Crosslinked polysilazane and composition containing same

Abstract

To provide a novel crosslinked polysilazane capable of forming a silicon-containing film that can be made thick and has excellent crack resistance. The present invention relates to a crosslinked polysilazane having a specific structure.

Description

[Technical Field]

[0001] The present invention relates to a crosslinked polysilazane. The present invention also relates to a composition containing a crosslinked polysilazane and a solvent, a silicon-containing film, a method for producing a crosslinked polysilazane, and a method for producing a silicon-containing film. [Background technology]

[0002] In the manufacture of electronic devices, particularly semiconductor devices, interlayer insulating films are formed between transistor elements and bit lines, between bit lines and capacitors, between capacitors and metal wiring, between multiple metal wirings, and the like. Furthermore, isolation trenches formed on the surface of a substrate or the like may be filled with insulating material. Furthermore, after semiconductor elements are formed on the surface of a substrate, a covering layer is formed using an encapsulating material, and packaging is performed. Interlayer insulating films and covering layers are often formed from silicon-containing materials.

[0003] To form silicon-containing films such as silicon films, silicon nitride films, silicon carbide films, and silicon carbonitride films, chemical vapor deposition (CVD), sol-gel processes, and methods involving applying and heating a composition containing a silicon-containing polymer are used. Among these methods, the method of applying and heating a composition to form a silicon-containing film is often used because it is a relatively simple method and has excellent filling properties for narrow trenches. Examples of silicon-containing polymers include polysilazanes, polysiloxanes, polycarbosilanes, and polysilanes.

[0004] Polysilazanes have the property of converting to siliceous substances upon heating. When a typical polysilazane is used alone, there are problems that need improvement, such as difficulty in forming a thick film, a slow conversion rate to a siliceous substance, and the need for high temperatures for conversion to a siliceous substance. Various studies have been conducted to address these issues. For example, attempts have been made to improve the above-mentioned problems by modifying the polysilazane itself or by combining a polysilazane-containing composition with a specific additive. For example, Patent Document 1 discloses a crosslinkable composition containing a polysilazane having a specific unsaturated hydrocarbon group. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] U.S. Patent No. 4,689,252 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention has been made based on the above-mentioned background art, and provides a novel crosslinked polysilazane and a composition containing the same. The silicon-containing film formed using this crosslinked polysilazane can be made thicker than conventional films, and even the thick film has sufficient crack resistance. [Means for solving the problem]

[0007] The crosslinked polysilazane according to the present invention comprises a repeating unit represented by the following formula (1): [ka] where: R 1 and R 2 are each independently a single bond, hydrogen, or C 1-4 alkyl, or a linking group represented by formula (a) to (c), and R 1 and R 2When is a single bond, it is bonded to an N atom contained in another repeating unit, and in the crosslinked polysilazane molecule, R 1 and R 2 at least two of the groups are linking groups represented by formulas (a) to (c), R 3 is a single bond, hydrogen, or C 1-4 alkyl, and R 3 When is a single bond, it is bonded to Si contained in another repeating unit, [ka] R a , R b1 , R b2 , R c1 and R c2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 is aryl, L a , L b1 , L b2 , L c1 and L c2 are each independently, C 2-8 Alkylene, or C 6-14 an arylene, wherein a methylene of the alkylene and arylene is unsubstituted or substituted with an oxy, provided that when substituted with an oxy, the oxy is not directly bonded to Si in formula (1); na is 1 to 3, nb1 and nb2 each independently represent 1 to 2; nc1 and nc2 are each independently 1 to 3; p and q each independently represent 1 to 3; Of the bonds of the linking groups of formulae (a) to (c), the bonds that are not bonded to Si in formula (1) are bonded to Si contained in other repeating units.

[0008] The method for producing crosslinked polysilazane according to the present invention comprises the steps of: A polysilazane containing a repeating unit represented by formula (2) and at least two Si-H bonds and at least one silicon compound represented by formulas (d) to (f) are heated or irradiated with light in the presence of a reaction initiator. The compound comprises: [ka] where: R 4 and R 5 are each independently a single bond, hydrogen, or C 1-4 alkyl, and R 4 and R 5 When is a single bond, it is bonded to N contained in another repeating unit, R 6 is a single bond, hydrogen, or C 1-4 alkyl, and R 6 When is a single bond, it is bonded to Si contained in another repeating unit, [ka] R d1 , R e1 , R e2 , R f1 and R f2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 is aryl, R d2 , R e3 , R e4 , R f3 and R f4 are each independently hydrogen or C 1-6 is alkyl, L d , L e1 , L e2 , L f1 and L f2 are each independently a single bond, C 1-6 Alkylene, or C 6-12 arylene, wherein the methylene of said alkylene and arylene is unsubstituted or replaced by oxy; nd is 2 to 4, ne1 and ne2 are each independently 1 to 2, nf1 and nf2 each independently represent 1 to 3; r and s each independently represent 1 to 3.

