JP7375757B2 - Resist underlayer film forming composition containing heteroatoms in polymer main chain - Google Patents

Description

The present invention relates to a reaction product between an epoxy adduct-forming compound and a compound having a specific structure having an epoxy group, a resist underlayer film forming composition containing the reaction product, a resist underlayer film, a method for producing a patterned substrate, and The present invention relates to a method for manufacturing a semiconductor device.

Patent Document 1 discloses a composition for forming a resist underlayer film for lithography, which includes a polymer that is a reaction product of at least one compound containing two epoxy groups (diepoxy compound) and at least one dicarboxylic acid containing a disulfide bond. A resist that has a high dry etching rate selectivity with respect to the resist film, has a low k value at short wavelengths such as ArF excimer laser, and has a high n value, and allows a resist pattern to be formed in a desired shape. Forming an underlayer film is disclosed.

WO2009/096340A1

However, it cannot be said that the etching selectivity of conventional products is still sufficiently high. Therefore, the problem to be solved by the present invention is to provide a resist underlayer film forming composition that provides a resist underlayer film with higher etching selectivity than conventional products. Another object of the present invention is to provide a resist underlayer film that can shorten dry etching time and suppress undesirable etching damage to the underlying substrate.

［式（１）中、Ａ^１は少なくとも１つの水素原子がハロゲン原子で置換されていてもよく且つ酸素原子、硫黄原子、ジスルフィド基、スルホニル基、カルボニル基若しくはイミノ基で中断されている炭素原子数２乃至１０の直鎖若しくは分岐アルキレン基を表す］で表される化合物、とのエポキシ付加生成物と、溶剤とを含む、レジスト下層膜形成組成物。
＜２＞ 前記エポキシ付加体形成化合物が、カルボン酸含有化合物、カルボン酸無水物含有化合物、ヒドロキシ基含有化合物、チオール基含有化合物、アミノ基含有化合物及びイミド基含有化合物からなる群より選ばれる少なくとも１種の化合物である、＜１＞に記載のレジスト下層膜形成組成物。
＜３＞ 前記エポキシ付加体形成化合物が、カルボン酸含有化合物またはチオール基含有化合物である、＜１＞又は＜２＞に記載のレジスト下層膜形成組成物。
＜４＞ 前記カルボン酸含有化合物が、硫黄原子を少なくとも１つ以上含むジカルボン酸である、＜２＞又は＜３＞に記載のレジスト下層膜形成組成物。
＜５＞ 前記硫黄原子を少なくとも１つ以上含むジカルボン酸が、硫黄原子を少なくとも１つ以上含む脂肪族ジカルボン酸である、＜４＞に記載のレジスト下層膜形成組成物。
＜６＞ 架橋触媒をさらに含む、＜１＞～＜５＞のいずれか１項に記載のレジスト下層膜形成組成物。
＜７＞ 架橋剤をさらに含む、＜１＞～＜６＞のいずれか１項に記載のレジスト下層膜形成組成物。
＜８＞ 界面活性剤をさらに含む、＜１＞～＜７＞のいずれか１項に記載のレジスト下層膜形成組成物。
＜９＞ ＜１＞～＜８＞のいずれか１項に記載のレジスト下層膜形成組成物からなる塗布膜の焼成物であることを特徴とするレジスト下層膜。
＜１０＞ 半導体基板上に、＜１＞～＜８＞のいずれか１項に記載のレジスト下層膜形成組成物を塗布しベークしてレジスト下層膜を形成する工程、前記レジスト下層膜上にレジストを塗布しベークしてレジスト膜を形成する工程、前記レジスト下層膜と前記レジストで被覆された半導体基板を露光する工程、露光後の前記レジスト膜を現像し、パターニングする工程を含む、パターニングされた基板の製造方法。
＜１１＞ 半導体基板上に、＜１＞～＜８＞の何れか１項に記載のレジスト下層膜形成組成物からなるレジスト下層膜を形成する工程と、
前記レジスト下層膜の上にレジスト膜を形成する工程と、
レジスト膜に対する光又は電子線の照射とその後の現像によりレジストパターンを形成する工程と、
形成された前記レジストパターンを介して前記レジスト下層膜をエッチングすることによりパターン化されたレジスト下層膜を形成する工程と、
パターン化された前記レジスト下層膜により半導体基板を加工する工程と、
を含むことを特徴とする、半導体装置の製造方法。
＜１２＞ 下記式（１）：

（式（１）中、Ａ^１は少なくとも１つの水素原子がハロゲン原子で置換されていてもよく且つ硫黄原子、ジスルフィド基、スルホニル基、カルボニル基若しくはイミノ基で中断されている炭素原子数２乃至１０の直鎖若しくは分岐アルキレン基を表す）で表される化合物。
＜１３＞ 下記式（１）：

［式（１）中、Ａ^１は少なくとも１つの水素原子がハロゲン原子で置換されてもよく且つ硫黄原子、ジスルフィド基、スルホニル基、カルボニル基若しくはイミノ基で中断されている炭素原子数２乃至１０の直鎖若しくは分岐アルキレン基を表す］で表される化合物と、
カルボン酸含有化合物、カルボン酸無水物含有化合物、ヒドロキシ基含有化合物、チオール基含有化合物、アミノ基含有化合物及びイミド基含有化合物からなる群より選択される少なくとも一種のエポキシ付加体形成化合物との反応生成物。The present invention includes the following.
<1> Epoxy adduct-forming compound and the following formula (1):

