Crosslinked polysilazanes and compositions comprising same

Abstract

Provided is a novel cross-linked polysilazane which is capable of forming a silicon-containing film having excellent crack resistance while being capable of forming a thick film. The invention relates to cross-linked polysilazane with a certain structure.

Description

Technical Field

[0001] The present invention relates to a crosslinked polysilazane. In addition, 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 Art

[0002] In the manufacture of electronic devices (especially semiconductor devices), it may be necessary to form an interlayer insulating film between transistor elements and bit lines, between bit lines and capacitors, between capacitors and metal wirings, between multiple metal wirings, etc. In addition, it may be necessary to fill an insulating material in isolation grooves provided on the surface of a substrate, etc. Further, after forming a semiconductor device on the surface of a substrate, it may be necessary to form a coating using a sealing material to form a package. The interlayer insulating film and the coating are usually formed of a silicon-containing material.

[0003] For a method of forming a silicon-containing film (such as a silica film, a silicon nitride film, a silicon carbide film, or a silicon carbonitride film), a chemical vapor deposition method (CVD method), a sol-gel method, a method of coating a composition containing a silicon-containing polymer and baking it, etc. can be adopted. Among them, the method of forming a silicon-containing film using a composition is often adopted because it is relatively simple. Examples of the silicon-containing polymer include polysilazane, polysiloxane, polycarbosilane, polysilane, etc.

[0004] Polysilazane has the property of being converted into a silica substance by heating. When ordinary polysilazane is used alone, there are problems such as difficulty in increasing the film thickness, slow conversion rate to the silica substance, and the need for high temperature for conversion into the silica substance. Currently, various studies have been carried out to improve these problems. For example, studies have been made to improve the above problems by modifying the polysilazane itself or combining certain additives in a composition containing polysilazane. For example, Patent Document 1 discloses a crosslinkable composition containing a polysilazane having a specific unsaturated hydrocarbon group.

[0005] [Prior Art Documents]

[0006] [Patent Documents]

[0007] [Patent Document 1] US 4,689,252 A Summary of the Invention

[0008] The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel crosslinked polysilazane and a composition containing the crosslinked polysilazane. The silicon-containing film formed using the crosslinked polysilazane can be thicker than before, and even for a thick film, it has sufficient crack resistance.

[0009] The crosslinked polysilazane according to the present invention contains a repeating unit represented by the following formula (1):

[0010]

[0011] Among them,

[0012] R 1 and R 2 are each independently a single bond, hydrogen, C 1-4 alkyl group or a linking group represented by formula (a) to formula (c). When R 1 and R 2 are single bonds, they are bonded to the N contained in other repeating units. And in this crosslinked polysilazane molecule, at least two of R 1 and R 2 are linking groups represented by formula (a) to formula (c);

[0013] R 3 is a single bond, hydrogen or C 1-4 alkyl group. When R 3 is a single bond, it is bonded to the Si contained in other repeating units:

[0014]

[0015] R a 、R b1 、R b2 、R c1 and R c2 are each independently hydrogen, C 1-6 alkyl group, C 1-6 alkenyl group or C 6-12 aryl group;

[0016] L a 、L b1 、L b2 、L c1 and L c2 are each independently C 2-8 alkylene group or C 6-14 arylene group, wherein the methylene group in the alkylene group and the arylene group is not substituted or is substituted by an oxy group, provided that when it is substituted by an oxy group, the oxy group is not directly bonded to the Si in formula (1);

[0017] na is from 1 to 3;

[0018] nb1 and nb2 are each independently from 1 to 2;

[0019] nc1 and nc2 are each independently from 1 to 3;

[0020] p and q are each independently from 1 to 3; and

[0021] Among the bonds of the linking groups of formula (a) to formula (c), the bonds not bonded to the Si of formula (1) are bonded to the Si contained in other repeating units.

[0022] The method for manufacturing a crosslinked polysilazane according to the present invention includes:

[0023] heating or irradiating with light, in the presence of a reaction initiator, a polysilazane containing repeating units represented by formula (2) and at least two Si-H bonds, and at least one silicon compound represented by formula (d) to formula (f):

[0024]

[0025] wherein,

[0026] R 4 and R 5 are each independently a single bond, hydrogen, or a C 1-4 alkyl group, and when R 4 and R 5 are single bonds, they are bonded to N contained in other repeating units; and

[0027] R 6 is a single bond, hydrogen, or a C 1-4 alkyl group, and when R 6 is a single bond, it is bonded to Si contained in other repeating units; and

[0028]

