JP2018182199A - Composition for film formation for semiconductor, method for producing composition for film formation for semiconductor, method for producing member for semiconductor, and method for producing process material for semiconductor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film forming composition for a semiconductor, which can obtain a film having high smoothness with few aggregates and pits. SOLUTION: A compound (A) having a ring structure and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom and having a weight average molecular weight of 90 or more and 600 or less, and a compound (A) in the molecule-. One of three or more -C (= O) OX groups having three or more C (= O) OX groups (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms). The above 6 or less are -C (= O) OH groups, and the cross-linking agent (B) having a weight average molecular weight of 200 or more and 600 or less and a weight average molecular weight of 46 or more and 195 or less having a carboxy group without an amino group. At least one additive (C) selected from the group consisting of the acid (C-1) of the above and a base (C-2) having a weight average molecular weight of 17 or more and 120 or less having a nitrogen atom and having no ring structure, and polarity. A composition for forming a film for a semiconductor, which comprises a solvent (D). [Selection diagram] None

Description

  The present invention relates to a composition for forming a film for semiconductor, a method for producing the composition for forming a film for semiconductor, a method for producing a member for semiconductor, and a method for producing a process material for semiconductor.

Heretofore, in various technical fields such as the field of electronic devices, it has been practiced to apply a composition containing a polymer to a member.
For example, a composition having a cationic functional group and a polymer such as polyethyleneimine and a polyethyleneimine derivative having a weight average molecular weight of 2000 to 100000 and having a pH of 2.0 to 11.0 is a member having predetermined conditions A method of producing a composite to be applied to the surface of A and member B is known (see, for example, Patent Document 1). Further, Patent Document 1 describes that the composite member to which the composition is applied is washed with a rinse solution containing a polyvalent carboxylic acid.

International Publication No. 2014/156616

  In patent document 1, after apply | coating polymers, such as a polyethylene imine, to a member and apply | coating the rinse solution containing polyvalent carboxylic acid on it, it is made to bridge | crosslink by heating reaction, and there are many processes. However, when it is attempted to prepare a composition in which a polymer such as polyethylene imine and a polyvalent carboxylic acid are mixed and applied to a member, the polymer and the polyvalent carboxylic acid aggregate to cause the composition to become cloudy, and the composition When it apply | coats to a member, there exists a problem that an unevenness | corrugation will be large by formation of an aggregate, a pit, etc. and it will become a film | membrane with inadequate smoothness.

  One aspect of the present invention is made in view of the above problems, and is a composition for forming a film for a semiconductor from which a film having a small amount of aggregates and pits and high smoothness can be obtained, a method for producing the same, and the film formation for the semiconductor It is an object of the present invention to provide a method for producing a semiconductor member using the composition for a semiconductor and a method for producing a semiconductor processing material using the composition for forming a film for a semiconductor.

The specific means for solving the said subject are as follows.
<1> ring structure and having a cationic functional group containing at least one of a nitrogen atom and 2 nitrogen atom, the weight average molecular weight of 90 to 600 or less is compound (A), -C in the molecule (= O) OX group (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) has three or more, and one or more of three or more —C (= O) OX groups A crosslinking agent (B) having 6 or less of -C (= O) OH group and having a weight average molecular weight of 200 to 600, and a weight average molecular weight of 46 to 195 having no amino group and having a carboxy group At least one additive (C) selected from the group consisting of an acid (C-1) and a base (C-2) having a weight average molecular weight of 17 or more and 120 or less having a nitrogen atom without having a ring structure, and a polar solvent The composition for film formation for semiconductors containing (D) and.
<2> The composition for forming a semiconductor film according to <1>, wherein the crosslinking agent (B) further has a ring structure in a molecule.
<3> The composition for forming a semiconductor film according to <1> or <2>, wherein the ring structure is at least one of a benzene ring and a naphthalene ring.
<4> Furthermore, in the three or more —C (= O) OX groups, in the crosslinker (B), at least one X is an alkyl group having 1 to 6 carbon atoms, <1> to < The composition for film formation for semiconductors as described in any one of 3>.
The composition for film formation for semiconductors as described in any one of <1>-<4> used for the filling material of the recessed part formed in the <5> board | substrate.
The composition for film formation for semiconductors as described in any one of <1>-<5> used for <6> multilayer resist method.

It is a manufacturing method which manufactures the composition for film formation for semiconductors as described in any one of <7><1>-<6>, Comprising: The said compound (A), the said crosslinking agent (B), and the said The manufacturing method of the composition for film formation for semiconductors containing the mixing process of mixing an additive (C).
<8> The additive (C) contains at least an acid (C-1) having a weight average molecular weight of 46 to 195 and not having an amino group and having a carboxy group, and the mixing step includes the acid (C-1) The manufacturing method of the composition for film formation for semiconductors as described in <7> which is the process of mixing the mixture of the said, and the said compound (A), and the said crosslinking agent (B).
<9> The additive (C) contains at least a base (C-2) having a weight average molecular weight of 17 or more and 120 or less having a ring structure and a nitrogen atom, and the mixing step contains the base (C-2) The manufacturing method of the composition for film formation for semiconductors as described in <7> which is the process of mixing the mixture of the said, and the said crosslinking agent (B), and the said compound (A).

It is a manufacturing method which manufactures the member for semiconductors using the composition for film formation for semiconductors in any one of <10> <1>-<6>, Comprising: The said composition for film formation for semiconductors is a board | substrate A manufacturing method of a member for semiconductors which has a heating process which heats the above-mentioned substrate to which temperature of 100 ° C or more and 425 ° C or less the above-mentioned substrate to which the composition for film formation for semiconductors given was given.

<11> A method for producing a semiconductor processing material using the composition for forming a film for a semiconductor according to any one of <1> to <6>, which is the composition for forming a film for a semiconductor A method for producing a semiconductor processing material, comprising: an applying step of applying to a substrate; and a heating step of heating the substrate to which the composition for forming a film for a semiconductor has been applied under conditions of a temperature of 100 ° C to 425 ° C.

  One aspect of the present invention is a composition for forming a film for a semiconductor which can obtain a film having high smoothness, which has few aggregates and pits, a method for producing the same, and a member for producing a semiconductor using the composition for forming a film for a semiconductor The method and the manufacturing method of the process material for semiconductors using the composition for film formation for semiconductors can be provided.

  In the present specification, a numerical range represented using "to" or "-" means a range including numerical values described before and after "to" or "-" as the lower limit value and the upper limit value.

[Composition for forming a film for semiconductor]
Hereinafter, one embodiment of the composition for film formation for semiconductors concerning the present invention is described. The composition for film formation for semiconductors according to this embodiment (hereinafter sometimes referred to as “composition”) has a cationic functional group containing a ring structure and at least one of a primary nitrogen atom and a secondary nitrogen atom. And a compound (A) having a weight average molecular weight of 90 or more and 600 or less, and a —C (OO) OX group (X is a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms) in the molecule And three or more, and among three or more -C (= O) OX groups, one or more and six or less are -C (= O) OH groups, and the weight average molecular weight is 200 or more and 600 or less A certain crosslinking agent (B), an acid (C-1) having a weight average molecular weight of 46 to 195 having no amino group and having a carboxy group, and a weight average molecular weight of 17 to 120 having no ring structure and having a nitrogen atom At least one addition selected from the group consisting of (C-2) Comprising (C), and a polar solvent (D), the.

  Using the composition for forming a film for a semiconductor according to the present embodiment, specifically, by applying the composition for forming a film for a semiconductor to a member to form a film, the number of aggregates and pits is small, and the smoothness is High membrane can be obtained. In addition, by using the composition for forming a film for a semiconductor according to the present embodiment, a film with high smoothness can be easily obtained as compared with the technology of the above-mentioned Patent Document 1 (International Publication No. 2014/156616).

  By using the composition for forming a film for a semiconductor according to the present embodiment, a film with small unevenness and good smoothness can be formed, and for example, for a semiconductor according to the present embodiment on a smooth substrate such as a silicon substrate. When film formation is carried out using a composition for film formation, the difference between the maximum value and the minimum value of the film thickness is 25 of the average film thickness within a 500 nm wide field of view at 200,000 magnification of SEM (scanning electron microscope). It is possible to form a film that is less than 10%.