[In formula (1), A ¹ is a carbon atom in which at least one hydrogen atom may be substituted with a halogen atom and is interrupted by an oxygen atom, a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group, or an imino group A composition for forming a resist underlayer film, comprising an epoxy addition product with a compound represented by the following formula (representing a straight chain or branched alkylene group having numbers 2 to 10), and a solvent.
<2> The epoxy adduct-forming compound is at least one compound selected from the group consisting of a carboxylic acid-containing compound, a carboxylic anhydride-containing compound, a hydroxy group-containing compound, a thiol group-containing compound, an amino group-containing compound, and an imide group-containing compound. The resist underlayer film forming composition according to <1>, which is a seed compound.
<3> The resist underlayer film forming composition according to <1> or <2>, wherein the epoxy adduct-forming compound is a carboxylic acid-containing compound or a thiol group-containing compound.
<4> The resist underlayer film forming composition according to <2> or <3>, wherein the carboxylic acid-containing compound is a dicarboxylic acid containing at least one sulfur atom.
<5> The resist underlayer film forming composition according to <4>, wherein the dicarboxylic acid containing at least one sulfur atom is an aliphatic dicarboxylic acid containing at least one sulfur atom.
<6> The resist underlayer film forming composition according to any one of <1> to <5>, further comprising a crosslinking catalyst.
<7> The resist underlayer film forming composition according to any one of <1> to <6>, further comprising a crosslinking agent.
<8> The resist underlayer film forming composition according to any one of <1> to <7>, further comprising a surfactant.
<9> A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film forming composition according to any one of <1> to <8>.
<10> A step of applying the resist underlayer film forming composition according to any one of <1> to <8> on a semiconductor substrate and baking it to form a resist underlayer film, a step of forming a resist underlayer film on the resist underlayer film. a step of applying and baking to form a resist film; a step of exposing the resist underlayer film and the semiconductor substrate covered with the resist; and a step of developing and patterning the resist film after exposure. Substrate manufacturing method.
<11> Forming a resist underlayer film made of the resist underlayer film forming composition according to any one of <1> to <8> on a semiconductor substrate;
forming a resist film on the resist underlayer film;
forming a resist pattern by irradiating the resist film with light or electron beam and subsequent development;
forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern;
processing a semiconductor substrate using the patterned resist underlayer film;
A method for manufacturing a semiconductor device, the method comprising:
<12> The following formula (1):

(In formula (1), A ¹ has at least one hydrogen atom optionally substituted with a halogen atom and is interrupted by a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group, or an imino group, and has a carbon atom number of 2 to 2. 10 straight-chain or branched alkylene groups).
<13> The following formula (1):

[In formula (1), A ¹ has 2 to 10 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom and is interrupted by a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group, or an imino group. represents a straight chain or branched alkylene group];
Reaction product with at least one epoxy adduct-forming compound selected from the group consisting of carboxylic acid-containing compounds, carboxylic anhydride-containing compounds, hydroxy group-containing compounds, thiol group-containing compounds, amino group-containing compounds, and imide group-containing compounds. thing.

According to the present invention, a reaction product of an epoxy adduct-forming compound such as a carboxylic acid-containing compound and a compound having a specific structure having a hetero atom (O, S, N, etc.) and a glycidyl ester group is used as a resist underlayer film forming composition. By applying this method to materials, it has become possible to achieve a higher etching rate than when using a heteroatom compound that does not have a glycidyl ester group.

［式（１）中、Ａ^１は少なくとも１つの水素原子がハロゲン原子で置換されていてもよく且つ酸素原子、硫黄原子、ジスルフィド基、スルホニル基、カルボニル基若しくはイミノ基で中断されている炭素原子数２乃至１０の直鎖若しくは分岐アルキレン基を表す］で表される化合物、とのエポキシ付加生成物と、溶剤とを含む。以下、順に説明する。[Resist underlayer film forming composition]
The resist underlayer film forming composition according to the present invention includes an epoxy adduct-forming compound and the following formula (1):

[In formula (1), A ¹ is a carbon atom in which at least one hydrogen atom may be substituted with a halogen atom and is interrupted by an oxygen atom, a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group, or an imino group Representing a straight chain or branched alkylene group having numbers 2 to 10], an epoxy addition product with a compound represented by the following formula, and a solvent. Below, they will be explained in order.

[Compound represented by formula (1)]
In the compound represented by the above formula (1), A ¹ may have at least one hydrogen atom substituted with a halogen atom and is interrupted by an oxygen atom, a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group, or an imino group. represents a straight chain or branched alkylene group having 2 to 10 carbon atoms.

Examples of straight chain or branched alkylene groups having 2 to 10 carbon atoms include ethylene group, n-propylene group, isopropylene group, n-butylene group, s-butylene group, n-pentylene group, 1-methylbutylene group, 2 -Methylbutylene group, 3-methylbutylene group, n-pentylene group, 1,1-dimethylpropylene group, 1,2-dimethylpropylene group, 2,2-dimethylpropylene group, 1,3-dimethylpropylene group, n- hexylene group, 1-methylheptylene group, 2-methylheptylene group, 3-methylheptylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 1,3-dimethylbutylene group, 2,2-dimethylbutylene group, 2,3-dimethylbutylene group, 3,3-dimethylbutylene group, 3,3-dimethylbutan-2-ylene group, 2,3-dimethylbutan-2-ylene group, 3-hexylene group, 2-ethylpentylene group group, 2-methylpentan-3-ylene group, heptylene group, octylene group, nonylene group, decylene group, etc.

