JP6264246B2 - Film-forming composition, film, method for producing substrate on which pattern is formed, and compound - Google Patents

Description

  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 semiconductor devices, a multilayer resist process is used to obtain a high degree of integration. In this process, a resist underlayer film is first formed by applying a resist underlayer film forming composition on a substrate, and a resist film is formed by applying the resist composition onto the resist underlayer film. Then, the resist film is exposed through a mask pattern or the like and developed with an appropriate developer to form a resist pattern. Then, the resist underlayer film is dry-etched using this resist pattern as a mask, and the substrate is further dry-etched using the obtained resist underlayer film pattern as a mask, whereby a desired pattern can be formed on the substrate. The resist underlayer film used in such a multilayer resist process is required to have general characteristics such as optical characteristics such as refractive index and extinction coefficient and etching resistance.

  In the multilayer resist process, recently, a method of forming a hard mask as an intermediate layer on a resist underlayer film has been studied. In this method, specifically, an inorganic hard mask is formed on the resist underlayer film by a CVD method. In particular, in the case of a nitride-based inorganic hard mask, the temperature is at least 300 ° C., usually 400 ° C. or higher. The resist underlayer film requires high heat resistance. If the heat resistance is insufficient, the components of the resist underlayer film sublimate, and this sublimated component reattaches to the substrate, resulting in a decrease in semiconductor device manufacturing yield.

  Recently, there is an increasing number of cases where a pattern is formed on a substrate having a plurality of types of trenches, particularly trenches having different aspect ratios, and the resist underlayer film sufficiently embeds these trenches and is high. It is required to have flatness.

  In response to these requirements, various studies have been conducted on the structure of polymers and the like contained in the composition and the functional groups contained therein (see Japanese Patent Application Laid-Open No. 2004-177668). However, the above conventional composition cannot sufficiently satisfy the above requirements.

JP 2004-177668 A

  The present invention has been made based on the above circumstances, and its purpose is to provide a film-forming composition capable of forming a film having excellent heat resistance and flatness while maintaining general characteristics such as etching resistance. There is to do.

（式（１）中、Ｒ^１〜Ｒ^４は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、ニトロ基又は炭素数１〜２０の１価の有機基である。ａ１及びａ２は、それぞれ独立して、０〜９の整数である。ｂ１及びｂ２は、それぞれ独立して、０〜４の整数である。Ｒ^１〜Ｒ^４がそれぞれ複数の場合、複数のＲ^１は同一でも異なっていてもよく、複数のＲ^２は同一でも異なっていてもよく、複数のＲ^３は同一でも異なっていてもよく、複数のＲ^４は同一でも異なっていてもよい。ｎ１及びｎ２は、それぞれ独立して、０〜２の整数である。ｋ１及びｋ２は、それぞれ独立して、０〜９の整数である。但し、ｋ１＋ｋ２は、１以上である。ａ１＋ｋ１及びａ２＋ｋ２は９以下である。＊は、上記部分構造以外の部分との結合部位を示す。） The invention made in order to solve the above problems is a compound (hereinafter referred to as “[A] compound”) having one partial structure represented by the following formula (1) (hereinafter also referred to as “partial structure (I)”). And a film-forming composition containing a solvent (hereinafter also referred to as “[B] solvent”).

(In Formula (1), R < ¹ > -R < ⁴ > is respectively independently a halogen atom, a hydroxy group, a nitro group, or a C1-C20 monovalent organic group. A1 and a2 are respectively independent. And b1 and b2 are each independently an integer of 0 to ^{4. When} there are a plurality of R ^{1 to} R ⁴ , a plurality of R ¹ may be the same or different. In addition, a plurality of R ² may be the same or different, a plurality of R ³ may be the same or different, and a plurality of R ⁴ may be the same or different. K1 and k2 are each independently an integer of 0 to 9. However, k1 + k2 is 1 or more, and a1 + k1 and a2 + k2 are 9 or less. (A binding site with a portion other than the partial structure is shown.)

  Another invention made to solve the above problems is a film formed from the film-forming composition.

  Still another invention made in order to solve the above problems is a process of forming a resist underlayer film on the upper surface side of the substrate (hereinafter also referred to as “resist underlayer film forming process”), and a resist pattern above the resist underlayer film. 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 pattern forming step”), It is a manufacturing method of the board | substrate with which the pattern which forms a resist underlayer film with the said film forming composition was formed.

  Yet another invention made to solve the above problems is a compound having one partial structure represented by the above formula (1).

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 that does not include a cyclic structure but includes only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. The term “alicyclic hydrocarbon group” refers to a hydrocarbon group that includes only an alicyclic structure as a ring structure and does not include an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group. Includes both hydrocarbon groups. However, it is not necessary to be composed only of the alicyclic structure, and a part thereof may include a chain structure. “Aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic structure.
The “organic group” refers to a group containing at least one carbon atom.

  The film forming composition of the present invention can form a film excellent in heat resistance and flatness while maintaining general characteristics such as etching resistance. The 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 this excellent characteristic is used for a substrate. A pattern can be formed. The compound can be suitably used as a component of the film-forming composition. Therefore, these can be suitably used for manufacturing semiconductor devices and the like that are expected to be further miniaturized in the future.

<Film forming composition>
The film-forming composition contains a [A] compound and a [B] solvent. The film-forming composition may contain a [C] acid generator and a [D] cross-linking agent as suitable components, and may contain other optional components as long as the effects of the present invention are not impaired. . Hereinafter, each component will be described.

<[A] Compound>
[A] The compound is a compound having one partial structure (I). Since the compound [A] is a compound having one partial structure (I), it is different from a polymer having a repeating unit containing the partial structure (I). By including the [A] compound, the film-forming composition can form a film having excellent heat resistance and flatness while maintaining general characteristics such as etching resistance. The reason why the film-forming composition has the above-described configuration provides the above-mentioned effect is not necessarily clear, but can be inferred as follows, for example. That is, the [A] compound has the partial structure (I). The partial structure (I) has a specific structure in which two aromatic rings are bonded to the 9th-position carbon atom of the fluorene skeleton as in the above formula (1). The film formed from the film-forming composition is considered to exhibit high heat resistance due to this specific structure. In addition, since the compound [A] has only one partial structure (I), the molecular size is moderately small, and as a result, the voids can be sufficiently filled, so that a film having excellent flatness can be formed. it is conceivable that.

[Partial structure (I)]
The partial structure (I) is represented by the following formula (1).

In the above formula (1), R ^{1 to} R ⁴ are each independently a halogen atom, a hydroxy group, a nitro group, or a monovalent organic group having 1 to 20 carbon atoms. a1 and a2 are each independently an integer of 0 to 9. b1 and b2 are each independently an integer of 0 to 4. When there are a plurality of R ^{1 to} R ⁴ , the plurality of R ¹ may be the same or different, the plurality of R ² may be the same or different, and the plurality of R ³ may be the same or different. A plurality of R ⁴ may be the same or different. n1 and n2 are each independently an integer of 0-2. k1 and k2 are each independently an integer of 0 to 9. However, k1 + k2 is 1 or more. a1 + k1 and a2 + k2 are 9 or less. * Indicates a binding site with a portion other than the partial structure.

