more, and the upper limit is more preferably 65% or less.

When the calcination temperature is low, there is a concern that the hardening is insufficient. On the other hand, when the firing temperature is high, there is a disadvantage that the step time becomes long. From the viewpoint, the firing temperature is preferably 600 ° C. to 1000 ° C. Further, from the viewpoint of removing organic components and improving film strength or insulation withstand voltage and shortening the firing time, 800 ° C. is preferred.

Specific examples of the filler having a shrinkage rate of the filler particle diameter of 10% to 85% when calcined at at least a temperature of 500 ° C to 1200 ° C include "quartron (registered trademark) ) BS-3 "(trade name, manufactured by Fuso Chemical Industry Co., Ltd., the dispersion solution is water with a primary particle diameter of 31 nm, silica particles (containing amine compounds))," quartron " "BS-2H" (trade name, manufactured by Fuso Chemical Industry Co., Ltd., the dispersion solution is water silica particles (containing amine compounds) with a primary particle diameter of 26 nm), "quartron (registered trademark) BS -1H "(trade name, manufactured by Fuso Chemical Industry Co., Ltd., the dispersion solution is water-containing silicon dioxide particles with a primary particle diameter of 14 nm (containing amine compounds)), and the organic silica sol" MEK-EC-6150P "( Trade name, manufactured by Nissan Chemical Industries, Ltd., dispersion solution is methyl ethyl ketone silica particles with a particle diameter of 30 nm to 40 nm), organic silica sol "MEK-EC-7150P" Manufacturing and dispersion of Nissan Chemical Industries The solution is methyl ethyl ketone (silica dioxide particles with a particle size of 50 nm to 60 nm) and the like. Moreover, the filler containing any of the said catalyst which controls the shrinkage of a filler, and / or the organic compound which thermally decomposes at 500 degreeC or more is also mentioned.

(Solvent)
The resin composition of the present invention may contain a solvent. The type of the solvent is not particularly limited, and a compound having an alcoholic hydroxyl group, a compound having a carbonyl group, and a compound having three compounds can be preferably used in terms of uniformly dissolving each component and improving the flatness of the obtained fired film. The above ether-bonded compounds and the like. These solvents may be used alone or in combination of two or more.

In addition, a compound having a boiling point of 110 ° C to 250 ° C at atmospheric pressure is more preferred. By setting the boiling point to 110 ° C. or higher and drying the coating film with appropriate evaporation of the solvent during coating, a good coating film without uneven coating can be obtained. In addition, by setting the boiling point to 250 ° C. or less, the amount of the solvent remaining in the coating film can be suppressed to a small extent, and the amount of film shrinkage during firing can be reduced, so that better flatness can be obtained.

Specific examples of the compound having an alcoholic hydroxyl group and a boiling point at 110 ° C to 250 ° C under atmospheric pressure include, for example, hydroxyacetone, 4-hydroxy-2-butanone, and 3-hydroxy-3-methyl-2-butan Ketone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone Alcohol), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether Ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, tetrahydrofurfuryl alcohol , N-butanol, n-pentanol and so on.

Among these, from the viewpoint of coating properties, diacetone alcohol, ethyl lactate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol, tetrahydrofurfuryl alcohol, and the like.

Specific examples of the compound having a carbonyl group and a boiling point at 110 ° C to 250 ° C at atmospheric pressure include n-butyl acetate, isobutyl acetate, 3-methoxy-n-butyl acetate, and 3-methyl-acetate. 3-methoxy-n-butyl ester, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl n-butyl ketone, methyl isobutyl ketone, diisobutyl ketone, 2-heptane Ketones, acetoacetone, cyclopentanone, cyclohexanone, cycloheptanone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide, 1,3-dimethyl-2-imidazolidone, and the like.

Among these, from the viewpoint of coating properties, 3-methoxyn-butyl acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, and the like are preferred.

Specific examples of the compound having three or more ether bonds and a boiling point of 110 ° C to 250 ° C at atmospheric pressure include, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl ester. Methyl ether, diethylene glycol di-n-propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether, dipropylene glycol di-n-propyl ether, and the like.

