TW201721289A - composition for film formation, film, manufacturing method of forming patterned substrate, and compound fully meeting requirements of general characteristics of etching resistance and the like as well as excellent heat resistance and flatness - Google Patents

Abstract

An objective of this invention is to provide a composition for film formation which is excellent in solubility in PGMEA and other solvents, and can form a film fully meeting requirements of general characteristics of etching resistance and the like as well as excellent heat resistance and flatness. This invention is a composition for film formation containing a compound having a moiety represented by the following formula (1) and having an intermolecular bond formation group, and a solvent. In the following formula (1), X1 and X2 each independently represent a ring structure having a substituted or unsubstituted number of ring members of 4 to 10 composed of a spiro carbon atom and a carbon atom of an aromatic ring. a1 and a2 are each independently an integer of 0 to 8. n1 and n2 are each independently an integer of 0 to 2. k1 and k2 are each independently an integer of 0 to 8. However, k1+k2 is 1 or more.

Description

Film forming composition, film, method and compound for forming a substrate on which a pattern is formed

The present invention relates to a film forming composition, a film, a method for producing a substrate on which a pattern is formed, and a compound.

In the manufacture of a semiconductor device, in order to obtain a high degree of bulk, a multilayer resist process is used. In this process, a resist underlayer film is first formed on a substrate by a resist underlayer film forming composition, and a resist film is formed by coating a resist composition on the resist underlayer film. Next, the resist film is exposed through a mask pattern or the like, and developed with a suitable developer to form a resist pattern. Then, using the resist pattern as a mask, the resist underlayer film is dry etched, and the obtained underlayer film pattern is used as a mask, and the substrate is further dry etched to form a desired pattern on the substrate. . The resist underlayer film used in the multilayer resist process requires general characteristics such as optical characteristics such as refractive index and light absorption coefficient, and etching resistance.

In the above multilayer resist process, a method of forming a hard mask as an intermediate layer on the underlayer film of the resist has recently been discussed. In the method, specifically, in order to form an inorganic hard mask by a CVD method on the resist underlayer film, When it is a nitride-based inorganic hard mask, it is at most 300 ° C and usually has a high temperature of 400 ° C or higher. Therefore, the resist underlayer film needs high heat resistance. When the heat resistance is insufficient, the component of the underlayer film of the resist is sublimated, and the sublimated component is further adhered to the substrate, which may cause an undesired decrease in the production yield of the semiconductor device.

Further, in recent cases, a pattern has been formed in a substrate having a plurality of grooves, particularly grooves having mutually different aspect ratios, and the underlayer film is required to be sufficiently buried in the grooves and has High flatness.

In view of the above-mentioned requirements, various structures such as compounds contained in the composition are reviewed. (Japanese Unexamined Patent Publication No. 2012-214720, No. 2012/077640, No. 2011/021555, and International Publication No. 2010 Reference is made to /055852. However, in the above conventional composition, the above requirements cannot be sufficiently satisfied.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2012-214720

[Patent Document 2] International Publication No. 2012/077640

[Patent Document 3] International Publication No. 2011/021555

[Patent Document 4] International Publication No. 2010/055852

The present invention has been made in view of the above-mentioned reasons, and it is an object of the present invention to provide a film-forming composition which is excellent in solubility in PGMEA and the like, and which is excellent in heat resistance and flatness, and which can satisfy general characteristics such as etching resistance. .

In order to solve the problem, the invention has a partial structure (hereinafter also referred to as "partial structure (I)") represented by the following formula (1) and has an intermolecular bond forming group (hereinafter, also referred to as A film-forming composition which is a compound which forms "base (a)") (hereinafter referred to as "[A] compound") and a solvent (hereinafter, also referred to as "[B] solvent") .

(In the formula (1), X ¹ and X ² are each independently, and represent a ring structure of a substituted or unsubstituted ring member number 4 to 10 composed of a carbon atom of a spiro carbon atom and an aromatic ring. Each of R ¹ and R ² Independently, it is a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group. a1 and a2 are each independently an integer of 0 to 8. When each of R ¹ and R ² has a plurality of plural, the plural R ¹ may be the same or different. The plural R ² may be the same or different. n1 and n2 are independent, and are integers of 0 to 2. k1 and k2 are independent, and are integers of 0 to 8. However, k1+k2 is 1 or more. a1+k1 And a2+k2 is 8 or less. * indicates a bonding portion with a portion other than the above-described partial structure).

Another invention which has been made to solve the above problems is a film formed of the film-forming composition.

In order to solve the above problems, a further step of forming a resist underlayer film on the upper surface side of the substrate (hereinafter also referred to as "resistant underlayer film forming step") and forming a resist on the resist underlayer film are provided. a step of patterning (hereinafter, also referred to as "resist pattern forming step"), and a step of forming a pattern on the substrate by etching using the resist pattern as a mask (hereinafter, also referred to as "substrate" The pattern forming step ") is a method for producing a pattern-formed substrate formed by the film forming composition of the resist underlayer film.

Further, in order to solve the above problems, a compound having a partial structure (I) and having an intermolecular bond forming group (a) is further invented.

Here, the "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The "chain hydrocarbon group" refers to a hydrocarbon group which does not include a cyclic structure and has only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. The "alicyclic hydrocarbon group" means a hydrocarbon group which contains only an alicyclic structure and does not contain an aromatic ring structure, and includes both a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic hydrocarbon group. However, it is not necessary to be constituted only by an alicyclic structure, and a part thereof may have a chain structure. The "aromatic hydrocarbon group" means a hydrocarbon group having a structure of an aromatic ring as a ring structure. However, it is not necessary to have only an aromatic ring structure, and a part thereof may have a chain structure or an alicyclic structure.

Further, "organic group" means a group containing at least one carbon atom.

The film-forming composition of the present invention contains a compound having a specific partial structure and an intermolecular bond-forming group, and is excellent in solubility in a solvent such as PGMEA, and satisfies general characteristics such as etching resistance and heat resistance. A film excellent in flatness. This film is excellent in heat resistance and flatness. According to the method for producing a substrate on which the pattern is formed, a resist underlayer film excellent in heat resistance and flatness can be easily formed, and a resist underlayer film having such excellent characteristics can be used to form a good pattern on the substrate. This compound is preferably used as a component of the film-forming composition. Therefore, it is possible to use such a semiconductor device that is expected to be more refined in the future.

[Best Mode for Carrying Out the Invention] <Composition for film formation>

This film-forming composition contains the [A] compound and the [B] solvent. The suitable component of the film-forming composition may contain a [C] acid generator and a [D] crosslinking agent, and may contain other optional components without impairing the effects of the present invention. Each component will be described below.

<[A] compound>

The [A] compound is a compound having a partial structure (I) and having an intermolecular bond forming group (a). In the film-forming composition, by containing the [A] compound, it is possible to maintain a film having excellent heat resistance and flatness while maintaining general characteristics such as etching resistance. Although the film forming composition has the above-described configuration, the reason for achieving the above effects is not clear, but it can be inferred as follows. That is, the [A] compound has a partial structure (I) and an intermolecular bond forming group (a). Partial Structure (I) As in the above formula (1), the ring of X ¹ and X ² which share a spiro carbon atom is configured to have a specific structure in which each ring is condensed to an aromatic ring. It is considered that the film formed of the film-forming composition exhibits high heat resistance by combining the above specific structure and the molecular connection structure formed by the intermolecular bond formation group (a). Further, in the film-forming composition, since the [A] compound has the above specific structure, the molecular structure is formed by the intermolecular bond forming group (a) to form a film, and the groove can be sufficiently embedded to form flatness. Excellent film.

[Partial Construction (I)]

Part of the structure (I) is represented by the following formula (1).

In the above formula (1), X ¹ and X ² are each independently, and represent a ring structure of a substituted or unsubstituted ring number of 4 to 10 which is composed of a carbon atom of a spiro carbon atom and an aromatic ring. R ¹ and R ² are each independently a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group. A1 and a2 are independent, and are integers from 0 to 8. When R ¹ and R ² are each plural, the plural R ¹ may be the same or different, and the plural R ² may be the same or different. N1 and n2 are independent, and are integers of 0-2. K1 and k2 are independent, and are integers from 0 to 8. However, k1+k2 is 1 or more. A1+k1 and a2+k2 are 8 or less. * indicates a bonding portion with a portion other than the above-described partial structure.

The ring structure represented by the above X ¹ and X ² is not particularly limited, and may have an alicyclic structure or a ring structure having a ring forming a double bond between carbon atoms, or may contain the above formula (1). The ring structure of a part of the aromatic ring other than the aromatic ring shown may contain a hetero atom other than a carbon atom as a ring constituent atom, or may have a substituent bonded to a ring-constituting atom. Further, the ring structures represented by X ¹ and X ² may be the same or different, but from the viewpoint of further improving the heat resistance of the film and the ease of synthesis of the compound of the partial structure (I), the same is good.

The ring number of the ring structure is preferably 4 or more and 8 or less, more preferably 5 or more, and even more preferably 5, from the viewpoint of further improving the heat resistance of the formed film.

Examples of the substituent which the ring structure may have include, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an alkenyl group such as a vinyl group or a propylene group, an ethynyl group or a propyne group. a chain hydrocarbon group such as an alkynyl group; a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, a cyclopentenyl group, a cyclohexenyl group, or a norbornyl group; An alicyclic hydrocarbon group such as a cycloalkenyl group such as an alkenyl group; an aryl group such as an aryl group such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group or a decyl group; an aralkyl group such as a benzyl group, a phenethyl group or a naphthylmethyl group; a hydrocarbon group such as an aromatic hydrocarbon group; an oxygen such as a methoxy group, an ethoxy group, a propoxy group, a phenoxy group or a naphthyloxy group; a hydrocarbon; a carbonyloxy hydrocarbon group such as a methoxycarbonyl group or a phenoxycarbonyl group; a mercapto group such as a methyl group, an ethyl group, a propyl group, a benzyl group or the like; an ethyl carbonyl group or a propylene group a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; and a divalent substituent such as a benzyl group; a chain hydrocarbon group such as a methyl group, an ethylene group or a propylene group; an alicyclic hydrocarbon group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group or a norbornyl group; a benzylidene group; a hydrocarbon group such as an aromatic hydrocarbon group such as a phenethyl group, a naphthylmethylene group or an anthranylene group; a pendant oxy group (=O) or the like.

Of these substituents, The monovalent substituent is preferably a hydrocarbon group, a chain hydrocarbon group and an aromatic hydrocarbon group, more preferably an alkyl group or an aryl group, a methyl group, an ethyl group and a phenyl group, and a methyl group.

The divalent substituent is preferably a hydrocarbon group or a pendant oxy group, more preferably an aromatic hydrocarbon group and a pendant oxy group, and more preferably an anthracene group or a pendant oxy group.

Examples of the hetero atom which the ring structure may contain include an oxygen atom, a nitrogen atom, a sulfur atom and the like. Among these, an oxygen atom is preferred from the viewpoint of further improving the heat resistance of the film. The number of hetero atoms which the ring structure may contain is preferably 1 or 2 and more preferably 1.

Examples of the ring structure represented by the above X ¹ and X ^{2 include} a ring structure represented by the following formulas (1-1) to (1-3).

In the above formulae (1-1) to (1-3), R ^a is ^a spiro carbon atom shared by a ring structure of both X ¹ and X ² . R ^b and R ^c are a ring structure of X ¹ or X ² and two carbon atoms shared by the aromatic ring. R ^A is a monovalent group of a hydrogen atom which is substituted by a carbon atom constituting the ring structure, or a divalent group which is a combination of these groups and a carbon atom bonded thereto. When R ^A is plural, the plural R ^A may be the same or different.

