Composition for producing a film for semiconductor devices and each production method

Abstract

A composition for producing a film for semiconductor devices, comprising: a compound (A) having a Si-O bond and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom; a crosslinking agent (B) having 3 or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in a molecule, 1 or more and 6 or less of the 3 or more -C(=O)OX groups being -C(=O)OH groups, the weight average molecular weight of the crosslinking agent (B) being 200 or more and 600 or less; an additive (C) being at least one selected from the group consisting of an acid (C-1) having a carboxyl group and having a weight average molecular weight of 46 or more and 195 or less and a base (C-2) having a nitrogen atom and having a weight average molecular weight of 17 or more and 120 or less, and a polar solvent (D), the crosslinking agent (B) having a ring structure in a molecule, the ratio of the number of carboxyl groups in the crosslinking agent (B) to the number of all nitrogen atoms in the compound (A), that is, COOH / N, being 0.1 or more and 3.0 or less.

Description

[0001] This application is a divisional application of the original application, the original application having an application date of November 16, 2016, an application number of 201680066760.X, and an invention title of "Film composition for semiconductor, each manufacturing method, and semiconductor device". TECHNICAL FIELD

[0002] The present application relates to a film composition for semiconductor, a manufacturing method of the film composition for semiconductor, a manufacturing method of a member for semiconductor, a manufacturing method of a processing material for semiconductor, and a semiconductor device. BACKGROUND

[0003] Conventionally, in various technical fields such as the field of electronic devices, an operation of imparting a composition containing a polymer to a member is performed.

[0004] For example, a manufacturing method of a composite body in which a composition containing a polymer such as polyethyleneimine having a cationic functional group and having a weight average molecular weight of 2000 to 1,000,000 and a pH of 2.0 to 11.0 is imparted to the surfaces of a member A and a member B having predetermined conditions is known (for example, refer to Patent Literature 1). Further, in Patent Literature 1, a scheme in which a rinse solution containing a polybasic carboxylic acid is used to clean the composite member to which the composition is imparted is described.

[0005] Patent Literature 1: International Publication No. 2014 / 156616 SUMMARY

[0006] Problems to be Solved by the Invention

[0007] In Patent Literature 1, the polymer such as polyethyleneimine is coated on the member, and after the rinse solution containing the polybasic carboxylic acid is coated thereon, it is crosslinked by a heat reaction, and the number of steps is large. However, if the polymer such as polyethyleneimine and the polybasic carboxylic acid are mixed to prepare the composition to be coated on the member, there is a problem that the polymer and the polybasic carboxylic acid coagulate to cause the composition to become turbid, and when the composition is coated on the member, a film having large unevenness and insufficient smoothness is formed due to the formation of coagulum, pits, and the like.

[0008] One aspect of the present application is achieved in view of the above-described problems, and an object thereof is to provide a film composition for semiconductor capable of obtaining a film having few coagulum and pits and high smoothness, a manufacturing method thereof, a manufacturing method of a member for semiconductor using the film composition for semiconductor, and a manufacturing method of a processing material for semiconductor using the film composition for semiconductor, and a semiconductor device provided with a reactant having high smoothness.

[0009] Means for Solving the Problems

[0010] A specific means for solving the problem is as follows.

[0011] A film composition for semiconductor comprising: a compound (A) having a Si-O bond and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom; a crosslinking agent (B) having 3 or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in a molecule, 1 or more and 6 or less of the 3 or more -C(=O)OX groups being -C(=O)OH groups, the crosslinking agent (B) having a weight average molecular weight of 200 or more and 600 or less; and a polar solvent (D).

[0012] A film composition for semiconductor comprising: a compound (A) having a Si-O bond and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, the compound (A) having a weight average molecular weight of 130 or more and 10,000 or less; a crosslinking agent (B) having 3 or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in a molecule, 1 or more and 6 or less of the 3 or more -C(=O)OX groups being -C(=O)OH groups, the crosslinking agent (B) having a weight average molecular weight of 200 or more and 600 or less; and a polar solvent (D).

[0013] A film composition for semiconductor according to <1> or <2>, further wherein the crosslinking agent (B) has a ring structure in a molecule.

[0014] A film composition for semiconductor according to <3>, wherein the ring structure is at least one of a benzene ring and a naphthalene ring.

[0015] A film composition for semiconductor according to any one of <1> to <4>, further wherein at least one X of the 3 or more -C(=O)OX groups in the crosslinking agent (B) is an alkyl group having 1 or more and 6 or less carbon atoms.

[0016] A film composition for semiconductor according to any one of <1> to <5>, further comprising an additive (C) selected from at least one of an acid (C-1) having a carboxyl group and having a weight average molecular weight of 46 or more and 195 or less, and a base (C-2) having a nitrogen atom and having a weight average molecular weight of 17 or more and 120 or less.

[0017] A film composition for semiconductor according to any one of <1> to <6>, comprising at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 100,000 or more and 400,000 or less, and an amine compound having a ring structure in a molecule and having a weight average molecular weight of 90 or more and 600 or less.

[0018] The film composition for semiconductor according to any one of <1> to <7> for a filling material of a recess formed in a substrate.

[0019] The film composition for semiconductor according to any one of <1> to <7> for a multilayer resist method.

[0020] The film composition for semiconductor according to any one of <1> to <7> for a multilayer resist method.

[0021] The film composition for semiconductor according to any one of <1> to <7> for a multilayer resist method.

[0022] The film composition for semiconductor according to any one of <1> to <7> for a multilayer resist method.

[0023] The film composition for semiconductor according to any one of <1> to <7> for a multilayer resist method.

[0024] The film composition for semiconductor according to any one of <1> to <7> for a multilayer resist method.

[0025] A semiconductor device including: a substrate, and a reaction product of a compound (A) having a Si-O bond and a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom, and having a weight average molecular weight of 130 or more and 10,000 or less, and a crosslinking agent (B) having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having a carbon number of 1 or more and 6 or less) in a molecule, in which one or more and six or less of the three or more -C(=O)OX groups are -C(=O)OH groups, the crosslinking agent (B) having a weight average molecular weight of 200 or more and 600 or less.

[0026] A semiconductor device according to <15>, the reaction product having at least one of an amide bond and an imide bond.

[0027] Effects of the Invention

[0028] One aspect of the present application can provide a semiconductor film composition capable of obtaining a film having few condensates and pits and high smoothness, a method for producing the same, a method for producing a semiconductor member using the semiconductor film composition, a method for producing a semiconductor processing material using the semiconductor film composition, and a semiconductor device provided with a reaction product having high smoothness. DETAILED DESCRIPTION

[0029] In the present specification, a numerical range represented by "〜" or "-" means a range including the numerical values recited before and after "〜" or "-" as lower limit values and upper limit values.

[0030] [Semiconductor Film Composition]

[0031] Hereinafter, one embodiment of a semiconductor film composition according to the present application will be described. The semiconductor film composition according to the present embodiment includes: a compound (A) having a Si-O bond and a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom; a crosslinking agent (B) having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having a carbon number of 1 or more and 6 or less) in a molecule, in which one or more and six or less of the three or more -C(=O)OX groups are -C(=O)OH groups, the crosslinking agent (B) having a weight average molecular weight of 200 or more and 600 or less; and a polar solvent (D).

[0032] By using the semiconductor film composition according to the present embodiment, specifically, by forming a film by applying the semiconductor film composition to a member, a film having few condensates and pits and high smoothness can be obtained. Further, by using the semiconductor film composition according to the present embodiment, a film having high smoothness can be more easily obtained compared to the technology of the above-described Patent Literature 1 (International Publication No. 2014 / 156616).

[0033] By using the semiconductor film composition according to the present embodiment, a film having a small unevenness and a good smoothness can be formed. For example, in a case where the semiconductor film composition according to the present embodiment is used to form a film on a smooth substrate such as a silicon substrate, a film can be formed in which the difference between the maximum value and the minimum value of the film thickness within a field of view of 500 nm wide at a magnification of 200,000 times in SEM (scanning electron microscope) is 25% or less of the average film thickness.

[0034] Further, in the technology of Patent Document 1, since a polymer such as polyethyleneimine is coated on a member and a rinsing solution containing a polycarboxylic acid is coated thereon, and then cross-linked by a heat reaction, the coated polymer can be dissolved in the rinsing solution containing the polycarboxylic acid. Therefore, it is difficult to make the film thickness in-plane of a large-diameter wafer uniform, and it is not easy to control the film thickness.

[0035] Further, in the technology of Patent Document 1, in a case where a thick film of several tens of nanometers or more is formed, since the polycarboxylic acid is difficult to penetrate to the interface between the member and the polymer, it is difficult to make the composition in the film thickness direction uniform.

[0036] On the other hand, in the present embodiment, by coating a semiconductor film composition containing the compound (A) and the cross-linking agent (B) on a member to form a film, the smoothness can be improved, and the uniformity of the composition in the film thickness direction can be improved.

[0037] By using the semiconductor film composition according to the present embodiment, a film having a good smoothness and a good uniformity of the composition in the film thickness direction, for example, a film having a film thickness of 0.5 nm or more and 5 μm or less, can be formed. Further, a film having a good smoothness can be formed on the surface of a large-diameter silicon substrate, for example, when the film thickness is set to 5 nm or more and 150 nm or less, the film thickness deviation between the center and the end of a 300 mmφ silicon substrate can be set to 15% or less, and preferably can be set to 10% or less.

[0038] Further, the semiconductor film composition according to the present embodiment is a composition for forming a film for a semiconductor device (hereinafter, sometimes referred to as "composition"), for example, for forming: a gap filling material (buried planarization film) filled in a recess formed in a substrate; an insulating material (buried insulating film) filled in a recess formed in a substrate; a barrier material (barrier film) having insulating properties, adhesion, pore sealing properties, and the like, provided between a low dielectric constant material such as a porous material and a metal; an insulating material having adhesion and insulating properties, provided between a metal and a silicon substrate or between a metal and an insulating film at a via sidewall of a silicon through via substrate; and the like.

[0039] In particular, a filling material (buried planarization film) formed in a recess of a substrate is sometimes used in complex processing of the substrate.

[0040] As one of methods of transferring a lithography pattern to a substrate using a hard mask, there is a multilayer resist method. The multilayer resist method uses a photoresist film, i.e., an upper layer resist film, and an etching-selectivity-different lower layer film, i.e., a lower layer resist film. The multilayer resist method is, for example, a method of interposing a lower layer resist film containing silicon between an upper layer resist film and a substrate to be processed, transferring a pattern to the lower layer resist film with the upper layer resist pattern as an etching mask after a pattern is provided on the upper layer resist film, and further transferring a pattern to the substrate to be processed with the lower layer resist pattern as an etching mask.

[0041] As a composition of the lower layer resist film used in such a multilayer resist method, there are a silicon-containing inorganic film made by CVD, a SiO2 film, a SiON film, and the like.

[0042] However, as the miniaturization of semiconductor devices further progresses, not only the line width of a pattern becomes fine, but also the film thickness of an upper layer resist film is thinned in order to prevent collapse of a pattern, and in terms of the performance required for a lower layer resist film, it is also required to improve the embeddability of a finer pattern than before and the etching selectivity.

[0043] Further, for a recent manufacturing process of semiconductor devices in a limit region of lithography, a complex process such as double patterning as described above is proposed. Further, further complication of devices such as integrated circuit elements is also advanced, and a method of performing a multilayer resist pattern formation, a method of forming a complex pattern by performing pattern formation a plurality of times, and the like are also performed for a substrate patterned with a wiring groove (trench), a plug hole (via hole), and the like.

[0044] On the other hand, in the multilayer resist method, for example, when an upper layer resist pattern is transferred to a lower layer resist film, or when a lower layer resist pattern is transferred to a substrate to be processed, dry etching such as plasma etching is widely used.

[0045] The resist film that has been put into practical use in the conventional multilayer resist method is mostly an organic film, a silicon-containing inorganic film made by CVD as described above, or the like. However, the conventional CVD method is increasingly difficult to fill a fine groove without a gap due to a problem such as overhang.

[0046] Further, heat resistance (for example, resistance to heat treatment that is sometimes performed after formation of a resist film) is sometimes required for a resist film.

[0047] Note that from the viewpoint of achieving formation of a fine pattern, the above-mentioned embedding property, etching selectivity, and heat resistance are required also for films other than resist films, such as buried insulating films (shallow trench element isolation films (STI films), metal pre-insulating films (PMD films), wiring interlayer insulating films (IMD films), and the like).

[0048] The composition according to the present embodiment is excellent in embedding property, etching selectivity, and heat resistance, and thus can be used in the production of resist films used in a multilayer resist method, and the above-mentioned films other than resist films.

[0049] Further, as another method of forming a fine pattern, the composition according to the present embodiment can be used for the purpose of forming an inverted resist by coating on a photosensitive resist after light exposure and displacing the photosensitive resist or non-photosensitive portion. By forming an inverted resist, a film excellent in etching resistance and less in pattern collapse can be formed.

[0050] (Compound (A))

[0051] The composition according to the present embodiment contains a compound (A) having a Si-O bond and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. As the compound (A), a compound having a Si-O bond and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and having a weight average molecular weight of 130 or more and 10,000 or less can be used.

[0052] The compound (A) is a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. As the cationic functional group, there is no particular limitation as long as it is a functional group capable of carrying a positive charge and containing at least one of a primary nitrogen atom and a secondary nitrogen atom.

[0053] Further, the compound (A) can contain a tertiary nitrogen atom in addition to the primary nitrogen atom and the secondary nitrogen atom.

[0054] In the present specification, a "primary nitrogen atom" refers to a nitrogen atom bonded to only two hydrogen atoms and one atom other than a hydrogen atom (for example, a nitrogen atom contained in a primary amino group (-NH2 group)), or a nitrogen atom bonded to only three hydrogen atoms and one atom other than a hydrogen atom (a cation).

[0055] Further, a "secondary nitrogen atom" refers to a nitrogen atom bonded to only one hydrogen atom and two atoms other than a hydrogen atom (that is, a nitrogen atom contained in a functional group represented by the following formula (a)), or a nitrogen atom bonded to only two hydrogen atoms and two atoms other than a hydrogen atom.

[0056] Further, a "tertiary nitrogen atom" means a nitrogen atom bonded to three atoms other than a hydrogen atom (i.e., a nitrogen atom of a functional group represented by the following formula (b)), or a nitrogen atom bonded to one hydrogen atom and three atoms other than a hydrogen atom (a cation).

[0057] [Chemical Formula 1]

[0058]

[0059] In formula (a) and formula (b), * indicates a bonding position to an atom other than a hydrogen atom.

[0060] Here, the functional group represented by the above formula (a) can be a functional group that is a part of a secondary amino group (-NHR a group; here, R a represents an alkyl group), or a divalent linking group contained in a backbone of a polymer.

[0061] Further, the functional group represented by the above formula (b) (i.e., a tertiary nitrogen atom) can be a functional group that is a part of a tertiary amino group (-NR b R c group; here, R b and R c each independently represent an alkyl group), or a trivalent linking group contained in a backbone of a polymer.

[0062] The weight average molecular weight of the compound (A) is preferably 130 or more and 10,000 or less, more preferably 130 or more and 5,000 or less, and further preferably 130 or more and 2,000 or less.

[0063] Note that, in the present specification, the weight average molecular weight refers to a weight average molecular weight converted to polyethylene glycol, which is measured by a GPC (Gel Permeation Chromatography) method.

[0064] Specifically, the weight average molecular weight is calculated by using a sodium nitrate aqueous solution having a concentration of 0.1 mol / L as an elution solvent, using an analysis device Shodex DET RI-101 and two kinds of analysis columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP manufactured by Tosoh) to detect a refractive index at a flow rate of 1.0 mL / min, using polyethylene glycol / polyoxyethylene as a standard, and by a resolution software (Empower3 manufactured by Waters).