Among these, from the viewpoint of coating properties, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, and the like are preferred.

The content of the solvent is not particularly limited, and may be contained in any amount depending on the coating method and the like. For example, when the film is formed by spin coating, it is generally 50% to 95% by weight of the entire resin composition.

(Hardened film)
The elastic modulus of the cured film formed of the resin composition is preferably 5 GPa or more. From the viewpoint of having mechanical strength capable of withstanding chemical mechanical polishing (CMP), the elastic modulus is 5 GPa or more, more preferably 7 GPa or more, and even more preferably 10 GPa or more.

The coefficient of elasticity can be measured using a nanoindenter (G200 manufactured by Toyo Technica) with a calcined film having a thickness of 1 μm as a target. During the measurement, in the open method, select "DCM / DCM-SA2 Basic Hardness Modulus, Tip Ca, Load Control", and select "Surface find Parameters" The "permissible drift rate" is selected as 0.5, and the Passon ratio is selected as 0.18.

From the viewpoint of improving the high-frequency characteristics when the cured film is applied to a device semiconductor device, the refractive index of the cured film is preferably 1.2 to 1.4. Generally, the SiO ₂ film formed by CVD is 1.45, which is slightly affected at high frequencies. However, if it is a hardened film formed of the resin composition, the refractive index is 1.40 or less, and it is difficult to receive high-frequency signals. News. The refractive index can be measured using a 633 nm light source and using a rubidium coupler manufactured by Metricon. The film thickness was set to about 3 μm after firing.

A method for forming a cured film using the resin composition of the present invention will be described by way of example. First, the resin composition of the present invention is coated on a substrate. As the substrate, a wafer such as silicon, silicon carbide, gallium nitride, or diamond, or a metal such as copper, gold, and titanium formed as electrodes or wirings can be used, but it is not limited to these. As a coating method, there are methods such as micro gravure coating, spin coating, dip coating, curtain coating, roll coating, spray coating, and slit coating. The thickness of the coating film varies depending on the coating method, the solid content concentration or viscosity of the resin composition, and the coating is usually applied so that the film thickness after coating and pre-baking becomes 0.1 μm to 15 μm.

Next, the substrate coated with the resin composition is pre-baked to prepare a pre-baked film of the resin composition. The pre-baking is preferably performed at 50 ° C. to 150 ° C. for 1 minute to several hours using an oven, a hot plate, and infrared rays. If necessary, pre-baking at 80 ° C. for 2 minutes, and pre-baking at 120 ° C. for 2 minutes, etc., may be performed in two or more stages.

Next, in order to produce a cured film of the resin composition of the present invention, the pre-baked film is heated at a temperature of 200 ° C to 1200 ° C. The heating temperature is more preferably 500 ° C or higher. This heat treatment can be performed in an air environment or an inert gas environment such as nitrogen. In addition, it is preferable that this heat treatment is a stepwise temperature increase or a continuous temperature increase, and is performed for 0.5 minute-5 hours. For example, the following methods can be mentioned: heat treatment at 800 ° C. for 1 minute using lamp annealing, heat treatment at 130 ° C., 200 ° C., and 800 ° C. for 30 minutes each using a calciner, or linearly heating up from room temperature for 2 hours Until 800 ° C.

The cured film of the present invention may be peeled off after chemical mechanical polishing (CMP). Examples of the peeling method include, but are not limited to, a wet process using hydrofluoric acid, buffered hydrofluoric acid, nitrofluoric acid, or TMAH, and a dry process such as plasma processing. From the viewpoint of low cost, a wet process is preferred.

The method for manufacturing a semiconductor element of the present invention includes at least a step of forming a film by using the method and using a resin composition, and a step of heating the film at 500 ° C. or higher and 1200 ° C. or lower. More specifically, the method includes a step of applying a resin composition of the present invention on a semiconductor substrate to form a pre-baked film, and a step of making the pre-baked film a sintered surface to obtain a cured film. In the case of peeling after CMP, a step of peeling the cured film is included.

In the method for manufacturing a semiconductor device, a cured film having a film thickness of 3 μm or more can be formed by one-time film formation and heating at 500 ° C. or higher.