  Furthermore, in the technique of Patent Document 1 described above, a polymer such as polyethylene imine is applied to a member, a rinse solution containing a polyvalent carboxylic acid is applied thereon, and then crosslinking is performed by a heating reaction. The polymer may be dissolved in the rinse solution containing polyvalent carboxylic acid. Therefore, in the film formed on the member, the in-plane film thickness of the large-diameter wafer does not easily become uniform, and control of the film thickness is not easy.

  Further, in the case of forming a thick film of several tens of nanometers or more, the polyvalent carboxylic acid hardly penetrates to the interface between the member and the polymer, so that the composition in the film thickness direction becomes uniform. Hateful.

  On the other hand, in the present embodiment, the composition for forming a film for a semiconductor containing the compound (A), the crosslinking agent (B), and the additive (C) is applied to a member to form a film, thereby enhancing smoothness. And, the uniformity of the composition in the film thickness direction can be enhanced.

  By using the composition for forming a film for a semiconductor according to the present embodiment, it is possible to form a film having excellent smoothness and uniformity of composition in the film thickness direction, for example, having a film thickness of 0.5 nm or more and 5 μm or less. it can. In addition, a film excellent in smoothness can be formed on the surface of a large-diameter silicon substrate. For example, when the film thickness is 5 nm or more and 150 nm, the film thickness variation between the center and the end of a 300 mmφ silicon substrate It can be 15% or less, preferably ± 10% or less.

The composition for forming a film for a semiconductor according to the present embodiment is a composition for forming a film for a semiconductor device, and, for example, a gap fill material (embedding planarization to be filled in a recess formed in a substrate Film, an insulating material (embedded insulating film) filled in a recess formed in a substrate, or a low dielectric constant material such as a porous material and a metal, and having insulating property, adhesion property, pore sealing property, etc. A barrier material (barrier film), an insulating material having adhesion and insulation provided between metal and silicon substrate or between metal and insulating film on a via sidewall of a through silicon via substrate (insulating for through silicon via Film, etc.).
In particular, the filling material (embedded planarization film) of the recess formed in the substrate may be used for complex processing of the substrate.

  There is a multilayer resist method as one of methods for transferring a lithography pattern to a substrate to be processed using a hard mask. In this multilayer resist method, for example, a photoresist film, that is, an upper layer resist film, an intermediate resist film having different etching selectivity, and a buried planarization film in which unevenness of a substrate to be processed is filled with a gap fill film, that is, a lower layer resist film And. In the multilayer resist method, for example, after providing a lower resist film formed on the unevenness of a substrate to be processed, an intermediate resist film further containing silicon is interposed between the upper resist film and the lower resist film to form an upper resist film. The upper layer resist pattern is used as an etching mask to transfer the pattern to the intermediate resist film, and the intermediate resist pattern is used as an etching mask to transfer the pattern to the substrate to be processed.

As a composition of the lower layer resist film used by such a multilayer resist method, there is, for example, an amorphous carbon film by CVD (for example, US Patent Application Publication No. 2016/0314964 etc.).
However, as the miniaturization of semiconductor devices progresses further, not only the line width of the pattern becomes finer, but also the film thickness of the upper layer resist film becomes thinner in order to prevent pattern collapse, which is required for the lower layer resist film Also in the performance, improvement of the embeddability in a finer pattern than ever has been required.

  In addition, in the process of manufacturing a semiconductor device in the limit area of the recent lithography, complicated processes such as double patterning as described above have been proposed. Further, as the complexity of devices such as integrated circuit elements is further advanced, a method of forming a multilayer resist pattern on a patterned substrate such as a wiring trench (trench), a plug trench (via), etc. Therefore, methods of forming complicated patterns are also performed.

The lower layer resist film put into practical use by the conventional multilayer resist method is mostly an amorphous carbon film or the like by CVD as described above. However, in the conventional CVD method, it is becoming difficult to embed fine grooves without voids due to problems such as overhangs.
In addition, the lower resist film may be required to have heat resistance (for example, resistance to heat treatment which may be applied after forming the lower resist film).
From the viewpoint of realizing the formation of a fine pattern, the above-mentioned requirements for the burying property and heat resistance are films other than the resist film (for example, a burying insulating film (shallow trench isolation film (STI film), premetal Film), wiring interlayer insulating film (IMD film), etc.

  Since the composition for forming a film for a semiconductor according to the present embodiment is excellent in embedding property and heat resistance, it can be used for the production of the above-mentioned films other than the lower layer resist film used in the multilayer resist method and the lower layer resist film. .

  In addition, as another method of forming a fine pattern, the semiconductor according to the present embodiment is applied to a photo resist after photosensitivity, and for forming a reverse resist which is formed by replacing the photo resist of photo sensitive or non photo sensitive portion. You may use the composition for film formation. By forming the reverse resist, it becomes possible to form a film which is excellent in etching resistance and less in pattern collapse.

(Compound (A))
The composition for forming a film for a semiconductor according to the present embodiment has a ring structure and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and has a weight average molecular weight of 90 or more and 600 or less. It contains a certain compound (A).

The compound (A) has a ring structure in the molecule as described above. As a ring structure which a compound (A) has, an alicyclic structure, an aromatic ring structure, a heterocyclic structure (hetero ring structure) etc. are mentioned, for example. The compound (A) may have only one ring structure in the molecule, or may have a plurality of ring structures. Furthermore, when the compound (A) has a plurality of ring structures, the plurality of ring structures may be the same or different from each other, and a condensed ring structure in which a plurality of ring structures are fused (ie, two or more rings Is a ring structure in which two or more atoms are shared and bonded.
The compound (A) preferably has an aromatic ring structure from the viewpoint of the thermal stability of the composition for forming a film for a semiconductor, and preferably has an aromatic ring structure other than an aromatic heterocycle.

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

  The aromatic ring structure is not particularly limited as long as it is a ring structure exhibiting aromaticity, and is, for example, an aromatic ring such as benzene ring, benzene ring such as naphthalene ring, anthracene ring and perylene ring, pyridine ring and thiophene ring Heterocyclic rings (that is, ring structures having an aromatic ring structure and a heterocyclic ring structure), non-benzene aromatic rings such as a fluorene ring, an indene ring and an azulene ring, and the like can be mentioned.

  As the heterocyclic structure, a heterocyclic ring containing a sulfur atom as a hetero atom (for example, thiophene ring), or a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, pyrrole ring, pyrrolidine ring, pyrazole ring, pyrazole ring, imidazole ring, triazole ring 6 membered rings such as isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, triazine ring, etc .; indole ring, indoline ring, quinoline ring, quinoline ring, acridine ring, naphthyridine ring, And quinazoline rings, purine rings, fused rings such as quinoxaline rings, and the like.

  As a ring structure which a compound (A) has in a molecule, For example, At least one selected from the group which consists of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, a naphthalene ring, and a fluorene ring is preferable, The film for semiconductors From the viewpoint of further improving the heat resistance of the film obtained from the composition for formation, at least one of a benzene ring, a naphthalene ring and a fluorene ring is more preferable.

  The compound (A) is a compound having a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom. The cationic functional group is not particularly limited as long as it can be positively charged and is a functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom.

The compound (A) is at least one of a cationic functional group containing a primary nitrogen atom, a cationic functional group containing a secondary nitrogen atom, and a cationic functional group containing a primary nitrogen atom and a secondary nitrogen atom. As long as you have That is, the compound (A) may have one or more cationic functional groups containing a primary nitrogen atom or a secondary nitrogen atom, and a cationic functional group containing a primary nitrogen atom and a secondary nitrogen atom. May be included.
However, from the viewpoint of obtaining a film having high heat resistance, the compound (A) preferably has a cationic functional group containing at least a primary nitrogen atom, and has two or more cationic functional groups containing a primary nitrogen atom. Is more preferred.
In addition, the compound (A) contains at least one of a primary nitrogen atom and a secondary nitrogen atom as described above, but may further contain a tertiary nitrogen atom.

