[0001]The present invention relates to a semiconductor membrane composition, method of manufacturing a semiconductor membrane composition, a method of manufacturing a semiconductor member, a manufacturing method and a semiconductor device for a semiconductor process material.
Background technique
[0002]Conventionally, in various technical fields such as electronic devices fields, it has been made to impart a composition containing the polymer member.
　For example, polyethyleneimine weight average molecular weight has a cationic functional group is 2,000 to 1,000,000, a composition of pH 2.0 to 11.0 containing a polymer such as polyethylene imine derivatives, members having a predetermined condition the method of producing a composite body to be applied to the surface of a and member B are known (e.g., see Patent Document 1). In Patent Document 1, the composite member composition has been applied, it has been described that washing with a rinse solution containing a polycarboxylic acid. [Patent Document 1] International Publication No. WO 2014/156616
Disclosure of the Invention
Problems that the Invention is to Solve
[0003]
　In Patent Document 1, by applying a polymer such as polyethylene imine member, after applying a rinsing solution containing a polycarboxylic acid thereon, and is crosslinked by heating the reaction, there are many number of steps. However, an attempt to prepare the composition applied to the member by mixing the polymer and the polycarboxylic acid, such as polyethyleneimine, compositions polymers and polycarboxylic acid aggregate ends up clouding, the composition aggregates when applied to members, large irregularities due to the formation of such pits, there is a problem that smoothness becomes insufficient film.
[0004]
　One aspect of the present invention has been made in view of the above problems, aggregates and pits is small, the semiconductor membrane composition highly smooth film is obtained, a method of manufacturing the same, the semiconductor membrane composition and to provide a semiconductor device comprising a semiconductor member manufacturing method and a manufacturing method and smoothness high reactant for a semiconductor process material using the semiconductor membrane composition used.
Means for Solving the Problems
[0005]
　Specific means for solving the problems are as follows.
<1> 1 nitrogen atom and secondary compounds having a cationic functional group and Si-O bond containing at least one nitrogen atom and (A), -C in the molecule (= O) OX group (X is has a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group) 3 or more, three or more -C (= O) of the OX group, one or more than six is -C (= O ) is OH group, weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), and includes a polar solvent (D), a semiconductor membrane composition.
<2> primary nitrogen has atoms and 2 nitrogen atom and a Si-O bond and a cationic functional group containing at least one compound weight average molecular weight of 130 to 10,000 and (A), in the molecule a -C (= O) OX group (X is a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group) has three or more, three or more -C (= O) of the OX group, is one or more than six is -C (= O) OH group, weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), and includes a polar solvent (D), a semiconductor membrane composition .
<3> In addition, the crosslinking agent (B) having a ring structure in the molecule, <1> or semiconductor membrane composition according to <2>.
<4> the ring structure is at least one benzene ring and a naphthalene ring, a semiconductor membrane composition according to <3>.
<5> In addition, the crosslinking agent (B), in the three or more -C (= O) OX group, at least one X is an alkyl group having 1 to 6 carbon atoms, <1> to < 4 for semiconductor film composition according to any one of>.
<6> weight having a carboxyl group average molecular weight over 46 195 following acids (C-1) and a weight average molecular weight 17 to 120 below having the nitrogen atom base (C-2) at least one selected from the group consisting of further comprising additives (C), <1> ~ for semiconductor film composition according to any one of <5>.
<7> contains at least one selected from the group consisting of weight-average molecular weight of 10,000 or more 400,000 following weight-average molecular weight of 90 or more and 600 or less of the amine compound having a ring structure in its aliphatic amine and intramolecular <1> - for semiconductor film composition according to any one of <6>.
<8> used in the filler material of the recess formed in the substrate, <1> to semiconductor membrane composition according to any one of <7>.
<9> used in the multilayer resist method, <1> to semiconductor membrane composition according to any one of <7>.
[0006]
<10> <1> to <9> A method of manufacturing a semiconductor membrane composition according to any one of, mixing the compound (A), the crosslinking agent (B), and the the method of manufacturing a semiconductor membrane composition comprising mixing process.
<11> The mixing step is a step of mixing a mixture of weight average molecular weight over 46 195 following acids having a carboxy group (C-1) and the compound (A), the crosslinking agent (B), and the the method of manufacturing a semiconductor membrane composition according to certain <10>.
<12> The mixing step, a mixture of weight average molecular weight 17 to 120 or less bases (C-2) and the crosslinking agent (B) having a nitrogen atom, the compound (A), in the step of mixing the method of manufacturing a semiconductor membrane composition according to certain <10>.
[0007]
<13> <1> - A method of manufacturing a semiconductor member by using a semiconductor membrane composition according to any one of <9>, imparting to impart the semiconductor membrane composition to a substrate process and has a heating step of the semiconductor membrane composition is heated granted following conditions 425 ° C. temperature of 250 ° C. or higher the substrate, a manufacturing method of the semiconductor member.
[0008]
<14> <1> - A method of manufacturing a semiconductor for process material using a semiconductor membrane composition according to any one of <7>, imparts the semiconductor membrane composition to a substrate imparting step and has a heating step of the semiconductor membrane composition is heated granted following conditions 425 ° C. temperature of 250 ° C. or higher the substrate, a manufacturing method for a semiconductor process material.
[0009]
<15> substrate and, 1 nitrogen atom and compound weight average molecular weight of 130 to 10,000 and a cationic functional group Si-O bond and comprising at least one of the secondary nitrogen atom (A), and molecular -C (= O) OX group within (X is a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group) has three or more, three or more -C (= O) of the OX group is one or more than six is ​​-C (= O) OH groups, comprising the reaction product of weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), the semiconductor device.
[0010]
<16> the reactant has at least one amide bond and an imide bond, a semiconductor device according to <15>.
Effect of the invention
[0011]
　One aspect of the present invention, aggregates and pits is small, the semiconductor membrane composition highly smooth film is obtained, a method of manufacturing the same, a manufacturing method and a semiconductor for a semiconductor member using the semiconductor membrane composition it is possible to provide a semiconductor device comprising the use coating composition manufacturing method as well as smoothness high reactant for a semiconductor process material used.
DESCRIPTION OF THE INVENTION
[0012]
　As used herein, "-" or "-" numerical range represented by the "-" or - means a range including numerical values ​​described before and after as a lower limit and an upper limit "".
[0013]
[For semiconductor film Composition
　The following describes one embodiment of a semiconductor membrane composition of the present invention. For semiconductor film composition according to the present embodiment (hereinafter, also referred to as "composition".) Is, Si-O bond and a cationic functional group containing at least one of a nitrogen atom and 2 nitrogen atom compounds with bets and (a), -C (= O ) OX group (X is a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group) in the molecule has 3 or more, three or more -C (= O) of the OX group is one or more than six is -C (= O) OH group, weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), and a polar solvent (D ) and, including.
[0014]
　A semiconductor membrane composition according to the present embodiment, specifically, the semiconductor membrane composition was applied to the member by forming a film, aggregates and pits is small, highly smooth film can get. Further, by using the semiconductor membrane composition according to the present embodiment, it is possible to easily obtain a smooth high film than technique of Patent Document 1 described above (WO 2014/156616).
[0015]
　By using the semiconductor membrane composition according to the present embodiment, it is possible irregularities to form a reduced smoothness good film, for example, for semiconductor film composition according to the present embodiment on a smooth substrate such as a silicon substrate when grown using things at SEM (scanning electron microscope) of 200,000 magnifications at 500nm wide field of view, the difference between the maximum value and the minimum value of the film thickness is 25% or less of the average thickness it is possible to form a film.
[0016]
　Further, in the technique of Patent Document 1 described above, coated with polymers such as polyethylene imine member, after applying a rinsing solution containing a polycarboxylic acid thereon, since the crosslinked by heating the reaction was applied there is a possibility that the polymer had dissolved to a rinse solution containing a polycarboxylic acid. Therefore, in the film formed on member, hardly becomes uniform thickness in the plane of the large diameter wafers, it is not easy control of film thickness.
[0017]
　Further, in the technique of Patent Document 1 described above, when forming the tens nm or more thick film, because the polycarboxylic acid is hardly penetrates to the interface between member and the polymer becomes uniform composition in the film thickness direction Hateful.
[0018]
　On the other hand, in this embodiment, by by coating the semiconductor membrane composition member forming a film comprising a compound (A) and the crosslinking agent (B), increasing the smoothness and uniformity of composition in the film thickness direction it is possible to increase the sex.
[0019]
　By using the semiconductor membrane composition according to the present embodiment, excellent uniformity of composition in the smoothness and thickness direction, for example, it is possible to form a film having a thickness of at least 5μm below 0.5 nm. Further, it is possible to form a film excellent in smoothness on the surface of the large diameter silicon substrate, for example, a variation in thickness between the center and the edge of 300mm φ silicon substrate when the film thickness was 150nm or more 5 nm ± it can be 15% or less, preferably to less than 10% ±.
[0020]
　Further, for semiconductor film composition according to the present embodiment is a composition for producing a film for a semiconductor device, for example, the gap fill material filled in a recess formed in the substrate (embedding planarization film) , an insulating material (buried insulating film) which is filled in a recess formed in the substrate, is provided between the low dielectric constant material and a metal, such as a porous material, a barrier having an insulating property, adhesion, etc. pore seal material (barrier film), in the via sidewall of the through silicon via substrate, metal and provided or between a metal and an insulating film of a silicon substrate, adhesion, insulating material (silicon vias insulating film) having insulation properties used in the formation of such.
　In particular, the filling material (embedding planarization film) of a recess formed in the substrate in some cases used for complex processing of the substrate.
[0021]
　As one method of transferring a lithographic pattern onto a substrate using a hard mask, there is a multi-layer resist method. The multilayer resist process is used photoresist film, i.e., the upper resist film, different underlying film etch selectivity, i.e. the lower resist film. Multilayer resist process, for example a lower resist film containing silicon is interposed between the upper resist film and the substrate to be processed, after providing a pattern on the upper resist film, the upper layer resist pattern as an etching mask, the lower resist film transferring the pattern, it is further used as an etching mask the underlying resist pattern, a method of transferring a pattern to a substrate to be processed.
[0022]
　Compositions of the lower resist film used in such a multilayer resist method, silicon-containing inorganic film, SiO by CVD 2 film, there is a SiON film or the like.
　However, as miniaturization of semiconductor devices progresses further, the line width of the pattern not only becomes finer, the thickness of the upper resist film in order to prevent collapse of the pattern becomes thin, required for the lower resist film also in performance, embeddability and etch selectivity than conventional in the fine pattern it has come to improve the is obtained.
[0023]
　In the manufacturing process of the semiconductor device in the limit range of today's lithography, complicated process of double patterning such as described above have been proposed. Furthermore, advances even further complicated devices such as integrated circuit devices, wiring trench (trench), with respect to patterned substrate such as a plug groove (via), a plurality of times the method, the patterning of performing multilayer resist pattern formation by, it has been performed a method such as to form a complex pattern.
[0024]
　On the other hand, in the multilayer resist process, for example, when transferring the upper layer resist pattern to the lower resist film, or the lower layer resist pattern when transferring substrate to be processed, a dry etching such as plasma etching is widely used.
　Resist film which is put into practical use in the conventional multi-layer resist method, the organic film, a silicon-containing inorganic film, by CVD as described above was almost. However, in the conventional CVD method to embed without voids fine grooves by problems such as overhang it has become difficult.
　Further, the resist film may be heat resistant (e.g., resistance to heat treatment it is to be applied after the resist film formation) are required.
　Note that the embedding of the above, the etching selectivity and heat resistance of the request, from the viewpoint of realizing a fine pattern formation, the resist film other than the film (e.g., a buried insulating film (shallow trench isolation layer (STI film), a pre-metal insulating film (PMD film), it is also a need to interconnect interlayer insulating film (IMD film), etc.).
[0025]
　For semiconductor film composition according to the present embodiment, embedding properties and excellent etch selectivity and heat resistance, can be used for the manufacture of the resist film, said membrane other than the resist film used in a multilayer resist method .
[0026]
　The semiconductor according to another as a technique, was applied on the photoresist after exposure, this embodiment for the purpose of forming a reversible resist formed by replacing the photoresist photosensitive or non-photosensitive portion forming a fine pattern it may be used use coating composition. By forming a reversible resist, excellent etching resistance, and it is possible to form a small layer of pattern collapse.
[0027]
(Compound (A))
　for semiconductor film composition according to the present embodiment, a compound having an Si-O bond and a cationic functional group containing at least one of a nitrogen atom and secondary nitrogen atom (A) including. The compound (A), and a cationic functional group Si-O bonds and containing at least one of 1 nitrogen atom and 2 nitrogen atom, a compound weight average molecular weight of 130 to 10,000 it may be.
[0028]
　Compound (A) is a compound having a cationic functional group containing at least one of a nitrogen atom and 2 nitrogen atom. The cationic functional group, can be positively charged, and is not particularly limited as long as it is a functional group containing at least one of the primary nitrogen atoms and 2 nitrogen atom.
[0029]
　Further, compound (A), in addition to 1 nitrogen atom and 2 nitrogen atom, may contain a tertiary nitrogen atom.
[0030]
　As used herein, "primary nitrogen atom", a hydrogen atom two and nitrogen atom linked to the atom only one other than hydrogen atom (e.g., primary amino groups (-NH 2 contained in the group) nitrogen atom), or refers to a hydrogen atom three and nitrogen atom linked to the atom only one other than a hydrogen atom (cation).
　Further, the "secondary nitrogen atom", a hydrogen atom and one nitrogen atom linked to the atom only two non-hydrogen atoms (i.e., the nitrogen atom contained in the functional group represented by the following formula (a) ), or refers to a hydrogen atom two and nitrogen atom linked to the atom only two non-hydrogen atoms (cations).
　Further, "tertiary nitrogen atom", the nitrogen atom attached to the atom only three non-hydrogen atoms (i.e., the nitrogen atom is a functional group represented by the following formula (b)), or a hydrogen atom It refers to one or nitrogen atom linked to the atom only three non-hydrogen atoms (cations).
[0031]
[Formula 1]

[0032]
　In formula (a) and Formula (b), * indicates the bonding position of the atoms other than hydrogen atoms.
　Here, the functional group represented by the formula (a) is a secondary amino group (-NHR a group, wherein R a represents an alkyl group) or may be a functional group that forms part of the and it may be a divalent linking group contained in the backbone of the polymer.
　Further, the formula (b) represented by a functional group (i.e., tertiary nitrogen atom) is a tertiary amino group (-NR b R c group; wherein, R b and R c are each independently an alkyl it may be a functional group that forms part of a group), or a trivalent linking group contained in the backbone of the polymer.
[0033]
　The weight average molecular weight of the compound (A) is preferably 130 to 10,000, more preferably at 130 to 5,000, and more preferably 130 to 2,000.
[0034]
　In the present specification, the weight average molecular weight was measured by GPC (Gel Permeation Chromatography) method, it refers to the weight average molecular weight of the polyethylene glycol conversion.
　Specifically, the weight average molecular weight, with an aqueous solution of sodium nitrate concentration 0.1 mol / L as a developing solvent, analyzer Shodex DET RI-101 and two analytical column (Tosoh TSKgel G6000PWXL-CP and TSKgel G3000PWXL- detecting the refractive index at a flow rate of 1.0 mL / min using a CP), it is calculated by the analysis software the polyethylene glycol / polyethylene oxide as a standard (Waters Ltd. Empower3).
[0035]
　Further, compound (A), if necessary, an anionic functional group, may further have a nonionic functional group.
　The nonionic functional group may be a hydrogen bond acceptor group, may be a hydrogen bond donor group. Examples of the nonionic functional groups, e.g., hydroxy group, a carbonyl group, an ether group (-O-), an the like.
　The anionic functional group is not particularly limited as long as it is a functional group capable of negatively charged. Examples of the anionic functional groups, such as carboxylic acid group, a sulfonic acid group, can be exemplified sulfuric acid group.
[0036]
　The compound having an Si-O bond and an amino group, for example, a siloxane diamine, a silane coupling agent having an amino group, and siloxane polymers.
　The silane coupling agent having an amino group, for example, a compound represented by the following formula (A-3) can be mentioned.
[0037]
[Formula 2]

