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> has a cationic functional group containing at least one of the primary nitrogen atoms and 2 nitrogen atom, the compound weight average molecular weight of 400,000 or less than 10,000 and (A), -C in the molecule ( is = O) OX group (X, have 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 6 One following is -C (= O) OH group, weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), and water (D), wherein the said compound (a) is an aliphatic amine there, a semiconductor membrane composition.
<2> In addition, the crosslinking agent (B) having a ring structure in the molecule, for semiconductor film composition according to <1>.
<3> the ring structure is at least one benzene ring and a naphthalene ring, a semiconductor membrane composition according to <2>.
<4> 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 < 3 for semiconductor film composition according to any one of>.
<5> 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 <4>.
<6> The weight average molecular weight of said compound (A) is 200,000 or less than 10,000, <1> to semiconductor membrane composition according to any one of <5>.
<7> is pH at 25 ° C. of 7.0 or less, <1> to semiconductor membrane composition according to any one of <6>.
<8> metal and used in the adhesion layer of the insulating film, <1> to semiconductor membrane composition according to any one of <7>.
<9> low dielectric constant used in the pore sealing material of the material, <1> to semiconductor membrane composition according to any one of <8>.
<10> use in the filler material of the recess formed in the substrate, <1> to semiconductor membrane composition according to any one of <9>.
[0006]
<11> <1> - A method of manufacturing a semiconductor membrane composition according to any one of <10>, mixing the compound (A), the crosslinking agent (B), and the the method of manufacturing a semiconductor membrane composition comprising mixing process.
<12> 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 manufacturing method of a semiconductor membrane composition according to <11>.
<13> 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 manufacturing method of a semiconductor membrane composition according to <11>.
[0007]
<14> <1> - A method of manufacturing a semiconductor member by using a semiconductor membrane composition according to any one of <10>, 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]
<15> <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]
<16> a substrate having a primary nitrogen atom and secondary nitrogen cationic functional group containing at least one atom, the compound weight average molecular weight of 400,000 or less 10,000 or more (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) has three or more, three or more -C (= O) of the OX group, 1 one or more than six is -C (= O) are OH groups comprises a reaction product having a weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), the semiconductor device.
<17> the reactant has at least one amide bond and an imide bond, a semiconductor device according to <16>.
Effect of the invention
[0010]
　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
[0011]
　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 "".
[0012]
[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".) Has one nitrogen atom and secondary nitrogen cationic functional group containing at least one atom, weight average molecular weight of 10,000 or more 400,000 less is compound (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 three above have, among the three or more -C (= O) OX group, one or more than six is -C (= O) an OH group, a weight average molecular weight of 200 or more 600 or less is the cross-linking agent ( It includes a B), and water (D), the. Compound (A) is an aliphatic amine.
[0013]
　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).
[0014]
　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.
[0015]
　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.
[0016]
　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.
[0017]
　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.
[0018]
　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 5% or less.
[0019]
　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 porous material, pore seal material having insulating property, adhesion, etc. pore seal properties (pore seal film), in the via sidewall of the through silicon vias 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 a porous material by soaking into the pores of the porous material for the formation of such pore filling material to protect it from such etching damage (pore-filling film). Particularly as applications are suitable for pore sealing material having a low dielectric constant material, the adhesion layer between the metal and the insulating film, filling material of a recess formed in the substrate (embedding planarization film).
[0020]
(Compound (A))
　for semiconductor film composition according to the present embodiment has a primary nitrogen atom and secondary nitrogen cationic functional group containing at least one atom, the weight average molecular weight of 10,000 or more 400,000 less a compound include (a), compound (a) is an aliphatic amine. Further, compound (A) preferably has no siloxane bond (Si-O bond).
[0021]
　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.
[0022]
　Further, compound (A), in addition to 1 nitrogen atom and 2 nitrogen atom, may contain a tertiary nitrogen atom.
[0023]
　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).
[0024]
[Formula 1]

[0025]
　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.
[0026]
　The weight average molecular weight of the compound (A) is 10,000 or more 400,000 or less, is preferably 10,000 or more to 200,000. When the weight average molecular weight is 10,000 or more, there is a tendency that can form a high yield smooth film.
[0027]
　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 GPC-101 and two analytical column (Tosoh TSKgel G6000PWXL-CP and TSKgel G3000PWXL-CP ) and detects the refractive index at a flow rate of 1.0 mL / min using a reference column (manufactured by Tosoh TSKgel SCX), are calculated by the analysis software polyethylene glycol as a standard (SIC manufactured 480II data station).
[0028]
　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.
[0029]
　Examples of the aliphatic amine, Compound (A), more specifically, ethyleneimine, propyleneimine, butylene imine, pentylene imine, hexylene imine, Hepuchiren'imin, Okuchiren'imin, trimethylene imine, tetramethylene imine, pentamethylene imine , hexamethyleneimine, polyalkyleneimine is a polymer of an alkylene imine such as octamethylene imine; polyallylamine; polyacrylamide.
[0030]
　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.
[0031]
　Compound (A) is a derivative of polyalkyleneimine 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. Resulting Specifically, polyalkyleneimine an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms), polyalkyleneimine derivatives obtained by introducing an aryl group or the like, by introducing a crosslinkable group such as a hydroxyl group polyalkyleneimine polyalkyleneimine derivatives which are can be given.
　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.
[0032]
　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 a method in which substituted by cationic functional group-containing monomers at least a portion of, and the like.
　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.
[0033]
　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.
[0034]
　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.
[0035]
　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.
[0036]
　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%.
[0037]
　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 0.01 mass% to 10 mass%, more preferably at most 0.04 mass% to 5 mass%.
[0038]
(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).
[0039]
　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.
[0040]
　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.
[0041]
　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.
[0042]
　Crosslinking agent (B) is a compound of 200 or more and 600 or less weight-average molecular weight. Preferably, a 200 to 400 compounds.
[0043]
　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.
[0044]
　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.
[0045]
　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.
[0046]
　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.
[0047]
　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.
[0048]
　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.
[0049]
　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.
[0050]
　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.
[0051]
　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.
[0052]
　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.
[0053]
　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,
[0054]
　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.
[0055]
[Formula 2]