The halogen atom represented by R ¹ to R ^4, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ^{1 to} R ⁴ include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a carbon-carbon bond or a bond of the hydrocarbon group. A group (α) containing a divalent heteroatom-containing group at the terminal on the hand side, a group obtained by substituting a part or all of the hydrogen atoms of the hydrocarbon group and group (α) with a monovalent heteroatom-containing group, etc. Is mentioned.

  Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a monovalent chain hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and carbon. Examples thereof include monovalent aromatic hydrocarbon groups of several 6 to 20.

Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms include:
Alkyl groups such as methyl, ethyl, propyl and butyl groups;
Alkenyl groups such as ethenyl group, propenyl group, butenyl group, pentenyl group;
Examples thereof include alkynyl groups such as ethynyl group, propynyl group, butynyl group, and pentynyl group.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include:
A cycloalkyl group such as a cyclopentyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, a cyclodecyl group, a norbornyl group, an adamantyl group;
And cycloalkenyl groups such as cyclopentenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, norbornenyl group, and the like.

Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include:
Aryl groups such as phenyl, tolyl, xylyl, naphthyl and anthryl;
Examples thereof include aralkyl groups such as benzyl group, phenethyl group, and naphthylmethyl group.

  Examples of the hetero atom contained in the monovalent and divalent heteroatom-containing group include an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a silicon atom. Among these, an oxygen atom, a nitrogen atom, and a sulfur atom are preferable, and an oxygen atom and a nitrogen atom are more preferable.

  Examples of the divalent heteroatom-containing group include —CO—, —CS—, —O—, —NR′—, —S—, and the like. R ′ is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

Examples of the monovalent heteroatom-containing group include a halogen atom, a hydroxy group, a fanyl group, a carboxy group, a cyano group, and a nitro group.
Moreover, as a substituent of the said hydrocarbon group and group ((alpha)), the oxygen atom which substitutes two hydrogen atoms couple | bonded with the same carbon atom of the said hydrocarbon group and group ((alpha)) is also contained.

R ^{1 to} R ⁴ are preferably a halogen atom or a monovalent organic group, more preferably a fluorine atom or a monovalent chain hydrocarbon group, and further preferably a fluorine atom or an alkyl group.

As said a1 and a2, the integer of 0-2 is preferable from a heat resistant viewpoint of a film | membrane, 0 or 1 is more preferable, and 0 is further more preferable.
As said b1 and b2, the integer of 0-2 is preferable from a heat resistant viewpoint of a film | membrane, 0 or 1 is more preferable, and 0 is further more preferable.

  As said n1 and n2, 0 or 1 is preferable and 1 is more preferable from a viewpoint which makes the heat resistance and flatness of a film | membrane compatible on a higher level.

  As said k1 and k2, the integer of 0-2 is preferable from a viewpoint of improving the flatness of a film | membrane, and the synthetic | combination ease of a [A] compound, 1 or 2 is more preferable, and 1 is further more preferable.

  [A] The compound preferably has an intermolecular bond-forming group. The “intermolecular bond-forming group” refers to a group that can form a covalent bond between molecules by, for example, an addition reaction, a condensation reaction or the like. When the compound [A] has an intermolecular bond-forming group, the strength of the film can be increased by the bond between the compounds [A]. The compound [A] may have the intermolecular bond-forming group in the partial structure (I) or in a part other than the partial structure (I). From the viewpoint of enhancing the properties, it is preferable to have it in a portion other than the partial structure (I).

  Examples of the intermolecular bond-forming group include a carbon-carbon double bond-containing group, a carbon-carbon triple bond-containing group, a hydroxy chain hydrocarbon group, an acyl group, an acyloxy group, a carbonyloxy hydrocarbon group, an epoxy group, An alkoxymethyl group, a dialkylaminomethyl group, a dimethylolaminomethyl group, etc. are mentioned. Among these, a carbon-carbon double bond-containing group, a carbon-carbon triple bond-containing group, and an acyl group are preferable. As the intermolecular bond forming group, a carbon-carbon triple bond-containing group and a carbon-carbon double bond-containing group are more preferable. At this time, an intermolecular bond can be formed by an addition reaction between carbon-carbon multiple bonds, and it can be cured without requiring elimination of the group, so that a film can be formed while suppressing film shrinkage. As a result, a film with more excellent flatness can be formed.

  Examples of the carbon-carbon double bond-containing group include a (meth) acryloyl group, a substituted or unsubstituted vinylphenyl group, and a group represented by the following formula (3-1) (hereinafter referred to as “group (3-1 ) ")) And the like. Examples of the carbon-carbon triple bond-containing group include a substituted or unsubstituted ethynyl group, a substituted or unsubstituted propargyl group, and a group represented by the following formula (3-2) (hereinafter referred to as “group (3 -2) ").

In said formula (3-1), R < ⁵ >, R < ⁶ > and R < ⁷ > are respectively independently a hydrogen atom or a C1-C20 monovalent hydrocarbon group.
In said formula (3-2), R < ⁸ > and R < ⁹ > are respectively independently a hydrogen atom or a C1-C20 monovalent hydrocarbon group. q is 1 or 2. When q is 2, the plurality of R ⁸ may be the same or different.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ^{5 to} R ⁸ include those exemplified as the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{1 to} R ^4. And the like groups.

From the viewpoint of improving the curability of the film-forming composition, R ⁵ is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. For the same reason, R ⁶ and R ⁷ are preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.
As said R < ⁸ > and R < ⁹ >, a hydrogen atom and an alkyl group are preferable from a viewpoint of the sclerosis | hardenability improvement of the said film forming composition, and a hydrogen atom is more preferable.
The q is preferably 2 from the viewpoint of improving the curability of the film-forming composition.

  Examples of the hydroxy chain hydrocarbon group include monovalent groups such as hydroxymethyl group, 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxy-2-propyl group, hydroxymethanediyl group, 1- And divalent groups such as a hydroxy-1,1-ethanediyl group and a 1-hydroxy-1,1-propanediyl group. Among these, 1-hydroxyethyl group, 2-hydroxy-2-propyl group, hydroxymethanediyl group, and 1-hydroxy-1,1-ethanediyl group are preferable.

  Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group and the like. Among these, a formyl group and an acetyl group are preferable.

  Examples of the acyloxy group include formyloxy group, acetyloxy group, propionyloxy group, butyryloxy group, and the like. Of these, a formyloxy group and an acetyloxy group are preferable.

  Examples of the carbonyloxy hydrocarbon group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a phenoxycarbonyl group, and a naphthoxycarbonyl group. Of these, a methoxycarbonyl group is preferred.

