Composition, laminate and substrate laminate for forming semiconductor film

Abstract

A composition for forming a film for a semiconductor, the composition comprising: an aliphatic diamine (A) which includes a main chain containing carbon atoms, and a primary amino group and a secondary amino group, and in which the total number of the primary and secondary amino groups is at least two, and the number of carbon atoms included in the main chain is 2-180; and a crosslinking agent (D) which has weight-average molecular weight of 200-2000, which includes, in the molecule, at least three -C(=O)OX groups (X represents a hydrogen atom or an alkyl group having 1-6 carbon atoms), and in which 1-6 of the at least three -C(=O)OX groups are a -C(=O)OH group. An application of the composition for forming a film for a semiconductor.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to compositions, laminates and substrate stacks for forming films for semiconductor applications. [Background technology]

[0002] As electronic devices become smaller, lighter, and more powerful, there is a demand for higher integration of semiconductor chips and the like. However, it is difficult to fully meet this demand through circuit miniaturization alone. In response to this, in recent years, a method has been proposed for achieving higher integration by vertically stacking multiple semiconductor substrates (wafers) to form a multilayer, three-dimensional structure. Proposed methods for stacking semiconductor substrates (wafers) include direct bonding of substrates and methods using bonding materials (see, for example, JP-A-4-132258, JP-A-2010-226060, and JP-A-2016-47895). Summary of the Invention [Problem to be solved by the invention]

[0003] When semiconductor substrates are bonded together using a bonding material, it is assumed that a resin is applied to the surface of the semiconductor substrate, and then a bonding layer is formed by drying, heating, etc., and the semiconductor substrates are bonded together via the bonding layer. At this time, warping is likely to occur in the semiconductor substrate on which the bonding layer is formed due to factors such as the difference in thermal expansion coefficient between the bonding layer and the semiconductor substrate. If the warping is large, there is a risk of misalignment occurring when the semiconductor substrates are bonded together.

[0004] When semiconductor substrates are bonded together using a bonding material, if the bonding layer formed from the bonding material has low adhesion, the semiconductor substrates are likely to peel off or become misaligned after bonding.

[0005] From the above points of view, it is desirable that when a bonding layer is formed on a substrate such as a semiconductor substrate using a composition for forming a semiconductor film, warping of the substrate can be suppressed, and further that the bonding strength between the substrates is high. One aspect of the present invention has been made in view of the above, and aims to provide a composition for forming a semiconductor film that can suppress warping of a substrate when a bonding layer is formed on the substrate and can form a bonding layer that has high bonding strength between substrates, as well as a laminate and a substrate laminate formed using this composition for forming a semiconductor film. [Means for solving the problem]

[0006] Specific means for solving the above problems are as follows. <1> an aliphatic diamine (A) having a main chain containing at least one of a primary amino group and a secondary amino group and carbon atoms, the total number of primary amino groups and secondary amino groups being two or more, the number of carbon atoms constituting the main chain being 2 or more and 180 or less, and the weight average molecular weight being 60 or more and 2000 or less; a crosslinking agent (D) containing three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, of which one to six of the three or more -C(=O)OX groups are -C(=O)OH groups, and having a weight average molecular weight of 200 to 2000; A composition for forming a film for a semiconductor, comprising: <2> The composition further comprises a silane compound (B) that contains at least one of a primary amino group and a secondary amino group and a silicon atom, and the relationship between the silicon atom and the non-polar group bonded to the silicon atom satisfies the relationship (non-polar group) / Si<1.8 in terms of molar ratio. <1> 10. A composition for forming a film for a semiconductor according to claim 1. <3> The weight average molecular weight of the silane compound (B) is 130 or more and 10,000 or less. <2> 10. A composition for forming a film for a semiconductor according to claim 1. <4> The composition further comprises a linear siloxane compound (C) that contains at least one of a primary amino group and a secondary amino group, a silicon atom, and a non-polar group bonded to the silicon atom, wherein the total number of primary amino groups and secondary amino groups is two or more, and the relationship between the silicon atom and the non-polar group bonded to the silicon atom satisfies the relationship (non-polar group) / Si≧1.8 in terms of molar ratio. <1> ~ <3> 10. A composition for forming a semiconductor film according to any one of the above items. <5> The weight average molecular weight of the siloxane compound (C) is 200 or more and 2000 or less. <4> 10. A composition for forming a film for a semiconductor according to claim 1. <6> The aliphatic diamine (A) does not contain a cyclic structure. <1> ~ <5> 10. A composition for forming a semiconductor film according to any one of the above items. <7> The molar ratio of the content of the crosslinking agent (D) to the total content of the components having an amino group contained in the composition for forming a semiconductor film, component having an amino group / crosslinking agent (D), is 0.1 or more and 10 or less. <1> ~ <6> 2. The composition for forming a semiconductor film according to claim 1, <8> The ratio of the number of -C(=O)OX groups in the crosslinking agent (D) to the total number of amino groups in components having amino groups contained in a composition for forming a semiconductor film, COOX / amino groups, is 0.1 or more and 5.0 or less. <1> ~ <7> 10. The composition for forming a semiconductor film according to claim 9, wherein the composition is a film for semiconductor use. <9> The crosslinking agent (D) is such that, among the three or more —C(═O)OX groups, at least one X is an alkyl group having 1 to 6 carbon atoms. <1> ~ <8> 10. A composition for forming a semiconductor film according to any one of the above items. <10> Both ends of the main chain of the aliphatic diamine (A) are independently a primary amino group or a secondary amino group. <1> ~ <9> 10. A composition for forming a semiconductor film according to any one of the above items. <11> <1> ~ <10> 10. A laminate comprising a substrate and a bonding layer formed from the composition for forming a semiconductor film according to any one of the above items. <12> a first substrate; <1> ~ <10> 1. A substrate laminate comprising a bonding layer formed from the composition for forming a semiconductor film according to any one of 1 to 8 above, and a second substrate laminated in this order. <13> a first substrate; <1> ~ <10> a first laminated region formed by laminating, in this order, a bonding layer formed from the composition for forming a semiconductor film described in any one of the above, and a second substrate; and a second laminated region formed by laminating, in this order, the first substrate, an electrode, and a second substrate, wherein at least one first laminated region and at least one second laminated region are arranged in a plane direction perpendicular to the lamination direction. <14> The first stacking region has two or more layers stacked in the stacking direction, and the second stacking region has two or more layers stacked in the stacking direction. <13> The substrate laminate according to claim 1. <15> At least one of the first substrate and the second substrate is a semiconductor substrate containing at least one element selected from the group consisting of Si, Ga, Ge, and As. <12> ~ <14> 10. The substrate laminate according to claim 9, wherein the substrate laminate is a laminate of a first type and a second type. [Effects of the Invention]

[0007] According to one aspect of the present invention, it is possible to provide a composition for forming a semiconductor film that can suppress warping of a substrate when a bonding layer is formed on the substrate and that can form a bonding layer that has high bonding strength between substrates, as well as a laminate and a substrate laminate formed using this composition for forming a semiconductor film. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the present disclosure, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, the term "substrate laminate" refers to a laminate having a structure in which two substrates are bonded via a bonding layer formed by the method for manufacturing a substrate laminate of the present disclosure. Note that the substrate laminate may have three or more substrates, and may have a structure in which two of the three or more substrates are bonded via a bonding layer formed by the method for manufacturing a substrate laminate of the present disclosure.

[0009] [Composition for forming a semiconductor film] The composition for forming a semiconductor film of the present disclosure includes an aliphatic diamine (A) (hereinafter also referred to simply as "aliphatic diamine (A)") that contains a main chain containing at least one of a primary amino group and a secondary amino group and a carbon atom, wherein the total number of primary amino groups and secondary amino groups is two or more, the number of carbon atoms constituting the main chain is 2 to 180, and the weight-average molecular weight is 60 to 2000; and a crosslinker (D) (hereinafter also referred to simply as "crosslinker (D)") that contains three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, wherein one to six of the three or more -C(=O)OX groups are -C(=O)OH groups, and has a weight-average molecular weight of 200 to 2000.

[0010] The composition for forming a semiconductor film of the present disclosure contains the aforementioned aliphatic diamine (A) and crosslinking agent (D). This allows for suppressing warpage of the substrate when the composition for forming a semiconductor film is applied to a substrate such as a semiconductor substrate to form a bonding layer from the composition for forming a semiconductor film on the substrate, and also provides high bonding strength between the substrates. This, for example, allows for suppressing misalignment when bonding the substrates together.

[0011] (Aliphatic diamine (A)) The composition for forming a semiconductor film according to the present disclosure includes an aliphatic diamine (A) that includes a main chain containing at least one of a primary amino group and a secondary amino group and carbon atoms, the total number of primary amino groups and secondary amino groups being two or more, the number of carbon atoms constituting the main chain being 2 or more and 180 or less, and the weight-average molecular weight being 60 or more and 2,000 or less. The aliphatic diamine (A) has a main chain containing 2 or more and 180 or less carbon atoms and a weight-average molecular weight of 60 or more and 2000 or less. This allows the aliphatic diamine (A) to contribute to the formation of a flexible skeleton in the bonding layer formed by reaction with the crosslinking agent (D) described below, thereby improving the flexibility of the bonding layer and effectively suppressing warpage of the substrate. In the present disclosure, the aliphatic diamine (A) is not limited to a compound whose main chain is composed only of carbon atoms, and some of the carbon atoms in the main chain may be substituted with a divalent or higher atom such as an oxygen atom or a sulfur atom, or a functional group such as a carbonyl group, a secondary amino group, a tertiary amino group, an amide group, or an ester group.

[0012] Hereinafter, the amino group contained in the aliphatic diamine (A) and which is a primary amino group or a secondary amino group will also be referred to as a “specific amino group.” Examples of the aliphatic diamine (A) containing a specific amino group include a compound containing two or more primary amino groups and no secondary amino groups, a compound containing no primary amino groups and two or more secondary amino groups, and a compound containing at least one primary amino group and one secondary amino group.

[0013] From the viewpoint of suppressing an increase in crosslink density due to a reaction with the crosslinking agent (D) described below and suitably forming a bonding layer having a flexible skeleton that suitably contributes to suppressing warpage of the substrate, the aliphatic diamine (A) preferably contains two or more specific amino groups in the main chain, more preferably contains two specific amino groups in the main chain, further preferably has both terminals of the main chain each independently be a primary amino group or a secondary amino group, and particularly preferably has both terminals of the main chain be primary amino groups.

[0014] The aliphatic diamine (A) preferably has two amino groups in the main chain, and from the viewpoint of suitably forming a bonding layer having a flexible skeleton that suitably contributes to suppressing warpage of the substrate, it is preferable that the number of specific amino groups in the side chain is one or less, and it is preferable that the side chain does not contain any specific amino groups.

[0015] From the viewpoint of more suitably forming a bonding layer having a flexible skeleton, the number of carbon atoms constituting the main chain of the aliphatic diamine (A) is preferably 3 or more, more preferably 5 or more, and even more preferably 6 or more. From the viewpoint of obtaining a bonding layer with high thickness uniformity, the number of carbon atoms constituting the main chain of the aliphatic diamine (A) is preferably 100 or less, more preferably 50 or less, and even more preferably 20 or less.