[0029] R d1 、R e1 、R e2 、R f1 and R f2 are each independently hydrogen, a C 1-6 alkyl group, a C 1-6 alkenyl group, or a C 6-12 aryl group;

[0030] R d2 、R e3 、R e4 、R f3 and R f4 are each independently hydrogen or a C 1-6 alkyl group;

[0031] L d 、L e1 、L e2 、L f1 and L f2 are each independently a single bond, a C 1-6 alkylene group, or a C 6-12 arylene group, wherein the methylene group in the alkylene group and the arylene group is unsubstituted or substituted by an oxygen group;

[0032] nd is from 2 to 4;

[0033] ne1 and ne2 are each independently 1 to 2;

[0034] nf1 and nf2 are each independently 1 to 3; and

[0035] r and s are each independently 1 to 3.

[0036] The composition according to the present invention contains the above crosslinked polysilazane and a solvent.

[0037] The method for manufacturing a silicon-containing film according to the present invention includes:

[0038] forming a coating film above a substrate using the above composition; and

[0039] heating the coating film.

[0040] The silicon-containing film according to the present invention can be obtained by the above method.

[0041] The method for manufacturing an electronic device according to the present invention includes the above method.

[0042] The present invention has been made in view of the above circumstances, and its object is to provide a novel crosslinked polysilazane and a composition containing the crosslinked polysilazane. The silicon-containing film formed using the crosslinked polysilazane can be thicker than before, and even for a thick film, it has sufficient crack resistance.

[0043] The present invention provides a novel crosslinked polysilazane and a composition containing the crosslinked polysilazane. The silicon-containing coating film formed using the crosslinked polysilazane can be thickened and has sufficient crack resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 show the 13 C-NMR measurement results of the crosslinked polysilazane according to the present invention; and

[0045] Figure 2 show the 29 Si-NMR measurement results of the crosslinked polysilazane according to the present invention. DETAILED DESCRIPTION

[0046] [DEFINITIONS]

[0047] Unless otherwise specified, the terms used in this specification shall have the following meanings.

[0048] In this specification, the singular forms also include the plural forms. Unless otherwise clearly stated, words such as "a", "an", and "the" mean "at least one". Unless otherwise specified in this specification, the elements of a concept can be represented by multiple species. When describing a quantity (e.g., mass % or mole %), it refers to the sum of multiple species. The term "and / or" refers to any combination of the above elements, including the use of a single element.

[0049] In this specification, when using "to" or "- / ~" to represent a numerical range, both endpoints are included and their units are the same. For example, 5 to 25 mole % means 5 mole % or more and 25 mole % or less.

[0050] In this specification, an alkyl group refers to a group obtained by removing any one hydrogen atom from a straight-chain or branched-chain saturated hydrocarbon, including straight-chain alkyl groups and branched-chain alkyl groups; a cycloalkyl group refers to a group obtained by removing one hydrogen atom from a saturated hydrocarbon containing a cyclic structure, and the cyclic structure may optionally contain a straight-chain or branched-chain alkyl group as a side chain.

[0051] In this specification, an alkenyl group refers to a group obtained by removing any one hydrogen atom from a straight-chain or branched-chain hydrocarbon having a carbon-carbon double bond.

[0052] In this specification, descriptions such as "C x-y ", "C x -C y ", and "C x " all refer to the number of carbon atoms in a molecule or substituent. For example, C 1-6 alkyl refers to an alkyl group having 1 or more and 6 or less carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.). The fluoroalkyl group used in this specification refers to an alkyl group in which one or more hydrogen atoms are replaced by fluorine, and the fluoroaryl group refers to an aryl group in which one or more hydrogen atoms are replaced by fluorine.

[0053] In this specification, when a polymer has multiple repeating units, these repeating units undergo copolymerization. These copolymerizations can be any one of alternating copolymerization, random copolymerization, block copolymerization, and graft copolymerization, or a mixed form of these copolymerizations.

[0054] In this specification, "%" means "mass %" and "parts" means "parts by mass".

[0055] In this specification, the temperature unit is degrees Celsius. For example, 20 degrees is 20 degrees Celsius.

[0056] The embodiments of the present invention will be described in detail below.

[0057] <Crosslinked polysilazane>

[0058] The crosslinked polysilazane according to the present invention contains repeating units represented by the following formula (1):

[0059]

[0060] Wherein,

[0061] R 1 and R 2 are each independently a single bond, hydrogen, C 1-4 alkyl group or a linking group represented by formula (a) to formula (c), preferably a single bond, hydrogen or a linking group represented by formula (a) to formula (c). When R 1 and R 2 are single bonds, they are bonded to N in other repeating units, and in the crosslinked polysilazane molecule, at least two of R 1 and R 2 are linking groups represented by formula (a) to formula (c).