[0065] Further, the compound (A) can further have an anionic functional group, a nonionic functional group, and the like, as needed.

[0066] The nonionic functional group can be a hydrogen bond-accepting group or a hydrogen bond-donating group. As the nonionic functional group, for example, a hydroxyl group, a carbonyl group, an ether group (-0-), and the like can be given.

[0067] The anionic functional group is not particularly limited as long as it is a functional group capable of carrying a negative charge. As the anionic functional group, for example, a carboxylic acid group, a sulfonic acid group, a sulfuric acid group, and the like can be given.

[0068] As the compound having a Si-O bond and an amino group, for example, a siloxane diamine, a silane coupling agent having an amino group, a siloxane polymer, and the like can be given.

[0069] As the silane coupling agent having an amino group, for example, a compound represented by the following formula (A-3) can be given.

[0070] [Chemical 2]

[0071]

[0072] In formula (A-3), R 1 represents an alkyl group having a carbon number of 1 to 4 which can be substituted. R 2 and R 3 each independently represent an alkylene group having a carbon number of 1 to 12 which can be substituted (may contain a carbonyl group, an ether group, and the like in the skeleton), an ether group, or a carbonyl group. R 4 and R 5 each independently represent an alkylene group having a carbon number of 1 to 4 which can be substituted or a single bond. Ar represents a 2-valent or 3-valent aromatic ring. X 1 represents hydrogen or an alkyl group having a carbon number of 1 to 5 which can be substituted. X 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an alkyl group having a carbon number of 1 to 5 which can be substituted (may contain a carbonyl group, an ether group, and the like in the skeleton). A plurality of R 1 , R 2 , R 3 , R 4 , R 5 , X 1 may be the same or different.

[0073] As the alkyl group and the alkylene group in R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 each independently, an amino group, a hydroxyl group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, a halogen, and the like can be given.

[0074] As the 2-valent or 3-valent aromatic ring in Ar, for example, a 2-valent or 3-valent benzene ring can be given. As X 2As the aryl group in the aryl group in the above-mentioned aryl group, for example, a phenyl group, a methylbenzyl group, a vinylbenzyl group, and the like can be given.

[0075] As specific examples of the silane coupling agent represented by formula (A-3), for example, N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutyl dimethylmethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldimethylmethoxysilane, trimethoxy[2-(2-aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane, and hydrolysis products thereof can be given.

[0076] As the silane coupling agent containing an amino group other than formula (A-3), for example, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, piperazinylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-(4-(methoxydimethylsilyl)phenyl)benzamide, 3,5-diamino-N-(4-(triethoxysilyl)phenyl)benzamide, 5-(ethoxydimethylsilyl)benzene-1,3-diamine, and hydrolysis products thereof can be given.

[0077] The above-mentioned silane coupling agent having an amino group can be used alone or in combination with two or more. Furthermore, a silane coupling agent having an amino group and a silane coupling agent not having an amino group can be used in combination. For example, a silane coupling agent having a mercapto group can also be used in order to improve adhesion to metals.

[0078] Further, a polymer (siloxane polymer) formed by these silane coupling agents via a siloxane bond (Si-O-Si) can be used. For example, from a hydrolyzate of 3-aminopropyltrimethoxysilane, a polymer having a linear siloxane structure, a polymer having a branched siloxane structure, a polymer having a cyclic siloxane structure, a polymer having a cage siloxane structure, and the like can be obtained. The cage siloxane structure is represented by the following formula (A-1), for example.

[0079] [Chem. 3]

[0080]

[0081] As the siloxane diamine, a compound represented by the following formula (A-2) can be given, for example. Note that in formula (A-2), i is an integer of 0 to 4, j is an integer of 1 to 3, and Me is a methyl group.

[0082] [Chem. 4]

[0083]

[0084] Further, as the siloxane diamine, 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in formula (A-2), i = 0, j = 1), 1,3-bis(2-aminoethylamino)propyltetramethyldisiloxane (in formula (A-2), i = 1, j = 1) can be given.

[0085] The compound (A) is easily dissolved in the polar solvent (D) described later due to the amino group. If the ratio of the total number of primary and secondary nitrogen atoms to the number of silicon atoms (total number of primary and secondary nitrogen atoms / number of silicon atoms) in the compound (A) is 0.2 or more and 5 or less, it is preferable from the viewpoint of solubility.

[0086] By using the compound (A) which is easily dissolved in the polar solvent (D), the affinity to the hydrophilic surface such as a silicon substrate becomes high, and thus a smooth film can be formed.

[0087] As the more preferable compound (A), from the viewpoint of plasma resistance, the non-crosslinking group such as a methyl group bonded to Si preferably satisfies the relationship of (non-crosslinking group) / Si < 2 in terms of molar ratio. It is presumed that by satisfying this relationship, the crosslinking (crosslinking of Si-O-Si bond and amide bond, imide bond, and the like) density of the formed film is increased, and a film more resistant to plasma can be formed.

[0088] As described above, the compound (A) has a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom. Here, in the case where the compound (A) includes a primary nitrogen atom, the proportion of the primary nitrogen atom in the compound (A) in all nitrogen atoms is preferably 20 mol% or more, more preferably 25 mol% or more, and further preferably 30 mol% or more. In addition, the compound (A) can have a cationic functional group including a primary nitrogen atom and not including a nitrogen atom other than the primary nitrogen atom (for example, a secondary nitrogen atom, a tertiary nitrogen atom).

[0089] In addition, in the case where the compound (A) includes a secondary nitrogen atom, the proportion of the secondary nitrogen atom in the compound (A) in all nitrogen atoms is preferably 5 mol% or more and 50 mol% or less, and more preferably 10 mol% or more and 45 mol% or less.

[0090] In addition, the compound (A) can include a tertiary nitrogen atom in addition to the primary nitrogen atom and the secondary nitrogen atom, and in the case where the compound (A) includes a tertiary nitrogen atom, the proportion of the tertiary nitrogen atom in the compound (A) in all nitrogen atoms is preferably 20 mol% or more and 50 mol% or less, and preferably 25 mol% or more and 45 mol% or less.

[0091] In the present embodiment, the content of the compound (A) in the composition is not particularly limited, and for example, can be 0.001 mass% or more and 20 mass% or less, preferably 0.01 mass% or more and 20 mass% or less, and more preferably 0.04 mass% or more and 20 mass% or less, with respect to the entire composition.

[0092] (Crosslinking agent (B))

[0093] The composition according to the present embodiment includes a crosslinking agent (B) having 3 or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in a molecule, 1 or more and 6 or less of the 3 or more -C(=O)OX groups are -C(=O)OH groups (hereinafter, also referred to as "COOH"), and the weight average molecular weight of the crosslinking agent (B) is 200 or more and 600 or less.

[0094] The crosslinking agent (B) is a compound having 3 or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in a molecule, and preferably a compound having 3 or more and 6 or less -C(=O)OX groups in a molecule, and more preferably a compound having 3 or 4 -C(=O)OX groups in a molecule.

[0095] As X in the -C(=O)OX group in the crosslinking agent (B), a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms can be given, and a hydrogen atom, a methyl group, an ethyl group, a propyl group are preferable. Note that X in the -C(=O)OX group can be the same or different.

[0096] The crosslinking agent (B) is a compound having 1 or more and 6 or less -C(=O)OH groups in which X is a hydrogen atom in the molecule, and preferably a compound having 1 or more and 4 or less -C(=O)OH groups in the molecule, more preferably a compound having 2 or more and 4 or less -C(=O)OH groups in the molecule, and further preferably a compound having 2 or 3 -C(=O)OH groups in the molecule.

[0097] The crosslinking agent (B) is a compound having a weight average molecular weight of 200 or more and 600 or less. A compound having a weight average molecular weight of 200 or more and 400 or less is preferable.

[0098] The crosslinking agent (B) preferably has a ring structure in the molecule. As the ring structure, an alicyclic structure, an aromatic ring structure, and the like can be given. In addition, the crosslinking agent (B) can have a plurality of ring structures in the molecule, and the plurality of ring structures can be the same or different.

[0099] As the alicyclic structure, for example, an alicyclic structure having 3 or more and 8 or less carbon atoms, and preferably an alicyclic structure having 4 or more and 6 or less carbon atoms can be given, and the ring structure can be saturated or unsaturated. More specifically, as the alicyclic structure, a saturated alicyclic structure such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, and the like; and an unsaturated alicyclic structure such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, a cyclooctene ring, and the like can be given.

[0100] As the aromatic ring structure, there is no particular limitation as long as it is a ring structure showing aromaticity, and a benzene-based aromatic ring such as a benzene ring, a naphthalene ring, an anthracene ring, a perylene ring, and the like; an aromatic heterocyclic ring such as a pyridine ring, a thiophene ring, and the like; a non-benzene-based aromatic ring such as an indene ring, an azulene ring, and the like can be given.

[0101] As the ring structure possessed in the molecule of the crosslinking agent (B), at least one selected from the group consisting of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a naphthalene ring is preferable from the viewpoint of further improving the heat resistance of the film obtained from the composition, and at least one of a benzene ring and a naphthalene ring is more preferable.

[0102] As described above, the crosslinking agent (B) can have a plurality of ring structures in the molecule, and in the case where the ring structure is a benzene ring, a biphenyl structure, a benzophenone structure, a diphenyl ether structure, and the like can be given.

[0103] The crosslinking agent (B) preferably has a fluorine atom in the molecule, more preferably 1 or more and 6 or less fluorine atoms in the molecule, and further preferably 3 or more and 6 or less fluorine atoms in the molecule. For example, the crosslinking agent (B) can have a fluoroalkyl group in the molecule, and specifically can have a trifluoroalkyl group or a hexafluoroisopropyl group.

[0104] Further, as the crosslinking agent (B), carboxylic acid compounds such as alicyclic carboxylic acid, benzenecarboxylic acid, naphthalenecarboxylic acid, diphenyldicarboxylic acid, fluorinated aromatic ring carboxylic acid, and the like; carboxylic acid ester compounds such as alicyclic carboxylic acid ester, benzenecarboxylic acid ester, naphthalenecarboxylic acid ester, diphenyldicarboxylic acid ester, fluorinated aromatic ring carboxylic acid ester, and the like can be exemplified. Note that the carboxylic acid ester compound is a compound having a carboxyl group (-C(=O)OH group) in the molecule, and at least one X in the -C(=O)OX group is an alkyl group having 1 or more and 6 or less carbon atoms (i.e., having an ester bond). In the composition according to the present embodiment, since the crosslinking agent (B) is a carboxylic acid ester compound, agglomeration due to association of the compound (A) with the crosslinking agent (B) in the composition is suppressed, a film having fewer agglomerates and pits and higher smoothness or a film having a larger film thickness is easily obtained, and the film thickness is easily adjusted.

[0105] As the carboxylic acid compound, a 4-membered or less carboxylic acid compound having 4 or less -C(=O)OH groups is preferable, and a 3-membered or 4-membered carboxylic acid compound having 3 or 4 -C(=O)OH groups is more preferable.

[0106] As the carboxylic acid ester compound, a compound having 3 or less carboxyl groups (-C(=O)OH groups) in the molecule and having 3 or less ester bonds is preferable, and a compound having 2 or less carboxyl groups in the molecule and having 2 or less ester bonds is more preferable.

[0107] Further, in the case where X in the -C(=O)OX group in the carboxylic acid ester compound is an alkyl group having 1 or more and 6 or less carbon atoms, X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or the like, and is more preferably an ethyl group or a propyl group from the viewpoint of further suppressing agglomeration due to association of the compound (A) with the crosslinking agent (B) in the composition.

[0108] As specific examples of the carboxylic acid compound, without being limited thereto, mention can be made of alicyclic carboxylic acids such as 1,2,3,4-cyclobutane tetra carboxylic acid, 1,2,3,4-cyclopentane tetra carboxylic acid, 1,3,5-cyclohexane tri carboxylic acid, 1,2,4-cyclohexane tri carboxylic acid, 1,2,4,5-cyclohexane tetra carboxylic acid, 1,2,3,4,5,6-cyclohexane hexa carboxylic acid, and the like; benzenecarboxylic acids such as 1,2,4-benzene tri carboxylic acid, 1,3,5-benzene tri carboxylic acid, pyromellitic acid, benzene penta carboxylic acid, benzene hexa carboxylic acid, and the like; naphthalene carboxylic acids such as 1,4,5,8-naphthalene tetra carboxylic acid, 2,3,6,7-naphthalene tetra carboxylic acid, and the like; diphenyl carboxylic acids such as 3,3',5,5'-tetracarboxy diphenyl methane, biphenyl-3,3',5,5'-tetra carboxylic acid, biphenyl-3,4',5-tri carboxylic acid, biphenyl-3,3',4,4'-tetra carboxylic acid, benzophenone-3,3',4,4'-tetra carboxylic acid, 4,4'-oxybis phthalic acid, 3,4'-oxybis phthalic acid, 1,3-bis(phthalic acid) tetramethyl disiloxane, 4,4'-(ethyne-1,2-diyl)diphthalic acid, 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid, and the like; perylene carboxylic acids such as perylene-3,4,9,10-tetra carboxylic acid, and the like; anthracene carboxylic acids such as anthracene-2,3,6,7-tetra carboxylic acid, and the like; fluorinated aromatic ring carboxylic acids such as 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetra carboxylic acid, 1,4-bistrifluoromethyl pyromellitic acid, and the like.

[0109] As specific examples of the carboxylic acid ester compound, mention can be made of compounds in which at least one carboxyl group in the specific examples of the carboxylic acid compound described above is replaced with an ester group. As the carboxylic acid ester compound, mention can be made of, for example, compounds represented by the following general formulae (B-1) to (B-6) which are half-esterified.

[0110] [Chemical 5]

[0111]

[0112] R in General Formulae (B-1) to (B-6) is an alkyl group having a carbon number of 1 or more and 6 or less, and is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and is more preferably an ethyl group or a propyl group.

[0113] The semi-esterified compound can be obtained, for example, by mixing a carboxylic acid anhydride, which is an anhydride of the above carboxylic acid compound, in an alcohol solvent and ring-opening the carboxylic acid anhydride.

[0114] In the present embodiment, the content of the crosslinking agent (B) in the composition is not particularly limited, and for example, the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) (COOH / N) is preferably 0.1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and further preferably 0.4 or more and 2.2 or less. Since the COOH / N is 0.1 or more and 3.0 or less, a film having an amide, an imide, or the like as a crosslinking structure between the compound (A) and the crosslinking agent (B) after heat treatment, and having more excellent heat resistance and insulating properties can be produced by using the composition.

[0115] When at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 100,000 or more and 400,000 or less and an amine compound having a ring structure in the molecule and having a weight average molecular weight of 90 or more and 600 or less is further contained as a component other than the compound (A) and the crosslinking agent (B), the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms contained in them and the total number of nitrogen atoms contained in the compound (A) (COOH / N) is preferably 0.1 or more and 3.0 or less.

[0116] (Polar solvent (D))

[0117] The composition according to the present embodiment contains a polar solvent (D). Here, the polar solvent (D) refers to a solvent having a relative dielectric constant of 5 or more at room temperature. As the polar solvent (D), specifically, there can be mentioned, for example, protic inorganic compounds such as water, heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isoamyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerol; ethers such as tetrahydrofuran, dimethoxyethane; aldehydes and ketones such as furfural, acetone, ethyl methyl ketone, cyclohexanone; acid derivatives such as acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methylformamide, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and hexamethylphosphoramide; nitriles such as acetonitrile, propionitrile; nitro compounds such as nitromethane, nitrobenzene; and sulfur compounds such as dimethyl sulfoxide. As the polar solvent (D), it is preferable to contain a protic solvent, and it is more preferable to contain water, and further to contain ultrapure water.

[0118] The content of the polar solvent (D) in the composition is not particularly limited, and for example, it is preferably 1.0% by mass or more and 99.99896% by mass or less, more preferably 40% by mass or more and 99.99896% by mass or less, relative to the entire composition.