[0016] The aliphatic diamine (A) preferably does not contain a cyclic structure. When the aliphatic diamine (A) does not contain a cyclic structure such as a non-aromatic carbon ring, an aromatic ring, or a heterocyclic ring (heterocycle), a bonding layer having a flexible skeleton can be suitably formed, and warpage of the substrate can be more suitably suppressed.

[0017] The weight average molecular weight of the aliphatic diamine (A) can be, for example, 60 or more and 2000 or less. From the viewpoint of more suitably forming a bonding layer having a flexible skeleton, it is preferably 80 or more, more preferably 100 or more, and even more preferably 130 or more. From the viewpoint of obtaining a bonding layer with high thickness uniformity, it is preferably 1000 or less, more preferably 500 or less, and even more preferably 300 or less.

[0018] In the present disclosure, the weight average molecular weight is determined by the GPC (Gel Permeation Chromatography) method. It refers to the weight average molecular weight measured by the above method and converted into polyethylene glycol. Specifically, the weight-average molecular weight was measured by measuring the refractive index at a flow rate of 1.0 mL / min using an aqueous solution of sodium nitrate with a concentration of 0.1 mol / L as the developing solvent, a Shodex DET RI-101 analyzer, and two types of analytical columns (TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP manufactured by Tosoh). The detected values ​​are calculated using analytical software (Waters Empower3) with polyethylene glycol / polyethylene oxide as the standard.

[0019] The aliphatic diamine (A) is preferably a compound having a main chain that contains primary amino groups at both ends of the main chain and has a structure in which the carbon chain or part of the carbon chain is substituted with an atom other than carbon atom or a functional group. Examples of atoms other than carbon atoms include oxygen atoms and sulfur atoms. Examples of functional groups that substitute a part of the carbon chain include carbonyl groups, secondary amino groups, tertiary amino groups, amide groups, and ester groups.

[0020] Examples of the aliphatic diamine (A) include compounds having a main chain made of a carbon chain, such as trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and 3-methylpentamethylenediamine; and compounds having a main chain made of a structure in which part of the carbon chain is substituted with an atom other than carbon atom or with a functional group, such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 3,3'-diaminodipropylamine, and 1,2-bis(2-aminoethoxy)ethane. The aliphatic diamine (A) may be used alone or in combination of two or more.

[0021] Aliphatic diamine (A) / amino group, which is the ratio of the content of aliphatic diamine (A) to the total content of components having amino groups contained in a composition for forming a semiconductor film. The molar ratio of the aliphatic diamine (A) / component having an amino group may be 0.05 or more, 0.2 or more, or 0.5 or more. When the aliphatic diamine (A) / component having an amino group ratio is 0.1 or more, the flexibility of the bonding layer is further improved, and warpage of the substrate can be more suitably suppressed. The upper limit of the ratio of aliphatic diamine (A) to component having an amino group is not particularly limited as long as it is 1.0 or less, and may be 0.8 or less.

[0022] In the present disclosure, the component having an amino group refers to a component containing at least one of a primary amino group and a secondary amino group that can react with the crosslinking agent (D). The component having an amino group may be, for example, only the aliphatic diamine (A), or a combination of the aliphatic diamine (A) with at least one of the silane compound (B) and the siloxane compound (C) described below, or a combination of the aliphatic amine (A) with at least one of the silane compound (B), the siloxane compound (C), and other amino group-containing components described below.

[0023] (Silane Compound (B)) The composition for forming a semiconductor film of the present disclosure preferably contains a silane compound (B) (hereinafter simply referred to as "silane compound (B)") that contains at least one of a primary amino group and a secondary amino group and a silicon atom, and the relationship between the silicon atom and a nonpolar group bonded to the silicon atom satisfies the relationship (nonpolar group) / Si<1.8 in molar ratio. By using a composition for forming a semiconductor film containing silane compound (B), a bonding layer with excellent heat resistance can be formed due to its high glass transition temperature. The relationship between the silicon atoms contained in the silane compound (B) and the nonpolar groups bonded to the silicon atoms, expressed as a molar ratio of (nonpolar groups) / Si<1.8, means that the ratio of the number of nonpolar groups bonded to the silicon atoms to the number of silicon atoms satisfies (nonpolar groups) / Si<1.8.

[0024] When the silane compound (B) satisfies the relationship (non-polar group) / Si<1.8, it means that the amount of non-polar groups bonded to silicon atoms is less than a predetermined amount. As a result, the structure derived from the silane compound (B) contributes to the heat resistance of the bonding layer formed by the reaction with the crosslinking agent (D) described below.

[0025] The silane compound (B) contains a primary amino group (-NH2 group) and a secondary amino group (e.g., -NHR a group; where R a represents an alkyl group. The total number of primary amino groups and secondary amino groups in the silane compound (B) is not particularly limited as long as it is one or more. For example, from the viewpoint of suppressing an increase in crosslink density due to a reaction with the crosslinking agent (D) described below, the total number is preferably one or two, and more preferably one.

[0026] The silane compound (B) is a tertiary amino group (e.g., —NR b R c group; where R b and R c each independently represents an alkyl group.

[0027] The number of silicon atoms in the silane compound (B) is not particularly limited as long as it is 1 or more, and may be, for example, 1 or 2, or may be 1.

[0028] The weight average molecular weight of the silane compound (B) is preferably 130 or more and 10,000 or less, more preferably 130 or more and 5,000 or less, and even more preferably 130 or more and 2,000 or less.

[0029] In the silane compound (B), the relationship between the silicon atom and the nonpolar group bonded to the silicon atom satisfies the molar ratio (nonpolar group) / Si<1.8, where the nonpolar group bonded to the silicon atom is the same as the nonpolar group in the siloxane compound (C).

[0030] In the silane compound (B), from the viewpoint of further improving heat resistance, it is preferable that (non-polar group) / Si≦1.5, and more preferably that (non-polar group) / Si≦1.0. The lower limit of (non-polar group) / Si is not particularly limited, and may be, for example, (non-polar group) / Si≧0.5, and more preferably (non-polar group) / Si≧0.8, in order to facilitate stabilization of the composition and make it less likely to gel.

[0031] From the viewpoint of further improving heat resistance, it is preferable that the silane compound (B) has a polar group bonded to the silicon atom. When a polar group is bonded to the silicon atom, the polar group undergoes hydrolysis, dehydration condensation, etc. to form a siloxane bond (-Si-O-Si), which enhances the crosslinking property of the film and improves the heat resistance (glass transition temperature). Examples of polar groups include functional groups that can be converted to a hydroxy group by hydrolysis, and specific examples include alkoxy groups having 1 to 5 carbon atoms, such as a hydroxy group, a methoxy group, and an ethoxy group. The siloxane bond (-Si-O-Si) is not classified as either a polar group or a non-polar group bonded to the silicon atom of the silane compound (B).

[0032] The silane compound (B) may be, for example, a compound represented by the following general formula (B-1).

[0033] [ka]

[0034] In general formula (B-1), R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted. 2 and R 3 R each independently represents an optionally substituted alkylene group having 1 to 12 carbon atoms, an ether group, or a carbonyl group, and the optionally substituted alkylene group having 1 to 12 carbon atoms may contain a carbonyl group, an ether group, or the like in the skeleton. 4 and R 5 each independently represents an optionally substituted alkylene group having 1 to 4 carbon atoms or a single bond. Ar represents a divalent or trivalent aromatic ring. X 1 represents hydrogen or an alkyl group having 1 to 5 carbon atoms which may be substituted. X 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group, or an optionally substituted alkyl group having 1 to 5 carbon atoms, and the optionally substituted alkyl group having 1 to 5 carbon atoms may contain a carbonyl group, an ether group, etc. in the skeleton. 1 , R 2 , R 3 , R 4 , R5 , X 1 may be the same or different. In general formula (B-1), p1 represents 0 or 1, and q1 represents 2 or 3, provided that p1+q1=3. n1 represents an integer of 1 to 3, and r1, s1, t1, u1, V1, and w1 each independently represent 0 or 1.

[0035] In general formula (B-1), R 1 , R 2 , R 3 , R 4 , R 5 , X 1 , X 2 In the above, the substituents on the alkyl group and alkylene group each independently include an amino group, a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, and halogens. The divalent or trivalent aromatic ring in Ar includes, for example, a divalent or trivalent benzene ring. 2 Examples of the aryl group in the formula (I) include a phenyl group, a methylbenzyl group, and a vinylbenzyl group. n1 is preferably 1 or 2, and more preferably 1. s1, t1, V1 and w1 are preferably 0.

[0036] Specific examples of the silane compound (B) include N-(2-aminoethyl)-3-aminopropylmethyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminoisobutylmethyldimethoxysilane, N-(2-aminoethyl)-11-aminoundecyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl Nyl-3-aminopropyltrimethoxysilane, (aminoethylaminoethyl)phenyltriethoxysilane, methylbenzylaminoethylaminopropyltrimethoxysilane, benzylaminoethylaminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, (aminoethylaminoethyl)phenethyltrimethoxysilane, (aminoethylaminomethyl)phenethyltrimethoxysilane, N-[2-[3-(trimethoxysilyl)propylamino]ethyl]ethylenediamine, 3-aminopropyldiethoxymethylsilane, 3-aminopropyldimethoxymethylsilane, trimethoxy[2-(2-aminopropyl)propyl]methylsilane (aminoethyl)-3-aminopropyl]silane, diaminomethylmethyldiethoxysilane, Methylaminomethylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, N-methylaminopropyltriethoxysilane, N-methylaminopropylmethyldiethoxysilane, (phenylaminomethyl)methyldiethoxysilane, acetamidopropyltrimethoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis[(3-triethoxysilyl)propyl]amine, pipera Examples include diphenylpropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]urea, bis(methyldiethoxysilylpropyl)amine, 2,2-dimethoxy-1,6-diaza-2-silacyclooctane, 3,5-diamino-N-(4-(triethoxysilyl)phenyl)benzamide, and hydrolysates thereof; 3-aminopropyldihydroxymethylsilane, 3-aminopropyltrihydroxysilane, and N-2-(aminoethyl)-3-aminopropyltrihydroxysilane. The silane compound (B) may be used alone or in combination of two or more.