The cured film of the present invention is suitable for semiconductor devices, and is preferably used as a flattening / insulating film for flattening an uneven surface of a device with metal wiring, and is used as an anti-reflection film for optical elements such as microlenses Film, an impurity-doped diffusion barrier film for a semiconductor substrate facing a solar cell or a power semiconductor. In addition, the semiconductor element is preferably a memory element or an optical element or a solar cell, and more preferably a memory element.
[Example]

Hereinafter, the present invention will be described more specifically with examples, but the present invention is not limited to these examples. The abbreviations used in the compounds used are as follows.

DPM: Dipropylene glycol monomethyl ether
GPC: Gel Permeation Chromatography
IPA: isopropanol
BS-3: "quartron (registered trademark) BS-3" (trade name, manufactured by Fuso Chemical Industry Co., Ltd.), the dispersion solution is water with a primary particle diameter of 31 nm (containing alkanol) Amine containing polyalkylene glycol (silica dioxide concentration: 20.1 wt%)))
BS-2H: "quartron (registered trademark) BS-2H" (trade name, manufactured by Fuso Chemical Industry Co., Ltd.), and the dispersion solution is water with a primary particle diameter of 14 nm and silica particles (containing alkanol Amine containing polyalkylene glycol (silica dioxide concentration: 20.1 wt%)))
BS-1H: "quartron (registered trademark) BS-1H" (trade name, manufactured by Fuso Chemical Industry Co., Ltd.), the dispersion solution is water-containing silica particles with a particle diameter of 15 to 20 nm (containing Alkanolamine containing polyalkanediol (silica dioxide concentration: 20.1 wt%)))
PL-2L-IPA: "quartron (registered trademark) PL-2L-IPA" (trade name, manufactured by Fuso Chemical Industry Co., Ltd.), using isopropanol as a dispersion medium, particle size 15 nm to 20 nm Silica particles).