"Interrupted" refers to an embodiment in which an oxygen atom, sulfur atom, disulfide group, sulfonyl group, carbonyl group, or imino group is inserted between the carbon-carbon bonds of the alkylene group.
Examples of the halogen atoms include fluorine, chlorine, bromine, and iodine.
The at least one hydrogen atom may be substituted with a halogen atom means that at least one hydrogen atom of the linear or branched alkylene group having 2 to 10 carbon atoms may be substituted with a halogen atom. say something The number of halogen atoms substituted is preferably 5 or less, preferably 3 or less, preferably 2 or less, preferably 1 or less, and preferably 0 (that is, not substituted with a halogen atom).
Preferred specific examples are as follows, but are not limited thereto.
-CH ₂ -O-CH ₂ -, -C ₂ H ₄ -O-C ₂ H ₄ -, -C ₃ H ₆ -O-C ₃ H ₆ -, -CH ₂ -S-CH ₂ -, -C ₂ H ₄ -S-C ₂ H ₄ -, -C ₃ H ₆ -S-C ₃ H ₆ -, -CH ₂ -S-C ₂ H ₄ -, -CH ₂ -S-C ₃ H ₆ -, -C ₂ H ₄ -S-C ₃ H ₆ -, -CH ₂ -S-C ₂ H ₄ -S-CH ₂ -, -CH ₂ -SS-CH ₂ -, -C ₂ H ₄ -SS-C ₂ H ₄ -, -C ₃ H ₆ -SS-C ₃ H ₆ -, -CH ₂ -SO ₂ -CH ₂ -, -C ₂ H ₄ -SO ₂ -C ₂ H ₄ -, -C ₃ H ₆ -SO ₂ -C ₃ H ₆ -, -CH ₂ -CO-CH ₂ -, -C ₂ H ₄ -CO-C ₂ H ₄ -, -C ₃ H ₆ -CO-C ₃ H ₆ -, -CH ₂ -NH-CH ₂ -, -C ₂ H ₄ -NH-C ₂ H ₄ -, -C ₃ H ₆ -NH-C ₃ H ₆ -
Further, the number of times that the alkylene group is interrupted by the inserted group may be one time, but may be two or more times as long as the stability of the bond is maintained. In that case, the groups inserted may be the same or different.

Specific examples of the compound represented by formula (1) are as follows, but the compound is not limited thereto.

[Epoxy adduct-forming compound]
The epoxy adduct-forming compound refers to a compound that can react with the compound represented by the above formula (1) to produce a polymer or oligomer. Usually, it is a compound having 1 to 4 functional groups per molecule that are reactive with epoxy groups. Although only one type of epoxy adduct-forming compound may be used, a mixture of two or more types may be used. In that case, from the viewpoint of lengthening the main chain of the product to some extent, it is preferable that a compound having two or more functional groups reactive with an epoxy group per molecule accounts for the majority of the mixture.

The epoxy adduct-forming compound is preferably at least one selected from the group consisting of carboxylic acid-containing compounds, carboxylic anhydride-containing compounds, hydroxy group-containing compounds, thiol group-containing compounds, amino group-containing compounds, and imide group-containing compounds. More preferably, they are carboxylic acid-containing compounds or thiol group-containing compounds.
Preferably, the epoxy adduct-forming compound has a heteroatom. Preferably, the epoxy adduct-forming compound has one or more heteroatoms. Preferably, the epoxy adduct-forming compound has 2 or more and 10 or less heteroatoms.
The heteroatom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.
The carboxylic acid-containing compound is preferably a dicarboxylic acid containing at least one sulfur atom, more preferably an aliphatic dicarboxylic acid containing at least one sulfur atom.

Specific examples of the epoxy adduct-forming compound are listed below, but are not limited thereto.

[Epoxy addition product]
The epoxy adduct is a reaction product of the compound represented by the formula (1) and an epoxy adduct-forming compound. That is, the reaction product of the compound represented by formula (1), which is a raw material monomer, and the epoxy adduct-forming compound is dissolved in a solvent at an appropriate molar ratio, and a catalyst for activating the epoxy group is prepared. It can be obtained by polymerization in the presence of

The catalyst that activates the epoxy group is, for example, a quaternary phosphonium salt such as triphenylmonoethylphosphonium bromide, or a quaternary ammonium salt such as benzyltriethylammonium chloride, and is a raw material monomer represented by formula (1). An appropriate amount can be selected from the range of 0.1% by mass to 10% by mass based on the total mass of the compound represented by and the epoxy adduct-forming compound.

The optimum temperature and time for the polymerization reaction are selected from the range of 80° C. to 160° C. and 2 hours to 50 hours.

Although the above reaction may be carried out without a solvent, it is usually carried out using a solvent. Any solvent can be used as long as it does not inhibit the reaction. Examples include ethers such as 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, tetrahydrofuran, and dioxane.

The weight average molecular weight Mw of the epoxy addition product obtained as described above is usually 500 or 600 or more and 1,000,000 or 500,000 or less.

[solvent]
As the solvent for the resist underlayer film forming composition according to the present invention, any solvent that can dissolve the above-mentioned reaction product can be used without particular limitation. In particular, since the resist underlayer film forming composition according to the present invention is used in a uniform solution state, in consideration of its coating performance, it is recommended to use a solvent commonly used in lithography processes. .

Such solvents include, for example, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, Ether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate , ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate , ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate , isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate , propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-Methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, toluene , xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone , 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

（式（ｉ）中のＲ^１、Ｒ^２及びＲ^３は各々水素原子、酸素原子、硫黄原子又はアミド結合で中断されていてもよい炭素原子数１～２０のアルキル基を表し、互いに同一であっても異なっても良く、互いに結合して環構造を形成しても良い。）Additionally, the following compounds described in Japanese Patent Application No. 2017-140193 can also be used.