[0037] The silane compound (B) may be, for example, a polymer containing a branched siloxane structure, a polymer containing a cyclic siloxane structure, a polymer containing a cage siloxane structure, etc. The cage siloxane structure is, for example, represented by the following formula (X):

[0038] [ka]

[0039] (Siloxane Compound (C)) The composition for forming a semiconductor film according to the present disclosure preferably includes a linear siloxane compound (C) (hereinafter also simply referred to as "siloxane compound (C)") that contains at least one of a primary amino group and a secondary amino group, a silicon atom, and a non-polar group bonded to the silicon atom, wherein the total number of primary amino groups and secondary amino groups is two or more, and the relationship between the silicon atom and the non-polar group bonded to the silicon atom satisfies the relationship (non-polar group) / Si≧1.8 in terms of molar ratio. The relationship between the silicon atoms and the nonpolar groups bonded to the silicon atoms satisfies the relationship (nonpolar groups) / Si≧1.8 in terms of molar ratio, which means that the ratio of the number of nonpolar groups bonded to the silicon atoms to the number of silicon atoms satisfies (nonpolar groups) / Si≧1.8. In the present disclosure, a linear siloxane compound means that the siloxane bonds (Si-O-Si bonds) are present in a straight chain, and refers to a compound that does not contain any branched siloxane structure, cyclic siloxane structure, cage siloxane structure, etc. Since the siloxane compound (C) is a linear siloxane compound, the siloxane compound (C) contributes to the formation of a flexible skeleton in the bonding layer formed by reaction with the crosslinking agent (D) described below, and the flexibility of the bonding layer is improved, thereby more effectively suppressing warpage of the substrate.

[0040] Furthermore, the siloxane compound (C) satisfies the relationship (non-polar group) / Si≧1.8, which means that the amount of non-polar groups bonded to silicon atoms is greater than or equal to a predetermined amount. This allows the non-polar groups to contribute to a decrease in crosslink density in the bonding layer formed by the reaction with the crosslinking agent (D) described below, improving the flexibility of the bonding layer and thereby more effectively suppressing warpage of the substrate.

[0041] The siloxane compound (C) contains a primary amino group (-NH2 group) and a secondary amino group (e.g., -NHR a group; where R a represents an alkyl group.) and the total number of primary amino groups and secondary amino groups is 2 or more. In the siloxane compound (C), the total number of primary amino groups and secondary amino groups is preferably 2 or more and 4 or less, more preferably 2 or 3, and even more preferably 2.

[0042] The siloxane compound (C) contains a tertiary amino group (e.g., —NR b R c group; where R b and R c each independently represents an alkyl group.

[0043] The weight average molecular weight of the siloxane compound (C) is, for example, from 200 to 2000. From the viewpoint of facilitating a more flexible structure, the lower limit is preferably 200 or more, more preferably 230 or more, and even more preferably 240 or more. From the viewpoint of facilitating the formation of a coating film using the composition, the upper limit is preferably 1500 or less, more preferably 1000 or less, and even more preferably 800 or less.

[0044] In the siloxane compound (C), the molar ratio between the silicon atom and the non-polar group bonded to the silicon atom satisfies the relationship (non-polar group) / Si≧1.8. Examples of the non-polar group bonded to the silicon atom include alkyl groups, aryl groups, and aralkyl groups. Preferred alkyl groups include methyl, ethyl, and propyl groups. Preferred aryl groups include phenyl groups, and preferred aralkyl groups include benzyl groups. In the present disclosure, structures in which a portion of a nonpolar group such as an alkyl group, aryl group, or aralkyl group is substituted with a hydrophilic group such as a hydroxy group or amino group are not classified as nonpolar groups. A siloxane bond (-Si-O-Si) is not classified as either a polar group or a nonpolar group bonded to a silicon atom of the silane compound (B).

[0045] In the siloxane compound (C), it is preferable that (non-polar group) / Si≧2.0, from the viewpoint that the non-polar group contributes to a decrease in crosslink density in the bonding layer formed by the reaction with the crosslinking agent (D) described below, thereby more suitably suppressing warpage of the substrate. The upper limit of (non-polar group) / Si may be, for example, (non-polar group) / Si≦2.5 or (non-polar group) / Si≦2.0. As an example, (non-polar group) / Si=2.0.

[0046] Hereinafter, the amino group contained in the siloxane compound (C) and which is a primary amino group or a secondary amino group will also be referred to as a “specific amino group.” Examples of the siloxane compound (C) containing a specific amino group include a compound containing two or more primary amino groups and no secondary amino groups, a compound containing no primary amino groups and two or more secondary amino groups, and a compound containing at least one primary amino group and one secondary amino group.

[0047] From the viewpoint of suppressing an increase in crosslink density due to a reaction with the crosslinking agent (D) described below and suitably forming a bonding layer having a flexible skeleton that suitably contributes to suppressing warpage of the substrate, the siloxane compound (C) preferably contains two or more specific amino groups in the main chain, more preferably contains two specific amino groups in the main chain, further preferably has both terminals of the main chain each independently be a primary amino group or a secondary amino group, and particularly preferably has both terminals of the main chain be primary amino groups.

[0048] The siloxane compound (C) preferably has two amino groups in the main chain, and from the viewpoint of suitably forming a bonding layer having a flexible skeleton that suitably contributes to suppressing warpage of the substrate, it is preferable that the number of specific amino groups in the side chain is one or less, and it is preferable that the side chain does not contain any specific amino groups.

[0049] The siloxane compound (C) may be, for example, a compound represented by the following general formula (C-1).

[0050] [ka]

[0051] In general formula (C-1), R 1 each independently represents a hydrogen atom or an optionally substituted alkyl group, R 2 each independently represents a divalent linking group, R 3 each independently represents a non-polar group, and j represents an integer of 1 or more and 10 or less. R 1 The substituents on the alkyl group in each of the above formulas are independently a hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group, a halogen atom, and the like.

[0052] In general formula (C-1), R 1 is preferably a hydrogen atom. In general formula (C-1), R 2 Examples of the divalent linking group in each group independently include an alkylene group, a divalent linking group in which a hydrogen atom in an alkylene group is substituted with another atom, a functional group, etc., and a divalent linking group in which a methylene group in an alkylene group is substituted with -NH-. The number of carbon atoms in the divalent linking group is, for example, preferably 1 to 20, more preferably 2 to 10, and even more preferably 3 to 5. In general formula (C-1), R 3 The non-polar groups in each of the formulas are independently an alkyl group, Examples of the alkyl group include an aryl group and an aralkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, etc., the aryl group is preferably a phenyl group, etc., and the aralkyl group is preferably a benzyl group, etc. In general formula (C-1), j is 1 or more and 10 or less, and from the viewpoint of preferably forming a bonding layer having a flexible skeleton that preferably contributes to suppressing warpage of the substrate, the lower limit of j is preferably 1 or more. From the viewpoint of facilitating the formation of a uniform coating film with little phase separation, the upper limit of j is preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.

[0053] From the viewpoint of suitably forming a bonding layer having a flexible skeleton that favorably contributes to suppressing warpage of the substrate, the siloxane compound (C) preferably has a longest straight chain (excluding hydrogen atoms and side chain atoms) with a number of atoms of 7 or more and 50 or less. From the viewpoint of suitably forming a bonding layer having a flexible skeleton that favorably contributes to suppressing warpage of the substrate, the longest straight chain (excluding hydrogen atoms) with a number of atoms of 8 or more is preferable, and 10 or more is more preferable. From the viewpoint of facilitating the formation of a uniform coating with little phase separation, the upper limit of the number of atoms of the longest straight chain (excluding hydrogen atoms) is preferably 30 or less, and more preferably 20 or less. In the case of general formula (C-1), R 1 When R is an alkyl group, the longest linear chain is 1 -NR 2 -Si-(O-Si) j -R 2 -NR 1 is the number of atoms in 1 The longest linear chain when is a hydrogen atom is NR 2 -Si-(O-Si) j -R 2 - is the number of N atoms.

[0054] The siloxane compound (C) may be, for example, a compound represented by the following general formula (C-2).

[0055] [ka]

[0056] In general formula (C-2), R 1 each independently represents a hydrogen atom or an optionally substituted alkyl group, R 3 each independently represents a non-polar group, i represents an integer of 0 to 4, and j represents an integer of 1 or more and 10 or less.

[0057] In formula (C-2), each i is preferably an integer of 0 to 2, more preferably 0 or 1, and even more preferably 0. R in general formula (C-2) 1 , R3 A preferred embodiment of j is R 1 , R 3 The same as the preferred embodiments of and j.

[0058] The siloxane compound (C) is, for example, 1,3-bis(3-aminopropyl)tetramethyldisiloxane (in general formula (C-2), R 1 is a hydrogen atom, R 3 is a methyl group, i=0, j=1), 1,3-bis(2-aminoethylamino)propyltetramethyldisiloxane (in general formula (C-2), R 1 is a hydrogen atom, R 3 is a methyl group, i=1, j=1). The siloxane compound (C) may be used alone or in combination of two or more kinds.

[0059] The composition for forming a semiconductor film of the present disclosure comprises a silane compound (B) and a siloxane compound (C). When the resin composition contains the compound (C), from the viewpoint of suppressing warpage, the molar ratio of the siloxane compound (C) to the silane compound (B) is preferably 0.01 or more, more preferably 0.1 or more, and even more preferably 0.2 or more. From the viewpoint of bonding strength, the molar ratio of the siloxane compound (C) to the silane compound (B) is preferably 10 or less, more preferably 5 or less.

[0060] When the composition for forming a semiconductor film of the present disclosure contains a silane compound (B) and a siloxane compound (C), from another viewpoint, for example, from the viewpoint of easily suppressing contamination of an apparatus when forming a semiconductor film, the molar ratio of the siloxane compound (C) to the silane compound (B) is preferably 1 or less, more preferably 0.5 or less, more preferably 0.1 or less, and even more preferably 0.

[0061] (Crosslinking agent (D)) The composition for forming a semiconductor film of the present disclosure contains a crosslinking agent (D) having three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, of which one to six of the three or more -C(=O)OX groups (hereinafter also referred to as "COOX") are -C(=O)OH groups (hereinafter also referred to as "COOH"), and having a weight average molecular weight of 200 to 2000.

[0062] From the viewpoint of obtaining a highly smooth film with few aggregates and pits when the composition of the present disclosure is applied to a member to form a film, the crosslinking agent (D) is a compound containing three or more -C(=O)OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, and may be a compound containing three to six -C(=O)OX groups in the molecule, or may be a compound containing three or four -C(=O)OX groups in the molecule. From the viewpoint of improving heat resistance, the crosslinking agent (D) is preferably a compound containing four to six -C(=O)OX groups in the molecule. From the viewpoint of reducing moisture absorption and outgassing, the crosslinking agent (D) is preferably a compound containing four -C(=O)OX groups in the molecule.

[0063] In the crosslinking agent (D), X in the -C(=O)OX group may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and among these, a hydrogen atom, a methyl group, an ethyl group, or a propyl group is preferred. Note that X in the -C(=O)OX group may be the same or different.

[0064] The crosslinking agent (D) is a compound containing one to six -C(=O)OH groups in which X is a hydrogen atom in the molecule, preferably a compound containing one to four -C(=O)OH groups in the molecule, more preferably a compound containing two to four -C(=O)OH groups in the molecule, and even more preferably a compound containing two or three -C(=O)OH groups in the molecule.

[0065] The crosslinking agent (D) is a compound having a weight average molecular weight of 200 or more and 2000 or less. The weight average molecular weight of the crosslinking agent (D) is preferably 200 or more and 1000 or less, more preferably 200 or more and 600 or less, and even more preferably 200 or more and 400 or less.