[0062] R 3 is a single bond, hydrogen or C 1-4 alkyl group, preferably a single bond or hydrogen. When R 3 is a single bond, it is bonded to Si in other repeating units.

[0063] Examples of the linking group represented by formula (a) include:

[0064]

[0065] Wherein,

[0066] R a are each independently hydrogen, C 1-6 alkyl group, C 1-6 alkenyl group or C 6-12 aryl group, preferably methyl, ethyl, vinyl, allyl or phenyl.

[0067] L a are each independently C 2-8 alkylene group or C 6-14 arylene group, preferably C 2-6 alkylene group, more preferably -CH2-CH2- or -CH2-CH2-CH2-. The methylene group in the alkylene group and arylene group is unsubstituted or substituted by an oxygen group, preferably unsubstituted. However, when the methylene group is substituted by an oxygen group, the oxygen group is not directly bonded to Si in formula (1).

[0068] na is 1 to 3, preferably 2 or 3, more preferably 3.

[0069] In the bond of the linking group of formula (a), the bond not bonded to Si in formula (1) is bonded to Si contained in other repeating units.

[0070] Exemplary embodiments of the linking group shown in formula (a) include:

[0071]

[0072] Examples of the linking group shown in formula (b) include:

[0073]

[0074] Wherein,

[0075] R b1 and R b2 are each independently hydrogen, C 1-6 alkyl, C 1-6 alkenyl or C 6-12 aryl, preferably hydrogen or methyl.

[0076] L b1 and L b2 are each independently C 2-8 alkylene or C 6-14 arylene, preferably C 2-6 alkylene, more preferably -CH2-CH2- or -CH2-CH2-CH2-. The methylene groups in the alkylene and arylene are unsubstituted or substituted by an oxygen group, preferably unsubstituted. However, when the methylene group is substituted by an oxygen group, the oxygen group is not directly bonded to the Si in formula (1).

[0077] nb1 and nb2 are each independently 1 to 2, preferably 2.

[0078] p and q are each independently 1 to 3, preferably 1 or 2, more preferably 1.

[0079] In the bonds of the linking group of formula (b), the bonds not bonded to the Si in formula (1) are bonded to the Si contained in other repeating units.

[0080] Exemplary embodiments of the linking group shown in formula (b) include:

[0081]

[0082] Examples of the linking group shown in formula (c) include:

[0083]

[0084] 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 alkyl, more preferably methyl or ethyl.

[0085] L c1 and L c2 each independently represents C 2-8 alkylene or C 6-14 arylene, preferably C 2-6 alkylene, more preferably -CH2-CH2- or -CH2-CH2-CH2-. The methylene group in alkylene and arylene is unsubstituted or substituted by an oxy group, preferably unsubstituted. However, when the methylene group is substituted by an oxy group, the oxy group is not directly bonded to the Si in formula (1).

[0086] nc1 and nc2 each independently represent a number from 1 to 3, preferably 2.

[0087] In the bonds of the linking group of formula (c), the bonds not bonded to the Si in formula (1) are bonded to the Si contained in other repeating units.

[0088] Exemplary embodiments of the linking group shown in formula (c) include:

[0089]

[0090] In the crosslinked polysilazane according to the present invention, the linking groups of formula (a) to formula (c) are crosslinking groups that link the Si atoms in the silazane structure.

[0091] Examples of the partial structure of the crosslinked polysilazane according to the present invention include:

[0092]

[0093] The crosslinked polysilazane according to the present invention preferably consists essentially of the repeating units shown in formula (1). In the present invention, "essentially" means that 95% by mass or more of all the structural units contained in the crosslinked polysilazane are the repeating units shown in formula (1).

[0094] More preferably, the crosslinked polysilazane does not contain repeating units other than the repeating units shown in formula (1).

[0095] Preferably, the crosslinked polysilazane has -SiH3 end groups.

[0096] The amount of Si derived from formula (a) to formula (c) contained in the crosslinked polysilazane is preferably 0.5 to 10.0% of the total amount of Si in the crosslinked polysilazane, more preferably 0.8 to 9.0%.

[0097] The weight-average molecular weight of the crosslinked polysilazane is preferably from 3,000 to 50,000, more preferably from 4,000 to 40,000, and still more preferably from 5,000 to 35,000. Here, the weight-average molecular weight is the weight-average molecular weight in terms of polystyrene and can be measured by gel permeation chromatography based on polystyrene.