[0009] The composition according to the present invention comprises the above-described crosslinked polysilazane and a solvent.

[0010] The method for producing a silicon-containing film according to the present invention includes: forming a coating on a substrate using the composition; and Heating the coating film The compound comprises:

[0011] The silicon-containing film according to the present invention is obtained by the above method.

[0012] The method for producing an electronic device according to the present invention comprises the above-described method. [Effects of the Invention]

[0013] The present invention has been made based on the above-mentioned background art, and provides a novel crosslinked polysilazane and a composition containing the same. The silicon-containing film formed using this crosslinked polysilazane can be made thicker than conventional films, and even the thick film has sufficient crack resistance. According to the present invention, a novel crosslinked polysilazane and a composition containing the same are provided. The silicon-containing film formed using the crosslinked polysilazane can be thickened and has sufficient crack resistance. [Brief explanation of the drawings]

[0014] [Figure 1] 1 is a result of measuring 13C-NMR of the crosslinked polysilazane according to the present invention. [Figure 2] 29Si-NMR measurement results of the crosslinked polysilazane of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0015] [Definition] In this specification, unless otherwise limited, the terms used shall have the following meanings:

[0016] In this specification, unless otherwise specified, the singular includes the plural, and "one" and "the" mean "at least one." In this specification, unless otherwise specified, elements of a concept may be expressed by a plurality of species, and when an amount (e.g., mass % or mole %) is described, the amount refers to the sum of the plurality of species. "And / or" includes all combinations of elements and also includes the use of a single element.

[0017] In this specification, when a numerical range is indicated using ~ or -, it includes both endpoints and the units are the same. For example, 5 to 25 mol % means 5 mol % or more and 25 mol % or less.

[0018] In this specification, alkyl refers to a group in which any one hydrogen atom has been removed from a linear or branched saturated hydrocarbon, and includes linear alkyl and branched alkyl. Cycloalkyl refers to a group in which one hydrogen atom has been removed from a saturated hydrocarbon containing a cyclic structure, and the cyclic structure may optionally contain a linear or branched alkyl atom as a side chain.

[0019] As used herein, alkenyl refers to a straight or branched chain hydrocarbon group having one carbon-carbon double bond and having one hydrogen removed from any carbon.

[0020] As used herein, "C x~y "," "C x ~C y " and "C x " refers to the number of carbons in a molecule or substituent. For example, C 1~6Alkyl refers to an alkyl having 1 to 6 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). In addition, as used herein, fluoroalkyl refers to an alkyl in which one or more hydrogen atoms have been replaced with fluorine atoms, and fluoroaryl refers to an aryl in which one or more hydrogen atoms have been replaced with fluorine atoms.

[0021] In this specification, when a polymer has multiple types of repeating units, these repeating units are copolymerized, and the copolymerization may be alternating copolymerization, random copolymerization, block copolymerization, graft copolymerization, or a mixture thereof. In this specification, % means mass % and ratio means mass ratio.

[0022] In this specification, the unit of temperature is Celsius. For example, 20 degrees means 20 degrees Celsius.

[0023] Hereinafter, embodiments of the present invention will be described in detail.

[0024] <Crosslinked polysilazane> The crosslinked polysilazane according to the present invention comprises a repeating unit represented by formula (1). [ka] where: R 1 and R 2 are each independently a single bond, hydrogen, or C 1-4 R is an alkyl group or a linking group represented by any one of formulas (a) to (c), and is preferably a single bond, hydrogen, or a linking group represented by any one of formulas (a) to (c). 1 and R 2 When is a single bond, it is bonded to an N atom contained in another repeating unit, and in the crosslinked polysilazane molecule, R 1 and R 2 At least two of the groups are linking groups represented by formulae (a) to (c). R 3 is a single bond, hydrogen, or C 1-4R is alkyl, preferably a single bond or hydrogen. 3 When is a single bond, it is bonded to Si contained in another repeating unit.

[0025] The linking group represented by formula (a) is as follows: [ka] where: R a are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 Aryl, preferably methyl, ethyl, vinyl, allyl, or phenyl. L a are each independently, C 2-8 Alkylene, or C 6-14 arylene, preferably C 2-6 It is alkylene, more preferably -CH-CH- or -CH-CH-CH-. The methylene in the alkylene and arylene is unsubstituted or substituted with oxy, preferably unsubstituted. However, when substituted with oxy, the oxy does not directly bond to Si in formula (1). na is 1 to 3, preferably 2 or 3, and more preferably 3. Of the bonds of the linking group of formula (a), the bonds that are not bonded to Si in formula (1) are bonded to Si contained in another repeating unit.