[0066] The crosslinking agent (D) preferably contains a ring structure in the molecule. Examples of the ring structure include an alicyclic structure and an aromatic ring structure. The crosslinking agent (D) may contain multiple ring structures in the molecule, and the multiple ring structures may be the same or different.

[0067] Examples of the alicyclic structure include an alicyclic structure having from 3 to 8 carbon atoms, preferably from 4 to 6 carbon atoms, and the ring structure may be saturated or unsaturated. More specific examples of the alicyclic structure include saturated alicyclic structures such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, and a cyclooctane ring; and unsaturated alicyclic structures such as a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, a cycloheptene ring, and a cyclooctene ring.

[0068] The aromatic ring structure is not particularly limited as long as it is a ring structure that exhibits aromaticity. For example, Examples of aromatic rings include benzene-based aromatic rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a perylene ring; aromatic heterocycles such as a pyridine ring and a thiophene ring; and non-benzene-based aromatic rings such as an indene ring and an azulene ring.

[0069] The ring structure contained in the molecule of the crosslinking agent (D) is preferably 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, and from the viewpoint of further improving the heat resistance of the bonding layer obtained from the composition for forming a semiconductor film, at least one of a benzene ring and a naphthalene ring is more preferred.

[0070] As described above, the crosslinking agent (D) may contain multiple ring structures in the molecule, and when the ring structure is benzene, it may contain a biphenyl structure, a benzophenone structure, a diphenyl ether structure, or the like.

[0071] The crosslinking agent (D) preferably contains a fluorine atom in the molecule, more preferably contains 1 to 6 fluorine atoms in the molecule, and even more preferably contains 3 to 6 fluorine atoms in the molecule. For example, the crosslinking agent (D) may contain a fluoroalkyl group in the molecule, and specifically may contain a trifluoroalkyl group or a hexafluoroisopropyl group.

[0072] Examples of the crosslinking agent (D) include carboxylic acid compounds such as alicyclic carboxylic acids, benzenecarboxylic acids, naphthalenecarboxylic acids, diphthalic acids, and fluorinated aromatic carboxylic acids; and carboxylic acid ester compounds such as alicyclic carboxylic acid esters, benzenecarboxylic acid esters, naphthalenecarboxylic acid esters, diphthalic acid esters, and fluorinated aromatic carboxylic acid esters. The carboxylic acid ester compound is a compound containing a carboxy group (—C(═O)OH group) in the molecule, and three or more —C(═O)OX groups, where at least one X is an alkyl group having 1 to 6 carbon atoms (i.e., containing an ester bond). In the composition for forming a semiconductor film of the present disclosure, the crosslinking agent (D) is a carboxylic acid ester compound, which inhibits aggregation due to association between the crosslinking agent (D) and the aliphatic diamine (A), the silane compound (B) and the siloxane compound (C) that are optionally included in the composition. This tends to reduce aggregates and pits, and also tends to facilitate the formation of a bonding layer with excellent smoothness and the adjustment of the thickness of the bonding layer.

[0073] The carboxylic acid compound is preferably a tetravalent or less carboxylic acid compound containing four or less -C(=O)OH groups, and more preferably a trivalent or tetravalent carboxylic acid compound containing three or four -C(=O)OH groups.

[0074] The carboxylic acid ester compound is preferably a compound containing one to three carboxy groups (-C(=O)OH groups) and one to three ester bonds in the molecule, and more preferably a compound containing one or two carboxy groups and one or two ester bonds in the molecule.

[0075] In the carboxylic acid ester compound, when X is an alkyl group having 1 to 6 carbon atoms in three or more -C(=O)OX groups, X is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or the like, and is preferably an ethyl group or a propyl group from the viewpoint of further suppressing aggregation due to association between the aliphatic diamine (A), the silane compound (B) and the siloxane compound (C) contained as needed, and the crosslinking agent (D) in the composition.

[0076] Specific examples of the carboxylic acid compound include, but are not limited to, alicyclic carboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; benzenecarboxylic acids such as 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, 3,4'-biphthalic acid, p-phenylenebis(trimellitate acid), benzenepentacarboxylic acid, and mellitic acid; 1,4 Naphthalene carboxylic acids such as 2,3,6,7-naphthalene tetracarboxylic acid, 3,3',5,5'-tetracarboxydiphenylmethane, biphenyl-3,3',5,5'-tetracarboxylic acid, biphenyl-3,4',5-tricarboxylic acid, biphenyl-3,3',4,4'-tetracarboxylic acid, benzophenone-3,3',4,4'-tetracarboxylic acid, 4,4'-oxydiphthalic acid, 3,4'-oxydiphthalic acid, 1,3-bis(phthalic acid) tetramethyldisiloxane, 4,4'-(ethyn-1,2-diyl)diphthalic acid diphthalic acids such as 4,4'-(1,4-phenylenebis(oxy))diphthalic acid, 4,4'-([1,1'-biphenyl]-4,4'-diylbis(oxy))diphthalic acid, and 4,4'-((oxybis(4,1-phenylene))bis(oxy))diphthalic acid; perylene carboxylic acids such as perylene-3,4,9,10-tetracarboxylic acid; and anthracene carboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid;Examples of fluorinated aromatic carboxylic acids include 4,4'-(hexafluoroisopropylidene)diphthalic acid, 9,9-bis(trifluoromethyl)-9H-xanthene-2,3,6,7-tetracarboxylic acid, and 1,4-ditrifluoromethylpyromellitic acid.

[0077] Specific examples of the carboxylic acid ester compound include compounds in which at least one carboxy group in the specific examples of the carboxylic acid compound described above is substituted with an ester group. Examples of the carboxylic acid ester compound include half-esterified compounds represented by the following general formulas (D-1) to (D-5).

[0078] [ka]

[0079] In the general formulae (D-1) to (D-5), R is an alkyl group having 1 to 6 carbon atoms, and among these, a methyl group, an ethyl group, a propyl group, and a butyl group are preferred, and an ethyl group and a propyl group are more preferred. In general formula (D-2), Y is a single bond, O, C=O, or C(CF3)2. As the carboxylic acid ester compound, in order to facilitate smoothing of the surface of the semiconductor film to be formed, a half-esterified compound represented by general formula (C-2) is preferred, and a half-esterified compound in which Y in general formula (C-2) is O is more preferred.

[0080] The half-esterified compound can be produced, for example, by mixing a carboxylic acid anhydride, which is an anhydride of the above-mentioned carboxylic acid compound, with an alcohol solvent and ring-opening the carboxylic acid anhydride.

[0081] The ratio of the content of the crosslinking agent (D) to the total content of the components having an amino group contained in the composition for forming a semiconductor film, component having an amino group / crosslinking agent (D), is not particularly limited. For example, from the viewpoint of suppressing gelation of the composition and balancing the crosslinking reaction, the molar ratio of component having an amino group / crosslinking agent (D) is preferably 0.1 or more and 10 or less, more preferably 0.2 or more and 5 or less, and even more preferably 0.4 or more and 2.5 or less.

[0082] In a composition for forming a semiconductor film, the ratio of the number of -C(=O)OH groups in the crosslinking agent (D) to the total number of amino groups in the component having an amino group, COOH / amino group, is preferably 0.3 to 3.0, more preferably 0.5 to 2.0, from the viewpoint of suppressing gelation of the composition. The amino group in the above COOH / amino group means an amino group capable of reacting with a —C(═O)OH group, and refers to at least one of a primary amino group and a secondary amino group.

[0083] The ratio of the number of -C(=O)OX groups in the crosslinking agent (D) to the total number of amino groups in the amino group-containing components contained in the composition for forming a semiconductor film, COOX / amino groups, is preferably 0.1 to 5.0, more preferably 0.1 to 3.0, even more preferably 0.3 to 2.5, and particularly preferably 0.4 to 2.2. When the COOX / amino group ratio is 0.1 to 5.0, a crosslinked structure such as amide, amide-imide, or imide is formed between the amino group-containing component, such as the aliphatic diamine (A), and the crosslinking agent (D) after heat treatment of the composition for forming a semiconductor film, and a bonding layer with excellent heat resistance and insulating properties can be suitably produced. The amino group in COOX / amino group means an amino group capable of reacting with a —C(═O)OH group, and refers to at least one of a primary amino group and a secondary amino group.

[0084] (Other amino group-containing components) The composition for forming a semiconductor film according to the present disclosure may contain, as a component other than the aliphatic amine (A), the silane compound (B), the siloxane compound (C), and the crosslinking agent (D), another amino group-containing component, which is a component containing an amino group.

[0085] Examples of other amino group-containing components include acyclic aliphatic amines other than the aliphatic amine (A) and cyclic amines.

[0086] Examples of the acyclic aliphatic amine other than the aliphatic amine (A) include aliphatic amines having a weight average molecular weight of 10,000 or more and 400,000 or less.

[0087] The aliphatic amine having a weight-average molecular weight of 10,000 to 400,000 preferably contains at least one of a primary amino group and a secondary amino group. Specific examples of the aliphatic amine having a weight-average molecular weight of 10,000 to 400,000 include polyalkyleneimines, which are polymers of alkyleneimines such as ethyleneimine, propyleneimine, butyleneimine, pentyleneimine, hexyleneimine, heptyleneimine, octyleneimine, trimethyleneimine, tetramethyleneimine, pentamethyleneimine, hexamethyleneimine, and octamethyleneimine; polyallylamine; and polyacrylamide.

[0088] Polyethyleneimine (PEI) can be produced by known methods described in Japanese Patent Publication Nos. 43-8828, 49-33120, JP 2001-2123958 A, WO 2010 / 137711, etc. Polyalkyleneimines other than polyethyleneimine can also be produced by the same methods as polyethyleneimine.

[0089] The aliphatic amine having a weight-average molecular weight of 10,000 to 400,000 is also preferably a derivative of the above-mentioned polyalkyleneimine (a polyalkyleneimine derivative; particularly preferably a polyethyleneimine derivative). The polyalkyleneimine derivative is not particularly limited as long as it is a compound that can be produced using the above-mentioned polyalkyleneimine. Specific examples include polyalkyleneimine derivatives obtained by introducing an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) or an aryl group into a polyalkyleneimine, and polyalkyleneimine derivatives obtained by introducing a crosslinkable group such as a hydroxyl group into a polyalkyleneimine. These polyalkyleneimine derivatives can be produced using the above-mentioned polyalkyleneimines by a method commonly used, specifically, for example, by the method described in JP-A-6-016809.

[0090] Examples of the cyclic amine other than the aliphatic amine (A) include alicyclic amines other than the aliphatic amine (A), aromatic ring amines, and heterocyclic (heterocyclic) amines. The cyclic amine may contain multiple ring structures in the molecule, and the multiple ring structures may be the same or different. The cyclic amine is preferably an aromatic ring amine, since it is easier to obtain a thermally stable compound. The cyclic amine is preferably an amine compound containing a ring structure in the molecule and having a weight average molecular weight of 90 or more and 600 or less.