[0038]
　Wherein (A-3), R 1 represents an alkyl group having 1 to 4 carbon atoms which may be substituted. R 2 and R 3 each independently represent a substituted (backbone a carbonyl group, which may contain an ether group) is 1 carbon atoms which may be ~ 12 alkylene group, an ether group or carbonyl group. R 4 and R 5 each independently represent an alkylene group or a single bond substituted 1 carbon atoms which may be 1-4. Ar represents a divalent or trivalent aromatic ring. X 1 represents a hydrogen or substituted 1 carbon atoms which may be 1-5 alkyl group. X 2 represents hydrogen, a cycloalkyl group, a heterocyclic group, an aryl group or a substituted (backbone a carbonyl group, which may contain an ether group) is 1 carbon atoms which may be 1-5 alkyl group a,. A plurality of R 1 , R 2 , R 3 , R 4 , R 5 , X 1 may be different even in the same.
　R 1 , R 2, R 3 , R 4 , R 5 , X 1 , X 2 as the substituent of the alkyl group and alkylene group for each independently, an amino group, hydroxy group, an alkoxy group, a cyano group, a carboxylic acid group, a sulfonic acid group , halogen and the like.
　Examples of the divalent or trivalent aromatic ring in Ar, for example, divalent or trivalent benzene ring. X 2 The aryl group in, for example, a phenyl group, methylbenzyl group, and vinyl benzyl group.
[0039]
　Formula Specific examples of the silane coupling agent represented by (A-3) is for example, N- (2- aminoethyl) -3-aminopropyl methyl diethoxy silane, N- (2- aminoethyl) -3 - aminopropyltriethoxysilane, N- (2- aminoethyl) -3-amino isobutyl dimethyl silane, N- (2- aminoethyl) -3-amino isobutyl methyl dimethoxy silane, N- (2- aminoethyl) - 11-amino-undecyl trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- phenyl-3-aminopropyltrimethoxysilane, (aminoethyl aminoethyl) phenyl triethoxysilane, methyl benzyl aminoethyl aminopropyltrimethoxysilane, benzylamino Chill aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, (aminoethyl aminoethyl) phenethyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N-[2-[3- (trimethoxysilyl) propylamino] ethyl] ethylenediamine, 3-aminopropyl diethoxymethylsilane, 3-aminopropyl dimethoxymethyl silane, 3-aminopropyl dimethylethoxysilane, 3-aminopropyl dimethyl silane, trimethoxy [2- (2-aminoethyl) 3-aminopropyl] silane, diamino methyl diethoxy silane, methyl amino methyl diethoxy silane, p- aminophenyl trimethoxy silane, N- methyl-aminopropyl triethoxysilane Emissions, N- methyl aminopropyl methyl diethoxy silane, (phenylamino) methyl diethoxy silane, acetamide trimethoxysilane, and their hydrolysis products thereof.
[0040]
　The silane coupling agent containing an amino group other than the formula (A-3), for example, N, N-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N'-bis [3- (trimethoxy silyl) propyl] ethylenediamine, bis [(3-triethoxysilyl) propyl] amine, piperazinyl methyl dimethoxy silane, bis [3- (triethoxysilyl) propyl] urea, bis (methyldiethoxysilyl propyl) amine, 2,2-dimethoxy -1,6-diaza-2-silacyclooctane, 3,5-diamino -N- (4- (methoxy dimethyl silyl) phenyl) benzamide, 3,5-diamino -N- (4- (tri triethoxysilyl) phenyl) benzamide, 5- (ethoxy dimethylsilyl) benzene-1,3-diamine, Oyo These hydrolysis products thereof.
[0041]
　Silane coupling agent having an amino group described above may be used singly or may be used in combination of two or more kinds. Further, a silane coupling agent having an amino group, may be used in combination with no silane coupling agent of amino group. For example, it may be used silane coupling agents having a mercapto group to improve adhesion between the metal.
[0042]
　Further, these silane coupling agents, the polymer (siloxane polymer) formed through a siloxane bond (Si-O-Si) may be used. For example, from the hydrolyzate of 3-aminopropyltrimethoxysilane, a polymer having a linear siloxane structure, a polymer having a branched siloxane structure, a polymer having a cyclic siloxane structure, a polymer or the like having a cage siloxane structure It is obtained. Cage siloxane structure, for example, represented by the following formula (A-1).
[0043]
[Formula 3]

[0044]
　The siloxane diamine, for example, compounds represented by the following formula (A-2). In the formula (A-2), i is an integer of 0 ~ 4, j is an integer of 1 to 3, Me is a methyl group.
[0045]
[Chemical Formula 4]

[0046]
　As the siloxane diamine, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (Formula (A-2), i = 0, j = 1), 1,3- bis (2-aminoethyl in amino) propyl tetramethyldisiloxane (formula (A-2), i = 1, j = 1) and the like.
[0047]
　Compound (A) has an amino group, readily soluble in a polar solvent (D) described below. The total number of 1 nitrogen atom and 2 nitrogen atom in the compound (A), the ratio of the number of silicon atoms (the number of the total number / silicon atoms of 1 nitrogen atom and 2 nitrogen atom) is 0.2 If it is 5 or less or more, from the viewpoint of solubility.
[0048]
　By using the compound readily soluble in polar solvent (D) to (A), since the affinity between the hydrophilic surface of the silicon substrate is increased, it is possible to form a smooth film.
[0049]
　More preferred compounds (A), from the viewpoint of plasma resistance, a non-crosslinking group molar ratio, such as methyl groups bonded to Si, preferably satisfies (non-crosslinkable group) / Si <2 relationship. Inferred by satisfying this relationship, the crosslinking of the film formed is improved density (Si-O-Si bond and amide bond, cross-linking with imide bond, etc.), a stronger film is formed for the plasma It is.
[0050]
　As described above, compound (A) having a cationic functional group containing at least one of a nitrogen atom and 2 nitrogen atom. Here, when the compound (A) comprises one nitrogen atom is preferably a ratio of 1 nitrogen atom in the total nitrogen atom in the compound (A) is 20 mol% or more, 25 mol% by more preferably more, further preferably 30 mol% or more. Further, compound (A) comprises one nitrogen atom, and a nitrogen atom other than 1 nitrogen atom (e.g., secondary nitrogen atom, tertiary nitrogen atom) which may have a do not contain a cationic functional group good.
[0051]
　Further, when the compound (A) contains a secondary nitrogen atom is preferably the proportion of secondary nitrogen atoms in the total nitrogen atom in the compound (A) is not more than 5 mol% to 50 mol%, more preferably 10 mol% or more and 45 mol% or less.
[0052]
　Further, compound (A), in addition to 1 nitrogen atom and 2 nitrogen atom, it may include a tertiary nitrogen atom, the case where the compound (A) contains a tertiary nitrogen atom, the compound (A) preferably the ratio of the tertiary nitrogen atom in the total nitrogen atoms is not more than 20 mol% to 50 mol% in, preferably not more than 25 mol% 45 mol%.
[0053]
　In the present embodiment, the content of the compound in the semiconductor membrane composition (A) is not particularly limited, for example, it can be more than 20 mass% 0.001 mass% or more based on the entire composition, preferably not more than 20 wt% 0.01 wt%, more preferably at most 0.04% by weight to 20% by weight.
[0054]
(Crosslinking agent (B))
　for semiconductor film composition according to the present embodiment, -C in the molecule (= O) OX group (X is a hydrogen atom or a number of 1 to 6. The alkyl group having a carbon) has three or more, three or more -C (= O) OX group (hereinafter, also referred to as "COOX".) among the one or more six less -C (= O) OH group (hereinafter, " also referred to as COOH. "), and including a weight-average molecular weight of 200 or more 600 or less is the crosslinking agent (B).
[0055]
　Crosslinking agent (B), -C (= O) OX group (X is a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group.) In the molecule is a compound having three or more, preferably , -C in the molecule (= O) is a compound having three or more than six the OX group, more preferably a -C (= O) OX group three or four compounds having in the molecule.
[0056]
　In the cross-linking agent (B), as the X in the -C (= O) OX group, a hydrogen atom or include an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group It is preferred. Incidentally, -C (= O) X in OX group may be the same as each other or may be different.
[0057]
　Crosslinking agent (B), -C X in the molecule is a hydrogen atom (= O) is the OH group is a compound having one or more than six, preferably, -C in the molecule (= O) OH a compound having a group of one or more 4 or less, more preferably, -C in the molecule (= O) is a compound having two or more than four OH groups, more preferably, -C in the molecule ( = O) is OH group two or compounds having three.
[0058]
　Crosslinking agent (B) is a compound of 200 or more and 600 or less weight-average molecular weight. Preferably, a 200 to 400 compounds.
[0059]
　Crosslinking agent (B) preferably has a ring structure in the molecule. The ring structure, an alicyclic structure, and the like aromatic ring structure. Further, the crosslinking agent (B) may have a plurality of ring structures in the molecule, a plurality of ring structures, may be different even in the same.
[0060]
　The alicyclic structure, for example, alicyclic structure having 3 to 8 carbon atoms, preferably include alicyclic structure having 4 to 6 carbon atoms, the ring structure may be saturated or unsaturated good. More specifically, the alicyclic structure, a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, saturated alicyclic structure such as cyclooctane ring; cyclopropene ring, cyclobutene ring, cyclopentene ring, cyclohexene ring, cycloheptene ring, and unsaturated alicyclic structure such as cyclooctene ring.
[0061]
　Examples of the aromatic ring structure is not particularly limited as long as the ring structure showing aromaticity, for example, a benzene ring, a naphthalene ring, an anthracene ring, a benzene aromatic ring, pyridine ring, and other aromatic thiophene ring such as perylene ring heterocyclic ring, an indene ring, such as a non-benzene aromatic ring, such as azulene ring.
[0062]
　The ring structure crosslinking agent (B) has in the molecule, e.g., cyclobutane ring, cyclopentane ring, cyclohexane ring, at least one selected from the group consisting of a benzene ring and a naphthalene ring are preferred, from the semiconductor membrane composition from the viewpoint of enhancing the heat resistance of the resulting film, at least one of the benzene ring and naphthalene ring are more preferable.
[0063]
　As described above, the crosslinking agent (B) may have a plurality of ring structures in the molecule, when the ring structure is benzene, biphenyl structure, a benzophenone structure or may have a diphenyl ether structure.
[0064]
　Crosslinking agent (B) preferably has a fluorine atom in its molecule, more preferably having one or more 6 or fewer fluorine atoms in the molecule, three or more than six fluorine atoms in the molecule it is further preferred to have. For example, the crosslinking agent (B) may have a fluoroalkyl group in the molecule, specifically, may have a trifluoroalkyl group or hexafluoroisopropyl group.
[0065]
　Further, as the crosslinking agent (B), an alicyclic carboxylic acid, a benzene carboxylic acid, naphthalene carboxylic acid, diphthalic acid, carboxylic acid compounds, such as fluorinated aromatic carboxylic acid; alicyclic carboxylic acid esters, benzenesulfonic acid ester, a naphthalene carboxylic acid esters, diphthalic acid esters, carboxylic acid ester compounds such as fluorinated aromatic carboxylic acid ester. Incidentally, the carboxylic acid ester compound has a carboxyl group in the molecule (-C (= O) OH group), and, in three or more -C (= O) OX group, at least one of X carbon atoms 1 to 6 alkyl groups (i.e., an ester bond) is a compound which is. The semiconductor membrane composition according to the present embodiment, by the cross-linking agent (B) is a carboxylic acid ester compound, aggregation by association of a compound in the composition (A) and the crosslinking agent (B) is suppressed, aggregates and pits are reduced, and it becomes easy to adjust things and thickness smoothness to obtain a higher film or film thickness larger film.
[0066]
　As the carboxylic acid compound, -C (= O) is preferably OH groups tetravalent following carboxylic acid compounds comprising four or less, -C (= O) OH group three or four including trivalent or more preferably a tetravalent carboxylic acid compound.
[0067]
　Examples of the carboxylic acid ester compound, comprising the following three carboxy groups (-C (= O) OH group) in the molecule, and is preferably a compound containing an ester bond three or less, the carboxyl groups in the molecule It includes two or less, and is more preferably a compound containing an ester bond 2 or less.
[0068]
　In the above carboxylic acid ester compound, in three or more -C (= O) OX group and X is an alkyl group having 1 to 6 carbon atoms, X is a methyl group, an ethyl group, a propyl group, while a butyl group are preferable, it is preferable from the compound (a) and the crosslinking agent (B) and more suppression of aggregation by association in the composition, an ethyl group or a propyl group.
[0069]
　Specific examples of the carboxylic acid compounds include, but are not limited to, 1,2,3,4-cyclobutane tetracarboxylic acid, 1,2,3,4-cyclopentane tetracarboxylic acid, 1,3,5-cyclohexane tricarboxylic acid, 1,2,4-cyclohexane tricarboxylic acid, 1,2,4,5-cyclohexane tetracarboxylic acid, alicyclic carboxylic acids such as 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; 1 , 2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, pyromellitic acid, benzene pentacarboxylic acid, benzene carboxylic acids such as mellitic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 2 , 3,6,7- naphthalene carboxylic acids such as naphthalene tetracarboxylic acid; 3,3 ', 5,5'-tetra-carboxy diphenyl main Emissions, 3,3 ', 5,5'-tetracarboxylic acid, biphenyl-3,4', 5-tricarboxylic acid, 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' - (ethyne - 1,2 Jiniru) diphthalic acid (4,4 '- (ethyne-1,2-diyl) diphthalic acid), 4,4' - (1,4- phenylenebis (oxy)) diphthalic acid (4,4 ' - (1,4-phenylenebis (oxy)) diphthalic acid), 4,4 '- ([1,1'- biphenyl] -4,4' Jirubisu (oxy)) diphthalic acid (4,4' - ([ 1,1'-biphenyl] -4,4'-diylbis (oxy)) diphthalic acid), 4,4 '- ((oxybis (4,1-phenylene)) bis (oxy)) diphthalic acid (4,4' - ((oxybis (4,
[0070]
　Specific examples of the carboxylic acid ester compound include compounds in which at least one carboxyl group is substituted with an ester group in the specific example of the aforementioned carboxylic acid compound. The carboxylic acid ester compound, for example, compounds half-esterification represented by the following general formula (B-1) ~ (B-6) can be mentioned.
[0071]
[Formula 5]