[0026] Specific examples of the linking group represented by formula (a) are as follows: [ka]

[0027] The linking group represented by formula (b) is as follows: [ka] where: R b1and R b2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 It is aryl, preferably hydrogen or methyl. L b1 and L b2 are each independently, C 2-8 Alkylene, or C 6-14 arylene, preferably C 2-6 It is alkylene, more preferably -CH-CH- or -CH-CH-CH-. The methylene of alkylene and arylene is unsubstituted or substituted with oxy, preferably unsubstituted. However, when substituted with oxy, the oxy does not directly bond to Si in formula (1). nb1 and nb2 each independently represent 1 to 2, and preferably 2. p and q each independently represent 1 to 3, preferably 1 or 2, and more preferably 1. Of the bonds of the linking group of formula (b), the bonds that are not bonded to Si in formula (1) are bonded to Si contained in another repeating unit.

[0028] Specific examples of the linking group represented by formula (b) are as follows: [ka]

[0029] The linking group represented by formula (c) is as follows: [ka] R c1 and R c2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 aryl, preferably C 1-6 It is alkyl, and more preferably methyl or ethyl. Lc1 and L c2 are each independently, C 2-8 Alkylene, or C 6-14 arylene, preferably C 2-6 It is alkylene, more preferably -CH-CH- or -CH-CH-CH-. The methylene of alkylene and arylene is unsubstituted or substituted with oxy, preferably unsubstituted. However, when substituted with oxy, the oxy does not directly bond to Si in formula (1). nc1 and nc2 each independently represent 1 to 3, and preferably 2. Of the bonds of the linking group of formula (c), the bonds that are not bonded to Si in formula (1) are bonded to Si contained in another repeating unit.

[0030] Specific examples of the linking group represented by formula (c) are as follows: [ka]

[0031] In the crosslinked polysilazane of the present invention, the linking groups of the formulae (a) to (c) are crosslinking groups that link Si atoms in the silazane structure together.

[0032] An example of the partial structure of the crosslinked polysilazane according to the present invention is as follows: [ka]

[0033] The crosslinked polysilazane according to the present invention preferably consists essentially of repeating units represented by formula (1). In the present invention, "substantially" means that 95 mass % or more of all the structural units contained in the crosslinked polysilazane are repeating units represented by formula (1). More preferably, the crosslinked polysilazane does not contain any repeating units other than the repeating unit represented by formula (1). The end groups of the crosslinked polysilazane are preferably -SiH3.

[0034] The number of Si atoms derived from the formulae (a) to (c) contained in the crosslinked polysilazane is preferably 0.5 to 10.0%, more preferably 0.8 to 9.0%, based on the total number of Si atoms in the crosslinked polysilazane.

[0035] The mass average molecular weight of the crosslinked polysilazane is preferably 3,000 to 50,000, more preferably 4,000 to 40,000, and even more preferably 5,000 to 35,000. Here, the mass average molecular weight is a polystyrene-equivalent mass average molecular weight, and can be measured by gel permeation chromatography using polystyrene as a standard.

[0036] <Method of manufacturing crosslinked polysilazane> The method for producing crosslinked polysilazane according to the present invention comprises the steps of: A polysilazane (hereinafter sometimes referred to as raw material polysilazane) containing a repeating unit represented by formula (2) and at least two Si-H bonds; At least one silicon compound represented by formulas (d) to (f) (hereinafter sometimes referred to as silicon compound), by heating or irradiating with light in the presence of a reaction initiator. The compound comprises: The crosslinked polysilazane is thought to be formed by crosslinking polymers of the raw material polysilazane with each other through a hydrosilylation reaction using, for example, a silicon compound as a crosslinking agent.

[0037] (raw material polysilazane) The starting polysilazane contains a repeating unit represented by formula (2) and contains at least two Si—H bonds. Equation (2) is as follows: [ka] where: R 4 and R 5 are each independently a single bond, hydrogen, or C 1-4R is alkyl, preferably a single bond or hydrogen. 4 and R 5 When is a single bond, it is bonded to N contained in another repeating unit. R 6 is a single bond, hydrogen, or C 1-4 R is alkyl, preferably a single bond or hydrogen. 6 When is a single bond, it is bonded to Si contained in another repeating unit.

[0038] The starting polysilazane is preferably perhydropolysilazane (hereinafter, sometimes referred to as PHPS). PHPS is a polymer containing Si-N bonds as repeating units and consisting only of Si, N, and H. In this PHPS, all elements bonded to Si and N, except for the Si-N bonds, are H, and it is substantially free of other elements, such as carbon and oxygen. PHPS may have a branched or cyclic structure within the molecule.

[0039] From the viewpoints of solubility in solvents and reactivity, the mass average molecular weight of the raw material polysilazane is preferably 2,000 to 20,000, and more preferably 3,000 to 15,000. Here, the mass average molecular weight is the weight average molecular weight in terms of polystyrene, and can be measured by gel permeation chromatography using polystyrene as the standard.