In the above formula (1-1), p1 and p2 are each independently and are an integer of 0 to 4. However, p1+p2 is 1 or more and 7 or less. S1 is an integer from 0 to 14.

In the above formula (1-2), q1, q2 and q3 are each independently and are an integer of 0 to 4. However, q1+q2+q3 is 0 or more and 5 or less. S2 is an integer from 0 to 14.

In the above formula (1-3), r1, r2 and r3 are each independently and are an integer of 0 to 4. However, r1+r2+r3 is 0 or more and 6 or less. S3 is an integer from 0 to 14.

In the above formula (1-1), p1 is preferably an integer of 0 to 2, and 0. 1 is better, 0 is better. P2 is preferably an integer of 0 to 3, more preferably 1 and 2, and even more preferably 2. P1+p2 is preferably 1 or more and 4 or less, 2 and 3 is more preferable, and 2 is more preferable. S1 is preferably an integer of 0 to 4, an integer of 0 to 2 is better, and 2 is more preferable.

In the above formula (1-2), q1 is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 0. Q2 is preferably an integer of 0 to 2, more preferably 0 and 1, and 0 is more preferable. Q3 is preferably an integer of 0 to 2, more preferably 0 and 1, and 0 is more preferable. It is preferable that q1+q2+q3 is 0 or more and 2 or less, 0 and 1 are better, and 0 is more preferable. S2 is preferably an integer of 0 to 4, an integer of 0 to 2 is better, and 1 is more preferable.

In the above formula (1-3), r1 is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 0. R2 is preferably an integer of 0 to 2, more preferably 0 and 1, and more preferably 0. R3 is preferably an integer from 0 to 3, more preferably 1 and 2, and even more preferably 2. R1+r2+r3 is preferably 0 or more and 4 or less, 1 and 2 is more preferable, and 2 is more preferable. S3 is preferably an integer of 0 to 4, an integer of 0 to 2 is better, and 2 is more preferable.

The monovalent or divalent group represented by the above R ^A may, for example, be the same as the monovalent or divalent group exemplified as the substituent which the ring structure represented by the above X ¹ and X ² may have.

The monovalent organic group represented by R ¹ and R ² in the above formula (1) may, for example, be a monovalent hydrocarbon group, an oxyhydrocarbyl group, a decyl group, a decyloxy group or a carbonyloxy hydrocarbon group. The respective groups of the above-mentioned groups may be, for example, the same groups as the monovalent group which the ring structure represented by the above X ¹ and X ² may have.

A1 and a2 are preferably 0 to 2 integers, 0 and 1 are better, 0 Better yet.

N1 and n2 are preferably 0 and 1 and more preferably 0.

K1 and k2 are preferably integers from 1 to 8, integers from 1 to 4 are better, integers from 1 to 3 are better, and 1 and 2 are particularly preferred.

K1+k2 is preferably an integer of 2 to 16, an integer of 2 to 8 is better, an integer of 2 to 4 is better, and 2 and 4 are particularly preferable.

The partial structure (I) is, for example, a structure represented by the following formulas (1-1-1) to (1-3-3) (hereinafter, also referred to as "partial structure (I-1-1) to (I- 3-3)") and so on.

In the above formulae (1-1-1) to (1-3-3), k1, k2 and * are synonymous with the above formula (1).

Among these, part of the structure (I) is preferably a partial structure (I-1-1) to (I-1-5), a partial structure (I-2-1), and a partial structure (I-3-1). Partial construction (I-1-1) is better.

[Intermolecular bond formation base (a)]

The intermolecular bond forming group (a) is a group capable of forming a covalent bond between molecules by, for example, an addition reaction or a condensation reaction. The [A] compound can form a group (a) by intermolecular bonding, and the [A] compounds can be bonded to each other to increase the strength of the film. The compound [A] may have the above-described intermolecular bond forming group (a) in the above partial structure (I), or may have the above-described intermolecular bond forming group (a) in a portion other than the above partial structure (I). However, from the viewpoint of further improving the heat resistance of the film, it is preferred to have a portion other than the above partial structure (I).

The above-mentioned intermolecular bond forming group (a) may, for example, be a carbon-carbon triple bond-containing group, a carbon-carbon double bond-containing group, a hydroxy chain hydrocarbon group, a fluorenyl group, a decyloxy group, an epoxy group or an alkoxy group. Methyl, dialkylaminomethyl, dimethylolaminomethyl and the like. Among these, a group containing a carbon-carbon triple bond, a group containing a carbon-carbon double bond, a hydroxyl chain hydrocarbon group, a mercapto group, and a carbonyloxy hydrocarbon are preferred. The intermolecular bond forming group (a) is more preferably a group containing a carbon-carbon triple bond and a carbon-carbon double bond. In this case, the intermolecular bond can be formed by the addition reaction of the carbon-carbon multiple bonds, and as a result, the base can be hardened without leaving the base, so that the film can be formed while suppressing the film shrinkage, and as a result, flatness can be formed. Membrane.

The group containing a carbon-carbon triple bond may, for example, be a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propargyl group, or a group represented by the following formula (3-1) (hereinafter, also referred to as "base" (3-1)") and so on.

The group containing a carbon-carbon double bond may, for example, be a (meth)acryloyl group, an allyl group, an allyloxy group, a phenylallyloxy group, a cyclohexenylmethoxy group or a styryl group. a methoxy group, a group represented by the following formula (3-2) (hereinafter, also referred to as "base (3-2)"), and a group represented by the following formula (3-3) (hereinafter, also referred to as "base (3-3)") and so on.

In the above formula (3-1), R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. q is 1 or 2. When q is 2, the plural R ³ may be the same or different.

In the above formula (3-2), R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

In the above formula (3-3), R ^{4 '} , R ^5' , R ^6' and R ^7' are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. q' is 1 or 2. When q' is 2, the plural R ^{5 '} , R ^6' and R ⁷ may be the same or different.

The monovalent hydrocarbon group having 1 to 20 carbon atoms represented by the above R ³ to R ⁷ and R ⁴ ' to R ⁷ ' may be, for example, the same groups as those exemplified for R ¹ and R ² in the above formula (1).

In the above-mentioned R ³ and R ⁴ , from the viewpoint of improving the curability of the film-forming composition, a hydrogen atom and an alkyl group are preferred, and a hydrogen atom is more preferable.

The above q and q' are preferably 2 from the viewpoint of improving the curability of the film-forming composition.

The above-mentioned R ⁵ , R ⁶ and R ^{7 are} preferably a hydrogen atom or an alkyl group and more preferably a hydrogen atom from the viewpoint of improving the curability of the film-forming composition.

From the viewpoint of improving the curability of the film-forming composition, the above-mentioned R ^{4 '} to R ^{7 ' is} preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

The hydroxy chain hydrocarbon group may, for example, be a monovalent group such as a hydroxymethyl group, a 1-hydroxyethyl group, a 1-hydroxypropyl group or a 2-hydroxy-2-propyl group, a hydroxymethanediyl group or a 1-hydroxy-1 group. A divalent group such as a 1-ethanediyl group or a 1-hydroxy-1,1-propanediyl group. Among these, 1-hydroxyethyl, 2-hydroxy-2-propyl, hydroxymethanediyl and 1-hydroxy-1,1-ethanediyl are preferred.

Examples of the above mercapto group include a methyl group, an ethyl group, a propyl group, a butyl group, and the like. Among these, it is preferred to use a methyl group and an ethyl group.

The carbonyloxy hydrocarbon group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a phenoxycarbonyl group or a naphthyloxycarbonyl group. Among these, a methoxycarbonyl group is preferred.

The number of the intermolecular bond forming groups (a) of the [A] compound may be one or two or more, but two or more are preferable from the viewpoint of further improving the heat resistance of the film.

The aspect of the compound [A] may, for example, be a compound having one partial structure (I) (hereinafter also referred to as "[A1] compound"), having two or more partial structures (I) and having a partial structure ( I) A polymer as a repeating unit (hereinafter also referred to as "[A2] polymer"). Hereinafter, the [A1] compound and the [A2] polymer will be described in order.

<[A1] compound>

The compound [A1] is a compound having one partial structure (I). The film-forming composition can be further improved by making the compound [A] into the compound [A1]. The embedding property of the trenches results in the formation of a film having more excellent flatness.

The compound [A1] is not particularly limited as long as it has one partial structure (I), and examples thereof include a compound represented by the following formula (2). Since the compound represented by the following formula (2) is composed of an aromatic ether bond, the heat resistance of the film can be further improved.

In the above formula (2), Z ¹ is a partial structure represented by the above formula (1). K1 and k2 are synonymous with the above formula (1). Ar ¹ and Ar ² are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms. P1 and p2 are independent of each other and are integers from 0 to 3. Ar ^{3 is} a group in which (j1+1) hydrogen atoms are removed from an aromatic ring of a substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms. Ar ^{4 is} a group in which (j2+1) hydrogen atoms are removed from an aromatic ring of a substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms. J1 and j2 are independent, and are integers from 1 to 9. Y ¹ and Y ² are each independently a monovalent intermolecular bond forming group having a carbon number of 1 to 20. When Ar ¹ ~Ar ⁴ , Y ¹ , Y ² , p1, p2, j1 and j2 each have a plurality of plural, the plural Ar ¹ may be the same or different, and the plural Ar ² may be the same or different, the plural Ar ³ may be the same or different, Ar ⁴ may be the same or different, the plural Y ¹ may be the same or different, the plural Y ² may be the same or different, the plural p1 may be the same or different, plural The p2 may be the same or different, the plural j1 may be the same or different, and the plural j2 may be the same or different.

Examples of the aromatic hydrocarbon diyl group having 6 to 20 carbon atoms represented by the above Ar ¹ and Ar ² include a benzenediyl group, a toluenediyl group, a xylene diyl group, a naphthalenediyl group, and a fluorenyldiyl group. Among these, from the viewpoint of further improving the flatness of the film, a benzenediyl group and a naphthalenediyl group are preferred, and a benzenediyl group is more preferable.

The substituent of the aromatic hydrocarbon diradical group of Ar ¹ and Ar ² may, for example, be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, a hydroxyl group, an amine group, a nitro group or a monovalent organic group having a carbon number of 1 to 20. Base. Among these, from the viewpoint of further improving the heat resistance of the film and the ease of synthesis of the compound [A], a nitro group and a monovalent organic group having 1 to 20 carbon atoms are preferred, and a nitro group and a cyano group are preferred, and cyanide is preferred. The base is even better.

The above p1 and p2 are preferably an integer of 0 to 2, more preferably 1 or 2, and even more preferably 1 from the viewpoint of heat resistance of the film and improvement of flatness.

Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms which are added to the groups represented by Ar ³ and Ar ⁴ include benzene, toluene, xylene, biphenyl, naphthalene, methylnaphthalene, anthracene and the like.

The substituent of the group represented by the above Ar ³ and Ar ⁴ may, for example, be the same as those exemplified as the substituent of the aromatic hydrocarbon diradical of Ar ¹ and Ar ² described above.

The monovalent intermolecular bond forming group having 1 to 20 carbon atoms represented by the above Y ¹ and Y ² may be, for example, the same group as the one of the exemplified bases of the above-mentioned intermolecular bond forming group (a) ( However, it is limited to those with a carbon number of 1 to 20).