In the present specification, the term "primary nitrogen atom" refers to a nitrogen atom (eg, primary amino group (-NH ₂ group)) bonded to only two hydrogen atoms and one atom other than hydrogen atoms. A nitrogen atom) or a nitrogen atom (cation) bonded to only three hydrogen atoms and one atom other than a hydrogen atom.
In addition, “secondary nitrogen atom” means a nitrogen atom bonded to only one hydrogen atom and two atoms other than hydrogen atom (ie, a nitrogen atom contained in a functional group represented by the following formula (a)) Or a nitrogen atom (cation) bonded to only two hydrogen atoms and two atoms other than hydrogen atoms.
In addition, “tertiary nitrogen atom” refers to a nitrogen atom bonded to only three atoms other than a hydrogen atom (ie, a nitrogen atom which is a functional group represented by the following formula (b)), or a hydrogen atom It refers to a nitrogen atom (cation) bound to only one and three atoms other than hydrogen atoms.

In Formula (a) and Formula (b), * indicates a bonding position to an atom other than a hydrogen atom.
Here, the functional group represented by the above-mentioned formula (a) may be a functional group constituting a part of ^a secondary amino group (-NHR ^a group; here, R ^a represents an alkyl group) And other divalent linking groups.
In addition, the functional group represented by the formula (b) (ie, tertiary nitrogen atom) is a tertiary amino group (-NR ^b R ^c group; wherein R ^b and R ^c are each independently alkyl It may be a functional group that constitutes a part of the group) or may be another trivalent linking group.

  The weight average molecular weight of the compound (A) is 90 or more and 600 or less, preferably 100 or more and 400 or less, and more preferably 100 or more and 300 or less.

In addition, the compound (A) may further have an anionic functional group or a nonionic functional group, as necessary.
The nonionic functional group may be a hydrogen bond accepting group or a hydrogen bond donating group. As said nonionic functional group, a hydroxy group, a carbonyl group, an ether group (-O-) etc. can be mentioned, for example.
The anionic functional group is not particularly limited as long as it can be negatively charged. As said anionic functional group, a carboxylic acid group, a sulfonic acid group, a sulfuric acid group etc. can be mentioned, for example.

  Examples of the compound (A) include amines having a ring structure (for example, primary amines, secondary amines and the like), and more specifically, for example, alicyclic amines, aromatic amines, heterocycles (Heterocyclic) amines and the like. As described above, the compound (A) may have a plurality of ring structures in the molecule, and the plurality of ring structures may be the same or different. As the amine compound having a ring structure, a compound having an aromatic ring structure is more preferable because a thermally more stable compound is easily obtained.

  Moreover, as an amine compound having a weight average molecular weight of 90 or more and 600 or less having a ring structure in the molecule, the number of thermally crosslinked structures such as imide structure, imidamide structure, and amide structure can be easily increased with the crosslinking agent (B), and heat resistance From the viewpoint of being able to further enhance, it is preferable to use a diamine compound having two primary amino groups, a triamine compound having three primary amino groups, and the like.

Examples of alicyclic amines include cyclohexylamine, N-methylcyclohexylamine and the like.
Examples of aromatic amines include diaminodiphenyl ether, xylene diamine (preferably paraxylene diamine), diaminobenzene, diaminotoluene, methylenedianiline, dimethyldiaminobiphenyl, bis (trifluoromethyl) diaminobiphenyl, diaminobenzophenone, diaminobenzanilide Bis (aminophenyl) fluorene, bis (aminophenoxy) benzene, bis (aminophenoxy) biphenyl, dicarboxydiaminodiphenylmethane, diaminoresorcinol, dihydroxybenzidine, diaminobenzidine, 1,3,5-triaminophenoxybenzene, 2,2 '-Dimethylbenzidine, tris (4-aminophenyl) amine, 2,7-diaminofluorene, 1,9-diaminofluorene, dibenzyl An amine etc. are mentioned.

As the heterocyclic amine, for example, as a heterocyclic amine having a heterocyclic structure containing a nitrogen atom, melamine, ammerin, melam, melem etc. may be mentioned. Moreover, as a heterocyclic amine which has a heterocyclic structure containing a sulfur atom, 5-thiazole amine, 2-amino benzothiazole etc. are mentioned, for example.
Furthermore, as an amine compound having both a heterocyclic structure and an aromatic ring structure other than an aromatic heterocyclic ring, N2, N4, N6-tris (4-aminophenyl) -1,3,5-triazine-2,4 can be used. , 6-triamine, 2,4-diamino-6-phenyl-1,3,5-triazine and the like.

  As the compound (A), one type may be used alone, or two or more types may be used in combination.

  In the present embodiment, the content of the compound (A) in the composition for film formation for a semiconductor is not particularly limited, but may be, for example, 0.001% by mass or more and 20% by mass or less with respect to the entire composition. The content is preferably 0.01% by mass or more and 20% by mass or less, and more preferably 0.05% by mass or more and 10% by mass or less.

(Crosslinking agent (B))
The composition for forming a film for a semiconductor according to the present embodiment has three or more —C (= O) OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule. Among the three or more —C (= O) OX groups (hereinafter also referred to as “COOX”), one or more and six or less are also referred to as —C (= O) OH groups (hereinafter also referred to as “COOH”). And a cross-linking agent (B) having a weight average molecular weight of 200 or more and 600 or less.

  The crosslinking agent (B) is a compound having three or more —C (= O) OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, but preferably And a compound having three or more and six or less -C (= O) OX group in the molecule, and more preferably a compound having three or four -C (= O) OX group in the molecule.

  In the crosslinking agent (B), examples of X in -C (= O) OX group include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and among them, a hydrogen atom, a methyl group, an ethyl group and a propyl group Is preferred. In addition, X in -C (= O) OX group may mutually be the same, and may differ.

  The crosslinking agent (B) is a compound having in the molecule one or more and six or less -C (= O) OH group in which X is a hydrogen atom, but preferably, in the molecule, -C (= O) OH It is a compound having one or more and four or less groups, more preferably a compound having two or more and four or less -C (= O) OH groups in the molecule, and still more preferably -C (in the molecule). OO) a compound having two or three OH groups.

  The crosslinking agent (B) is a compound having a weight average molecular weight of 200 or more and 600 or less. Preferably, it is a compound of 200 or more and 400 or less.

  The crosslinking agent (B) preferably has a ring structure in the molecule. The ring structure includes an alicyclic structure, an aromatic ring structure and the like. The crosslinking agent (B) may have a plurality of ring structures in the molecule, and the plurality of ring structures may be the same or different.

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

  The aromatic ring structure is not particularly limited as long as it is a ring structure exhibiting aromaticity, and is, for example, an aromatic ring such as benzene ring, benzene ring such as naphthalene ring, anthracene ring and perylene ring, pyridine ring and thiophene ring Heterocyclic rings (that is, ring structures having an aromatic ring structure and a heterocyclic ring structure), non-benzene aromatic rings such as a fluorene ring, an indene ring and an azulene ring, and the like can be mentioned.

  As the heterocyclic structure, a heterocyclic ring containing a sulfur atom as a hetero atom (for example, thiophene ring), or a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, pyrrole ring, pyrrolidine ring, pyrazole ring, pyrazole ring, imidazole ring, triazole ring 6 membered rings such as isocyanuric ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, triazine ring, etc .; indole ring, indoline ring, quinoline ring, quinoline ring, acridine ring, naphthyridine ring, And quinazoline rings, purine rings, fused rings such as quinoxaline rings, and the like.

  As a ring structure which a crosslinking agent (B) has in a molecule | numerator, at least one selected from the group which consists of a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a benzene ring, and a naphthalene ring is preferable, for example, The composition for film formation for semiconductors From the viewpoint of further improving the heat resistance of the film obtained from the material, at least one of a benzene ring and a naphthalene ring is more preferable.

  As described above, the crosslinking agent (B) may have a plurality of ring structures in the molecule, and when the ring structure is benzene, it may have a biphenyl structure, a benzophenone structure, a diphenyl ether structure, and the like.

  The crosslinking agent (B) preferably has a fluorine atom in the molecule, more preferably has 1 or more and 6 or less fluorine atoms in the molecule, and has 3 or more and 6 or less fluorine atoms in the molecule. It is more preferable to have. For example, the crosslinking agent (B) may have a fluoroalkyl group in the molecule, and specifically, may have a trifluoroalkyl group or a hexafluoroisopropyl group.