Synthesis Example 1: Synthesis of polysiloxane solution (A-1) A three-necked flask was charged with 44.70 g (90.0 mol%) of a 50 wt% IPA solution of 1-naphthyltrimethoxysilane, and 2.62 g (10.0 mol) %) Of 3-trimethoxysilylpropylsuccinic anhydride, 75.68 g of DPM. Nitrogen was passed through the flask at 0.05 L / min, and the mixed solution was heated and stirred to 40 ° C with an oil bath while stirring. Furthermore, 111.50 g (55.0 wt% with respect to the weight of the polysiloxane containing silicon dioxide particles) of BS-3 (silicon dioxide concentration: 20.1 wt% aqueous solution) was added while stirring the mixed solution, and then After stirring at 40 ° C for 30 minutes, the silane compound was hydrolyzed. After that, the bath temperature was set to 70 ° C and stirred for 1 hour, and then the bath temperature was raised to 130 ° C. After the temperature rise started, the internal temperature of the solution reached 100 ° C. after about 1 hour, and heating and stirring was started for 4 hours (the internal temperature was 100 ° C. to 110 ° C.). After the resin solution obtained by heating and stirring in an ice bath for 4 hours was cooled, 2 wt% of an anion exchange resin and a cation exchange resin were added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (A-1). The solid content concentration of the obtained polysiloxane solution (A-1) was 40% by weight, and the weight average molecular weight of the polysiloxane was 3200. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 2: Synthesis of polysiloxane solution (A-2) was set to 111.50 g (55.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles) of BS-2H (20.1 wt% Except for using BS-3 instead of BS-3, a polysiloxane solution (A-2) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the obtained polysiloxane solution (A-2) was 41 wt%, and the weight average molecular weight of the polysiloxane was 4,000. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 3: Synthesis of polysiloxane solution (A-3): 111.50 g (55.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles) of BS-1H (20.1 wt% Except for using BS-3 instead of BS-3, a polysiloxane solution (A-3) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the obtained polysiloxane solution (A-3) was 40% by weight, and the weight average molecular weight of the polysiloxane was 4,500. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 4: Synthesis of polysiloxane solution (A-4) BS-3 was set to 74.64 g (45.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles). A polysiloxane solution (A-4) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the obtained polysiloxane solution (A-4) was 40% by weight, and the weight average molecular weight of the polysiloxane was 3,300. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 5: Synthesis of polysiloxane solution (A-5) BS-3 was set to 169.42 g (65.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles). A polysiloxane solution (A-5) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the obtained polysiloxane solution (A-5) was 40% by weight, and the weight average molecular weight of the polysiloxane was 3500. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 6: Synthesis of polysiloxane solution (A-6) BS-3 was set to 253.6 g (75.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles), and all were otherwise A polysiloxane solution (A-6) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the obtained polysiloxane solution (A-6) was 40% by weight, and the weight average molecular weight of the polysiloxane was 3500. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 7: Synthesis of polysiloxane solution (A-7) BS-3 was set to 516.94 g (85.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles). A polysiloxane solution (A-7) was obtained in the same manner as in Synthesis Example 1. The solid content concentration of the obtained polysiloxane solution (A-7) was 40% by weight, and the weight average molecular weight of the polysiloxane was 3500. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 8: Synthesis of polysiloxane solution (A-8) A three-necked flask was charged with 42.22 g (85.0 mol%) of a 50 wt% IPA solution of 1-naphthyltrimethoxysilane, and 2.62 g (10.0 mol) %) Of 3-trimethoxysilylpropylsuccinic anhydride, 0.76 g (5.0 mol%) of tetramethoxysilane, and 95.13 g of DPM. Nitrogen was passed through the flask at 0.05 L / min, and the mixed solution was heated and stirred to 40 ° C with an oil bath while stirring. Further, 163.91 g (65.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles) of BS-3 (20.1 wt% aqueous solution) was added while stirring the mixed solution, and then stirred at 40 ° C for 30 minutes. In minutes, the silane compound was hydrolyzed. After that, the bath temperature was set to 70 ° C and stirred for 1 hour, and then the bath temperature was raised to 130 ° C. After the temperature rise started, the internal temperature of the solution reached 100 ° C. after about 1 hour, and heating and stirring was started for 4 hours (the internal temperature was 100 ° C. to 110 ° C.). After the resin solution obtained by heating and stirring in an ice bath for 4 hours was cooled, 2 wt% of an anion exchange resin and a cation exchange resin were added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (A-8). The solid content concentration of the obtained polysiloxane solution (A-8) was 40% by weight, and the weight average molecular weight of the polysiloxane was 5,000. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 85.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 9: Synthesis of polysiloxane solution (A-9) A three-necked flask was charged with 17.85 g (90.0 mol%) of phenyltrimethoxysilane and 2.62 g (10.0 mol%) of 3-trimethoxy Silylpropylsuccinic anhydride, 48.53 g DPM. Nitrogen was passed through the flask at 0.05 L / min, and the mixed solution was heated and stirred to 40 ° C with an oil bath while stirring. Furthermore, while stirring the mixed solution, 71.50 g (55.0 wt% with respect to the weight of the polysiloxane containing silicon dioxide particles) of BS-3 (20.1 wt% aqueous solution) was added, followed by stirring at 40 ° C for 30 minutes. In minutes, the silane compound was hydrolyzed. After that, the bath temperature was set to 70 ° C and stirred for 1 hour, and then the bath temperature was raised to 130 ° C. After the temperature rise started, the internal temperature of the solution reached 100 ° C. after about 1 hour, and heating and stirring was started for 4 hours (the internal temperature was 100 ° C. to 110 ° C.). After the resin solution obtained by heating and stirring in an ice bath for 4 hours was cooled, 2 wt% of an anion exchange resin and a cation exchange resin were added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (A-9). The solid content concentration of the obtained polysiloxane solution (A-9) was 40% by weight, and the weight average molecular weight of the polysiloxane was 4,000. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 90.0 mol% based on the entire molar ratio of the polysiloxane to the Si atom mole ratio of the Si atom derived from the organosilane.