Y ¹ and Y ^{2 have} a carbon number of 1 to 20 in the form of a monovalent intermolecular bond forming group, and among these, a group containing a carbon-carbon double bond and a carbon-carbon triple bond group are preferred, and the above group ( 3-1), the above group (3-2) and the above group (3-3) are more preferable (but limited to a carbon number of 20 or less).

J1 and j2 are preferably integers from 1 to 4, integers from 1 to 3 are better, and 1 and 2 are better.

J1+j2 is preferably an integer of 2~8, an integer of 2~6 is better, an integer of 2~4 is better, 2 and 4 are particularly good.

K1 and k2 are preferably integers of 1 to 4, integers of 1 to 3 are more preferable, and 1 and 2 are more preferable.

K1+k2 is preferably an integer of 2~8, an integer of 2~6 is better, an integer of 3~6 is better, an integer of 4~6 is particularly good, and 4 and 6 are more excellent.

The compound represented by the following formula (2-1) to (2-36) (hereinafter, also referred to as "compound (2-1) to (2-36)")).

Among these, compounds (2-1), (2-4) to (2-7), (2-11) to (2-28), and (2-29) to (2-36) are preferred. Compounds (2-1), (2-4) to (2-7), (2-11) to (2-16), and (2-29) to (2-36) are particularly preferred.

The content of the compound (A1) is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more based on the total solid content of the film-forming composition.

<Method for synthesizing [A1] compound>

[A1] The compound (B') may be, for example, a polyol component (A') containing a polyol compound represented by the following formula (2-m) (hereinafter also referred to as "polyol (2-m)") The monohalogen component (B') containing an aromatic monohalide having an intermolecular bond forming group (a) is synthesized by reacting in an organic solvent in the presence of an alkali metal or an alkali metal compound. In addition to the above reaction method, the polyol component (A') may be reacted with an alkali metal or an alkali metal compound in an organic solvent to obtain an alkali metal salt of the polyol component (A'), and the obtained metal salt and the single salt may be obtained. The halogen component (B') reacts. The monohalogen component (B') may be, for example, an aromatic dihalogen compound having a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group, and an aromatic unit alcohol compound having an intermolecular bond forming group (a). It is obtained by reaction or the like in the presence of a basic compound. Further, in place of the monohalogen component (B'), a component containing an aromatic monohalogen which can be converted into a group capable of converting into an intermolecular bond-forming group (a) (for example, an amine group) can be used together with the polyol component (A). After the reaction, the group convertible to the intermolecular bond forming group (a) is converted into an intermolecular bond forming group (a) (for example, a group represented by the above formula (3-1)). The above aromatic unit alcohol compound having an intermolecular bond forming group (a), For example, vinyl phenol, vinyl naphthol, methyl decyl phenol, methyl decyl naphthol, ethyl decyl phenol, ethyl decyl naphthol, vinyl phenol, vinyl oxy naphthol, propargyloxy Phenol, propargyloxynaphthol, methoxycarbonylphenol, methoxycarbonylnaphthol, allylphenol, propenyl naphthol, and the like.

In the above formula (2-m), X ¹ , X ² , R ¹ , R ² , a1, a2, n1, n2, k1 and k2 have the same meanings as in the above formula (1).

The basic compound and the organic solvent are used for the above reaction, and examples thereof include the same compounds as those of the synthetic user of the above [A2] polymer. The amount of the basic compound is preferably from 1 to 3 equivalents, more preferably from 1 to 2 equivalents, and from 1 to 1.5 times, relative to the -OH group of the polyol component (A'). The equivalent is better.

The amount of the monohalogen component (B') used is preferably from 1 to 3 equivalents, more preferably from 1 to 2 equivalents, and more preferably 1 to 2 times the amount of the -OH group of the polyol component (A'). Equivalent to 1.5 times equivalent and better.

The reaction temperature is preferably 60 ° C to 250 ° C, more preferably 80 ° C to 200 ° C. The reaction time is preferably from 15 minutes to 100 hours, more preferably from 1 hour to 24 hours.

The synthesized compound can be returned from the reaction solution by reprecipitation Collection, refining. The solvent used for the reprecipitation may, for example, be an alcohol solvent, and among them, methanol is preferred.

The lower limit of the molecular weight of the [A1] compound is preferably 300, more preferably 600, and still more preferably 800. The upper limit of the above molecular weight is preferably 3,000, more preferably 2,000, still more preferably 1,500. The [A1] compound can improve the flatness of the film by setting the molecular weight between the lower limit and the upper limit.

<[A2]polymer>

[A2] The polymer is a polymer having a repeating unit represented by the following formula (4) (hereinafter also referred to as "repeating unit (I)"). The film-forming composition can further improve the heat resistance of the film by containing the [A2] polymer as the [A] compound. "Polymer" means a compound having two or more repeating units, and generally includes both those classified as oligomers and those classified as polymers.

In the above formula (4), Z ² is a partial structure represented by the above formula (1). K1 is synonymous with the above formula (1).

[A2] The polymer may have a repeating unit (II) and/or a repeating unit (III) having an intermolecular bond forming group described later, in addition to the repeating unit (I), and may have other units other than the repeating unit. Repeat the unit. Each repeating unit will be described below.

[repeating unit (I)]

The repeating unit (I) is a repeating unit represented by the above formula (4). The repeating unit (I) may be, for example, a repeating unit represented by the following formula (1P-1-1) to (1P-3-3) (hereinafter, also referred to as "repeating unit (1P-1-1) to (1P). -3-3)") and so on.

In the above formulas (1P-1-1) to (1P-3-3), k1 and k2 are synonymous with the above formula (1). * is a bonding portion with a portion other than the partial structure (I).

In this case, the repeating unit (1P-1-1) and the repeating unit (1P-3-1) are preferable, and the repeating unit (1P-1-1) and k1+k2 in which k1+k2 is 3 or more and 6 or less. It is better to repeat units (1P-3-1) of 3 or more and 6 or less, k1+k2 A repeating unit of 4 or 6 (1P-1-1) and a repeating unit of k1+k2 of 4 (1P-3-1) are more preferable.

The content ratio of the repeating unit (I) is preferably 0.1 mol% to 20 mol%, more preferably 0.2 mol% to 10 mol%, and 0.5 mol% relative to the total repeat unit constituting the [A2] polymer. ~7 mole% is better, 1 mole%~5 mole% is particularly good. The content ratio of the repeating unit (I) can be improved by the heat resistance and flatness of the film by the above range.

The [A] polymer may have a repeating unit (I) in either the main chain or the side chain, but is preferably present in the main chain. [A] When the polymer has a repeating unit (I) in the main chain, the heat resistance and flatness of the film are superior. Here, the "main chain" means the longest of the chains in which a plurality of atoms constituting the [A] polymer are bonded. "Side chain" means any other than the main chain in the chain of [A] polymer.

When the above k1 and k2 are 1, the structure including the above repeating unit (I) is preferably represented by the following formula (X).

[Chemical 20]-Ar ¹ -ZO-Ar ² - (X)

In the above formula (X), Z is the above partial structure (I). Ar ¹ and A _r ² are each independently a substituted or unsubstituted aromatic hydrocarbon dialkyl group having 6 to 40 carbon atoms.

The aromatic hydrocarbon diradical having 6 to 40 carbon atoms represented by the above Ar ¹ and Ar ² may, for example, be a benzenediyl group, a naphthalenediyl group, a fluorenyldiyl group or a phenanthrenyl group.

[repeating unit (II)]

The repeating unit (II) is a repeating unit represented by the following formula (5-1) or formula (5-2). The repeating unit (II) has an intermolecular bond forming group Y ³ or Y ⁴ . [A2] The polymer has a repeating unit (II), and the hardenability of the film-forming composition is further improved, and as a result, the heat resistance of the film is further increased.

In the above formula (5-1), Y ³ is a monovalent intermolecular bond forming group having 1 to 20 carbon atoms. b is an integer from 1 to 8. R ⁸ is a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group. c is an integer from 0 to 8. However, b+c is 8 or less. When Y ³ and R ⁸ each have a plurality of plural, the plural Y ³ may be the same or different, and the plural R ⁸ may be the same or different. m is an integer from 0 to 2. When m is 1 or 2, Y ³ and R ⁸ may be bonded to either ring. In the above formula (5-2), Y ⁴ is a divalent intermolecular bond forming group having 1 to 20 carbon atoms. R ⁹ and R ¹⁰ are each independently a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group. d and e are independent, and are integers from 0 to 8. When R ⁹ is plural, the plural R ⁹ may be the same or different. When R ¹⁰ is plural, the plural R ¹⁰ may be the same or different. M1 and m2 are independent, and are integers of 0-2.

The monovalent intermolecular bond forming group having 1 to 20 carbon atoms represented by the above Y ³ is, for example, the same as the monovalent group in the above-mentioned intermolecular bond forming group (a) (however, Limited to carbon number 1~20).

In these, a group having a carbon-carbon double bond and a carbon-carbon triple bond are preferred, and the above group (3-1), the above group (3-2), and the above group (3-3) are more preferable. (However, it is limited to those with a carbon number of 20 or less).

The divalent intermolecular bond forming group having 1 to 20 carbon atoms represented by the above-mentioned Y ⁴ may be, for example, the same as the divalent group in the above-mentioned intermolecular bond forming group (a) (however, Limited to carbon number 1~20).

Among these, hydroxymethanediyl, 1-hydroxy-1,1-ethanediyl and 1-hydroxy-1,1-propanediyl are preferred, hydroxymethanediyl and 1-hydroxy-1,1- The ethane diyl group is more preferred.

The halogen atom represented by the above R ⁸ to R ¹⁰ may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a fluorine atom and a chlorine atom are preferred, and a chlorine atom is more preferable.

The monovalent organic group represented by the above R ⁸ to R ¹⁰ may, for example, be the same as the monovalent organic group exemplified as R ¹ and R ² in the above formula (1). Among these, cyano and formazan are preferred.

The above R ⁸ to R ^{10 are} preferably a halogen atom, a nitro group or a cyano group, a chlorine atom, a nitro group and a cyano group, and a cyano group. By the above R ⁸ to R ¹⁰ being an electron withdrawing group, the polymerization of the synthesized [A2] polymer can be promoted.

The above b is preferably an integer of 1 to 3, more preferably 1 and 2, and even more preferably 1.

The above c is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 0.

The above m is preferably 0 and 1 and more preferably 0.

The above d is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 0.

The above e is preferably an integer of 0 to 2, more preferably 0 and 1, and still more preferably 0.

The above m1 is preferably 0 and 1 and more preferably 0.

The above m2 is preferably 0 and 1 and more preferably 0.

In the repeating unit (II), when m is 0, the position of the two bonding bonds of the aromatic ring is preferably a meta position. By repeating the position of the bonding bond in the unit (II) to a meta position, the linearity of the main chain of the [A2] polymer can be lowered, and as a result, the flatness of the film can be further improved.

The repeating unit (II) may be, for example, a repeating unit represented by the following formulas (3-1) to (3-12) (hereinafter, also referred to as "repeating unit (II-1) to (II-12)"), etc.) .

In the above formulae (3-2) and (3-6), Hal is a halogen atom.

In the above formulas (3-9) to (3-11), R is a monovalent hydrocarbon group.

In this case, the repeating unit (II) is preferably a repeating unit (II-1)~(II-8), (II-12), and (II-13), and the repeating unit (II-1)~(II-4) And (II-13) are better, and the repeating units (II-1) and (II-13) are even better.

The content of the repeating unit (II) is preferably from 5 mol% to 95 mol%, more preferably from 20 mol% to 80 mol%, and more preferably 30 mol%, relative to the total repeat unit of the [A2] polymer. ~75 mol% is better. The content ratio of the repeating unit (II) can be improved by the coating ratio of the [A2] polymer by the above range.