[0119] (additive (C))

[0120] The composition according to the present embodiment can contain an additive (C) in addition to the above-mentioned compound (A), crosslinking agent (B), and polar solvent (D). As the additive (C), an acid (C-1) having a carboxyl group and having a weight average molecular weight of 46 or more and 195 or less, and a base (C-2) having a nitrogen atom and having a weight average molecular weight of 17 or more and 120 or less can be exemplified.

[0121] The acid (C-1) is an acid having a carboxyl group and having a weight average molecular weight of 46 or more and 195 or less. It is presumed that the composition according to the present embodiment, by containing the acid (C-1) as the additive (C), the amino group in the compound (A) forms an ionic bond with the carboxyl group in the acid (C-1), and thus the aggregation due to the association of the compound (A) and the crosslinking agent (B) is suppressed. In more detail, it is presumed that the aggregation is suppressed because the interaction (for example, electrostatic interaction) between the ammonium ion derived from the amino group in the compound (A) and the carboxylate ion derived from the carboxyl group in the acid (C-1) is stronger than the interaction between the ammonium ion derived from the amino group in the compound (A) and the carboxylate ion derived from the carboxyl group in the crosslinking agent (B). Note that the present application is not limited to the above presumption.

[0122] As the acid (C-1), a compound having a carboxyl group and having a weight average molecular weight of 46 or more and 195 or less is not particularly limited, and a monocarboxylic acid compound, a dicarboxylic acid compound, an oxodipicarboxylic acid compound, and the like can be exemplified. In more detail, as the acid (C-1), formic acid, acetic acid, malonic acid, oxalic acid, citric acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, terephthalic acid, pyridine-2-carboxylic acid, salicylic acid, 3,4,5-trihydroxybenzoic acid, and the like can be exemplified.

[0123] In the present embodiment, the content of the acid (C-1) in the composition is not particularly limited, and for example, the ratio of the number of carboxyl groups in the acid (C-1) to the total number of nitrogen atoms in the compound (A) (COOH / N) is preferably 0.01 or more and 10 or less, more preferably 0.02 or more and 6 or less, and further preferably 0.5 or more and 3 or less.

[0124] When at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 100,000 or more and 400,000 or less and an amine compound having a ring structure in the molecule and a weight average molecular weight of 90 or more and 600 or less is further contained as a component other than the compound (A) and the crosslinking agent (B), the ratio (COOH / N) of the number of carboxyl groups in the acid (C-1) to the total number of nitrogen atoms contained in them and the total number of nitrogen atoms contained in the compound (A) is preferably 0.01 or more and 10 or less.

[0125] The base (C-2) is a base having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less. With the composition according to the present embodiment, it is presumed that, because the base (C-2) is contained as the additive (C), the carboxyl group in the crosslinking agent (B) forms an ionic bond with the amino group in the base (C-2), and thus the aggregation due to the association of the compound (A) and the crosslinking agent (B) is inhibited. In more detail, it is presumed that, because the interaction between the carboxylate ion derived from the carboxyl group in the crosslinking agent (B) and the ammonium ion derived from the amino group in the base (C-2) is stronger than the interaction between the ammonium ion derived from the amino group in the compound (A) and the carboxylate ion derived from the carboxyl group in the crosslinking agent (B), the aggregation is inhibited. Note that the present application is not limited to the above presumption.

[0126] As the base (C-2), there is no particular limitation as long as it is a compound having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less, and a monoamine compound, a diamine compound, and the like can be given. In more detail, as the base (C-2), ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylenediamine, N-(2-aminoethyl)ethanolamine, N-(2-aminoethyl)glycine, and the like can be given.

[0127] In the present embodiment, the content of the base (C-2) in the composition is not particularly limited, and, for example, the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) is preferably 0.5 or more and 5 or less, and more preferably 0.9 or more and 3 or less.

[0128] (Other components)

[0129] In the composition according to the present embodiment, the content of sodium and potassium is each preferably 10 mass ppb or less on an elemental basis. If the content of sodium or potassium is each 10 mass ppb or less on an elemental basis, it is possible to inhibit the occurrence of an adverse situation in the electrical characteristics of a semiconductor device, such as malfunction of a transistor.

[0130] The composition can further contain at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 100,000 or more and 400,000 or less and an amine compound having a ring structure in the molecule and a weight average molecular weight of 90 or more and 600 or less.

[0131] As the aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less, it is preferable to have a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom. Further, as a specific example of the aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less, there can be mentioned polymers of alkylene imines such as ethylene imine, propylene imine, butylene imine, pentylene imine, hexylene imine, heptylene imine, octylene imine, trimethylene imine, tetramethylene imine, pentamethylene imine, hexamethylene imine, octamethylene imine, and the like, i.e., polyalkylene imines; polyallylamine; and polyacrylamide.

[0132] The polyethylene imine (PEI) can be produced by a publicly known method described in Japanese Patent Application Publication No. 43-8828, Japanese Patent Application Publication No. 49-33120, Japanese Patent Application Publication No. 2001-2123958, International Publication No. 2010 / 137711, and the like. As for polyalkylene imines other than polyethylene imine, it can be produced in the same manner as polyethylene imine.

[0133] Further, as the aliphatic amine having a weight average molecular weight of 10,000 or more and 400,000 or less, it is also preferable to be a derivative of the above polyalkylene imine (polyalkylene imine derivative; particularly preferably, polyethylene imine derivative). As the polyalkylene imine derivative, there is no particular limitation as long as it is a compound that can be produced using the above polyalkylene imine. Specifically, there can be mentioned polyalkylene imine derivatives obtained by introducing an alkyl group (preferably, an alkyl group having 1 to 10 carbons), an aryl group, or the like into polyalkylene imine, polyalkylene imine derivatives obtained by introducing a cross-linking group such as a hydroxyl group into polyalkylene imine, and the like.

[0134] These polyalkylene imine derivatives can be produced by a publicly known method using the above polyalkylene imine. Specifically, it can be produced in accordance with a method described in Japanese Patent Application Publication No. 6-016809 and the like.

[0135] Further, as the polyalkylene imine derivative, it is also preferable to be a highly branched polyalkylene imine obtained by increasing the degree of branching of polyalkylene imine by reacting a monomer containing a cationic functional group with polyalkylene imine.

[0136] As a method for obtaining the highly branched polyalkylene imine, there can be mentioned, for example, a method of reacting a monomer containing a cationic functional group with polyalkylene imine having a plurality of secondary nitrogen atoms in the backbone, substituting at least a part of the plurality of secondary nitrogen atoms with the monomer containing a cationic functional group; a method of reacting a monomer containing a cationic functional group with polyalkylene imine having a plurality of primary nitrogen atoms at the terminal, substituting at least a part of the plurality of primary nitrogen atoms with the monomer containing a cationic functional group; and the like.

[0137] Examples of cationic functional groups introduced to increase the degree of branching include aminoethyl, aminopropyl, diaminopropyl, aminobutyl, diaminobutyl, and triaminobutyl. However, from the viewpoint of reducing the equivalent amount of the cationic functional group and increasing the density of the cationic functional group, aminoethyl is preferred.

[0138] Aliphatic amines with a weight-average molecular weight of 10,000 to 400,000 preferably have cationic functional groups containing at least one of primary and secondary nitrogen atoms. Here, when the aliphatic amine contains a primary nitrogen atom, the proportion of the primary nitrogen atom in the total nitrogen atoms is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more. Furthermore, aliphatic amines may also have cationic functional groups containing a primary nitrogen atom but not nitrogen atoms other than the primary nitrogen atom (e.g., secondary nitrogen atoms, tertiary nitrogen atoms).

[0139] Furthermore, when the aliphatic amine contains a secondary nitrogen atom, the proportion of the secondary nitrogen atom in the aliphatic amine to all nitrogen atoms is preferably 5 mol% or more and 50 mol% or less, more preferably 10 mol% or more and 45 mol% or less.

[0140] In addition, aliphatic amines may contain tertiary nitrogen atoms in addition to primary and secondary nitrogen atoms. When aliphatic amines contain tertiary nitrogen atoms, the proportion of tertiary nitrogen atoms in all nitrogen atoms in the aliphatic amine is preferably 20 mol% to 50 mol% and more preferably 25 mol% to 45 mol%.

[0141] Furthermore, the polyethylene imide and its derivatives may also be commercially available products. For example, suitable options may be selected from polyethylene imide and its derivatives sold by companies such as Nippon Shokubai Co., Ltd., BASF Corporation, and MP-Biomedicals Co., Ltd.

[0142] Examples of amine compounds that have an intramolecular ring structure and a weight-average molecular weight of 90 to 600 include alicyclic amines, aromatic cyclic amines, and heterocyclic (heterocyclic) amines. They may also have multiple intramolecular ring structures, which can be identical or different. As amine compounds with ring structures, compounds with aromatic rings are more preferred because they are more thermally stable.

[0143] Further, as the amine compound having a ring structure in the molecule and having a weight average molecular weight of 90 or more and 600 or less, from the viewpoint of easily forming imide, imide amide, amide or the like thermal crosslinking structure together with the crosslinking agent (B) and being able to improve heat resistance, a compound having a primary amino group is preferred. Furthermore, as the above-mentioned amine compound, from the viewpoint of easily increasing the number of imide, imide amide, amide or the like thermal crosslinking structure together with the crosslinking agent (B) and being able to further improve heat resistance, a diamine compound having two primary amino groups, a triamine compound having three primary amino groups or the like is preferred.

[0144] As the alicyclic amine, for example, cyclohexylamine, dimethylaminocyclohexane or the like can be given.

[0145] As the aromatic amine, for example, diamino diphenyl ether, xylene diamine (preferably p-xylenediamine), diamino benzene, diamino toluene, methylene dianiline, dimethyl diamino diphenyl, bis(trifluoromethyl) diamino diphenyl, diamino benzophenone, diamino benzamide aniline, bis(amino phenyl) fluorene, bis(amino phenoxy) benzene, bis(amino phenoxy) diphenyl, dicarboxy diamino diphenyl methane, diamino resorcinol, dihydroxy benzidine, diamino benzidine, 1,3,5-triamino phenoxy benzene, 2,2'-dimethyl benzidine, tris(4-aminophenyl) amine or the like can be given.

[0146] As the heterocyclic ring of the heterocyclic amine, a heterocyclic ring containing a sulfur atom as a hetero atom (for example, a thiophene ring) or a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a five-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring or the like; a six-membered ring such as an isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine ring, a piperazine ring, a triazine ring or the like; a condensed ring such as an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthylidine ring, a quinazoline ring, a purine ring, a quinoxaline ring or the like) or the like can be given.

[0147] For example, as the heterocyclic amine having a nitrogen-containing heterocyclic ring, melamine, melam, melon, tris(4-aminophenyl) amine or the like can be given.

[0148] Furthermore, as the amine compound having both a heterocyclic ring and an aromatic ring, N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine or the like can be given.

[0149] As to the composition involved in the present embodiment, in the case where plasma etching resistance is required for selectivity (for example, gap filling material, buried insulating film use), it can be made to contain a metal alkoxide represented by General Formula (I).

[0150] R1 n M(OR2) m-n (I)

[0151] (In the formula, R1is a non-hydrolyzable group, R2is an alkyl group having a carbon number of 1 to 6, M represents at least one metal atom selected from the group consisting of Ti, Al, Zr, Sr, Ba, Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, Nd, and In, m is the valence number of the metal atom M, and is 3 or 4, n is an integer of 0 to 2 in the case where m is 4, and is 0 or 1 in the case where m is 3, in the case where a plurality of R1are present, each R1may be the same or different from each other, and in the case where a plurality of OR2are present, each OR2may be the same or different from each other.)

[0152] In the case where the film produced from the composition according to the present embodiment is required to have insulating properties (for example, insulating film for silicon through-hole, buried insulating film), in order to improve the insulating properties or mechanical strength, tetraethoxysilane, tetramethoxysilane, bis(triethoxysilyl)ethane, bis(triethoxysilyl)methane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxycyclosiloxane, 1,2-bis(dimethylethoxysilyl)ethane, 1,3,5-triethoxy-1,3,5-trimethyl-1,3,5-trisilacyclohexane can also be mixed. Further, in order to improve the hydrophobicity of the insulating film, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, or the like can also be mixed. These compounds can also be mixed in order to control the etching selectivity.

[0153] The composition according to the present embodiment can also contain a solvent other than the polar solvent (D), and for example, n-hexane or the like can be mentioned.

[0154] Further, the composition according to the present embodiment can also contain phthalic acid, benzoic acid, or the like, or a derivative thereof, for example, in order to improve the electrical properties.

[0155] Further, the composition according to the present embodiment can contain benzotriazole or a derivative thereof, for example, in order to suppress copper corrosion.

[0156] The pH of the composition according to the present embodiment is not particularly limited, and is preferably 2.0 or higher and 12.0 or lower.

[0157] [Method for producing the composition]

[0158] The following describes a method for producing the composition according to one embodiment of the present application. The method for producing the composition according to the present embodiment includes a mixing step of mixing the compound (A) and the crosslinking agent (B). Note that, as described above, the composition includes the polar solvent (D), and the polar solvent (D) can be added to the compound (A), the crosslinking agent (B), or a mixture of the compound (A) and the crosslinking agent (B) at any timing during the production of the composition. Further, the timing of adding other components is not particularly limited.

[0159] In the method for producing the composition according to the present embodiment, at least one additive (C) selected from the group consisting of an acid (C-1) having a carboxyl group and a weight average molecular weight of 46 or more and 195 or less and a base (C-2) having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less can be further added to the compound (A) or the crosslinking agent (B) in the mixing step. Note that the timing of adding the additive (C) is not particularly limited.

[0160] Further, in the case where the acid (C-1) is added as the additive (C), the mixing step is preferably a step of mixing a mixture of the acid (C-1) and the compound (A) and the crosslinking agent (B). That is, it is preferable to mix the compound (A) and the acid (C-1) in advance before mixing the compound (A) and the crosslinking agent (B). Thus, when the compound (A) and the crosslinking agent (B) are mixed, the haze and gelation of the composition can be suitably suppressed (if gelled, the time taken for the composition to become transparent is sometimes long, which is not preferable).

[0161] Further, in the case where the base (C-2) is added as the additive (C), the mixing step is preferably a step of mixing a mixture of the base (C-2) and the crosslinking agent (B) and the compound (A). That is, it is preferable to mix the crosslinking agent (B) and the base (C-2) in advance before mixing the compound (A) and the crosslinking agent (B). Thus, when the compound (A) and the crosslinking agent (B) are mixed, the haze and gelation of the composition can be suitably suppressed (if gelled, the time taken for the composition to become transparent is sometimes long, which is not preferable).

[0162] [Method for producing semiconductor member]

[0163] The following describes a method for producing a semiconductor member according to the present embodiment. The method for producing a semiconductor member according to the present embodiment includes a step of applying a composition to a substrate and a step of heating the substrate to which the composition is applied at a temperature of 250°C or higher and 425°C or lower.

[0164] <Step of applying>

[0165] The step of applying according to the present embodiment is a step of applying a composition to a substrate.

[0166] As the substrate, a semiconductor substrate such as a silicon substrate, a glass substrate, a quartz substrate, a stainless steel substrate, a plastic substrate, and the like can be given. The shape of the substrate is not particularly limited, and can be any shape such as a plate shape, a disc shape, and the like. For example, as the silicon substrate, a silicon substrate on which an interlayer insulating layer (Low-k film) is formed can be given, and in addition, a fine groove (recess), a fine through-hole, and the like can be formed in the silicon substrate.

[0167] In the imparting step in the present embodiment, the method of imparting the composition is not particularly limited, and a commonly used method can be employed.