[0072]
　R in the general formula (B-1) ~ (B-6), an alkyl group having 1 to 6 carbon atoms, among them methyl group, an ethyl group, a propyl group, a butyl group are preferred, an ethyl group, a propyl group more preferable.
[0073]
　Half esterified compound, for example, a carboxylic acid anhydride is an anhydride of the aforementioned carboxylic acid compound are mixed in an alcohol solvent, it is possible to produce by ring-opening a carboxylic acid anhydride.
[0074]
　In the present embodiment, the content of the crosslinking agent (B) in the semiconductor membrane composition is not particularly limited, for example, carboxyl groups in the crosslinking agent (B) to the number of total nitrogen atom in the compound (A) ratio of the number of (COOH / N) is preferably 0.1 to 3.0, more preferably 0.3 to 2.5, it is 0.4 to 2.2 it is more preferable. By COOH / N is 0.1 to 3.0, by using the semiconductor membrane composition, the amide between the compound after the heat treatment (A) and crosslinking agent (B), and cross-linking of such imide has a structure, it is possible to produce a superior film by heat resistance and insulation properties.
[0075]
　Compound (A) and further as a component other than the crosslinking agent (B), described below, the weight average molecular weight of 10,000 or more 400,000 or less of an aliphatic amine, and a weight average molecular weight of 90 to 600 below having a ring structure in the molecule If containing at least one selected from the group consisting of an amine compound to the total number of all the nitrogen atoms contained in the total nitrogen atom and the compound (a) contained in these, the number of carboxyl groups in the crosslinking agent (B) ratio (COOH / N) is preferably 0.1 to 3.0.
[0076]
(Polar solvent (D))
　for semiconductor film composition according to the present embodiment includes a polar solvent (D). Here, the polar solvent (D) refers to a solvent having a relative dielectric constant at room temperature of 5 or more. The polar solvent (D), specifically, water, a protic inorganic compounds such as heavy water; 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, alcohols such as glycerin; ethers such as tetrahydrofuran and dimethoxyethane; furfural, acetone, ethyl methyl ketone , aldehydes ketones such as cyclohexane; acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N- methylformamide, N, - dimethylformamide, N- methylacetamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, acid derivatives such as hexamethylphosphoramide; nitriles such as acetonitrile, propylonitrile carbonitrile; nitromethane, nitro, such as nitrobenzene compounds; sulfur compounds such as dimethyl sulfoxide. The polar solvent (D), preferably includes a protic solvent, more preferably containing water, more preferably containing deionized water.
　The content of the polar solvent (D) in the semiconductor membrane composition is not particularly limited, for example, not more than 99.99896 wt% 1.0 wt% or more based on the total composition, more than 40 wt% 99 it is preferably not more than .99896% by weight.
[0077]
(Additives (C))
　for semiconductor film composition according to the present embodiment, also include the foregoing of the compound (A), crosslinking agent (B) and polarity in addition to the additives of the solvent (D) (C) good. As the additive (C), the weight average molecular weight over 46 195 following acids having a carboxy group (C-1), the weight average molecular weight 17 to 120 or less bases having a nitrogen atom (C-2) can be mentioned.
[0078]
　Acid (C-1), the weight average molecular weight over 46 195 following acids having a carboxyl group. For semiconductor film composition according to the present embodiment, by including acid (C-1) as an additive (C), ionic bond and a carboxyl group in the amino group with an acid in the compound (A) (C-1) by forming the aggregation by association of a compound (a) and the crosslinking agent (B) it is presumed to be suppressed. More specifically, interaction between carboxylate ions derived from the carboxy groups in ammonium ions and acid derived from the amino group in the compound (A) (C-1) (e.g., electrostatic interactions) is, the compound (A ) stronger than the interaction with the carboxylate ions derived from the carboxy groups in ammonium ion and a crosslinking agent derived from an amino group (B) in the aggregation is presumed to be suppressed. The present invention is in no way limited by the above guess.
[0079]
　The acid (C-1), having a carboxyl group, and is not particularly limited as long as the weight average molecular weight over 46 195 The following compounds, monocarboxylic acid compounds, dicarboxylic acid compounds, and oxy dicarboxylic acid compound . More specifically, the acid (C-1), formic acid, acetic acid, malonic acid, oxalic acid, citric acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxy acetic acid, phthalic acid, terephthalic acid, picolinic acid, salicylic acid, etc. 3,4,5-trihydroxy benzoic acid.
[0080]
　In the present embodiment, content of the acid (C-1) in the semiconductor membrane composition is not particularly limited, for example, compound acid to the number of total nitrogen atom in (A) (C-1) in the ratio of the number of carboxy groups (COOH / N) is preferably 0.01 to 10, more preferably 0.02 to 6, more preferably 0.5 to 3.
　Compound (A) and further as a component other than the crosslinking agent (B), described below, the weight average molecular weight of 10,000 or more 400,000 or less of an aliphatic amine, and a weight average molecular weight of 90 to 600 below having a ring structure in the molecule If containing at least one selected from the group consisting of amine compounds, the number of carboxy groups of the total nitrogen atom with the compound to the total number of all the nitrogen atom contained (a), the in acid (C-1) contained in these the ratio of (COOH / N) is preferably 0.01 to 10.
[0081]
　Base (C-2), is 120 or less bases weight average molecular weight more than 17 with a nitrogen atom. For semiconductor film composition according to the present embodiment, by including a base (C-2) as an additive (C), an amino group and an ionic at the carboxy group and a base in the cross-linking agent (B) (C-2) by forming the bond, aggregation by association of a compound (a) and the crosslinking agent (B) it is presumed to be suppressed. More particularly, the interaction with ammonium ions derived from an amino group in the carboxylate ion and a base derived from the carboxy groups in the crosslinking agent (B) (C-2) is derived from an amino group in the compound (A) stronger than the interaction with the carboxylate ions derived from the carboxy groups in the ammonium ion and the cross-linking agent (B), aggregation is presumed to be suppressed. The present invention is in no way limited by the above guess.
[0082]
　The base (C-2), a nitrogen atom, and is not particularly limited as long as the weight-average molecular weight 17 to 120 The following compounds, monoamine compounds, and diamine compounds. More specifically, as the base (C-2), ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N- acetyl ethylenediamine, N- (2- aminoethyl) ethanolamine, N- (2-amino ethyl) such as glycine and the like.
[0083]
　In the present embodiment, the content of base (C-2) in the semiconductor membrane composition is not particularly limited, for example, the base to the number of carboxyl groups in the crosslinking agent (B) (C-2) in the the ratio of the number of nitrogen atoms (N / COOH) is preferably 0.5 to 5, more preferably 0.9 to 3.
[0084]
(Other components)
　for semiconductor coating composition according to the present embodiment, it is preferable that the content of sodium and potassium is 10 mass ppb or less on an elemental basis, respectively. If 10 mass ppb or less in content of each element base of sodium or potassium, can be suppressed inconvenience occurs in the electrical characteristics of the malfunction, such as a semiconductor device of the transistor.
[0085]
　For semiconductor film composition further, weight-average molecular weight of 10,000 or more 400,000 or less of an aliphatic amine, and at least one selected from the group consisting of weight-average molecular weight of 90 or more and 600 or less of the amine compound having a cyclic structure in the molecule it may contain the seeds.
　The weight average molecular weight of 10,000 or more 400,000 or less aliphatic amines, it is preferable to have a primary nitrogen atom and secondary cationic functional group containing at least one nitrogen atom. Specific examples of the weight-average molecular weight of 10,000 or more 400,000 or less aliphatic amine, ethylene imine, propylene imine, butylene imine, pentylene imine, hexylene imine, Hepuchiren'imin, Okuchiren'imin, trimethylene imine, tetramethylene imine, polyallylamine; polyacrylamides pentamethylene imine, hexamethylene imine, polyalkylene imine is a polymer of an alkylene imine such as octamethylene imine.
[0086]
　Polyethylene imine (PEI) Sho 43-8828, JP-Sho 49-33120, JP 2001-2123958 and JP by known methods described in WO 2010/137711 pamphlet or the like, to produce be able to. For even polyalkyleneimine other than polyethyleneimine can be prepared by the same method as polyethyleneimine.
[0087]
　The weight average molecular weight of 10,000 or more 400,000 or less aliphatic amines, derivatives of polyalkyleneimines described above; it is also preferable that the (polyalkyleneimine derivatives particularly preferably polyethyleneimine derivatives). The polyalkyleneimine derivatives is not particularly limited as long as manufacturable compounds using the polyalkyleneimine. Specifically, the alkyl group in the polyalkyleneimine obtained by introducing a (preferably an alkyl group having 1 to 10 carbon atoms), polyalkyleneimine derivatives obtained by introducing an aryl group, a crosslinkable group such as a hydroxyl group polyalkyleneimine polyalkyleneimine derivatives and the like.
　These polyalkyleneimine derivatives can be prepared by conventional method performed by using the above polyalkyleneimine. Specifically, for example, it can be prepared according to the method described in JP-A-6-016809 Patent Publication.
[0088]
　As the polyalkyleneimine derivative, by reacting the cationic functional group-containing monomer relative to the polyalkylene imine, highly branched type polyalkyleneimine obtained by improving the degree of branching polyalkyleneimines it is also preferred.
　As a method of obtaining a high branched polyalkyleneimine, for example, by reacting a cationic functional group-containing monomer relative to polyalkyleneimine having multiple secondary nitrogen atom in the backbone, of said plurality of secondary nitrogen atom how to replace the cationic functional group-containing monomers at least a portion of the inner, it is reacted with a cationic functional group-containing monomer relative to polyalkyleneimine having a plurality of primary nitrogen atom at the terminal, the plurality of primary nitrogen atom and a method of replacing the cationic functional group-containing monomer are mentioned at least a portion of the.
　The cationic functional groups to be introduced in order to improve the degree of branching, aminoethyl group, aminopropyl group, di-aminopropyl group, aminobutyl group, diaminobutyric group, there may be mentioned a tri-aminobutyl group, etc., cationic from the viewpoint of reducing the sexual functional group equivalent increase the cationic functional group density, aminoethyl group.
[0089]
　The weight average molecular weight of 10,000 or more 400,000 or less aliphatic amine preferably has 1 nitrogen atom and secondary cationic functional group containing at least one nitrogen atom. In this case, when the aliphatic amine contains one nitrogen atom is preferably a ratio of 1 nitrogen atom in the total nitrogen atom in the aliphatic amine is 20 mol% or more, 25 mol% or more more preferably in, further preferably 30 mol% or more. Further, aliphatic amines include a primary nitrogen atom, and a nitrogen atom other than 1 nitrogen atom (e.g., secondary nitrogen atom, tertiary nitrogen atom) may have not containing a cationic functional group .
[0090]
　Further, when the aliphatic amine contains a secondary nitrogen atom is preferably the proportion of secondary nitrogen atoms in the total nitrogen atom in the aliphatic amine is less than 50 mol% 5 mol%, 10 mol % or more and more preferably 45 mol% or less.
[0091]
　Further, aliphatic amines, in addition to 1 nitrogen atom and 2 nitrogen atom, may include a tertiary nitrogen atom, when the aliphatic amine contains a tertiary nitrogen atom, the total of the aliphatic amine preferably the ratio of the tertiary nitrogen atom occupying the nitrogen atom is not more than 20 mol% to 50 mol%, preferably not more than 25 mol% 45 mol%.
[0092]
　Further, the polyethylene imine and its derivatives, may be commercially available. For example, Ltd. Nippon Shokubai, BASF Corp., polyethyleneimine and derivatives thereof are commercially available from MP-Biomedicals, Inc. and the like, may be appropriately selected and used.
[0093]
　The 600 following amine compound weight average molecular weight of 90 or more having a cyclic structure in the molecule, alicyclic amines, aromatic amines, heterocyclic (heterocyclic) amine. May have a plurality of ring structures in the molecule, a plurality of ring structures, may be different even in the same. The amine compound having a ring structure, thermally, for a more stable compound easily obtained, a compound having an aromatic ring is more preferred.
[0094]
　As the 600 following amine compound weight average molecular weight of 90 or more having a cyclic structure in the molecule, an imide with the crosslinking agent (B), Imidoamido, easy to form a thermally crosslinked structure such as an amide, it is possible to enhance the heat resistance from the point, a compound having a primary amino group. Furthermore, as the aforementioned amine compound, an imide with the crosslinking agent (B), Imidoamido, easily increasing the number of thermal crosslinking structure such as an amide, from viewpoint of increasing the heat resistance, the two primary amino groups diamine compounds having triamine compound having three primary amino groups are preferred.
[0095]
　The alicyclic amines, e.g., cyclohexylamine, dimethyl amino cyclohexane.
　The aromatic ring amines such as diaminodiphenyl ether, xylene diamine (preferably para-xylene diamine), diaminobenzene, diaminotoluene, methylenedianiline, dimethyl amino, bis (trifluoromethyl) diaminobiphenyl, diamino benzophenone, diamino benzanilide , bis (aminophenyl) fluorene, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, dicarboxylate Siji diaminodiphenylmethane, diamino resorcinol, dihydroxy benzidine, diaminobenzidine, 1,3,5-aminophenoxy benzene, 2,2 '- dimethyl benzidine, and tris (4-aminophenyl) amine.
　The heterocyclic heterocyclic amines, heterocyclic (e.g., thiophene ring) containing a sulfur atom as a hetero atom, or a heterocyclic ring (e.g., containing a nitrogen atom as a hetero atom, a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring , 5-membered ring such as triazole ring; isocyanuric ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, piperidine ring, piperazine ring, 6-membered ring such as triazine ring; indole ring, indoline ring, a quinoline ring, an acridine ring, naphthyridine ring, quinazoline ring, a purine ring, a fused ring of the quinoxaline ring, and the like) and the like.
　For example, the heterocyclic amines having a heterocyclic ring containing nitrogen, melamine, ammeline, melam, melem, and tris (4-aminophenyl) amine.
　Furthermore, as the amine compound having both a heterocyclic ring and an aromatic ring, N2, N4, N6-tris (4-aminophenyl) -1,3,5-triazine-2,4,6-triamine, and the like.
[0096]
　A semiconductor membrane composition according to the present embodiment, if the selectivity of the plasma etching resistance is required (e.g., gap fill material, the buried insulating film applications), also contain a metal alkoxide represented by the general formula (I) good.
　R1 n M (OR @ 2) m-n · · · (I) (wherein, R1 is a non-hydrolyzable group, R2 is an alkyl group having 1 to 6 carbon atoms, M is Ti, Al, Zr, Sr, Ba, showed Zn, B, Ga, Y, Ge, Pb, P, Sb, V, Ta, W, La, at least one metal atom selected from a metal atom group Nd and an in, m is a metal atom M in the valence is 3 or 4, n is, m is 4 when a is an integer of 0 to 2, m is 0 or 1 in the case of 3, if R1 is plural, each R1 is the same with each other or different even if the OR2 there are a plurality, each OR2 may be the being the same or different.)
[0097]
　If the insulation resistance is required in the film produced from the semiconductor membrane composition according to the present embodiment in (e.g. through-silicon via insulating film applications, the buried insulating film applications), for insulating or mechanical strength improvement, tetraethoxy silane, tetramethoxysilane, bis triethoxysilyl ethane, bis triethoxysilyl methane, bis (methyldiethoxysilyl) ethane, 1,1,3,3,5,5 hexaethoxy-1,3,5-silacyclohexane, 1,3,5,7-tetramethyl-1,3,5,7-tetra hydroxyl cyclosiloxane, 1,1,4,4-tetramethyl-1,4-diethoxy-di silethylene 1,3,5 - it may be mixed trimethyl-1,3,5-trimethyl-1,3,5-triethoxy-1,3,5-silacyclohexane. Furthermore, methyltriethoxysilane for hydrophobic improvement of the insulating film, dimethyl diethoxy silane, may be mixed trimethyl ethoxy silane. These compounds may be mixed for the control of etch selectivity.
[0098]
　For semiconductor film composition according to the present embodiment may contain a polar solvent (D) other than a solvent, such as n-hexane and the like.
[0099]
　Further, for semiconductor film composition according to the present embodiment, for example, for electrical characteristics improvement, phthalic acid, such as benzoic acid, or may contain these derivatives.
　Further, for semiconductor film composition according to the present embodiment, for example, to inhibit the corrosion of copper, it may contain benzotriazole or a derivative thereof.
[0100]
　The pH of the semiconductor membrane composition according to the present embodiment is not particularly limited, is preferably 2.0 to 12.0.
[0101]
Manufacturing method of a semiconductor membrane composition]
　Hereinafter, a method for manufacturing the semiconductor membrane composition according to one embodiment of the present invention. The method of manufacturing a semiconductor membrane composition according to the present embodiment includes compound (A), crosslinking agent (B), and a mixing step of mixing a. As described previously, the semiconductor membrane composition, but comprising a polar solvent (D), at any time of manufacturing the semiconductor membrane composition, the polar solvent (D), Compound (A) it may be added to the mixture of the crosslinking agent (B), and compound (a) and the crosslinking agent (B). The timing of adding the other components is not particularly limited.
[0102]
　In the method of manufacturing a semiconductor membrane composition according to the present embodiment, further, the weight average molecular weight over 46 195 following acids having a carboxy group (C-1) and a weight-average molecular weight 17 to 120 or less bases having a nitrogen atom ( at least one additive selected from the group consisting of C-2) the (C), may be added to the compound in the mixing step (a) or crosslinking agent (B). The timing of adding the additive (C) is not particularly limited.
[0103]
　Also, when adding additive (C) as an acid (C-1), the mixing step, mixing the mixture of acids (C-1) and the compound (A), crosslinking agent (B), and the it is preferable that. That is, prior to mixing the compound (A) and the crosslinking agent (B), it is preferable to pre-mix the compound (A) and acid (C-1). Thus, upon mixing the compound (A) and the crosslinking agent (B), (might take longer to transparency of the composition to gel, preferred) cloudiness and gelation of the composition suitably it can be suppressed.
[0104]
　Further, if the addition of a base (C-2) as an additive (C), the mixing step, mixing a mixture of a base (C-2) and the crosslinking agent (B), compound (A), the it is preferable that. That is, prior to mixing the compound (A) and the crosslinking agent (B), it is preferable to premix the crosslinking agent (B) a base and (C-2). Thus, upon mixing the compound (A) and the crosslinking agent (B), (might take longer to transparency of the composition to gel, preferred) cloudiness and gelation of the composition suitably it can be suppressed.
[0105]
[The method of manufacturing a semiconductor member]
　Hereinafter, a method for manufacturing a semiconductor member according to the present embodiment. The method of manufacturing a semiconductor member according to the present embodiment, heating the semiconductor membrane composition and step of applying to the substrate, the substrate on which the semiconductor membrane composition has been applied under the following conditions Temperature 250 ° C. or higher 425 ° C. a heating step.
[0106]