[repeating unit (III)]

The repeating unit (III) is a repeating unit represented by the following formula (4). By having the repeating unit (III) of the [A2] polymer, the heat resistance of the film can be further improved.

In the above formula (4), R ^B1 to R ^B4 are each independently a halogen atom, a nitro group or a monovalent organic group. T1 and t2 are independent, and are integers from 0 to 6. T3 and t4 are independent, and are integers of 0-4. I1 and i2 are integers from 0 to 2.

The halogen atom represented by the above R ^B1 to R ^B4 may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The monovalent organic group represented by the above R ^B1 to R ^B4 may, for example, be the same as the monovalent organic group exemplified as R ¹ and R ² in the above formula (1).

The above R ^B1 to R ^{B4 are} preferably a monovalent hydrocarbon group, a halogen atom or a cyano group, and more preferably a monovalent hydrocarbon group.

The above t1 and t2 are preferably 0 to 2 integers, 0 and 1 are better, and 0 is more preferable.

The above t3 and t4 are preferably an integer of 0 to 2, more preferably 0 and 1, and more preferably 0.

It is preferable that i1 and i2 are 0 and 1, and 1 is more preferable. By making i1 and i2 1, which is a naphthalene ring, the absorption coefficient of the film can be improved.

The repeating unit (III) may be, for example, a repeating unit represented by the following formulas (4-1) to (4-6) (hereinafter, also referred to as "repeating unit (III-1) to (III-6))"). .

Among these, the repeating unit (III) is preferably a repeating unit (III-1) and a repeating unit (III-2).

In the case of the ratio of the repeating unit (III), when k1+k2 is 3 or more, the total repeating unit constituting the [A2] polymer is preferably 5 mol% to 95 mol%, and 10 mol% to 70 mol. The ear% is better, 15%%~50%% is better. Further, when k1 and k2 are 1, the total repeat unit constituting the [A2] polymer is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 55 mol%, and 15 mol%. ~35 moles is even better. When the content ratio of the repeating unit (III) is in the above range, the heat resistance of the [A2] polymer and the solvent solubility of PGMEA or the like can be further improved, and as a result, the coating property of the film forming composition can be improved. The heat resistance of the obtained film is further improved.

[other repeat units]

[A2] The polymer may have other than the above repeating units (I) to (III) Repeat the unit. The other repeating unit may be, for example, a repeating unit represented by the following formulas (5-1) to (5-6) (hereinafter, also referred to as "repetitive unit (IV-1) to (IV-6)").

In the above formula (5-3), j1 and j2 are each independently and are an integer of 0 to 2.

In this case, other repeating units are preferably in repeating units (IV-1) to (IV-4).

The [A2] polymer may have a repeating unit other than the above repeating units (IV-1) to (IV-6) as another repeating unit. The repeating unit may be an aromatic ring-free one or an ether-free one.

The content ratio of the other repeating unit is preferably 60 mol% or less, more preferably 40 mol% or less, more preferably 10 mol% or less, relative to the total repeating unit of the [A2] polymer.

[A2] The content of the polymer relative to the composition for forming the film The total solid content of the material is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 85% by mass or more.

<[A2] Method for synthesizing polymer>

[A2] The polymer, for example, when k1 and k2 in the above formula (1) are 1, when the repeating unit (II) contains an intermolecular bond forming group (a), the formula (1) a polyol component (A) of the polyol compound (hereinafter also referred to as "polyol (1-m)") represented by -m) and an aromatic dihalide containing an intermolecular bond forming group (a) The dihalogen component (B) is synthesized by reacting in an organic solvent in the presence of an alkali metal or an alkali metal compound. In addition to the above reaction method, the polyol component (A) may be reacted with an alkali metal or an alkali metal compound in an organic solvent to obtain an alkali metal salt of the polyol component (A), and the resulting metal salt and dihalogen component may be obtained ( B) Reaction. Further, in place of the dihalogen component (B), a component containing an aromatic dihalogen compound having a group which can be converted into an intermolecular bond forming group (a) is used, and after reacting with the polyol component (A), it can be converted into The intermolecular bond forming group (a) is converted to an intermolecular bond forming group (a). In addition to the above-mentioned polyol (1-m), the polyol component (A) may contain, for example, a diol compound represented by the following formula (4-m), another diol compound, or the like. The dihalogen component (B) may, for example, be a compound represented by the following formula (3-m).

In the above formula (1-m), X ¹ , X ² , R ¹ , R ² , a1, a2, n1, and n2 have the same meanings as in the above formula (1).

In the above formula (3-m), R ³ is the above-mentioned intermolecular bond forming group (a), and b is an integer of 1 to 8. m is an integer from 0 to 2. Y is a halogen atom.

In the above formula (4-m), R ^B1 to R ^B4 , t1 to t4 , and i1 and i2 have the same meanings as the above formula (4).

The halogen atom represented by the above Y may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. Among these, a fluorine atom and a chlorine atom are preferred, and a fluorine atom is more preferable.

The alkali metal may, for example, be lithium, sodium or potassium.

The above alkali metal compound may, for example, Alkali metal carbonate such as lithium carbonate, sodium carbonate or potassium carbonate; alkali metal hydrogencarbonate such as lithium hydrogencarbonate, sodium hydrogencarbonate or potassium hydrogencarbonate; alkali metal hydrogen such as lithium hydroxide, sodium hydroxide or potassium hydroxide An oxide; an alkali metal hydride such as lithium hydride, sodium hydride or potassium hydride.

Among these, an alkali metal carbonate is preferred, and potassium carbonate is more preferred. These alkali metals and alkali metal compounds may be used alone or in combination of two or more.

When the aromatic ring of the aromatic dihalide of the dihalogen component (B) has an electron-withdrawing group (for example, R ³ in the above formula (3-m) is an electron-withdrawing group), the component (A) and the component are promoted. (B) The reaction is good. The electron withdrawing group may, for example, be a cyano group or a nitro group.

The amount of the above-mentioned alkali metal or alkali metal compound is preferably from 1 to 3 equivalents, more preferably from 1 to 2 equivalents, and from 1 to 1 equivalent to 1.5 equivalents to the OH group of the diol component (A). The equivalent is better.

The organic solvent used in the reaction may, for example, be dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ- Butyrolactone, cyclobutyl hydrazine, dimethyl hydrazine, diethyl hydrazine, dimethyl hydrazine, diethyl hydrazine, diisopropyl hydrazine, diphenyl hydrazine, diphenyl ether, benzophenone And dialkoxybenzene (carbon number of the alkoxy group is 1 to 4), trialkoxybenzene (carbon number of alkoxy group 1 to 4), and the like. Among these solvents, a polar organic solvent having a high dielectric constant such as N-methyl-2-pyrrolidone, dimethylacetamide, cyclobutyl hydrazine, diphenylphosphonium or dimethyl hydrazine is used. good. Above organic The solvent may be used singly or in combination of two or more.

In the reaction, benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, and the like may be further used. A solvent which azeotropes with water, such as an alkane, tetrahydrofuran, anisole or phenethyl ether. These may be used alone or in combination of two or more.

When k1+k2 is 3 or more, the amount of the polyol component (A) used is 100 mol% based on the total of the polyol component (A) and the dihalogen component (B), and is 45 mol% or more and 70 mol. The following is preferably less than 48% by mole, more preferably less than 65 moles, more preferably more than 53% by mole, and more preferably less than 65 moles. The amount of the dihalogen component (B) to be used is preferably 30 mol% or more and 55 mol% or less, more preferably 35 mol% or more and 52 mol% or less, more preferably more than 35 mol% and 47 mol% or less. Further, when k1 and k2 are 1, the amount of the polyol (A) used is 100 mol% based on the total of the polyol component (A) and the dihalogen component (B), and is 45 mol% or more and 75 mol. The following is preferably less than 48% by mole, more preferably 70% by mole or less, more preferably 60% by mole or less and less than 70% by mole. The amount of the dihalogen component (B) to be used is preferably 25 mol% or more and 55 mol% or less, more preferably 30 mol% or more and 52 mol% or less, more preferably more than 30 mol% and 40 mol% or less.

The reaction temperature is preferably 60 ° C to 250 ° C, more preferably 80 ° C to 200 ° C. The reaction time is preferably from 15 minutes to 100 hours, more preferably from 1 hour to 24 hours.

The synthesized polymer can be recovered and purified from the reaction liquid by a reprecipitation method or the like. The solvent used for the reprecipitation may, for example, be an alcohol solvent, and among them, methanol is preferred.

The lower limit of the weight average molecular weight (Mw) of the polymer [A2] is preferably 600, more preferably 1,500, more preferably 2,500, and particularly preferably 3,000. [A2] The upper limit of the Mw of the polymer is preferably 100,000, more preferably 50,000, more preferably 15,000, and particularly preferably 6,000. [A2] The Mw of the polymer can further improve the heat resistance of the film by the above lower limit and the above upper limit.

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight of the polymer is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less, still more preferably 1 or more and 2.5 or less. [A2] The Mw/Mw ratio of the polymer can further improve the flatness of the film by the above range.

[A2] The polymer is preferably obtained by using two or more kinds of polyol compounds as the above polyol component (A). The [A2] polymer thus obtained has a reduced linearity of the main chain, and as a result, the solvent solubility to PGMEA or the like can be further improved. In the case of the above two or more kinds of polyol compounds, a combination of a compound which imparts a repeating unit (I) and a compound which imparts a repeating unit other than the repeating unit (I) is preferred. Thereby, the linearity of the main chain of the [A2] polymer can be further lowered. When two kinds of polyol compounds are used, it is preferred to use a combination of a compound which imparts a repeating unit (I) and a compound which imparts a repeating unit (III).

Further, in such a [A2] polymer, it is preferred to randomly arrange two or more kinds of repeating units derived from the polyol compound. That is, the polymerization of the synthesized [A2] polymer is preferably carried out by random copolymerization. [A2] The polymer has two linear repeating units, and the linearity of the main chain is further lowered. As a result, the solvent solubility to PGMEA or the like can be further improved.

<[B]solvent>

This film-forming composition contains a [B] solvent. [B] The solvent is not particularly limited as long as it can dissolve or disperse the [A] compound and any component contained as necessary.

The solvent (B) may, for example, be an alcohol solvent, a ketone solvent, a guanamine solvent, an ether solvent or an ester solvent. [B] The solvent is used singly or in combination of two or more kinds.

The alcohol solvent may, for example, be methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, t-butanol, n-pentanol or iso-pentyl Monool solvent such as alcohol, sec-pentanol or t-pentanol; ethylene glycol, 1,2-propanediol, 1,3-butanediol, 2,4-pentanediol, 2-methyl- A polyol solvent such as 2,4-pentanediol, 2,5-hexanediol or 2,4-heptanediol.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, and methyl group. An aliphatic ketone solvent such as -n-amyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone or trimethyl fluorenone; cyclopentanone, ring a cyclic ketone solvent such as ketone, cycloheptanone, cyclooctanone or methylcyclohexanone; 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, methyl n-pentyl Ketone and the like.

The above amide-based solvent may, for example, a cyclic amide-based solvent such as 1,3-dimethyl-2-imidazolidinone or N-methyl-2-pyrrolidone; formamide, N-methylformamide, N,N-di Chain of methylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide A guanamine solvent or the like.