[0098] <Method for producing crosslinked polysilazane>

[0099] The method for producing a crosslinked polysilazane according to the present invention includes:

[0100] heating or irradiating with light the following substances in the presence of a reaction initiator:

[0101] a polysilazane containing the repeating unit represented by formula (2) and at least two Si-H bonds (hereinafter referred to as "starting polysilazane"); and

[0102] at least one silicon compound represented by formula (d) to formula (f) (hereinafter referred to as "silicon compound").

[0103] It is considered that the crosslinked polysilazane is formed, for example, by using a silicon compound as a crosslinking agent to crosslink the polymer of the starting polysilazane through a hydrosilylation reaction.

[0104] [Starting polysilazane]

[0105] The starting polysilazane contains the repeating unit represented by formula (2) and at least two Si-H bonds.

[0106] Formula (2) is as follows:

[0107]

[0108] Wherein,

[0109] R 4 and R 5 are each independently a single bond, hydrogen or C 1-4 alkyl group, preferably a single bond or hydrogen. When R 4 and R 5 are single bonds, they are bonded to N in other repeating units.

[0110] R 6 is a single bond, hydrogen or C 1-4 alkyl group, preferably a single bond or hydrogen. When R 6 is a single bond, it is bonded to Si in other repeating units.

[0111] The raw material polysilazane is preferably perhydropolysilazane (hereinafter referred to as "PHPS"). PHPS is a polymer with Si-N bonds as repeating units and is composed only of Si, N, and H. In PHPS, the elements bonded to Si and N are all H except for the Si-N bond, and other elements such as carbon and oxygen are not necessary. PHPS may have a branched structure or a cyclic structure in the molecule.

[0112] From the viewpoints of solubility in solvents and reactivity, the weight-average molecular weight of the raw material polysilazane is preferably 2,000 to 20,000, more preferably 3,000 to 15,000. Here, the weight-average molecular weight refers to the weight-average molecular weight in terms of polystyrene and can be measured by gel permeation chromatography based on polystyrene.

[0113] [Silicon compound]

[0114] The silicon compound is at least one of those represented by formula (d) to formula (f).

[0115] Formula (d) is as follows:

[0116]

[0117] Among them,

[0118] R d1 are each independently hydrogen, C 1-6 alkyl, C 1-6 alkenyl, or C 6-12 aryl, preferably methyl, ethyl, or phenyl.

[0119] R d2 are each independently hydrogen or C 1-6 alkyl, preferably hydrogen or methyl, more preferably hydrogen.

[0120] 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 alkylene, more preferably a single bond or -CH2-. The methylene group in the alkylene and arylene is unsubstituted or substituted by an oxy group, preferably unsubstituted.

[0121] nd is 2 to 4, more preferably 4.

[0122] As the silicon compound represented by the formula (d), for example, the following can be cited: divinylsilane, trivinylsilane, tetravinylsilane, dimethyldivinylsilane, methyltrivinylsilane, diethyldivinylsilane, ethyltrivinylsilane, diphenyldivinylsilane, phenyltrivinylsilane, diallylsilane, triallylsilane, tetraallylsilane, dimethyldiallylsilane, methyltriallylsilane, diethyldiallylsilane, ethyltriallylsilane, diphenyldiallylsilane, phenyltriallylsilane, dibutenylsilane, dimethyldibutenylsilane.

[0123] The formula (e) is as follows:

[0124]

[0125] Among them,

[0126] 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 alkyl, more preferably methyl or hydrogen.

[0127] R e3 and R e4 are each independently hydrogen or C 1-6 alkyl, preferably hydrogen or methyl, more preferably hydrogen.

[0128] 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 alkylene, more preferably a single bond or -CH2-. The methylene group in the alkylene and arylene is unsubstituted or substituted by an oxy group, preferably unsubstituted.

[0129] ne1 and ne2 are each independently 1 to 2, preferably 2.

[0130] r and s are each independently 1 to 3, preferably 1 or 2, more preferably 1.

[0131] Exemplary embodiments 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, 1,1,3,3-tetravinyl-1,3-disilacyclobutane, 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.

[0132] Formula (f) is as follows:

[0133]

[0134] Wherein,

[0135] R f1 and R f2 are each independently hydrogen, C 1-6 alkyl, C 1-6 alkenyl or C 6-12 aryl, preferably C 1-6 alkyl, more preferably methyl or ethyl.

[0136] R f3 and R f4 are each independently hydrogen or C 1-6 alkyl, preferably hydrogen or methyl, more preferably hydrogen.