(R ¹ , R ² and R ³ in formula (i) each represent a hydrogen atom, an oxygen atom, a sulfur atom, or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and are the same as each other. They may be present or different, and may be combined with each other to form a ring structure.)

Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups that may or may not have substituents, such as methyl group, ethyl group, n-propyl group, etc. , isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, cyclohexyl group , 2-ethylhexyl group, n-nonyl group, isononyl group, p-tert-butylcyclohexyl group, n-decyl group, n-dodecylnonyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , heptadecyl group, octadecyl group, nonadecyl group and eicosyl group. Preferably it is an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.

Examples of the alkyl group having 1 to 20 carbon atoms interrupted by an oxygen atom, a sulfur atom or an amide bond include the structural unit -CH ₂ -O-, -CH ₂ -S-, -CH ₂ -NHCO- or - Examples include those containing CH ₂ -CONH-. -O-, -S-, -NHCO- or -CONH- may have one or more units in the alkyl group. Specific examples of alkyl groups having 1 to 20 carbon atoms interrupted by -O-, -S-, -NHCO- or -CONH- units include methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio. group, propylthio group, butylthio group, methylcarbonylamino group, ethylcarbonylamino group, propylcarbonylamino group, butylcarbonylamino group, methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, etc. , furthermore, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, or an octadecyl group, each of which is a methoxy group, an ethoxy group, group, propoxy group, butoxy group, methylthio group, ethylthio group, propylthio group, butylthio group, methylcarbonylamino group, ethylcarbonylamino group, methylaminocarbonyl group, ethylaminocarbonyl group, etc. Preferred are methoxy group, ethoxy group, methylthio group, and ethylthio group, more preferred are methoxy group and ethoxy group.

Since these solvents have relatively high boiling points, they are also effective for imparting high embedding properties and high flattening properties to the resist underlayer film forming composition.

[Crosslinking agent component]
The resist underlayer film forming composition of the present invention can contain a crosslinking agent component. Examples of the crosslinking agent include melamine type, substituted urea type, and polymer type thereof. Preferably, the crosslinking agent has at least two crosslinking substituents, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, Compounds such as methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. Moreover, condensates of these compounds can also be used.
Preferred examples include tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174).

Moreover, as the above-mentioned crosslinking agent, a crosslinking agent with high heat resistance can be used. As a crosslinking agent with high heat resistance, a compound containing a crosslinking substituent having an aromatic ring (eg, benzene ring, naphthalene ring) in the molecule can be preferably used.

上記Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４は水素原子又は炭素数１乃至１０のアルキル基であり、これらのアルキル基は上述の例示を用いることができる。Examples of this compound include a compound having a partial structure of the following formula (4), and a polymer or oligomer having a repeating unit of the following formula (5).

The above R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and the above-mentioned examples can be used for these alkyl groups.

The compounds, polymers, and oligomers of formulas (4) and (5) are exemplified below.

The above compounds are available as products from Asahi Yokuzai Kogyo Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above-mentioned crosslinking agents, the compound of formula (4-24) is available from Asahi Yakuzai Kogyo Co., Ltd. under the trade name TM-BIP-A.
The amount of the crosslinking agent added varies depending on the coating solvent used, the base substrate used, the required solution viscosity, the required film shape, etc., but is preferably 0.001 to 80% by mass based on the total solid content. The content is 0.01 to 50% by mass, more preferably 0.05 to 40% by mass. These crosslinking agents may cause a crosslinking reaction by self-condensation, but if a crosslinking substituent is present in the reaction product of the present invention, they can cause a crosslinking reaction with those crosslinking substituents.

[Acid and/or acid generator]
The resist underlayer film forming composition of the present invention may contain an acid and/or an acid generator.
Examples of acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, pyridinium trifluoromethanesulfonic acid, pyridinium-p-phenolsulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, Examples include camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and the like.
Only one kind of acid can be used, or two or more kinds can be used in combination. The blending amount is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 3% by mass, based on the total solid content.

Examples of the acid generator include thermal acid generators and photoacid generators.
Examples of the thermal acid generator include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters.

A photoacid generator generates an acid when the resist is exposed to light. Therefore, the acidity of the lower layer film can be adjusted. This is one method for matching the acidity of the lower layer film to the acidity of the upper layer resist. Further, by adjusting the acidity of the lower layer film, the pattern shape of the resist formed on the upper layer can be adjusted.
Examples of the photoacid generator contained in the resist underlayer film forming composition of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

Onium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor Sulfonates and iodonium salt compounds such as bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethane. Examples include sulfonium salt compounds such as sulfonates.

Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide. Can be mentioned.

Examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, and bis(2,4-dimethylbenzenesulfonyl). ) diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

Only one type of acid generator can be used, or two or more types can be used in combination.
When an acid generator is used, the proportion thereof is 0.01 to 5 parts by weight, or 0.1 to 3 parts by weight, or 0.01 to 5 parts by weight, or 0.1 to 3 parts by weight, based on 100 parts by weight of the solid content of the resist underlayer film forming composition. 5 to 1 part by mass.

[Other ingredients]
A surfactant may be added to the resist underlayer forming composition of the present invention in order to prevent the formation of pinholes, striations, etc., and to further improve the coating properties against surface unevenness. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether. polyoxyethylene alkyl allyl ethers, polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. sorbitan fatty acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc. Nonionic surfactants such as fatty acid esters, FTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), Megafac F171, F173, R-40, R-40N, R-40LM (DIC Co., Ltd., product name), Florado FC430, FC431 (Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Examples include fluorine-containing surfactants such as (manufactured by Shin-Etsu Chemical Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film material. These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 parts by mass per 100 parts by mass of the solid content of the resist underlayer film forming composition. 0.5 part by mass.