[0056]
　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.
[0057]
　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.
[0058]
　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.
[0059]
(Water (D))
　for semiconductor film composition according to the present embodiment, water (D) (preferably ultrapure water) containing. Water (D) may be a heavy water may contain heavy water.
　The content of water (D) in the semiconductor membrane composition is not particularly limited, for example, not more than 99.9985 wt% 1.0 wt% or more based on the total composition, 40% by weight or more 99. it is preferably not more than 9985% by mass.
[0060]
(Additives (C))
　for semiconductor coating composition according to the present embodiment, the aforementioned of the compound (A), may contain a cross-linking agent (B) and other additives in water (D) (C) . 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.
[0061]
　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.
[0062]
　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.
[0063]
　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 from 0.02 to 1.5, particularly preferably 0.02 to 1.2.
[0064]
　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.
[0065]
　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.
[0066]
　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.
[0067]
(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.
[0068]
　For semiconductor film composition according to the present embodiment, the weight average molecular weight of 90 or more and 600 or less, may further comprise an amine compound having a cyclic structure in the molecule. The weight average molecular weight of 90 or more and 600 or less, the amine compound 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 liable to obtain an amine compound having an aromatic ring is more preferred.
　Further, the following weight average molecular weight of 90 to 600, the amine compound having a cyclic structure in the molecule, an imide and a crosslinking agent (B), Imidoamido, easy to form a crosslinked structure such as an amide, it is possible to enhance the heat resistance from the point, a compound having a primary amine is preferred. Furthermore, as the aforementioned amine compounds, imide with the crosslinking agent (B), Imidoamido, easily increase the number of cross-linked structure such as an amide, from viewpoint of increasing the heat resistance, the two primary amines diamine compounds having triamine compound having three primary amine is more preferable.
　The alicyclic amine, cyclohexylamine, etc. dimethylamino cyclohexane.
　The aromatic ring amines such as diaminodiphenyl ether, 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, tris ( such as 4-aminophenyl) amine.
　The heterocyclic heterocyclic amines, heterocyclic (e.g., thiophene ring) containing a sulfur atom as a hetero atom, or a heterocyclic ring containing a nitrogen atom as a hetero atom (e.g., pyrrole ring, pyrrolidine ring, 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.
　The heterocyclic amines having a heterocyclic ring containing nitrogen atom, 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.
[0069]
　For semiconductor film composition according to the present embodiment may also contain water (D) other than the solvent (aqueous solvent). The solvent other than water (D), for example, protic inorganic compounds; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclohexanol, ethylene glycol, aldehydes such as furfural, acetone, ethyl methyl ketone, cyclohexane; propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol, alcohols such as glycerin; ethers such as tetrahydrofuran, dimethoxyethane ketones; acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N- methylformamide, N, N- Jimechiruho Muamido, N- methylacetamide, N, N- dimethylacetamide, N- methyl-2-pyrrolidone, acid derivatives such as hexamethylphosphoramide; acetonitrile, nitriles such as propylonitrile carbonitrile; nitromethane, nitro compounds such as nitrobenzene; polar solvents such as sulfur compounds such as dimethyl sulfoxide.
[0070]
　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.
[0071]
　The pH of the semiconductor membrane composition according to the present embodiment is not particularly limited, is preferably 2.0 to 12.0, and more preferably 7.0 or less. If it is pH7.0 or less, when used as a pore sealing material having a low dielectric constant material, the surface of the low dielectric constant material film is formed on the surface of the conductive portion of the metal or the like becomes less film is formed, You can have selectivity depending on the material of the formation surface of the film.
[0072]
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 has included water (D), at any time of manufacturing the semiconductor membrane composition, the water (D), the compound (A), crosslinked agent (B), and compound (a) may be added to the mixture with the crosslinking agent (B). The timing of adding the other components is not particularly limited.
[0073]
　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.
[0074]
　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.
[0075]
　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.
[0076]
[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.
[0077]

　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.
[0078]
　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.
[0079]
　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.
[0080]

　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.
[0081]
　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.
[0082]
　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.
[0083]

　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.
[0084]

　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.
[0085]
　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.
[0086]
　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.
[0087]
　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.
[0088]
　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.
[0089]

　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, pore sealing material (pore seal 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 has provided a semiconductor member, pore filling material a porous material by soaking the pores of the substrate including a porous material protected from etching damage (the pore filling membrane) Like conductor member and the like.
[0090]
　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.
[0091]
　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.
[0092]
　Between the substrate and the metal containing low dielectric constant material such as a porous material, insulation, adhesion, the semiconductor member which pore seal film is provided with such pore sealing property, the thickness of the pore seal 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 that is disposed in the through hole, may be a member pore seal film is provided comprising an adhesion layer between.
[0093]
　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.
[0094]
　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.
[0095]
　The semiconductor member having a pore filling membrane soaks into the pores of the substrate comprising a porous material, the thickness of the pore filling membrane is, for example, 30nm or more 200nm or less, preferably 50nm or 150nm or less.
[0096]
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.
[0097]
　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.
[0098]
[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 having a primary nitrogen atom and secondary nitrogen cationic functional group containing at least one atom, the weight average molecular weight of 10,000 or more 400,000 less is Compound (A ), and -C in the molecule (= O) OX group (X 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 OX group comprises one or more 6 or less is -C (= O) OH groups, and reaction of the crosslinking agent (B) weight average molecular weight of 200 or more and 600 or less, the reaction product. 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
[0099]
　Following illustratively describes the invention based on examples, the present invention is not limited to these examples.
　In the following, as "water", using ultra-pure water (Millipore Corp. Milli-Q water, resistance 18MΩ · cm (25 ℃) or below).
[0100]

　was prepared branched polyethyleneimine 1-3 used in the following Examples and Comparative Examples (branched polyethyleneimines). The branched polyethylene imine 1, using commercially available ones, as the branched polyethylene imine 3, were synthesized by the procedure described below.
[0101]

　The branched polyethylene imine 1, MP-Biomedicals Inc. polyethyleneimine (Mw = 16,000 ~ 145,000,1 nitrogen atom / secondary nitrogen atom / tertiary nitrogen atoms = 32 / 38/30) was used.
　The branched polyethylene imine 2, BASF Corp. polyethyleneimine (Mw = 70,000,1 nitrogen atom / secondary nitrogen atom / tertiary nitrogen atoms = 31/40/29)
[0102]

(Synthesis of modified polyethylene imine 3)
　according to the following reaction scheme 1, polyethyleneimine as a starting material was synthesized modified polyethylene imine 3. Incidentally, the polymer structure in the following reaction scheme 1 and reaction scheme 2 has a structure schematically showing the arrangement of a tertiary nitrogen atom and secondary nitrogen atom, secondary nitrogen atom substituted by Boc amino ethyl group to be described later the proportion or the like, and various changed by synthesis conditions.
[0103]
[Formula 3]