[0137] 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 alkylene, more preferably a single bond or -CH2-. The methylene group in the alkylene and arylene is unsubstituted or substituted with an oxygen group, preferably unsubstituted.

[0138] nf1 and nf2 are each independently 1 to 3, preferably 2.

[0139] Examples of the silicon compound represented by the 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-hexaa llyldisiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane, and the like.

[0140] The molar ratio of the silicon compound to the raw polysilazane (silicon compound / raw polysilazane) is preferably 0.5 to 10, more preferably 0.75 to 8.

[0141] The reaction of the raw polysilazane with the silicon compound is carried out by heating or light irradiation in the presence of a reaction initiator.

[0142] Examples of reaction initiators 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 persulfate, tert-butyl hydroperoxide, benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(2-methylpropionic acid) dimethyl ester, 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, dibenzocycloheptanone, benzoin ethyl ether, lithium phenyl(2,4,6-trimethylbenzoyl)phosphinate, 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, 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, acetophenone, 4,4'-Bis(diethylamino)benzophenone, imidazole, oxime ester, α-hydroxyalkyl phenyl ketone, α-alkylaminobenzophenone, benzyl dimethyl ketal, acylphosphine oxide, triethylborane, chloro(1,5-cyclooctadiene)rhodium, (1,5-cyclooctadiene)ruthenium chloride, ruthenium acetylacetonate, dichloro(1,5-cyclooctadiene)palladium, hexachloroplatinic acid, platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex, dichloro(1,5-cyclooctadiene)platinum, chloro(tris(triphenylphosphine))rhodium, chloro(1,5-cyclooctadiene)rhodium dimer, chloro(triphenylphosphine)dicarbonylrhodium, nickel acetylacetonate, pyridine bis(oxazoline)cobalt complex, bis(imino)pyridine cobalt. Preferably 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile) and triethylborane.,

[0143] The heating temperature is preferably 50 to 120 °C, more preferably 60 to 100 °C. The wavelength of light irradiation is preferably a peak wavelength of 150 to 450 nm, more preferably 240 to 440 nm.

[0144] <Composition>

[0145] The composition according to the present invention contains the above crosslinked polysilazane and a solvent.

[0146] 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. Specifically, the following substances are included: aromatic compounds (such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene and triethylbenzene); saturated hydrocarbon compounds (such as cyclohexane, decalin, dipentene, n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, ethylcyclohexane, methylcyclohexane, cyclohexane and p-menthane); unsaturated hydrocarbon compounds (such as cyclohexene); ether compounds (such as dipropyl ether, dibutyl ether and anisole); ester compounds (such as n-butyl acetate, isobutyl acetate, n-pentyl acetate and isopentyl acetate); and ketone compounds (such as methyl isobutyl ketone (MIBK)).

[0147] These can be used alone or in combination of two or more.

[0148] The composition according to the present invention preferably contains 1 to 70% by mass, more preferably 1 to 60% by mass of the crosslinked polysilazane based on the total mass of the composition.

[0149] The composition according to the present invention may optionally contain other components. These components are described below. In addition to the crosslinked polysilazane and the solvent, the content of other components in the whole composition is preferably 10% or less, more preferably 5% or less, and further preferably 1% or less (based on the total mass of the composition).

[0150] <Optional components>

[0151] Examples of optional components include surfactants.

[0152] Since surfactants can improve coatability, surfactants are preferably used. Examples of surfactants that can be used in the composition according to the present invention include nonionic surfactants, anionic surfactants, amphoteric surfactants, and the like.

[0153] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene cetyl ether; polyoxyethylene fatty acid diesters; polyoxy fatty acid monoesters; polyoxyethylene-polyoxypropylene block polymers; alkynols; alkynediols; alkynol derivatives such as alkynol polyethoxylates; alkynediol derivatives such as alkynediol polyethoxylates; fluorosurfactants such as Fluorad (trade name, manufactured by 3M Japan Limited), MEGAFACE (trade name, manufactured by DIC Corporation), Surufuron (trade name, manufactured by Asahi Glass Co., Ltd.); and silicone surfactant such as KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Examples of the alkynediols include 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3,6-dimethyl-4-octyn-3,6-diol, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 2,5-dimethyl-3-hexyn-2,5-diol, and 2,5-dimethyl-2,5-hexanediol.

[0154] Examples of anionic surfactants include ammonium salts or organic amine salts of alkyl diphenyl ether disulfonic acid, ammonium salts or organic amine salts of alkyl diphenyl ether sulfonic acid, ammonium salts or organic amine salts of alkyl benzene sulfonic acid, ammonium salts or organic amine salts of polyoxyethylene alkyl ether sulfuric acid, and ammonium salts or organic amine salts of alkyl sulfuric acid.