A light absorbing agent, a rheology modifier, an adhesion auxiliary agent, etc. can be added to the resist underlayer forming composition of the present invention. The rheology modifier is effective in improving the fluidity of the underlayer film forming composition. The adhesion aid is effective in improving the adhesion between the semiconductor substrate or resist and the underlying film.

Examples of the light absorbing agent include commercially available light absorbing agents described in "Technology and Market of Industrial Colorants" (CMC Publishing) and "Dye Handbook" (edited by the Organic Synthetic Chemistry Association), such as C.I. I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124;C. I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C. I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; C. I. Disperse Violet 43;C. I. Disperse Blue 96;C. I. Fluorescent Brightening Agents 112, 135 and 163; C. I. Solvent Orange 2 and 45; C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; C. I. Pigment Green 10;C. I. Pigment Brown 2 etc. can be suitably used. The above-mentioned light absorbing agent is usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist under film forming composition.

The rheology modifier mainly improves the fluidity of the resist underlayer film forming composition, and improves the uniformity of the resist underlayer film thickness and the filling ability of the resist underlayer film forming composition into the holes, especially in the baking process. It is added for the purpose of enhancing. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butylisodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; Examples include maleic acid derivatives such as normal butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; and stearic acid derivatives such as normal butyl stearate and glyceryl stearate. can. These rheology modifiers are usually blended in a proportion of less than 30% by mass based on the total solid content of the resist underfilm forming composition.

The adhesion auxiliary agent is added mainly for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film forming composition, and particularly for preventing the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, and phenyltriethoxy. Alkoxysilanes such as silane, silazane such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, methyloltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyl Silanes such as triethoxysilane, γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, Examples include heterocyclic compounds such as mercaptoimidazole and mercaptopyrimidine, urea such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion aids are generally blended in an amount of less than 5% by mass, preferably less than 2% by mass, based on the total solid content of the resist underfilm forming composition.

The solid content of the resist underlayer film forming composition according to the present invention is generally 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the content of all components in the resist underlayer film forming composition excluding the solvent. The proportion of the reaction product in the solid content is preferably in the order of 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

One of the measures to evaluate whether the resist underlayer film forming composition is in a uniform solution state is to observe the permeability of a specific microfilter, and the resist underlayer film forming composition according to the present invention , it passes through a microfilter with a pore size of 0.1 μm and presents a uniform solution state.

The above-mentioned microfilter materials include fluororesins such as PTFE (polytetrafluoroethylene), PFA (tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra high molecular weight polyethylene), PP ( Although examples thereof include polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, it is preferably made of PTFE (polytetrafluoroethylene).

[Method for manufacturing resist lower layer film and semiconductor device]
Hereinafter, a method for manufacturing a resist underlayer film and a semiconductor device using the resist underlayer film forming composition according to the present invention will be described.

Substrates used in the manufacture of semiconductor devices (e.g. silicon wafer substrates, silicon/silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low dielectric constant material (low-k material) coated substrates) etc.), the resist underlayer film forming composition of the present invention is applied by a suitable coating method such as a spinner or coater, and then baked to form a resist underlayer film. The firing conditions are appropriately selected from among a firing temperature of 80° C. to 250° C. and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 250°C and the firing time is 0.5 to 2 minutes. Here, the thickness of the lower layer film to be formed is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 300 nm, or 50 to 200 nm.

Furthermore, an inorganic resist underlayer film (hard mask) can also be formed on the organic resist underlayer film according to the present invention. For example, in addition to the method of forming a silicon-containing resist underlayer film (inorganic resist underlayer film) forming composition by spin coating as described in WO2009/104552A1, a Si-based inorganic material film can be formed by a CVD method or the like.

Furthermore, by applying the resist underlayer film forming composition according to the present invention onto a semiconductor substrate having a portion with a step and a portion without a step (a so-called step substrate) and baking it, It is possible to form a resist underlayer film having a level difference between 3 and 50 nm from a portion without a level difference.

A resist film, such as a layer of photoresist, is then formed on the resist underlayer film. Formation of the photoresist layer can be performed by a well-known method, that is, by applying a photoresist composition solution onto the underlying film and baking. The film thickness of the photoresist is, for example, 50 to 10,000 nm, 100 to 2,000 nm, or 200 to 1,000 nm.

The photoresist formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative photoresists and positive photoresists can be used. A positive photoresist consisting of a novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist consisting of a binder having a group that decomposes with acid and increases the rate of alkali dissolution, and a photoacid generator; A chemically amplified photoresist comprising a low molecular weight compound that decomposes to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a binder having a group that decomposes with an acid to increase the alkali dissolution rate. There are chemically amplified photoresists that are made of a photoacid generator and a low-molecular compound that decomposes with acid to increase the alkali dissolution rate of the photoresist. For example, the product name APEX-E manufactured by Shipley, the product name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and the product name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. may be mentioned. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. Examples include fluorine-containing atom polymer photoresists such as those described in 3999, 365-374 (2000).

Next, a resist pattern is formed by irradiation with light or electron beam and development. First, exposure is performed through a predetermined mask. Near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (for example, EUV (wavelength 13.5 nm)), etc. are used for exposure. Specifically, a KrF excimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength: 193 nm), an F ₂ excimer laser (wavelength: 157 nm), etc. can be used. Among these, ArF excimer laser (wavelength: 193 nm) and EUV (wavelength: 13.5 nm) are preferred. After exposure, post-exposure bake can be performed as needed. The post-exposure heating is performed under conditions appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 to 10 minutes.