　application process in this embodiment is a step of applying a semiconductor membrane composition on the substrate.
　As the substrate, a semiconductor substrate such as a silicon substrate, a glass substrate, a quartz substrate, a stainless steel substrate, a plastic substrate, and the like. The shape of the substrate is not particularly limited, it may be any plate, dish or the like. For example, a silicon substrate, an interlayer insulating layer (Low-k film) may be a silicon substrate formed with, also, a silicon substrate, fine grooves (recesses), such fine through holes are formed it may be.
[0107]
　In application step in the present embodiment, no particular limitation on the method for imparting semiconductor membrane composition, it is possible to use a generally used method.
　As a method generally used, for example, dipping, spraying, spin coating, and bar code method. For example, when forming a film having a thickness of micron size, it is preferable to use a bar code method, when forming a film having a thickness of nano-sized (several nm ~ several hundred nm), using a spin coating method it is preferable.
[0108]
　For example, no particular limitation on the method applied for semiconductor film composition by the spin coating method, for example, while rotating the substrate at a spin coater, was dropped for semiconductor film composition to the surface of the substrate, then the rotational speed of the substrate it is possible to use a method of drying by increasing the.
　In the application method of a semiconductor membrane composition by the spin coating method, the rotation speed of the substrate, dropping amount and dropping time of the semiconductor membrane composition, no particular limitation is imposed on the various conditions such as the rotational speed of the substrate upon drying, form etc. the thickness of the membrane can be appropriately adjusted taking into account.
[0109]

　manufacturing method according to the present embodiment, prior to the heating step described later, the substrate on which the semiconductor membrane composition has been applied, a dry step of drying under the following conditions Temperature 80 ° C. or higher 250 ° C. it may be. Incidentally, the temperature refers to the temperature of the surface on which the semiconductor membrane composition of the substrate has been applied.
　The above temperature is more preferably 90 ° C. or higher 200 ° C. or less, more preferably 100 ° C. or higher 0.99 ° C. or less.
[0110]
　Drying in this step may be carried out by conventional methods, it can be performed using for example a hot plate.
　There is no particular limitation on the atmosphere in which the drying in this step, for example, may be carried out in an air atmosphere, an inert gas (nitrogen gas, argon gas, helium gas, etc.) may be carried out in an atmosphere.
[0111]
　No particular limitation is imposed on the drying time is preferably 300 seconds or less, more preferably 200 seconds or less, more preferably 120 seconds or less, particularly preferably 80 seconds or less.
　There is no particular limitation on the lower limit of drying time, the lower limit is, for example, 10 seconds (preferably 20 seconds, more preferably 30 seconds) can be.
[0112]

　manufacturing method according to the present embodiment, prior to the heating step described below, in order to remove the excess semiconductor membrane composition applied to the substrate, the substrate on which the semiconductor membrane composition has been applied cleaning step of cleaning with water or the like may be included. The manufacturing method according to this embodiment, when having the above-mentioned drying step, after the drying step, it is preferable to perform the cleaning process.
[0113]

　manufacturing method according to the present embodiment further comprises a heating step of a semiconductor membrane composition substrate granted, heated under the following conditions 425 ° C. temperature of 200 ° C. or higher.
　Incidentally, the temperature refers to the temperature of the surface on which the semiconductor membrane composition of the substrate has been applied.
　By having this heating step, the compound (A) and the crosslinking agent (B) is the reaction product reacts is obtained by heating, a film containing the reaction product is formed.
　The temperature is preferably 250 ° C. or higher 400 ° C. or less, more preferably 300 ° C. or higher 400 ° C. or less.
[0114]
　Although there is no particular limitation on the pressure to be performed heated in the heating step, preferably less than or equal to the absolute pressure 17Pa superatmospheric pressure.
　The absolute pressure is more preferably less than atmospheric pressure 1000 Pa, more preferably less than atmospheric pressure 5000 Pa, and particularly preferably more than 10000Pa atmospheric pressure.
[0115]
　Heating in the heating step may be carried out by conventional methods using a furnace or hot plate. The furnace, for example, can be used Apex Co. SPX-1120, Koyo Thermo System Co., Ltd. VF-1000LP like.
　The heating in this step may be performed in an air atmosphere, an inert gas (nitrogen gas, argon gas, helium gas, etc.) may be carried out in an atmosphere.
[0116]
　No particular limitation is imposed on the heating time in the heating step, for example, not more than 1 hour, preferably 30 minutes, more preferably not more than 10 minutes, particularly preferably not more than 5 minutes. No particular restriction on the lower limit of the heating time, but may be, for example, between 0.1 minutes.
[0117]
　For the purpose of shortening the heating process time may be irradiated with ultraviolet rays on the surface semiconductor membrane composition has been applied to the substrate. Ultraviolet light having a wavelength of 170 nm ~ 230 nm is the ultraviolet, wavelength 222nm excimer light, preferably including wavelengths 172nm excimer light. It is preferable to perform the UV irradiation in an inert gas atmosphere.
[0118]

　as an example of a semiconductor member for a semiconductor member for gap fill material (embedding planarization film) is filled in a recess formed in the substrate, the recess formed on the substrate insulating material (buried semiconductor member having an insulating film) is filled, insulation between the substrate and the metal containing low dielectric constant material such as a porous material, adhesion, barrier material (barrier film having such pore seal property) provided semiconductor member, in the via sidewall of the through silicon vias substrate, provided or between a metal and an insulating film between the metal and the silicon substrate, the adhesion, the insulating film having an insulating property (through silicon via insulating film) It provided a semiconductor member, such as a semiconductor member for reversible resist formation and the like.
[0119]
　The semiconductor member for flattening film is filled embedded in a recess formed in the substrate, the thickness of the planarization layer buried, for example, a 30nm or more 200nm or less, preferably 50nm or 150nm or less.
　Incidentally, the semiconductor member, at the time of forming a multilayer copper wiring by the dual damascene process, for example in the via-first process can be used as a member for flattening film is provided embedded in the via.
　Also, narrow width of the recess, in the case of forming a flattening film buried in the large groove of the aspect ratio (depth / width), from the viewpoint of enhancing the filling property of the groove, for semiconductor film composition according to the present embodiment grant the recess objects (preferably, applied by spin coating) it is preferable to form the planarizing film buried in.
[0120]
　The semiconductor member of the buried insulating film is filled in a recess formed in the substrate, the thickness of the buried insulating film, for example, a 30nm or more 200nm or less, preferably 50nm or 150nm or less.
　As the semiconductor member, for example, a technique for forming a device isolation region is provided a buried insulating film having an insulating property into the groove of the silicon substrate: a member using the (STI shallow trench isolation), the insulation member provided between the switching element such as MOSFET, which is previously formed a buried insulating film (metal-oxide-semiconductor field- effect transistor), is provided a buried insulating film having an insulating property as a pre-metal dielectric layer over the MOSFET (PMD) members, the lowermost layer wiring is previously formed buried insulating film having insulating properties (W, Ti / TiN / AlCu / TiN , etc.) member provided between, inter a buried insulating film on the lowermost layer wiring having insulation properties member provided as a metal insulator (IMD), the wiring in the groove between the preformed copper wiring buried insulating film having insulating properties Such member provided as an interlayer insulating film (ILD) and the like.
　Also, narrow width of the recess, in the case of forming a buried insulating film in the large trench aspect ratio (depth / width), from the viewpoint of enhancing the filling property of the groove, the semiconductor membrane composition according to the present embodiment grant the recess (preferably spin imparted by coating) it is preferable to form the to the buried insulating film.
[0121]
　Between the substrate and the metal containing low dielectric constant material such as a porous material, insulation, adhesion, the semiconductor member for the barrier film is provided with such pore sealing property, the thickness of the barrier film, for example, and at 0.5nm or 15nm or less, preferably 1.5nm or 12nm or less. The semiconductor member is, for example, a wall surface of the through hole formed in the substrate, a metal which is arranged in the through-hole, or may be a member of the barrier film is provided comprising an adhesion layer between.
[0122]
　The semiconductor member of the through silicon via insulating film is provided between the metal and the silicon substrate in the via sidewall of the through silicon vias substrate, the thickness of the through silicon via an insulating film is, for example, 100nm or 5μm or less, preferably is 500nm or more 2μm or less.
[0123]
　The semiconductor member of the through silicon via insulating film is provided between the via sidewall of the through silicon vias substrate metal and the insulating film, the thickness of the through silicon via an insulating film, for example, be 0.5 nm ~ 100 nm , preferably from 1 nm ~ 30 nm.
[0124]
Manufacturing method for a semiconductor process material]
　Hereinafter, a method for manufacturing a semiconductor for process material according to the present embodiment. The method of manufacturing a semiconductor for process material according to the present embodiment, heating the semiconductor membrane composition and step of applying to the substrate, the substrate on which the semiconductor membrane composition has been applied under the following conditions Temperature 250 ° C. or higher 425 ° C. a heating step of.
　Each step of the manufacturing method for semiconductor process material is the same as the steps in the method for manufacturing the aforementioned semiconductor member, and a description thereof will be omitted.
[0125]
　As the semiconductor for process material is temporarily formed in the manufacturing process of a semiconductor device, such as a sacrificial layer to be removed in a later step and the like.
[0126]
[Semiconductor device]
　Hereinafter, a description will be given of a semiconductor device according to the present embodiment.
　The semiconductor device according to this embodiment, the substrate and the compound weight average molecular weight and a cationic functional group Si-O bond and of 130 to 10,000 containing at least one of 1 nitrogen atom and 2 nitrogen atom and (a), -C in the molecule (= O) OX group (X is a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group) has three or more, three or more -C (= O) of the OX group is one or more than six is -C (= O) OH groups, comprising the reaction product of weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B). Compound reaction product of (A) and the crosslinking agent (B), smoothness is high, excellent uniformity of the composition in the film thickness direction.
　The reaction of a compound (A) and the crosslinking agent (B) preferably has at least one amide bond and imide bond.
Example
[0127]
　Following illustratively describes the invention based on examples, the present invention is not limited to these examples.
　In the following, those wherein the solvent is not indicated water was used.
　In the following, as "water", using ultra-pure water (Millipore Corp. Milli-Q water, resistance 18MΩ · cm (25 ℃) or below).
[0128]
　A semiconductor membrane compositions of Examples A1 ~ Example C1 was prepared. Details are as follows.
　Incidentally, a solution of the compound (A), a solution of the crosslinking agent (B), a base (C-2) when mixing each added solution of the crosslinking agent (B), there is no precipitation in the solution mixed They were mixed after confirming.
[0129]
[Examples A1 ~ A8]
　used in Example 3-aminopropyltriethoxysilane; as (3APTES (3-Aminopropyl) triethoxysilane ), 3-aminopropyltriethoxysilane 25g was dropped into water 25g, 50 wt% after dissolution so that, after standing overnight at room temperature, it was confirmed that the alkoxysilane is hydrolyzed by proton NMR spectrum. It was then prepared 3APTES solution to a concentration shown in Table 1.
　Further, as the crosslinking agent (B), 1,3,5-benzenetricarboxylic acid (135BTC), 1,2,4- benzenetricarboxylic acid (124BTC; 1,2,4-Benzenetricarboxylic acid) , pyromellitic acid (PMA; pyromellitic acid), ethyl half ester of pyromellitic acid (ehePMA; ethyl half ester PMA) , 1- propyl half ester 1,2,4-benzenetricarboxylic acid (1Prhe124BTC; was prepared 1-propyl half ester 124BTC).
　ehePMA are ethanol was added with pyromellitic dianhydride, and heated for 3 hours 30 minutes in a water bath heated to 50 ° C., was prepared by completely dissolving pyromellitic dianhydride powder. Proton NMR, it was confirmed that the ester group is formed on the manufactured EhePMA.
　1Prhe124BTC adds the 124BTC anhydride 1-propanol, and stirring at room temperature, was prepared by completely dissolving the 124BTC anhydride powder. Proton NMR, it was confirmed that the ester group is formed on the manufactured 1Prhe124BTC.
[0130]
　In Example A1, A3, A5, A7, A8, the crosslinking agent (B) a base (C-2) without the addition of ethanol (EtOH) solution of the crosslinking agent (B) is a concentration shown in Table 1, aqueous solutions or 1-propanol (1PrOH) was prepared and cross-linking agent solution of a compound of the crosslinking agent (B) to the number of total nitrogen atom in (a) the ratio of the number of carboxy groups in (B) (COOH / N) There was added dropwise to 3APTES solution until 1-2 ( "the scope of example the COOH / N" in Table 1).
[0131]
　Example A2, A4, A6 in the crosslinking agent (B) in which 135BTC, 124BTC or ammonia is a base (C-2) to the PMA, the base to the number of carboxyl groups in the crosslinking agent (B) (C-2 the ratio of the number of) the nitrogen atoms in the (N / COOH) is added until 1.5, then 135BTC, to prepare an aqueous solution of 124BTC or PMA (9.5 mass%). Then, 135BTC, an aqueous solution of 124BTC or PMA, compound (A) in the number of carboxyl groups in the crosslinking agent (B) to the number of total nitrogen atomic ratio (COOH / N) is 1-2 (Table 1 " was added dropwise to 3APTES solution until range ") embodiment the COOH / N.
[0132]
　When dropping a solution of the crosslinking agent to 3APTES solution in Examples A1 ~ A8 (B), dropwise addition of the solution the solution is added dropwise a crosslinking agent (B) becomes clouded (cohesive) when the cross-linking agent (B) the amount was evaluated by determining the ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atom in the above compound (a) (COOH / N) . The results are shown in the "range of the composition is transparent COOH / N" in Table 1.
　Whether or not the solution is cloudy, it was visually confirmed.
[0133]
EXAMPLES B1 ~ B5]
　used in Example 3-aminopropyltrimethoxysilane; as (3APTS (3-Aminopropyl) trimethoxysilane ), and 50 wt% of 3-aminopropyltrimethoxysilane 25g was dropped into water 25g after dissolution so that it was confirmed that the alkoxysilane is hydrolyzed by proton NMR spectrum after standing overnight at room temperature. It was then prepared 3APTS solution to a concentration shown in Table 1. In the in 3APTS aqueous solution, hydrolyzate of 3-aminopropyltrimethoxysilane or their siloxane polymer may be present.
　Further, as the crosslinking agent (B), 135BTC, ehePMA, ethyl half ester 1,2,4-benzenetricarboxylic acid; it was prepared (ehe124BTC ethyl half ester 124BTC).
　ehe124BTC is ethanol added 124BTC anhydride, stirred at room temperature, was prepared by completely dissolving the 124BTC anhydride powder. Proton NMR, it was confirmed that the ester group is formed on the manufactured Ehe124BTC.
[0134]
　In Example B1, B4, B5, the crosslinking agent (B) a base (C-2) without adding, to prepare an ethanol solution of the crosslinking agent (B) is a concentration shown in Table 1, the crosslinking agent (B) the ethanol solution, the compound (a) ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atoms in the (COOH / N) was added dropwise to 3APTS solution until 1.
[0135]
　In Example B2, B3, ammonia is a base (C-2) in a cross-linking agent (B) 135BTC, base to the number of carboxyl groups in the crosslinking agent (B) (C-2) in the nitrogen atom of the It was added until the number of the ratio (N / COOH) of 2.0, and then prepare the 135BTC solution (10.1 wt%). Then, the 135BTC aqueous compound (A) ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atoms in the (COOH / N) was added dropwise to 3APTS solution until 1.
[0136]
　When dropping a solution of the crosslinking agent to 3APTS solution in Examples B1 ~ B5 (B), dropwise addition of the solution the solution is added dropwise a crosslinking agent (B) becomes clouded (cohesive) when the cross-linking agent (B) the amount of above was evaluated by determining the compound ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atom in (a) (COOH / N) . The results are shown in the "range of the composition is transparent COOH / N" in Table 1.
　It should be noted, is whether or not the solution is cloudy, was confirmed by visual observation.
[0137]
Example C1]
　1,3-bis (3-aminopropyl) - tetramethyldisiloxane; mixed solvent (BATDS 1,3-bis (3- aminopropyl) -tetramethyldisiloxane, corresponding to the compound (A)) (ethanol / water = 0.24, dissolved in by weight)), to prepare a BATDS solution (2 wt%) was prepared 135BTC ethanol solution (9.5 wt%).
　Then, the BATDS solution (2 wt%), the 135BTC ethanol solution, the compound ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atom in (A) (COOH / N) is 1 It was added dropwise until to prepare a semiconductor membrane composition.
[0138]
　When dropping the 135BTC ethanol solution BATDS solution in Example C1, to clouding solution 135BTC ethanol solution was added dropwise the above-mentioned dropping amount of 135BTC of (cohesive) time, total nitrogen atom in the compound (A) It was assessed by determining the ratio of the number of carboxy groups in the crosslinking agent (B) to the number of (COOH / N). The results are shown in the "range of the composition is transparent COOH / N" in Table 1.
　It should be noted, is whether or not the solution is cloudy, was confirmed by visual observation.
[0139]
　The composition of the semiconductor membrane composition obtained in each example are shown in Table 1 below.
　Note that brackets the item "type of compound (A)" represents the concentration of the compound (A) compound in the solution (A).
　Further, "concentration in the composition" of a compound (A), the compound ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atom in (A) "COOH / N" is the maximum value in case of dropping the crosslinking agent (B) as, it represents the concentration of the compound to the whole semiconductor membrane composition (a).
　Further, brackets in the item "type of the crosslinking agent (B)", the crosslinking agent (B) a solution of the crosslinking agent represents the concentration of (B), crosslinking agent (B) in the base (C-2) when the dropwise represents the concentration of base (C-2) a crosslinking agent after the dropping (B) a solution of the crosslinking agent (B).
　Further, embodiments in Examples A1 ~ A8, 3- aminopropyltriethoxysilane was used as the compound (A) (3APTES) is to include one primary nitrogen atom in the molecule, 1 nitrogen atom / secondary nitrogen atom It was described as / tertiary nitrogen atom = 1/0/0. In the solution, 3APTES may be a hydrolyzate may be a siloxane polymer.
　Further, embodiments in Examples B1 ~ B5, 3- aminopropyltrimethoxysilane was used as the compound (A) (3APTS) is to include one primary nitrogen atom in the molecule, 1 nitrogen atom / secondary nitrogen atom It was described as / tertiary nitrogen atom = 1/0/0. In the solution, 3APTS may be a hydrolyzate may be a siloxane polymer.
　Further, in Example C1, it was used as the compound (A) 1,3-bis (3-aminopropyl) - for tetramethyldisiloxane (BATDS) is containing two primary nitrogen atoms per molecule, a primary It was described as a nitrogen atom / secondary nitrogen atom / tertiary nitrogen atom = 2/0/0.
[0140]
[Table 1]