[0168] As the commonly used method, for example, a dipping method, a spraying method, a spin coating method, a bar coating method, and the like can be given. For example, in the case of forming a film having a film thickness of micrometer size, a bar coating method is preferably employed, and in the case of forming a film having a film thickness of nanometer size (several nm to several hundred nm), a spin coating method is preferably employed.

[0169] For example, as the method of imparting the composition using the spin coating method, there is no particular limitation, and for example, a method in which the substrate is rotated with a spin coater while dropping the composition onto the surface of the substrate, and then the substrate is dried by increasing the rotation speed can be employed.

[0170] In the method of imparting the composition using the spin coating method, the rotation speed of the substrate, the dropping amount and dropping time of the composition, the rotation speed of the substrate at the time of drying, and the like are not particularly limited, and can be appropriately adjusted in consideration of the thickness of the film to be formed and the like.

[0171] < Drying Step >

[0172] The manufacturing method according to the present embodiment can have a drying step in which the substrate to which the composition has been imparted is dried at a temperature of 80°C or higher and 250°C or lower before the heating step described later. Note that the above temperature refers to the temperature of the surface of the substrate to which the composition has been imparted.

[0173] The above temperature is more preferably 90°C or higher and 200°C or lower, and more preferably 100°C or higher and 150°C or lower.

[0174] The drying in the present step can be performed by a common method, and for example, a hot plate can be used.

[0175] The atmosphere in which the drying is performed in the present step is not particularly limited, and for example, the drying can be performed in an atmospheric air atmosphere, or can be performed in a non-active gas (nitrogen, argon, helium, and the like) atmosphere.

[0176] The drying time is not particularly limited, and is preferably 300 seconds or less, more preferably 200 seconds or less, further preferably 120 seconds or less, and particularly preferably 80 seconds or less.

[0177] The lower limit of the drying time is not particularly limited, and can be set to, for example, 10 seconds (preferably 20 seconds, more preferably 30 seconds).

[0178] <cleaning step>

[0179] The production method according to the present embodiment can have a cleaning step before the heating step described later, in which the substrate to which the composition has been applied is cleaned with water or the like in order to remove the excess composition applied to the substrate. Further, in the case where the production method according to the present embodiment has the aforementioned drying step, it is preferable that the cleaning step be performed after the drying step.

[0180] <heating step>

[0181] The production method according to the present embodiment further has a heating step in which the substrate to which the composition has been applied is heated at a temperature of 200°C or higher and 425°C or lower.

[0182] Note that the above temperature refers to the temperature of the surface of the substrate to which the composition has been applied.

[0183] By having this heating step, the compound (A) and the crosslinking agent (B) react due to the heating, and a reaction product is obtained, and a film containing the reaction product is formed.

[0184] The above temperature is preferably 250°C or higher and 400°C or lower, and more preferably 300°C or higher and 400°C or lower.

[0185] Further, the pressure at which the heating is performed in the heating step is not particularly limited, and it is preferable that the absolute pressure be higher than 17 Pa and be lower than the atmospheric pressure.

[0186] The above absolute pressure is more preferably 1000 Pa or higher and lower than the atmospheric pressure, further preferably 5000 Pa or higher and lower than the atmospheric pressure, and particularly preferably 10000 Pa or higher and lower than the atmospheric pressure.

[0187] The heating in the heating step can be performed by a general method using a furnace or a hot plate. As the furnace, for example, SPX-1120 manufactured by APEX, VF-1000LP manufactured by Yamato Scientific Co., Ltd., or the like can be used.

[0188] Further, the heating in the present step can be performed in an atmosphere of air, or can be performed in an atmosphere of an inactive gas (nitrogen, argon, helium, or the like).

[0189] The heating time in the heating step is not particularly limited, and is, for example, 1 hour or less, preferably 30 minutes or less, more preferably 10 minutes or less, and particularly preferably 5 minutes or less. The lower limit of the heating time is not particularly limited, and can be, for example, 0.1 minute.

[0190] For the purpose of shortening the heating step time, the surface of the substrate to which the composition is applied can also be subjected to ultraviolet irradiation. As the ultraviolet, ultraviolet light having a wavelength of 170 nm to 230 nm, excimer light having a wavelength of 222 nm, excimer light having a wavelength of 172 nm, or the like is preferable. In addition, the ultraviolet irradiation is preferably performed in an inactive gas atmosphere.

[0191] <Examples of the semiconductor member>

[0192] As examples of the semiconductor member, there can be mentioned a semiconductor member in which a gap filling material (buried planarization film) is filled in a recess formed in a substrate; a semiconductor member in which an insulating material (buried insulating film) is filled in a recess formed in a substrate; a semiconductor member in which a barrier material (barrier film) having insulating properties, adhesion properties, pore sealing properties, or the like is provided between a substrate containing a low dielectric constant material such as a porous material and a metal; a semiconductor member provided with an insulating film (silicon through-hole insulating film) having adhesion properties and insulating properties, which is provided between a metal and a silicon substrate or between a metal and an insulating film at a through-hole side wall of a silicon through-hole substrate; a semiconductor member for resist inversion formation, and the like.

[0193] For the semiconductor member in which the buried planarization film is filled in the recess formed in the substrate, the thickness of the buried planarization film is, for example, 30 nm or more and 200 nm or less, and is preferably 50 nm or more and 150 nm or less.

[0194] Note that, in the case of the semiconductor member, when a copper multilayer wiring is formed by a dual damascene process, for example, a member in which a buried planarization film is provided at a through-hole can be used in a first via process.

[0195] In addition, in the case where the buried planarization film is formed in a groove having a narrow recess width and a large aspect ratio (depth / width), from the viewpoint of improving the filling properties to the groove, it is preferable to apply (preferably, by a spin coating method) the composition according to the present embodiment to the recess to form the buried planarization film.

[0196] For the semiconductor member in which the buried insulating film is filled in the recess formed in the substrate, the thickness of the buried insulating film is, for example, 30 nm or more and 200 nm or less, and is preferably 50 nm or more and 150 nm or less.

[0197] Note that as the semiconductor member, for example, a member obtained using a method (STI: Shallow Trench Isolation) in which an insulating buried insulating film is provided to a groove of a silicon substrate to form an element separation region; a member obtained in which an insulating buried insulating film is provided between switch elements such as MOSFETs (metal-oxide-semiconductor field-effect transistors) formed in advance; a member obtained in which an insulating buried insulating film is provided on a MOSFET as a pre-metal insulating film (PMD); a member obtained in which an insulating buried insulating film is provided between lowermost wiring lines (W, Ti / TiN / AlCu / TiN, etc.) formed in advance; a member obtained in which an insulating buried insulating film is provided on a lowermost wiring line as an intermetal insulating film (IMD); a member obtained in which an insulating buried insulating film is provided to a groove between copper wiring lines formed in advance as a wiring layer insulating film (ILD); and the like can be given.

[0198] Further, in a case where the buried insulating film is formed in a groove having a narrow recess width and a large aspect ratio (depth / width), from the viewpoint of improving the filling property to the groove, it is preferable to impart the composition according to the present embodiment to the recess (preferably by spin coating) to form the buried insulating film.

[0199] For a semiconductor member in which a barrier film having insulating properties, adhesion properties, pore sealing properties, and the like is provided between a substrate containing a low dielectric constant material such as a porous material and a metal, the thickness of the barrier film is, for example, 0.5 nm or more and 15 nm or less, and is preferably 1.5 nm or more and 12 nm or less. The semiconductor member can also be, for example, a member in which a barrier film as an adhesion layer is provided between a wall surface of a through-hole formed in a substrate and a metal arranged in the through-hole.

[0200] For a semiconductor member in which a silicon through-hole insulating film is provided between a metal and a silicon substrate at a through-hole side wall of a silicon through-hole substrate, the thickness of the silicon through-hole insulating film is, for example, 100 nm or more and 5 μm or less, and is preferably 500 nm or more and 2 μm or less.

[0201] For a semiconductor member in which a silicon through-hole insulating film is provided between a metal and an insulating film at a through-hole side wall of a silicon through-hole substrate, the thickness of the silicon through-hole insulating film is, for example, 0.5 nm to 100 nm, and is preferably 1 nm to 30 nm.

[0202] [Method for manufacturing semiconductor processing material]

[0203] Next, a manufacturing method of a semiconductor processing material according to the present embodiment will be described. The manufacturing method of the semiconductor processing material according to the present embodiment includes a step of applying a composition to a substrate, and a step of heating the substrate to which the composition is applied at a temperature of 250°C or higher and 425°C or lower.

[0204] Note that each step of the manufacturing method of the semiconductor processing material is the same as each step of the manufacturing method of the semiconductor member described above, and thus the description thereof will be omitted.

[0205] As the semiconductor processing material, a sacrificial film that is temporarily formed in a manufacturing process of a semiconductor device and is removed in a later process, or the like can be given.

[0206] [Semiconductor device]

[0207] Next, a semiconductor device according to the present embodiment will be described.

[0208] The semiconductor device according to the present embodiment includes a substrate, and a reaction product of a compound (A) and a crosslinking agent (B). The compound (A) includes a Si-O bond and a cationic functional group having at least one of a primary nitrogen atom and a secondary nitrogen atom, and has a weight average molecular weight of 130 or more and 10,000 or less. The crosslinking agent (B) has three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having a carbon number of 1 or more and 6 or less) in a molecule. Of the three or more -C(=O)OX groups, one or more and six or less are -C(=O)OH groups. The crosslinking agent (B) has a weight average molecular weight of 200 or more and 600 or less. The reaction product of the compound (A) and the crosslinking agent (B) has high smoothness and excellent uniformity of composition in a film thickness direction.

[0209] The reaction product of the compound (A) and the crosslinking agent (B) preferably has at least one of an amide bond and an imide bond.

[0210] Examples

[0211] The present application will be further specifically described below by way of examples, but the present application is not limited to these examples.

[0212] Hereinafter, water was used when a solvent was not shown.

[0213] Hereinafter, as "water", ultrapure water (Milli-Q water manufactured by Millipore Corporation, electric resistance of 18 MΩ·cm (25°C) or less) was used.

[0214] The compositions of Examples Al to Example Cl were prepared. Details are shown below.

[0215] Note that when the solution of the compound (A), the solution of the crosslinking agent (B), and the solution of the base (C-2) added to the crosslinking agent (B) are mixed, respectively, the solutions to be mixed are confirmed to have no precipitates before the mixing.

[0216] [Examples Al to A8]

[0217] As the 3-aminopropyltriethoxysilane (3APTES: (3-Aminopropyl)triethoxysilane) used in this example, 3-aminopropyltriethoxysilane 25 g was added dropwise to water 25 g, dissolved in a manner of 50 mass%, and left to stand at room temperature for one night, and then the alkoxysilane was confirmed to have been hydrolyzed by proton NMR spectroscopy. Next, the 3APTES aqueous solution was prepared in a concentration shown in Table 1.

[0218] Further, as the crosslinking agent (B), 1,3,5-benzene tricarboxylic acid (135BTC), 1,2,4-benzene tricarboxylic acid (124BTC: 1,2,4-Benzenetricarboxylic acid), pyromellitic acid (PMA: Pyromellitic acid), ethyl half ester pyromellitic acid (ehePMA: ethyl half ester PMA), 1-propyl half ester 1,2,4-benzene tricarboxylic acid (1Prhe124BTC: 1-propyl half ester 124BTC) were prepared.

[0219] As for ehePMA, by adding pyromellitic dianhydride to ethanol, heating for 3 hours and 30 minutes in a water bath heated to 50°C, the pyromellitic dianhydride powder was completely dissolved. It was confirmed by proton NMR that ester groups were formed in the manufactured ehePMA.

[0220] As for 1Prhe124BTC, by adding 124BTC anhydride to 1-propanol, stirring at room temperature, the 124BTC anhydride powder was completely dissolved. It was confirmed by proton NMR that ester groups were formed in the manufactured 1Prhe124BTC.

[0221] In Examples Al, A3, A5, A7, and A8, the ethanol (EtOH) solution, the aqueous solution, or the 1-propanol (1PrOH) solution of the crosslinking agent (B) shown in Table 1 was prepared without adding the base (C-2) to the crosslinking agent (B), and the solution of the crosslinking agent (B) was added dropwise to the 3APTES aqueous solution until the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) (COOH / N) became 1 to 2 (Table 1 "Range of COOH / N implemented").

[0222] In Examples A2, A4, and A6, ammonia was added as the base (C-2) to 135BTC, 124BTC, or PMA as the crosslinking agent (B) until the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5, and then an aqueous solution (9.5 mass%) of 135BTC, 124BTC, or PMA was prepared. Next, the aqueous solution of 135BTC, 124BTC, or PMA was added dropwise to the aqueous solution of 3APTES until the ratio (COOH / N) of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) became 1 to 2 ("Range of COOH / N at which the composition was transparent" in Table 1).

[0223] In Examples A1 to A8, when the solution of the crosslinking agent (B) was added dropwise to the aqueous solution of 3APTES, the amount of the crosslinking agent (B) at which the solution to which the crosslinking agent (B) solution was added became turbid (agglomerated) was evaluated by calculating the ratio (COOH / N) of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A). The results are shown in "Range of COOH / N at which the composition was transparent" in Table 1.

[0224] It is noted that whether the solution was turbid or not was confirmed by visual observation.

[0225] [Examples B1 to B5]

[0226] As the 3-aminopropyltrimethoxysilane (3APTS: (3-Aminopropyl)trimethoxysilane) used in the present examples, 3-aminopropyltrimethoxysilane 25 g was added to water 25 g and dissolved so as to be 50 mass%, and then left to stand at room temperature overnight, and then it was confirmed by proton NMR spectroscopy that the alkoxysilane had hydrolyzed. Next, an aqueous solution of 3APTS was prepared so as to have the concentrations shown in Table 1. It is noted that in the aqueous solution of 3APTS, there can be present hydrolyzates of 3-aminopropyltrimethoxysilane or siloxane polymers thereof.

[0227] Further, as the crosslinking agent (B), 135BTC, ehePMA, and ethyl half ester 1,2,4-benzene tricarboxylic acid (ehe124BTC) were prepared.

[0228] As for ehe124BTC, it was manufactured by adding 124BTC anhydride to ethanol, stirring at room temperature, and dissolving the 124BTC anhydride powder completely. It was confirmed by proton NMR that ester groups were formed in the manufactured ehe124BTC.

[0229] In Examples B1, B4, and B5, no base (C-2) was added to the crosslinking agent (B), an ethanol solution of the crosslinking agent (B) was prepared at the concentration shown in Table 1, and the ethanol solution of the crosslinking agent (B) was added dropwise to the 3APTS aqueous solution until the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) (COOH / N) became 1.

[0230] In Examples B2 and B3, ammonia was added as the base (C-2) to 135BTC as the crosslinking agent (B) until the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) became 2.0, and then an aqueous solution of 135BTC (10.1 mass%) was prepared. Next, the aqueous solution of 135BTC was added dropwise to the 3APTS aqueous solution until the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) (COOH / N) became 1.

[0231] In Examples B1 to B5, when the solution of the crosslinking agent (B) was added dropwise to the 3APTS aqueous solution, the amount of the crosslinking agent (B) at which the solution to which the solution of the crosslinking agent (B) was added became turbid (agglomerated) was evaluated by calculating the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) (COOH / N) described above. The results are shown in Table 1 under "Range of COOH / N in which the composition is transparent".

[0232] Note that whether the solution was turbid or not was confirmed by visual observation.

[0233] [Example C1]

[0234] An aqueous solution of 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (BATDS: corresponding to the compound (A)) was prepared by dissolving the BATDS in a mixed solvent (ethanol / water = 0.24, mass basis) to prepare a BATDS solution (2 mass%) and an ethanol solution of 135BTC (9.5 mass%) was prepared.

[0235] Next, the ethanol solution of 135BTC was added dropwise to the aqueous solution of BATDS (2 mass%) until the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) (COOH / N) became 1, and the composition was prepared.