Further, in the present invention, a resist for electron beam lithography can be used as the resist instead of a photoresist. Both negative and positive types can be used as electron beam resists. A chemically amplified resist consisting of an acid generator and a binder having a group that decomposes with acid to change the alkali dissolution rate, an alkali-soluble binder, an acid generator, and a low molecular compound that decomposes with acid to change the alkali dissolution rate of the resist. A chemically amplified resist consisting of an acid generator, a binder having a group that decomposes with acid to change the alkali dissolution rate, and a low molecular compound that decomposes with acid to change the alkali dissolution rate of the resist. There are non-chemically amplified resists made of binders that have groups that are decomposed by electron beams to change the alkali dissolution rate, and non-chemically amplified resists that are made of binders that have groups that are cleaved by electron beams to change the alkali dissolution rate. Even when these electron beam resists are used, a resist pattern can be formed in the same manner as when a photoresist is used with an electron beam as the irradiation source.

Next, development is performed using a developer. In this way, for example, if a positive photoresist is used, the exposed portions of the photoresist are removed and a photoresist pattern is formed.
Examples of developing solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, ethanolamine, propylamine, Examples include alkaline aqueous solutions such as amine aqueous solutions such as ethylenediamine. Furthermore, surfactants and the like can also be added to these developers. The conditions for development are appropriately selected from a temperature of 5 to 50° C. and a time of 10 to 600 seconds.

Then, the inorganic lower layer film (intermediate layer) is removed using the pattern of the photoresist (upper layer) formed in this way as a protective film, and then the patterned photoresist and the inorganic lower layer film (intermediate layer) are removed. The organic underlayer film (lower layer) is removed using the film as a protective film. Finally, the semiconductor substrate is processed using the patterned inorganic lower layer film (intermediate layer) and organic lower layer film (lower layer) as protective films.

First, the inorganic lower film (intermediate layer) in the area where the photoresist has been removed is removed by dry etching to expose the semiconductor substrate. For dry etching of the inorganic underlayer film, tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, and Gases such as sulfur fluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used. It is preferable to use a halogen-based gas, and more preferably a fluorine-based gas, for dry etching the inorganic underlayer film. Examples of fluorine-based gases include tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, and difluoromethane (CH ₂ F ₂ ). Can be mentioned.

Thereafter, the organic underlayer film is removed using the patterned photoresist and the inorganic underlayer film as a protective film. The organic lower layer film (lower layer) is preferably etched by dry etching using an oxygen-based gas. This is because an inorganic lower layer film containing many silicon atoms is difficult to remove by dry etching using an oxygen-based gas.

Finally, the semiconductor substrate is processed. Preferably, the semiconductor substrate is processed by dry etching using a fluorine-based gas.
Examples of fluorine-based gases include tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, and difluoromethane (CH ₂ F ₂ ). Can be mentioned.

Furthermore, an organic antireflection film can be formed on the resist underlayer film before forming the photoresist. The antireflection coating composition used therein is not particularly limited and can be arbitrarily selected from those conventionally used in lithography processes. The antireflection film can be formed by coating with a coater and baking.

In the present invention, after forming an organic lower layer film on a substrate, an inorganic lower layer film can be formed thereon, and then a photoresist can be further coated thereon. As a result, the pattern width of the photoresist becomes narrower, and even if the photoresist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, it is possible to process the resist underlayer film using a fluorine-based gas that has a sufficiently fast etching rate for photoresist, and it is also possible to process the resist underlayer film using a fluorine-based gas that has a sufficiently fast etching rate for inorganic underlayer films. It is possible to process the substrate as a gas, and furthermore, it is possible to process the substrate using an oxygen-based gas as the etching gas, which has a sufficiently high etching rate for the organic underlayer film.

The resist underlayer film formed from the resist underlayer film forming composition may also absorb light depending on the wavelength of the light used in the lithography process. In such a case, it can function as an antireflection film that has the effect of preventing reflected light from the substrate. Furthermore, the underlayer film formed from the resist underlayer film forming composition of the present invention can also function as a hard mask. The lower layer film of the present invention has a layer for preventing interaction between the substrate and the photoresist, and a function of preventing the material used for the photoresist or the substance generated during exposure of the photoresist from having an adverse effect on the substrate. It can also be used as a layer, a layer that has the function of preventing substances generated from the substrate during heating and baking from diffusing into the upper photoresist layer, and a barrier layer to reduce the poisoning effect of the photoresist layer by the semiconductor substrate dielectric layer. It is possible.

Further, the lower layer film formed from the resist lower layer film forming composition can be applied to a substrate in which a via hole is formed, which is used in a dual damascene process, and can be used as a filling material that can fill the hole without any gaps. Moreover, it can also be used as a planarizing material for planarizing the surface of a semiconductor substrate having unevenness.

Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

The weight average molecular weights of the polymers shown in the synthesis examples below in this specification are the results of measurements by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows.
GPC column: Shodex [registered trademark] / Asahipak [registered trademark] (Showa Denko (
KK))
Column temperature: 40℃
Solvent: Tetrahydrofuran (THF)
Flow rate: 0.35ml/min
Standard sample: Polystyrene (Tosoh Corporation)

冷却管、温度計及び攪拌機を備えた１Ｌフラスコにジグリコール酸５０．０１ｇ（東京化成工業（株）製）、炭酸カリウム１２８．８１ｇ（０．８９ｍｏｌ，関東化学，特級）、アセトン３５０．０ｇを入れて５℃以下に冷却し、臭化アリル１３５．３３ｇ（１．１２ｍｏｌ，東京化成工業（株）製）を滴下した。その後、５５℃に昇温して２３時間撹拌した後、室温まで冷却し、不溶物をろ過してアセトン５０．０ｇで２回洗浄した。ろ液を減圧下４０℃にて溶媒を留去し、濃縮物にジクロロメタン２５０．０ｇ及び純水２５０．０ｇを加えて分液した。さらに有機層を純水２５０．０ｇで２回水洗した後、有機層を減圧下４０℃にて溶媒を留去して、上記式（Ａ）で表される化合物を薄黄色の液体として２４．４７ｇで得た（収率３０．６％）。この化合物の^１Ｈ－ＮＭＲスペクトル（５００ＭＨｚ，Ａｃｅｔｏｎｅ－ｄ６）におけるδ値は下記のとおりであった。
６．００（ｍ，２Ｈ），５．３８（ｄｄ，２Ｈ），５．２６（ｓ，２Ｈ），４．６８（ｄ，４Ｈ），４．３２（ｓ，４Ｈ）(Synthesis of raw material monomer)
<Synthesis example 1>
(Synthesis of diallyl-2,2'-oxydiacetate)

In a 1 L flask equipped with a cooling tube, a thermometer, and a stirrer, 50.01 g of diglycolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 128.81 g of potassium carbonate (0.89 mol, Kanto Kagaku, special grade), and 350.0 g of acetone were added. The mixture was cooled to below 5° C., and 135.33 g (1.12 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of allyl bromide was added dropwise. Thereafter, the temperature was raised to 55° C. and stirred for 23 hours, then cooled to room temperature, insoluble matter was filtered and washed twice with 50.0 g of acetone. The solvent of the filtrate was distilled off at 40° C. under reduced pressure, and 250.0 g of dichloromethane and 250.0 g of pure water were added to the concentrate to separate the layers. Furthermore, after washing the organic layer twice with 250.0 g of pure water, the solvent was distilled off from the organic layer at 40° C. under reduced pressure to obtain the compound represented by the above formula (A) as a pale yellow liquid.24. Obtained in 47 g (yield 30.6%). The δ value of this compound in the ¹ H-NMR spectrum (500 MHz, Acetone-d6) was as follows.
6.00 (m, 2H), 5.38 (dd, 2H), 5.26 (s, 2H), 4.68 (d, 4H), 4.32 (s, 4H)

温度計及び攪拌機を備えた５００ｍＬフラスコに、合成例１で得たジアリル－２，２’－オキシジアセテート２３．０１ｇ（０．１１ｍｏｌ）、クロロホルム２３０．０ｇを入れて５℃以下に冷却し、３－クロロ過安息香酸６８．４１ｇ（０．２６ｍｏｌ，東京化成工業（株）製，３５％含水品）を徐々に添加した。その後、２５℃に昇温して９１．５時間撹拌した。反応混合物をクロロホルム２３０．０ｇで希釈し、５％炭酸水素ナトリウム水溶液４６０．０ｇを加えて分液した。さらに、有機層を１０％亜硫酸水素ナトリウム水溶液４６０．０ｇ、５％炭酸水素ナトリウム水溶液４６０．０ｇ、純水４６０．０ｇで分液した後、有機層を減圧下４０℃にて溶媒を留去して、上記式（Ｂ）で表されるジグリシジル－２，２’－オキシジアセテートを白色固体として１７．６３ｇで得た（収率６６．７％）。この化合物の^１Ｈ－ＮＭＲスペクトル（５００ＭＨｚ，ＤＭＳＯ－ｄ６）におけるδ値は下記のとおりであった。
４．４６（ｄｄ，２Ｈ），４．３０（ｓ，４Ｈ），３．８８（ｄｄ，２Ｈ），３．２１（ｍ，２Ｈ），２．７９（ｄｄ，２Ｈ），２．６５（ｄｄ，２Ｈ）<Synthesis example 2>
(Synthesis of diglycidyl-2,2'-oxydiacetate) (DG-DGA)

23.01 g (0.11 mol) of diallyl-2,2'-oxydiacetate obtained in Synthesis Example 1 and 230.0 g of chloroform were placed in a 500 mL flask equipped with a thermometer and a stirrer, and cooled to below 5°C. 68.41 g (0.26 mol, manufactured by Tokyo Kasei Kogyo Co., Ltd., 35% water content) of 3-chloroperbenzoic acid was gradually added. Thereafter, the temperature was raised to 25° C. and stirred for 91.5 hours. The reaction mixture was diluted with 230.0 g of chloroform, and 460.0 g of 5% aqueous sodium hydrogen carbonate solution was added to separate the layers. Furthermore, after separating the organic layer with 460.0 g of a 10% aqueous sodium bisulfite solution, 460.0 g of a 5% aqueous sodium bicarbonate solution, and 460.0 g of pure water, the solvent was distilled off from the organic layer at 40°C under reduced pressure. Thus, 17.63 g of diglycidyl-2,2'-oxydiacetate represented by the above formula (B) was obtained as a white solid (yield: 66.7%). The δ value in the ¹ H-NMR spectrum (500 MHz, DMSO-d6) of this compound was as follows.
4.46 (dd, 2H), 4.30 (s, 4H), 3.88 (dd, 2H), 3.21 (m, 2H), 2.79 (dd, 2H), 2.65 (dd , 2H)