  Furthermore, as the crosslinking agent (B), carboxylic acid compounds such as alicyclic carboxylic acid, benzene carboxylic acid, naphthalene carboxylic acid, diphthalic acid and fluorinated aromatic carboxylic acid; alicyclic carboxylic acid ester, benzene carboxylic acid ester, naphthalene Examples thereof include carboxylic acid ester compounds such as carboxylic acid ester, diphthalic acid ester and fluorinated aromatic ring carboxylic acid ester. In addition, a carboxylic acid ester compound has a carboxy group (-C (= O) OH group) in the molecule, and at least one X in the three or more -C (= O) OX group is a carbon number It is a compound which is an alkyl group of 1 or more and 6 or less (that is, having an ester bond). In the composition for forming a film for a semiconductor according to the present embodiment, the crosslinking agent (B) is a carboxylic acid ester compound, thereby suppressing aggregation due to association between the compound (A) and the crosslinking agent (B) in the composition. As a result, the number of aggregates and pits is reduced, and a film having a higher smoothness and a larger film thickness can be easily obtained and the film thickness can be easily adjusted.

  The carboxylic acid compound is preferably a tetravalent or less carboxylic acid compound containing four or less —C (= O) OH groups, and a trivalent containing three or four —C ((O) OH groups. Or a tetravalent carboxylic acid compound is more preferred.

  The carboxylic acid ester compound is preferably a compound containing three or less carboxy groups (-C (= O) OH group) in the molecule and three or less ester bonds, and the carboxy group is preferably contained in the molecule. It is more preferable that it is a compound containing two or less and containing two or less ester bonds.

  In the carboxylic acid ester compound, when X is an alkyl group having 1 to 6 carbon atoms in three or more -C (= O) OX groups, X is a methyl group, an ethyl group, a propyl group, Although a butyl group etc. are preferable, it is preferable that it is an ethyl group or a propyl group from the point which suppresses aggregation more by association with a compound (A) and a crosslinking agent (B) in a composition more.

  Specific examples of the carboxylic acid compounds include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,3,5-cyclohexane Alicyclic carboxylic acids such as tricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid; 1 , 2,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, pyromellitic acid, benzene pentacarboxylic acid, benzene carboxylic acids such as mellitic acid; 1,4,5,8-naphthalene tetracarboxylic acid, 2 Naphthalene carboxylic acids such as 3,3,6,7-naphthalene tetracarboxylic acid; 3,3 ', 5,5'-tetracarboxydiphenyl Tan, biphenyl-3,3 ', 5,5'-tetracarboxylic acid, biphenyl-3,4', 5-tricarboxylic acid, biphenyl-3,3 ', 4,4'-tetracarboxylic acid, benzophenone-3, 3 ', 4,4'-tetracarboxylic acid; 4,4'-oxydiphthalic acid, 3,4'-oxydiphthalic acid, 1,3-bis (phthalic acid) tetramethyldisiloxane, 4,4'-(ethine-) 1,2-Dinyl) diphthalic acid (4,4 ′-(Ethyne-1,2-diyl) diphthalic acid), 4,4 ′-(1,4-phenylene bis (oxy)) diphthalic acid (4,4 ′ -(1,4-phenylenebis (oxy)) diphthalic acid), 4,4 '-([1,1'-biphenyl] -4,4'-zylbis (oxy)) diphthalic acid (4,4'-([ 1,1'-biphenyl] -4,4'-diylbis (oxy) diphthalic acid), 4,4 '-((oxybis (4,1-phenylene)) bis (oxy)) diphthalic acid Diphthalic acid such as acid (4,4 ′-((oxybis (4,1-phenylene)) bis (oxy)) diphthalic acid; perylene carboxylic acid such as perylene-3,4,9,10-tetracarboxylic acid; Anthracene carboxylic acids such as anthracene-2,3,6,7-tetracarboxylic acid; 4,4 '-(hexafluoroisopropylidene) diphthalic acid, 9,9-bis (trifluoromethyl) -9H-xanthene-2, A fluorinated aromatic carboxylic acid carboxylic acid such as 3,6,7-tetracarboxylic acid, 1,4-ditrifluoromethyl pyromellitic acid; 3,3 ′, 3 ′ ′-(2,4,6-trioxo-1,3 , 5-Triazine-1,3,5-tolyl) tripropionic acid (3,3 ', 3' '-(2,4,6-trioxo-1,3,5-triazinane-1,3,5-triyl) and heterocyclic carboxylic acids such as tripropionic acid) and the like.

  As a specific example of the said carboxylic acid ester compound, the compound by which the at least 1 carboxy group in the specific example of the above-mentioned carboxylic acid compound was substituted by the ester group is mentioned. As a carboxylic acid ester compound, the half-esterified compound represented by the following general formula (B-1)-(B-6) is mentioned, for example.

  R in the general formulas (B-1) to (B-6) is an alkyl group having 1 to 6 carbon atoms, among which a methyl group, an ethyl group, a propyl group and a butyl group are preferable, and an ethyl group and a propyl group are preferable. More preferable.

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

  In the present embodiment, the content of the crosslinking agent (B) in the composition for film formation for a semiconductor is not particularly limited, and, for example, the content in the crosslinking agent (B) relative to the number of total nitrogen atoms in the compound (A). The ratio of the number of carboxy groups (COOH / N) is preferably 0.1 or more and 3.0 or less, more preferably 0.3 or more and 2.5 or less, and 0.4 or more and 2.2 or less It is further preferred that When COOH / N is 0.1 or more and 3.0 or less, by using the composition for forming a film for a semiconductor, an amide, an imide, or the like can be formed between the compound (A) and the crosslinking agent (B) after the heat treatment. It is possible to produce a film which has a cross-linked structure and is more excellent in heat resistance.

(Additive (C))
The composition for forming a film for a semiconductor according to this embodiment has a weight average molecular weight of 46 or more and 195 or less acid (C-1) having no amino group and having a carboxy group, and a weight having a nitrogen atom without having a ring structure. It includes at least one additive (C) selected from the group consisting of bases (C-2) having an average molecular weight of 17 or more and 120 or less.
The composition for film formation for semiconductors may contain only an acid (C-1) as an additive (C), may contain only a base (C-2), an acid (C-1) and a base (C). -2) may be included.

  An acid (C-1) is an acid which has a weight average molecular weight 46 or more and 195 or less which does not have an amino group and has a carboxy group. By containing the acid (C-1) as the additive (C), the composition for forming a film for a semiconductor according to the present embodiment is such that the amino group in the compound (A) and the carboxy group in the acid (C-1) are By forming an ionic bond, it is speculated that aggregation due to association of the compound (A) with the crosslinker (B) is suppressed. More specifically, the interaction (for example, electrostatic interaction) between the ammonium ion derived from the amino group in the compound (A) and the carboxylate ion derived from the carboxy group in the acid (C-1) is the compound (A). Since it is stronger than the interaction between the ammonium ion derived from the amino group in (1) and the carboxylate ion derived from the carboxy group in the crosslinker (B), it is presumed that the aggregation is suppressed. The present invention is not limited by the above estimation.

  The acid (C-1) is not particularly limited as long as it is a compound having no amino group, a carboxy group, and a weight average molecular weight of 46 or more and 195 or less, and a monocarboxylic acid compound, a dicarboxylic acid compound, oxy A dicarboxylic acid compound etc. are mentioned. More specifically, as the acid (C-1), formic acid, acetic acid, malonic acid, oxalic acid, citric acid, benzoic acid, lactic acid, glycolic acid, glyceric acid, butyric acid, methoxyacetic acid, ethoxyacetic acid, phthalic acid, Terephthalic acid, picolinic acid, salicylic acid, 3,4,5-trihydroxybenzoic acid and the like can be mentioned.

  In the present embodiment, the content of the acid (C-1) in the composition for film formation for a semiconductor is not particularly limited, and, for example, the acid (C-1) with respect to the number of total nitrogen atoms in the compound (A) The ratio (COOH / N) of the number of carboxy groups in the group is preferably 0.01 or more and 10 or less, more preferably 0.02 or more and 6 or less, and still more preferably 0.5 or more and 3 or less.