[0236] When the 135BTC ethanol solution was added dropwise to the BATDS aqueous solution in Example C1, the 135BTC addition amount at which the solution to which the 135BTC ethanol solution was added became turbid (coagulated) was evaluated by calculating the ratio of the number of carboxyl groups in the crosslinking agent (B) described above to the total number of nitrogen atoms in the compound (A) (COOH / N). The results are shown in Table 1 under "Range of COOH / N in which the composition is transparent".

[0237] Note that whether the solution was turbid or not was confirmed by visual observation.

[0238] The composition, etc. of the composition obtained in each example is shown in Table 1 below.

[0239] Note that the bracketed notation in the item of "kind of compound (A)" indicates the concentration of the compound (A) in the compound (A) solution.

[0240] Further, the "concentration in the composition" of the compound (A) indicates the concentration of the compound (A) with respect to the entire composition when the crosslinking agent (B) is added in such a manner that the ratio of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) (COOH / N) becomes a maximum value.

[0241] Further, the bracketed notation in the item of "kind of crosslinking agent (B)" indicates the concentration of the crosslinking agent (B) in the crosslinking agent (B) solution, and indicates the concentration of the crosslinking agent (B) in the crosslinking agent (B) solution after the addition of the base (C-2) when the base (C-2) is added to the crosslinking agent (B).

[0242] Further, in Examples A1 to A8, 3-aminopropyltriethoxysilane (3APTES) used as the compound (A) contains one primary nitrogen atom in one molecule, and is therefore described as primary nitrogen atom / secondary nitrogen atom / tertiary nitrogen atom = 1 / 0 / 0. Note that in the solution, the 3APTES can be a hydrolyzate or a siloxane polymer.

[0243] Further, in Examples B1 to B5, 3-aminopropyltrimethoxysilane (3APTS) used as the compound (A) contains one primary nitrogen atom in one molecule, and is therefore described as primary nitrogen atom / secondary nitrogen atom / tertiary nitrogen atom = 1 / 0 / 0. Note that in the solution, the 3APTES can be a hydrolyzate or a siloxane polymer.

[0244] Further, in Example C1, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (BATDS) used as the compound (A) contains two primary nitrogen atoms in one molecule, and is therefore described as primary nitrogen atom / secondary nitrogen atom / tertiary nitrogen atom = 2 / 0 / 0.

[0245] [Table 1]

[0246]

[0247] In the case where the ratio (COOH / N) of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) is 0 to 1 in Example Al, the solution of 135BTC was added dropwise without causing turbidity and was transparent. In Examples A3 and A5, where the COOH / N was more than 0.7 and more than 0.79, respectively, the solution of 124BTC or PMA was added dropwise with turbidity. That is, under the condition where the COOH / N is 0.7 or less and 0.79 or less, respectively, a composition in which turbidity does not occur and aggregation is suppressed can be prepared. Furthermore, it is presumed that by using a composition in which turbidity does not occur and aggregation is suppressed to form a film, a smooth film with few irregularities can be formed.

[0248] Furthermore, in Examples A2 and A4 in which the base (C-2) was added to the crosslinking agent (B), and Examples A7 and A8 in which the crosslinking agent (B) had an ester bond, in all ranges of the ratio (COOH / N) of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) in the crosslinking agent (B) prepared, the solution of each crosslinking agent (B) was added dropwise without causing turbidity, and the transparency of the composition could be maintained.

[0249] It is presumed that by using a composition in which turbidity does not occur and aggregation is suppressed to form a film, a smooth film with few irregularities can be formed.

[0250] In Example Bl in which 3-aminopropyltrimethoxysilane (3APTS) was used as the compound (A), it was shown that even in the case where the base (C-2) was not added to the crosslinking agent (B) and the crosslinking agent (B) did not have an ester bond, a large amount of the crosslinking agent (B) could be added dropwise while maintaining the transparency of the composition.

[0251] Furthermore, in Examples B2 and B3 in which the base (C-2) was added to the crosslinking agent (B), and Examples B4 and B5 in which the crosslinking agent (B) had an ester bond, in all ranges of the ratio (COOH / N) of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in the compound (A) in the crosslinking agent (B) prepared, the solution of each crosslinking agent (B) was added dropwise without causing turbidity, and the transparency of the composition could be maintained.

[0252] <Preparation of composition>

[0253] [Examples 1 to 17, Comparative Examples 1 to 3]

[0254] The composition having the composition and pH shown in Table 2 below was prepared. Note that in the case of using acid (C-1) as additive (C), acid (C-1) was added to the compound (A) solution after mixing the crosslinking agent (B), and in the case of using base (C-2) as additive (C), base (C-2) was added to the crosslinking agent (B), and then the solution obtained by dissolving the crosslinking agent (B) in the solvent was mixed in the compound (A) solution.

[0255] Further, in Table 2, the concentration of compound (A) is the concentration of compound (A) in the composition, and the concentration in parentheses of the solvent other than water is the concentration of the solvent other than water in the composition.

[0256] Further, in Table 2, the concentration of the amine other than compound (A) is the concentration of the amine other than compound (A) in the composition.

[0257] Further, in Table 2, the value in parentheses of crosslinking agent (B) or the COOX-containing compound other than crosslinking agent (B) indicates the ratio of the number of carboxyl groups in crosslinking agent (B) to the total number of nitrogen atoms in compound (A) (COOH / N), or the ratio of the number of COOX groups in the COOX-containing compound other than crosslinking agent (B) to the total number of nitrogen atoms in compound (A) (COOX / N).

[0258] Further, in Table 2, the value in parentheses of acid (C-1) indicates the ratio of the number of carboxyl groups in acid (C-1) to the total number of nitrogen atoms in compound (A) (COOH / N), and the value in parentheses of base (C-2) indicates the ratio of the number of nitrogen atoms in base (C-2) to the number of carboxyl groups in crosslinking agent (B) (N / COOH).

[0259] [Example 1]

[0260] For 3-aminopropyltriethoxysilane (3APTES) of compound (A), after dissolving in water to prepare a 50 mass% aqueous solution, the solution was left to stand overnight, and then proton NMR spectroscopy was used to confirm that the alkoxysilane had hydrolyzed material was used for the preparation of the composition. The weight average molecular weight (Mw) after hydrolysis was 430.

[0261] 135BTC as crosslinking agent (B) was mixed with ammonia as base (C-2) and water to prepare a mixed solution of 135BTC (14 mass%) and ammonia. The ammonia was added so that the ratio of the number of nitrogen atoms in base (C-2) to the number of carboxyl groups in crosslinking agent (B) (N / COOH) became 1.5.

[0262] Next, the 3APTES aqueous solution, the mixed solution of 135BTC and ammonia, and water were mixed so as to have the concentrations shown in Table 2, and the composition was prepared.

[0263] (Examples 2 to 5, 7, 8, 14 to 16)

[0264] The composition was prepared in the same manner as in Example 1, so as to have the composition and concentration shown in Table 2.

[0265] Here, for 3-aminopropyl diethoxymethyl silane (3APDES) of Compound (A) in Examples 7 and 8, after being dissolved in water to prepare a 50 mass% aqueous solution and left standing overnight, a substance in which the alkoxysilane had been hydrolyzed was confirmed by proton NMR spectroscopy for use in the composition preparation. The weight average molecular weight (Mw) after the hydrolysis was 230.

[0266] Further, for 3-aminopropyl trimethoxysilane (3APTS) of Compound (A) in Examples 14 to 16, after being dissolved in water to prepare a 50 mass% aqueous solution and left standing overnight, a substance in which the alkoxysilane had been hydrolyzed was confirmed by proton NMR spectroscopy for use in the composition preparation.

[0267] (Example 6)

[0268] For 3-aminopropyl diethoxymethyl silane (3APDES) of Compound (A), after being dissolved in water to prepare a 50 mass% aqueous solution and left standing overnight, a substance in which the alkoxysilane had been hydrolyzed was confirmed by proton NMR spectroscopy for use in the composition preparation. The weight average molecular weight (Mw) after the hydrolysis was 230.

[0269] After mixing a formic acid (FA) aqueous solution (4.4 mass%) in the resulting 3APDES solution in such a manner that the ratio of the number of carboxyl groups in the acid (C-1) to the number of all nitrogen atoms in Compound (A) (COOH / N) becomes 0.92, an ethanol solution of PMA as the crosslinking agent (B), and water were mixed in the 3APDES solution in such a manner that the concentrations shown in Table 2, and the composition was prepared.

[0270] (Example 9)

[0271] 3-aminopropyl diethoxymethyl silane (3APDES) 4 g of Compound (A) was added to 1-propanol (1PrOH) 56 g, and a formic acid (FA) aqueous solution (8.8 mass%) 20 g was added dropwise. After stirring at room temperature for 1 hour, stirring was performed in a water bath at 60°C for 1 hour, and a 3APDES solution was obtained.

[0272] For 1-propanol half ester 1,2,4-benzene tricarboxylic acid (1Prhe124BTC) as the crosslinking agent (B), a substance in which an ester group was formed was confirmed by proton NMR using 1-propanol (1PrOH) in which trimellitic anhydride was dissolved.

[0273] The 1Prhe124BTC solution obtained was mixed in the 3APDES solution obtained, and water and 1-propanol were further mixed so as to have the concentrations shown in Table 2, and the composition was prepared.

[0274] [Example 10]

[0275] The composition was prepared so as to have the composition and concentrations shown in Table 2, in the same manner as in Example 9.

[0276] [Example 11]

[0277] For 3-aminopropyldiethoxymethylsilane (3APDES) of compound (A), the substance obtained by dissolving in water to prepare a 50 mass% aqueous solution and leaving it for one night was used for the composition preparation. The weight average molecular weight (Mw) after hydrolysis was 230.

[0278] For the ethyl half ester oxydiphthalic acid (eheOPDA) solution as the crosslinking agent (B), 4,4'-oxydiphthalic anhydride was dissolved in ethanol to obtain.

[0279] The 3APDES aqueous solution obtained, the eheOPDA solution, water, ethanol (EtOH), and 1-propanol were mixed so as to have the concentrations shown in Table 2, and the composition was prepared.

[0280] [Example 12]

[0281] For 3-aminopropyldiethoxymethylsilane (3APDES) of compound (A), the substance obtained by dissolving in water to prepare a 50 mass% aqueous solution and leaving it for one night was used for the composition preparation. The weight average molecular weight (Mw) after hydrolysis was 230.

[0282] An ethanol solution of ethyl half ester PMA (ehePMA) as the crosslinking agent (B) was prepared.

[0283] An ethanol solution of 1,2,4,5-cyclohexanetetracarboxylic ethyl half ester (eheHPMA 1,2,4,5-Cyclohexanetetracarboxylic ethyl half ester) as the crosslinking agent (B) was prepared.

[0284] The 3APDES aqueous solution obtained, the ehePMA solution, the eheHPHA solution, water, ethanol (EtOH), and 1-propanol were mixed so as to have the concentrations shown in Table 2, and the composition was prepared.

[0285] [Example 13]

[0286] For N-methylaminopropylmethyldimethoxysilane (N-MAPDS) of Compound (A), a substance obtained by dissolving in water to make a 50 mass% aqueous solution and then standing overnight was used for the composition preparation.

[0287] For the eheOPDA solution as the crosslinking agent (B), eheOPDA was dissolved in ethanol to obtain.

[0288] The obtained N-MAPDS aqueous solution, eheOPDA solution, water, ethanol (EtOH), and 1-propanol were mixed so as to have the concentrations shown in Table 2, and the composition was prepared.

[0289] [Example 17]

[0290] <Branching polyethyleneimine 2>

[0291] As the branching polyethyleneimine 2 (BPEI_2), polyethyleneimine (Mw = 70,000, primary / secondary / tertiary nitrogen atoms = 31 / 40 / 29) manufactured by BASF was used.

[0292] The amount of primary nitrogen atoms (mol%), the amount of secondary nitrogen atoms (mol%), and the amount of tertiary nitrogen atoms (mol%) were calculated by dissolving the polymer sample in heavy water, and for the obtained solution, the amount of primary nitrogen atoms, the amount of secondary nitrogen atoms, and the amount of tertiary nitrogen atoms were determined by single pulse inversion gated decoupling at 80°C using an AVANCE 500 type nuclear magnetic resonance device manufactured by Bruker. 13 C-NMR, based on the integral values calculated from the obtained results. For the assignment, it is described in European Polymer Journal, 1973, Vol. 9, pp. 559, etc.

[0293] The weight average molecular weight was calculated by using an analysis device Shodex GPC-101, using a column Asahipak GF-7MHQ, and using polyethylene glycol as a standard. In addition, an elution solvent was an aqueous solution of 0.5 mol / L acetic acid and 0.1 mol / L sodium nitrate.

[0294] Here, the amount of primary nitrogen atoms (mol%), the amount of secondary nitrogen atoms (mol%), and the amount of tertiary nitrogen atoms (mol%) were the amounts represented by the following formulas A to C, respectively.

[0295] Amount of primary nitrogen atom (mol%) = (number of mol of primary nitrogen atom / (number of mol of primary nitrogen atom + number of mol of secondary nitrogen atom + number of mol of tertiary nitrogen atom)) x 100... Equation A

[0296] Amount of secondary nitrogen atom (mol%) = (number of mol of secondary nitrogen atom / (number of mol of primary nitrogen atom + number of mol of secondary nitrogen atom + number of mol of tertiary nitrogen atom)) x 100... Equation B

[0297] Amount of tertiary nitrogen atom (mol%) = (number of mol of tertiary nitrogen atom / (number of mol of primary nitrogen atom + number of mol of secondary nitrogen atom + number of mol of tertiary nitrogen atom)) x 100... Equation C

[0298] For 3-aminopropyltrimethoxysilane (3APTS: (3-Aminopropyl)trimethoxysilane) of compound (A), a substance obtained by dissolving in water to make a 50 mass% aqueous solution and then standing overnight was used for composition preparation after confirming that the alkoxysilane had been hydrolyzed by proton NMR spectroscopy.

[0299] 135BTC as crosslinking agent (B) was mixed with ammonia as base (C-2) and water to make a mixed solution of 135BTC (14 mass%) and ammonia. Ammonia was added in such a way that the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5.

[0300] An aqueous solution of branched polyethyleneimine 2 (BPEI_2) was prepared.

[0301] The 3APTS aqueous solution, the mixed solution of 135BTC and ammonia, the BPEI_2 aqueous solution, and water were mixed in such a way that the concentrations shown in Table 2 were obtained to prepare the composition.

[0302] [Comparative Example 1]

[0303] For 3-aminopropyltriethoxysilane (3APTES) of compound (A), a substance obtained by dissolving in water to make a 50 mass% aqueous solution and then standing overnight was used for composition preparation.

[0304] [Comparative Example 2]

[0305] For 3-aminopropyltriethoxysilane (3APTES) of compound (A), a substance obtained by dissolving in water to make a 50 mass% aqueous solution and then standing overnight was used for composition preparation.

[0306] A 3APTES (50 mass%) aqueous solution, a tripropyl-1,2,4-benzene tricarboxylic acid (TrPr124BTC) 1-propanol solution having no carboxyl group and having three ester bonds, and 1-propanol were mixed so as to have concentrations shown in Table 2, and a composition was prepared.

[0307] [Comparative Example 3]

[0308] A 3APDES aqueous solution was prepared in the same manner as in Comparative Example 1 so as to have a composition and a concentration shown in Table 2.

[0309] [Table 2]

[0310]

[0311] <Formation of Film>

[0312] As a substrate of a coating composition (hereinafter, also referred to as "composition"), a silicon substrate was prepared. The silicon substrate was placed on a spin coater, 1.0 mL of the composition prepared in each of the examples and the comparative examples was dropped at a constant speed for 10 seconds, and after being left for 13 seconds, dried by being rotated at 2000 rpm (rpm is a rotational speed) for 1 second, at 600 rpm for 30 seconds, and at 2000 rpm for 10 seconds. Thus, a film was formed on the silicon substrate.