[0040] (Silicon compounds) The silicon compound is at least one of the compounds represented by formulas (d) to (f).

[0041] Equation (d) is as follows: [ka] where: R d1 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 Aryl, preferably methyl, ethyl or phenyl. Rd2 are each independently hydrogen or C 1-6 It is alkyl, preferably hydrogen or methyl, more preferably hydrogen. L d are each independently a single bond, C 1-6 Alkylene, or C 6-12 arylene, preferably a single bond or C 1-4 It is alkylene, more preferably a single bond or -CH2-. The methylene of alkylene and arylene is unsubstituted or substituted with oxy, preferably unsubstituted. nd is 2 to 4, preferably 4.

[0042] Specific examples of the silicon compound represented by formula (d) include divinylsilane, trivinylsilane, tetravinylsilane, dimethyldivinylsilane, methyltrivinylsilane, diethyldivinylsilane, ethyltrivinylsilane, diphenyldivinylsilane, phenyltrivinylsilane, diallylsilane, triallylsilane, tetraallylsilane, dimethyldiallylsilane, methyltriallylsilane, diethyldiallylsilane, ethyltriallylsilane, diphenyldiallylsilane, phenyltriallylsilane, dibutenylsilane, and dimethyldibutenylsilane.

[0043] Equation (e) is as follows: [ka] where: R e1 and R e2 are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 aryl, preferably hydrogen or C 1-6 It is alkyl, more preferably methyl, or hydrogen. R e3 and R e4 are each independently hydrogen or C 1-6It is alkyl, preferably hydrogen or methyl, more preferably hydrogen. L e1 are each independently a single bond, C 1-6 Alkylene, or C 6-12 arylene, preferably a single bond or C 1-4 It is alkylene, more preferably a single bond or -CH2-. The methylene of alkylene and arylene is unsubstituted or substituted with oxy, preferably unsubstituted. ne1 and ne2 each independently represent 1 to 2, preferably 2. r and s each independently represent 1 to 3, preferably 1 or 2, and more preferably 1.

[0044] Specific examples of the silicon compound represented by formula (e) include 1,3-divinyl-1,3-disilacyclobutane, 1,1-divinyl-1,3-disilacyclobutane, 1,1,3-trivinyl-1,3-disilacyclobutane, 1,3-divinyl-1,3-dimethyl-1,3-disilacyclobutane, 1,1-divinyl-3,3-dimethyl-1,3-disilacyclobutane, 1-methyl-1,3,3-trivinyl-1,3-disilacyclobutane, and 1,1,3,3-tetravinyl-1,3-di Examples thereof include silacyclobutane, 1,3-diallyl-1,3-disilacyclobutane, 1,1-diallyl-1,3-disilacyclobutane, 1,1,3-triallyl-1,3-disilacyclobutane, 1,3-diallyl-1,3-dimethyl-1,3-disilacyclobutane, 1,1-diallyl-3,3-dimethyl-1,3-disilacyclobutane, 1-methyl-1,3,3-triallyl-1,3-disilacyclobutane, and 1,1,3,3-tetraallyl-1,3-disilacyclobutane.

[0045] Equation (f) is as follows: [ka] where: R f1 and R f2are each independently hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, or C 6-12 aryl, preferably C 1-6 It is alkyl, and more preferably methyl or ethyl. R f3 and R f4 are each independently hydrogen or C 1-6 It is alkyl, preferably hydrogen or methyl, more preferably hydrogen. L f1 and L f2 are each independently a single bond, C 1-6 Alkylene, or C 6-12 arylene, preferably a single bond or C 1-4 It is alkylene, more preferably a single bond or -CH2-. The methylene of alkylene and arylene is unsubstituted or substituted with oxy, preferably unsubstituted. nf1 and nf2 each independently represent 1 to 3, and preferably 2.

[0046] Specific examples of the silicon compound represented by formula (e) include 1,1,3,3-tetravinyldimethyldisiloxane, 1,1,3,3-tetravinyldiethyldisiloxane, 1,1,1,3,3,3-hexavinyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,3,3-tetraallyldimethyldisiloxane, 1,1,3,3-tetraallyldiethyldisiloxane, 1,1,1,3,3,3-hexaallyldisiloxane, and 1,1,3,3-tetramethyl-1,3-diallyldisiloxane.

[0047] The molar ratio of the silicon compound to the raw material polysilazane (silicon compound / raw material polysilazane) is preferably 0.5-10, and more preferably 0.75-8.