  The base (C-2) is a base having a ring structure and having a nitrogen atom and having a weight average molecular weight of 17 or more and 120 or less. The composition for forming a film for a semiconductor according to the present embodiment contains the base (C-2) as the additive (C), whereby the carboxy group in the crosslinking agent (B) and the amino group in the base (C-2) It is inferred that aggregation due to association between the compound (A) and the crosslinking agent (B) is suppressed by the formation of an ionic bond. More specifically, the interaction between the carboxylate ion derived from the carboxy group in the crosslinking agent (B) and the ammonium ion derived from the amino group in the base (C-2) is derived from the amino group in the compound (A) It is speculated that aggregation is suppressed because the interaction between the ammonium ion and the carboxylate ion derived from the carboxy group in the crosslinking agent (B) is stronger. The present invention is not limited by the above estimation.

  The base (C-2) is not particularly limited as long as it is a compound having no ring structure, a nitrogen atom, and a weight average molecular weight of 17 or more and 120 or less, and a monoamine compound, a diamine compound, etc. may be mentioned. More specifically, as the base (C-2), ammonia, ethylamine, ethanolamine, diethylamine, triethylamine, ethylenediamine, N-acetylethylenediamine, N- (2-aminoethyl) ethanolamine, N- (2-amino) Ethyl) glycine and the like.

  In the present embodiment, the content of the base (C-2) in the composition for forming a film for a semiconductor is not particularly limited. For example, the base (C-2) relative to the number of carboxy groups in the crosslinking agent (B) The ratio of the number of nitrogen atoms (N / COOH) is preferably 0.5 or more and 15 or less, and more preferably 0.9 or more and 10 or less. In addition, in the crosslinking agent (B), when it has an alkyl group having 1 to 6 carbon atoms as X in -C (= O) OX group, the base (C-to the number of carboxy groups in the crosslinking agent (B) More preferably, the ratio (N / COOH) of the number of nitrogen atoms in 2) is 5 or more and 10 or less.

(Polar solvent (D))
The composition for film formation for semiconductors concerning this embodiment contains a polar solvent (D). Here, the polar solvent (D) refers to a solvent having a dielectric constant of 5 or more at room temperature (25 ° C.). Specific examples of the polar solvent (D) include protic inorganic compounds such as water and heavy water; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, Alcohols such as cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, benzyl alcohol, diethylene glycol, triethylene glycol and glycerin; ethers such as tetrahydrofuran and dimethoxyethane; furfural, acetone, ethyl methyl ketone Aldehydes and ketones such as cyclohexane; acetic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, formaldehyde, N-methyl formamide, N, -Acid derivatives such as dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and hexamethylphosphoric acid amide; Nitriles such as acetonitrile and propronitrile; Nitro such as nitromethane and nitrobenzene Compounds; sulfur compounds such as dimethyl sulfoxide; and the like. The polar solvent (D) preferably contains a protic solvent, more preferably water, and still more preferably ultrapure water.
Although content of the polar solvent (D) in the composition for film formation for semiconductors is not specifically limited, For example, 1.0 mass% or more and 99.99896 mass% or less are mentioned with respect to the whole composition, 40 mass It is preferable that it is% or more and 99.99896 mass% or less.

(Other ingredients)
The composition for forming a film for a semiconductor according to this embodiment preferably has a content of sodium and potassium of 10 mass ppb or less on an element basis. When the content of sodium or potassium is 10 mass ppb or less on an element basis, occurrence of inconvenience in the electrical characteristics of the semiconductor device such as malfunction of the transistor can be suppressed.

  The composition for forming a film for a semiconductor according to the present embodiment may contain a solvent other than the polar solvent (D), and examples thereof include normal hexane and the like.

  Further, the composition for forming a film for a semiconductor according to the present embodiment may contain, for example, benzotriazole or a derivative thereof in order to suppress corrosion of copper.

  The pH of the composition for forming a film for a semiconductor according to the present embodiment is not particularly limited, but is preferably 2.0 or more and 12.0 or less.

[Method for producing composition for film formation for semiconductor]
Hereinafter, the manufacturing method of the composition for film formation for semiconductors which concerns on one Embodiment of this invention is demonstrated. The method for producing a composition for forming a film for a semiconductor according to the present embodiment comprises a compound (A), a crosslinking agent (B), and an acid (C-1) having a weight average molecular weight of 46 to 195 having a carboxy group and nitrogen The mixing process which mixes the at least 1 sort (s) of additive (C) chosen from the group which consists of a base (C-2) which does not have a ring structure of weight average molecular weight 17 or more and 120 or less which has an atom is included. In addition, the timing which adds an additive (C) is not specifically limited.
As mentioned above, although the composition for film formation for semiconductors contains a polar solvent (D), a polar solvent (D) is added at arbitrary timing which manufactures a composition for film formation for semiconductors. You may That is, the polar solvent (D) may be added to the compound (A), the crosslinking agent (B), and the additive (C), respectively, or a mixture thereof (for example, the compound (A) and the additive (C) Mixtures of the cross-linking agent (B) and the additive (C), and mixtures of the compound (A), the cross-linking agent (B) and the additive (C), etc. Good. Moreover, the timing which adds another component is not specifically limited, either.

  Moreover, when adding an acid (C-1) as an additive (C), a mixing process mixes the mixture of an acid (C-1) and a compound (A), and a crosslinking agent (B) Is preferred. That is, it is preferable to previously mix a compound (A) and an acid (C-1), before mixing a compound (A) and a crosslinking agent (B). Thereby, when the compound (A) and the crosslinking agent (B) are mixed, clouding and gelation of the composition (the gelation may take a long time to clarify the composition, which is not preferable) are preferable. It can be suppressed.

  Moreover, when adding a base (C-2) as an additive (C), a mixing process mixes the mixture of a base (C-2) and a crosslinking agent (B), and a compound (A) Is preferred. That is, before mixing a compound (A) and a crosslinking agent (B), it is preferable to mix a crosslinking agent (B) and a base (C-2) previously. Thereby, when the compound (A) and the crosslinking agent (B) are mixed, clouding and gelation of the composition (the gelation may take a long time to clarify the composition, which is not preferable) are preferable. It can be suppressed.

[Method of manufacturing member for semiconductor]
Hereinafter, the manufacturing method of the member for semiconductors concerning this embodiment is explained. In the method for manufacturing a member for a semiconductor according to the present embodiment, an applying step of applying a composition for forming a film for a semiconductor to a substrate, and a substrate to which the composition for forming a film for a semiconductor is applied And the heating step of heating under the conditions of 250 ° C. or more and 425 ° C. or less).

<Applying process>
The applying step in the present embodiment is a step of applying the composition for forming a film for semiconductor to a substrate.
Examples of the substrate include semiconductor substrates such as silicon substrates, glass substrates, quartz substrates, stainless steel substrates, plastic substrates and the like. The shape of the substrate is also not particularly limited, and may be plate-like, plate-like or the like. For example, the silicon substrate may be a silicon substrate on which an interlayer insulating layer (low-k film) is formed, and a fine groove (concave portion), a fine through hole, etc. are formed in the silicon substrate. It may be

There is no restriction | limiting in particular as a method to apply the composition for film formation for semiconductors in the provision process in this embodiment, The method used normally can be used.
Examples of commonly used methods include dipping, spraying, spin coating, and barcode methods. For example, in the case of forming a film having a film thickness of micron size, it is preferable to use the barcode method, and in the case of forming a film having a film thickness of nanosize (several nm to several hundreds of nm), a spin coating method is used. Is preferred.

For example, the method for applying the composition for film formation for a semiconductor by spin coating is not particularly limited. For example, while rotating the substrate with a spin coater, the composition for film formation for a semiconductor is dropped on the surface of the substrate and then It is possible to use a method in which the number of rotations of the substrate is increased and dried.
In the method of applying the composition for film formation for semiconductor by spin coating method, various conditions such as the number of rotations of the substrate, the dropping amount and dropping time of the composition for film formation for semiconductor, and the number of rotations of the substrate at drying are particularly limited. However, the thickness can be appropriately adjusted in consideration of the thickness of the film to be formed.

<Drying process>
The manufacturing method according to the present embodiment has a drying step of drying the substrate to which the composition for film formation for a semiconductor is applied under the conditions of a temperature of 80 ° C. or more and 250 ° C. or less before the heating step described later. It is also good. In addition, the said temperature points out the temperature of the surface where the composition for film formation for semiconductors of the board | substrate was provided.
As for the said temperature, 90 degreeC or more and 200 degrees C or less are more preferable, and 100 degreeC or more and 150 degrees C or less are more preferable.