[0104]
　Detailed procedures for the above reaction scheme 1 is as follows.
　The MP-Biomedicals Inc. polyethyleneimine (50% aqueous solution) 61.06G was dissolved in isopropanol 319ML, (in this embodiment, also referred to as "Boc" a t- butoxycarbonyl group) N-t- butoxycarbonyl aziridine 102 g ( 710Mmol) was added, subjected to heating under reflux for 3 hours to obtain a modified polyethylene imine 3 of Boc amino ethyl group in polyethyleneimine is introduced structures. Ensure that there are no more N-Boc aziridine material by thin layer chromatography (TLC), and a small amount sampled 1 confirmed the structure H-NMR. 1 from H-NMR, the introduction rate of the Boc amino ethyl group with respect to the polyethyleneimine was calculated as 95%.
NMR measurement results of the ~ modified polyethylene imine
　 ~ 3 1 H-NMR (CD 3 OD); Deruta3.3-3.0 (br. S, 2), 2.8-2.5 (br. S, 6.2 ), 1.45 (s, 9)
[0105]
(Branch Synthesis of polyethyleneimine 3)
　the modified polyethylene imine 3 as a starting material was synthesized branched polyethylene imine 3 in accordance with the following reaction scheme 2. Incidentally, branched polyethylene imine 3, the ratio of tertiary nitrogen atom is a greater than branched polyethyleneimine 1,2 hyperbranched polyethyleneimine (hyper branched polyethyleneimine).
[0106]
[Chemical Formula 4]