Synthesis Example 10: Synthesis of polysiloxane solution (A-10) A three-necked flask was charged with 4.09 g (30.0 mol%) of methyltrimethoxysilane and 29.80 g (60.0 mol%) of 1-naphthyltrimethyl A 50 wt% IPA solution of oxysilane, 2.62 g (10.0 mol%) of 3-trimethoxysilylpropylsuccinic anhydride, and 61.79 g of DPM. Nitrogen was passed through the flask at 0.05 L / min, and the mixed solution was heated and stirred to 40 ° C with an oil bath while stirring. Furthermore, while stirring the mixed solution, 91.04 g (55.0 wt% with respect to the weight of the polysiloxane containing silicon dioxide particles) of BS-3 (20.1 wt% aqueous solution) was added, followed by stirring at 40 ° C for 30 minutes. In minutes, the silane compound was hydrolyzed. After that, the bath temperature was set to 70 ° C and stirred for 1 hour, and then the bath temperature was raised to 130 ° C. After the temperature rise started, the internal temperature of the solution reached 100 ° C. after about 1 hour, and heating and stirring was started for 4 hours (the internal temperature was 100 ° C. to 110 ° C.). After the resin solution obtained by heating and stirring in an ice bath for 4 hours was cooled, 2 wt% of an anion exchange resin and a cation exchange resin were added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (A-10). The solid content concentration of the obtained polysiloxane solution (A-10) was 40% by weight, and the weight average molecular weight of the polysiloxane was 4,000. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 60.0 mol% based on the Si atom mole ratio of the entire polysiloxane to the Si atom mole number derived from the organosilane.

Synthesis Example 11: Synthesis of polysiloxane solution (A-11) A three-necked flask was charged with 6.81 g (50.0 mol%) of methyltrimethoxysilane and 19.87 g (40.0 mol%) of 1-naphthyltrimethyl A 50 wt% IPA solution of oxysilane, 2.62 g (10.0 mol%) of 3-trimethoxysilylpropylsuccinic anhydride, and 52.53 g of DPM. Nitrogen was passed through the flask at 0.05 L / min, and the mixed solution was heated and stirred to 40 ° C with an oil bath while stirring. Furthermore, 77.40 g (55.0 wt% based on the weight of the polysiloxane containing silicon dioxide particles) of BS-3 (20.1 wt% aqueous solution) was added while stirring the mixed solution, and then stirred at 40 ° C for 30 minutes. In minutes, the silane compound was hydrolyzed. After that, the bath temperature was set to 70 ° C and stirred for 1 hour, and then the bath temperature was raised to 130 ° C. After the temperature rise started, the internal temperature of the solution reached 100 ° C. after about 1 hour, and heating and stirring was started for 4 hours (the internal temperature was 100 ° C. to 110 ° C.). After the resin solution obtained by heating and stirring in an ice bath for 4 hours was cooled, 2 wt% of an anion exchange resin and a cation exchange resin were added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (A-11). The solid content concentration of the obtained polysiloxane solution (A-11) was 40% by weight, and the weight average molecular weight of the polysiloxane was 4,500. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 40.0 mol% based on the Si atom mole ratio of the entire polysiloxane to the Si atom mole number derived from the organosilane.

Synthesis Example 12: Synthesis of polysiloxane solution (A-12) A three-necked flask was charged with 4.09 g (30.0 mol%) of methyltrimethoxysilane and 29.80 g (60.0 mol%) of 1-naphthyltrimethyl A 50 wt% IPA solution of oxysilane, 2.62 g (10.0 mol%) of 3-trimethoxysilylpropylsuccinic anhydride, and 61.79 g of DPM. Nitrogen was passed through the flask at 0.05 L / min, and the mixed solution was heated and stirred to 40 ° C with an oil bath while stirring. Furthermore, while stirring the mixed solution, 72.91 g (55 wt% with respect to the weight of the polysiloxane containing silicon dioxide particles) of PL-2L-IPA (25.1 wt% IPA solution) was charged, and then at 40 ° C. After stirring for 30 minutes, the silane compound was hydrolyzed. After that, the bath temperature was set to 70 ° C and stirred for 1 hour, and then the bath temperature was raised to 130 ° C. After the temperature rise started, the internal temperature of the solution reached 100 ° C. after about 1 hour, and heating and stirring was started for 4 hours (the internal temperature was 100 ° C. to 110 ° C.). After the resin solution obtained by heating and stirring in an ice bath for 4 hours was cooled, 2 wt% of an anion exchange resin and a cation exchange resin were added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (A-12). The solid content concentration of the obtained polysiloxane solution (A-12) was 40% by weight, and the weight average molecular weight of the polysiloxane was 4,000. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 60.0 mol% based on the Si atom mole ratio of the entire polysiloxane to the Si atom mole number derived from the organosilane.