[0141]
　In Example A1, a solution 135BTC is dropped the ratio of the number of carboxy groups in the crosslinking agent (B) (COOH / N) is in the 0-1 to the number of total nitrogen atom in the compound (A) is not clouded It was clear to. In Example A3, A5, COOH / N are respectively greater than 0.7, the solution 124BTC or PMA is added dropwise in 0.79 than was cloudy. That, COOH / N are each 0.7 or less, 0.79 under the following conditions, aggregation without cloudiness could be prepared for semiconductor film composition is suppressed. Further, by forming a film by using a semiconductor membrane composition aggregation is suppressed without white turbidity, it is estimated that less smooth film unevenness can be formed.
　Further, the crosslinking agent (B) in the base example (C-2) was added A2, A4, A6, and the crosslinking agent (B) embodiment has an ester bond A7, the A8, the compound was carried out ( solution each crosslinking agent (B) is dropped in all the range of the ratio of the number of carboxy groups in the crosslinking agent (B) (COOH / N) to the number of total nitrogen atom in a) is not cloudy, the semiconductor We were able to maintain the transparency of the use coating composition.
　Using the semiconductor membrane composition aggregation is suppressed without cloudiness by forming a film, it is estimated that less smooth film unevenness can be formed.
[0142]
　In Compound Example with (A) as a 3-aminopropyltrimethoxysilane (3APTS) B1, no addition of a base (C-2) a crosslinking agent (B), and the crosslinking agent (B) is an ester even if you do not have a binding, it was shown that can dropwise a number of crosslinking agents (B) while maintaining the transparency of the semiconductor membrane composition.
　Further, the crosslinking agent (B) in the base example (C-2) was added B2, B3, and the crosslinking agent (B) In Example B4, B5 having an ester bond, compounds were performed (A) solution each crosslinking agent (B) is dropped in all the range of the cross-linking agent to the number of total nitrogen atoms in the ratio of carboxy groups in (B) (COOH / N) is not clouded in a semiconductor membrane We were able to maintain the transparency of the composition.
[0143]

[Examples 1 to 17 and Comparative Examples 1 to 3]
　to prepare a semiconductor membrane composition having the composition and pH shown in Table 2 below. In the case of using the additive (C) as an acid (C-1), and mixing the crosslinking agent (B) After addition acid (C-1) to the compound (A) solution, it added agents in the case of using the base (C-2) as (C), the base (C-2) a crosslinking agent is added to (B), then a solution of the compound in which crosslinking agent (B) is dissolved in a solvent ( They are mixed in a) solution.
　In Table 2, the concentration of the compound (A) is the concentration of compound (A) in the semiconductor membrane composition, the concentration in the parenthesis in the solvent other than water, other than water in the semiconductor membrane composition it is the concentration of the solvent.
　In Table 2, the concentration of "amine other than the compound (A)" is the concentration of "amine other than the compound (A)" in the semiconductor membrane composition.
　In Table 2, numerical values in parentheses in the crosslinking agent (B) or COOX containing compound other than the crosslinking agent (B) is a carboxyl group in the crosslinking agent (B) to the number of total nitrogen atom in the compound (A) It represents the ratio of the number of (COOH / N), or a compound ratio of the number of COOX groups in COOX containing compound other than the crosslinking agent (B) to the number of total nitrogen atom in (a) (COOX / N) .
　In Table 2, the acid numbers in parentheses in (C-1), compound the ratio of the number of carboxyl groups in the acid to the number of total nitrogen atom (C-1) in (A) (COOH / N) the stands, the values in parentheses in the nucleotide (C-2), represents the base number of the ratio of (C-2) a nitrogen atom in (N / COOH) on the number of carboxyl groups in the crosslinking agent (B).
[0144]
Example 1
　3-aminopropyltriethoxysilane compound (A) (3APTES), after a 50 wt% aqueous solution was dissolved in water, the alkoxysilane is hydrolyzed by proton NMR spectra after standing overnight It was used in the composition preparing what it was confirmed that the. The weight average molecular weight after hydrolysis (Mw) of, was 430.
　To a crosslinking agent (B) 135BTC base (C-2) a is to ammonia and water are mixed, and a mixed solution of ammonia and 135BTC (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
　Then, a mixed solution of 3APTES solution, 135BTC ammonia, and water were mixed so that the concentration shown in Table 2, were prepared for semiconductor film composition.
[0145]
[Examples 2 to 5,7,8,14-16]
　in the same manner as in Example 1, such that the composition and concentration shown in Table 2, were prepared for semiconductor film composition.
　Here, the compounds in Examples 7 and 8 of (A) 3- aminopropyl diethoxymethylsilane (3APDES), after dissolved in water and 50% by weight aqueous solution, alkoxy proton NMR spectra after standing overnight silane was used in the compositions prepared what was confirmed to be hydrolyzed. The weight average molecular weight after hydrolysis (Mw) of, was 230.
　Further, 3-aminopropyl trimethoxysilane of the compounds in Examples 14 ~ 16 (A) (3APTS ) , after a 50 wt% aqueous solution was dissolved in water, alkoxysilanes by proton NMR spectra after standing overnight what was confirmed that it was hydrolyzed using the compositions prepared.
[0146]
Example 6
　3-aminopropyl diethoxymethyl silane compound (A) (3APDES), after a 50 wt% aqueous solution was dissolved in water, alkoxysilanes by proton NMR spectra After standing overnight hydrolysis it has been used in the compositions prepared what was confirmed. The weight average molecular weight after hydrolysis (Mw) of, was 230.
　The resulting 3APDES solution in formic acid (FA) solution (4.4 wt%) of compound acid to the number of total nitrogen atom in (A) the ratio of the number of (C-1) a carboxyl group in (COOH / N) after There was mixed so that 0.92 to 3APDES solution, ethanol solution of a crosslinking agent (B) PMA, and water were mixed so that the concentration shown in Table 2, the semiconductor membrane composition It was prepared.
[0147]
Example 9
　3-aminopropyl diethoxymethyl silane (3APDES) 4g of the compound (A), was added to 1-propanol (1PrOH) 56g, formic acid (FA) solution (8.8 wt%) dropwise 20g did. After stirring for 1 h at room temperature, and stirred for 1 hour in a water bath at 60 ° C., to obtain a 3APDES solution.
　A crosslinking agent (B) 1-propanol half ester 1,2,4-benzenetricarboxylic acid (1Prhe124BTC; 1-propanol half ester 124BTC) can be prepared by dissolving the trimellitic anhydride to 1-propanol (1PrOH), proton It was used to confirm that the ester group is formed by NMR.
　To the resulting 3APDES solution, mixed 1Prhe124BTC solution, further water, and 1-propanol were mixed at a concentration shown in Table 2, were prepared for semiconductor film composition.
[0148]
Example 10
　As in Example 9, so that the composition and concentration shown in Table 2, were prepared for semiconductor film composition.
[0149]
Example 11
　3-aminopropyl diethoxymethyl silane compound (A) (3APDES), after it dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 230.
　A crosslinking agent (B) ethyl half ester oxydicarboxylic phthalate (eheOPDA; ethylhalf ester oxydiphthalic acid) solution was obtained by dissolving 4,4'-oxydiphthalic anhydride in ethanol.
　Resulting 3APDES aqueous, EheOPDA solution, water, ethanol (EtOH), and 1-propanol were mixed at a concentration shown in Table 2, were prepared for semiconductor film composition.
[0150]
EXAMPLE 12
　3-aminopropyl diethoxymethyl silane compound (A) (3APDES), after it dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 230.
　A crosslinking agent (B) ethyl half ester of pyromellitic acid; ethanol solution (ehePMA ethyl half ester PMA) was prepared.
　Ethanol solution of a crosslinking agent (B) 1,2,4,5-cyclohexane tetracarboxylic ethyl half ester (eheHPMA 1,2,4,5-Cyclohexanetetracarboxylic ethyl half ester ) was prepared.
　Resulting 3APDES aqueous, EhePMA solution, EheHPHA solution, water, ethanol (EtOH), and 1-propanol were mixed at a concentration shown in Table 2, were prepared for semiconductor film composition.
[0151]
Example 13
　N-METHYLAMINOPROPYLMETHYLDIMETHOXYSILANE of Compound (A) (N-MAPDS), after dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight.
　EheOPDA solution is the cross-linking agent (B) was obtained by dissolving the oxydiphthalic anhydride in ethanol.
　N-MAPDS aqueous solution obtained, EheOPDA solution, water, ethanol (EtOH), and 1-propanol were mixed at a concentration shown in Table 2, were prepared for semiconductor film composition.
[0152]
Example 17