[0048] The reaction between the raw material polysilazane and the silicon compound is carried out by heating or irradiating with light in the presence of a reaction initiator.Examples of the reaction initiator include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylbutyronitrile), cumene hydroperoxide, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2,4-dimethylvaleronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride, ammonium peroxodisulfate, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, and di-tert-butyl benzoate. peroxide, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methylpropionate) dimethyl, diisopropyl peroxydicarbonate, dipropyl peroxydicarbonate, benzoin, acetophenone, 4,4'-bis(diethylamino)benzophenone, benzoin isopropyl ether, 3'-hydroxyacetophenone, 2-methylbenzophenone, 9,10-phenanthrenequinone, benzoin isobutyl ether, dibenzoyl, dibenzosuberenone, benzoin ethyl ether, phenyl( Lithium 2,4,6-trimethylbenzoylphosphinate, camphorquinone, 4-hydroxybenzophenone, 4-phenylbenzophenone, 2-hydroxy-2-methylpropiophenone, 2-ethylanthraquinone, 4,4'-dihydroxybenzophenone, 4,4'-dimethylbenzyl, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, methyl benzoylformate, 2-benzoylbenzoic acid, 4,4'-dichlorobenzophenone, 2,2-diethoxyacetophenone Non, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 9,10-phenanthrenequinone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2-isopropylthioxanthone, 2,2-dimethoxy-2-phenylacetophenone, 1,4-dibenzoylbenzene, 3,4-dimethylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzoin methyl ether, methyl 2-benzoylbenzoate, 2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 4-benzoylbenzoic acid, 4-(dimethylamino)benzophenone, ferrocene, p-anisyl, 3-hydroxybenzophenone, sodium anthraquinone-2-sulfonate, anthraquinone, anisoin, 4'-hydroxyacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, phenyl(2,4,6-trimethylbenzoyl)phosphine Ethyl 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,1'-biimidazole, bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanocene, 1-chloro-4-propoxy-9H-thioxanthen-9-one, 2,7-dimethoxy-9H-thioxanthen-9-one, 2,7-dimethoxy-9H-thioxanthen-9-one, 1-([1,1'-biphenyl]-4-yl)-2-methyl-2-morpholino propan-1-one, 4'-hydroxyacetophenone, acetophenone, 4,4'-bis(diethylamino)benzophenone, imidazoles, oxime esters, α-hydroxyalkylphenone, α-alkylaminophenone, benzil dimethyl ketal, acylphosphine oxide, triethylborane, chloro(1,5-cyclooctadiene)rhodium, (1,5-cyclooctadiene)ruthenium chloride, ruthenium acetylacetonate, dichloro(1,5-cyclooctadiene)rhodium, (1,5-cyclooctadiene)ruthenium chloride, ruthenium acetylacetonate, Examples of suitable chloro(1,5-cyclooctadiene)palladium, hexachloroplatinic acid, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, dichloro(1,5-cyclooctadiene)platinum, chlorotris(triphenylphosphine)rhodium, chloro(1,5-cyclooctadiene)rhodium dimer, chloro(triphenylphosphine)dicarbonylrhodium, nickel acetylacetonate, pyridine bis(oxazoline) cobalt complex, and bis(imino)pyridine cobalt are preferred. 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), and triethylborane are also preferred. The heating temperature is preferably 50 to 120° C., more preferably 60 to 100° C. The wavelength of the light irradiation is preferably a peak wavelength of 150 to 450 nm, more preferably 240 to 440 nm.

[0049] <Composition> The composition according to the present invention comprises the above-described crosslinked polysilazane and a solvent.

[0050] The solvent is preferably at least one selected from the group consisting of aromatic compounds, saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, ether compounds, ester compounds, and ketone compounds. Specific examples include aromatic compounds (e.g., benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene); saturated hydrocarbon compounds (e.g., cyclohexane, decahydronaphthalene, dipentene, n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, n-octane, i-octane, n-nonane, i-nonane, n-decane, ethylcyclohexane, methylcyclohexane, cyclohexane, p-menthane); unsaturated hydrocarbons (e.g., cyclohexene); ether compounds (e.g., dipropyl ether, dibutyl ether, anisole); ester compounds (e.g., n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate); and ketone compounds (e.g., methyl isobutyl ketone (MIBK)). These can be used alone or in combination.

[0051] The composition according to the present invention preferably contains 1 to 70% by mass, more preferably 1 to 60% by mass of crosslinked polysilazane, based on the total mass of the composition.

[0052] The composition of the present invention can be combined with additional components as needed. These components are described below. The total mass of the composition, other than the crosslinked polysilazane and the solvent, is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less, of the total mass.

[0053] <Optional ingredients> An example of an optional component is a surfactant.