The ether solvent may, for example, be a polyol partial ether solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether or ethylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate a glycol partial ether acetate solvent such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA) or propylene glycol monoethyl ether acetate; diethyl ether, two a di-aliphatic ether solvent such as propyl ether, dibutyl ether, butyl methyl ether, butyl ethyl ether or diisoamyl ether; an aliphatic-aromatic ether such as anisole or phenylethyl ether a solvent; tetrahydrofuran, tetrahydropyran, two A cyclic ether solvent such as an alkane.

Examples of the ester solvent include methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, and acetic acid. Iso-butyl ester, sec-butyl acetate, n-pentyl acetate, sec-amyl acetate, 3-methoxybutyl acetate, methyl amyl acetate, 2-ethylbutyl acetate Carboxylic acid, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-decyl acetate, methyl ethyl acetate, ethyl acetate, etc. An ester solvent; a lactone solvent such as γ-butyrolactone or γ-valerolactone; A carbonate-based solvent such as diethyl carbonate or propylene carbonate.

Among these, an ether solvent, a ketone solvent, and an ester solvent are preferred, and an ether solvent is more preferred. In terms of the ether solvent, the polyol partial ether acetate solvent and the dialiphatic ether solvent are preferred, the polyol partial ether acetate solvent is preferred, the propylene glycol monoalkyl ether acetate is preferred, and the PGMEA is particularly preferred. good. The ketone solvent is preferably a methyl n-amyl ketone or a cyclic ketone solvent, more preferably cyclohexanone or cyclopentanone, and more preferably cyclohexanone. The ester solvent is preferably a carboxylic acid ester solvent or a lactone solvent, more preferably a carboxylic acid ester solvent, and more preferably a lactated ethyl group.

The coating property of the film-forming composition on a substrate such as a wafer can be obtained by a polyol partial ether acetate solvent, wherein propylene glycol monoalkyl ether acetate, and particularly PGMEA is contained in the [B] solvent. Better and better. The solvent-soluble property of the [A] compound contained in the film-forming composition is high in PGMEA or the like, and the film-forming composition can be exhibited by containing a polyol partial ether acetate-based solvent in the solvent [B]. Excellent coating properties. [B] The content of the polyol partial ether acetate solvent in the solvent is preferably 20% by mass or more, more preferably 40% by mass or more.

When k1 and k2 are 1, when the Mw of the [A2] polymer is, for example, 2,000 or more, the solubility of the [A2] polymer to the [B] solvent is improved, and the coating property of the film-forming composition is improved. The solvent [B] is preferably a solvent containing a polyol partial ether acetate solvent and a solvent mixture of a ketone solvent and/or an ester solvent. In this case, the total content of the ketone solvent and the ester solvent in the solvent of [B] is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 70% by mass or more.

<[C]acid generator>

The [C] acid generator is a component which generates an acid by the action of heat or light and promotes crosslinking of the [A] compound. The film-forming composition accelerates the crosslinking reaction of the [A] compound by containing a [C] acid generator, and the hardness of the formed film can be further improved. The [C] acid generators may be used alone or in combination of two or more.

The [C] acid generator may, for example, be an onium salt compound or an N-sulfonyloxyphthalimide compound.

The onium salt compound may, for example, be a phosphonium salt, a tetrahydrothiophene salt or an iodonium salt.

The onium salt may, for example, be triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate or triphenylene.鋶2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylphosphonium trifluoromethanesulfonate, 4- Cyclohexylphenyldiphenylphosphonium nonabutane sulfonate, 4-cyclohexylphenyldiphenylphosphonium perfluoro-n-octane sulfonate, 4-cyclohexylphenyldiphenylphosphonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methylsulfonylphenyldiphenylphosphonium trifluoromethanesulfonate, 4 -Methanesulfonylphenyldiphenylphosphonium nonabutanesulfonate, 4-methylsulfonylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-methanesulfonate Phenylphenyldiphenylfluorene2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and the like.

The tetrahydrothiophene sulfonium salt may, for example, be 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate or 1-(4-n-butoxynaphthalene-1- Tetrahydrothiophene nonafluoro-n-butanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene Perfluoro-n-octanesulfonate, 1-(4-n-butoxynaphthalen-1-yl)tetrahydrothiophene 2-cyclo-2-[2.2.1]hept-2-yl-1,1 , 2,2-tetrafluoroethane sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-(6-n-butoxy Naphthalen-2-yl)tetrahydrothiophene nonafluorobutane sulfonate, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene fluorene perfluoro-n-octane sulfonic acid Salt, 1-(6-n-butoxynaphthalen-2-yl)tetrahydrothiophene 2-cyclobi[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonic acid Salt, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene trifluoromethanesulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene嗡9-fluoro-n-butane sulfonate, 1-(3,5-dimethyl-4-hydroxyphenyl)tetrahydrothiophene perfluoro-n-octane sulfonate, 1-(3,5 -Dimethyl-4-hydroxyphenyl)tetrahydrothiophene 2-cyclobi[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate and the like.

The iodonium salt may, for example, be diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate or diphenyliodonium perfluoro-n-octanesulfonate. , diphenyliodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis(4-t-butylphenyl)iodonium Fluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, bis(4-t-butylphenyl)iodonium perfluoro-n-octane Sulfonate, bis(4-t-butylphenyl)iodonium 2-bicyclo[2.2.1]hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, and the like.

The N-sulfonyloxy quinone imine compound may, for example, be N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(perfluoro-n-octanesulfonyl) Oxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2-bicyclo[2.2.1]hept-2-yl-1,1,2,2- Tetrafluoroethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine Wait.

Among these, the [C] acid generator is preferably a phosphonium salt compound, a iodonium salt is preferred, and a bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate is further good.

The content of the [C] acid generator is preferably 0 parts by mass to 20 parts by mass, more preferably 1 part by mass to 15 parts by mass, more preferably 3 parts by mass to 10 parts by mass, based on 100 parts by mass of the [A] compound. . The content of the [C] acid generator can more effectively promote the crosslinking reaction of the [A] compound by the above range.

<[D] Crosslinker>

The [D] crosslinking agent is a component which forms a cross-linking bond between the components of the [A] compound or the like in the film-forming composition by the action of heat or acid. The film-forming composition can increase the hardness of the formed film by containing a [D] crosslinking agent. The [D] crosslinking agent may be used singly or in combination of two or more kinds.

The above [D] crosslinking agent may, for example, be a polyfunctional (meth) acrylate compound, an epoxy compound, a hydroxymethyl substituted phenol compound, an alkoxyalkyl group-containing phenol compound, or an alkoxyalkylated group. A compound of the amine group, a random copolymer of a terpene and a hydroxymethyl decene represented by the following formula (6-P), a compound represented by the following formula (6-1) to (6-12), and the like .

Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri(meth) acrylate, ditrimethylolpropane tetra(meth) acrylate, and pentaerythritol tri(meth) acrylate. Pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Tetraol hexa(meth) acrylate, glycerol tri(meth) acrylate, cis (2-hydroxyethyl) isocyanurate tri(meth) acrylate, ethylene glycol di(meth) acrylate , 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl Alcohol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, bis(2-hydroxyethyl) Isocyanurate di(meth) acrylate or the like.

Examples of the epoxy compound include a novolac type epoxy resin, a bisphenol type epoxy resin, an alicyclic epoxy resin, and an aliphatic epoxy resin.

The above hydroxymethyl-substituted phenol compound may, for example, be 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene or 3,5-dihydroxymethyl-4-methyl. Oxytoluene [2,6-bis(hydroxymethyl)-p-cresol] and the like.

The phenolic compound containing an alkoxyalkyl group may, for example, be a methoxymethyl group-containing phenol compound or an ethoxymethyl group-containing phenol compound.

The above compound having an alkoxyalkylated amine group may, for example, be (poly)methylolated melamine, (poly)methylolated glycoluril, (poly)methylolated benzoguanamine, ( a compound having a plurality of active methylol groups in a molecule such as polymethylolated urea, and a compound in which at least one of hydrogen atoms of a hydroxyl group of a methylol group is substituted with an alkyl group such as a methyl group or a butyl group Wait. Further, the compound having an amino group alkylated with an alkoxy group may be a mixture of a plurality of substituted compounds or a part of a self-condensed oligomer component.

In the above formulae (6-6), (6-8), (6-11) and (6-12), Ac is an ethylidene group.

Further, each of the compounds represented by the above formulae (6-1) to (6-12) can be synthesized by referring to the following documents.

a compound represented by the formula (6-1): Guo, Qun-Sheng; Lu, Yong-Na; Liu, Bing; Xiao, Jian; Li, Jin-Shan Journal of Organometallic Chemistry, 2006, vol. 691, #6 p .1282-1287

a compound represented by the formula (6-2): Badar, Y. et al. Journal of the Chemical Society, 1965, p. 1412-1418

Compound represented by formula (6-3): Hsieh, Jen-Chieh; Cheng, Chien-Hong Chemical Communications (Cambridge, United Kingdom), 2008, #26 p. 2992-2994

A compound represented by the formula (6-4): JP-A-H05-238990

Compound represented by formula (6-5): Bacon, R.G.R.; Bankhead, R. Journal of the Chemical Society, 1963, p. 839-845

Compounds represented by formula (6-6), (6-8), (6-11), and (6-12): Macromolecules 2010, vol 43, p2832-2839

Compounds represented by formula (6-7), (6-9), and (6-10): Polymer Journal 2008, vol. 40, No. 7, p645-650, and Journal of Polymer Science: Part A, Polymer Chemistry, Vol 46, p4949-4958

Among these [D] crosslinking agents, a methoxymethyl group-containing phenol compound, a compound having an alkoxyalkylated amine group, and a random copolymer of decene and hydroxymethyl decene are used. Preferably, the compound having an alkoxyalkylated amine group is more preferred, and the 1,3,4,6-tetrakis(methoxymethyl)glycolide is more preferably.

The content of the [D] crosslinking agent is preferably from 0 to 100 parts by mass, more preferably from 0.5 part by mass to 50 parts by mass, more preferably from 1 part by mass to 30 parts by mass, based on 100 parts by mass of the [A] compound. It is particularly preferable to be less than 20 parts by mass. The content of the [D] crosslinking agent can more effectively produce the crosslinking reaction of the [A] compound by the above range.

<Other optional ingredients>

Examples of the other optional components include other resins, surfactants, and adhesion promoters.

[Other resins]

The film forming composition may contain other resins.

The other resin may, for example, be a naphthol novolak resin, a naphthol novolak resin containing a carbon-carbon triple bond, a terpene resin or a vinyl naphthalene resin.

The naphthol novolac resin may, for example, be a resin having a structural unit represented by the following formula.

A repeating unit represented by the following formula (7-1) is required The constituent unit further includes a repeating unit represented by the following formula (7-2), a repeating unit represented by the following formula (7-3), and a repeating unit represented by the following formula (7-4). A resin selected from at least one repeating unit of the group.

In the above formula (7-1), R ²¹ is a hydroxyl group or hydrogen, and g1 is an integer of 0 to 6. However, when g1=2~6, the plural R ²¹ may be the same or different. Q ¹ is a substitutable alkyl group having 1 to 20 carbon atoms or a substitutable aryl group having 6 to 14 carbon atoms, and f1 is an integer of 1 to 8. However, when f1=2~8, the complex Q ¹ may be the same or different. G1+f1 is an integer from 1 to 8.