Drying in this step can be performed by a conventional method, but can be performed using, for example, a hot plate.
There is no restriction | limiting in particular in the atmosphere which performs the drying in this process, For example, you may carry out in air | atmosphere atmosphere, and you may carry out in inert gas (nitrogen gas, argon gas, helium gas, etc.) atmosphere.

The drying time is not particularly limited, but is preferably 300 seconds or less, more preferably 200 seconds or less, still more preferably 120 seconds or less, and particularly preferably 80 seconds or less.
The lower limit of the drying time is not particularly limited, but the lower limit can be, for example, 10 seconds (preferably 20 seconds, more preferably 30 seconds).

<Washing process>
In the manufacturing method according to the present embodiment, the substrate to which the composition for forming a film for semiconductor is applied in order to remove the excess composition for forming a film for semiconductor applied to the substrate before the heating step described later It may have a washing step of washing with water or the like. Moreover, when the manufacturing method which concerns on this embodiment has the above-mentioned drying process, it is preferable to perform a washing process after a drying process.

<Heating process>
The manufacturing method according to the present embodiment further includes a heating step of heating the substrate provided with the composition for forming a film for a semiconductor under the conditions of a temperature of 100 ° C. or more and 425 ° C. or less.
In addition, the said temperature points out the temperature of the surface where the composition for film formation for semiconductors of the board | substrate was provided.
By having this heating step, the compound (A) and the crosslinking agent (B) react by heating to obtain a reactant, and a film containing the reactant is formed.
The temperature is preferably 200 ° C. or more and 425 ° C. or less, more preferably 250 ° C. or more and 400 ° C. or less, and still more preferably 300 ° C. or more and 400 ° C. or less.

Further, the pressure at which heating is performed in the heating step is not particularly limited, but an absolute pressure of 17 Pa or more and an atmospheric pressure or less is preferable.
The absolute pressure is more preferably 1000 Pa or more and atmospheric pressure or less, still more preferably 5000 Pa or more and atmospheric pressure or less, and particularly preferably 10000 Pa or more and atmospheric pressure or less.

The heating in the heating step can be carried out by the usual method using a furnace or a hot plate. As the furnace, for example, SPX-1120 manufactured by Apex, VF-1000LP manufactured by Koyo Thermo System Co., Ltd., or the like can be used.
Further, the heating in this step may be performed in the air, or may be performed in an inert gas (nitrogen gas, argon gas, helium gas, etc.) atmosphere.

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

  In order to shorten the heating process time, the surface of the substrate to which the composition for forming a film for a semiconductor is applied may be irradiated with ultraviolet light. As the ultraviolet light, ultraviolet light of wavelength 170 nm to 230 nm, wavelength 222 nm excimer light, wavelength 172 nm excimer light and the like are preferable. In addition, it is preferable to perform ultraviolet irradiation in an inert gas atmosphere.

<Example of member for semiconductor>
As an example of a member for a semiconductor, a member for a semiconductor in which a gap fill material (embedded planarization film) is filled in a recess formed in a substrate, an insulating material (embedded insulating film) is filled in a recess formed in a substrate Semiconductor member, semiconductor member provided with barrier material (barrier film) having insulating property, adhesion property, pore sealing property, etc. between substrate and metal containing low dielectric constant material such as porous material, through silicon via A member for a semiconductor provided on a via sidewall of a substrate between a metal and a silicon substrate or between a metal and an insulating film, wherein an insulating film having adhesion and insulating properties (insulating film for through silicon via) is provided. The member for semiconductors for inversion resist formation etc. are mentioned.

In the member for a semiconductor, in which the planarizing film is filled in the concave portion formed in the substrate, the thickness of the planarizing film is, for example, 30 nm or more and 200 nm or less, preferably 50 nm or more and 150 nm or less.
The semiconductor member can be used as a member having a buried planarizing film in a via, for example, in a via first process when forming a copper multilayer wiring by a dual damascene process.
In addition, in the case of forming a planarizing film embedded in a groove having a narrow width and a large aspect ratio (depth / width), the film formation for a semiconductor according to this embodiment from the viewpoint of enhancing the filling property to the groove. It is preferable to apply the composition for a recessed part (preferably by spin coating method), and to form an embedding planarizing film.

In the semiconductor member in which the recess formed in the substrate is filled with the buried insulating film, the thickness of the buried insulating film is, for example, 30 nm or more and 200 nm or less, preferably 50 nm or more and 150 nm or less.
As the semiconductor member, for example, a member using a method (STI: shallow trench isolation) for forming an element isolation region by providing a buried insulating film having an insulating property in a groove of a silicon substrate, the insulating property is provided. A member provided between switching elements such as a MOSFET (metal-oxide-semiconductor field-effect transistor) in which a buried insulating film is formed in advance, and a buried insulating film having insulation property are provided as a premetal insulating film (PMD) on the MOSFET A member, a member provided between the lowermost layer wiring (W, Ti / TiN / AlCu / TiN etc.) in which a buried insulating film having insulating properties is formed in advance, an embedded buried insulating film having insulating properties on the lowermost layer wiring A member provided as a metal insulating film (IMD), a buried insulating film having an insulating property is formed in a groove between copper wirings formed in advance A member provided as an interlayer insulating film (ILD) may, for example, be mentioned.
In addition, in the case of forming a buried insulating film in a groove having a narrow width and a large aspect ratio (depth / width), the filling property to the groove is enhanced. The composition is preferably applied to the recess (preferably applied by spin coating) to form a buried insulating film.

  In a semiconductor member in which a barrier film having insulating properties, adhesion properties, pore sealing properties and the like is provided between a substrate containing a low dielectric constant material such as a porous material and a metal, the thickness of the barrier film is, for example, 0.5 nm or more and 15 nm or less, preferably 1.5 nm or more and 12 nm or less. The member for semiconductor may be, for example, a member provided with a barrier film to be an adhesive layer between the wall surface of the through hole formed in the substrate and the metal disposed in the through hole.

  In the semiconductor member in which the insulating film for through silicon via is provided between the metal and the silicon substrate on the via sidewall of the through silicon via substrate, the thickness of the through silicon via insulating film is, for example, 100 nm to 5 μm, Preferably they are 500 nm or more and 2 micrometers or less.

  In the semiconductor member in which the insulating film for through silicon via is provided between the metal and the insulating film on the via sidewall of the through silicon via substrate, the thickness of the through silicon via insulating film is, for example, 0.5 nm to 100 nm. , Preferably 1 nm to 30 nm.

[Method of manufacturing process material for semiconductor]
Hereinafter, a method of manufacturing a semiconductor processing material according to the present embodiment will be described. In the method for manufacturing a semiconductor processing material according to the present embodiment, an applying step of applying a composition for film formation for a semiconductor to a substrate, and a substrate provided with the composition for forming a film for a semiconductor are at a temperature of 100 ° C. to 425 ° C. It has the heating process heated on the conditions of (preferably 250 degreeC or more and 425 degrees C or less).
In addition, since each process of the manufacturing method of the process material for semiconductors is the same as each process of the manufacturing method of the above-mentioned member for semiconductors, the description is abbreviate | omitted.

<Example of process material for semiconductor>
Examples of the semiconductor processing material include a sacrificial film which is temporarily formed in the manufacturing process of the semiconductor device and removed in a later process.

EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.
In the following, as “water”, ultrapure water (Millipore Milli-Q water, resistance 18 MΩ · cm (25 ° C. or less)) was used.

<Mixing test>
The composition for film formation for semiconductors of Example 1- Example 4 was prepared. Details are as follows. In the mixing step, a solution of compound (A), a solution of acid (C-1) added to compound (A), a solution of crosslinking agent (B), and a base (C-2) as crosslinking agent (B) It was mixed after making sure that there was no precipitate in each solution to which the solution was added.
The compositions of Comparative Examples 1 to 3 were prepared in the same manner. Details are as follows. In the mixing step, the solution of the compound (A) and the solution of the crosslinking agent (B) were mixed after it was confirmed that there was no precipitate.