[0054] The use of a surfactant is preferred because it can improve the coating properties. Examples of surfactants that can be used in the composition of the present invention include nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0055] Examples of the nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters, polyoxyethylene fatty acid monoesters; polyoxyethylene polyoxypropylene block polymers; acetylene alcohol derivatives such as acetylene alcohol, acetylene glycol, and polyethoxylates of acetylene alcohol; acetylene glycol derivatives such as polyethoxylates of acetylene glycol; fluorine-containing surfactants such as Fluorad (trade name, manufactured by 3M Limited), MEGAFACE (trade name, manufactured by DIC Corporation), and Sulfuron (trade name, manufactured by Asahi Glass Co., Ltd.); and organic siloxane surfactants such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the acetylene glycol include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyne-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0056] Examples of anionic surfactants include ammonium salts or organic amine salts of alkyldiphenyletherdisulfonic acids, ammonium salts or organic amine salts of alkyldiphenylethersulfonic acids, ammonium salts or organic amine salts of alkylbenzenesulfonic acids, ammonium salts or organic amine salts of polyoxyethylene alkylethersulfonic acids, and ammonium salts or organic amine salts of alkylsulfuric acids.

[0057] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine and lauric acid amidopropyl hydroxysulfone betaine.

[0058] These surfactants can be used alone or in combination of two or more kinds, and the blending ratio thereof is usually 50 to 10,000 ppm, preferably 100 to 5,000 ppm, based on the total mass of the composition.

[0059] <Method for producing silicon-containing film> The method for producing a silicon-containing film according to the present invention comprises: forming a coating on a substrate using the composition; and Heating the coating The compound comprises: In the present invention, the term "on a substrate" includes cases where the composition is applied directly to the substrate, and cases where the composition is applied to the substrate via one or more intermediate layers.

[0060] The method for applying the composition to the substrate surface can be selected from conventionally known methods, such as spin coating, dipping, spraying, transfer coating, roll coating, bar coating, brush coating, doctor coating, flow coating, and slit coating. The substrate to which the composition is applied can be any suitable substrate, such as a silicon substrate, a glass substrate, or a resin film. These substrates may have various semiconductor elements formed thereon, as needed. When the substrate is a film, gravure coating can also be used. If desired, a drying step can be separately performed after the coating. If desired, the coating step can be repeated two or more times to form a coating film with a desired thickness.

[0061] After forming a coating film of the composition according to the present invention, the coating film may be prebaked (heat-treated) to dry the coating film and reduce the amount of residual solvent. The prebaking step can be carried out in an oxidizing or non-oxidizing atmosphere, preferably at a temperature of 80 to 300°C, for 10 to 300 seconds using a hot plate, or for 1 to 30 minutes using a clean oven.

[0062] The coating film, which has been pre-baked as needed, is then heated and cured to form a silicon-containing film, preferably in an oxidizing atmosphere. The heating is preferably carried out in a temperature range of 200 to 700°C, more preferably 300 to 600°C. The oxidizing atmosphere has an oxygen partial pressure of 20 to 101 kPa, preferably 40 to 101 kPa, and more preferably 1.5 to 80 kPa of water vapor partial pressure when the total pressure is 101 kPa.

[0063] When heating at high temperatures (e.g., temperatures above 600°C) in a water vapor-containing atmosphere, there may be concerns about adverse effects on other elements, such as electronic devices, that are simultaneously exposed to the heat treatment. In such cases, the heating process can be divided into two or more stages (more preferably, three or more stages). For example, first, heating can be performed at a low temperature (e.g., in the range of 200 to 400°C) in a water vapor-containing atmosphere, then heating can be performed at a relatively low temperature (e.g., in the range of 300 to 600°C) in a water vapor-containing atmosphere, and finally heating can be performed at a higher temperature (e.g., 400 to 800°C) in a water vapor-free atmosphere.

[0064] As a component other than water vapor in the water vapor-containing atmosphere (hereinafter, sometimes referred to as a dilution gas), any gas can be used, for example, air, oxygen, nitrogen, nitrogen oxide, ozone, helium, and argon. Considering the film quality of the silicon-containing film, it is preferable to use oxygen as the dilution gas.

[0065] The rate of temperature increase and decrease up to the target temperature during heating is not particularly limited, but can generally be in the range of 1 to 100°C / min. The heating retention time after reaching the target temperature is also not particularly limited, but can generally be in the range of 1 minute to 10 hours.

[0066] The thickness of the silicon-containing film is preferably 1.0 to 4.0 μm, and more preferably 1.0 to 3.5 μm.

[0067] The method for producing an electronic device according to the present invention comprises the above-described production method. Preferably, the electronic device according to the present invention is a semiconductor device, a solar cell chip, an organic light-emitting diode, or an inorganic light-emitting diode. A preferred embodiment of the electronic device according to the present invention is a semiconductor device.

[0068] [Example] The present invention will now be described with reference to examples, which are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0069] In the following examples, the weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) using polystyrene as a standard. GPC is performed using an alliance™ e2695 high-speed GPC system (Nihon Waters K.K.) and a Super Multipore HZ-N GPC column (Tosoh Corporation). Measurements are performed using monodisperse polystyrene as a standard sample, chloroform as a developing solvent, at a flow rate of 0.6 mL / min, and a column temperature of 40°C, and Mw is calculated as the molecular weight relative to the standard sample.