In the above formula (7-2), R ²² is a substitutable alkyl group having 1 to 6 carbon atoms, a substitutable alkenyl group having 1 to 6 carbon atoms, a substitutable alkoxy group having 1 to 6 carbon atoms, and carbon. The number of 2 to 10 substituted alkoxycarbonyl groups, the carbon number 6 to 14 substitutable aryl group or the glycidyl ether group, and g2 is an integer of 0 to 6. However, when g2=2~6, the plural R ²² may be the same or different. Q ² is an optionally substituted alkyl group having 1 to 20 carbon atoms or a substitutable aryl group having 6 to 14 carbon atoms, and f 2 is an integer of 1 to 8. However, when f2=2~8, the complex Q ² may be the same or different. G2+f2 is an integer from 1 to 8.

In the above formula (7-3), Q ³ is an optionally substituted alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group having 6 to 14 carbon atoms, and f3 is an integer of 1 to 8. However, when f3=2~8, the complex Q ³ may be the same or different. h is an integer from 0 to 2, and f3+h is an integer from 1 to 8.

In the above formula (7-4), A is a single bond or a double bond, and Q ⁴ is a substitutable alkyl group having 1 to 20 carbon atoms or a substitutable aryl group having 6 to 14 carbon atoms, and f4 is 1 An integer of ~6.

In addition, the naphthol novolac resin may, for example, be a resin having a structural unit represented by the following formula (8).

In the above formula (8), R ²³ is a hydroxyl group, a substitutable alkyl group having 1 to 6 carbon atoms, a substitutable alkoxy group having 1 to 6 carbon atoms, and a substitutable alkoxycarbonyl group having 2 to 10 carbon atoms. a substitutable aryl group having 6 to 14 carbon atoms or a substitutable glycidyl ether group having 2 to 6 carbon atoms. G3 is an integer from 0 to 6. However, when g3 is 2 to 6, the plural R ²³ may be the same or different. Q ⁵ is a methyl group, a substituted alkyl group having 2 to 20 carbon atoms, a substituted aryl group having 6 to 14 carbon atoms, or an alkyl ether group. F5 is an integer from 1 to 8. When f5 is 2~8, the complex Q ⁵ may be the same or different. Also, g3+f5 is an integer from 1 to 8.

The naphthol novolak resin containing a carbon-carbon triple bond may, for example, be a resin having a structural unit represented by the following formula (9).

In the above formula (9), k is 0 or 1. R ²⁴ is a methyl group which may be substituted, an alkyl group which may be substituted with 2 to 20 carbon atoms, or an extended aryl group which may be substituted with a carbon number of 6 to 20. R ²⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms which may be substituted. R ²⁶ to R ³⁰ are a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or a substituted alkoxycarbonyl group; An aryl group having 6 to 14 carbon atoms which may be substituted or a glycidyl ether group having 2 to 6 carbon atoms which may be substituted. R ³¹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic alkyl ether group having 1 to 10 carbon atoms, or carbon. Number 6 to 10 aryl groups.

The terpene resin may, for example, be a resin having a structural unit represented by the following formula (10).

In the above formula (10), R ³² is a hydrogen atom or a monovalent organic group, and R ³³ and R ³⁴ are each independently a monovalent atom or a monovalent organic group.

The vinyl naphthalene resin may, for example, have a structural unit represented by the following formula (11-1) and formula (11-2), and may further have a structural unit derived from a terpene which may have a substituent, and A resin such as a structural unit of an acrylate.

In the above formula (11-1) and formula (11-2), R ³⁵ and R ³⁷ are each independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ³⁶ and R ³⁸ are each independently and are an alkyl group. Q1 and q2 are independent, and are integers from 0 to 7.

The other resin may have one or two or more structural units in combination.

The lower limit of the content of the other resin is preferably 1 part by mass, more preferably 5 parts by mass, more preferably 10 parts by mass, based on 100 parts by mass of the compound [A]. The upper limit of the above content is preferably 500 parts by mass, more preferably 200 parts by mass, and still more preferably 100 parts by mass. These other resins may be used alone or in combination of two or more.

[Surfactant]

The film-forming composition can improve the coatability by containing a surfactant, and as a result, the uniformity of the coated surface of the formed film is improved, and the occurrence of coating spots can be suppressed. The surfactants may be used alone or in combination of two or more.

The surfactant may, for example, be polyoxyethylene lauryl ether, polyoxyethylene stearate, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyethylene oxide-n-壬A nonionic surfactant such as phenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate. In addition, as a commercial item, KP341 (Shin-Etsu Chemical Industry Co., Ltd.), Polyflow No. 75, the same No. 95 (above, Kyoei Oil & Fat Chemical Industry Co., Ltd.), EFTOP EF101, the same EF204, the same EF303, and the same EF352 are mentioned. (above, Thochem Products.), MEGAFAC F171, F172, F173 (above, Dainippon Ink Chemical Industry Co., Ltd.) Fluorad FC430, FC431, FC135, FC93 (above, Sumitomo 3M), Asahiguard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 (above, Asahi Glass).

The content of the surfactant is preferably from 0 parts by mass to 10 parts by mass, more preferably from 0.001 part by mass to 5 parts by mass, even more preferably from 0.005 part by mass to 1 part by mass, per 100 parts by mass of the [A] compound. When the content of the surfactant is in the above range, the coating property of the film-forming composition can be further improved.

[Adhesive auxiliaries]

The adhesion aid is a component that enhances the adhesion to the underlying layer. When the film-forming composition contains an adhesion promoter, the adhesion between the formed film and the substrate as the underlayer can be improved. The adhesion aids may be used alone or in combination of two or more.

As the adhesion aid, for example, a conventional adhesion aid can be used.

The content of the adhesion aid is preferably from 0 part by mass to 10 parts by mass, more preferably from 0.01 part by mass to 10 parts by mass, even more preferably from 0.01 part by mass to 5 parts by mass per 100 parts by mass of the [A] compound.

<Modulation method of composition for film formation>

The film-forming composition can be prepared by mixing the [A] compound, the [B] solvent, and, if necessary, the [C] acid generator, the [D] crosslinking agent, and other optional components in a predetermined ratio. The solid content concentration of the composition is 0.1% by mass~ 50% by mass is more preferably 1% by mass to 30% by mass, more preferably 3% by mass to 20% by mass, and particularly preferably 5% by mass to 15% by mass.

As described above, the film-forming composition can form a film excellent in heat resistance and flatness, and is suitable for film formation. The film-forming composition can be used particularly for forming a resist underlayer film in a multilayer resist process or the like which is desired to have a high degree of such a property.

<Method of Manufacturing Substrate Forming a Pattern>

The method for producing a patterned substrate of the present invention includes a resist underlayer film forming step, a resist pattern forming step, and a substrate pattern forming step. The above-mentioned resist underlayer film is formed by the film forming composition.

According to the method for producing a substrate on which the pattern is formed, a resist underlayer film excellent in heat resistance and flatness can be easily formed, and a resist underlayer film having such excellent characteristics can be used to form a favorable pattern.

[Resistant underlayer film forming step]

In this step, a resist underlayer film is formed on the upper surface side of the substrate by the film-forming composition. The formation of the resist underlayer film is usually carried out by applying the film-forming composition onto the upper surface side of the substrate to form a coating film, and heating the coating film.

Examples of the substrate include a tantalum wafer, a wafer coated with aluminum, and the like. Moreover, the method of applying the film-forming composition to the substrate is not particularly limited, and can be carried out by a suitable method such as spin coating, cast coating, or roll coating.

The heating of the above coating film is usually carried out under the atmosphere. The heating temperature is usually from 150 ° C to 500 ° C, preferably from 200 ° C to 450 ° C. When the heating temperature is less than 150 ° C, the oxidative crosslinking does not sufficiently proceed, and there is no need to exhibit the necessary characteristics as a resist underlayer film. The heating time is usually from 30 seconds to 1,200 seconds, preferably from 60 seconds to 600 seconds.

The oxygen concentration at the time of heating is preferably 5% by volume or more. When the oxygen concentration at the time of heating is low, the oxidative crosslinking of the underlayer film of the resist is not sufficiently performed, and the intrinsic property as a resist underlayer film cannot be expressed.

The coating film may be preheated at a temperature of from 60 ° C to 250 ° C before being heated at a temperature of from 150 ° C to 500 ° C. Although the heating time of the preliminary heating is not particularly limited, it is preferably from 10 seconds to 300 seconds, more preferably from 30 seconds to 180 seconds. By performing the preliminary heating, the solvent is vaporized in advance to make the film dense, and the dehydrogenation reaction can be efficiently performed.

Further, in the method for forming a resist underlayer film, the coating film is usually heated to form a resist underlayer film, and when the resist underlayer film forming composition contains a photoacid generator, it may be combined by exposure and heating. The coating film is hardened to form a resist underlayer film. The radiation used for the exposure is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, molecular line, ion beam, etc. depending on the type of photoacid generator.

The film thickness of the formed underlayer film is preferably 0.05 μm to 5 μm, more preferably 0.1 μm to 3 μm.

After the resist underlayer film forming step, a step of forming an intermediate layer (intermediate film) on the resist underlayer film may be further required as necessary. The intermediate layer refers to the lower layer of the resist in order to form the resist pattern. The function of the film and/or the resist film, imparting such functions, and imparting the functions of the above functions. For example, when an antireflection film is formed as an intermediate layer, the antireflection function of the underlayer film of the resist can be further complemented.

The intermediate layer can be formed by an organic compound or an inorganic oxide. For the above-mentioned organic compounds, for example, "DUV-42", "DUV-44", "ARC-28", "ARC-29" (above, Brewer Science); "AR-3", "AR" -19" (above, Rohm and Haas company) and so on. Examples of the above-mentioned inorganic oxides include "NFC SOG01", "NFC SOG04", and "NFC SOG080" (above, JSR). Further, polysiloxane, titanium oxide, aluminum oxide, tungsten oxide or the like formed by a CVD method can be used.

The method for forming the intermediate layer is not particularly limited, and for example, a coating method, a CVD method, or the like can be used. Among these, a coating method is preferred. When the coating method is used, an intermediate layer can be continuously formed after forming a resist underlayer film. Further, the film thickness of the intermediate layer is not particularly limited, and is preferably 10 nm to 3,000 nm, more preferably 20 nm to 300 nm, depending on the function required for the intermediate layer.

[Resistance pattern formation step]

In this step, a resist pattern is formed over the lower film of the above resist. The method of performing this step may, for example, be a method of using a resist composition.

In the method of using the above-mentioned resist composition, specifically, after the resist film is applied to a predetermined film thickness, the resist composition is applied, and the solvent in the coating film is volatilized by prebaking to form a resist. membrane.

The above-mentioned resist composition may, for example, contain a photoacid generator a positive or negative chemically amplified resist composition, a positive resist composition composed of an alkali-soluble resin and a quinonediazide sensitizer, and a negative resist composed of an alkali-soluble resin and a crosslinking agent Composition and the like.

The total solid content concentration of the above-mentioned resist composition is usually from 1% by mass to 50% by mass. Moreover, in general, the above-mentioned resist composition is filtered by a filter having a pore diameter of about 0.2 μm, and then a resist film is formed. Further, in this step, a commercially available resist composition can also be used as it is.

The coating method of the resist composition is not particularly limited, and examples thereof include a spin coating method and the like. Further, the temperature of the prebaking is appropriately adjusted depending on the type of the resist composition to be used, and is usually 30 ° C to 200 ° C and preferably 50 ° C to 150 ° C.

Next, the resist film formed as described above is exposed by selective radiation irradiation. The radiation used for the exposure is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, molecular line, ion beam, etc. depending on the type of photo-acid generator used in the resist composition. Among them, far ultraviolet rays are preferred, KrF excimer laser light (248 nm), ArF excimer laser light (193 nm), F ₂ excimer laser light (wavelength 157 nm), Kr ₂ excimer laser light (wavelength 147 nm), ArKr Excimer laser light (wavelength 134 nm) and extreme ultraviolet light (wavelength 13 nm, etc.) are more preferable.