[0107]
　Detailed procedures for the above reaction scheme 2 is as follows.
　It was slowly added 12N hydrochloric 124mL isopropanol solution of the modified polyethylene imine 3. The resulting solution was heated for 4 hours stirring at 50 ° C. while paying attention to the generation of gas. The generation of gas, gum reactant was generated in the reaction system. Then cooled gas evolution is complete, after cooling, the solvent is eliminated separated from the gummy reaction was washed 3 times with methanol 184 mL. The reaction product after washing is dissolved in water, remove the chloride ions in the anion exchange polymer, a branched polyethylene imine 3 to obtain an aqueous solution containing 58 g.
~ NMR measurement results of branched polyethylene imine
　 ~ 3 1 H-NMR (D 2 O); Deruta2.8-2.4
　 (br. M) 13 C-NMR (D 2 O); [delta] (integration ratio) 57.2 (1.0), 54.1 (0.38) 52.2 (2.26) 51.6 (0.27) 48.5 (0.07) 46.7 (0.37) , 40.8 (0.19) 38.8 (1.06).
[0108]
　For the branched polyethylene imine 3, weight average molecular weight, the amount of 1 nitrogen atom (mol%), the amount of secondary nitrogen atom (mol%), the amount of tertiary nitrogen atoms (mol%) were measured.
　As a result, the weight amount of average molecular weight 75,000,1 nitrogen atom is 45 mol%, the amount of secondary nitrogen atom by 11 mol%, the amount of tertiary nitrogen atoms was 44 mol%.
[0109]
　The amount of 1 nitrogen atom (mol%), the amount of secondary amount of nitrogen atoms (mol%) and tertiary nitrogen atom (mol%), the polymer sample (branched polyethylene imine 3) was dissolved in heavy water, the obtained solution, by decoupling method with a single pulse reverse gate with Bruker AVANCE500-type nuclear magnetic resonance apparatus, at 80 ° C. 13 from the results of measurement of C-NMR, The attribution, European Polymer Journal, 1973, Vol . 9, pp. 559 is described in,.
[0110]
　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.
[0111]
　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
[0112]
　Using the foregoing as the prepared branched polyethyleneimine 1-3 respectively, were prepared for semiconductor film compositions of Examples A1 ~ Example C11. Details are as follows.
　Incidentally, a solution of the compound (A), a solution of the crosslinking agent (B), a solution obtained by adding acid to the compound (A) (C-1) , the crosslinking agent (B) a base was added a solution of (C-2) when mixing each was mixed after confirming that there is no precipitation in the solution to be mixed.
[0113]
Example A1]
　branched polyethyleneimines obtained as described above 1; number of aqueous solution (concentration 2 wt%) and a carboxy group (BPEI_1 branched polyethyleneimine, compound (corresponding to A)) is three 1,3 It was prepared 5- benzenetricarboxylic acid (135BTC, the corresponding cross-linking agent (B)) ethanol solution (concentration 2 wt%). And BPEI_1 aqueous solution was added dropwise 135BTC ethanol solution little by little. At this time (in this embodiment, BPEI_1) Compound (A) (in this embodiment, 135BTC) crosslinking agent (B) to the number of total nitrogen atoms in the ratio of the number of carboxy groups in (COOH / N) is It was added dropwise 135BTC ethanol solution BPEI_1 solution until 0.7, to prepare a semiconductor membrane composition. Aforementioned COOH / N, the dropwise before starting 135BTC ethanol solution is 0, the number is increased as it dropwise 135BTC ethanol solution, and 0.7 after completion of the dropwise addition of 135BTC ethanol solution.
[0114]
Example A2]
　in branched polyethylene imine 1 (BPEI_1) aqueous solution (concentration 2% by weight after addition acetate), acetic acid; was added (AA acetic acid). In this case, Compound (A) (in this embodiment, BPEI_1) acid to the number of total nitrogen atom in (C-1) (in this example, acetic acid) ratio of the number of carboxy groups in (COOH / N) There until 0.5, acetic acid was added to BPEI_1 solution. It was then added dropwise 135BTC ethanol solution (concentration 2% by weight) in BPEI_1 solution. Then, Example A1 Similarly, the compound (A) 135BTC ethanol solution until the ratio of the number of carboxy groups in the crosslinking agent (B) (COOH / N) is 0.7 to the number of total nitrogen atoms in BPEI_1 It was added dropwise to an aqueous solution, to prepare a semiconductor membrane composition.
[0115]
　When dropping the 135BTC ethanol solution BPEI_1 solution in Examples A1 and A2, 135BTC was dripped solution becomes clouded the dropping amount of 135BTC of (aggregating) the time, described above, total nitrogen in the compound (A) It was assessed by determining the cross-linking agent to the number of atoms in the ratio of carboxy groups in (B) (COOH / N) . The results are shown in Table 1.
　It should be noted, is whether or not the solution is cloudy, was confirmed by visual observation.
[0116]
Example B1, B2]
　branched polyethyleneimines obtained as described above 2; aqueous (BPEI_2 branched polyethyleneimine, compound (corresponding to A)) (2 wt%) and 135BTC ethanol solution (Example B1 in 2 wt% It was prepared embodiments example B2 9.5 wt%). And BPEI_2 aqueous solution was added dropwise 135BTC ethanol solution little by little. In this case, dropwise 135BTC ethanol solution BPEI_2 solution until 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 0.71, a semiconductor membrane composition was prepared.
[0117]
Example B3]
　to the branched polyethylene imine 2 (BPEI_2) aqueous solution (concentration 2% by weight after addition acetate), acetic acid (AA), the ratio of the number of carboxy groups in the acid to the number of total nitrogen atoms in BPEI_2 ( COOH / N) is added until a 0.29, and then added dropwise 135BTC ethanol (2 mass%). Example B1 Similarly, compounds BPEI_2 aqueous 135BTC ethanol solution until the ratio of the number of carboxy groups (COOH / N) is 0.71 in the crosslinking agent (B) to the number of total nitrogen atom in (A) It dropped to prepare a semiconductor membrane composition.
[0118]
Example B4 ~ B7, B9, B11, B12 ]
　135BTC as the crosslinking agent (B), oxydiphthalic (ODPA; 4,4'-Oxydiphthalic Acid) , mellitic acid (MeA; Mellitic acid), 1,2,4- benzenetricarboxylic acid (124BTC), and were prepared, respectively pyromellitic acid (PMA), a base (C-2) as an ammonia were prepared respectively;; (ethylamine EA) (NH3 amnonia), ethylamine.
　First, the crosslinking agent (B) adding a base (C-2), then crosslinking agent (B) is dissolved in water or a mixed solvent (ethanol / water = 0.24, by weight). The concentration of the solution containing the crosslinking agent (B) and a base (C-2) are shown in Table 1. Also, the basic (C-2), until the ratio of the number of nitrogen atoms in the base (C-2) to the number of carboxyl groups in the crosslinking agent (B) (N / COOH) becomes a value shown in Table 1 It was added to the base (C-2) a crosslinking agent (B).
　Then, it was added dropwise a solution of the crosslinking agent (B) to the BPEI_2 solution (solution of the compound (A)). In this case, Examples B4 ~ B7, B9 is Example B1 Similarly, 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 0 until .71, examples B11 to COOH / N is 1.07, example B12 until COOH / N is 1.42, was added dropwise a solution of the crosslinking agent (B) in BPEI_2 solution, a semiconductor membrane composition was prepared.
[0119]
Example B8]
　aqueous solution of branched polyethyleneimine 2 (BPEI_2) (2 wt%) and ethyl half ester of pyromellitic acid; ethanol solution (6.4 mass (ehePMA ethyl half ester PMA, corresponding to the cross-linking agent (B)) %) was prepared. 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. And BPEI_2 aqueous solution was added dropwise ehePMA ethanol solution little by little. At this time, Example B1 Similarly, the ehePMA ethanol solution until the ratio of the number of carboxy groups in the crosslinking agent (B) (COOH / N) is 0.71 to the number of total nitrogen atom in the compound (A) It was added dropwise to BPEI_2 solution, to prepare a semiconductor membrane composition.
[0120]
Example B10]
　branched polyethyleneimines 2; was prepared an aqueous solution (2 wt%) and 124BTC ethanol solution (9.5 wt%) of (BPEI_2 branched polyethyleneimine, corresponding to the compound (A)). And BPEI_2 aqueous solution was added dropwise 124BTC ethanol solution little by little. In this case, dropwise 124BTC ethanol solution BPEI_2 solution until 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 1.07, a semiconductor membrane composition was prepared.
[0121]
Example C3]
　branched polyethyleneimines 3 is a highly branched polyethylene imine; an aqueous solution of (BPEI_3 hyper branchedpolyethyleneimine, corresponding to the compound (A)) (2 wt%), an aqueous solution of 135BTC (2 wt%) was added dropwise little by little . In this case, dropped 135BTC aqueous BPEI_3 solution until 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 0.56, the semiconductor the use coating composition was prepared.
[0122]
Example C4 ~ C11]
　crosslinking agent as (B), 124BTC, 135BTC, methyl half ester of pyromellitic acid (mhePMA; methyl half ester PMA) , ehePMA, ethyl half ester 1,2,4-benzenetricarboxylic acid (ehe124BTC; ethyl half ester 124BTC) and 1-propyl half ester 1,2,4-benzenetricarboxylic acid (1Prhe124BTC; a 1-propyl half ester 124BTC) were prepared, respectively, was prepared acetic acid (AA) as an acid (C-1).
　mhePMA, in addition to pyromellitic dianhydride in methanol and refluxed for 120 minutes in an oil bath heated to 80 ° C., was prepared by completely dissolving pyromellitic dianhydride powder. Proton NMR, it was confirmed that the ester group is formed on the manufactured MhePMA.
　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.
　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.
　Then, Example C4, C5, C10, the C11, the branched polyethylene imine 3 (BPEI_3) aqueous solution of acetic acid (AA), the ratio of the number of carboxy groups in the acid to the number of total nitrogen atoms in BPEI_3 (COOH / N) is added until the value shown in Table 1, cross-linking agent dissolved in a solvent shown in subsequent Table 1 (B), in the crosslinking agent (B) to the number of total nitrogen atom in the compound (a) ratio of the number of carboxy groups (COOH / N) was added dropwise to a 0.56.
　In Examples C6 ~ C9, the branched polyethylene imine 3 (BPEI_3) aqueous solution, without the addition of acid (C-1), cross-linking agent dissolved in a solvent shown in Table 1 (B), 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 a 0.56. Incidentally, 1PrOH in Table 1, 1 represents a propanol (1-propanol).
[0123]
Example D1 ~ D8]
　polyallylamine; preparing an aqueous solution of (PAA polyallylamine, Mw = 88,000, Sigma-Aldrich Corp., corresponding to the compound (A)) (2 wt%), as a crosslinking agent (B), 124BTC , 135BTC, pyromellitic acid (PMA; pyromellitic acid), prepared mhePMA, ehePMA, the Ehe124BTC, dissolve the crosslinking agent (B) in ethanol to a concentration shown in Table 1.
　Then, in Examples D1 ~ D6, the PAA aqueous solution, without the addition of acid (C-1), the crosslinking agent shown in Table 1 with an aqueous solution of (B), crosslinked to the number of total nitrogen atom in the compound (A) agents the ratio of the number of carboxy groups in (B) (COOH / N) was added dropwise to a 1.
　In Example D7, D8, the PAA aqueous solution of acetic acid (AA), the ratio of the number of carboxy groups in the acid to the number of total nitrogen atoms in the PAA solution (COOH / N) and the values shown in Table 1 made up by adding each aqueous solution COOH / N of the crosslinking agent shown in subsequent table 1 (B) (compound (crosslinking agent to the number of total nitrogen atom in a) (the ratio of the number of carboxy groups in B)) is It was added dropwise until the 1.
[0124]
　The composition of the semiconductor membrane composition obtained in Examples and Comparative Examples are as shown in Table 1 below.
　Note that brackets the item "type of compound (A)" represents the concentration of the compound (A) a solution compound in (A), when dropped acid (C-1) to the compound (A) to represent the concentration of the acid (C-1) compound after dropping (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).
[0125]
[Table 1]