[0070] <Synthesis of Polysilazane Intermediate A> After flushing the air inside a 10-liter reactor equipped with a cooling condenser, mechanical stirrer, and temperature controller with dry nitrogen, 7,500 ml of dry pyridine was added and cooled to -3°C. 500 g of dichlorosilane was then added, producing a white solid adduct (SiH2Cl2·2C5H5N). After confirming that the reaction mixture was below -3°C, 350 g of ammonia was slowly bubbled into the mixture while stirring. After stirring for 30 minutes, dry nitrogen was bubbled into the liquid layer for 30 minutes to remove excess ammonia. The resulting slurry was pressure-filtered under a dry nitrogen atmosphere using a 0.2 μm Teflon® filter to obtain 6,000 ml of filtrate. 3,000 ml of dry xylene was added, and the pyridine was removed using an evaporator. Concentration yielded a 39.8% polysilazane xylene solution. The Mw of the obtained polysilazane was measured by gel permeation chromatography and was found to be 1220 in polystyrene equivalent. The polysilazane obtained by this recipe will be referred to as polysilazane intermediate A hereinafter.

[0071] <Synthesis of crosslinked polysilazane A> A 200 mL three-neck flask equipped with a magnetic stirrer bar, nitrogen inlet, and reflux condenser was charged with 30.0 g of polysilazane intermediate A in xylene, 0.78 g of tetravinylsilane as a crosslinker in 8 g of toluene, and 0.35 g of azabisisobutyronitrile (AIBN) as a reaction initiator. Xylene was then added to the reaction solution to obtain a 20% polysilazane intermediate A content by mass. N2 was bubbled through the reaction solution (50 mL / min) for 10 minutes while stirring. The mixture was then heated at 80°C for 3-6 hours and concentrated under reduced pressure at 40°C to obtain a 40% crosslinked polysilazane A solution. The resulting crosslinked polysilazane A had an Mw of 6,900.

[0072] <Synthesis of crosslinked polysilazanes B to H> Solutions of crosslinked polysilazanes B to H were obtained in the same manner as in the synthesis of crosslinked polysilazane A, except that the polysilazane, the compound and the amount of crosslinking agent added, and the compound and the amount of reaction initiator added were changed as shown in Table 1. The Mw of each was shown in Table 1. [Table 1]

[0073] <Synthesis of Polysilazane I> After purging the inside of a 10L reaction vessel equipped with a cooling condenser, mechanical stirrer, and temperature control device with dry nitrogen, 4710g of dry pyridine, 150g of dry xylene, and 1650g of the polysilazane intermediate A obtained above with a concentration of 39.8% were added, and the mixture was stirred to homogenize while bubbling with nitrogen gas at 0.5NL / min. The subsequent modification reaction was carried out at 110°C for 8.6 hours to obtain polysilazane I. The pyridine was distilled off to obtain a polysilazane I solution. Polysilazane I is a perhydropolysilazane with an Mw of 5,800.

[0074] <Synthesis of Polysilazane J> The synthesis of polysilazane J was carried out by changing the modification reaction conditions from the synthesis of polysilazane I to 110°C for 10.0 hours. Polysilazane J was a perhydropolysilazane with an Mw of 8,300.

[0075] The crosslinked polysilazanes A to H were analyzed by infrared absorption spectroscopy using an FTIR6100 (JASCO Corporation). 13 C-NMR, and 29 Si-NMR analysis reveals that the compound is a crosslinked perhydropolysilazane. Figure 1 shows the cross-linked polysilazane A. 13 The C-NMR shows a peak at around 9 ppm that is attributed to -CH2-. 29 This is Si-NMR, and a peak due to the formation of a new Si bond is confirmed around -15 ppm, indicating that Si-CH2- is being produced.

[0076] Example 1 The composition of Example 1 is prepared by mixing the crosslinked polysilazane A synthesized above with xylene so that the concentration of crosslinked polysilazane A becomes 40 mass %. The composition of Example 1 is applied to a 4-inch Si substrate prewetted with xylene using a spin coater (1HDX2, Mikasa Corporation) to form a coating film. The resulting coating film is heated (prebaked) on a hot plate at 150°C for 3 minutes. The film thickness (post-prebaking film thickness) at this stage is measured to be 2.4 μm. The prebaked coating film is then heated (cured) at 350°C for 30 minutes in a water vapor atmosphere, and further heated (annealed) at 850°C for 30 minutes in a nitrogen atmosphere to obtain the silicon-containing film of Example 1. The film thickness (post-annealing film thickness) at this stage is 2.0 μm. The film thickness is measured at 17 points on the diameter using a reflection spectroscopic film thickness meter (FE-3000 manufactured by Otsuka Electronics Co., Ltd.), and the average value is used.