[0155] Examples of amphoteric surfactants include 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole betaine and lauric acid amide propyl hydroxy sulfobetaine.

[0156] These surfactants can be used alone or in combination of two or more, and their content is usually 50 to 10,000 ppm, preferably 100 to 5,000 ppm based on the total mass of the composition.

[0157] <Method for manufacturing a silicon-containing film>

[0158] The method for manufacturing a silicon-containing film according to the present invention includes:

[0159] forming a coating film above the substrate using the above composition; and

[0160] heating the coating film.

[0161] In the present invention, "above the substrate" includes the case where the composition is directly coated on the substrate and the case where the composition is coated on the substrate with one or more intermediate layers therebetween.

[0162] The method of coating the composition on the substrate can be selected from common methods, such as spin coating, dip coating, spray coating, transfer method, roll coating, bar coating, knife coating, brush coating, flow coating or slot coating, etc. Any suitable substrate can be used for coating the composition, such as a silicon substrate, a glass substrate and a resin film. Various semiconductor devices, etc. can be formed on these substrates as needed. When the substrate is a film, gravure coating can also be used. If necessary, an additional drying step can be provided after coating the film. If necessary, the coating step can be repeated two or more times to form a coating film with a desired film thickness.

[0163] After forming the coating film of the composition according to the present invention, pre-baking can be carried out to dry the coating film and reduce the solvent residue amount. The pre-baking step can be carried out in an oxidizing atmosphere and a non-oxidizing atmosphere. When curing in a non-oxidizing atmosphere, it is preferably carried out in an inert gas atmosphere, and when curing in an oxidizing atmosphere, it is preferably carried out in air. The pre-baking temperature is preferably 80 to 300 °C, baking for 10 to 300 seconds on a hot plate, or baking for 1 to 30 minutes in a clean oven.

[0164] Then, the coating film pre-baked as needed is cured by heating to form a silicon-containing film. This heating is preferably carried out in an oxidizing atmosphere.

[0165] The heating is preferably carried out in a temperature range of 200 to 700 °C, more preferably 300 to 600 °C.

[0166] The oxidizing atmosphere means that when the total pressure is 101 kPa, the oxygen partial pressure is 20 to 101 kPa, preferably 40 to 101 kPa, and more preferably an atmosphere containing a water vapor partial pressure of 1.5 to 80 kPa.

[0167] Sometimes, heating in a high-temperature atmosphere containing water vapor (e.g., above 600 °C) may affect other components (e.g., electronic devices) undergoing heat treatment simultaneously. In such cases, the heating step can be divided into two or more stages (more preferably three or more stages). For example, heating can first be carried out in a low-temperature oxidation atmosphere (e.g., in the temperature range of 200 to 400 °C), then in a water-vapor-containing atmosphere at a relatively low temperature (e.g., in the temperature range of 300 to 600 °C), and then in an atmosphere without water vapor at a higher temperature (e.g., 400 to 800 °C).

[0168] In the atmosphere containing water vapor (hereinafter referred to as "dilution gas"), other components besides water vapor can be any gas, and examples thereof include, for example, air, oxygen, nitrogen, nitrous oxide, ozone, helium, argon, etc. Considering the quality of the resulting silicon-containing film, oxygen is preferably used as the dilution gas.

[0169] The heating rate to reach the target temperature and the cooling rate during the heating process are not particularly limited and can generally be in the range of 1 to 100 °C / min. The holding time after reaching the target temperature is also not particularly limited and can generally be in the range of 1 minute to 10 hours.

[0170] The film thickness of the silicon-containing film is preferably 1.0 to 4.0 μm, more preferably 1.0 to 3.5 μm.

[0171] The method for manufacturing an electronic device according to the present invention includes the above 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 of the present invention is a semiconductor device.

[0172] [Examples]

[0173] The present invention will be described in detail below in conjunction with examples. These examples are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0174] In the following examples, the weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) based on polystyrene. GPC was measured using an Alliance e2695 high-performance GPC system (Nihon Waters K.K.) and a Super Multipore HZ-N GPC column (Tosoh Corporation). The measurement was carried out using monodisperse polystyrene as a standard sample, chloroform as an eluent, under the conditions of a flow rate of 0.6 mL / min and a column temperature of 40 °C, and then Mw was calculated based on the relative molecular weight with respect to the standard sample.