Example 1
After dissolving para-xylene diamine (hereinafter also referred to as “pXDA”) which is the compound (A) in a mixed solvent of water and 1-propanol (hereinafter also referred to as “1PrOH”), the mixture is allowed to stand overnight to obtain pXDA solution 1 I got
A cross-linking agent (B) 1,3,5-benzenetricarboxylic acid (hereinafter also referred to as “135 BTC”) is mixed with ethylamine (hereinafter also referred to as “EA”) as a base (C-2) and water. , 135 BTC and EA as a mixed solution 1.
Subsequently, pXDA solution 1, a mixed solution 1 of 135 BTC and EA, and water were mixed so as to have the concentrations shown in Table 1 to prepare a composition for forming a semiconductor film.

Example 2
The compound (A) pXDA was dissolved in a mixed solvent of water and 1PrOH, and allowed to stand overnight to obtain pXDA solution 2.
A mixed solution of 124 BTC and EA is prepared by mixing EA, which is the base (C-2), with water in 1,2,4-benzenetricarboxylic acid (hereinafter also referred to as "124 BTC") which is the crosslinking agent (B). It was 2.
Subsequently, pXDA solution 2, a mixed solution 2 of 124 BTC and EA, and water were mixed so as to have the concentrations shown in Table 1 to prepare a composition for forming a film for semiconductor.

[Example 3]
The compound (A) pXDA was dissolved in a mixed solvent of water and ethanol (hereinafter also referred to as “EtOH”), and allowed to stand overnight to obtain pXDA solution 3.
Ammonia (hereinafter also referred to as "NH3") which is a base (C-2), EtOH and water are mixed with ethyl half ester oxydiphthalic acid (hereinafter also referred to as "eheOPDA") which is a crosslinking agent (B), It was set as the mixed solution 3 of eheOPDA and NH3.
Subsequently, pXDA solution 3, a mixed solution 3 of eheOPDA and NH3, and water were mixed so as to have the concentrations shown in Table 1 to prepare a composition for forming a film for semiconductor.

Example 4
Compound (A) 2,7-diaminofluorene (hereinafter also referred to as “DAF”) is a mixed solvent of acetic acid (hereinafter also referred to as “AA”) as acid (C-1), water and ethanol (EtOH) The solution was allowed to stand overnight to obtain a mixed solution 4 of DAF and AA.
A crosslinker (B), ethyl half ester oxydiphthalic acid (eheOPDA) and ethyl half ester benzophenone tetracarboxylic acid (hereinafter also referred to as "eheBTDA") are respectively dissolved in EtOH, and eheOPDA solution 4 and eheBTDA solution 4 did.
Subsequently, a mixed solution 4 of DAF and AA, eheOPDA solution 4, eheBTDA solution 4 and water were mixed so as to have the concentrations shown in Table 2 to prepare a composition for forming a semiconductor film.

Comparative Example 1
After dissolving paraxylene diamine (pXDA) which is a compound (A) in the mixed solvent of water and 1-propanol (1PrOH), it was left to stand overnight to obtain pXDA solution C1.
After dissolving the crosslinking agent (B) 1,3,5-benzenetricarboxylic acid (135 BTC) in EtOH, it was allowed to stand overnight to obtain a 135 BTC solution C1.
Next, the pXDA solution C1, 135 BTC solution C1, 1 PrOH, and water were mixed so as to have the concentrations shown in Table 1 to prepare a composition for forming a semiconductor film.

Comparative Example 2
After dissolving paraxylene diamine (pXDA) which is a compound (A) in the mixed solvent of water and 1-propanol (1PrOH), it was left to stand overnight to obtain pXDA solution C2.
After dissolving the crosslinking agent (B) 1,2,4-benzenetricarboxylic acid (124 BTC) in EtOH, the solution was allowed to stand overnight to obtain 124 BTC solution C2.
Next, the pXDA solution C2, 124 BTC solution C2, 1 PrOH, and water were mixed so as to have the concentrations shown in Table 1 to prepare a composition for forming a semiconductor film.

Comparative Example 3
After dissolving paraxylene diamine (pXDA) which is the compound (A) in a mixed solvent of water and ethanol (EtOH), it was allowed to stand overnight to obtain pXDA solution C3.
After dissolving ethyl half ester pyromellitic acid (hereinafter also referred to as "ehePMA") which is a crosslinking agent (B) in EtOH, it was allowed to stand overnight to obtain an ehePMA solution C3.
Subsequently, pXDA solution C3, ehePMA solution C3, 1 PrOH, and water were mixed so as to obtain the concentrations shown in Table 1 to prepare a composition for forming a semiconductor film.

In Table 1, the concentrations in parentheses in pXDA (3% by mass), pXDA (1% by mass), and DAF (1.7% by mass) represent the concentrations of pXDA and DAF in the composition. .
Further, in Table 1, the numerical values in parentheses in 135 BTC [1], 124 BTC [1.5], ehePMA [1], eheOPDA [1], eheOPDA [0.5], and eheBTDA [0.5] are compounds. It represents the ratio (COOH / N) of the number of carboxy groups in 135 BTC, 124 BTC, ehePMA, and eheOPDA relative to the total number of nitrogen atoms in (A). The same applies to Tables 2 to 4.
Further, in Table 1, the numerical values in parentheses of EA <1.1> and NH3 <8> indicate the ratio of the number of nitrogen atoms in EA and NH3 to the number of carboxy groups in the crosslinking agent (B) (N / COOH) is shown. The same applies to Tables 2 to 4.
Further, in Table 1, the numerical values in parentheses of AA {0.52} represent the ratio of the number of carboxy groups in AA to the number of total nitrogen atoms in compound (A) (COOH / N). The same applies to Tables 2 to 4.
In Table 1, 1PrOH (50% by mass), EtOH (29.3% by mass), 1PrOH (12% by mass), 1PrOH (33.3% by mass), EtOH (44.1% by mass), EtOH (22%) The concentrations in parentheses in .1 wt%), 1PrOH (71 wt%), EtOH (60.3 wt%), and EtOH (74.6 wt%) represent the concentrations of 1PrOH and EtOH in the composition. There is. The same applies to Tables 2 to 4.
The presence or absence of white turbidity of the prepared composition for film formation for semiconductors was visually observed. The results are shown in Table 1.

In Examples 1 to 4, the composition for forming a film for a semiconductor did not become cloudy, and the transparency could be maintained. By forming a film using the composition for forming a film for a semiconductor in which aggregation is suppressed without causing white turbidity, it is presumed that a smooth film with less unevenness can be formed.
In Comparative Examples 1 to 3, the mixed solution of the compound (A) and the crosslinking agent (B) was cloudy.

<Preparation of composition for film formation for semiconductors>
[Examples 5 to 8 and Comparative Examples 4 to 6]
<Formation of film>
In Examples 5 to 8 and Comparative Examples 4 to 6, a film was formed using the composition for forming a film for a semiconductor prepared in Examples 1 to 4 and Comparative Examples 1 to 3.
The silicon substrate was prepared as a board | substrate which apply | coats the composition for film formation for semiconductors (henceforth a "composition"). The silicon substrate is placed on a spin coater, and 1.0 mL of the composition prepared in each of the examples and comparative examples is dropped at a constant speed for 10 seconds and held for 13 seconds, and then 1 minute at 2000 rpm (rpm is the rotation speed). After rotating at 600 rpm for 30 seconds, it was dried by rotating at 2000 rpm for 10 seconds. Thus, a film was formed on the silicon substrate.
Then, after drying the film at 125 ° C. for 1 minute in the air, the film was heated at 300 ° C. for 10 minutes under a nitrogen atmosphere (30 kPa), and then heated at 400 ° C. for 10 minutes (that is, the same sample Processed continuously).

<Measurement of refractive index, extinction coefficient, and film thickness>
The refractive index and extinction coefficient of the film formed on the silicon substrate were measured in the sample after heating at 400 ° C. for 10 minutes. The refractive index and extinction coefficient were measured using an ellipsometer. The film thickness was calculated from optical data obtained by measurement with an ellipsometer. The film thickness was determined by fitting with an optical model of air / (Cauchy + Lorentz oscillator model) / natural oxide film / silicon substrate.
The results are shown in Table 2.
In Table 2, "N633" represents the refractive index at a wavelength of 633 nm.
In Table 2, "K633" represents the extinction coefficient at a wavelength of 633 nm.