Synthesis Example 13: Synthesis of polysiloxane solution (A-13) A three-necked flask was charged with 6.81 g (50.0 mol%) of methyltrimethoxysilane and 19.87 g (40.0 mol%) of 1-naphthyltrimethyl A 50 wt% IPA solution of oxysilane, 2.62 g (10.0 mol%) of 3-trimethoxysilylpropylsuccinic anhydride, and 52.53 g of DPM. Nitrogen was passed through the flask at 0.05 L / min, and the mixed solution was heated and stirred to 40 ° C with an oil bath while stirring. Furthermore, while stirring the mixed solution, 61.99 g (55 wt% with respect to the weight of the polysiloxane containing silicon dioxide particles) of PL-2L-IPA (25.1 wt% IPA solution) was charged, and then at 40 ° C. After stirring for 30 minutes, the silane compound was hydrolyzed. After that, the bath temperature was set to 70 ° C and stirred for 1 hour, and then the bath temperature was raised to 130 ° C. After the temperature rise started, the internal temperature of the solution reached 100 ° C. after about 1 hour, and heating and stirring was started for 4 hours (the internal temperature was 100 ° C. to 110 ° C.). After the resin solution obtained by heating and stirring in an ice bath for 4 hours was cooled, 2 wt% of an anion exchange resin and a cation exchange resin were added to the resin solution and stirred for 12 hours. After stirring, the anion exchange resin and the cation exchange resin were filtered off to obtain a polysiloxane solution (A-13). The solid content concentration of the obtained polysiloxane solution (A-13) was 40% by weight, and the weight average molecular weight of the polysiloxane was 4,500. The content ratio of the organosilane unit having an aryl group in the polysiloxane is 40.0 mol% based on the Si atom mole ratio of the entire polysiloxane to the Si atom mole number derived from the organosilane.

The composition of Synthesis Example 1 to Synthesis Example 13 is shown in Table 1. In addition, the evaluation method in each Example and a comparative example is shown below.

(1) Solid content concentration of polysiloxane solution A 1 g polysiloxane solution was measured in an aluminum cup with a measured weight, and a heating plate "HP-1SA" (trade name, AS ONE) ( (Manufactured)) was heated at 250 ° C. for 30 minutes to evaporate and solidify. After heating, the weight of the remaining aluminum cup with a solid content was measured, and the weight of the remaining solid content was calculated based on the difference between the weights before and after heating, to determine the solid content concentration of the polysiloxane solution.

(2) The weight-average molecular weight of polysiloxane was measured by GPC using a GPC analyzer "HLC-8220" (manufactured by Tosoh Corporation), using THF as a fluidized layer, and obtained by polystyrene conversion.

(3) The content ratio of each organic silane unit in the polysiloxane is measured by ²⁹ Si-NMR, and the integrated value of Si derived from the specific organic silane unit is calculated relative to the integrated value of Si derived from the entire organic silane. Ratio, and calculate the content ratio. A sample (liquid) was poured into an NMR sample tube made of "Teflon (registered trademark)" having a diameter of 10 mm and used for measurement. The ²⁹ Si-NMR measurement conditions are shown below.
Device: Nuclear magnetic resonance device "JNM-GX270" (manufactured by Japan Electronics Co., Ltd.)
Measurement method: gated decoupling method to determine nuclear frequency: 53.6693 MHz ( ²⁹ Si core)
Spectral width: 20000 Hz
Pulse width: 12 μs (45 ° pulse)
Pulse wave repetition time: 30.0 s
Solvent: Acetone-d6
Standard substance: Tetramethylsilane Measurement temperature: Room temperature Sample speed: 0.0 Hz.