[0175] [Synthesis of polysilazane intermediate A]

[0176] The 10 L reactor equipped with a condenser, a mechanical stirrer, and a thermostat was purged with dry nitrogen, and then 7500 mL of dry pyridine was charged and cooled to -3 °C. Subsequently, 500 g of dichlorosilane was added to form a white solid adduct (SiH2Cl2·2C5H5N). After confirming that the temperature of the reaction mixture had dropped below -3 °C, 350 g of ammonia water was slowly blown in with stirring. Stirring was continued for 30 minutes, and then dry nitrogen was blown into the liquid layer for 30 minutes to remove the excess ammonia. The resulting slurry product was pressure-filtered through a Teflon (registered trademark) filter with a pore size of 0.2 μm under a dry nitrogen atmosphere to obtain 6000 mL of filtrate. 3000 mL of anhydrous xylene was added, and pyridine was removed by evaporation with an evaporator. After concentration, a xylene solution of polysilazane with a concentration of 39.8% was obtained. As determined by gel permeation chromatography, the Mw of the resulting polysilazane was 1220 in terms of polystyrene. Hereinafter, the polysilazane obtained by this preparation will be referred to as polysilazane intermediate A.

[0177] <Synthesis of crosslinked polysilazane A>

[0178] In a 200 mL three-necked flask equipped with a magnetic stir bar, a nitrogen inlet, and a reflux condenser, 30.0 g of polysilazane intermediate A (dissolved in xylene), 0.78 g of tetravinylsilane as a crosslinking agent (dissolved in 8 g of toluene), and 0.35 g of azobisisobutyronitrile (AIBN) as a reaction initiator were charged, and then xylene was added to make the content of polysilazane intermediate A reach 20% by mass to prepare a reaction solution. While stirring, N2 was passed through it at a flow rate of 50 mL / min for 10 minutes. Then, the mixture was heated at 80 °C for 3 to 6 hours and concentrated under reduced pressure at 40 °C to obtain a crosslinked polysilazane A solution with a concentration of 40% by mass. The Mw of the resulting crosslinked polysilazane A was 6,900.

[0179] <Synthesis of crosslinked polysilazanes B to H>

[0180] The preparation method of the crosslinked polysilazane B to H solutions is the same as that of the synthesis of crosslinked polysilazane A, except that the compounds of the polysilazane and the crosslinking agent and their addition amounts and the compounds of the reaction initiator and their addition amounts are changed as shown in Table 1. Each Mw is shown in Table 1.

[0181]

[0182] <Synthesis of polysilazane I>

[0183] The 10 L reactor equipped with a condenser, a mechanical stirrer, and a thermostat was purged with dry nitrogen, and then 4710 g of dry pyridine, 150 g of dry xylene, and 1650 g of the poly(silazane) intermediate A with a concentration of 39.8% obtained above were charged into the reactor. While introducing nitrogen at 0.5 NL / min, the mixture was stirred until homogeneous, and then a modification reaction was carried out at 110 °C for 8.6 hours to obtain poly(silazane) I. Pyridine was removed by distillation to obtain a poly(silazane) I solution.

[0184] Poly(silazane) I is a perhydropolysilazane with an Mw of 5,800.

[0185] <Synthesis of poly(silazane) J>

[0186] Relative to the synthesis of poly(silazane) I, the conditions of the modification reaction were changed to 110 °C for 10.0 hours for synthesis to obtain poly(silazane) J. Poly(silazane) J is a perhydropolysilazane with an Mw of 8300.

[0187] By using FTIR6100 (JASCO Corporation), 13 C-NMR, and 29 Si-NMR to measure the infrared absorption spectrum, crosslinked poly(silazanes) A to H were identified as crosslinked perhydropolysilazanes.

[0188] Figure 1 The 13 C-NMR spectrum of crosslinked poly(silazane) A was shown, and a peak attributed to -CH2- was confirmed at around 9 ppm. Figure 2 The 29 Si-NMR spectrum of crosslinked poly(silazane) A was shown, and a peak attributed to the formation of a new Si bond was confirmed at around -15 ppm, indicating the formation of Si-CH2-.

[0189] <Example 1>

[0190] The composition of Example 1 was prepared by using the above-synthesized crosslinked poly(silazane) A and xylene such that the concentration of crosslinked poly(silazane) A was 40% by mass.

[0191] The composition of Example 1 was coated on a 4-inch Si substrate pre-wetted with xylene using a spin coater (1HDX2, Mikasa Co., Ltd.) to form a coating film. The obtained coating film was heated on a hot plate at 150 °C (pre-baked) for 3 minutes. The film thickness at this time (film thickness after pre-baking) was measured to be 2.4 μm. The pre-baked coating film was heated in a steam atmosphere at 350 °C (cured) for 30 minutes and then heated in a nitrogen atmosphere at 850 °C (annealed) for 30 minutes to obtain the silicon-containing film of Example 1. The film thickness at this time (film thickness after annealing) was 2.0 μm.