[0091] Examples of the alicyclic amine other than the aliphatic amine (A) include cyclohexylamine and dimethylaminocyclohexane. Examples of aromatic ring amines include diaminodiphenyl ether, xylylenediamines such as paraxylenediamine, diaminobenzene, diaminotoluene, methylenedianiline, dimethyldiaminobiphenyl, bis(trifluoromethyl)diaminobiphenyl, diaminobenzophenone, diaminobenzanilide, bis(aminophenyl)fluorene, bis(aminophenoxy)benzene, bis(aminophenoxy)biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcinol, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2′-dimethylbenzidine, and tris(4-aminophenyl)amine. Examples of the heterocyclic ring of the heterocyclic amine include a heterocyclic ring containing a sulfur atom as a heteroatom (e.g., a thiophene ring), and a heterocyclic ring containing a nitrogen atom as a heteroatom (e.g., a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, or a triazole ring; a 6-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, or a triazine ring; and a fused ring such as an indole ring, an indoline ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, a purine ring, or a quinoxaline ring). For example, heterocyclic amines containing a nitrogen-containing heterocycle include melamine, ammeline, melam, melem, tris(4-aminophenyl)amine, and the like. Furthermore, examples of amine compounds containing both a heterocycle and an aromatic ring include N2,N4,N6-tris(4-aminophenyl)-1,3,5-triazine-2,4,6-triamine.

[0092] In the composition for forming a semiconductor film of the present disclosure, the molar ratio of the other amino group-containing component to the aliphatic amine (A), or the aliphatic amine (A), the silane compound (B), and the siloxane compound (C), i.e., "other amino group-containing component / aliphatic amine (A), or other amino group-containing component / [aliphatic amine (A), the silane compound (B), and the siloxane compound (C)]", may be, for example, 0 to 0.5, 0 to 0.3, or 0 to 0.1.

[0093] (Polar solvent (E)) The composition for forming a semiconductor film of the present disclosure may contain a polar solvent (E), where the polar solvent (E) refers to a solvent having a relative dielectric constant of 5 or more at room temperature. Specific examples of polar solvents (E) include protic inorganic compounds such as water and heavy water; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, and glycerin; ethers such as tetrahydrofuran and dimethoxyethane; aldehydes and ketones such as furfural, acetone, ethyl methyl ketone, and cyclohexane; 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 and propionitrile; nitro compounds such as nitromethane and nitrobenzene; and sulfur compounds such as dimethyl sulfoxide. The polar solvent (E) preferably contains a protic solvent, more preferably contains water, and further preferably contains ultrapure water. The content of the polar solvent (E) in the composition for forming a semiconductor film is not particularly limited, and may be, for example, 1.0 mass% or more and 99.99896 mass% or less, or 40 mass% or more and 99.99896 mass% or less, based on the total mass of the composition. The boiling point of the polar solvent (E) is preferably 150°C or less, and more preferably 120°C or less, from the viewpoint of volatilizing the polar solvent (E) by drying when forming the bonding layer and reducing the amount of residual solvent in the bonding layer.

[0094] (Additive (F)) The composition for forming a semiconductor film according to the present disclosure may contain an additive (F) in addition to the aliphatic amine (A), the silane compound (B), the siloxane compound (C), the crosslinking agent (D), and the polar solvent (E). Examples of the additive (F) include an acid (F-1) containing a carboxy group and having a weight average molecular weight of 46 to 195, and a base (F-2) containing a nitrogen atom and having a weight average molecular weight of 17 to 120.

[0095] The acid (F-1) is a carboxyl-containing acid having a weight-average molecular weight of 46 or more and 195 or less. By including the acid (F-1) as the additive (F), the composition for forming a semiconductor film of the present disclosure is presumed to suppress aggregation due to association between the aliphatic amine (A), the silane compound (B) that is included as needed, the siloxane compound (C), etc. and the carboxyl group in the acid (F-1) by forming an ionic bond. More specifically, it is presumed that aggregation is suppressed because the interaction (e.g., electrostatic interaction) between the ammonium ions derived from amino groups in the aliphatic diamine (A), the silane compound (B) that is included as needed, the siloxane compound (C), etc., and the carboxylate ions derived from carboxy groups in the acid (F-1) is stronger than the interaction between the ammonium ions derived from amino groups in the aliphatic diamine (A), the silane compound (B) that is included as needed, the siloxane compound (C), etc., and the carboxylate ions derived from carboxy groups in the crosslinker (D). Note that the embodiments disclosed in relation to the present invention are in no way limited by the above presumption.

[0096] The acid (F-1) is not particularly limited as long as it contains a carboxy group and has a weight-average molecular weight of 46 to 195, and examples thereof include monocarboxylic acid compounds, dicarboxylic acid compounds, and oxydicarboxylic acid compounds. More specific examples of the acid (F-1) include 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, picolinic acid, salicylic acid, and 3,4,5-trihydroxybenzoic acid.

[0097] In the present disclosure, the content of the acid (F-1) in the composition for forming a semiconductor film is not particularly limited, and for example, the ratio of the number of carboxy groups in the acid (F-1) to the total number of amino groups in the component having an amino group (COOH / amino group) is preferably 0.01 or more and 10 or less, more preferably 0.02 or more and 6 or less, and even more preferably 0.5 or more and 3 or less.

[0098] The base (F-2) is a nitrogen-containing base having a weight-average molecular weight of 17 to 120. It is believed that the composition for forming a semiconductor film of the present disclosure contains the base (F-2) as an additive (F), and thus the carboxy groups in the crosslinker (D) and the amino groups in the base (F-2) form ionic bonds, thereby suppressing aggregation due to association between the crosslinker (D) and the aliphatic diamine (A), the optional silane compound (B), the siloxane compound (C), etc. More specifically, it is believed that the interaction between the carboxylate ions derived from the carboxy groups in the crosslinker (D) and the ammonium ions derived from the amino groups in the base (F-2) is stronger than the interaction between the ammonium ions derived from the amino groups in the aliphatic diamine (A), the optional silane compound (B), the siloxane compound (C), etc., and the carboxylate ions derived from the carboxy groups in the crosslinker (D), thereby suppressing aggregation. It should be noted that the various aspects disclosed herein are in no way limited by the above speculation.

[0099] The base (F-2) is not particularly limited as long as it contains a nitrogen atom and has a weight-average molecular weight of 17 to 120, and examples thereof include monoamine compounds and diamine compounds. More specific examples of the base (F-2) include ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N-(2-aminoethyl)ethanolamine, and N-(2-aminoethyl)glycine.

[0100] In the present disclosure, the content of the base (F-2) in the composition for forming a semiconductor film is not particularly limited, and for example, the ratio (N / COOH) of the number of nitrogen atoms in the base (F-2) to the number of carboxy groups in the crosslinking agent (D) is preferably 0.5 or more and 5 or less, more preferably 0.9 or more and 3 or less.

[0101] When insulating properties are required for the bonding layer of the substrate laminate of the present disclosure, from the viewpoint of improving insulating properties or mechanical strength, the composition for forming a semiconductor film of the present disclosure may contain tetraethoxysilane, tetramethoxysilane, bistriethoxysilylethane, bistriethoxysilylmethane, bis(methyldiethoxysilyl)ethane, 1,1,3,3,5,5-hexaethoxy-1,3,5-trisilacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydroxylcyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxydisilethylene, or 1,3,5-trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-trisilacyclohexane. The composition for forming a semiconductor film of the present disclosure may contain methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, etc. to improve the hydrophobicity of the insulating bonding layer. The composition for forming a semiconductor film of the present disclosure may contain these compounds to control etching selectivity.

[0102] The composition for forming a semiconductor film of the present disclosure may contain a solvent other than the polar solvent (E), such as normal hexane.

[0103] Furthermore, the composition for forming a semiconductor film according to the present disclosure may contain phthalic acid, benzoic acid, or the like, or a derivative thereof, for example, to improve electrical properties. The composition for forming a semiconductor film of the present disclosure may also contain benzotriazole or a derivative thereof, for example, to inhibit copper corrosion.

[0104] The pH of the composition for forming a semiconductor film of the present disclosure is not particularly limited, but is preferably 2.0 or more and 12.0 or less.

[0105] <Method of manufacturing a composition for forming a semiconductor film> A method for producing a composition for forming a semiconductor film according to the present disclosure will be described below. The method for producing a composition for forming a semiconductor film according to the present disclosure includes a mixing step of mixing an aliphatic diamine (A) and a crosslinking agent (D). In the mixing step, a silane compound (B), a siloxane compound (C), a polar solvent (E), an additive (F), etc. may also be mixed. The timing of adding each component in the mixing step is not particularly limited.

[0106] In the method for producing a composition for forming a semiconductor film according to the present disclosure, at least one additive (F) selected from the group consisting of a carboxyl-containing acid (F-1) having a weight-average molecular weight of 46 to 195 and a nitrogen-containing base (F-2) having a weight-average molecular weight of 17 to 120 may be added to the aliphatic diamine (A), and optionally the silane compound (B) or siloxane compound (C) (hereinafter also referred to as "aliphatic amine (A) etc."), or crosslinker (D) in the mixing step. The timing of adding the additive (F) is not particularly limited.

[0107] Furthermore, when an acid (F-1) is added as the additive (F), the mixing step is preferably a step of mixing a mixture of the acid (F-1) and the aliphatic diamine (A) with the crosslinking agent (D). That is, it is preferable to premix the aliphatic diamine (A) with the acid (F-1) before mixing the aliphatic diamine (A) with the crosslinking agent (D). This makes it possible to suitably suppress clouding and gelation of the composition when the aliphatic diamine (A) and the crosslinking agent (D) are mixed (for example, gelation may undesirably cause a long time for the composition to become transparent).

[0108] Furthermore, when a base (F-2) is added as the additive (F), the mixing step is preferably a step of mixing a mixture of the base (F-2) and the crosslinking agent (D) with the aliphatic diamine (A) and the like. That is, it is preferable to premix the crosslinking agent (D) with the base (F-2) before mixing the aliphatic diamine (A) and the like with the crosslinking agent (D). This makes it possible to suitably suppress clouding and gelation of the composition when the aliphatic diamine (A) and the like are mixed with the crosslinking agent (D) (for example, gelation may undesirably cause a long time for the composition to become transparent).

[0109] [Laminate] The laminate of the present disclosure is formed by laminating a substrate and a bonding layer formed from the composition for forming a semiconductor film of the present disclosure. In the laminate of the present disclosure, the composition for forming a semiconductor film is used to form the bonding layer. As a result, warping of the substrate is suppressed in the laminate of the present disclosure. The laminate of the present disclosure is used, for example, to bond a substrate included in the laminate to another member such as another substrate via a bonding layer.