[0126]
　In Example A1, a solution 135BTC is dropped the ratio of the number of carboxy groups in the crosslinking agent (B) (COOH / N) is at 0-0.15 to the number of total nitrogen atom in the compound (A) is cloudy It is transparent without a solution 135BTC was dripped in COOH / N 0.15 than was cloudy. That, COOH / N 0.15 under the following conditions, it was possible to prepare a semiconductor membrane composition aggregation is suppressed without cloudiness. 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.
[0127]
　In the compound example was added acid (C-1) to (A) A2, 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 0 solution 135BTC was added dropwise at ~ 0.7 is transparent without white turbidity, it was possible to maintain the transparency of the semiconductor membrane composition be dropped many 135BTC than example A1.
[0128]
　In the compound example was added acid (C-1) to (A) B3, 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 0 solution 135BTC was added dropwise at ~ 0.71 is transparent without white turbidity, it is possible to maintain the transparency of the semiconductor membrane composition be dropped many 135BTC than example B1, B2 It was. Therefore, it is possible to mix the compound (A) more crosslinking agent (B) without the composition becomes cloudy, amides between compound after the heat treatment (A) and crosslinking agent (B), crosslinking the imide have more structure, it is possible to produce a superior film by heat or insulating.
[0129]
　Further, the crosslinking agent (B) a base in (C-2) was added Example B4 ~ B7, B9, and the crosslinking agent (B) Example B8 has an ester bond, in the compound (A) solution the ratio of the number of carboxy groups in the crosslinking agent (B) (COOH / N) each crosslinker in 0 ~ 0.71 (B) is added dropwise to the number of total nitrogen atoms are transparent without white turbidity , in the same manner as in example B3, it was possible to maintain the transparency of the semiconductor membrane composition be dropped example B1, a number of cross-linking agent than B2 (B).
[0130]
　It was added base (C-2) a crosslinking agent (B) Example B11, the B12, 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 transparent without a solution in which each cross-linking agent (B) is dropped in each of 0 to 1.07,0 ~ 1.42 cloudy, dropping a number of cross-linking agent than in example B10 (B) We were able to maintain the transparency of the semiconductor membrane composition also.
[0131]
　Further, also in Example D1, D6, towards the D6 crosslinking agent (B) has an ester bond, a transparency of more crosslinking agent (B) for semiconductor film composition also was added dropwise to It can be maintained has been shown.
[0132]
　Compound was added acid (C-1) to (A) Example C4, in C5, 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 0 solution crosslinking agent (B) was dripped in to 0.56 are transparent without white turbidity, a semiconductor membrane composition be dropped many crosslinking agent than example C3 (B) It was able to maintain transparency.
[0133]
　When the crosslinking agent (B) comparing Examples C6, C7 which has an ester bond in Examples C7, be dropped many crosslinking agent than in Example C6 (B) of the semiconductor membrane composition It was able to maintain transparency. Further, when the crosslinking agent (B) comparing Examples C8, C9 having an ester bond, in Example C9, a semiconductor membrane composition be dropped a number of crosslinking agent (B) than that of Example C8 We were able to maintain the transparency of the object. Therefore, from the viewpoint of maintaining the transparency of the semiconductor membrane composition more suitably, the number of carbon atoms in the ester bond is presumed that is preferably larger.
　Moreover, it was observed the same tendency also in Example D4, D5.
[0134]
　Crosslinking agent (B) has an ester bond, and the compound in Example with the addition of acid (C-1) to (A) C10, C11, respectively Example C8, a number of crosslinking agents than C6 and (B) be added dropwise was able to maintain the transparency of the semiconductor membrane composition. Therefore, from the viewpoint of maintaining the transparency of the semiconductor membrane composition more suitably, it is preferable that the crosslinking agent (B) has an ester bond, and adding an acid to the compound (A) (C-1) , It is presumed that.
　Moreover, it was observed the same tendency also in Example D7, D8.
[0135]

[Examples 1 to 19 and Comparative Examples 1 to 6]
　was prepared for semiconductor film composition having the composition and pH shown in Table 2 below. Incidentally, similarly to the respective embodiments described above, in the case of using the additive (C) as an acid (C-1), acid (C-1) The compound (A) cross-linking agent from the addition to the solution (B ) are mixed, in the case of using the additive (C) a base (C-2) as the base (C-2) was added to the crosslinking agent (B), then the crosslinking agent (B) a solvent and mixing the solution prepared by dissolving the compound (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, 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).
　In Table 2, in Example 3 Acid (C-1) as benzoic acid; using (BA benzoic acid). As COOX containing compounds other than Comparative Examples 2 and 4 the cross-linking agent (B), malonic acid; using (MA malonic acid). In Comparative Examples 5 and 6, as COOX containing compound other than the crosslinking agent (B), tripropylamine 1,2,4-benzenetricarboxylic acid; using (TrPr124BTC tripropyl-124BTC).
[0136]
[Table 2]

[0137]

　semiconductor membrane composition (hereinafter, also referred to as "composition".) Silicon substrate was prepared as a substrate for applying the. After placing the silicon substrate was cleaned for 5 minutes with UV ozone on the spin coater, the composition 1.0mL prepared in Examples and Comparative Examples was added dropwise at 10 seconds a constant speed, and held for 13 seconds, 2000 rpm (rpm 1 sec at a rotational 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..
[0138]

　after 400 ° C. heating was measured refractive index of the film 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, the air / SiO 2 were fitted with / natural oxide 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. Although the refractive index be better the less change, the change is small is not essential.
　The results are shown in Table 3.
[0139]

　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 rate is more than 20% 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.
[0140]

　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.
[0141]

　The film thickness of 20nm or more 300nm 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.
[0142]

　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, if the measured mean-square surface roughness at SPM (RMS) is less than 25% was judged as "Yes smoothness".
　The results are shown in Table 3. Incidentally, the film was heated for 10 minutes at 300 ° C. or 400 ° C. was subjected to SPM morphological observation.
[0143]
　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).
[0144]
[table 3]

[0145]
　As shown in Table 3, Examples 1, 2, 4-thickness residual ratio at 15, 17 and 19 but were both 20% or more, any thickness residual rate in Comparative Examples 1-4 It was also less than 5%. Films formed from the semiconductor membrane composition in each example from this is estimated to be excellent in heat resistance.
　In Examples 1,2,7,9,13,17, SEM morphological observation result of the film was smooth.
　On the other hand, in Comparative Examples 5 and 6, the film surface is not a mirror surface was not smooth. Comparative Examples 5 and 6, the cross-linking agent (B) without the use of crosslinking agents having no COOH group, unevenness of the film surface is increased, it was found that not a mirror surface.
　Further, in Examples 10,11,18, SPM morphological observation result of the film was smooth. When using a base (C-2), it was found to be formed a smooth film even in an extremely thin film of about 2 nm.
[0146]