(4) Production of hardened film The polysiloxane solution was filtered with a 0.45 μm filter, and a spin coater "MS-A100" (product name, manufactured by Mikasa (KK)) was used at an arbitrary speed. It was applied on a Si wafer by spin coating, and then pre-baked at 100 ° C for 2 minutes using a hot plate "SCW-636" (trade name, manufactured by Dainippon Screen Manufacturing Co., Ltd.). Thereafter, it was calcined at 800 ° C using a large electric muffle furnace "FUW263PA" (trade name, manufactured by Advantec Toyo Co., Ltd.). Regarding the calcination conditions, when the calcination was performed at 800 ° C, the temperature was raised to 800 ° C in 1 hour and 20 minutes under an atmospheric air flow, and the temperature was maintained at 800 ° C for 1 hour. Thereafter, natural cooling was performed to produce a cured film. In the case of calcination at 1000 ° C, the temperature was raised to 1000 ° C under an air current for 1 hour and 40 minutes, and the temperature was maintained at 1000 ° C for 1 hour. Thereafter, natural cooling was performed to produce a cured film.

(5) For film thickness measurement, an optical interference film thickness measuring device "Lambda Ace VM-1030" (trade name, manufactured by Dainippon Screen Manufacturing Co., Ltd.) was used, and the refractive index was set to 1.55. Perform the measurement.

(6) Shrinkage of average filler particle diameter In the method described above, a pre-baked film of a resin composition is produced on a Si wafer. Thereafter, a fired film was produced at 800 ° C. Using a field emission scanning electron microscope "S-4800" (trade name, manufactured by Hitachi High-Technologies), the cross-sections of the pre-baked film and the calcined film were observed at 10,000 times, and an arbitrary 200 was measured. The maximum diameter of the ten particles observed in the square is shown in nm, and divided by the number of measured particles to calculate the average value, thereby measuring the average particle diameter. The shrinkage of the filler average particle diameter is defined as follows. When the average particle diameter of the filler before calcination is set to a and the average particle diameter of the filler after calcination is set to b, the shrinkage ratio is expressed as ((ab) / a) × 100 (%).

(7) Anti-cracking film thickness In the method described above, a firing film of a resin composition was prepared on each Si wafer with a film thickness of 1.0 μm to 8.0 μm and a scale of 0.1 μm. After the calcination, the presence or absence of cracks on the surface of the calcined film was observed using an FPD inspection microscope "MX-61L" (trade name, manufactured by Olympus). The maximum film thickness value of the cracked fired film was taken as the crack resistance film thickness, and the respective crack resistance film thicknesses were compared. The larger the crack resistance film thickness, the better the crack resistance.

(8) The coefficient of elasticity can be measured using a nanoindenter DCM made by Toyo Technica (strand) and the nanoindentation method. A cured film of the resin composition to be measured was formed on a Si wafer, and the surface of the cured film was measured using a nanoindenter DCM manufactured by Toyo Technica Co., Ltd. As the measurement, DCM Basic Hardness, Modulus, Tip Cal, Load Control.msm (MultiLoad Method) were used, and the parameters of the push-in test were set to Unload To (Percent To Unload) = 90%, Maximum Load = 1 gf, Load Rate Multiple For Unlosd Rate = 1, Number Of Times to Load = 5, Peak Hold Time (Peak Hold time) = 10 s, Time To Load = 15 s, Poisson's ratio = 0.18. The Young's modulus is set to the value of "Modulas At Max Load".

(9) Measurement of refractive index In the method described above, a pre-baked film of a resin composition is produced on a Si wafer. Thereafter, a fired film was produced at 1000 ° C. Using a pseudo-coupler model (MODEL) 2010 (manufactured by Metricon), the refractive index (TE) perpendicular to the film surface at 633 nm (using He-Ne laser) was measured at 22 ° C (TE). ).

(10) Evaluation of filterability When filtering the polysiloxane solution with a filter of 0.45 μm in the item (4) for the production of the cured film, the filterability is less than 0.1 Mpa, which is set to A, which is 0.1. If the filter is Mpa or higher, B is set.