[0077] <Examples 2 to 8 and Comparative Example 1> The silicon-containing films of Examples 2 to 8 and Comparative Example 1 were obtained in the same manner as in Example 1, except that the composition used was changed to the crosslinked polysilazane (polysilazane in the case of Comparative Example 1) and the content thereof shown in Table 2. [Table 2]

[0078] [crack] The cracks in each of the silicon-containing films were observed using an optical microscope and evaluated according to the following criteria. The results are shown in Table 2. A: No cracks were found B: Slight cracks are observed C: Partial cracks are observed D: Cracks are observed throughout the entire surface.

Claims

1. A crosslinked polysilazane comprising a repeating unit represented by formula (1): 【Chemistry 1】 (where, R １ and R ２ are each independently a single bond, hydrogen, or C １－４ alkyl, or a linking group represented by formula (a) to (c), R １ and R ２ When is a single bond, it is bonded to N contained in another repeating unit, and in the crosslinked polysilazane molecule, R １ and R ２ at least two of the groups are linking groups represented by formulas (a) to (c), R ３ is a single bond, hydrogen, or C １－４ alkyl, and R ３ is a single bond, it is bonded to Si contained in another repeating unit, 【Chemistry 2】 R ａ , R ｂ１ , R ｂ２ , R ｃ１ and R ｃ２ are each independently hydrogen, C １－６ Alkyl, C １－６ alkenyl, or C ６－１２ is aryl, L ａ , L ｂ１ , L ｂ２ , L ｃ１ and L ｃ２ are each independently C ２－８ Alkylene, or C ６－１４ an arylene, wherein a methylene of the alkylene and arylene is unsubstituted or substituted with an oxy, provided that when substituted with an oxy, the oxy is not directly bonded to Si in formula (1); na is 1 to 3, nb1 and nb2 each independently represent 1 to 2; nc1 and nc2 each independently represent 1 to 3; p and q each independently represent 1 to 3; Among the bonds of the linking groups of formulas (a) to (c), the bonds that are not bonded to Si in formula (1) are bonded to Si contained in another repeating unit.

2. R １ and R ２ are each independently a single bond, hydrogen, or a linking group represented by formula (a) to (c), and R ３ 2. The crosslinked polysilazane of claim 1, wherein is a single bond or hydrogen.

3. 3. The crosslinked polysilazane according to claim 1, which has a polystyrene-equivalent weight average molecular weight of 3,000 to 50,000 as measured by gel permeation chromatography.

4. 4. The crosslinked polysilazane according to claim 1, wherein the number of Si atoms derived from formulas (a) to (c) contained in the crosslinked polysilazane is 0.5 to 10.0% based on the total number of Si atoms in the crosslinked polysilazane.

5. a polysilazane containing a repeating unit represented by formula (2) and at least two Si—H bonds; At least one silicon compound represented by formulas (d) to (f), and heating or irradiating the compound (I) with light in the presence of a reaction initiator. 【Transformation 3】 (where, R ４ and R ５ are each independently a single bond, hydrogen, or C １－４ is alkyl, R ４ and R ５ is a single bond, it is bonded to N contained in another repeating unit, R ６ is a single bond, hydrogen, or C １－４ alkyl, and R ６ is a single bond, it is bonded to Si contained in another repeating unit, 【Chemistry 4】 R ｄ１ , R ｅ１ , R ｅ２ , R ｆ１ and R ｆ２ are each independently hydrogen, C １－６ Alkyl, C １－６ alkenyl, or C ６－１２ is aryl, R ｄ２ , R ｅ３ , R ｅ４ , R ｆ３ and R ｆ４ are each independently hydrogen or C １－６ is alkyl, L ｄ , L ｅ１ , L ｅ２ , L ｆ１ and L ｆ２ are each independently a single bond, C １－６ Alkylene, or C ６－１２ arylene, wherein the methylene of said alkylene and arylene is unsubstituted or replaced by oxy; nd is 2 to 4, ne1 and ne2 are each independently 1 to 2; nf1 and nf2 each independently represent 1 to 3; r and s each independently represent 1 to 3.

6. The method of claim 5 wherein the polysilazane is a perhydropolysilazane.

7. A composition comprising the crosslinked polysilazane of any one of claims 1 to 4 and a solvent.

8. The composition according to claim 7, wherein the solvent is at least one selected from the group consisting of aromatic compounds, saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, ether compounds, ester compounds, and ketone compounds.

9. 9. The composition according to claim 7, wherein the content of the crosslinked polysilazane is 1 to 70% by mass, based on the total mass of the composition.

10. A method for producing a silicon-containing film, comprising: forming a coating on a substrate using the composition according to any one of claims 7 to 9; and Heating the coating film The method comprising:

11. The method for producing a silicon-containing film according to claim 10, wherein the heating is carried out in an oxidizing atmosphere.

12. A silicon-containing film obtainable by the method of claim 10 or 11.

13. An electronic device comprising the silicon-containing film of claim 12.

14. A method for producing an electronic device, comprising the method according to claim 10 or 11.

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