  [A] The number of intermolecular bond-forming groups possessed by the 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.

  [A] It is also preferred that the compound does not substantially contain an intermolecular bond-forming group. Since the compound [A] does not substantially contain an intermolecular bond-forming group, film shrinkage during film formation can be suppressed, and as a result, a film with better flatness can be formed.

  The compound [A] only needs to be a compound having one partial structure (I), and the structure of the part other than the partial structure (I) is not particularly limited. Examples of the [A] compound include the following formula (2): The compound etc. which are represented by these are mentioned. Since the compound represented by the following formula (2) has an aromatic ether bond, the heat resistance of the film formed from the film-forming composition can be further increased.

In the above formula (2), Z 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 arenediyl group having 6 to 20 carbon atoms. Ar ³ and Ar ⁴ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. p1 and p2 are each independently an integer of 0 to 3. When Ar ^{1 to} Ar ⁴ , p1 and p2 are plural, plural Ar ¹ may be the same or different, plural Ar ² may be the same or different, and plural Ar ³ are the same or different. The plurality of Ar ⁴ may be the same or different, the plurality of p1 may be the same or different, and the plurality of p2 may be the same or different.

Examples of the C6-C20 arenediyl group represented by Ar ¹ and Ar ² include a benzenediyl group, a toluenediyl group, a xylenediyl group, a naphthalenediyl group, and an anthracenediyl group. Among these, from the viewpoint of further improving the flatness of the film, a benzenediyl group and a naphthalenediyl group are preferable, and a benzenediyl group is more preferable.

Examples of the substituent for the arenediyl group of Ar ¹ and Ar ² include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, a hydroxy group, an amino group, a nitro group, and a monovalent group having 1 to 20 carbon atoms. The organic group of these is mentioned. Among these, a monovalent organic group having 1 to 20 carbon atoms is preferable, and a cyano group is more preferable from the viewpoint of enhancing the heat resistance of the film and the ease of synthesis of the [A] compound.

  As said p1 and p2, the integer of 0-2 is preferable from a viewpoint of making the heat resistance and flatness of a film | membrane compatible on a higher level, 1 or 2 is preferable and 1 is more preferable.

Examples of the aryl group having 6 to 20 carbon atoms represented by Ar ³ and Ar ⁴ include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group.

Examples of the substituent for the aryl group of Ar ³ and Ar ⁴ include a halogen atom, a hydroxy group, a nitro group, a monovalent organic group having 1 to 20 carbon atoms, and a monovalent intermolecular bond having 1 to 20 carbon atoms. And forming groups.
Among these, an aralkyl group having 7 to 20 carbon atoms and a monovalent intermolecular bond-forming group having 1 to 20 carbon atoms are preferable, an aralkyl group having 7 to 12 carbon atoms, the above group (3-1), the above group ( 3-2) is more preferable, and a phenyl-2-propyl group and a di (propargyl) amino group are more preferable.

  [A] Examples of the compound include compounds represented by the following formulas (i-1) to (i-23) (hereinafter also referred to as “compounds (i-1) to (i-23)”). It is done.

  Among these, the compound (i-1), the compound (i-6), and the compounds (i-11) to (i-23) are preferable.

  [A] As a minimum of the molecular weight of a compound, 300 is preferred, 400 is more preferred, 500 is still more preferred, and 600 is especially preferred. The upper limit of the molecular weight is preferably 3,000, more preferably 2,500, still more preferably 2,000, and particularly preferably 1,500. By setting the molecular weight of the compound [A] between the lower limit and the upper limit, the flatness of the film-forming composition can be further improved.

  The content of the compound [A] is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 85% by mass or more from the viewpoint of further improving the heat resistance of the film.

<[A] Compound Synthesis Method>
The [A] compound includes, for example, a polyol component (A) containing a polyol compound represented by the following formula (4) (hereinafter also referred to as “polyol (4)”), and a monohalo component containing an aromatic monohalide ( B) can be synthesized by reacting in an organic solvent in the presence of an alkali metal or an alkali metal compound.

In the formula ^(4), R 1 ^{to R} 4, a1 and a2, b1 and b2, n1 and n2 and k1 and k2 are the same as defined for the formula (1).

  In addition to the above reaction method, the polyol component (A) and an alkali metal or an alkali metal compound are reacted in an organic solvent to obtain an alkali metal salt of the polyol component (A), and then the obtained metal salt and monohalo component (B) may be reacted. The monohalo component (B) can be obtained, for example, by reacting an aromatic dihalo compound with an aromatic monool compound in the presence of a basic compound. As said aromatic dihalo compound, the compound etc. which are represented by following formula (5) are mentioned, for example.

In the above formula ^{(5), R 10} is a monovalent organic group of the nitro group or having 1 to 20 carbon atoms. c is an integer of 0-8. If R ¹⁰ is plural, the plurality of R ¹⁰ may be the same or different. m is an integer of 0-2. Y is each independently a halogen atom.

  Examples of the aromatic monool compound include unsubstituted or substituted phenol and unsubstituted or substituted naphthol. Examples of the substituents of phenol and naphthol include phenyl group, hydroxy group, amino group, phenylamino group, monovalent aralkyl group having 7 to 20 carbon atoms, and monovalent molecule having 1 to 20 carbon atoms. Examples include inter-bond forming groups.

  Examples of the alkali metal include lithium, sodium, and potassium.

Examples of the alkali metal compound include:
Alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate;
Alkali metal hydrogen carbonates such as lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate;
Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide;
Alkali metal hydrides such as lithium hydride, sodium hydride, potassium hydride and the like can be mentioned.
Of these, alkali metal carbonates are preferred, and potassium carbonate is more preferred. These alkali metals and alkali metal compounds can be used singly or in combination of two or more.

When an electron withdrawing group is bonded to the aromatic ring of the aromatic dihalide of the dihalo component (B) (for example, R ¹⁰ in the above formula (5) is an electron withdrawing group), the component (A ) And the component (B) are preferable. Examples of the electron withdrawing group include a cyano group and a nitro group.

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

  Examples of the organic solvent used in the reaction include dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, γ-butyrolactone, sulfolane, dimethyl sulfoxide, diethyl sulfoxide, dimethyl Examples include sulfone, diethyl sulfone, diisopropyl sulfone, diphenyl sulfone, diphenyl ether, benzophenone, dialkoxybenzene (1 to 4 carbon atoms of alkoxy group), trialkoxybenzene (1 to 4 carbon atoms of alkoxy group), and the like. Among these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, dimethylacetamide, sulfolane, diphenylsulfone, and dimethylsulfoxide are preferable. The said organic solvent can be used individually or in combination of 2 or more types.

  In the reaction, a solvent azeotropic with water, such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole, and phenetole can also be used. These can be used alone or in combination of two or more.