Example 20
　BPEI_2 an aqueous solution, NH as the base (C-2) in 135BTC 3 with a solution obtained by adding (N / COOH = 1.1), the nitrogen atoms in 135BTC the ratio of the number of carboxy groups in BPEI_2 to the number of (COOH / N) were mixed so that 0.9 was obtained for semiconductor film composition (coating liquid).
　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.
[0147]
Comparative Example 7
　to 300mm φ silicon substrate, was added dropwise BPEI_2 solution 6 mL, the 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.. Then, while rotating the wafer at 3000 rpm, it was dropped on BPEI_2 drying the 135BTC isopropanol (IPA) solution (1.4 wt%) 10 mL. After the dropwise addition, the mixture was heated for 1 minute at 250 ° C., was 10 minutes heat treatment at 400 ° C.. Thus, the film is formed on a silicon substrate.
[0148]
　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.
　Incidentally, in Table 4, BPEI_2 aqueous solution (2 wt%), the concentration in the parenthesis in BPEI_2 solution (1.7 wt%) represents the concentration of BPEI_2 in the composition, 135BTC (1.4 wt% , the concentration in the parenthesis in the solvent IPA) represents the concentration of 135BTC in the composition
.
[0149]
[Table 4]

[0150]
　As shown in Table 4, 1 cm and a thickness difference (%) in 13cm from the center, towards the Example (5%) showed a value smaller than the comparative example (5 percent). Accordingly, by using the semiconductor membrane composition according to Example 20, it was shown to obtain a smooth film having excellent in-plane uniformity in 300mm φ silicon wafers in a more simple process.
[0151]

Example 21
　(ratio of the number of carboxy groups in the acid to the number of nitrogen atoms in BPEI_2) BPEI_2 aqueous acid (C-1) as acetic acid (AA) COOH / N 1 It was added to a 2.0. Then mixed in BPEI_2 aqueous 124BTC as COOH / N (the ratio of the number of carboxy groups in 124BTC to the number of nitrogen atoms in BPEI_2) is 0.81, the concentration of ethanol (EtOH) to the entire composition so it becomes 27 mass%, ethanol were mixed and semiconductor membrane composition (solution 1) was prepared.
[0152]
　Then, after dropping a 100nm width, composition 0.5mL silicon oxide substrate having a trench pattern of 200nm depth, a silicon oxide 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..
　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.
　Incidentally, in Table 5, the concentration in the parenthesis in BPEI_2 solution (3.1 wt%) represents the concentration of BPEI_2 in the composition.
[0153]
[table 5]

[0154]

Example 22
　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 2) was prepared.
[0155]
Example 23
　and BPEI_2 aqueous, NH as the base (C-2) in 135BTC 3 with a solution obtained by adding (N / COOH = 1.5), carboxy group in BPEI_2 to the number of nitrogen atoms in 135BTC the number ratio (COOH / N) is mixed in BPEI_2 aqueous 135BTC so that 0.9, so that the concentration of ethanol (EtOH) to the total composition is 33 wt%, was mixed with ethanol, semiconductor coating composition (solution 3) was prepared.
[0156]
　After the addition of the composition 5mL low resistance silicon substrate, a low resistance silicon substrate, 5 seconds at 1000 rpm, and it 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.
[0157]
(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.
[0158]
(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, and the value of the measured field strength 1 MV / cm and leakage current density.
　The results are shown in Table 6.
[0159]
　In Table 6, the composition of the samples in Examples 22 and 23 show the dielectric constant and the leak current density.
　In the In Table 6, BPEI_2 aqueous solution (1.8 mass%), the concentration in the parenthesis in BPEI_2 solution (1.7 wt%) represents the concentration of BPEI_2 in the composition.
[0160]
[Table 6]

[0161]
Example 24
　COOH / N BPEI_2 aqueous solution ehePMA like (the ratio of the number of carboxy groups in ehePMA to the number of nitrogen atoms in BPEI_2) is 1.01 (0.05 mass relative to the entire composition mixed%), so that the concentration of ethanol (EtOH) to the total composition is 56 wt% ethanol were mixed and semiconductor membrane composition (solution 4) was prepared.
[0162]

(precursor Preparation of
　solution) after the ethanol bis triethoxysilyl ethane and 70.9g of 77.4g were mixed and stirred at room temperature, 1 mol / L It was added nitric acid 80 mL, and stirred for 1 hour at 50 ° C.. It was then mixed a solution of polyoxyethylene (20) stearyl ether 20.9g of ethanol 280 g. After mixing, the mixture was stirred for 4 hours at 30 ° C.. The resulting solution 25 ° C. and under a reduced pressure of 30 hPa, and concentrated to 105 g. After concentration, 2 1-propyl alcohol and 2-butyl alcohol by volume: mixed solution was added to 1, to obtain a precursor solution 1800 g.
[0163]
(Porous Preparation of silica-forming composition)
　in the precursor solution 472 g, was added dimethyldiethoxysilane 3.4g and hexamethyldisiloxane 1.8g, stirred for 1 hour at 25 ° C., the composition for forming porous silica to obtain things. Dimethyl diethoxy silane at this time, the addition amount of hexamethyldisiloxane, 10 mol% respectively bis triethoxysilyl ethane was 5 mol%.
[0164]
(Interlayer insulating layer forming)
　the porous silica-forming composition 1.0mL was dropped on a silicon substrate surface, a silicon substrate, is rotated 60 seconds 2000 rpm, was coated on a silicon substrate surface, under a nitrogen atmosphere , 1 minute at 0.99 ° C., then heated at 350 ° C. 10 min. Thereafter, a heat treatment up to 350 ° C. in a chamber equipped with a wavelength 172nm excimer lamp, output 14 mW / cm at a pressure 1 Pa 2 by, by irradiating ultraviolet rays for 10 minutes to obtain an interlayer insulating layer (porous silica film).
　Thus, the interlayer insulating layer (hereinafter, also referred to as "Low-k film") was obtained with the silicon substrate.
[0165]
　The Low-k film (contact angle 30 ° or less) with the silicon substrate obtained as described above, under nitrogen (30 kPa), and pre-baked for 10 minutes at 380 ° C.. After prebaking, the Low-k film with a silicon substrate, placed on a spin coater, the composition 1.0mL was added dropwise at 10 seconds a constant speed, after holding for 13 seconds, 1 seconds at 2000 rpm, the rotation for 30 seconds at 600rpm after, it dried by rotating 10 seconds at 2000 rpm. Thereafter, the composition was dried for 1 minute at 125 ° C., a heat treatment atmosphere of nitrogen (30 kPa) 400 ° C. for 10 minutes was performed. Thus, the laminate consisting of the silicon substrate / interlayer insulating layer (Low-k film) / film was obtained.
[0166]
　In the Low-k film with a silicon substrate and a laminated body obtained as described above, the film thickness of the Low-k, Low-k film voids thickness was sealed in, the refractive index of the Low-k film, the surface the aperture ratio of the pore radius of the surface was determined using an ellipsometer device SEMILAB manufactured optical porosimeter (PS-1200). Incidentally, in the laminate, and we analyzed Low-k film / film (pore sealing layer) with an optical two-layer model.
　The results are shown in Table 7.
[0167]
　Sealing resistance was evaluated by toluene adsorption measurements in the pore sealing layer surface of the sample (Si / Low-k film / pore sealing layer). In the toluene adsorption measurement, indicating that a high sealing property for preventing the penetration of the less toluene adsorption, Low-k film into the interconnect material (such as copper).
　Toluene adsorption measurements were carried out using SEMILAB manufactured optical porosimeter (PS-1200).
　The measurement method, MR Baklanov, KP Mogilnikov, VG Polovinkin, and FN Dultsey, Journal of Vacuum Science and Technology B (2000) 18, was carried out according to the procedure described in 1385-1391.
　Specifically, in the temperature range 23 ~ 26 ° C., after evacuating the contained sample chamber of the sample (Si / Low-k film / pore sealing layer) to 5 mTorr, and slow enough introducing toluene gas sample chamber. In each pressure, the refractive index of the Low-k film was situ measured by an ellipsometer device. This operation, sample chamber pressure was repeated until the saturated vapor pressure of toluene. Similarly, while gradually exhausting the sample chamber atmosphere was measured for refractive index at each pressure. By the above operation, it was determined adsorption and refractive index change due to elimination of toluene to Low-k film. Furthermore, using a Lorentz-Lorenz equation to obtain the toluene gas adsorption-desorption isotherms of relative pressure characteristics of the refractive index.
　The toluene gas adsorption-desorption isotherms, toluene relative pressure (P / P 0 ; here, P is represents the partial pressure at room temperature of toluene, P 0Represents a saturated vapor pressure at room temperature of toluene. ) And the volume fraction of the toluene adsorption amount (the ratio of the adsorption volume at room temperature of toluene for Low-k film total volume; unit is isotherms showing the "%"), the relationship. The volume fraction of the toluene adsorption amount was determined based on the refractive index of the Low-k film using a Lorentz-Lorenz equation.
[0168]
　Based on the above toluene gas adsorption-desorption isotherms, toluene relative pressure (P / P 0 ) toluene adsorption amount of volume fraction of the time is 1.0 (%) determined based on the obtained value, sealability It was evaluated. In this evaluation, indicating the higher volume fraction of the toluene adsorption (%) is small, it is high sealing properties.
　Pore radius was calculated from the desorption isotherm of the toluene. Pore radius calculations, MR Baklanov, KP Mogilnikov, VG Polovinkin, and FN Dultsey, Journal of Vacuum Science and Technology B (2000) 18, according to the technique described in 1385-1391 was performed using a Kelvin equation.
　The results are shown in Table 7.
[0169]
[Table 7]