[0110] (substrate) The material of the substrate is not particularly limited, and may be any material that is commonly used as a semiconductor substrate or the like. The substrate preferably contains at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb. Examples of substrate materials include semiconductors such as Si, InP, GaN, GaAs, InGaAs, InGaAlAs, and SiC; oxides, carbides, and nitrides such as borosilicate glass (Pyrex (registered trademark)), quartz glass (SiO2), sapphire, ZrO2, Si3N4, and AlN; piezoelectrics and dielectrics such as BaTiO3, LiNbO3, SrTiO3, and diamond; and metals such as Al, Ti, Fe, Cu, Ag, Au, Pt, Pd, Ta, and Nb.

[0111] The substrate may also be made of other materials such as polydimethylsiloxane (PDMS), epoxy resin, phenol resin, polyimide, benzocyclobutene resin, polybenzoxazole, and the like.

[0112] The substrate may have a multi-layer structure. For example, a silicon substrate or the like may have a surface layer of silicon oxide, nitride, or the like. Examples of such structures include a structure in which an inorganic layer such as silicon or SiCN (silicon carbonitride) is formed, a structure in which an organic layer such as a polyimide resin, polybenzoxazole resin, epoxy resin, or benzocyclobutene resin such as Cyclotene (registered trademark) is formed on the surface of a silicon substrate, and a structure in which a composite of an inorganic material and an organic material is formed on a silicon substrate.

[0113] The uses of the substrate based on the material are as follows, for example: Si: semiconductor memory, LSI stacking, CMOS image sensors, MEMS encapsulation, optical devices, LEDs, etc.; SiO2 is used in semiconductor memory, LSI stacking, MEMS sealing, microfluidics, CMOS image sensors, optical devices, LEDs, etc.; PDMS microchannels; InGaAlAs, InGaAs, InP optical devices; InGaAlAs, GaAs, and GaN are used in LEDs, etc.

[0114] The thickness of the substrate is preferably 0.5 μm to 1 mm, more preferably 1 μm to 900 μm, and even more preferably 2 μm to 900 μm.

[0115] The shape of the substrate is not particularly limited. For example, when the substrate is a silicon substrate, it may be a silicon substrate on which an interlayer insulating layer (low-k film) is formed, and the silicon substrate may have fine grooves (recesses), fine through-holes, etc. formed therein.

[0116] For example, the laminate of the present disclosure can be produced by a laminate production method including a step of applying the composition for forming a semiconductor film of the present disclosure onto the surface of a substrate. The laminate production method may, as necessary, include a step of heating, drying, or the like, the composition for forming a semiconductor film applied to the substrate after the step of applying the composition for forming a semiconductor film.

[0117] Methods for applying the composition for forming a semiconductor film of the present disclosure to the surface of a substrate include, for example, vapor phase deposition methods such as vapor deposition polymerization, CVD (chemical vapor deposition), and ALD (atomic layer deposition), and coating methods such as dipping, spraying, spin coating, and bar coating. When applying the composition for forming a semiconductor film by a coating method, it is preferable to apply the composition for forming a semiconductor film in a solution state. For example, when forming a film with a micron-sized thickness, it is preferable to use bar coating, and when forming a film with a nano-sized thickness (several nm to several hundred nm), it is preferable to use spin coating. The thickness of the composition for forming a semiconductor film can be adjusted appropriately depending on the intended thickness of the bonding layer.

[0118] For example, the method of applying a composition for forming a semiconductor film by spin coating is not particularly limited, and for example, a method can be used in which the composition for forming a semiconductor film is dropped onto the surface of a substrate while the substrate is being rotated by a spin coater, and then the rotation speed of the substrate is increased to dry the substrate. In the method of applying a composition for forming a semiconductor film by spin coating, various conditions such as the rotation speed of the substrate, the viscosity of the composition for forming a semiconductor film, the amount and time of dropping, and the rotation speed of the substrate during drying are not particularly limited, and may be appropriately adjusted taking into consideration the thickness of the composition for forming the semiconductor film to be formed, etc.

[0119] In order to remove excess of the applied composition from a substrate to which the composition for forming a semiconductor film has been applied, the substrate to which the composition for forming a semiconductor film has been applied may be washed. Examples of the washing method include wet washing with a rinse liquid such as a polar solvent, plasma cleaning, etc.

[0120] <Electrode formation 1> The substrate may have an electrode on the surface onto which the composition for forming a semiconductor film is applied. For example, before the composition for forming a semiconductor film is applied to the substrate, an electrode may be formed on the surface onto which the composition for forming a semiconductor film is applied. The electrodes may be formed in a convex shape on the surface of the substrate, may be formed so as to penetrate the substrate, or may be formed so as to be embedded in the substrate. When an electrode is provided on the surface to which the composition for forming a semiconductor film is applied, and when the composition for forming a semiconductor film is applied to the surface of the substrate having the electrode, it is preferable to form the electrode in a convex shape on the surface of the substrate. Even if the substrate has an electrode on its surface, when the composition for forming a semiconductor film is not applied to the surface of the substrate having the electrode, the electrode on the substrate surface may have any shape.

[0121] <Electrode formation 2> After the bonding layer is formed on the substrate, an electrode may be formed on the surface on which the bonding layer is formed. For example, a hole in which an electrode is to be formed may be formed in the bonding layer by dry etching, and the electrode may be formed in the formed hole.

[0122] <Electrode formation 3> When the composition for forming a semiconductor film has photosensitivity, holes in which electrodes will be formed may be formed by photolithography in the composition for forming a semiconductor film applied to a substrate, and after a step of forming a bonding layer by drying, heating, or the like of the composition for forming a semiconductor film as necessary, an electrode may be formed in the formed hole.

[0123] Examples of materials for the electrodes include copper, solder, tin, gold, silver, and aluminum. In the above-mentioned electrode formation 1 to 3, examples of the method for forming the electrodes include electrolytic plating, electroless plating, sputtering, and inkjet method.

[0124] When a composition for forming a semiconductor film is applied to an electrode, the composition for forming a semiconductor film on the electrode may be removed. This removes the composition for forming a semiconductor film applied to the electrode surface, exposing the electrode. Examples of methods for removing a composition for forming a semiconductor film applied to the electrode surface include fly-cutting, chemical mechanical polishing (CMP), and plasma dry etching. One method may be used alone, or two or more methods may be used in combination. For example, in the fly-cutting method, a surface planer (DFS8910 (manufactured by Disco Corporation)) or the like may be used. When using CMP, the slurry may be, for example, a slurry containing silica or alumina, which is commonly used for polishing resins, or a slurry containing hydrogen peroxide and silica, which is commonly used for polishing metals. When using plasma dry etching, fluorocarbon plasma, oxygen plasma, or the like may be used.

[0125] When the bonding layer on the electrode surface is removed to expose the electrode, the oxide on the electrode surface may be reduced as needed. The reduction method includes heating the substrate in an acid atmosphere such as formic acid at 100 to 300°C, or heating the substrate in a hydrogen atmosphere.

[0126] (Joining layer) In the laminate of the present disclosure, the bonding layer formed on the substrate may be uncured, semi-cured, or cured. The cured state of the bonding layer may be adjusted by the degree to which the composition for forming a semiconductor film applied to the substrate is dried, heated, or the like.

[0127] In the laminate of the present disclosure, the bonding layer may be cured. For example, a cured bonding layer can be formed by heating a composition for forming a semiconductor film applied to the surface of a substrate. The heating conditions for forming the cured bonding layer are described below.

[0128] The heating temperature of the composition for forming a semiconductor film applied to the surface of the substrate is preferably 100°C to 450°C, more preferably 150°C to 450°C, and even more preferably 180°C to 400°C. The above temperature refers to the temperature of the surface of the composition for forming a semiconductor film applied onto the surface. By heating the composition for forming a semiconductor film, the solvent in the composition for forming a semiconductor film is removed, and the components in the composition for forming a semiconductor film react to obtain a cured product, and a bonding layer containing the cured product is formed.

[0129] There is no particular limitation on the pressure when the composition for forming a semiconductor film is heated, but an absolute pressure of 17 Pa or greater and equal to or less than atmospheric pressure is preferred. The absolute pressure is more preferably 1000 Pa or more and equal to or less than atmospheric pressure, further preferably 5000 Pa or more and equal to or less than atmospheric pressure, and particularly preferably 10000 Pa or more and equal to or less than atmospheric pressure.

[0130] The composition for forming a semiconductor film can be heated by a conventional method using a furnace or a hot plate, such as an SPX-1120 furnace manufactured by APEX Corporation or a VF-1000LP furnace manufactured by Koyo Thermo Systems Co., Ltd. Furthermore, the composition for forming a semiconductor film may be heated in an air atmosphere or in an inert gas atmosphere (nitrogen gas, argon gas, helium gas, etc.).

[0131] The heating time of the composition for forming a semiconductor film applied to the surface of the substrate is not particularly limited, and is, for example, 3 hours or less, preferably 1 hour or less. The lower limit of the heating time is not particularly limited, and can be, for example, 5 minutes.

[0132] To shorten the heating time, the composition for forming a semiconductor film applied to the surface of the substrate may be irradiated with ultraviolet (UV) light. Preferred examples of ultraviolet light include ultraviolet light with a wavelength of 170 nm to 230 nm, excimer light with a wavelength of 222 nm, and excimer light with a wavelength of 172 nm. It is also preferred to irradiate the composition with ultraviolet light in an inert gas atmosphere.

[0133] Whether or not a composition for forming a semiconductor film has cured can be confirmed, for example, by measuring the peak intensity of specific bonds and structures by Fourier transform infrared spectroscopy (FT-IR). Examples of specific bonds and structures include bonds and structures generated by a crosslinking reaction. For example, when an amide bond, an imide bond, or the like is formed, it can be determined that the composition for forming a semiconductor film has cured, and this can be confirmed by measuring the peak intensity resulting from these bonds, structures, or the like using FT-IR. The amide bond is at approximately 1650 cm -1 and approximately 1520 cm -1 This can be confirmed by the presence of a vibration peak. The imide bond is at approximately 1770 cm -1 and approximately 1720 cm -1 This can be confirmed by the presence of a vibration peak.

[0134] The surface of the hardened bonding layer may be planarized. Examples of planarization methods include fly-cutting and chemical mechanical polishing (CMP). One planarization method may be used alone, or two or more methods may be used in combination.

[0135] The bonding layer formed on the substrate preferably has functional groups capable of forming chemical bonds on the surface of the bonding layer opposite the substrate, from the viewpoint of increasing the bonding strength between the substrate and other components, such as other substrates. Examples of such functional groups include amino groups, epoxy groups, vinyl groups, and silanol groups (Si-OH groups). From the viewpoint of heat resistance, silanol groups are preferred. These functional groups may be formed by surface treatment after the formation of the bonding layer, or by treatment with a silane coupling agent. Alternatively, compounds containing these functional groups may be mixed into a composition for forming a semiconductor film. Whether or not the surface of the bonding layer has silanol groups can be evaluated by surface analysis of the bonding layer using time-of-flight secondary ion mass spectrometry (TOF-SIMS). Specifically, using a TOF-SIMS PHI nanoTOFII (ULVAC-PHI, Inc.), whether or not the surface of the bonding layer has silanol groups can be evaluated based on the presence or absence of a peak with a mass-to-charge ratio (m / Z) of 45.