[0313] Next, after being dried at 125°C for 1 minute, the film was heated at 300°C for 10 minutes under a nitrogen atmosphere (30 kPa). In order to evaluate heat resistance, further, the film was heated at 350°C, 380°C, and 400°C for 10 minutes, respectively (the same sample was continuously treated).

[0314] <Measurement of Refractive Index>

[0315] After heating at 400°C, the refractive index of the film formed on the silicon substrate was measured. The refractive index was measured using a polarizing ellipsometer. The film thickness was calculated from the measured optical data. When the film thickness was 10 nm or more, an optical model of air / (Cassie + Lorentz oscillator model) / native oxide film / silicon substrate was used for fitting. When the film thickness was less than 10 nm, an optical model of air / (Cassie + Lorentz oscillator model) / native oxide film / silicon substrate was used for fitting, the Cassie + Lorentz oscillator model used in the optical model used a complex refractive index of a material having the same composition as that of a thick film of 10 nm or more. Since the film thickness was calculated, the result can also be a negative value.

[0316] In Table 3, N633 represents the refractive index at a wavelength of 633 nm.

[0317] The results are shown in Table 3.

[0318] <Heat resistance evaluation>

[0319] The film thickness residual ratio was calculated from the film thickness after heating at 300°C for 10 minutes and the film thickness after heating at 380°C for 10 minutes, and the heat resistance of the film was evaluated based on the film thickness residual ratio. The formula of the film thickness residual ratio is shown below, and the case where the film thickness residual ratio was 70% or more was judged to be "having heat resistance".

[0320] Film thickness residual ratio (%) = (film thickness after heating at 380°C / film thickness after heating at 300°C) x 100

[0321] The results are shown in Table 3.

[0322] <Crosslinking structure>

[0323] The crosslinking structure of the film was measured by FT-IR (Fourier Transform Infrared Spectroscopy). The analysis device used is shown below.

[0324] ~ FT-IR analysis device ~

[0325] Infrared absorption analysis device (DIGILAB Excalibur (manufactured by DIGILAB))

[0326] ~ Measurement conditions ~

[0327] IR light source: air-cooled ceramic, beam splitter: wide-range KBr, detector: Peltier-cooled DTGS, measurement wave number range: 7500 cm -1 400 cm -1 , resolution: 4 cm -1 , number of accumulations: 256, back plate: Si wafer was used, measurement atmosphere: N2(10 L / min), incident angle of IR (infrared): 72° (= Brewster's angle of Si)

[0328] ~ Judgment conditions ~

[0329] The imide bond was judged by the presence of the vibration peak at 1770 cm -1 , 1720 cm -1 . The amide bond was judged by the presence of the vibration peak at 1650 cm -1 , 1520 cm -1 .

[0330] The results are shown in Table 3.

[0331] <SEM morphology observation>

[0332] For films having a film thickness of 20 nm or more and 150 nm or less, the smoothness of the film was evaluated by observing the morphology using SEM. The measurement was performed using S-5000 (manufactured by Hitachi, Ltd.) as a scanning electron microscope (SEM) at an acceleration voltage of 3 kV, 200,000 times, and a field of view of 500 nm wide. In the case where the difference between the maximum film thickness and the minimum film thickness was 25% or less with respect to the average film thickness, it was judged as "having smoothness".

[0333] The results are shown in Table 3. Note that the film after heating at 400°C for 10 minutes was used as the object of SEM morphology observation.

[0334] <SPM Morphology Observation>

[0335] For films having a film thickness of less than 20 nm, the unevenness of the film was evaluated by observing the morphology using SPM. The measurement was performed using SPA400 (manufactured by Hitachi High-Technologies Corporation) as a scanning probe microscope (SPM) using a dynamic force microscope mode in a 3 micrometer x 3 micrometer square region. In the case where the root mean square surface roughness measured by SPM was 25% or less with respect to the film thickness measured by a polarizing light ellipsometer, it was judged as "having smoothness".

[0336] The results are shown in Table 3. Note that the film after heating at 400°C for 10 minutes was used as the object of SPM morphology observation.

[0337] The measurement results and evaluation results of each property of the film formed using the composition related to each of the examples and comparative examples are shown in Table 3. Note that the blank in Table 3 indicates that it was not confirmed (crosslinking structure) or not performed (SEM morphology observation and SPM morphology observation).

[0338] [Table 3]

[0339]

[0340] As shown in Table 3, the film thickness residual rate in each of Examples 1 to 8 and 12 to 17 was 70% or more, but the film thickness residual rate in Comparative Example 1 was less than 66%. It is thus presumed that the heat resistance of the film formed from the composition in each of the examples is excellent.

[0341] Example 12 used 3APDES, which is a compound having a primary amino group, as the crosslinking agent (B), and thus the film thickness residual rate was higher than that of Example 13 which used N-MAPDS, which is a compound having a secondary amine. It is thus presumed that the heat resistance of the film formed from the composition using a compound having a primary amino group as the crosslinking agent (B) is more excellent.

[0342] In addition, in each of Examples 1 to 3, 7, 9 to 11, 13, and 14, the result of SEM morphology observation was that the film was smooth.

[0343] On the other hand, in Comparative Examples 2 and 3, the film surface did not become a mirror surface or a large number of minute pinholes were present, and was not smooth.

[0344] Further, in Example 4, the result of SPM topography observation was that the film was smooth.

[0345] Film thickness distribution in the plane of the silicon substrate

[0346] [Example 18]

[0347] In the same manner as in Example 9, the 3APDES solution, the 1Prhe124BTC solution, water, and 1-propanol were mixed to prepare a composition (Solution 1).

[0348] In Solution 1, the concentration of Compound (A) in the composition was 2 mass%, the ratio (COOH / N) of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in Compound (A) was 1.0, the ratio (COOH / N) of the number of carboxyl groups in the acid (C-1) to the total number of nitrogen atoms in Compound (A) was 1.83, and the concentration of 1-propanol in the composition was 91 mass%.

[0349] Next, in the same manner as in Example 18, a film was formed on a silicon substrate. After 6 mL of the coating solution was dropped onto the silicon substrate, the silicon substrate was rotated at 1000 rpm for 1 second, at 600 rpm for 60 seconds, at 1000 rpm for 5 seconds, and then dried at 100°C for 2 minutes, heated at 250°C for 1 minute, and further subjected to heat treatment at 400°C for 10 minutes in nitrogen at atmospheric pressure. Thus, a film was formed on the silicon substrate.

[0350] [Example 19]

[0351] In the same manner as in Example 9, the 3APDES solution, the 1Prhe124BTC solution, water, and 1-propanol were mixed to prepare a composition (Solution 2).

[0352] In Solution 2, the concentration of Compound (A) in the composition was 0.2 mass%, the ratio (COOH / N) of the number of carboxyl groups in the crosslinking agent (B) to the total number of nitrogen atoms in Compound (A) was 1.0, the ratio (COOH / N) of the number of carboxyl groups in the acid (C-1) to the total number of nitrogen atoms in Compound (A) was 1.83, and the concentration of 1-propanol in the composition was 99.1 mass%.

[0353] Next, in the same manner as in Example 18, a film was formed on a silicon substrate.

[0354] [Example 20]

[0355] For 3-aminopropyldiethoxymethylsilane (3APDES) of Compound (A), the substance obtained by dissolving in water to make a 50 mass% aqueous solution and standing overnight was used for composition preparation. The weight average molecular weight (Mw) after hydrolysis was 230.

[0356] For a solution of ethyl half ester oxydiphthalic acid (eheOPDA) as Crosslinking Agent (B), 4,4'-oxydiphthalic anhydride was dissolved in ethanol to obtain.

[0357] The obtained 3APDES aqueous solution, eheOPDA solution, water, ethanol (EtOH), and 1-propanol were mixed so as to have concentrations shown in Table 4, and a composition (Solution 3) was prepared.

[0358] Using the obtained composition (Solution 3), a film was formed on a silicon substrate in the same manner as in Example 18.

[0359] The distance The film thickness at 1 cm from the center of the silicon substrate, the film thickness at 5 cm, the film thickness at 9 cm, the film thickness at 13 cm, and the difference in film thickness (%) between 1 cm and 13 cm from the center were evaluated for the in-plane film thickness distribution of the silicon substrate.

[0360] The results are shown in Table 4.

[0361] Note that in Table 4, the concentrations in parentheses in 3APDES (2 mass%), 3APDES (0.2 mass%), and 3APDES (1.8 mass%) indicate the concentrations of 3APDES in the compositions.

[0362] The values in parentheses in 1Prhe124BTC [1.0], eheOPDA [1.0] indicate the ratio of the number of carboxyl groups in 1Prhe124BTC or eheOPDA as Crosslinking Agent (B) to the total number of nitrogen atoms in 3APDES as Compound (A) (COOH / N).

[0363] The value in parentheses in FA, 1.83, indicates the ratio of the number of carboxyl groups in FA as Acid (C-1) to the total number of nitrogen atoms in 3APDES as Compound (A) (COOH / N).

[0364] The concentrations in parentheses in 1PrOH (91 mass%), 1PrOH (99.1 mass%), 1PrOH (33 mass%), and EtOH (29 mass%) indicate the concentrations of 1PrOH and EtOH in the compositions.

[0365] Further, the film thickness difference (%) at 1 cm from the center and at 13 cm from the center was calculated as follows, that is, "((film thickness at 1 cm from the center) - (film thickness at 13 cm from the center)) / ((film thickness at 1 cm from the center) + (film thickness at 5 cm from the center) + (film thickness at 9 cm from the center) + (film thickness at 13 cm from the center)) / 4)" multiplied by 100.

[0366] [Table 4]

[0367]

[0368] As shown in Table 4, the film thickness difference (%) at 1 cm from the center and at 13 cm from the center was 15% or less in the examples, showing a small value. Thus, it was shown that by using the composition relating to Examples 18 to 20, a smooth film excellent in in-plane uniformity on a 300 mmφ silicon wafer can be obtained with a more simple process.

[0369] <Fillability in Trench>

[0370] [Example 21]

[0371] A BPEI_2 aqueous solution and a 3-aminopropyltriethoxysilane (3APTES; (3-Aminopropyl)triethoxysilane) aqueous solution were mixed, and ammonia (NH3) was mixed as a base (C-2) in 135 BTC in such a manner that the N / COOH (ratio of the number of nitrogen atoms in ammonia to the number of carboxyl groups in 135 BTC) became 1.5. Here, 3APTES was used as a material obtained by standing as a 50% aqueous solution for one night.

[0372] Next, 135 BTC was mixed to the mixed solution of BPEI_2 and 3APTES in such a manner that the COOH / N (ratio of the number of carboxyl groups in 135 BTC to the number of nitrogen atoms in BPEI_2 and 3APTES) became 0.9, and a composition (solution 4) was prepared.

[0373] [Example 22]

[0374] A composition (solution 5) prepared in Example 2 was prepared.

[0375] [Example 23]

[0376] A composition (solution 1) prepared in Example 18 was prepared.

[0377] [Example 24]

[0378] A composition (solution 3) prepared in Example 20 was prepared.

[0379] [Example 25]

[0380] A mixed solution of 3-aminopropyldiethoxymethylsilane (3APDES) of compound (A) and p-xylenediamine (pXDA) was prepared by adding 3APDES to water to make a 50% aqueous solution and leaving it overnight, and mixing a 1-propanol solution of pXDA in the resulting material.

[0381] To the mixed solution, an ethanol solution of eheOPDA as crosslinking agent (B), 1-propanol, ethanol, and water were mixed so as to have the concentrations shown in Table 5, and a composition (solution 7) was prepared.

[0382] [Example 26]

[0383] A mixed solution of 3-aminopropyldiethoxymethylsilane (3APDES) of compound (A) and p-xylenediamine (pXDA) was prepared by adding 3APDES to water to make a 50% aqueous solution and leaving it overnight, and mixing a 1-propanol solution of pXDA in the resulting material.

[0384] To the mixed solution, an ethanol solution of eheOPDA as crosslinking agent (B), 1-propanol, ethanol, and water were mixed so as to have the concentrations shown in Table 5, and a composition (solution 7) was prepared.

[0385] [Example 27]

[0386] A mixed solution of 3-aminopropyldiethoxymethylsilane (3APDES) of compound (A) and bis(triethoxysilyl)ethane (BTESE) (a solution presumed to contain a siloxane polymer of 3APDES and BTESE) was prepared by adding 3APDES 2.0 g to 1-propanol 26.15 g, adding dropwise a water solution of formic acid (FA) (8.8 mass%) 10 g, adding BTESE 1.85 g, stirring at room temperature for one hour, and heating in a water bath at 60°C for one hour.

[0387] To the mixed solution, a 1-propanol solution of 1Prhe124BTC as crosslinking agent (B), and water were mixed so as to have the compositions shown in Table 5, and a composition (solution 8) was prepared.

[0388] [Example 28]

[0389] A mixed solution (a presumed solution containing a siloxane polymer of 3APDES and HETSC in the solution) of 3-aminopropyldiethoxymethylsilane (3APDES) of compound (A) and 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane (HETSC) was prepared by adding 3APDES 2.0 g to 1-propanol 28.6 g, adding an aqueous formic acid (FA) solution (8.8 mass%) 10 g dropwise, adding HETSC 1.4 g, and stirring at room temperature for one hour and then heating in a water bath at 60°C for one hour.

[0390] To the mixed solution, a 1-propanol solution of 1Prhe124BTC as the crosslinking agent (B) and water were mixed in a manner to become the composition shown in Table 5, and a composition (solution 9) was prepared.

[0391] [Example 29]

[0392] A 1-propanol solution of 1,3-bis(3-aminopropyl)-tetramethyldisiloxane (BATDS) as compound (A), an ethanol solution of eheOPDA as the crosslinking agent (B), 1-propanol, and ethanol were mixed in a manner to become the composition shown in Table 5, and a composition (solution 10) was prepared.

[0393] Note that in Table 5, the concentration in parentheses in BPEI_2 (1.7 mass%), 3APTES (3.3 mass%), 3APTES (3 mass%), 3APDES (2 mass%), 3APDES (1.8 mass%), 3APDES (4 mass%), 3APDMS (0.6 mass%), pXDA (5 mass%), BTESE (3.7 mass%), HETSC (2.8 mass%), and BATDS (2 mass%) indicates the respective concentrations of BPEI_2, 3APTES, 3APDES, 3APDMS, pXDA, BTESE, HETSC, and BATDS in each composition.

[0394] The value in parentheses in 135BTC [0.9], 124BTC [1.5], 1Prhe124BTC [1.0], 1Prhe124BTC [1.15], and eheOPDA [1.0] indicates the ratio of the number of carboxyl groups in 135BTC, 124BTC, 1Prhe124BTC, and eheOPDA to the total number of nitrogen atoms in compound (A) (COOH / N).

[0395] The value 1.83 in parentheses for FA indicates the ratio of the number of carboxyl groups in FA to the total number of nitrogen atoms in compound (A) (COOH / N).

[0396] The value in parentheses of NH3 <1.5> indicates the ratio of the number of nitrogen atoms in NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH).

[0397] 1PrOH (91 mass%), 1PrOH (33 mass%), 1PrOH (28 mass%), 1PrOH (2 mass%), 1PrOH (69 mass%), 1PrOH (37 mass%), EtOH (29 mass%), EtOH (43 mass%), EtOH (36 mass%), and EtOH (59 mass%) indicate the concentrations of 1PrOH and EtOH in the composition.

[0398] Next, the composition 0.5 mL was dropped onto a silicon oxide substrate provided with a trench pattern of 100 nm wide and 200 nm deep at a constant speed for 10 seconds, left for 13 seconds, and then dried by rotating at 2000 rpm for 1 second, at 600 rpm for 30 seconds, and at 2000 rpm for 10 seconds. Next, the dropped composition was dried at 100°C for 1 minute, heated at 300°C for 1 minute, and further subjected to a heating treatment at 400°C for 10 minutes.