　The branched polyethylene imine 2 (BPEI_2), BASF Corp. polyethyleneimine (Mw = 70,000,1 nitrogen atom / secondary nitrogen atom / tertiary nitrogen atoms = 31 / 40/29) was used.
[0153]
　The amount of 1 nitrogen atom (mol%), the amount of secondary amount of nitrogen atoms (mol%) and tertiary nitrogen atom (mol%) is a polymer sample was dissolved in heavy water, the obtained solution, manufactured by Bruker the decoupling method with a single pulse reverse gate with AVANCE500 type nuclear magnetic resonance apparatus, at 80 ° C. 13 analyzes the results of measurement of C-NMR, The attribution, European Polymer Journal, 1973, Vol . 9, pp. 559 is described in,.
[0154]
　The weight average molecular weight, using an analytical device Shodex GPC-101 was determined using a column Asahipak GF-7M HQ, was calculated polyethylene glycol as a standard. The developing solvent used was acetic acid concentration 0.5 mol / L, an aqueous solution of sodium nitrate concentration 0.1 mol / L.
[0155]
　Wherein the amounts of 1 nitrogen atom (mol%), the amount of secondary nitrogen atom (mol%), and the amount of tertiary nitrogen atom (mol%), respectively, the amount represented by the following formula A ~ C it is.
　The amount of 1 nitrogen atom (mol%) = (1 nitrogen atom of mol number / (mol number of primary mol number +3 nitrogen atom of mol number +2 nitrogen atom of a nitrogen atom)) × 100 ··· formula a
　quantity of secondary nitrogen atom (mol%) = (mol number of secondary nitrogen atoms / (mol number of primary mol number +3 nitrogen atom of mol number +2 nitrogen atom of a nitrogen atom)) × 100 · · · formula B
　the amount of tertiary nitrogen atom (mol%) = (tertiary nitrogen atom mol number / (mol number of primary mol number +3 nitrogen atom of mol number +2 nitrogen atom of a nitrogen atom)) × 100 · · · formula C
[0156]
　3-aminopropyl trimethoxysilane of the compound (A) (3APTS; (3 -Aminopropyl) trimethoxysilane) , after a 50 wt% aqueous solution was dissolved in water, alkoxysilanes by proton NMR spectra After standing overnight hydrolysis what was confirmed that it was resolved using the compositions prepared.
　To a crosslinking agent (B) 135BTC base (C-2) a is to ammonia and water are mixed, and a mixed solution of ammonia and 135BTC (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
　It was prepared an aqueous solution of branched polyethyleneimine 2 (BPEI_2).
　3APTS aqueous mixed solution of 135BTC ammonia, BPEI_2 solution, and water were mixed so that the concentration shown in Table 2, were prepared for semiconductor film composition.
[0157]
Comparative Example 1
　3-aminopropyltriethoxysilane compound (A) (3APTES), after dissolved in water and 50% by weight aqueous solution, the alkoxysilane is hydrolyzed by proton NMR spectra after standing overnight It was used in the composition preparing what it was confirmed that the. It was then prepared 3APTES solution to a concentration shown in Table 2.
[0158]
Comparative Example 2
　Compound of (A) 3- aminopropyltriethoxysilane (3APTES), after dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight.
　The resulting 3APTES (50 wt%) aqueous solution, having no carboxyl group, tripropyl-1,2,4-benzenetricarboxylic acid having three ester bonds (TrPr124BTC; tripropyl-124BTC) 1- propanol, and 1 - propanol were mixed at a concentration shown in Table 2, were prepared for semiconductor film composition.
[0159]
Comparative Example 3
　in the same manner as in Comparative Example 1, so that the composition and concentration shown in Table 2, were prepared 3APDES solution.
[0160]
[Table 2]

[0161]

　semiconductor membrane composition (hereinafter, also referred to as "composition".) Silicon substrate was prepared as a substrate for applying the. Place the silicon substrate on a spin coater, the composition 1.0mL prepared in Examples and Comparative Examples was added dropwise at 10 seconds a constant speed, after holding for 13 seconds, 1 seconds at 2000 rpm (rpm rotation speed) , after rotating 30 seconds at 600 rpm, dried by rotating 10 seconds at 2000 rpm. By this. Film was formed on a silicon substrate.
　Then, after 1 minute drying at 125 ° C., nitrogen atmosphere (30 kPa), 300 ° C. for 10 minutes to heat the film. For the evaluation of heat resistance, further, 350 ° C., 380 ° C., (continuous process the same sample), each 10 minutes, and heated the membrane at 400 ° C..
[0162]

　after 400 ° C. heating, a refractive index was measured, which is formed on a silicon substrate. Refractive index was measured using an ellipsometer. The film thickness was calculated from the measured optical data. Thickness when the above 10 nm, were fitted with air / (Cauchy + Lorentz oscillator model) / natural oxide film / silicon substrate optical model. Thickness when less than 10 nm, using Cauchy + Lorentz oscillator model using the complex refractive index of the material of the same composition which is more thick film 10 nm, the air / (Cauchy + Lorentz oscillator model) / natural oxide It was fitted with film / silicon substrate optical model. Thickness, since obtained by calculation, the results can also be negative.
　In Table 3, N633 denotes the refractive index at a wavelength of 633 nm.
　The results are shown in Table 3.
[0163]

　was based on the thickness residual ratio calculated from thickness after heating for 10 minutes at a film thickness after heating 10 minutes at 300 ° C. and 380 ° C. to evaluate the heat resistance of the film. Wherein the thickness of the residual ratio is as shown below, the film thickness residual ratio is 70% or more was judged as "Yes heat resistance".
　Thickness residual ratio (%) = (380 thickness after the thickness / 300 ° C. heating ℃ after heating) × 100
　The results are shown in Table 3.
[0164]

　a cross-linking structure of the film was measured by FT-IR (Fourier transform infrared spectroscopy). Analyzer used is as follows.
~ FT-IR spectrometer-
　infrared absorption spectrometer (DIGILAB Excalibur (manufactured DIGILAB Co.))
- Measurement conditions
　- IR light source: air-cooled ceramic, beamsplitter: Wide Range KBr, detector: Peltier cooling DTGS, measuring wavenumber range: 7500Cm -1 ~ 400 cm -1 , resolution: 4 cm -1 , the number of integrations: 256, background: Si bare wafer used, measurement atmosphere: N 2 (10L / min), the angle of incidence of the IR (infrared): 72 ° (= Si of Brewster angle)
~ judgment condition ~
　imide bond is 1770 cm -1 , 1720 cm -1 was determined in the presence of vibration peak of. Amide bond 1650 cm -1 , 1520 cm -1 was determined in the presence of vibration peak of.
　The results are shown in Table 3.
[0165]

　The film thickness of 20nm or more 150nm or less film was evaluated the smoothness of the film in the form observation by SEM. Using S-5000 is a scanning electron microscope (SEM) (manufactured by Hitachi, Ltd.), the acceleration voltage 3 kV, 200,000 times, was measured at 500nm wide field of view. With respect to the average thickness, when the difference between the maximum thickness and the minimum thickness is less than 25% was judged as "Yes smoothness".
　The results are shown in Table 3. Incidentally, the film after heating at 400 ° C. 10 minutes and subjected to SEM morphology observation.
[0166]

　For the film thickness is less than 20nm film, the unevenness of the film was evaluated by morphological observation by SPM. Using a scanning probe is a microscopic (SPM) SPA400 (manufactured by Hitachi High-Technologies), at dynamic force microscope mode was measured at 3 microns × 3 microns square area. For a film thickness measured with an ellipsometer, root-mean-square roughness measured in the SPM when 25% or less was judged as "Yes smoothness".
　The results are shown in Table 3. Incidentally, the film after heating at 400 ° C. 10 min were included in the SPM morphological observation.
[0167]
　The measurement results and evaluation results of the properties in each example and film formed by using the semiconductor membrane composition according to Comparative Examples shown in Table 3. Note that blank in the Table 3 represents an unconfirmed (crosslinked structure) or incomplete (SEM morphology observation and SPM morphological observation).
[0168]
[table 3]

[0169]
　As shown in Table 3, although the film thickness residual ratio in Examples 1 to 8 and 12 to 17 was 70% or more both film thickness residual rate in Comparative Example 1 was less than 66%. Films formed from the semiconductor membrane composition in each example from this is estimated to be excellent in heat resistance.
　Example 12, since using 3APDES a compound having a primary amino group as the crosslinking agent (B), the film thickness residual ratio was higher than that of Example 13 using N-MAPDS a compound having a secondary amine It was. Therefore, compound film formed of a semiconductor membrane composition using a primary amino group as the crosslinking agent (B), it is estimated that more excellent heat resistance.
　In Examples 1 ~ 3,7,9 ~ 11,13,14, SEM morphological observation result of the film was smooth.
　On the other hand, in Comparative Examples 2 and 3, or the film surface is not a mirror surface, or there are many small pinholes was not smooth.
　Further, in Example 4, SPM morphological observation result of the film was smooth.
[0170]

Example 18
　in the same manner as in Example 9, 3APDES solution, 1Prhe124BTC solution, a mixture of water and 1-propanol, the semiconductor membrane composition (solution 1) was prepared.
　In solution 1, the concentration is 2% by weight of the compound in the semiconductor membrane composition (A), the ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atom in the compound (A) (COOH / N) is 1.0, the ratio of the number of carboxyl groups in the acid to the number of total nitrogen atom in the compound (a) (C-1) (COOH / N) is 1.83, in the semiconductor membrane composition the concentration of 1-propanol was 91 mass%.
　Then, after dropping a coating solution 6mL to 300mm φ silicon substrate, a silicon substrate, one second 1000 rpm, 60 seconds at 600 rpm, 5 seconds after the rotation at 1000 rpm, and dried for 2 minutes at 100 ° C., heated for 1 minute at 250 ° C. and it was subjected to 10 minutes heat treatment further 400 ° C. in atmosphere of nitrogen. Thus, the film is formed on a silicon substrate.
[0171]
Example 19
　As in Example 9, 3APDES solution, 1Prhe124BTC solution, water, and 1-propanol were mixed and semiconductor membrane composition (solution 2) was prepared.
　In solution 2, the concentration is 0.2% by weight of the compound in the semiconductor membrane composition (A), the compound ratio of the number of carboxy groups in the crosslinking agent (B) to the number of total nitrogen atom in (A) ( COOH / N) is 1.0, the compound (ratio of the number of carboxyl groups in the acid to the number of total nitrogen atom (C-1) in a) (COOH / N) is 1.83, the semiconductor membrane composition the concentration of 1-propanol in the medium was 99.1 wt%.
　Then, the film was formed in the same manner as the silicon substrate as in Example 18.
[0172]
EXAMPLE 20
　3-aminopropyl diethoxymethyl silane compound (A) (3APDES), after it dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 230.
　A crosslinking agent (B) ethyl half ester oxydicarboxylic phthalate (eheOPDA; ethylhalf ester oxydiphthalic acid) solution was obtained by dissolving 4,4'-oxydiphthalic anhydride in ethanol.
　Resulting 3APDES aqueous, EheOPDA solution, water, ethanol (EtOH), and 1-propanol were mixed at a concentration shown in Table 4, the semiconductor membrane composition (solution 3) was prepared.
　By using the obtained semiconductor membrane composition (solution 3), film was formed in the same manner on a silicon substrate as in Example 18.
[0173]
　Film thickness at 1cm from the center of 300mm φ silicon substrate, determined film thickness at 5 cm, the film thickness at 9cm, difference in film thickness 1cm and 13cm from the film thickness and the center of at 13cm (percent), the silicon substrate It was evaluated in-plane film thickness distribution.
　The results are shown in Table 4.
　In the In Table 4, the concentration in the parenthesis in 3APDES (2 wt%), 3APDES (0.2 wt%), 3APDES (1.8 wt%) represents the concentration of 3APDES in the composition.
　1Prhe124BTC [1.0], the values in parentheses in eheOPDA [1.0], the compound (A) in which relative number of the total nitrogen atom in 3APDES, the ratio of the number of carboxy groups 1Prhe124BTC or in EheOPDA a crosslinking agent (B) it represents the (COOH / N).
　Is a numerical value in the parentheses of FA 1.83 represents the compound ratio of the number of carboxy groups of FA in an acid to the number of total nitrogen atom (C-1) in 3APDES is (A) (COOH / N) ing.
　1PrOH (91 wt%), 1PrOH (99.1 wt%), the concentration in the parenthesis in 1PrOH (33 wt%), and EtOH (29 wt%) represents the concentration of 1PrOH and EtOH in the composition .
　Furthermore, "difference in film thickness 1cm and 13cm from the center (%)" is (thickness at 1cm from (center) - (thickness at 13cm from the center)) "/ ((film at 1cm from the center thickness) + (thickness) + (thickness at 13cm from the film thickness) + (centers at 9cm from the center at 5cm from the center)) / 4) was calculated by multiplying by 100. "
[0174]
[Table 4]

[0175]
　As shown in Table 4, 1 cm and a thickness difference (%) in 13cm from the center, in the embodiment is 15% or less, it exhibited a small value. Accordingly, by using the semiconductor membrane compositions of Examples 18-20 it was shown to obtain a smooth film having excellent in-plane uniformity in 300mm φ silicon wafers in a more simple process.
[0176]

Example 21
　BPEI_2 solution and 3-aminopropyltriethoxysilane (3APTES; (3-Aminopropyl) triethoxysilane) aqueous solution were mixed, and ammonia (NH3) as the base (C-2) to 135BTC N / COOH (the ratio of the number of nitrogen atoms in the ammonia to the number of carboxyl groups in 135BTC) was mixed so that 1.5. Here, 3APTES used was left overnight as a 50% aqueous solution.
　Then, COOH / N (BPEI_2 and the ratio of the number of carboxy groups in 135BTC to the number of nitrogen atoms in 3APTES) is mixed 135BTC so that 0.9 in a mixed solution of BPEI_2 and 3APTES, for semiconductor film composition was prepared things (solution 4).
[0177]
Example 22
　was prepared for semiconductor film composition prepared in Example 2 (Solution 5).
[0178]
Example 23
　was prepared for semiconductor film composition prepared in Example 18 (solution 1).
[0179]
Example 24
　was for semiconductor film composition prepared in Example 20 (Solution 3) prepared.
[0180]
Example 25
　dissolved in a mixed solution of compound (A) and 3-amino propyl diethoxymethyl silane (3APDES) 3- aminopropyldimethylethoxysilane (3APDMS), the 3APDES18.75g and 3APDMS6.25g water 25g after, I was prepared and allowed to stand overnight.
　The mixed solution, an ethanol solution of a crosslinking agent (B) eheOPDA, 1- propanol, ethanol, and water were mixed so that the concentration shown in Table 5, the semiconductor membrane composition (solution 6) was prepared .
[0181]
Example 26
　After a 3-aminopropyl diethoxymethyl silane compound (A) (3APDES) a mixed solution of p-xylylenediamine (PXDA), 50% aqueous solution was added to 3APDES water overnight static to those who location, by mixing 1-propanol solution of PXDA, was prepared.
　The mixed solution, an ethanol solution of a crosslinking agent (B) EheOPDA, ethanol, water were mixed so that the concentration shown in Table 5, the semiconductor membrane composition (solution 7) was prepared.
[0182]
Example 27
　The mixed solution (solution of the 3-aminopropyl diethoxymethyl silane compound (A) (3APDES) bis triethoxysilyl ethane (BTESE) The inclusion of siloxane polymers of 3APDES and BTESE the estimated), was added to 3APDES2.0g 1-propanol 26.15G, formic acid (FA) solution (8.8 wt%) was 10g dropwise added BTESE1.85G, after stirring at room temperature for one hour, It was prepared by heating for one hour at 60 ℃ in a water bath.
　The mixed solution, 1-propanol solution of a crosslinking agent (B) 1Prhe124BTC, and water were mixed so that the compositions shown in Table 5, the semiconductor membrane composition (solution 8) were prepared.
[0183]
Example 28]
　and the compound (A) and 3-amino propyl diethoxymethyl silane (3APDES) 1,1,3,3,5,5- hexa ethoxy-1,3,5-silacyclohexane (HETSC) mixed solution (in the solution is estimated to include the siloxane polymer of 3APDES and HETSC), was added to 3APDES2.0g 1-propanol 28.6 g, formic acid (FA) solution (8.8 mass %) was 10g dropwise added HETSC1.4G, after stirring one hour at room temperature, was prepared by heating one hour at 60 ° C. in a water bath.
　The mixed solution, 1-propanol solution of a crosslinking agent (B) 1Prhe124BTC, and water were mixed so that the compositions shown in Table 5, the semiconductor membrane composition (solution 9) was prepared.
[0184]
Example 29]
　and; (1,3-bis (3- aminopropyl) -tetramethyldisiloxane BATDS) of 1-propanol solution, - the compound (A) 1,3-bis (3-aminopropyl) tetramethyldisiloxane ethanol solution of eheOPDA a crosslinking agent (B), and 1-propanol, and ethanol were mixed so that the compositions shown in Table 5, the semiconductor membrane composition (solution 10) was prepared.
[0185]
　In the In Table 5, BPEI_2 (1.7 wt%), 3APTES (3.3 wt%), 3APTES (3 wt%), 3APDES (2 wt%), 3APDES (1.8 wt%), 3APDES ( 4 mass%), 3APDMS (0.6 wt%), PXDA (5 wt%), BTESE (3.7 wt%), the concentration in the parenthesis in HETSC (2.8 wt%) and BATDS (2 wt%) is, BPEI_2,3APTES in each composition, 3APDES, represent 3APDMS, pXDA, BTESE, each concentration of HETSC and BATDS.
　135BTC [0.9], 124BTC [1.5 ], 1Prhe124BTC [1.0], 1Prhe124BTC [1.15], and the values in parentheses in eheOPDA [1.0] is to the number of total nitrogen atom in the compound (A), 135BTC, 124BTC, 1Prhe124BTC , and it represents the ratio of the number of carboxy groups (COOH / N) in EheOPDA.
　It is a numerical value in the parentheses of FA 1.83 represents the compound ratio of the number of carboxy groups in the FA against number of total nitrogen atom in (A) (COOH / N) .
　NH3 numbers in parentheses in <1.5> represents the ratio of the number of nitrogen atoms in the NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) .
　1PrOH (91 wt%), 1PrOH (33 wt%), 1PrOH (28 wt%), 1PrOH (2 wt%), 1PrOH (69 wt%), 1PrOH (37 wt%), EtOH (29 mass%), EtOH (43 wt%), EtOH (36 mass%), and the concentration in the parenthesis in EtOH (59 wt%) represents the concentration of 1PrOH and EtOH in the composition.
[0186]
　Next, 100 nm width, dropwise 200nm depth of the composition 0.5mL a trench pattern in the silicon oxide substrate provided in 10 seconds a constant speed, after holding for 13 seconds, 1 second 2000 rpm, was rotated for 30 seconds at 600rpm after, drying by rotating 10 seconds at 2000 rpm. Then, after drying 1 minute dropped compositions at 100 ° C., then heated for 1 minute at 300 ° C., was 10 minutes heat treatment at 400 ° C..
　Then, the composition in the trenches was observed whether it is filled with cross-section SEM. A case filled area of at least 90% of the area within the trench was A (filling property is good).
　The results are shown in Table 5.
[0187]
　Similarly, 50 nm wide, 200 nm depth of the composition 0.5mL a trench pattern in the silicon oxide substrate having added dropwise at 10 seconds a constant speed, after holding for 13 seconds, 1 seconds at 2000 rpm, 30 seconds at 600rpm rotational after, it dried by rotating 10 seconds at 2000 rpm. Then, after drying 1 minute dropped compositions at 100 ° C., then heated for 1 minute at 300 ° C., was 10 minutes heat treatment at 400 ° C..
　Then, the composition in the trenches was observed whether it is filled with cross-section SEM. A case filled area of at least 90% of the area within the trench and A (filling property is good), and the case is filled area is less than 90% of the area within the trench and B.
　The results are shown in Table 5.
[0188]
[table 5]