  As reaction temperature, 60 to 250 degreeC is preferable and 80 to 200 degreeC is more preferable. The reaction time is preferably 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

  The synthesized compound can be recovered and purified from the reaction solution by a reprecipitation method or the like. Examples of the solvent used for the reprecipitation include alcohol solvents, and among these, methanol is preferable.

<[B] Solvent>
The 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 optional components contained as necessary.

  [B] Examples of the solvent include alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, and the like. [B] A solvent can be used individually by 1 type or in combination of 2 or more types.

As the alcohol solvent, for example,
Mono, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, t-butanol, n-pentanol, iso-pentanol, sec-pentanol, t-pentanol Alcohol solvents;
Ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4-heptanediol, etc. Examples thereof include polyhydric alcohol solvents.

Examples of the ketone solvent include:
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso- Aliphatic ketone solvents such as butyl ketone and trimethylnonanone;
Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone;
2,4-pentanedione, acetonyl acetone, diacetone alcohol, acetophenone, methyl n-amyl ketone and the like can be mentioned.

As the amide solvent, for example,
Cyclic amide solvents such as 1,3-dimethyl-2-imidazolidinone and N-methyl-2-pyrrolidone;
And chain amide solvents such as formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropionamide and the like. It is done.

As the ether solvent, for example,
Polyhydric alcohol partial ether solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether;
Polyhydric alcohol partial ether acetate solvents such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate;
Dialiphatic ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, butyl methyl ether, butyl ethyl ether, diisoamyl ether;
Aliphatic-aromatic ether solvents such as anisole and phenylethyl ether;
Examples include cyclic ether solvents such as tetrahydrofuran, tetrahydropyran, and dioxane.

As the ester solvent, for example,
Methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-propyl acetate, iso-propyl acetate, n-butyl acetate, iso-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-acetate Carboxylic acid ester solvents such as methoxybutyl, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate and ethyl acetoacetate;
Lactone solvents such as γ-butyrolactone and γ-valerolactone;
Examples thereof include carbonate solvents such as diethyl carbonate and propylene carbonate.

  Among these, an ether solvent, a ketone solvent, and an ester solvent are preferable, an ether solvent and a ketone solvent are more preferable, and an ether solvent is more preferable. As the ether solvent, polyhydric alcohol partial ether acetate solvents and dialiphatic ether solvents are preferable, polyhydric alcohol partial ether acetate solvents are more preferable, propylene glycol monoalkyl ether acetates are more preferable, and PGMEA is particularly preferable. . The ketone solvent is preferably an aliphatic ketone solvent or a cyclic ketone solvent, more preferably methyl n-pentyl ketone, cyclohexanone, or cyclopentanone, and even more preferably cyclohexanone. As the ester solvent, a carboxylic acid ester solvent and a lactone solvent are preferable, a carboxylic acid ester solvent is more preferable, and ethyl lactate is more preferable.

<[C] acid generator>
[C] The acid generator is a component that generates an acid by the action of heat or light and promotes crosslinking of the [A] compound. When the film-forming composition contains a [C] acid generator, the crosslinking reaction of the [A] compound is promoted, and the hardness of the formed film can be further increased. [C] An acid generator can be used individually by 1 type or in combination of 2 or more types.

  [C] Examples of the acid generator include onium salt compounds and N-sulfonyloxyimide compounds.

  Examples of the onium salt compounds include sulfonium salts, tetrahydrothiophenium salts, iodonium salts, and the like.

  Examples of the sulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept. 2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro N-octane sulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept 2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium Examples include perfluoro-n-octane sulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonate, and the like.

  Examples of the tetrahydrothiophenium salt include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium. Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoro L-methanesulfonate, 1- (6-n-butoxynaphthalene- -Yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (6-n-butoxynaphthalene) -2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxy Phenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) Tetrahydrothiophenium perfluoro-n-octane Sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, and the like. Can be mentioned.

  Examples of the iodonium salt include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl. -1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4- t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-teto Fluoro ethanesulfonate.

  Examples of the N-sulfonyloxyimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyl). Oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide and the like.

  Among these, as the [C] acid generator, an onium salt compound is preferable, an iodonium salt is more preferable, and bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate is more preferable.

  [C] The content of the acid generator is preferably 0 part by mass to 20 parts by mass, more preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass of the compound [A], and 3 parts by mass to 10 parts by mass. Part is more preferred. [C] By making content of an acid generator into the said range, the crosslinking reaction of a [A] compound can be accelerated | stimulated more effectively.

<[D] Crosslinking agent>
[D] The cross-linking agent is a component that forms a cross-linking bond between components such as the [A] compound in the film-forming composition by the action of heat or acid. In the film-forming composition, the [A] compound may have an intermolecular bond-forming group, but the film hardness can be further increased by further containing a [D] crosslinking agent. [D] A crosslinking agent can be used individually by 1 type or in combination of 2 or more types.

  Examples of the [D] crosslinking agent include polyfunctional (meth) acrylate compounds, epoxy compounds, hydroxymethyl group-substituted phenol compounds, alkoxyalkyl group-containing phenol compounds, compounds having an alkoxyalkylated amino group, and the following formula ( Examples thereof include random copolymers of acenaphthylene and hydroxymethylacenaphthylene represented by 6-P), compounds represented by the following formulas (6-1) to (6-12), and the like.

  Examples of the polyfunctional (meth) acrylate compound include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol. Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butane Diol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (me ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate.

  Examples of the epoxy compound include novolac type epoxy resins, bisphenol type epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.

  Examples of the hydroxymethyl group-substituted phenol compound include 2-hydroxymethyl-4,6-dimethylphenol, 1,3,5-trihydroxymethylbenzene, 3,5-dihydroxymethyl-4-methoxytoluene [2,6. -Bis (hydroxymethyl) -p-cresol], 4,4 '-(1- (4- (1- (4-hydroxy-3,5-bis (methoxymethyl) phenyl) -1-methylethyl) phenyl) Ethylidene) bis (2,6-bis (methoxymethyl) phenol) and the like.

  Examples of the alkoxyalkyl group-containing phenol compound include methoxymethyl group-containing phenol compounds and ethoxymethyl group-containing phenol compounds.

  Examples of the compound having an alkoxyalkylated amino group include, for example, (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, (poly) methylolated urea in one molecule. A nitrogen-containing compound having a plurality of active methylol groups, in which at least one of the hydrogen atoms of the hydroxyl group of the methylol group is substituted with an alkyl group such as a methyl group or a butyl group. The compound having an alkoxyalkylated amino group may be a mixture in which a plurality of substituted compounds are mixed, or may include an oligomer component that is partially self-condensed.

  In the above formulas (6-6), (6-8), (6-11) and (6-12), Ac represents an acetyl group.