[0136] The thickness of the bonding layer is preferably 0.001 μm to 8.0 μm, more preferably 0.01 μm to 6.0 μm, and even more preferably 0.03 μm to 5.0 μm. When the thickness of the bonding layer is 0.001 μm or more, the bonding strength when bonding the substrate to another member via the bonding layer can be increased. When the thickness of the bonding layer is 8.0 μm or less, variations in the thickness of the bonding layer can be suppressed when the bonding layer is formed on a large-area substrate.

[0137] When an electrode is provided on the surface of the substrate on the bonding layer side, from the viewpoint of improving the bonding strength and suppressing variations in the thickness of the bonding layer, the thickness of the bonding layer is preferably 0.01 μm to 8.0 μm, more preferably 0.03 μm to 6.0 μm, and even more preferably 0.05 μm to 5.0 μm.

[0138] When no electrode is provided on the surface of the substrate facing the bonding layer, from the viewpoint of improving the bonding strength and suppressing variations in the thickness of the bonding layer, the thickness of the bonding layer is preferably 0.001 μm or more and less than 1.0 μm, more preferably 0.01 μm to 0.8 μm, and even more preferably 0.03 μm to 0.6 μm.

[0139] The bonding layer preferably contains sodium and potassium at an elemental content of 10 mass ppb or less, which can prevent problems with the electrical characteristics of the semiconductor device, such as transistor malfunctions.

[0140] [Substrate laminate] The substrate laminate of the present disclosure comprises a first substrate, a bonding layer formed from the composition for forming a semiconductor film of the present disclosure, and a second substrate laminated in this order. In the substrate laminate of the present disclosure, the first substrate and the second substrate are bonded via the bonding layer formed from the composition for forming the semiconductor film. This prevents the first substrate and the second substrate from misaligning when they are bonded together.

[0141] The substrate laminate of the present disclosure may be formed, for example, by bonding the above-described laminate of the present disclosure, which includes a substrate that is a first substrate and a bonding layer, to a second substrate via a bonding layer.

[0142] (First substrate and second substrate) The preferred materials and configurations of the first substrate and the second substrate are not particularly limited and are, for example, similar to the preferred materials and configurations of the substrates used in the laminate of the present disclosure described above. The materials and configurations of the first substrate and the second substrate may be independently the same or different. The first substrate and the second substrate may have an electrode on the surface to which the composition for forming a semiconductor film is applied or on the surface facing the bonding layer. The preferred configuration of the electrode is similar to the preferred configuration of the electrode in the laminate of the present disclosure described above.

[0143] As described above, the substrate preferably contains at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb, and in the laminate of the present disclosure, at least one of the first substrate and the second substrate is more preferably a semiconductor substrate containing at least one element selected from the group consisting of Si, Ga, Ge, and As.

[0144] In the substrate laminate of the present disclosure, at least one of the first substrate and the second substrate may have another substrate laminated on the surface opposite to the surface on the bonding layer side. Preferred materials for the other substrate are the same as those for the first substrate and the second substrate. The material of the other substrate may be the same as or different from that of at least one of the first substrate and the second substrate.

[0145] (Joining layer) In the substrate laminate of the present disclosure, the bonding layer disposed between the first substrate and the second substrate is preferably in a cured state. Other preferred forms of the bonding layer in the substrate laminate of the present disclosure are the same as the preferred forms of the bonding layer in the laminate of the present disclosure described above, and therefore description thereof will be omitted.

[0146] The substrate laminate of the present disclosure can be formed, for example, by the following method: An example of a method for manufacturing a substrate laminate of the present disclosure includes a step of applying a composition for forming a semiconductor film of the present disclosure onto a surface of at least one of a first substrate and a second substrate (hereinafter also referred to as a "first step"), and a step of bonding the first substrate and the second substrate via a bonding layer formed from the composition for forming a semiconductor film (hereinafter also referred to as a "second step").

[0147] A preferred embodiment of the first step is the same as the preferred embodiment of the method for applying the composition for forming a semiconductor film of the present disclosure onto the surface of a substrate in the laminate of the present disclosure described above.

[0148] In the second step, the composition for forming a semiconductor film applied to at least one surface of the first substrate and the second substrate may be at least partially cured by heating or the like to form a bonding layer, and then the first substrate and the second substrate may be bonded via the bonding layer; alternatively, the first substrate, the uncured bonding layer, and the second substrate may be stacked in this order, and then the stacked uncured bonding layer may be cured by heating or the like to form a bonding layer.

[0149] The heating conditions for heating the composition for forming a semiconductor film applied to the surface of at least one of the first substrate and the second substrate, and the preferred heating conditions for heating the laminated uncured bonding layer, are each independently the same as the preferred heating conditions for the composition for forming a semiconductor film applied to the surface of the substrate in the laminate of the present disclosure described above.

[0150] An example of a method for manufacturing a substrate laminate according to the present disclosure may further include a step (also referred to as a "surface treatment step") of forming at least one functional group selected from the group consisting of hydroxyl, epoxy, carboxy, amino, and mercapto groups by performing a surface treatment on the surface of at least one of the first and second substrates that comes into contact with the bonding layer, preferably the surfaces of the first and second substrates that come into contact with the bonding layer. This tends to increase the bonding strength between the substrates. In the laminate of the present disclosure, the surface of the substrate that comes into contact with the bonding layer may be subjected to a surface treatment.

[0151] Examples of surface treatments include plasma treatment, chemical treatment, and ozone treatment such as UV ozone treatment.

[0152] The hydroxyl groups can be provided on the surfaces of the first substrate and the second substrate by subjecting the surfaces of the substrate to surface treatment such as plasma treatment, chemical treatment, or ozone treatment such as UV ozone treatment. The hydroxyl group is preferably present in a state of being bonded to at least one element selected from the group consisting of Si, Al, Ti, Zr, Hf, Fe, Ni, Cu, Ag, Au, Ga, Ge, Sn, Pd, As, Pt, Mg, In, Ta, and Nb contained in the first substrate or the second substrate. In particular, it is more preferable that the surface of at least one of the first substrate and the second substrate on which the bonding layer is formed has a silanol group containing a hydroxyl group.

[0153] The epoxy groups can be provided on the surfaces of the first substrate and the second substrate by performing a surface treatment such as silane coupling using epoxy silane on the surfaces of the first substrate and the second substrate.

[0154] The carboxyl groups can be provided on the surfaces of the first substrate and the second substrate by performing a surface treatment such as silane coupling with carboxysilane on the surfaces of these substrates.

[0155] The amino groups can be provided on the surfaces of the first substrate and the second substrate by performing a surface treatment such as silane coupling with aminosilane on the surfaces of these substrates.

[0156] The mercapto groups can be provided on the surfaces of the first substrate and the second substrate by performing a surface treatment such as silane coupling with mercaptosilane on the surfaces of these substrates.

[0157] Furthermore, when a bonding layer is formed on both the first substrate and the second substrate, the above-mentioned surface treatment may be applied to at least one surface of the bonding layer in order to increase the bonding strength of the substrate laminate.

[0158] In addition, in order to increase the bonding strength of the substrate laminate, a primer such as a silane coupling agent may be formed on the surface of at least one of the first substrate and the second substrate to which the composition for forming a semiconductor film is applied, and if bonding layers are formed on both the first substrate and the second substrate, a primer such as a silane coupling agent may be formed on the surface of at least one of the bonding layers.

[0159] An example of the method for manufacturing a substrate laminate of the present disclosure may further include, after the second step, a step of performing thinning processing (backgrinding or back surface grinding) on ​​at least one of the first substrate and the second substrate, if necessary. Furthermore, an example of the method for manufacturing a substrate laminate according to the present disclosure may further include a step of dicing the substrate into individual pieces, as necessary, after the second step. For example, a dicer (DAD6340 (manufactured by Disco Corporation)) or the like can be used for the dicing step.

[0160] (Example of laminate structure of substrate laminate) Examples of the laminate structure of the substrate laminate for each application are shown below. For MEMS packaging; Si / junction layer / Si, SiO2 / junction layer / Si, SiO2 / junction layer / SiO2, Cu / junction layer / Cu, For microfluidic channels: PDMS / bonding layer / PDMS, PDMS / bonding layer / SiO2, For CMOS image sensors: SiO2 / bonding layer / SiO2, Si / bonding layer / Si, SiO2 / bonding layer / Si, For through silicon via (TSV); SiO2 (with Cu electrode) / bonding layer / SiO2 (with Cu electrode), Si (with Cu electrode) / bonding layer / Si (with Cu electrode), For optical devices: (InGaAlAs, InGaAs, InP, GaAs) / bonding layer / Si, For LEDs: (InGaAlAs, GaAs, GaN) / bonding layer / Si, (InGaAlAs, GaAs, GaN) / bonding layer / SiO2, (InGaAlAs, GaAs, GaN) / bonding layer / (Au, Ag, Al), (InGaAlAs, GaAs, GaN) / bonding layer / sapphire.

[0161] The substrate stack of the present disclosure may include multiple stacks. For example, the substrate laminate of the present disclosure may be a substrate laminate comprising a first laminate region formed by laminating, in this order, a first substrate, a bonding layer formed from the composition for forming a semiconductor film of the present disclosure, and a second substrate, and a second laminate region formed by laminating, in this order, the first substrate, an electrode, and the second substrate, with at least one first laminate region and at least one second laminate region arranged in a plane direction perpendicular to the lamination direction. That is, by providing a plurality of laminates in a plane direction perpendicular to the lamination direction, a substrate laminate can be obtained in which a plurality of laminate regions are arranged according to the purpose.

[0162] Furthermore, the substrate laminate may not only have a plurality of laminated regions in the surface direction, but may also have a structure in which two or more laminated bodies are stacked in the stacking direction. For example, the substrate stack may be such that the first stacked region is made up of two or more layers stacked in the stacking direction, and the second stacked region is made up of two or more layers stacked in the stacking direction. In this way, by arranging any number of laminates in the plane direction perpendicular to the stacking direction in the laminate and in the stacking direction in the laminate, a substrate laminate suitable for the intended three-dimensional substrate application can be produced, and the range of applications is wide. [Example]

[0163] EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the examples show one embodiment of the present invention, and the present invention is not limited to these examples. In the examples, "%" means "% by mass" unless otherwise specified. In the following, ultrapure water (Milli-Q water manufactured by Millipore, resistivity 18 MΩ·cm (25°C) or less) was used as "water." In Table 1, "-" means that no data is available.