[0399] Then, whether the composition was filled in the trench was observed with cross-sectional SEM. The case where the area filled was 90% or more of the area inside the trench was set as A (good filling property).

[0400] The results are shown in Table 5.

[0401] Likewise, the composition 0.5 mL was dropped onto a silicon oxide substrate provided with a trench pattern of 50 nm wide and 200 nm deep at a constant speed for 10 seconds, left for 13 seconds, and then dried by rotating at 2000 rpm for 1 second, at 600 rpm for 30 seconds, and at 2000 rpm for 10 seconds. Next, the dropped composition was dried at 100°C for 1 minute, heated at 300°C for 1 minute, and further subjected to a heating treatment at 400°C for 10 minutes.

[0402] Then, whether the composition was filled in the trench was observed with cross-sectional SEM. The case where the area filled was 90% or more of the area inside the trench was set as A (good filling property), and the case where the area filled was less than 90% of the area inside the trench was set as B.

[0403] The results are shown in Table 5.

[0404] [Table 5]

[0405]

[0406] As shown in Table 5, for 100 nm wide trenches, the filling was good. Thus, it was shown that by using the compositions relating to Examples 21 to 29, a film with excellent embeddability for 100 nm wide trenches could be obtained.

[0407] For 50 nm wide trenches, according to the results of Examples 23, 25, 26, the embeddability of the composition containing 3APDES and 1Prhe124BTC, the composition containing 3APDES, 3APDMS, and eheOPDA, and the composition containing 3APDES, pXDA, and eheOPDA was good. On the other hand, in Example 24, voids exceeding 10% were generated in the case of the composition containing 3APDES and eheOPDA.

[0408] From this, it can be inferred that the filling of the film having an amide-imide bond (Example 23) is more excellent than that of the film having an imide bond (Example 24). Furthermore, from Example 24 and Example 26, it can be inferred that the filling of the film formed from a solution containing pXDA, an amine having a ring structure (Example 26), is more excellent.

[0409] <Relative dielectric constant and leakage current density>

[0410] [Comparative Example 4]

[0411] To the aqueous solution of BPEI_2, acetic acid (AA) was added as an acid (C-1) so that the ratio of COOH / N (the number of carboxyl groups in acetic acid relative to the number of nitrogen atoms in BPEI_2) would be 0.14. Next, 135BTC was mixed in the aqueous solution of BPEI_2 so that the ratio of COOH / N (the number of carboxyl groups in 135BTC relative to the number of nitrogen atoms in BPEI_2) would be 0.67, and ethanol was mixed so that the concentration of ethanol relative to the entire composition would be 33 mass%, and the composition (solution 11) was prepared.

[0412] [Example 30]

[0413] For 3-aminopropylmethyldiethoxysilane (3APDES) of the compound (A), the material obtained by dissolving in water to prepare a 50 mass% aqueous solution and leaving it at rest overnight was used for the composition preparation. The weight average molecular weight (Mw) after hydrolysis was 230.

[0414] To 135BTC as the crosslinking agent (B), ammonia as a base (C-2) and water were mixed to prepare a mixed solution of 135BTC (14 mass%) and ammonia. The ammonia was added so that the ratio of the number of nitrogen atoms in the base (C-2) relative to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) would be 1.5.

[0415] To the 3APDES aqueous solution, a mixed solution of 135BTC and ammonia, water, and ethanol were mixed so as to have concentrations shown in Table 6, and a composition (solution 12) was prepared.

[0416] [Example 31]

[0417] A composition (solution 1) prepared in Example 18 was prepared.

[0418] [Example 32]

[0419] A composition (solution 2) prepared in Example 19 was prepared.

[0420] [Example 33]

[0421] A composition (solution 3) prepared in Example 20 was prepared.

[0422] After 5 mL of each of solutions 1 to 3, 11, and 12 was dropped to a low-resistance silicon substrate, the low-resistance silicon substrate was rotated at 1000 rpm for 5 seconds and at 500 rpm for 30 seconds. Subsequently, the dropped composition was dried at 1000C for 1 minute, heated at 2500C for 1 minute, and further subjected to heat treatment at 4000C for 10 minutes. Thus, a laminate including a low-resistance silicon substrate / film was obtained.

[0423] (Measurement of Relative Dielectric Constant)

[0424] The relative dielectric constant of the film in the obtained laminate was measured.

[0425] The relative dielectric constant was measured by a conventional method using a mercury probe device (SSM5130) at 25°C in an atmosphere having a relative humidity of 30% at a frequency of 100 kHz.

[0426] The results are shown in Table 6.

[0427] (Measurement of Leakage Current Density)

[0428] Subsequently, in order to evaluate the electrical properties, the leakage current density was measured as follows. Specifically, a mercury probe was brought into contact with the film surface of the obtained laminate, and the measured values of electric field intensity of 1 MV / cm and 2 MV / cm were set as the leakage current density.

[0429] The results are shown in Table 6.

[0430] The composition, relative dielectric constant, and leakage current density of the samples in Comparative Example 4 and Examples 30 to 33 are shown in Table 6.

[0431] Note that in Table 6, the concentrations in parentheses in the BPEI_2 aqueous solution (1.8 mass%), 3APDES (3 mass%), 3APDES (2 mass%), 3APDES (0.2 mass%), and 3APDES (1.8 mass%) represent the concentrations of BPEI_2 and 3APDES in the compositions.

[0432] 135BTC[0.67], 135BTC[1.0], 1Prhe124BTC[1.0], and eheOPDA[1.0] indicate the ratio of the number of carboxyl groups in 135BTC, 1Prhe124BTC, and eheOPDA to the total number of nitrogen atoms in Compound (A) (COOH / N).

[0433] The values in parentheses of AA and FA, 0.14 and 1.83, indicate the ratio of the number of carboxyl groups in AA or FA to the total number of nitrogen atoms in Compound (A) (COOH / N).

[0434] The value in parentheses of NH3<1.5> indicates the ratio of the number of nitrogen atoms in NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH).

[0435] The concentrations in parentheses in 1PrOH (91 mass%), 1PrOH (99.1 mass%), 1PrOH (33 mass%), EtOH (33 mass%), EtOH (30 mass%), and EtOH (29 mass%) represent the concentrations of 1PrOH and EtOH in the compositions.

[0436] [Table 6]

[0437]

[0438] As shown in Table 6, Examples 30 to 33 have a smaller relative dielectric constant than Comparative Example 4.

[0439] The leakage current density at an electric field strength of 1 MV / cm of Example 30 is equivalent to that of Comparative Example 4, but in the case of Examples 31 to 33, the leakage current density at an electric field strength of 1 MV / cm is smaller than that of Comparative Example 4. As for the leakage current density at an electric field strength of 2 MV / cm, which is an increased electric field strength, Examples 30 to 33 have a smaller leakage current density than Comparative Example 4. Thus, it is shown that by using the compositions involved in Examples 30 to 33, particularly Examples 31 to 33, a film having excellent electrical properties can be obtained.

[0440] <Adhesion to a silicon (Si) substrate>

[0441] [Example 34]

[0442] For 3-aminopropyltriethoxysilane (3APTES) of Compound (A), the substance obtained by dissolving in water to make a 50 mass% aqueous solution and standing overnight was used for the composition preparation. The weight average molecular weight (Mw) after hydrolysis was 430.

[0443] In PMA as the crosslinking agent (B), ammonia as the base (C-2) and water were mixed to make a mixed solution of PMA (14 mass%) and ammonia. The ammonia was added so that the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5.

[0444] In the 3APTES aqueous solution, the mixed solution of PMA and ammonia and water were mixed so as to have the concentrations shown in Table 7 to prepare the composition (solution 13).

[0445] [Example 35]

[0446] For 3-aminopropyltriethoxysilane (3APTES) of Compound (A), the substance obtained by dissolving in water to make a 50 mass% aqueous solution and standing overnight was used for the composition preparation. The weight average molecular weight (Mw) after hydrolysis was 430.

[0447] In 124BTC as the crosslinking agent (B), ammonia as the base (C-2) and water were mixed to make a mixed solution of 124BTC (14 mass%) and ammonia. The ammonia was added so that the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5.

[0448] In the 3APTES aqueous solution, 124BTC and ammonia were mixed so as to have the concentrations shown in Table 7 to prepare the composition (solution 14).

[0449] [Example 36]

[0450] For 3-aminopropyltriethoxysilane (3APTES) of Compound (A), the substance obtained by dissolving in water to make a 50 mass% aqueous solution and standing overnight was used for the composition preparation. The weight average molecular weight (Mw) after hydrolysis was 430.

[0451] In 135BTC as the crosslinking agent (B), ammonia as the base (C-2) and water were mixed to make a mixed solution of 135BTC (14 mass%) and ammonia. The ammonia was added so that the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5.

[0452] In the 3APTES aqueous solution, 135BTC and ammonia were mixed so as to have the concentrations shown in Table 7 to prepare the composition (solution 15).

[0453] Example 37

[0454] A solution of 3-aminopropyldiethoxymethylsilane (3APDES) as Compound (A) was prepared by adding 3APDES 2.0 g to 1-propanol 28 g, adding dropwise formic acid (FA) aqueous solution (8.8 mass%) 10 g, and stirring at room temperature for one hour, and then heating in a water bath at 60°C for one hour.

[0455] A composition (solution 16) was prepared by mixing a 1-propanol solution of 1-propanol half ester pyromellitic acid (1PrhePMA; 1-propanol half ester PMA) as Crosslinking Agent (B), 1-propanol, and water in a composition shown in Table 7 in the 3APDES solution.

[0456] (Preparation of Samples)

[0457] A silicon wafer on which silicon dioxide was present on the surface was placed on a spin coater, and 1.0 mL of the composition (solution 13 to 16) was added dropwise for 10 seconds at a constant speed, and after being held for 13 seconds, the silicon wafer was spun at 2000 rpm for one second, and then spun at 600 rpm for 30 seconds, and then spun at 2000 rpm for 10 seconds to dry.

[0458] A polymer layer was formed on the silicon wafer in the above manner to obtain a laminate (hereinafter, also referred to as "sample (polymer / Si)") in which the silicon wafer and the polymer layer were stacked.

[0459] The above sample (polymer / Si) was placed on a hot plate with the silicon wafer surface in contact with the hot plate, and soft baking (heat treatment) was performed at a soft baking temperature of 100°C for 60 seconds in an air atmosphere. Further, heating at 300°C for 10 minutes and heating at 400°C for 10 minutes were continuously performed in a nitrogen atmosphere.

[0460] (Evaluation of Adhesion)

[0461] After forming 5 x 5 squares of 0.2 cm squares on the surface of the laminate on the copper film side with a cutter, a transparent tape (Scotch tape) (No. 56 manufactured by 3M Company) was attached, and then peeled off at once, and the number of squares peeled off was measured.

[0462] The results are shown in Table 7.

[0463] Note that in Table 7, the concentrations in parentheses in 3APTES (10 mass%) and 3APDES (2.7 mass%) indicate the concentrations of 3APTES and 3APDES in the composition.

[0464] The value in the bracket of PMA [2.0], 124BTC [1.5], 135BTC [1.0], and 1PrhePMA [0.7] indicates the ratio of the number of carboxyl groups in PMA, 124BTC, 135BTC, and 1PrhePMA to the total number of nitrogen atoms in the compound (A) (COOH / N).

[0465] The value in the bracket of NH3<1.5> indicates the ratio of the number of nitrogen atoms in NH3to the number of carboxyl groups in the crosslinking agent (B) (N / COOH).

[0466] The concentration in the bracket of 1PrOH (88 mass%) indicates the concentration of 1PrOH in the composition.

[0467] <Adhesion to Copper (Cu) Substrate>

[0468] (Preparation of Samples)

[0469] A substrate was prepared in which a 100-nm copper film was formed on a silicon substrate by plating, and the copper film surface was cleaned using helium plasma treatment. On the copper film surface after plasma treatment, a sealing layer (polymer layer) was formed in the same manner as in the <Adhesion to Silicon (Si) Substrate>.

[0470] A polymer layer was formed on the copper in the above manner to obtain a laminate in which a copper and a polymer layer were stacked (hereinafter, also referred to as "sample (polymer / Cu)").

[0471] (Adhesion Evaluation)

[0472] After forming 5 x 5 squares of 0.2-cm squares on the copper film side surface of the laminate using a cutter, a transparent tape (No. 56 manufactured by 3M Company) was attached, and then peeled off at once, and the number of squares peeled off was measured.

[0473] The results are shown in Table 7.

[0474] [Table 7]

[0475]

[0476] As shown in Table 7, in the case where a film was formed using the composition related to Examples 34 to 37, no peeling occurred between the polymer and the silicon substrate or the copper substrate, and the adhesion was good.

[0477] <Decomposition Temperature Evaluation>

[0478] [Comparative Example 5]

[0479] Ammonia as the base (C-2) and water were mixed in PMA as the crosslinking agent (B) to prepare a mixed solution of PMA (14 mass%) and ammonia. Ammonia was added so that the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5.

[0480] [Comparative Example 6]

[0481] Ammonia as the base (C-2) and water were mixed in 124BTC as the crosslinking agent (B) to prepare a mixed solution of 124BTC (14 mass%) and ammonia. Ammonia was added so that the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5.

[0482] [Comparative Example 7]

[0483] Ammonia as the base (C-2) and water were mixed in 135BTC as the crosslinking agent (B) to prepare a mixed solution of 135BTC (14 mass%) and ammonia. Ammonia was added so that the ratio (N / COOH) of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) became 1.5.

[0484] [Comparative Example 8]

[0485] A BPEI_2 aqueous solution (1.5 mass%) was prepared.

[0486] [Comparative Example 9]

[0487] Ammonia as the base (C-2) and water were mixed in PMA as the crosslinking agent (B) to prepare a mixed solution of PMA and ammonia.

[0488] A BPEI_2 aqueous solution, the mixed solution of PMA and ammonia, and water were mixed so as to become the concentrations shown in Table 8 to prepare a composition (solution 17).

[0489] [Comparative Example 10]

[0490] Ammonia as the base (C-2) and water were mixed in 124BTC as the crosslinking agent (B) to prepare a mixed solution of 124BTC and ammonia.

[0491] A BPEI_2 aqueous solution, the mixed solution of 124BTC and ammonia, and water were mixed so as to become the concentrations shown in Table 8 to prepare a composition (solution 18).

[0492] [Comparative Example 11]

[0493] Ammonia as the base (C-2) and water were mixed in 135BTC as the crosslinking agent (B) to prepare a mixed solution of 135BTC and ammonia.

[0494] A solution 19 was prepared by mixing the BPEI_2 aqueous solution, the mixed solution of 135BTC and ammonia, and water in such a manner that the concentrations shown in Table 8 were obtained.

[0495] [Comparative Example 12]

[0496] A solution of 3-aminopropyltriethoxysilane (3APTES) as the compound (A) was prepared by dissolving 3APTES 2.0 g in 1-propanol 28 g, adding an aqueous formic acid (FA) solution (8.8 mass%) 10 g dropwise, stirring at room temperature for one hour, heating in a water bath at 60°C for one hour, and then adding 1-propanol 10 g.

[0497] [Examples 38 to 40]

[0498] The solutions 13 to 15 prepared in Examples 34 to 36 were used as they were.

[0499] [Comparative Example 13]

[0500] A solution of 3-aminopropyltriethoxysilane (3APTES) as the compound (A) was prepared by dissolving 3APTES 2.0 g in 1-propanol 28 g, adding an aqueous formic acid (FA) solution (8.8 mass%) 10 g dropwise, stirring at room temperature for one hour, heating in a water bath at 60°C for one hour, and then adding 1-propanol 10 g.

[0501] [Example 41]

[0502] The solution 3 prepared in Example 20 was used as it was.