The compounds represented by the above formulas (6-1) to (6-12) can be synthesized with reference to the following documents, respectively.
Compound represented by formula (6-1):
Guo, Qun-Shen; Lu, Yong-Na; Liu, Bing; Xiao, Jian; Li, Jin-Shan Journal of Organic Chemistry, 2006, vol. 691, # 6 p. 1282-1287
Compound represented by 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
Compound represented by formula (6-4):
JP-A-5-238990 A compound represented by the formula (6-5):
Bacon, R.A. G. R. Bankhead, R .; Journal of the Chemical Society, 1963, p. 839-845
Compounds represented by formulas (6-6), (6-8), (6-11) and (6-12):
Macromolecules 2010, vol43, p2832-2839
Compounds represented by formulas (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, p4949-4968.

  Among these [D] crosslinking agents, a methoxymethyl group-containing phenol compound, a compound having an alkoxyalkylated amino group, and a random copolymer of acenaphthylene and hydroxymethylacenaphthylene are preferred, and a methoxymethyl group-containing phenol More preferred are compounds having alkoxyalkylated amino groups, 4,4 ′-(1- (4- (1- (4-hydroxy-3,5-bis (methoxymethyl) phenyl) -1-methyl More preferred are ethyl) phenyl) ethylidene) bis (2,6-bis (methoxymethyl) phenol), 1,3,4,6-tetra (methoxymethyl) glycoluril.

  [D] The content of the crosslinking agent is preferably 0 to 100 parts by weight, more preferably 0.5 to 50 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the [A] compound. Is more preferable, and 3 parts by mass to 20 parts by mass is particularly preferable. [D] By setting the content of the crosslinking agent in the above range, the hardness of the film can be further increased.

<Other optional components>
Examples of the other optional components include surfactants and adhesion assistants.

[Surfactant]
The film-forming composition can improve the coating property by containing a surfactant, and as a result, the coating surface uniformity of the formed film is improved and the occurrence of coating spots is suppressed. Can do. Surfactant can be used individually by 1 type or in combination of 2 or more types.

  Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n-nonylphenyl ether, polyethylene glycol dilaurate, Nonionic surfactants such as polyethylene glycol distearate are listed. Commercially available products include KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 75, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Ftop EF101, EF204, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F172, F173 (manufactured by Dainippon Ink and Chemicals, Inc.) ), FLORAD FC430, FC431, FC135, FC93 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass) ) And the like.

  As content of surfactant, 0 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] compound, 0.001 mass part-5 mass parts are more preferable, 0.005 mass part-1 More preferred is less than or equal to parts by weight. By making content of surfactant into the said range, the applicability | paintability of the said film forming composition can be improved more.

[Adhesion aid]
The adhesion assistant is a component that improves the adhesion to the substrate. When the film-forming composition contains an adhesion assistant, adhesion between the film to be formed and a substrate or the like as a base can be improved. The adhesion assistant can be used singly or in combination of two or more.

  As the adhesion assistant, for example, a known adhesion assistant can be used.

  The content of the adhesion assistant is preferably 0 to 10 parts by mass, more preferably 0.01 to 10 parts by mass, and 0.01 to 5 parts by mass with respect to 100 parts by mass of the [A] compound. Part by mass is more preferable.

<Method for Preparing Film Forming Composition>
The film-forming composition is prepared by mixing [A] compound, [B] solvent, and if necessary, [C] acid generator, [D] cross-linking agent and other optional components at a predetermined ratio. it can. The solid content concentration of the film-forming composition is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, further preferably 3% by mass to 20% by mass, and more preferably 5% by mass to 15% by mass is particularly preferred.

  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 particularly suitably used for forming a resist underlayer film in a multilayer resist process or the like in which these properties are required at a high level.

<Manufacturing method of substrate on which pattern is formed>
The method of manufacturing the substrate on which the pattern of the present invention is formed is as follows.
A resist underlayer film forming step, a resist pattern forming step, and a substrate pattern forming step are provided. The resist underlayer film is formed from the film forming composition.
According to the method for producing a substrate on which the pattern is formed, a resist underlayer film having excellent heat resistance and flatness can be easily formed, and a good pattern is formed using the resist underlayer film having excellent characteristics. can do.

[Resist underlayer film forming step]
In this step, a resist underlayer film is formed on the upper surface side of the substrate using the film forming composition. The resist underlayer film is usually formed by applying the film-forming composition to the upper surface side of the substrate to form a coating film and heating the coating film.

  Examples of the substrate include a silicon wafer and a wafer coated with aluminum. Moreover, the application | coating method of the said film forming composition to a board | substrate is not specifically limited, For example, it can implement by appropriate methods, such as spin coating, cast coating, and roll coating.

  The coating film is usually heated in the air. As heating temperature, it is 150 to 500 degreeC normally, Preferably it is 200 to 450 degreeC. When the heating temperature is less than 150 ° C., the oxidative crosslinking does not proceed sufficiently, and there is a possibility that the characteristics necessary for the resist underlayer film will not be exhibited. The heating time is usually 30 seconds to 1,200 seconds, preferably 60 seconds to 600 seconds.

  The oxygen concentration during heating is preferably 5% by volume or more. When the oxygen concentration at the time of heating is low, the oxidative crosslinking of the resist underlayer film does not proceed sufficiently, and there is a possibility that the characteristics necessary for the resist underlayer film cannot be expressed.

  You may preheat at the temperature of 60 to 250 degreeC, before heating the said coating film at the temperature of 150 to 500 degreeC. The heating time in the preheating is not particularly limited, but is preferably 10 seconds to 300 seconds, and more preferably 30 seconds to 180 seconds. By performing this preheating, the dehydrogenation reaction can be efficiently advanced by vaporizing the solvent in advance to make the film dense.

  In the resist underlayer film forming step, the coating film is usually heated to form a resist underlayer film, but when the film-forming composition contains a radiation-sensitive acid generator, The resist underlayer film can also be formed by curing the coating film by combining exposure and heating. The radiation used for this exposure is appropriately selected from visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ-rays, molecular beams, ion beams and the like depending on the type of the radiation-sensitive acid generator.

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

  After the resist underlayer film forming step, it may further include a step of forming an intermediate layer (intermediate film) on the resist underlayer film, if necessary. This intermediate layer is a layer provided with the above functions in order to further supplement the functions of the resist underlayer film and / or the resist film or provide functions that these resist layers do not have in resist pattern formation. . For example, when the antireflection film is formed as an intermediate layer, the antireflection function of the resist underlayer film can be further supplemented.

  This intermediate layer can be formed of an organic compound or an inorganic oxide. Examples of the organic compound include commercially available products such as “DUV-42”, “DUV-44”, “ARC-28”, “ARC-29” (hereinafter, Brewer Science); “AR-3”, “ AR-19 "(above, Rohm and Haas). As said inorganic oxide, "NFC SOG01", "NFC SOG04", "NFC SOG080" (above, JSR company) etc. are mentioned as a commercial item, for example. Alternatively, polysiloxane, titanium oxide, alumina oxide, tungsten oxide, or the like formed by a CVD method can be used.