After the above exposure, in order to improve the resolution, pattern profile, developability, and the like, post-exposure baking can be performed. The temperature after the post-exposure baking is appropriately adjusted depending on the type of the resist composition to be used, etc., but it is usually 50 ° C to 200 ° C and preferably 70 ° C to 150 ° C.

Next, the exposed resist film is developed with a developing solution After forming a resist pattern. The above developer is appropriately selected depending on the type of the resist composition to be used. In the case of a developing solution, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, and di- N-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1, An alkaline aqueous solution of 8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-nonene or the like. In such an alkaline aqueous solution, a water-soluble organic solvent such as an alcohol such as methanol or ethanol, a surfactant, or the like may be added in an appropriate amount. In the development of the organic solvent, the developer may, for example, be an organic solvent or the like which is exemplified as the solvent of the above [B].

After development of the above developer, it is washed and dried to form a specified resist pattern.

In the method of forming the above-mentioned resist pattern forming step, in addition to the method of using the above resist composition, a method of a nanoimprint method, a method of using a self-organizing composition, or the like may be used.

[Substrate pattern forming step]

In this step, the resist pattern is used as a mask, and at least the resist underlayer film and the substrate are etched to form a pattern on the substrate. When the intermediate layer is not provided, the resist underlayer film and the substrate are sequentially etched, and when the intermediate layer is provided, the intermediate layer, the resist underlayer film, and the substrate are sequentially etched. Examples of the etching method include dry etching, wet etching, and the like. Among these, dry etching is preferred. For the dry etching, for example, a gas plasma such as an oxygen plasma can be used. on After the etching, a substrate having a specified pattern is obtained.

<film>

The film of the present invention is formed of the film forming composition. Since the film is formed of the above-described film-forming composition, it is possible to maintain a film having excellent heat resistance and flatness while maintaining general characteristics such as etching resistance. Since the film has the above characteristics, it can be suitably used as a resist underlayer film or the like.

<compound>

The compound of the present invention has a partial structure (I) and has an intermolecular bond forming group.

In the film-forming composition, the film can be used as a film-forming composition, and a film having excellent heat resistance and flatness can be formed while maintaining general characteristics such as etching resistance. This compound is the compound [A] contained in the above-mentioned film-forming composition, and is described above.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the invention is not limited to the examples. Each physical property value was measured by the following method.

[Mw and Mn]

The Mw and Mn of the polymer are used in the GPC column of Tosoh Corporation ("G2000HXL" 2 pieces and "G3000HXL" 1 piece) for the flow rate: 1.0 mL/min, elution solvent: tetrahydrofuran, column temperature: 40 ° C analysis conditions, measured by colloidal permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard.

[film thickness]

The film thickness was measured using a spectroscopic ellipsometer ("M2000D" by J.A. WOOLLAM).

<[A] Synthesis of Compounds> [[A1] Synthesis of Compounds] [Example 1] (Synthesis of Compound (A1-1))

In a separable flask equipped with a thermometer, 15 parts by mass of the following compound (M-1) and 17 parts by mass of the compound (M-2), 2 parts by mass of sodium hydride as a basic compound, and THF 50 as a solvent were added under a nitrogen atmosphere. The mass fraction was reacted at 0 ° C for 3 hours while stirring to obtain a reaction liquid. This reaction liquid was added to a mixed liquid of methanol and water, and reprecipitation was carried out, and the obtained precipitate was dried to obtain the following compound (M-4). Next, 17 parts by mass of the obtained compound (M-4) and the following compound (M-3), 17 parts by mass of potassium carbonate as a basic compound, and 80 parts by mass of dimethylacetamide as a solvent were mixed. The condensation reaction was carried out at 140 ° C for 4 hours while stirring to obtain a reaction liquid. After filtering the reaction mixture, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to give the following compound (M-5). Next, 33 parts by mass of the obtained compound (M-5) and bromopropyne, 19 parts by mass of potassium carbonate as a basic compound, and 80 parts by mass of dimethylacetamide as a solvent were mixed. The reaction was carried out at 60 ° C for 4 hours while stirring to obtain a reaction liquid. After the reaction mixture was filtered, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to obtain 60 parts by mass of the following compound (A1-1).

[Examples 2 to 4] (Synthesis of Compound (A1-2) to (A1-4))

In the first embodiment, the following compounds (A1-2) to (A1-4) were synthesized in the same reaction route as in Example 1 except that the starting materials were changed.

[Example 5] (Synthesis of Compound (A1-5))

In a separable flask equipped with a thermometer, 15 parts by mass of the following compound (M-6), 17 parts by mass of the compound (M-7), 2 parts by mass of sodium hydride as a basic compound, and THF 50 as a solvent were added under a nitrogen atmosphere. The mass fraction was reacted at 0 ° C for 3 hours while stirring to obtain a reaction liquid. A mixed liquid of methanol and water was added to the reaction liquid to carry out reprecipitation, and the obtained precipitate was dried to give the following compound (M-9). Mixing the obtained compound (M- 9), 17 parts by mass of the following compound (M-8), 17 parts by mass of potassium carbonate as a basic compound, and 80 parts by mass of dimethylacetamide as a solvent, and a condensation reaction at 140 ° C for 4 hours while stirring , the reaction solution was obtained. After the reaction solution was filtered, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to obtain 60 parts by mass of the following compound (A1-5).

[Examples 6 to 8] (Synthesis of Compound (A1-6) to (A1-8))

In the example 5, the following compounds (A1-6) to (A1-8) were synthesized in the same reaction route as in the examples except that the starting materials were changed.

[Example 9] (Synthesis of Compound (A1-9))

In a separable flask equipped with a thermometer, 15 parts by mass of the following compound (M-10) and 17 parts by mass of the compound (M-11), 2 parts by mass of sodium hydride as a basic compound, and THF 50 as a solvent were added under a nitrogen atmosphere. The mass fraction was reacted at 0 ° C for 3 hours while stirring to obtain a reaction liquid. In this A mixed liquid of methanol and water was added to the reaction liquid, followed by reprecipitation, and the obtained precipitate was dried to obtain the following compound (M-13). 17 parts by mass of the obtained compound (M-13), the following compound (M-12), 17 parts by mass of potassium carbonate as a basic compound, and 80 parts by mass of dimethylacetamide as a solvent were mixed while stirring The condensation reaction was carried out at 140 ° C for 4 hours to obtain a reaction liquid. After the reaction solution was filtered, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to obtain 60 parts by mass of the following compound (A1-9).

[Examples 10 to 13] (Synthesis of Compound (A1-10) to (A1-13))

In the same manner as in Example 9, except that the starting materials were changed, the following compounds (A1-10) to (A1-13) were synthesized.

[Example 14] (Synthesis of Compound (A1-14))

In a separable flask equipped with a thermometer, 10 parts by mass of the compound (A1-9) synthesized above, 37 parts by mass of a THF solution (concentration: 1 M) of methyl magnesium bromide, and 40 parts by mass of THF as a solvent were added under a nitrogen atmosphere. The reaction was carried out for 3 hours at 65 ° C with stirring to obtain a reaction liquid. To the reaction liquid, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to give the following compound (A1-14).

[Examples 15 to 20] (Synthesis of Compound (A1-15) to (A1-20))

In the fourteenth embodiment, the following compounds (A1-15) to (A1-20) were synthesized in the same reaction route as in Example 14 except that the starting materials were changed.

[Example 21] (Synthesis of Compound (A1-21))

In a separable flask equipped with a thermometer, 15 parts by mass of the following compound (M-14), 16 parts by mass of bromopropyne, 11 parts by mass of potassium carbonate as a basic compound, and dimethyl group B as a solvent were added under nitrogen atmosphere. 80 parts by mass of guanamine was reacted at 30 ° C for 4 hours while stirring to obtain a reaction liquid. A mixed liquid of methanol and water was added to the reaction liquid, followed by reprecipitation, and the obtained precipitate was dried to give the following compound (M-15). 19 parts by mass of the obtained compound (M-15), the following compound (M-16), 11 parts by mass of potassium carbonate as a basic compound, and 80 parts by mass of dimethylacetamide as a solvent, while stirring The condensation reaction was carried out at 120 ° C for 4 hours to obtain a reaction liquid. After filtering the reaction mixture, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to give the following compound (M-17). 10 parts by mass of the obtained compound (M-17), the following compound (M-18), 11 parts by mass of potassium carbonate as a basic compound, and 80 parts by mass of dimethylacetamide as a solvent were mixed while stirring The condensation reaction was carried out at 140 ° C for 4 hours to obtain a reaction liquid. After the reaction mixture was filtered, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to obtain 30 parts by mass of the following compound (A1-21).

[Examples 22 to 29] (Synthesis of Compound (A1-22) to (A1-29))

In Example 21, the following compounds (A1-22) to (A1-29) were synthesized in the same reaction route as in Example 21 except that the starting materials were changed.

[Example 30] (Synthesis of Compound (A1-30))

In the first embodiment, the following compound (A1-30) was synthesized in the same reaction route as in Example 1 except that the starting materials were changed.

[[A2] Synthesis of Polymers] [Example 31] (Synthesis of Polymer (A2-1))

In a separable flask equipped with a thermometer, 15 parts by mass of the following compound (M-19) and 8 parts by mass of the following compound (M-20), 4 parts by mass of potassium carbonate as a basic compound, and a solvent were added under a nitrogen atmosphere. 80 parts by mass of dimethylacetamide was subjected to a condensation reaction at 140 ° C for 4 hours while stirring to obtain a reaction liquid. After the reaction solution was filtered, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to obtain a polymer having a structural unit represented by the following formula (M-21). 35 parts by mass of the THF solution (concentration: 1 M) of the obtained polymer, methyl magnesium bromide, and 40 parts by mass of THF as a solvent were mixed, and the mixture was reacted at 65 ° C for 3 hours while stirring to obtain a reaction liquid. Methanol was added to the reaction liquid to carry out reprecipitation, and the obtained precipitate was dried to obtain a polymer (A2-1) having a structural unit represented by the following formula (A2-1). The Mw of the polymer (A2-1) was 4,000.

[Synthesis Example 1] (Synthesis of Polymer (a2-1))

In a separable flask equipped with a thermometer, 140 parts by mass of the following compound (M-22), 100 parts by mass of the following compound (M-23), 140 parts by mass of potassium carbonate as a basic compound, and a solvent were added under a nitrogen atmosphere. 500 parts by mass of dimethylacetamide was subjected to a condensation polymerization reaction at 140 ° C for 4 hours while stirring to obtain a reaction liquid. After the reaction solution was filtered, methanol was added to carry out reprecipitation, and the obtained precipitate was dried to obtain a polymer (a2-1) having a structural unit represented by the following formula (a-1). The Mw of the polymer (a2-1) was 4,000.

[Synthesis Example 2] (Synthesis of Polymer (a2-2))

For a separable flask equipped with a thermometer, 100 parts by mass of 2,7-dihydroxynaphthalene, 30 parts by mass of formaldehyde, and 1 mass of p-toluenesulfonic acid were added under nitrogen atmosphere. The mixture and 150 parts by mass of propylene glycol monomethyl ether as a solvent were subjected to a polymerization reaction at 80 ° C for 6 hours while stirring to obtain a reaction liquid. Next, the reaction liquid was diluted with 100 parts by mass of n-butyl acetate, and the obtained organic layer was washed with a large amount of a mixture of water and methanol (mass ratio 1:2), and the solvent was distilled off to obtain the following formula. (a-2) The structural unit polymer (a2-2) indicated. The Mw of the polymer (a2-2) was 1,800.