[0170]
　As shown in Table 7, by using the semiconductor membrane composition according to Example 24, by forming a pore sealing layer on the Low-k film surface, while maintaining a low refractive index of the Low-k film, low- k membrane surface can form a pore sealing layer of a high density (high refractive index), good sealing property was obtained.
[0171]
Example 25
　COOH / N (1% by weight, based on the total composition) EhePMA the PAA aqueous solution so that (the ratio of the number of carboxy groups in EhePMA to the number of nitrogen atoms in the PAA) is 0.99 mixed, so that the concentration of ethanol (EtOH) to the total composition is 40 wt% ethanol were mixed and semiconductor membrane composition (solution 5) were prepared.
[0172]
　Except for changing the amount of polyoxyethylene (20) stearyl ether from 20.9g to 41.8g was prepared a silicon substrate with an interlayer insulating layer (Low-k film) in the same manner as described above for the method. The Low-k film (contact angle 30 ° or less) with a silicon substrate manufactured under nitrogen (30 kPa), and pre-baked for 10 minutes at 380 ° C.. After prebaking, the Low-k film with a silicon substrate, placed on a spin coater, the composition 1.0mL was added dropwise at 10 seconds a constant speed, after holding for 13 seconds, 1 seconds at 2000 rpm, the rotation for 30 seconds at 600rpm after, it dried by rotating 10 seconds at 2000 rpm. Thereafter, the composition was dried for 1 minute at 125 ° C., then heated for 10 minutes at 400 ° C., further 20 minutes heating treatment was performed (heating time 30 minutes at 400 ° C.). Thus, the laminate consisting of the silicon substrate / interlayer insulating layer (Low-k film) / film was obtained.
[0173]
　Laminate after heating for 10 minutes at 400 ° C. of the foregoing, and was heated for 10 minutes at 400 ° C., another 20 minutes heating treatment (i.e., 30 min heat treatment at 400 ° C.) in the laminate after the the film thickness of the whole and the refractive index of the Low-k film / film (pore filling material) was determined using an ellipsometer device. Incidentally, the void volume was calculated from the refractive index at a wavelength of 633nm with voids, polymeric, a Lorentz-Lorenz equation to silica skeleton.
　The results are shown in Table 8.
[0174]
[Table 8]

[0175]
　Using the semiconductor membrane composition according to Example 25, pore-filling material and the film of the Low-k when deposited on the membrane pore-filling material is uniformly penetrate into the Low-k film, the void volume is better Diminished. Moreover, even after heated for 30 minutes at 400 ° C., the change in the void volume was very small.
[0176]
Example 26
　COOH / N (the ratio of the number of carboxy groups in ehePMA to the number of nitrogen atoms in BPEI_2) is BPEI_2 aqueous ehePMA such that 0.71 (1% by weight, based on the total composition) mixed, so that the concentration of ethanol (EtOH) to the total composition is 37 wt% ethanol were mixed and semiconductor membrane composition (solution 6) were prepared.
[0177]
Example 27
　COOH / N (the ratio of the number of carboxy groups in ehePMA to the number of nitrogen atoms in BPEI_2) is BPEI_2 aqueous 1Prhe124BTC such that 0.71 (1% by weight, based on the total composition) mixed, so that the concentration of 1-propanol (1PrOH) to the total composition is 33 wt%, were mixed 1-propanol, the semiconductor membrane composition (solution 7) was prepared.
[0178]
Example 28]
　BPEI_2 aqueous solution (1.5 wt% based on the total composition), NH as the base (C-2) in 135BTC 3 with a solution obtained by adding (N / COOH = 1.5), 135BTC ratio of the number of carboxy groups in BPEI_2 to the number of nitrogen atoms in the middle (COOH / N) is mixed in a 0.71, a semiconductor membrane composition (solution 8) were prepared.
[0179]
　Next, place the silicon substrate on a spin coater, the composition 1.0mL prepared in Examples 26-28 was added dropwise at 10 seconds a constant speed, after holding for 13 seconds, at 2000 rpm (rpm rotation speed) 1 seconds, after rotating 30 seconds at 600 rpm, dried by rotating 10 seconds at 2000 rpm. Thus, the film is formed on a silicon substrate.
　Then, after 1 minute drying at 125 ° C., nitrogen atmosphere (30 kPa), 400 ° C. for 10 minutes to heat the film.
[0180]

　for evaluation adhesion of the film, the electrode is formed by forming a copper film (thickness 100 nm) on a film by sputtering, the silicon substrate / film / electrodes (copper film) are laminated in this order It was to obtain a laminate.
　The adhesion in the laminate having electrodes formed were evaluated as follows. More specifically, 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 9.
[0181]
[Table 9]