  Although the formation method of an intermediate | middle layer is not specifically limited, For example, the apply | coating method, CVD method, etc. can be used. Among these, a coating method is preferable. When the coating method is used, the intermediate layer can be formed continuously after forming the resist underlayer film. Moreover, it does not specifically limit as a film thickness of an intermediate | middle layer, Although it selects suitably according to the function calculated | required by an intermediate | middle layer, 10 nm-3,000 nm are preferable and 20 nm-300 nm are more preferable.

[Resist pattern formation process]
In this step, a resist pattern is formed above the resist underlayer film. Examples of the method for performing this step include a method using a resist composition.

  In the method using the resist composition, specifically, after applying the resist composition so that the resulting resist film has a predetermined thickness, the solvent in the coating film is volatilized by pre-baking, A resist film is formed.

  Examples of the resist composition include a positive or negative chemically amplified resist composition containing a photoacid generator, a positive resist composition comprising an alkali-soluble resin and a quinonediazide-based photosensitizer, and an alkali-soluble resin. Examples thereof include a negative resist composition composed of a crosslinking agent.

  The total solid concentration of the resist composition is usually 1% by mass to 50% by mass. In addition, the resist composition is generally filtered through a filter having a pore diameter of about 0.2 μm and provided for forming a resist film. In this step, a commercially available resist composition can be used as it is.

  The method for applying the resist composition is not particularly limited, and examples thereof include a spin coating method. The pre-baking temperature is appropriately adjusted according to the type of resist composition used and the like, but is usually 30 ° C to 200 ° C, preferably 50 ° C to 150 ° C.

Next, the formed resist film is exposed by selective radiation irradiation. The radiation used for the exposure is appropriate from visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, γ rays, molecular beams, ion beams, etc., depending on the type of photoacid generator used in the resist composition. Selected. Among these, far ultraviolet rays are preferable, and 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), extreme ultraviolet light (wavelength 13 nm, etc.), etc. are more preferable.

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

  Next, the exposed resist film is developed with a developer to form a resist pattern. The developer is appropriately selected according to the type of resist composition used. As the developer, in the case of alkali development, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo An alkaline aqueous solution such as [4.3.0] -5-nonene may be mentioned. An appropriate amount of a water-soluble organic solvent such as alcohols such as methanol and ethanol, a surfactant, and the like can be added to these alkaline aqueous solutions. In the case of organic solvent development, examples of the developer include various organic solvents exemplified as the above-mentioned [B] solvent.

  A predetermined resist pattern is formed by washing and drying after development with the developer.

  As a method for performing the resist pattern forming step, in addition to the method using the resist composition described above, a method using a nanoimprint method, a method using a self-organizing composition, and the like can also be used.

[Substrate pattern formation process]
In this step, a pattern is formed on the substrate by etching using the resist pattern as a mask. 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 and wet etching. Among these, dry etching is preferable. For this dry etching, for example, gas plasma such as oxygen plasma is used. After the etching, a substrate having a predetermined pattern is obtained.

<Membrane>
The film of the present invention is formed from the film forming composition. Since the film is formed from the film-forming composition described above, it is excellent in 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 compounds of the present invention have one partial structure (I).
The compound can be suitably used as a component of the film-forming composition described above, and according to the film-forming composition, a film having excellent heat resistance and flatness while maintaining general characteristics such as etching resistance. Can be formed. The compound is the [A] compound contained in the film-forming composition described above, and has been described above.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Each physical property value was measured by the following method.

[Mw]
Mw of the polymer was monodispersed using the Tosoh GPC column (G2000HXL: 2, G3000HXL: 1), flow rate: 1.0 mL / min, elution solvent: tetrahydrofuran, column temperature: 40 ° C. It measured by the gel permeation chromatograph (detector: differential refractometer) which uses polystyrene as a standard.

[Film thickness]
The film thickness was measured using a spectroscopic ellipsometer (“M2000D” manufactured by JA WOOLLAM).

<Synthesis of [A] Compound>
[Example 1] (Synthesis of Compound (A-1))
In a separable flask equipped with a thermometer, under a nitrogen atmosphere, 15 parts by mass of the following compound (M-1), 18 parts by mass of compound (M-2), 6 parts by mass of sodium hydride as a basic compound, and as a solvent 100 parts by mass of tetrahydrofuran was added and reacted at 0 ° C. for 3 hours with stirring to obtain a reaction solution. This reaction solution was reprecipitated by adding methanol-water, and the resulting precipitate was dried to obtain a compound (M-4). Next, the total amount of the compound (M-4) obtained, 27 parts by mass of the compound (M-3), 19 parts by mass of potassium carbonate as a basic compound and 150 parts by mass of dimethylacetamide as a solvent were blended and stirred. While performing a condensation reaction at 140 ° C. for 4 hours, a reaction solution was obtained. After filtering this reaction liquid, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain a compound (M-5). Next, the total amount of the compound (M-5) obtained, 32 parts by mass of propargyl bromide, 19 parts by mass of potassium carbonate as a basic compound and 150 parts by mass of dimethylacetamide as a solvent were blended and stirred at 60 ° C. And reacted for 4 hours to obtain a reaction solution. After filtering this reaction liquid, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain 50 parts by mass of the following compound (A-1).

[Examples 2 to 4] (Synthesis of compounds (A-2) to (A-4))
The following compounds (A-2), (A-3) and (A-4) were synthesized by the same reaction scheme as in Example 1 except that the raw materials were changed.

[Example 5] (Synthesis of Compound (A-5))
In a separable flask equipped with a thermometer, under a nitrogen atmosphere, 15 parts by mass of the following compound (M-6), 17 parts by mass of compound (M-7), 5 parts by mass of sodium hydride as a basic compound, and as a solvent 80 parts by mass of tetrahydrofuran was added and reacted at 0 ° C. for 3 hours with stirring to obtain a reaction solution. This reaction solution was reprecipitated by adding methanol-water, and the resulting precipitate was dried to obtain a compound (M-9). Next, the total amount of the compound (M-9) obtained, 24.5 parts by mass of the compound (M-8), 17 parts by mass of potassium carbonate as a basic compound and 140 parts by mass of dimethylacetamide as a solvent were blended and stirred. Then, a condensation reaction was performed at 140 ° C. for 4 hours to obtain a reaction solution. After filtering this reaction liquid, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain 40 parts by mass of the following compound (A-5).

[Examples 6 to 8] (Synthesis of compounds (A-6) to (A-8))
The following compounds (A-6), (A-7) and (A-8) were synthesized by the same reaction scheme as in Example 5 except that the raw materials were changed.