[0503] [Comparative Example 14]

[0504] A solution of 3-aminopropyltriethoxysilane (3APTES) as the compound (A) was prepared by dissolving 3APTES 2.0 g in 1-propanol 28 g, adding an aqueous formic acid (FA) solution (8.8 mass%) 10 g dropwise, stirring at room temperature for one hour, heating in a water bath at 60°C for one hour, and then adding 1-propanol 10 g.

[0505] [Example 42]

[0506] A solution of 3-aminopropyltriethoxysilane (3APTES) as the compound (A) was prepared by dissolving 3APTES 2.0 g in 1-propanol 28 g, adding an aqueous formic acid (FA) solution (8.8 mass%) 10 g dropwise, stirring at room temperature for one hour, heating in a water bath at 60°C for one hour, and then adding 1-propanol 10 g.

[0507] A solution 20 was prepared by mixing a 1-propanol solution of 1Prhe124BTC as the crosslinking agent (B), 1-propanol, and water in such a manner that the compositions shown in Table 8 were obtained.

[0508] (Evaluation method)

[0509] The decomposition temperature of the polymer was evaluated by the following method.

[0510] Each sample of 100 mg prepared in Examples 38 to 42 and Comparative Examples 5 to 14 was placed in a sample cup, and using a thermogravimetric measurement device (manufactured by Shimadzu Corporation: DTG-60 (model)), the mass at each temperature was measured under a nitrogen atmosphere at a temperature increase rate of 30°C / minute from 30°C to 550°C. The temperature at which the mass decreased by 10% from 300°C is shown in Table 8.

[0511] Note that in Table 8, the concentration in parentheses in the BPEI_2 aqueous solution (1.5 mass%), 3APTES (10 mass%), 3APDES (50 mass%), 3APDES (1.8 mass%), and 3APDES (4 mass%) indicates the concentration of BPEI_2, 3APTES, and 3APDES in the composition.

[0512] The concentration in parentheses in PMA (14 mass%), 124BTC (14 mass%), and 135BTC (14 mass%) indicates the concentration of PMA, 124BTC, and 135BTC in the composition.

[0513] The numerical value in parentheses in PMA[1.8], 124BTC[1.35], 135BTC[0.9], PMA[2.0], 124BTC[1.5], 135BTC[1.0], eheOPDA[1.0], and 1Prhe124BTC[1.15] indicates the ratio of the number of carboxyl groups in PMA, 124BTC, 135BTC, eheOPDA, and 1Prhe124BTC to the total number of nitrogen atoms in the compound (A) (COOH / N).

[0514] The numerical value in parentheses in NH3<1.5> indicates the ratio of the number of nitrogen atoms in NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH).

[0515] The numerical value in parentheses in FA, 1.83 indicates the ratio of the number of carboxyl groups in FA to the total number of nitrogen atoms in the compound (A) (COOH / N).

[0516] The concentration in parentheses in 1PrOH (33 mass%), 1PrOH (76 mass%), 1PrOH (88 mass%), and EtOH (29 mass%) indicates the concentration of 1PrOH and EtOH in the composition.

[0517] [Table 8]

[0518]

[0519] At the stage of temperature increase to 300°C, each sample had become a solid, and weight reduction occurred if the polymer that had become a solid by further temperature increase decomposed. The decomposition temperature was evaluated as the temperature at which the mass at 300°C decreased by 10%.

[0520] As shown in Table 8, the solid obtained from the composition of Examples 38 to 42 containing the compound (A) having a Si-O bond and the crosslinking agent (B) had a high decomposition temperature, as compared with the solid obtained from the composition of Comparative Examples 12 to 14 not containing the crosslinking agent (B) and the solid obtained from the composition of Comparative Examples 9 to 11 containing an aliphatic amine not having a Si-O bond and the crosslinking agent (B).

[0521] From this result, it was shown that by using the composition of Examples 38 to 42 containing the compound (A) and the crosslinking agent (B), a polymer film having a high decomposition temperature could be formed.

[0522] < Solution storage stability evaluation >

[0523] [Comparative Example 15]

[0524] In a plastic container put in a water bath cooled to 5°C or less with ice water, 1.14 g of pyromellitic dianhydride (PMDA) was added, 24 g of ethanol was added, 2.18 g of 3-aminopropyl diethoxymethylsilane (3APDES) was slowly added dropwise, and then stirred for 2 hours. After confirming that all the compounds were dissolved, 3 g of water was added to obtain a composition for storage stability evaluation (solution 21). It was presumed that an amic acid of PMDA and 3APDES was formed in solution 21.

[0525] [Examples 43 to 45]

[0526] The composition (solution 13 to 15) prepared in Examples 34 to 36 was prepared.

[0527] (Evaluation method)

[0528] The storage stability evaluation of the solution was performed by the following method.

[0529] The solutions 13 to 15, 21 were put in a polyethylene-made closed container of 100 mL in volume at 20 mL to 50 mL, and kept in a refrigerator kept at 5°C without opening the door of the refrigerator for 20 days. After 20 days, it was taken out of the refrigerator, and after it was returned to room temperature, the formation of precipitates, turbidity and the like in the solution were confirmed by visual observation. The case where neither the formation of precipitates nor turbidity was observed was set as A, and the case where at least one of the formation of precipitates and turbidity was observed was set as B.

[0530] The evaluation results are shown in Table 9.

[0531] [Table 9]

[0532]

[0533] As shown in Table 9, for the solutions 13 to 15 of Examples 43 to 45, no abnormality such as formation of precipitates, turbidity, etc. was confirmed after cold storage at 5°C for 20 days. In the solution 21 of Comparative Example 15, a gel-like precipitate was formed.

[0534] For the solutions 13 to 15 of Examples 43 to 45, no abnormality such as precipitates, turbidity, etc. in the solutions was confirmed after further storage at room temperature for 10 weeks.

[0535] Thus, it was shown that for the solutions 13 to 15 of Examples 43 to 45, it was considered that the compound (A) and the crosslinking agent (B) were not aggregated but dispersed in the solutions, and the storage stability was excellent.

[0536] < Evaluation of Etching Selectivity >

[0537] [Comparative Example 16]

[0538] A 135BTC (14 mass%) and ammonia mixed solution was prepared by mixing ammonia as the base (C-2) and water in 135BTC as the crosslinking agent (B).

[0539] A 3APDES aqueous solution, the 135BTC and ammonia mixed solution, and water were mixed in such a manner as to become the concentrations shown in Table 10, and a composition (solution 23) was prepared.

[0540] [Example 46]

[0541] For 3-aminopropyl diethoxymethyl silane (3APDES) of the compound (A), a substance obtained by dissolving in water to prepare a 50 mass% aqueous solution and then standing overnight was used for the composition preparation. The weight average molecular weight (Mw) after hydrolysis was 230.

[0542] A 135BTC (14 mass%) and ammonia mixed solution was prepared by mixing ammonia as the base (C-2) and water in 135BTC as the crosslinking agent (B).

[0543] Next, a 3APDES aqueous solution, the 135BTC and ammonia mixed solution, and water were mixed in such a manner as to become the concentrations shown in Table 10, and a composition (solution 23) was prepared.

[0544] [Example 47]

[0545] A solution of 3-aminopropyldiethoxymethylsilane (3APDES) as compound (A) was prepared by adding 3APDES 2.0 g to 1-propanol 28 g, adding dropwise formic acid (FA) aqueous solution (8.8 mass %) 10 g, and stirring at room temperature for one hour, and then heating in a water bath at 60°C for one hour.

[0546] A composition (solution 24) was prepared by mixing a 1-propanol solution of 1-propyl hemi-ester oxybisphthalic acid (1PrheOPDA) as crosslinking agent (B), 1-propanol, and water in a manner to become the composition shown in Table 10, in the 3APDES solution.

[0547] [Example 48]

[0548] A composition (solution 10) prepared in Example 29 was prepared.

[0549] (Preparation of a sample)

[0550] A silicon wafer on which silicon dioxide was present on the surface was placed on a spin coater, and the composition 0.5 mL was added dropwise for 10 seconds at a constant speed, and after being held for 13 seconds, the silicon wafer was dried by being rotated at 2000 rpm for 1 second, and then at 600 rpm for 30 seconds, and then at 2000 rpm for 10 seconds.

[0551] A polymer layer was formed on the silicon wafer in the above manner, and a laminate (hereinafter, also referred to as "sample (polymer / Si)") in which the silicon wafer and the polymer layer were stacked was obtained.

[0552] The above sample (polymer / Si) was placed on a hot plate with the silicon wafer surface in contact with the hot plate, and soft baking (heating treatment) was performed at a soft baking temperature of 100°C for 60 seconds in an atmospheric atmosphere. Then, heating at 300°C for 10 minutes and heating at 400°C for 10 minutes were continuously performed in a nitrogen atmosphere.

[0553] The silicon wafer on which the polymer film was formed by the above method was placed in a chamber, and the chamber was evacuated to 5 x 10 -6 Torr (6.7 x 10 -4 Pa), and oxygen was caused to flow into the chamber at 50 seem (about 8.3 x 10 -7 m 3 / s), and the pressure in the chamber was adjusted to 0.15 Torr (20 Pa), and a 100 W oxygen plasma was irradiated.

[0554] The evaluation of the etching selectivity was performed as follows, that is, the film thickness of the polymer film after the irradiation of the oxygen plasma for 3 minutes and 5 minutes was subtracted from the film thickness of the polymer film after the heating at 400°C for 10 minutes, and the reduction amount (nm) of the film thickness was calculated. The results are shown in Table 10.

[0555] Note that in Table 10, the concentrations in parentheses in the BPEI_2 aqueous solution (1.5 mass%), 3APDES (10 mass%), 3APDES (2.7 mass%), and BATDS (2 mass%) represent the concentrations of BPEI_2, 3APDE, and BATDS in the compositions.

[0556] The values in parentheses in PMA [1.42], 135BTC [1.0], 1PrheOPDA [0.7], and eheOPDA [1.0] represent the ratio of the number of carboxyl groups in PMA, 135BTC, 1PrheOPDA, and eheOPDA to the total number of nitrogen atoms in Compound (A) (COOH / N).

[0557] The value 1.5 in parentheses in FA represents the ratio of the number of carboxyl groups in FA to the total number of nitrogen atoms in Compound (A) (COOH / N).

[0558] The value in parentheses in NH3 <1.5> represents the ratio of the number of nitrogen atoms in NH3 to the number of carboxyl groups in Crosslinking Agent (B) (N / COOH).

[0559] The concentrations in parentheses in 1PrOH (85 mass%), 1PrOH (37 mass%), and EtOH (59 mass%) represent the concentrations of 1PrOH and EtOH in the compositions.

[0560] [Table 10]

[0561]

[0562] As shown in Table 10, according to the results after the etching for 3 minutes, the Si-O containing film obtained using the composition of Example 46, 47 containing Compound (A) and Crosslinking Agent (B) had a smaller reduction amount of the film (i.e., etching rate) than the organic film obtained using the composition of Comparative Example 16 containing an aliphatic amine and Crosslinking Agent (B).

[0563] Similarly, according to the results after the etching for 5 minutes, the Si-O containing film obtained using the composition of Example 47, 48 containing Compound (A) and Crosslinking Agent (B) had a smaller reduction amount of the film (i.e., etching rate) than the organic film obtained using the composition of Comparative Example 16 containing an aliphatic amine and Crosslinking Agent (B).

[0564] As shown above, it was found that the Si-O containing film obtained using the composition of Examples 46 to 48 had a small etching rate by oxygen plasma, i.e., excellent etching selectivity, as compared with the organic film (Comparative Example 16).

[0565] Further, according to the results after etching for 5 minutes, the Si-O containing film obtained using the composition of Example 47 containing 3APDES as the compound (A) and 1PrheOPDA as the crosslinking agent (B) had a small film reduction (i.e., etching rate) as compared with the Si-O containing film obtained using the composition of Example 48 containing BATDS as the compound (A) and eheOPDA as the crosslinking agent (B).

[0566] The disclosure of Japanese Patent Application No. 2015-224196 filed on November 16, 2015 is incorporated by reference herein in its entirety.

[0567] All of the literature, patent applications and technical standards cited in the present specification are hereby incorporated by reference to the same extent as if each individual publication, patent application, or technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A composition for producing a film for a semiconductor device, comprising: a compound (A) having a Si-O bond and a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom; a crosslinking agent (B) having a ring structure in a molecule, wherein X is a hydrogen atom or an alkyl group having a carbon number of 1 or more and 6 or less, 1 or more and 6 or less of 3 or more -C(=0)OX groups are -C(=0)OH groups, and a weight average molecular weight of the crosslinking agent (B) is 200 or more and 600 or less; an additive (C) selected from at least one of an acid (C-1) having a carboxyl group and a weight average molecular weight of 46 or more and 195 or less and a base (C-2) having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less; and a polar solvent (D).

2. A composition for producing a film for a semiconductor device, comprising: a compound (A) having a Si-O bond and a cationic functional group including at least one of a primary nitrogen atom and a secondary nitrogen atom, and a weight average molecular weight of 130 or more and 10,000 or less; a crosslinking agent (B) having a ring structure in a molecule, wherein X is a hydrogen atom or an alkyl group having a carbon number of 1 or more and 6 or less, 1 or more and 6 or less of 3 or more -C(=0)OX groups are -C(=0)OH groups, and a weight average molecular weight of the crosslinking agent (B) is 200 or more and 600 or less; an additive (C) selected from at least one of an acid (C-1) having a carboxyl group and a weight average molecular weight of 46 or more and 195 or less and a base (C-2) having a nitrogen atom and a weight average molecular weight of 17 or more and 120 or less; and a polar solvent (D). a crosslinking agent (B) having 3 or more -C(=O)OX groups in a molecule, wherein 3. The composition for producing a film for a semiconductor device according to claim 1 or 2, wherein the ring structure is at least one of a benzene ring and a naphthalene ring.

4. The composition for producing a film for a semiconductor device according to claim 1 or 2, comprising at least one selected from the group consisting of an aliphatic amine having a weight average molecular weight of 100,000 or more and 400,000 or less and an amine compound having a ring structure in a molecule and a weight average molecular weight of 90 or more and 600 or less. ​ ​ ​ ​ ​ ​ a crosslinking agent (B) having 3 or more -C(=O)OX groups in a molecule, wherein ​ ​ ​ ​ ​ ​ ​ ​ 5. The composition for producing a film for a semiconductor device according to claim 1 or 2, which is used as a filling material for a recess formed in a substrate.

6. The composition for producing a film for a semiconductor device according to claim 1 or 2, which is used in a multilayer resist method.

7. A production method of a composition for producing a film for a semiconductor device, which is a production method of the composition for producing a film for a semiconductor device according to any one of claims 1 to 6, comprising a mixing step of mixing the compound (A) and the crosslinking agent (B).

8. The production method according to claim 7, wherein the mixing step is a step of mixing a mixture of the acid (C-1) and the compound (A) and the crosslinking agent (B).

9. The production method according to claim 7, wherein the mixing step is a step of mixing a mixture of the base (C-2) and the crosslinking agent (B) and the compound (A).

10. A production method of a semiconductor member, which is a production method of a semiconductor member using the composition for producing a film for a semiconductor device according to any one of claims 1 to 6, comprising: a step of applying the composition for producing a film for a semiconductor device to a substrate; and a step of heating the substrate to which the composition for producing a film for a semiconductor device is applied at a temperature of 250°C or higher and 425°C or lower.

11. A production method of a semiconductor processing material, which is a production method of a semiconductor processing material using the composition for producing a film for a semiconductor device according to any one of claims 1 to 6, comprising: a step of applying the composition for producing a film for a semiconductor device to a substrate; and a step of heating the substrate to which the composition for producing a film for a semiconductor device is applied at a temperature of 250°C or higher and 425°C or lower. ​ ​ ​ ​

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