[0164] [Example 1] <Preparation of a composition for forming a semiconductor film> A composition for forming a semiconductor film was prepared, the details of which are as follows. The aliphatic diamine (A), octamethylenediamine (diaminooctane, DAO), the silane compound (B), 3-aminopropyldiethoxymethylsilane (3APDES), and the crosslinker (D), asymmetric oxydiphthalic acid ethyl half ester (aODAPehe), were prepared. aODAPehe was prepared by adding asymmetric oxydiphthalic anhydride (aODPA) to ethanol and refluxing for 4 hours until a clear liquid was obtained. Furthermore, proton NMR confirmed the formation of ester groups in the prepared aODPAehe. The ethanol was removed using an evaporator, and a concentrated liquid was prepared until the concentration of the half-ester compound reached 70%-75%. This liquid was used as crosslinker (D). 25 g of silane compound (B) was added dropwise to 25 g of water to dissolve it to a concentration of 50% by mass, and the solution was allowed to stand overnight at room temperature. Hydrolysis of the ethoxysilane was then confirmed by proton NMR spectroscopy. Water was then added to the mixture to adjust the concentration of silane compound (B) to the concentration shown in Table 1. Furthermore, the mixture of silane compound (B) and aliphatic diamine (A) was added to the molar ratio shown in Table 1, followed by addition of crosslinker (D), and the mixture was stirred overnight at room temperature to prepare a composition for forming a semiconductor film.

[0165] [Examples 2 to 6] Compositions for forming semiconductor films in Examples 2 to 6 were prepared in the same manner as in Example 1, using each component in the molar ratio shown in Table 1. In Table 1, ODPAehe refers to symmetrical oxydiphthalic acid ethyl half ester, and was produced by reacting symmetrical oxydiphthalic anhydride (ODPA) with ethanol. The ethanol was removed using an evaporator, and a liquid was produced in which the concentration of the half ester compound was 70% to 75%, and this liquid was used as crosslinking agent (D).

[0166] [Comparative Examples 1 to 3] Compositions for forming semiconductor films in Comparative Examples 1 to 3 were prepared in the same manner as in Example 1, using each component in the molar ratio shown in Table 1. In Table 1, BPDAehe refers to biphenyltetracarboxylic acid ethyl half ester, and pXDA refers to paraxylylenediamine. BPDAehe was produced by reacting biphenyltetracarboxylic acid anhydride (BPDA) with ethanol. The ethanol was removed using an evaporator to produce a liquid concentrated to a concentration of 70% to 75% of the half ester compound. This liquid was used as crosslinker (D).

[0167] <Formation of bonding layer> To form a bonding layer with the thickness listed in Table 1 using the composition obtained in each Example and Comparative Example, water was added to the composition obtained in each Example and Comparative Example to adjust the concentration. A 4-inch diameter silicon substrate (silicon wafer) was prepared as the substrate onto which the concentration-adjusted composition was applied. After treating the silicon wafer with UV (ultraviolet) ozone for 5 minutes, the silicon wafer was placed on a spin coater, and approximately 5 mL of the concentration-adjusted composition was dropped onto the silicon wafer. The silicon wafer was then held for 13 seconds, spun at 2000 rpm (rpm = rotations per minute) for 1 second, 600 rpm for 30 seconds, and then spun at 2000 rpm for 10 seconds to dry. After leaving the composition overnight, it was further heated in an inert oven at 200°C for 1 hour to obtain a cured bonding layer. The composition obtained in Comparative Example 3 gelled and could not be used to form a film.

[0168] <Bonding layer thickness> The film thickness of the bonding layer formed on the silicon wafer was measured. Specifically, the film thickness was measured using a contact film thickness meter at the center of the silicon wafer, at a point 3 cm away from the center of the silicon wafer toward the orientation flat (orientation flat), and at a point 3 cm away from the center of the silicon wafer toward the opposite side of the orientation flat. Table 1 shows the average film thickness at these three points.

[0169] <Residual stress measurement> The residual stress σ of the bonding layer was calculated using the following formula (formula) from the curvature X of the silicon wafer with the bonding layer measured using a laser warpage measuring instrument DY-3000 (manufactured by Kohzu Seiki Co., Ltd.) and the curvature Y of the silicon wafer without the bonding layer measured in advance. σ = [E × t 2 / ((1-ν)×6×t _film )(1 / X-1 / Y) (Formula) A large residual stress σ in the bonding layer means that the substrates are likely to warp significantly, and thus are likely to be misaligned when the substrates are bonded together. In the above formula, E is the elastic modulus of the silicon wafer, t is the thickness of the silicon wafer, ν is the Poisson's ratio of the silicon wafer, and t _film represents the thickness of the bonding layer. In Comparative Example 2, cracks occurred in the bonding layer, and the layer could not be used as a bonding layer, so the residual stress was not calculated. The results are shown in Table 1.

[0170] <Measurement of surface energy of bonded interface> Water and 1-propanol were added to the compositions obtained in each Example and Comparative Example to adjust the concentration so that the thickness of the bonding layer on the silicon wafer was approximately 1 μm. Using the composition with the adjusted concentration, a bonding layer was formed on the silicon wafer, which was the first substrate, using the same method as described above. The concentration of 1-propanol contained in the composition with the adjusted concentration was 20% by mass. Furthermore, in forming the bonding layer, instead of leaving it to stand and drying overnight, the coating film was dried for 1 minute on a hot plate heated to 125°C. A silicon wafer, which was the second substrate, was bonded and temporarily fixed to the approximately 1 μm thick bonding layer obtained above at room temperature, and then heated in an inert oven at 200°C for 1 hour to produce a substrate laminate consisting of a first substrate / bonding layer / second substrate. The surface energy (bonding strength) of the bonded interface of a substrate laminate was measured by a blade insertion test according to the method described in the non-patent document M.P. Maszara, G. Goetz, A. Cavigila, and J.B.M. McKitterick, Journal of Applied Physics, 64 (1988) 4943-4950. A blade with a thickness of 0.1 mm to 0.3 mm was inserted into the bonded interface of the substrate laminate, and the distance from the blade edge to the substrate laminate peeled off was measured using an infrared light source and an infrared camera. The surface energy was then measured according to the following formula: γ=3×10 9 ×t b 2 ×E 2 ×t 6 / (32×L 4 ×E×t 3 ) where γ is the surface energy (J / m 2 ), t b is the blade thickness (m), E is the Young's modulus (GPa) of the silicon wafers included in the first substrate and the second substrate, t is the thickness (m) of the first substrate and the second substrate, and L is the peeling distance (m) of the substrate stack from the blade tip. The results are shown in Table 1.

[0171] <Measurement of glass transition temperature> The composition used to form the bonding layer during residual stress measurement in each example and comparative example was applied to a resin film with an applicator at a gap of 250 μm, and cured by baking in a nitrogen atmosphere at 200°C for 1 hour. The cured film was then peeled off from the resin film to obtain a free-standing film with a thickness of 10 μm to 70 μm. The dynamic viscoelastic properties of the free-standing film obtained above were measured using a dynamic viscoelasticity measuring device RSA-III (manufactured by TA Instruments), and the glass transition temperature was determined from the tan δ peak. The results are shown in Table 1.

[0172] [Table 1]

[0173] As shown in Table 1, in Examples 1 to 6, it was possible to form bonding layers with reduced residual stress compared to Comparative Example 1, which did not contain the aliphatic diamine (A). In particular, Examples 1 to 5 had higher glass transition temperatures than Example 6, which did not contain the silane compound (B). In Comparative Example 2, it is presumed that the residual stress in the bonding layer was too high, causing cracks.

[0174] The disclosure of Japanese Patent Application No. 2021-144612, filed on September 6, 2021, is incorporated herein by reference. All publications, patent applications, and technical standards mentioned in this disclosure are incorporated by reference into this disclosure 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. an aliphatic diamine (A) comprising a main chain containing at least one of a primary amino group and a secondary amino group and carbon atoms, wherein the total number of primary amino groups and secondary amino groups is two or more, the number of carbon atoms constituting the main chain is 2 or more and 180 or less, and the weight average molecular weight is 60 or more and 2,000 or less; a crosslinking agent (D) which is a half-esterified compound represented by general formula (D-2) and has a weight average molecular weight of 200 or more and 2000 or less; A composition for forming a film for a semiconductor, comprising: The aliphatic diamine (A) is a compound having a main chain in which both ends thereof are independently a primary amino group, and in which the carbon chain or a part of the carbon chain is substituted with an oxygen atom, a sulfur atom, a carbonyl group, a secondary amino group, a tertiary amino group, an amide group, or an ester group; A composition for forming a semiconductor film, wherein COOX / amino group, which is a ratio of the number of —C(═O)OX groups in the crosslinking agent (D) to the total number of amino groups of components having an amino group contained in the composition for forming a semiconductor film, is 0.4 or more and 2.2 or less. 【Chemistry 1】 [In formula (D-2), R is an alkyl group having 1 to 6 carbon atoms, and Y is an oxygen atom.]

2. 2. The composition for forming a semiconductor film according to claim 1, further comprising a silane compound (B) that contains at least one of a primary amino group and a secondary amino group and a silicon atom, wherein the relationship between the silicon atom and a nonpolar group bonded to the silicon atom satisfies the relationship (nonpolar group) / Si<1.8 in terms of molar ratio.

3. 3. The composition for forming a semiconductor film according to claim 2, wherein the weight average molecular weight of the silane compound (B) is 130 or more and 10,000 or less.

4. 3. The composition for forming a semiconductor film according to claim 1, further comprising a linear siloxane compound (C) that contains at least one of a primary amino group and a secondary amino group, a silicon atom, and a non-polar group bonded to the silicon atom, wherein the total number of primary amino groups and secondary amino groups is two or more, and the relationship between the silicon atom and the non-polar group bonded to the silicon atom satisfies the relationship (non-polar group) / Si≧1.8 in terms of molar ratio.

5. 5. The composition for forming a semiconductor film according to claim 4, wherein the weight average molecular weight of the siloxane compound (C) is 200 or more and 2,000 or less.

6. 3. The composition for forming a semiconductor film according to claim 1, wherein the aliphatic diamine (A) does not contain a cyclic structure.

7. 3. The composition for forming a semiconductor film according to claim 1, wherein the ratio of the content of the crosslinking agent (D) to the total content of the components having an amino group contained in the composition for forming a semiconductor film, component having an amino group / crosslinking agent (D), is in a molar ratio of 0.1 or more to 10 or less.

8. A laminate comprising a substrate and a bonding layer formed from the composition for forming a semiconductor film according to claim 1 or 2.

9. a first substrate; A bonding layer formed from the composition for forming a semiconductor film according to claim 1 or 2; a second substrate; A substrate laminate formed by stacking the above in this order.

10. a first laminated region formed by laminating a first substrate, a bonding layer formed from the composition for forming a semiconductor film according to claim 1 or 2, and a second substrate in this order; a second laminated region formed by laminating a first substrate, an electrode, and a second substrate in this order; Equipped with A substrate laminate in which at least one first laminated region and at least one second laminated region are arranged in a plane direction perpendicular to the lamination direction.

11. The substrate laminate according to claim 10 , wherein the first laminated region is formed by stacking two or more layers in the stacking direction, and the second laminated region is formed by stacking two or more layers in the stacking direction.

12. 10. The substrate stack according to claim 9, wherein at least one of the first substrate and the second substrate is a semiconductor substrate containing at least one element selected from the group consisting of Si, Ga, Ge, and As.

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