[Example 9] (Synthesis of Compound (A-9))
In a separable flask equipped with a thermometer, 15 parts by mass of the following compound (M-10), 16.5 parts by mass of compound (M-11), 5 parts by mass of sodium hydride as a basic compound and a solvent under a nitrogen atmosphere As a mixture, 80 parts by mass of tetrahydrofuran was added and reacted at 0 ° C. for 3 hours with stirring to obtain a reaction solution. This reaction solution was reprecipitated by adding methanol-water, and the resulting precipitate was dried to obtain a compound (M-13). Next, the total amount of the compound (M-13) obtained, 24 parts by mass of the compound (M-12), 16.5 parts by mass of potassium carbonate as a basic compound and 140 parts by mass of dimethylacetamide as a solvent were blended and stirred. Then, a condensation reaction was performed at 140 ° C. for 4 hours to obtain a reaction solution. After filtering this reaction liquid, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain 40 parts by mass of the following compound (A-9).

[Examples 10 to 12] (Synthesis of compounds (A-10) to (A-12))
The following compounds (A-10), (A-11) and (A-12) were synthesized by the same reaction scheme as in Example 9 except that the raw materials were changed.

[Example 13] (Synthesis of Compound (A-13))
In a separable flask equipped with a thermometer, 15 parts by mass of the following compound (M-14), 9.5 parts by mass of compound (M-15), 3 parts by mass of sodium hydride as a basic compound and a solvent under a nitrogen atmosphere As a mixture, 50 parts by mass of tetrahydrofuran was added and reacted at 0 ° C. for 3 hours with stirring to obtain a reaction solution. This reaction solution was reprecipitated by adding methanol-water, and the resulting precipitate was dried to obtain a compound (M-17). Subsequently, the total amount of the obtained (M-17), 14 parts by mass of the compound (M-16), 10 parts by mass of potassium carbonate as a basic compound, and 80 parts by mass of dimethylacetamide as a solvent were blended and stirred, 140 A condensation reaction was carried out at 4 ° C. for 4 hours to obtain a reaction solution. After filtering this reaction liquid, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain 28 parts by mass of the following compound (A-13).

[Examples 14 and 15] (Synthesis of Compounds (A-14) and (A-15))
The following compounds (A-14) and (A-15) were synthesized by the same reaction scheme as in Example 13 except that the raw materials were changed.

[Comparative Synthesis Example 1] (Synthesis of polymer (a-1))
In a separable flask equipped with a thermometer, under a nitrogen atmosphere, 140 parts by mass of the following compound (M-18), 100 parts by mass of compound (M-19), 140 parts by mass of potassium carbonate as a basic compound, and as a solvent 500 parts by mass of dimethylacetamide was blended, and a condensation polymerization reaction was performed at 140 ° C. for 4 hours with stirring to obtain a reaction solution. After filtering this reaction liquid, methanol was added for reprecipitation, and the resulting precipitate was dried to obtain a polymer (a-1) having a structural unit represented by the following formula (a-1). . Mw of the polymer (a-1) was 4,000.

[Comparative Synthesis Example 2] (Synthesis of Compound (a-2))
A separable flask equipped with a thermometer was charged with 100 parts by mass of 2,7-dihydroxynaphthalene, 30 parts by mass of formalin, 1 part by mass of p-toluenesulfonic acid and 150 parts by mass of propylene glycol monomethyl ether under a nitrogen atmosphere and stirred. While polymerization was performed at 80 ° C. for 6 hours, a reaction solution was obtained. The obtained reaction solution was diluted with 100 parts by mass of n-butyl acetate, and the organic layer was washed with a large amount of water / methanol (mass ratio: 1/2) mixed solvent. Then, the polymer (a-2) which has a structural unit represented by a following formula (a-2) was obtained by distilling a solvent off. Mw of the polymer (a-2) was 1,800.

<Preparation of composition for forming resist underlayer film>
Each component other than the component [A] is shown below.

[B] Solvent B-1: Propylene glycol monomethyl 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] Crosslinking agent D-1: 4,4 ′-(1- (4- (1- (4-hydroxy-3,5-bis (methoxymethyl) phenyl) -1-methylethyl) phenyl) ethylidene) bis (2,6-bis (methoxymethyl) phenol) (compound represented by the following formula (D-1))

[Example 16]
[A] 10 parts by mass of (A-1) as a compound and 100 parts by mass of (B-1) as a [B] solvent were mixed to obtain a solution. The solution was filtered through a membrane filter having a pore size of 0.1 μm to prepare a film-forming composition (J-1).

[Examples 17 to 30 and Comparative Examples 1 and 2]
The film forming compositions (J-2) to (J-15) and (CJ-1) were operated in the same manner as in Example 16 except that the components of the types and contents shown in Table 1 were used. And (CJ-2) were prepared. In Table 1, “-” indicates that the corresponding component was not used.

<Evaluation>
About the obtained film forming composition, etching resistance, heat resistance and flatness were evaluated by the following methods. The evaluation results are shown in Table 2.

[Etching resistance]
The obtained film-forming composition was spin-coated on a silicon wafer having a diameter of 8 inches to form a film having a thickness of 300 nm. Thereafter, this film was subjected to an etching process (pressure: 0.03 Torr, high-frequency power: 3000 W, Ar / CF ₄ = 40/100 sccm, substrate temperature: 20 ° C.), and the film thickness after the etching process was measured. The etching rate (nm / min) was calculated from the relationship between the amount of decrease in film thickness and the processing time, and the ratio to Comparative Example 2 was calculated. It shows that etching resistance is so favorable that this value is small.

[Heat-resistant]
The obtained film-forming composition was spin-coated on a silicon wafer having a diameter of 8 inches to form a coating film, and the film thickness of the coating film was measured using the spectroscopic ellipsometer (this measured value was measured as X And). Next, this film was heated at 350 ° C. for 120 seconds, and the film thickness of the heated film was measured using the above spectroscopic ellipsometer (this measured value is set as Y). The film thickness reduction rate (100 × (XY) / X) (%) before and after heating was calculated, and this value was defined as heat resistance. The heat resistance indicates that the smaller the value, the fewer sublimates and film decomposition products generated during heating of the film, and the better (high heat resistance).

[Flatness]
Trench with a width of 42 nm, a pitch of 84 nm and a depth of 180 nm (aspect ratio: 4.3), a trench with a width of 100 nm, a pitch of 150 nm and a depth of 180 nm (aspect ratio: 1.8) and a trench with a width of 5 μm and a depth of 180 nm (open) Each of the obtained film-forming compositions was applied onto a SiO ₂ stepped substrate (a ratio of the maximum value and the minimum value in different aspect ratios: 119) in which space) (aspect ratio: 0.036) was mixed. Thereafter, it was baked (baked) at 250 ° C. for 60 seconds in an air atmosphere to form a film with a thickness of 200 nm. The shape of the film was observed with a scanning electron microscope (“S-4800” manufactured by Hitachi High-Technologies Corporation), and the difference between the maximum value and the minimum value (ΔFT) of the film thickness on the trench or space was measured. The flatness was evaluated as “◯” (good) when ΔFT was less than 20 nm, and “x” (bad) when 20 nm or more.