[0192] Using a reflection spectroscopic thickness meter (FE-3000 manufactured by OTSUKA ELECTRONICS CO., LTD.), the film thickness was measured at 17 points in the diameter direction, and the average value thereof was taken as the film thickness.

[0193] <Examples 2 to 8 and Comparative Example 1>

[0194] 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 shown in Table 2 (polysilazane in the case of Comparative Example 1) and its content.

[0195]

[0196] [Crack]

[0197] The cracks of each of the above silicon-containing films were observed using an optical microscope and evaluated according to the following criteria. The results are shown in Table 2.

[0198] A: No cracks were observed.

[0199] B: Slight cracks were observed.

[0200] C: Cracks were partially observed.

[0201] D: Cracks were observed in all.

Claims

1. A crosslinked polysilazane, which comprises repeating units represented by formula (1): Wherein, R 1 and R 2 each independently represents a single bond, hydrogen, C 1-4 alkyl or a linking group represented by formula (a) to formula (c). When R 1 and R 2 are single bonds, they are bonded to N contained in other repeating units, and in the crosslinked polysilazane molecule, at least two of R 1 and R 2 are linking groups represented by formula (a) to formula (c); R 3 is a single bond, hydrogen or C 1-4 alkyl group, and when R 3 is a single bond, it is bonded to Si contained in other repeating units: R a 、R b1 、R b2 、R c1 and R c2 each independently represents hydrogen, C 1-6 alkyl, C 1-6 alkenyl or C 6-12 aryl; L a 、L b1 、L b2 、L c1 and L c2 each independently represents C 2-8 alkylene or C 6-14 arylene, wherein the methylene group in the alkylene and arylene is unsubstituted or substituted by an oxy group, provided that when substituted by an oxy group, the oxy group is not directly bonded to Si in formula (1); na is from 1 to 3; nb1 and nb2 are each independently from 1 to 2; nc1 and nc2 are each independently from 1 to 3; p and q are each independently from 1 to 3; and Among the bonds of the linking groups of formula (a) to formula (c), the bonds not bonded to Si in formula (1) are bonded to Si contained in other repeating units.

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

3. The crosslinked polysilazane according to claim 1 or 2, having a polystyrene-reduced weight average molecular weight measured by gel permeation chromatography of 3,000 to 50,000.

4. The crosslinked polysilazane according to any one of claims 1 to 3, wherein the amount of Si derived from formula (a) to formula (c) contained in the crosslinked polysilazane is 0.5 to 10.0% based on the total amount of Si in the crosslinked polysilazane.

5. A method for producing a crosslinked polysilazane, which comprises heating or irradiating with light the following substances in the presence of a reaction initiator: A polysilazane containing repeating units represented by formula (2) and at least two Si-H bonds; and At least one silicon compound represented by formula (d) to formula (f): Wherein, R 4 and R 5 each independently is a single bond, hydrogen or C 1-4 alkyl, and when R 4 and R 5 are single bonds, they are bonded to N contained in other repeating units; and R 6 is a single bond, hydrogen or C 1-4 alkyl group, and when R 6 is a single bond, it is bonded to Si contained in other repeating units; and R d1 、R e1 、R e2 、R f1 and R f2 each independently represents hydrogen, C 1-6 alkyl, C 1-6 alkenyl or C 6-12 aryl; R d2 、R e3 、R e4 、R f3 and R f4 each independently is hydrogen or C 1-6 alkyl; L d 、L e1 、L e2 、L f1 and L f2 each independently is a single bond, C 1-6 alkylene or C 6-12 arylene, wherein the methylene group in the alkylene and arylene is unsubstituted or substituted by an oxy group; nd is from 2 to 4; ne1 and ne2 are each independently from 1 to 2; nf1 and nf2 are each independently from 1 to 3; and r and s are each independently from 1 to 3.

6. The method according to claim 5, wherein the polysilazane is a perhydropolysilazane.

7. A composition, which comprises the crosslinked polysilazane according to 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. The composition according to claim 7 or 8, 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, which comprises: Forming a coating film above a substrate using the composition according to any one of claims 7 to 9; And Heating the coating film.

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

12. A silicon-containing film obtained by the method according to claim 10 or 11.

13. An electronic device, which comprises the silicon-containing film according to claim 12.

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

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