[0189]
　As shown in Table 5, the filling property was good in the 100nm wide trench. Therefore, by using the semiconductor membrane compositions of Examples 21-29 it was shown to obtain a film having excellent filling property in 100nm wide trench.
　The 50nm wide trench, from the results of Examples 23, 25, 26, for semiconductor film composition comprising 3APDES and 1Prhe124BTC, 3APDES, semiconductor membrane composition comprising 3APDMS and eheOPDA, 3APDES, semiconductor membrane comprising pXDA and EheOPDA embedding of the composition was good. On the other hand, in Example 24, it voids 10 percent in the semiconductor membrane composition comprising 3APDES and eheOPDA occurred.
　Therefore, than the membrane (Example 24) having an imide bond, better film (Example 23) with amide-imide bond it is presumed that the filling property is more excellent. Also, from Examples 24 and Example 26, films formed from a solution containing pXDA is an amine having a ring structure (Example 26) is inferred that the filling property is more excellent.
[0190]

Comparative Example 4
　BPEI_2 aqueous acid (C-1) as the ratio of the number of carboxyl groups in the acid acetic acid (AA) to the number of nitrogen atoms in the COOH / N (BPEI_2 ) was added to a 0.14. Then mixed in BPEI_2 aqueous 135BTC as COOH / N (the ratio of the number of carboxy groups in 135BTC to the number of nitrogen atoms in BPEI_2) is 0.67, the concentration of ethanol (EtOH) to the entire composition so it becomes 33 mass%, ethanol were mixed and semiconductor membrane composition (solution 11) was prepared.
[0191]
Example 30]
　3-aminopropyl methyl diethoxy silane compound (A) (3APDES), after it dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 230.
　To a crosslinking agent (B) 135BTC base (C-2) a is to ammonia and water are mixed, and a mixed solution of ammonia and 135BTC (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
　The 3APDES aqueous mixed solution of 135BTC and ammonia, water and ethanol were mixed at a concentration shown in Table 6, the semiconductor membrane composition (solution 12) was prepared.
[0192]
Example 31
　was prepared for semiconductor film composition prepared in Example 18 (solution 1).
[0193]
Example 32
　was prepared for semiconductor film composition prepared in Example 19 (Solution 2).
[0194]
Example 33
　was for semiconductor film composition prepared in Example 20 (Solution 3) prepared.
[0195]
　After each 5mL dropwise 1 ~ 3, 11, 12 to the low-resistance silicon substrate, a low resistance silicon substrate, 5 seconds at 1000 rpm, and rotated 30 seconds at 500 rpm. Then, after drying 1 minute dropped compositions at 100 ° C., then heated for 1 minute at 250 ° C., was 10 minutes heat treatment at 400 ° C.. Thus, the laminated body formed of a low resistance silicon substrate / film was obtained.
[0196]
(Ratio Measurement of dielectric constant)
　was measured relative dielectric constant of the film in the obtained laminate.
　The relative dielectric constant, using a mercury probe apparatus (SSM5130), 25 ℃, relative humidity of 30%, was measured by a conventional method at a frequency 100kHz.
　The results are shown in Table 6.
[0197]
(Measurement of leakage current density)
　Next, for evaluating electrical characteristics, of leak current density as follows. Specifically, applying a mercury probe on the membrane surface of the resulting laminate was measured field strength 1 MV / cm, and a value of 2 MV / cm and leakage current density.
　The results are shown in Table 6.
[0198]
　In Table 6, the composition of the samples in Comparative Example 4, Examples 30-33 show the dielectric constant and the leak current density.
　In the In Table 6, BPEI_2 aqueous solution (1.8 mass%), 3APDES (3 wt%), in 3APDES (2 wt%), 3APDES (0.2 wt%), and 3APDES (1.8 wt%) concentration in parentheses represent the concentrations of BPEI_2 and 3APDES in the composition.
　135BTC [0.67], 135BTC [1.0 ], the values in parentheses in 1Prhe124BTC [1.0] and eheOPDA [1.0] is to the number of total nitrogen atom in the compound (A), 135BTC, 1Prhe124BTC, and carboxy group in EheOPDA it represents the number of ratios (COOH / N).
　Numerical and is 0.14 and 1.83 in the parentheses of AA and FA is represents the compound ratio of the number of carboxy groups in the AA or FA to the number of total nitrogen atom in (A) (COOH / N) .
　NH3 numbers in parentheses in <1.5> represents the ratio of the number of nitrogen atoms in the NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) .
　1PrOH (91 wt%), 1PrOH (99.1 wt%), 1PrOH (33 wt%), the concentration in the parenthesis in EtOH (33 mass%), EtOH (30 mass%) and EtOH (29 mass%), it represents the concentration of 1PrOH and EtOH in the composition.
[0199]
[Table 6]

[0200]
　As shown in Table 6, in Examples 30-33, it was smaller relative dielectric constant than that of Comparative Example 4.
　Example 30 leakage current density in Comparative Example 4 and the electric field strength 1 MV / cm is was comparable, in Examples 31-33 were smaller leakage current density at the electric field intensity 1 MV / cm than in Comparative Example 4. The electric field strength was increased, the leakage current density at the electric field intensity 2 MV / cm is, in Examples 30-33, the leakage current density is smaller than that of Comparative Example 4. Thus, Examples 30 to 33 (in particular, Examples 31 to Example 33) By using the semiconductor membrane composition according to, that excellent film electrical characteristics can be obtained is shown.
[0201]

Example 34]
　3-aminopropyltriethoxysilane compound (A) (3APTES), after dissolved in water as a 50 wt% aqueous solution overnight static things that location using the compositions prepared. The weight average molecular weight after hydrolysis (Mw) of, was 430.
　And which is the crosslinking agent (B) PMA by mixing base (C-2) a is ammonia and water and a mixed solution of ammonia and PMA (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
　The 3APTES aqueous mixed solution of PMA and ammonia, and water were mixed so that the concentration shown in Table 7, the semiconductor membrane composition (solution 13) was prepared.
[0202]
Example 35]
　3-aminopropyltriethoxysilane compound (A) (3APTES), after it dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 430.
　To a crosslinking agent (B) 124BTC base (C-2) a is to ammonia and water are mixed, and a mixed solution of ammonia and 124BTC (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
　The 3APTES aqueous mixed solution of 124BTC and ammonia, and water were mixed so that the concentration shown in Table 7, the semiconductor membrane composition (solution 14) was prepared.
[0203]
Example 36
　3-aminopropyltriethoxysilane compound (A) (3APTES), after it dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 430.
　To a crosslinking agent (B) 135BTC base (C-2) a is to ammonia and water are mixed, and a mixed solution of ammonia and 135BTC (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
　The 3APTES aqueous mixed solution of 135BTC and ammonia, and water were mixed so that the concentration shown in Table 7, the semiconductor membrane composition (solution 15) was prepared.
[0204]
Example 37]
　Compound A solution of a (A) 3- aminopropyl diethoxymethylsilane (3APDES), was added to 3APDES2.0g 1-propanol 28 g, formic acid (FA) solution (8.8 wt%) was 10g dropwise, after stirring for one hour at room temperature, it was prepared by heating one hour at 60 ° C. in a water bath.
　The 3APDES solution, a crosslinking agent (B) 1-propanol half ester of pyromellitic acid; 1-propanol solution (1PrhePMA 1-propanol half ester PMA ), 1- propanol, and to the water a composition shown in Table 7 were mixed in, a semiconductor membrane composition (solution 16) was prepared.
[0205]
(Preparation of Sample)
　preparing a silicon wafer that silica is present on the surface, 1 the silicon wafer, placed on a spin coater, a semiconductor membrane composition (solution 13-16) in 10 seconds a constant speed. and 0mL dropwise, after holding for 13 seconds, the silicon wafer was rotated for 1 second at 2000 rpm, still after rotating for 30 seconds at 600 rpm, dried by rotating 10 seconds at 2000 rpm.
　Thus, on a silicon wafer, to form a polymer layer, laminate structure in which a silicon wafer and the polymer layer are laminated (hereinafter, "sample (polymer / Si)" also referred to) was obtained.
[0206]
　The sample (polymer / Si) in the hot plate, and placed in contact and the silicon wafer surface and a hot plate under an air atmosphere, 100 ° C. soft 60 seconds soft-baked at baking temperature (heat treatment) was. Additional 10 minutes at 300 ° C. in a nitrogen atmosphere, and was continuously heated for 10 minutes at 400 ° C..
[0207]
(Adhesion Evaluation)
　to the copper film surface of the laminate, after forming the square mass of 0.2cm angle 5 × 5 or cutters, after sticking a Scotch tape (3M Co. No.56), pull once peeled , it was to measure the number of peeled squares.
　The results are shown in Table 7.
[0208]
　In the In Table 7, 3APTES (10 wt%), and the concentration in the parenthesis in 3APDES (2.7 wt%) represents the concentration of 3APTES and 3APDES in the composition.
　PMA [2.0], 124BTC [1.5 ], 135BTC [1.0], and the values in parentheses in 1PrhePMA [0.7] is to the number of total nitrogen atom in the compound (A), PMA, 124BTC, 135BTC, and in 1PrhePMA it represents the ratio of the number of carboxy groups (COOH / N).
　NH3 numbers in parentheses in <1.5> represents the ratio of the number of nitrogen atoms in the NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) .
　Concentration in parenthesis in 1PrOH (88 wt%) represents the concentration of 1PrOH in the composition.
[0209]

(Preparation of Sample)
　The copper film was 100nm deposited by plating on the silicon substrate, the copper film surface was prepared substrate was cleaned with helium plasma treatment. The copper film plane after the plasma treatment, as in and form a seal layer (polymer layer).
　Thus, on the copper, to form a polymer layer, a laminate of copper and the polymer layer are laminated (hereinafter, "sample (polymer / Cu)" also referred to) was obtained.
[0210]
(Adhesion Evaluation)
　to the copper film surface of the laminate, after forming the square mass of 0.2cm angle 5 × 5 or cutters, after sticking a Scotch tape (3M Co. No.56), pull once peeled , it was to measure the number of peeled squares.
　The results are shown in Table 7.
[0211]
[Table 7]

[0212]
　As shown in Table 7, the case of forming a film by using a semiconductor membrane compositions of Examples 34-37, no peeling between the polymer and the silicon substrate or a copper substrate, the adhesion is good there were.
[0213]