  As is clear from the results in Table 2, the film formed from the film forming composition of the example satisfies the general characteristics of etching resistance and the like, and is a film formed from the film forming composition of the comparative example. Compared with high heat resistance and high flatness.

  The film forming composition of the present invention can form a film excellent in heat resistance and flatness while maintaining general characteristics such as etching resistance. The film has high 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 this excellent characteristic is used for a substrate. A pattern can be formed. The compound can be suitably used as a component of the film-forming composition. Therefore, these can be suitably used for manufacturing semiconductor devices and the like that are expected to be further miniaturized in the future.

Claims (12)

A film forming composition comprising a compound represented by the following formula ( 2 ) and having an intermolecular bond-forming group , and a solvent.

(In formula (2), Z is a partial structure represented by the following formula (1). K1 and k2 are each independently an integer of 0 to 9. However, k1 + k2 is 1 or more. there .Ar ¹ and Ar ² are, each independently, .Ar ³ and Ar ⁴ is a substituted or unsubstituted arenediyl group having 6 to 20 carbon atoms are each independently substituted or unsubstituted carbon atoms 6 an aryl group which .p1 and p2 of 20 are each independently, ^.Ar 1 ^{to Ar} 4 is an integer of 0 to 3, when p1 and p2 is plural respective plurality of Ar ¹ are either the same or different The plurality of Ar ² may be the same or different, the plurality of Ar ³ may be the same or different, the plurality of Ar ⁴ may be the same or different, and the plurality of p1 may be the same or different. Multiple p2s are the same It may be different.)

(In Formula (1), R < ¹ > -R < ⁴ > is respectively independently a halogen atom, a hydroxy group, a nitro group, or a C1-C20 monovalent organic group. A1 and a2 are respectively independent. And b1 and b2 are each independently an integer of 0 to ^{4. When} there are a plurality of R ^{1 to} R ⁴ , a plurality of R ¹ may be the same or different. In addition, a plurality of R ² may be the same or different, a plurality of R ³ may be the same or different, and a plurality of R ⁴ may be the same or different. And k1 and k2 have the same meanings as in the above formula (2), a1 + k1 and a2 + k2 are 9 or less, and * indicates a binding site with a portion other than the partial structure. Following formula (2) represented Ru of compound,
A film-forming composition containing a crosslinking agent and a solvent.

(In formula (2), Z is a partial structure represented by the following formula (1). K1 and k2 are each independently an integer of 0 to 9. However, k1 + k2 is 1 or more. there .Ar ¹ and Ar ² are, each independently, .Ar ³ and Ar ⁴ is a substituted or unsubstituted arenediyl group having 6 to 20 carbon atoms are each independently substituted or unsubstituted carbon atoms 6 an aryl group which .p1 and p2 of 20 are each independently, ^.Ar 1 ^{to Ar} 4 is an integer of 0 to 3, when p1 and p2 is plural respective plurality of Ar ¹ are either the same or different The plurality of Ar ² may be the same or different, the plurality of Ar ³ may be the same or different, the plurality of Ar ⁴ may be the same or different, and the plurality of p1 may be the same or different. Multiple p2s are the same It may be different.)

(In Formula (1), R < ¹ > -R < ⁴ > is respectively independently a halogen atom, a hydroxy group, a nitro group, or a C1-C20 monovalent organic group. A1 and a2 are respectively independent. And b1 and b2 are each independently an integer of 0 to ^{4. When} there are a plurality of R ^{1 to} R ⁴ , a plurality of R ¹ may be the same or different. In addition, a plurality of R ² may be the same or different, a plurality of R ³ may be the same or different, and a plurality of R ⁴ may be the same or different. And k1 and k2 have the same meanings as in the above formula (2), a1 + k1 and a2 + k2 are 9 or less, and * indicates a binding site with a portion other than the partial structure. The film forming composition according to claim 1 or 2, further comprising an acid generator . Substituents for the aryl groups Ar ³ and Ar ⁴ in the formula (2) is, according to claim 1 is a monovalent intermolecular bonds forming groups aralkyl group or C 1-20 7 to 20 carbon atoms, claim The film-forming composition according to claim 2 or claim 3 .   The film-forming composition according to claim 4, wherein the intermolecular bond-forming group is a carbon-carbon double bond-containing group, a carbon-carbon triple bond-containing group, an acyl group, or a combination thereof. The carbon-carbon double bond-containing group is a group represented by the following formula (3-1), and the carbon-carbon triple bond-containing group is a group represented by the following formula (3-2). The composition for film formation as described.

(In formula (3-1), 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 formula (3-2), R ⁸ and R ⁹ 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 plurality of R ⁸ may be the same or different. )   The film forming composition according to any one of claims 1 to 6, wherein the molecular weight of the compound is 300 or more and 3,000 or less.   The film forming composition according to any one of claims 1 to 7, wherein the solvent includes a polyhydric alcohol partial ether acetate solvent, a ketone solvent, a carboxylic acid ester solvent, or a combination thereof.   The composition for forming a film according to any one of claims 1 to 8, which is used for forming a resist underlayer film.   The film | membrane formed from the composition for film formation of any one of Claims 1-9. Forming a resist underlayer film on the upper surface side of the substrate;
A step of forming a resist pattern above the resist underlayer film, and a step of forming a pattern on the substrate by etching using the resist pattern as a mask,
The manufacturing method of the board | substrate with which the pattern which forms the said resist lower layer film with the composition for film formation of Claim 9 was formed. Following formula (2) represented Ru of compounds.

(In formula (2), Z is a partial structure represented by the following formula (1). K1 and k2 are each independently an integer of 0 to 9. However, k1 + k2 is 1 or more. there .Ar ¹ and Ar ² are, each independently, .Ar ³ and Ar ⁴ is a substituted or unsubstituted arenediyl group having 6 to 20 carbon atoms are each independently substituted or unsubstituted carbon atoms 6 an aryl group which .p1 and p2 of 20 are each independently, ^.Ar 1 ^{to Ar} 4 is an integer of 1 to 3, when p1 and p2 is plural respective plurality of Ar ¹ are either the same or different The plurality of Ar ² may be the same or different, the plurality of Ar ³ may be the same or different, the plurality of Ar ⁴ may be the same or different, and the plurality of p1 may be the same or different. Multiple p2s are the same It may be different.)

(In Formula (1), R < ¹ > -R < ⁴ > is respectively independently a halogen atom, a hydroxy group, a nitro group, or a C1-C20 monovalent organic group. A1 and a2 are respectively independent. And b1 and b2 are each independently an integer of 0 to ^{4. When} there are a plurality of R ^{1 to} R ⁴ , a plurality of R ¹ may be the same or different. In addition, a plurality of R ² may be the same or different, a plurality of R ³ may be the same or different, and a plurality of R ⁴ may be the same or different. And k1 and k2 have the same meanings as in the above formula (2), a1 + k1 and a2 + k2 are 9 or less, and * indicates a binding site with a portion other than the partial structure.