<Preparation of Composition for Film Formation>

The components other than the component [A] used for the preparation of the film-forming composition are as follows.

[[B]solvent]

B-1: propylene glycol methyl ether acetate

B-2: cyclohexanone

[[C]acid generator]

C-1: bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate (compound represented by the following formula (C-1))

[[D]crosslinker]

D-1: "NIKALACN-2702" of the company SANWA CHEMICAL CO., LTD. (a compound represented by the following formula (D-1))

D-2: 4,4'-(1-(4-(1-(4-hydroxy-3,5-bis(methoxymethyl)phenyl)-1-methylethyl)phenyl) Ethyl) bis(2,6-bis(methoxymethyl)phenol) (compound represented by the following formula (D-2))

[Example 32] (Preparation of film formation composition (J-1))

A solution was obtained by mixing 10 parts by mass of (A1-1) as the [A] compound and 100 parts by mass of (B-1) as the solvent of [B]. Then, the composition (J-1) for modulating the film formation was filtered by a membrane filter having a pore size of 0.1 μm.

[Examples 33 to 65 and Comparative Examples 1 and 2] (Preparation of Film Formation Compositions (J-2) to (J-34) and (CJ-1) and (CJ-2))

A film formation composition was prepared in the same manner as in Example 32 except that each component of the type and content shown in Table 1 below was used. Further, "-" in Table 1 indicates that the component is not used.

<evaluation>

Using the film-forming composition obtained above, the following items were as follows Method for evaluation. The evaluation results are shown in Table 2.

[Solubility to PGMEA]

The film formation composition obtained above was added to a PGMEA (propylene glycol monomethyl ether acetate) solvent to carry out a solubility test. The solubility of PGMEA was evaluated as "A" (good) in the absence of turbidity or precipitation in the solution, and "B" (bad) in the case of turbidity or precipitation in the solution.

[Optical characteristics (refractive index and attenuation coefficient)]

The film-forming composition obtained above was spin-coated on the surface of a tantalum wafer substrate having a diameter of 8 Å, and then heated at 350 ° C (however, only Example 57 was 400 ° C) for 2 minutes to form a resist having a film thickness of 250 nm. Lower film. Next, the refractive index and the attenuation coefficient at a wavelength of 193 nm of the formed underlayer film of the resist were measured using a spectroscopic ellipsometer ("M2000D" by J.A. WOOLLAM Co., Ltd.). The optical properties of the resist underlayer film can be evaluated as good when the refractive index is 1.3 or more and 1.6 or less and the attenuation coefficient is 0.2 or more and 0.8 or less.

[etching resistance]

The film-forming composition obtained above was spin-coated on a tantalum wafer having a diameter of 8 Å to form a resist underlayer film having a thickness of 300 nm. Next, the resist underlayer film was subjected to an etching treatment under the conditions of a pressure of 0.03 Torr, a high-frequency power: 3,000 W, Ar/CF ₄ = 40/100 sccm, and a substrate temperature of 20 ° C, and the film of the resist underlayer film after the etching treatment was measured. thick. The etching rate (nm/min) was calculated from the relationship between the film thickness reduction amount of the resist underlayer film and the treatment time in the above etching treatment, and the ratio to Comparative Example 2 was calculated. The smaller the value, the better the etching resistance.

[heat resistance]

The film-forming composition obtained above was spin-coated on a tantalum wafer having a diameter of 8 Å to form a resist underlayer film, and the film thickness of the resist underlayer film was measured using the above-described spectral ellipsometer (measured value) For X). Next, the resist underlayer film was heated at 350 ° C (however, only Example 57 was 400 ° C) for 120 seconds, and the film thickness of the resist underlayer film after heating was measured using the above-described spectral ellipsometer ( The measured value is Y). Next, the film thickness reduction rate (100 × (X - Y) / X) (%) of the resist underlayer film before and after heating was calculated, and the calculated value was heat resistance. The smaller the heat resistance value, the less the sublimate or membrane decomposition product produced when the resist underlayer film is heated, and the display is good (high heat resistance).

[flatness]

a trench having a width of 42 nm, a pitch of 84 nm, a depth of 180 nm (aspect ratio: 4.3), a width of 100 nm, a pitch of 150 nm, a depth of 180 nm (aspect ratio: 1.8), a width of 5 μm, and a depth of 180 nm ( In the SiO ₂ step-difference substrate (opening ratio: 0.036), the composition for film formation obtained above was applied to each of the SiO ₂ stepped substrates (ratio of the maximum value to the minimum value of the different aspect ratios: 119). Thereafter, the film was baked (baked) in an air atmosphere at 250 ° C for 60 seconds (however, only in Example 57 at 400 ° C for 120 seconds) to form a resist underlayer film having a film thickness of 200 nm. The shape of the underlayer film of the resist was observed by a scanning electron microscope ("S-4800" by Hitachi High-Technologies Co., Ltd.), and the maximum and minimum film thickness of the resist underlayer film on the trench or space were measured. The difference between the values (ΔFT). The flatness was evaluated as "A" (good) when the ΔFT was less than 20 nm, and "B" (bad) when it was 20 nm or more.

As is clear from Table 2, in the film-forming composition of the example, PGMEA can be used as the solvent, and the resist underlayer film formed satisfies the refractive index, The characteristics of the attenuation coefficient and the etching resistance are higher than that of the resist underlayer film formed of the film-forming composition of the comparative example, and have high heat resistance and high flatness.

[Industrial use]

The film-forming composition of the present invention contains a compound having a specific partial structure and an intermolecular bond-forming group, and is excellent in solubility in a solvent such as PGMEA, and satisfies general characteristics such as etching resistance and heat resistance. A film excellent in flatness. This film is excellent in heat resistance and flatness. According to the method for producing a substrate on which the pattern is formed, a resist underlayer film excellent in heat resistance and flatness can be easily formed, and a resist underlayer film having such excellent characteristics can be used to form a good pattern on the substrate. This compound can be suitably used as a component of the film formation composition. Therefore, these can be applied to the manufacture of semiconductor devices and the like which are expected to be further miniaturized in the future.

Claims (12)

A film-forming composition comprising a compound having a partial structure represented by the following formula (1) and having an intermolecular bond-forming group, and a solvent. (In the formula (1), X ¹ and X ² are each independently, and represent a ring structure of a substituted or unsubstituted ring member number 4 to 10 composed of a carbon atom of a spiro carbon atom and an aromatic ring, and each of R ¹ and R ² Independently, it is a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group. Each of a1 and a2 is independently an integer of 0 to 8. When each of R ¹ and R ² has a plurality of plural, the plural R ¹ may be the same or different. The complex R ² may be the same or different, n1 and n2 are independent, and are integers of 0~2, and k1 and k2 are independent, and are integers of 0-8, but k1+k2 is 1 or more, a1+k1 And a2+k2 is 8 or less, and * represents a bonding site of a portion other than the above partial structure). The composition for forming a film according to claim 1, wherein the intermolecular bond forming group is a carbon-carbon double bond-containing group, a carbon-carbon triple bond-containing group, a hydroxy chain hydrocarbon group, a fluorenyl group, or a carbonyl oxygen group. a hydrocarbyl group or a combination of these. The composition for forming a film according to claim 1 or claim 2, wherein the compound is represented by the following formula (2). (In the formula (2), Z ¹ is a partial structure represented by the above formula (1), k1 and k2 are synonymous with the above formula (1), and Ar ¹ and Ar ² are each independently a substituted or unsubstituted carbon number 6~ The aromatic hydrocarbon diyl group of 20, p1 and p2 are each independently an integer of 0 to 3, and Ar ^{3 is} a group of (j1+1) hydrogen atoms removed from the aromatic ring of the substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms. Ar ^{4 is} a group in which (j2+1) hydrogen atoms are removed from an aromatic ring of a substituted or unsubstituted aromatic hydrocarbon having 6 to 20 carbon atoms, and j1 and j2 are each independently an integer of 1 to 9, and Y ¹ and Y ² are each Independently, it is a monovalent intermolecular bond forming group having a carbon number of 1 to 20, and when Ar ¹ ~Ar ⁴ , Y ¹ , Y ² , p1, p2, j1 and j2 each have a plurality of plural, the plural Ar ¹ may be the same Or different, the plural Ar ² may be the same or different, the plural Ar ³ may be the same or different, Ar ⁴ may be the same or different, the plural Y ¹ may be the same or different, the plural Y ² The same or different, the plural p1 may be the same or different, the plural p2 may be the same or different, the plural j1 may be the same or different, and the plural j2 may be the same or different). The film formation composition according to claim 3, wherein the compound has a molecular weight of 300 or more and 3,000 or less. The composition for film formation according to claim 1 or 2, wherein the compound is a polymer having a repeating unit represented by the following formula (4). (In the formula (4), Z ² is a partial structure represented by the above formula (1), and k1 is synonymous with the above formula (1)). The film-forming composition according to claim 5, wherein the polymer further has a repeating unit represented by the following formula (5-1) or (5-2). (In the formula (5-1), Y ³ is a monovalent intermolecular bond forming group having a carbon number of 1 to 20, b is an integer of 1 to 8, and R ⁸ is a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group. , c is an integer from 0 to 8, but b+c is 8 or less, and when Y ³ and R ⁸ each have a plurality of plural, the plural Y ³ may be the same or different, and the plural R ⁸ may be the same or different. m is an integer of 0 to 2, and when m is 1 or 2, Y ³ and R ⁸ may be bonded to any ring. In the formula (5-2), Y ⁴ is a two-valent intermolecular bond having a carbon number of 1 to 20. a knot forming group, R ⁹ and R ¹⁰ are each independently a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group, and d and e are each independently an integer of 0 to 8, and when R ⁹ is plural, plural R ⁹ The same or different, when R ¹⁰ is plural, the plural R ¹⁰ may be the same or different, and m1 and m2 are independent, and are integers of 0 to 2). The film-forming composition according to claim 5, wherein the polymer has a weight average molecular weight of 600 or more and 100,000 or less. The film forming composition according to claim 1 or 2, wherein the solvent comprises a polyol partial ether acetate solvent, a ketone solvent, a carboxylic acid ester solvent, or a combination thereof. The film-forming composition according to claim 1 or 2, which is used for forming a resist underlayer film. A film comprising the film forming composition described in claim 1 or claim 2. A method for manufacturing a substrate on which a pattern is formed, comprising the steps of forming a resist underlayer film on an upper surface side of the substrate, forming a resist pattern on the resist underlayer film, and using the resist The pattern is a mask etching, a step of forming a pattern on the substrate, and the resist underlayer film is formed by the film forming composition described in claim 9. a compound having a partial structure represented by the following formula (1) and having an intermolecular bond forming group, (In the formula (1), X ¹ and X ² are each independently, and represent a ring structure of a substituted or unsubstituted ring member number 4 to 10 composed of a carbon atom of a spiro carbon atom and an aromatic ring, and each of R ¹ and R ² Independently, it is a halogen atom, a hydroxyl group, a nitro group or a monovalent organic group. Each of a1 and a2 is independently an integer of 0 to 8. When each of R ¹ and R ² has a plurality of plural, the plural R ¹ may be the same or different. The complex R ² may be the same or different, n1 and n2 are independent, and are integers of 0~2, and k1 and k2 are independent, and are integers of 0-8, but k1+k2 is 1 or more, a1+k1 And a2+k2 is 8 or less, and * represents a bonding site of a portion other than the above partial structure).