<Crosslinked structure>
The crosslinked structure of the membrane was measured by FT-IR (Fourier Transform Infrared Spectroscopy). The analyzers used are as follows.
~ FT-IR analyzer ~
Infrared absorption analyzer (DIGILAB Excalibur (made by DIGILAB))
~Measurement condition~
IR light source: air-cooled ceramic,
Beam splitter: wide range KBr,
Detector: Peltier cooling DTGS,
Measurement wave number range: 7500 cm ^{−1 to} 400 cm ⁻¹ ,
Resolution: 4 cm ^-1 ,
Number of integrations: 256,
Background: Using Si bare wafer,
Measurement atmosphere: N ₂ (10 L / min),
Incident angle of IR (infrared): 72 ° (= Brewster's angle of Si)
~ Judgment condition ~
The imide bond was judged by the presence of vibrational peaks at 1770 cm ^-1 and 1720 cm ^-1 . Amide bond ^{1650 cm} -1, was determined in the presence of vibration peak of 1520 cm ^-1.
The results are shown in Table 2.

<SEM morphology observation (smoothness)>
The smoothness of the film was evaluated by morphological observation by SEM. Using an S-5000 (manufactured by Hitachi, Ltd.) which is a scanning electron microscope (SEM), measurement was made at an acceleration voltage of 3 kV, 200,000 times, 500 nm wide field of view. When the difference between the maximum film thickness and the minimum film thickness is 25% or less with respect to the average film thickness, it was judged as "smooth", and the evaluation was made "A". Moreover, evaluation in case the difference of the largest film thickness and the minimum film thickness exceeds 25% was made into "B."
The results are shown in Table 2.

  Table 2 shows the measurement results and the evaluation results of the physical properties of the film formed using the composition for forming a film for a semiconductor according to each example and each comparative example. In Comparative Example 4 and Comparative Example 5 and Comparative Example 6 in which the evaluation of the smoothness is "B", the measurement of the film thickness, the refractive index, and the extinction coefficient is difficult. The structure was not measured.

In Example 5, Example 6, Example 7, and Example 8, as a result of SEM form observation, the film was smooth.
On the other hand, in Comparative Examples 4 to 6, the film surface did not become a mirror surface, or a large number of minute pinholes were present, and the film was not smooth.

<Fillability in trench>
Comparative Example 7
BPDA and pDA can be obtained by reacting biphenyltetracarboxylic acid dianhydride (hereinafter also referred to as “BPDA”) with paraphenylenediamine (hereinafter also referred to as “pDA”) in an N-methyl-2-pyrrolidone (NMP) solvent. The polyamic acid (2.5 mass%) which consists of these was adjusted by the conventional method.

Next, 0.5 mL of the composition is dropped at a constant speed for 10 seconds on a silicon oxide substrate provided with a trench pattern having a width of 100 nm and a depth of 200 nm, held for 23 seconds, and then rotated at 600 rpm for 1 second and rotated at 600 rpm for 30 seconds After drying, it was dried by rotating at 2000 rpm for 10 seconds. Next, the dropped composition was dried at 100 ° C. for 1 minute, heated at 300 ° C. for 10 minutes, and further heated at 400 ° C. for 10 minutes.
Then, it was observed whether or not the trench was filled with the composition by a cross-sectional SEM. The case where the filled area is 90% or more of the in-trench area is referred to as A (the fillability is good), and the case where the filled area is less than 90% of the in-trench area is referred to as B.
The results are shown in Table 3.

[Example 9]
The filling property was evaluated in the same manner as in Comparative Example 7 except that the composition for forming a film for a semiconductor prepared in Example 4 was used instead of the composition prepared in Comparative Example 7.
The results are shown in Table 3.

A polyimide film was formed from the composition of Comparative Example 7, but as a result of the embedding test, voids were observed in a 100 nm wide trench.
In Example 9, when the composition for film formation for semiconductors which consists of a liquid mixture of a compound (A), a crosslinking agent (B), and an acid (C-1), it is a favorable filling in a 100-nm width trench. Characteristics were observed.

<Evaluation of decomposition temperature>
[Examples 10 to 12]
The decomposition temperature evaluation was performed using the same composition for film formation for semiconductors as Examples 1-3.

(Evaluation method)
The decomposition temperature of the polymer was evaluated by the following method.
100 mg of each sample prepared in Examples 1 to 3 is placed in a sample cup, and the temperature rising rate from 30 ° C. to 550 ° C. in a nitrogen atmosphere using a thermogravimetric measurement apparatus (manufactured by Shimadzu Corporation: DTG-60 (model number)) It heated at 30 degrees C / min and measured the mass in each temperature. The temperature at 10% reduction from the mass at 300 ° C. is shown in Table 4.

When the temperature is raised to 300 ° C., each sample becomes solid, and when the temperature is further raised, weight loss occurs when the solid polymer is decomposed. The decomposition temperature was evaluated at a temperature that decreased 10% from the mass at 300 ° C.
As shown in Table 4, the solids obtained from the compositions of Examples 10 to 12 containing the compound (A), the crosslinking agent (B) and the base (C-2) have high decomposition temperatures of 350 ° C. or higher Had.
From this result, it was shown that a polymer film having a high decomposition temperature can be formed by using the compositions of Examples 10 to 12 containing the compound (A), the crosslinking agent (B) and the base (C-2). .

Claims (11)

A compound (A) having a ring structure and a cationic functional group containing at least one of a primary nitrogen atom and a secondary nitrogen atom, and having a weight average molecular weight of 90 or more and 600 or less;
It has three or more —C (= O) OX groups (X is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) in the molecule, and three or more —C (= O) OX groups Among them, a crosslinking agent (B) in which one or more and six or less are —C (= O) OH groups and the weight average molecular weight is 200 or more and 600 or less,
Acid (C-1) having a weight average molecular weight of 46 or more and 195 or less having an amino group and having a carboxy group and a base (C-2) having a ring structure and a nitrogen atom and having a weight average molecular weight of 17 or more and 120 or less At least one additive (C) selected from the group consisting of
Polar solvent (D),
And a composition for forming a semiconductor film.   Furthermore, the composition for film formation for semiconductors according to claim 1, wherein the crosslinking agent (B) has a ring structure in the molecule.   The composition for forming a film for a semiconductor according to claim 1, wherein the ring structure is at least one of a benzene ring and a naphthalene ring.   Furthermore, in the three or more —C (= O) OX groups, at least one X in the three or more —C (= O) OX groups is an alkyl group having 1 to 6 carbon atoms. The composition for film formation for semiconductors of any one statement.   The composition for film formation for semiconductors of any one of Claims 1-4 used for the filling material of the recessed part formed in the board | substrate.   The composition for film formation for semiconductors of any one of Claims 1-5 used for the multilayer resist method. It is a manufacturing method which manufactures the constituent for film formation for semiconductors according to any one of claims 1 to 6,
The manufacturing method of the composition for film formation for semiconductors containing the mixing process which mixes the said compound (A), the said crosslinking agent (B), and the said additive (C). The additive (C) contains at least an acid (C-1) having a weight average molecular weight of 46 or more and 195 or less having no amino group and having a carboxy group,
The composition for forming a film for a semiconductor according to claim 7, wherein the mixing step is a step of mixing a mixture of the acid (C-1) and the compound (A) with the crosslinking agent (B). Manufacturing method. The additive (C) contains at least a base (C-2) having a weight average molecular weight of 17 or more and 120 or less and having a nitrogen atom without having a ring structure,
The composition for forming a film for a semiconductor according to claim 7, wherein the mixing step is a step of mixing a mixture of the base (C-2) and the crosslinking agent (B) with the compound (A). Manufacturing method. It is a manufacturing method which manufactures a member for semiconductors using composition for film formation for semiconductors of a statement in any 1 paragraph of Claims 1-6,
Applying the composition for forming a film for a semiconductor to a substrate;
Heating the substrate to which the composition for forming a film for a semiconductor has been applied under conditions of a temperature of 100 ° C. or more and 425 ° C. or less;
The manufacturing method of the member for semiconductors which has. It is a manufacturing method which manufactures the process material for semiconductors using the composition for film formation for semiconductors according to any one of claims 1 to 6,
Applying the composition for forming a film for a semiconductor to a substrate;
Heating the substrate to which the composition for forming a film for a semiconductor has been applied under conditions of a temperature of 100 ° C. or more and 425 ° C. or less;
The manufacturing method of the process material for semiconductors which has these.