Comparative Example 5
　in the PMA is a crosslinking agent (B) is mixed with ammonia and water is a base (C-2), was mixed solution of ammonia and PMA (14 wt%) . Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
[0214]
Comparative Example 6
　with 124BTC by mixing ammonia and water is a base (C-2) in a cross-linking agent (B), and a mixed solution of ammonia and 124BTC (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
[0215]
Comparative Example 7
　and 135BTC by mixing ammonia and water is a base (C-2) in a cross-linking agent (B), and a mixed solution of ammonia and 135BTC (14 wt%). Ammonia, the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) was added to a 1.5.
[0216]
Comparative Example 8
　was prepared BPEI_2 solution (1.5 wt%).
[0217]
Comparative Example 9
　by mixing ammonia and water is a base (C-2) to the PMA is a crosslinking agent (B), and a mixed solution of PMA and ammonia.
　BPEI_2 aqueous mixed solution of PMA and ammonia, and water were mixed so that the concentration shown in Table 8, the semiconductor membrane composition (solution 17) was prepared.
[0218]
Comparative Example 10
　and 124BTC by mixing ammonia and water is a base (C-2) in a cross-linking agent (B), and a mixed solution of 124BTC and ammonia.
　BPEI_2 aqueous mixed solution of 124BTC and ammonia, and water were mixed so that the concentration shown in Table 8, the semiconductor membrane composition (solution 18) was prepared.
[0219]
Comparative Example 11
　and 135BTC by mixing ammonia and water is a base (C-2) in a cross-linking agent (B), and a mixed solution of 135BTC and ammonia.
　BPEI_2 aqueous mixed solution of 135BTC and ammonia, and water were mixed so that the concentration shown in Table 8, the semiconductor membrane composition (solution 19) was prepared.
[0220]
Comparative Example 12]
　Compound of (A) 3- aminopropyltriethoxysilane (3APTES), after dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 430. It was then prepared 3APTES aqueous solution with 10 wt% by adding water.
[0221]
[Examples 38-40]
　and for semiconductor film compositions prepared in Examples 34-36 (solution 13-15) prepared.
[0222]
Comparative Example 13]
　The compounds of (A) 3- aminopropyl diethoxymethylsilane (3APDES), after a 50 wt% aqueous solution was dissolved in water, and allowed to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 230.
[0223]
Example 41]
　was for semiconductor film composition prepared in Example 20 (Solution 3) prepared.
[0224]
Comparative Example 14]
　Compound solution is (A) 3- aminopropyl diethoxymethylsilane (3APDES), in addition to 3APDES2.0g 1-propanol 28 g, formic acid (FA) solution (8.8 wt%) was 10g dropwise, after stirring for one hour at room temperature, then heated for one hour at 60 ° C. in a water bath, then was prepared 1-propanol was added 10g.
[0225]
Example 42]
　Compound solution is (A) 3- aminopropyl diethoxymethylsilane (3APDES), in addition to 3APDES2.0g 1-propanol 28 g, formic acid (FA) solution (8.8 wt%) was 10g dropwise, after stirring for one hour at room temperature, it was prepared by heating one hour at 60 ° C. in a water bath.
　The 3APDES solution, 1-propanol solution of a crosslinking agent (B) 1Prhe124BTC, 1-propanol, and water are mixed so as to have the composition shown in Table 8, the semiconductor membrane composition (solution 20) was prepared .
[0226]
(Evaluation Method)
　decomposition temperature rating of the polymer was carried out in the following manner.
　Examples 38-42, each sample 100mg prepared in Comparative Example 5-14 was placed in the sample cup, thermogravimetric measuring apparatus: using (manufactured by Shimadzu Corporation DTG-60 (model number)), from 30 ° C. in a nitrogen atmosphere to 550 ° C. and heated at a Atsushi Nobori rate of 30 ° C. / min, the mass was measured at each temperature. The temperature at which 10% decrease from the mass at 300 ° C. Table 8 shows.
[0227]
　In the In Table 8, BPEI_2 aqueous solution (1.5 mass%), 3APTES (10 wt%), 3APDES (50 wt%), 3APDES (1.8 wt%), in parenthesis in 3APDES (4 wt%) concentration represents the concentration of BPEI_2,3APTES and 3APDES in the composition.
　PMA (14 wt%), 124BTC (14 wt%), and the concentration in the parenthesis in 135BTC (14 wt%) represents PMA, the concentration of 124BTC and 135BTC in the composition.
　PMA [1.8], 124BTC [1.35 ], 135BTC [0.9], PMA [2.0], 124BTC [1.5], 135BTC [1.0], the values in parentheses in eheOPDA [1.0], and 1Prhe124BTC [1.15], the compound (A ) to the number of total nitrogen atoms in, PMA, it represents 124BTC, 135BTC, the ratio of the number of carboxy groups in eheOPDA and 1Prhe124BTC a (COOH / N).
　NH3 numbers in parentheses in <1.5> represents the ratio of the number of nitrogen atoms in the NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) .
　Numerical and is 1.83 in parenthesis FA is represents the compound ratio of the number of carboxy groups in the FA against number of total nitrogen atom in (A) (COOH / N) .
　1PrOH (33 wt%), 1PrOH (76 wt%), the concentration in the parenthesis in 1PrOH (88 wt%), EtOH (29 wt%) represents the concentration of 1PrOH and EtOH in the composition.
[0228]
[Table 8]

[0229]
　At a heating stages to 300 ° C., the sample has become a solid, further by raising the temperature, weight loss when the polymer became solid decomposed takes place. It was evaluated decomposition temperature at a temperature at which decreased 10% by weight at 300 ° C..
　As shown in Table 8, compounds having a Si-O bond (A) and solid obtained from the compositions of Examples 38-42 containing a crosslinking agent (B) does not contain a cross-linking agent (B) compared to the solid obtained from the compositions of Comparative examples 9-11 containing solids obtained from the compositions of Comparative examples 12-14, and Si-O bond that does not have aliphatic amine and the crosslinking agent (B), high the decomposition temperature had.
　This result, by using the compound (A) and the compositions of Examples 38-42 containing a crosslinking agent (B), it was shown that the decomposition temperature can form a high polymer film.
[0230]

Comparative Example 15]
　Poly solution was placed in a water bath cooled to 5 ° C. or less with ice water, then added pyromellitic dianhydride (PMDA) 1.14 g, were added ethanol 24g , 3-aminopropyl diethoxymethylsilane (3APDES) was slowly added dropwise 2.18 g, was stirred for 2 hours. After confirming that all the compounds were dissolved, water was added 3g, to give storage stability evaluation composition (solution 21). Is in solution 21 is inferred that the amic acid of PMDA and 3APDES are formed.
[0231]
[Examples 43 to 45]
　were for semiconductor film compositions prepared in Examples 34-36 (solution 13-15) prepared.
[0232]
(Evaluation method)
　Evaluation of Storage Stability of the solution was carried out in the following manner.
　Solution 13 ~ put 20 mL ~ 50 mL to 15, 21 to polyethylene closed container capacity 100 mL, in a refrigerator held at 5 ° C., and held for 20 days without opening the refrigerator door. After 20 days, taken out from the refrigerator, the formation of precipitate in the solution was visually After returning to room temperature, was confirmed cloudy like. The case where formation of a precipitate and turbidity was not observed neither A, the case where at least one of the formation of a precipitate and turbidity was observed was B.
　The evaluation results are shown in Table 9.
[0233]
[Table 9]

[0234]
　As shown in Table 9, the formation of the solution 13-15 precipitate after 5 ° C. refrigerated storage 20 days of Examples 43-45, the white turbidity such abnormalities were not observed. In solution 21 of Comparative Example 15, the gel-like precipitate was formed.
　Solution 13 to 15 Examples 43 to 45, further precipitate in solution even after storage 10 weeks at room temperature, abnormalities clouding or the like was confirmed.
　Therefore, the solution 13 to 15 Examples 43-45, compounds (A) and the crosslinking agent (B) is believed to be dispersed without agglomeration in solution, indicates that the excellent storage stability It has been.
[0235]

Comparative Example 16]
　by mixing ammonia and water is a base (C-2) to the PMA is a crosslinking agent (B), and a mixed solution of PMA and ammonia.
　BPEI_2 aqueous mixed solution of PMA and ammonia, and water were mixed so that the concentration shown in Table 10, the semiconductor membrane composition (solution 22) was prepared.
[0236]
Example 46]
　3-aminopropyl diethoxymethyl silane compound (A) (3APDES), after it dissolved in water and 50 wt% aqueous solution was used in the preparation of compositions what was left to stand overnight. The weight average molecular weight after hydrolysis (Mw) of, was 230.
　By mixing ammonia and water is a base (C-2) in a cross-linking agent (B) 135BTC, was mixed solution of ammonia and 135BTC (14 wt%).
　Then, a mixed solution of 3APDES solution, 135BTC ammonia, and water were mixed so that the concentration shown in Table 10, the semiconductor membrane composition (solution 23) was prepared.
[0237]
Example 47]
　Compound A solution of a (A) 3- aminopropyl diethoxymethylsilane (3APDES), was added to 3APDES2.0g 1-propanol 28 g, formic acid (FA) solution (8.8 wt%) was 10g dropwise, after stirring for one hour at room temperature, it was prepared by heating one hour at 60 ° C. in a water bath.
　The 3APDES solution, 1-propanol solution of a crosslinking agent (B) 1-propyl half ester oxydicarboxylic phthalate (1PrheOPDA), 1- propanol, and water are mixed so as to have the composition shown in Table 10, the semiconductor use coating composition (solution 24) was prepared.
[0238]
Example 48]
　was prepared for semiconductor film composition prepared in Example 29 (solution 10).
[0239]
(Preparation of Sample)
　preparing a silicon wafer silica surface is present, placing the silicon wafer on a spin coater, a semiconductor membrane composition 0.5mL dropwise at 10 seconds a constant speed, 13 seconds holding after, the silicon wafer was rotated for 1 second at 2000 rpm, still after rotating for 30 seconds at 600 rpm, dried by rotating 10 seconds at 2000 rpm.
　Thus, the polymer layer is formed on a silicon wafer, laminate structure in which a silicon wafer and the polymer layer are laminated (hereinafter, "sample (polymer / Si)" also referred to) was obtained.
　The sample (polymer / Si) in the hot plate, and placed in contact and the silicon wafer surface and a hot plate under an air atmosphere, 100 ° C. soft 60 seconds soft-baked at baking temperature (heat treatment) was. It was heated an additional 10 minutes at 300 ° C. in a nitrogen atmosphere, and 400 sequentially ° C. for 10 minutes.
　Put silicon wafer to form a polymer film in the manner described above the chamber, the chamber × 10 5 -6 Torr (6.7 × 10 -4 was evacuated to Pa), oxygen 50 sccm (about 8.3 × 10 -7 m 3 / s) at flow into the chamber, after adjusting the chamber pressure to 0.15 Torr (20 Pa), was irradiated with oxygen plasma 100W.
[0240]
　Evaluation of the etching selectivity, the thickness of the polymer film after heating for 10 minutes at above 400 ° C., subtracting the thickness of the polymer film after the irradiation of oxygen plasma for 3 minutes and 5 minutes, the amount of decrease in film thickness (nm ) it was carried out by calculating the. The results are shown in Table 10.
[0241]
　In the In Table 10, BPEI_2 aqueous solution (1.5 mass%), 3APDES (10 wt%), 3APDES (2.7 wt%), and the concentration in the parenthesis in BATDS (2 wt%), the composition it represents the concentration of BPEI_2,3APDES and BATDS in.
　PMA [1.42], 135BTC [1.0 ], 1PrheOPDA [0.7], and the values in parentheses in eheOPDA [1.0] is to the number of total nitrogen atom in the compound (A), PMA, 135BTC, 1PrheOPDA, and in EheOPDA it represents the ratio of the number of carboxy groups (COOH / N).
　It is a numerical value in the parentheses of FA 1.5 represents the compound ratio of the number of carboxy groups in the FA against number of total nitrogen atom in (A) (COOH / N) .
　NH3 numbers in parentheses in <1.5> represents the ratio of the number of nitrogen atoms in the NH3 to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) .
　1PrOH (85 wt%), 1PrOH (37 wt%), the concentration in the parenthesis in EtOH (59 wt%) represents the concentration of 1PrOH and EtOH in the composition.
[0242]
[Table 10]

[0243]
　As shown in Table 10, 3 minutes from results after the etching, the compound (A) and Si-O obtained using the semiconductor membrane compositions of Examples 46 and 47 containing a cross-linking agent (B) containing film decrease of film than an organic film obtained by using the composition of Comparative example 16 containing an aliphatic amine and the crosslinking agent (B) (i.e., the etch rate) is small.
　Similarly, from the results after 5 minutes etching, compound (A) and Si-O-containing film obtained using the composition of Example 47 and 48 containing a cross-linking agent (B) are aliphatic amines and crosslinking agents decrease of film than an organic film obtained by using the composition of Comparative example 16 containing (B) (i.e., the etch rate) is small.
　As described above, Si-O-containing film obtained by using the semiconductor membrane compositions of Examples 46-48, it etching rate by oxygen plasma is less than that of the organic film (Comparative Example 16), i.e., etching It was found to be excellent in selectivity.
　Further, from the results after 5 minutes etching, Si-O-containing film obtained by using the semiconductor membrane composition of Example 47 containing the compound (A) is a 3APDES and the crosslinking agent (B) 1PrheOPDA is , compound (a) is a BATDS and decrease of film than Si-O-containing film obtained by using the semiconductor membrane composition of example 48 containing eheOPDA a crosslinking agent (B) (i.e., etching speed) was small.
[0244]
　Disclosure of 2015 November 16 has been Japanese patent application filed 2015-224196 its entirety is incorporated herein by reference.
　All documents described herein, patent applications, and technical standards, each individual publication, patent applications, and to the same extent as if it is marked specifically and individually incorporated by techniques standard reference, It incorporated by reference herein.

claims

[Claim 1]Compound having a Si-O bond and a cationic functional group containing at least one of a nitrogen atom and 2 nitrogen atom and (A),
　-C (= O) OX group (X in the molecule, a hydrogen atom has 1 or more carbon atoms 6 is an alkyl group) three or more, of the three or more -C (= O) OX group, one or more than six is -C (= O) OH group and the weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), and
　a polar solvent (D),
　including, for semiconductor film composition.
[Claim 2]
　And a cationic functional group Si-O bonds and containing at least one of 1 nitrogen atom and 2 nitrogen atom, the weight average molecular weight of 130 to 10,000 compounds (A),
　-C in the molecule (= O) OX group (X is a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group) has three or more, three or more -C (= O) of the OX group, one or more 6 or less is -C (= O) OH group, weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), and
　a polar solvent (D),
　including, for semiconductor film composition.
[Claim 3]
　Furthermore, the crosslinking agent (B) having a ring structure in the molecule, according to claim 1 or semiconductor membrane composition of claim 2.
[Claim 4]
　The ring structure is at least one benzene ring and a naphthalene ring, a semiconductor membrane composition of claim 3.
[Claim 5]
　Furthermore, the crosslinking agent (B), in the three or more -C (= O) OX group, at least one X is an alkyl group having 1 to 6 carbon atoms, of claims 1 to 4 for semiconductor film composition according to any one.
[Claim 6]
　The weight average molecular weight over 46 195 following acids having a carboxy group (C-1) and at least one additive selected from the group consisting of weight-average molecular weight 17 to 120 or less bases (C-2) having a nitrogen atom ( C) further comprising a semiconductor membrane composition according to any one of claims 1 to 5.
[Claim 7]
　Containing at least one selected from the group consisting of weight-average molecular weight of 10,000 or more 400,000 following weight-average molecular weight of 90 or more and 600 or less of the amine compound having a ring structure in its aliphatic amine and intramolecular claims 1 to 6 for semiconductor film composition according to any one of.
[8.]
　Used in the filling material of a recess formed in a substrate, a semiconductor membrane composition according to any one of claims 1 to 7.
[Claim 9]
　Used in the multilayer resist method, a semiconductor membrane composition according to any one of claims 1 to 7.
[Claim 10]
　A method of manufacturing a semiconductor membrane composition according to any one of claims 1 to 9,
　wherein the compound (A), the crosslinking agent (B), and a mixing step of mixing the the method of manufacturing a semiconductor membrane composition comprising.
[Claim 11]
　The mixing process, claim a step of mixing a mixture of weight average molecular weight over 46 195 following acids having a carboxy group (C-1) and the compound (A), the crosslinking agent (B), and the the method of manufacturing a semiconductor membrane composition according to 10.
[Claim 12]
　Claim wherein the mixing step is a step of mixing a mixture of a weight-average molecular weight more than 17 with a nitrogen atom than 120 bases (C-2) and the crosslinking agent (B), and the compound (A), the the method of manufacturing a semiconductor membrane composition according to 10.
[Claim 13]
　A method of manufacturing a semiconductor member by using a semiconductor membrane composition according to any one of claims 1 to 9,
　the step of applying said semiconductor membrane composition to a substrate,
　a heating step of heating the substrate on which the semiconductor membrane composition has been applied under the following conditions temperature 250 ° C. or higher 425 ° C., the manufacturing method of the semiconductor member.
[Claim 14]
　A method of manufacturing a semiconductor for process material using a semiconductor membrane composition according to any one of claims 1 to 7,
　the step of applying said semiconductor membrane composition to a substrate ,
　a heating step of heating the substrate on which the semiconductor membrane composition has been applied under the following conditions temperature 250 ° C. or higher 425 ° C., a manufacturing method for a semiconductor process material.
[Claim 15]
　A substrate,
　1 nitrogen atom and compound weight average molecular weight of 130 to 10,000 and a cationic functional group and Si-O bond containing at least one of secondary nitrogen atom (A), and in the molecule - C (= O) OX group (X is a hydrogen atom or 1 or more to 6 carbon atoms which is an alkyl group) having three or more, of the three or more -C (= O) OX group, one or 6 or less is -C (= O) OH groups, a reaction product having a weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B),
　comprising a semiconductor device.
[Claim 16]
　The reactant has at least one amide bond and an imide bond, a semiconductor device according to claim 15.