Example 1
The polysiloxane solution (A-1) obtained in Synthesis Example 1 was used to prepare a cured film by the method of (4), and the shrinkage of the film thickness and the average particle diameter of the filler were performed by the methods of (5) to (10). , Determination of anti-cracking film thickness, elastic coefficient, refractive index and filterability.

The average particle diameter of the filler was 50 nm in the pre-baked film and 38 nm in the calcined film, and the shrinkage was 24%. The refractive index of the cured film was 1.26 (633 nm). The elastic modulus of the cured film is 40 GPa. Micrographs of cross sections of the pre-baked film and the cured film are shown in FIGS. 1 and 2.

Examples 2 to 22, Comparative Examples 1 to 4
Using the polysiloxane solution (A-2) to the polysiloxane solution (A-13) obtained in Synthesis Example 2 to Synthesis Example 13, the film thickness and the average particle diameter of the filler were measured in the same manner as in Example 1. Measurement of shrinkage, crack resistance and elastic coefficient. These results are shown in Table 2.

[Table 1]

[Table 2]

no

FIG. 1 is a microscope photograph showing a cross-section of a pre-baked film of a resin composition used in Example 1 as a resin composition according to an embodiment of the present invention.

2 is a microscope photograph showing a cross section of a cured film of a resin composition used in Example 1 as a resin composition according to an embodiment of the present invention.

Claims (19)

A resin composition comprising a filler and polysiloxane. The resin composition is characterized in that at least one selected from the group consisting of an amine compound, an alkali metal, and an alkaline earth metal is contained in the interior of the filler and / or at 500 ° C. The above organic compounds undergo thermal decomposition. The resin composition according to item 1 of the scope of patent application, which contains an amine compound inside the filler. The resin composition according to item 2 of the scope of patent application, wherein the filler further contains an organic compound that is thermally decomposed at a temperature of 500 ° C. or more. The resin composition according to claim 1 or claim 3, wherein the organic compound that undergoes thermal decomposition at 500 ° C or higher is a compound having an alkanediol structure. A resin composition comprising a filler and a polysiloxane. The resin composition is characterized in that the filler is a coating film formed by using the resin composition at a temperature of 500 ° C to 1200 ° C. A filler having a shrinkage rate of an average particle diameter of 10% to 85% when calcined. The resin composition according to any one of claims 1 to 5, in which the temperature during the calcination is 800 ° C or higher. The resin composition according to any one of claims 1 to 6, in which the content of the filler is 40% by weight to the total amount of the filler and the polysiloxane. 80% by weight. The resin composition according to any one of claims 1 to 7, wherein the filler is a compound containing Si as a main component. The resin composition according to any one of claims 1 to 8 of the scope of the patent application, wherein the polysiloxane is grafted on the surface of the filler. The resin composition according to any one of claims 1 to 9, wherein the polysiloxane contains an acidic group. The resin composition according to any one of claims 1 to 10 in the scope of the patent application, wherein the polysiloxane contains an aryl group having 6 to 20 carbon atoms. The resin composition according to any one of claims 1 to 11, wherein the polysiloxane includes a naphthyl group. A cured film which is a cured film of the resin composition according to any one of claims 1 to 12 of the scope of patent application. The hardened film according to item 13 of the scope of patent application has an elastic coefficient of 5 GPa or more. The hardened film according to item 13 or item 14 of the scope of patent application has a refractive index of 1.2 to 1.4. A semiconductor device including the cured film according to any one of claims 13 to 15 in the scope of patent application. The semiconductor element according to item 16 of the scope of patent application, wherein the semiconductor element is a memory element. A method for manufacturing a semiconductor device, comprising: a step of forming a film using the resin composition according to any one of claims 1 to 12 of the scope of patent application; and The film is subjected to a heating step. According to the method for manufacturing a semiconductor device according to item 18 of the scope of patent application, a cured film having a film thickness of 3 μm or more is formed by primary film formation and heating at a temperature of 500 ° C. or higher and 1200 ° C. or lower.