[0182]
　When film is subjected to adhesion evaluated silicon substrate is not formed, 19 mass peeling (peeling surface; silicon substrate / copper) has occurred. On the other hand, the case of forming a film by using a semiconductor membrane compositions of Examples 26-28, no peeling between the silicon substrate and the copper film, the adhesion was good.
[0183]
Example 29

(semiconductor membrane preparation of composition)
　(the ratio of the number of carboxy groups in ehePMA to the number of nitrogen atoms in BPEI_2) COOH / N There were mixed ehePMA such that 0.71 to BPEI_2 solution (0.25 wt% based on the total composition), so that the concentration of ethanol (EtOH) to the total composition is 9 wt%, ethanol mixed and semiconductor membrane composition (solution 9) was prepared.
[0184]
(Thickness-measuring Preparation of Sample)
　preparing a silicon wafer that silica is present on the surface, the silicon wafer, placed on a spin coater, the solution 9 was 1.0mL dropwise at 10 seconds a constant speed, 13 after holding 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, also referred to as "sample (Si / polymer)") was obtained.
[0185]
　The sample (Si / polymer) on a hot plate, and placed in contact and the silicon wafer surface and a hot plate, in an air atmosphere for 60 seconds soft baked soft bake temperature of 120 ° C. (heat treatment).
　Soft bake temperature here is the temperature of the silicon wafer surface (the temperature of the surface to be deposited of the pre-deposition silicon wafer).
[0186]
(Washing treatment)
　the sample (Si / polymer), while rotating at 600rpm using a spin coater, onto the polymer layer, the dropping rate of the ultra pure water (liquid temperature 22 ° C.) 0.1 mL / sec as a rinse in dropwise for 30 seconds to wash the polymer layer, then dried by rotating 60 seconds the sample at 2000 rpm.
[0187]
(The thickness of the cleaning process after the polymer layer Evaluation)
　Next, to measure the thickness of the polymer layer of the cleaning after the sample obtained as described above. The thickness of the polymer layer (nm) was measured by a conventional method using an ellipsometer of SEMILAB manufactured optical porosimeter (PS-1200).
　The results are shown in Table 10.
[0188]

(Preparation of the thickness-measuring sample)
　a copper film was 100nm deposited by plating on the silicon substrate was cleaned copper film surface with helium plasma treatment substrate the use, in the plasma treatment after the copper film surface, to form a seal layer (polymer layer) was performed the same processing as .
　Thus, on the copper, to form a polymer layer, the laminate structure of copper and the polymer layer are laminated (hereinafter, also referred to as "sample (Cu / polymer)") was obtained.
[0189]
(Washing treatment)
　with the sample (Cu / polymer), while rotating at 600rpm using a spin coater, onto the polymer layer, the dropping rate of the ultra pure water (liquid temperature 22 ° C.) 0.1 mL / sec as a rinse in dropwise for 30 seconds to wash the polymer layer, then dried by rotating 60 seconds the sample at 2000 rpm.
[0190]
(The thickness of the cleaning process after the polymer layer Evaluation)
　Next, to measure the thickness of the polymer layer of the cleaning after the sample obtained as described above. The thickness of the polymer layer on a copper (Cu) (nm) was measured by the following method using the ellipsometer SEMILAB manufactured optical porosimeter (PS-1200).
　That is, the thickness of the optically flat copper polymeric layer on the substrate, the polarization parameters measured by ellipsometry, multilayer optical model using WinElli II; (air) / (polymer layer) / (copper substrate) in was calculated by regression. Range of light energy used is a 2.2 ~ 5.0eV. Here, always the silica (SiO the refractive index of the polymer layer 2 using the same values as). The refractive index and extinction coefficient of the copper substrate after measuring the polarization parameter of the copper substrate having no polymer layer was used the values obtained using the WinElli II analysis software.
　The results are shown in Table 10.
[0191]
[Table 10]

[0192]
[Examples 30-32]
　, except that the soft-bake temperature, as shown in Table 10 was changed to 130 ℃ ~ 150 ℃, each measured thickness of Si on the polymer and Cu on the polymer in the same manner as in Example 29 did.
　The results are shown in Table 10.
[0193]
　As shown in Table 10, in each embodiment, the thickness (Cu UemakuAtsu) of the polymer layer on the Cu is 1/4 or less of the thickness of the Si on the polymer layer (Si UemakuAtsu), polymer on Cu the thickness of the layer has been sufficiently reduced.
[0194]
　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]Having a cationic functional group containing at least one of the primary nitrogen atoms and 2 nitrogen atom, the compound weight average molecular weight of 10,000 or more 400,000 or less and (A),
　-C in the molecule (= O) OX groups (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 than six -C (= O) an OH group, a weight average molecular weight of 200 or more 600 or less is the cross-linking agent (B), and
　water (D),
　wherein the
　said compound (a) is an aliphatic amine, a semiconductor use membrane composition.
[Claim 2]
　Furthermore, the crosslinking agent (B) having a ring structure in the molecule, for semiconductor film composition according to claim 1.
[Claim 3]
　The ring structure is at least one benzene ring and a naphthalene ring, a semiconductor membrane composition of claim 2.
[Claim 4]
　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 3 for semiconductor film composition according to any one.
[Claim 5]
　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 4.
[Claim 6]
　The weight average molecular weight of the compound (A) is 200,000 or less than 10,000, for semiconductor film composition according to any one of claims 1 to 5.
[Claim 7]
　pH is 7.0 or less at 25 ° C., for semiconductor film composition according to any one of claims 1 to 6.
[8.]
　Used in the adhesion layer and the insulating film metal for semiconductor film composition according to any one of claims 1 to 7.
[Claim 9]
　Used in the pore sealing material having a low dielectric constant material for semiconductor film composition according to any one of claims 1 to 8.
[Claim 10]
　Used in the filling material of a recess formed in a substrate, a semiconductor membrane composition according to any one of claims 1 to 9.
[Claim 11]
　A method of manufacturing a semiconductor membrane composition according to any one of claims 1 to 10,
　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 12]
　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 11.
[Claim 13]
　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 11.
[Claim 14]
　A method of manufacturing a semiconductor member by using a semiconductor membrane composition according to any one of claims 1 to 10,
　a 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 15]
　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 16]
　Substrate and,
　having a primary nitrogen atom and secondary nitrogen cationic functional group containing at least one atom, the compound weight average molecular weight of 400,000 or less 10,000 or more (A), and -C in the molecule ( is = O) OX group (X, have 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 6 One following 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 17]
　The reactant has at least one amide bond and an imide bond, a semiconductor device according to claim 16.