温度計及び攪拌機を備えた５００ｍＬフラスコに、２，２’－チオジグリコール酸３０．０１ｇ（東京化成工業（株）製）、テトラヒドロフラン９０．０ｇ（関東化学，特級）を入れ、５℃に冷却してピリジン３２．４０ｇ（０．４１ｍｏｌ，関東化学，脱水）を添加した。ここにジシクロヘキシルカルボジイミド８２．４４ｇ（０．４０ｍｏｌ，関東化学，鹿特級）をＴＨＦ６０．０ｇに溶解させた溶液を滴下して１時間撹拌した。その後、グリシドール（０．４０ｍｏｌ，Ａｌｄｒｉｃｈ製）をＴＨＦ３０．０ｇに溶解させた溶液を滴下し、２３℃に昇温して２０時間撹拌した。反応混合物をＴＨＦ１２０．０ｇで希釈し、不溶物をろ過してＴＨＦ３０．０ｇで２回洗浄した。ろ液を減圧下３０℃にて溶媒を留去し、濃縮物に酢酸エチル３００．０ｇを加えて、不溶物をろ過して、酢酸エチル１５．０ｇで２回洗浄した。ここへ純水３００．０ｇを加えて分液し、さらに有機層を純水３００．０ｇで２回水洗した後、減圧下３０℃にて溶媒を留去した。得られた残留物をシリカゲルカラムクロマトグラフィー（酢酸エチル／ｎ－ヘプタン＝３／２→４／１（容量比））にて精製して、上記式（Ｃ）で表される化合物を白色固体として２０．６７ｇで得た（収率３９．４％）。この化合物の^１Ｈ－ＮＭＲスペクトル（５００ＭＨｚ，ＤＭＳＯ－ｄ６）におけるδ値は下記のとおりであった。
４．４３（ｄｄ，２Ｈ），３．８７（ｄｄ，２Ｈ），３．５３（ｓ，４Ｈ），３．２１（ｍ，２Ｈ），２．７９（ｄｄ，２Ｈ），２．６６（ｄｄ，２Ｈ）<Synthesis example 3>
(Synthesis of diglycidyl-2,2'-thiodiacetate) (DG-TDGA)

30.01 g of 2,2'-thiodiglycolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 90.0 g of tetrahydrofuran (Kanto Kagaku, special grade) were placed in a 500 mL flask equipped with a thermometer and a stirrer, and the mixture was cooled to 5°C. Then, 32.40 g (0.41 mol, Kanto Kagaku, Dehydrated) of pyridine was added. A solution of 82.44 g (0.40 mol, Kanto Kagaku, Shika Special Grade) of dicyclohexylcarbodiimide dissolved in 60.0 g of THF was added dropwise thereto, and the mixture was stirred for 1 hour. Thereafter, a solution of glycidol (0.40 mol, manufactured by Aldrich) dissolved in 30.0 g of THF was added dropwise, the temperature was raised to 23° C., and the mixture was stirred for 20 hours. The reaction mixture was diluted with 120.0 g of THF, and insoluble matter was filtered and washed twice with 30.0 g of THF. The solvent of the filtrate was distilled off at 30° C. under reduced pressure, 300.0 g of ethyl acetate was added to the concentrate, insoluble materials were filtered out, and the mixture was washed twice with 15.0 g of ethyl acetate. 300.0 g of pure water was added to separate the layers, and the organic layer was washed twice with 300.0 g of pure water, and then the solvent was distilled off at 30° C. under reduced pressure. The obtained residue was purified by silica gel column chromatography (ethyl acetate/n-heptane = 3/2 → 4/1 (volume ratio)) to obtain the compound represented by the above formula (C) as a white solid. Obtained in an amount of 20.67 g (yield 39.4%). The δ value in the ¹ H-NMR spectrum (500 MHz, DMSO-d6) of this compound was as follows.
4.43 (dd, 2H), 3.87 (dd, 2H), 3.53 (s, 4H), 3.21 (m, 2H), 2.79 (dd, 2H), 2.66 (dd , 2H)

温度計及び攪拌機を備えた２００ｍＬフラスコに合成例３で得たジグリシジル－２，２’－チオジアセテート８．０１ｇ、クロロホルム８０．０ｇを入れて５℃以下に冷却し、３－クロロ過安息香酸１９．４３ｇ（０．２６ｍｏｌ，東京化成工業（株）製）を徐々に添加した。その後、２３℃に昇温して４．５時間撹拌した。反応混合物をクロロホルム８０．０ｇで希釈し、５％炭酸水素ナトリウム水溶液１６０．０ｇを加えて分液した。さらに、有機層を１０％亜硫酸水素ナトリウム水溶液１６０．０ｇ、５％炭酸水素ナトリウム水溶液１６０．０ｇ、純水１６０．０ｇで分液した後、有機層を減圧下３０℃にて溶媒を留去して、上記式（Ｄ）で表される化合物を白色固体として４．３６ｇで得た（収率４８．６％）。この化合物の^１Ｈ－ＮＭＲスペクトル（５００ＭＨｚ，ＤＭＳＯ－ｄ６）におけるδ値は下記のとおりであった。
４．６５（ｓ，４Ｈ），４．５２（ｄｄ，２Ｈ），３．９８（ｄｄ，２Ｈ），３．２４（ｍ，２Ｈ），２．８１（ｄｄ，２Ｈ），２．７０（ｄｄ，２Ｈ）<Synthesis example 4>
(Synthesis of diglycidyl-2,2'-sulfonyl diacetate) (DG-SDGA)

8.01 g of diglycidyl-2,2'-thiodiacetate obtained in Synthesis Example 3 and 80.0 g of chloroform were placed in a 200 mL flask equipped with a thermometer and a stirrer, cooled to below 5°C, and 3-chloroperbenzoic acid was added. 19.43 g (0.26 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added. Thereafter, the temperature was raised to 23°C and stirred for 4.5 hours. The reaction mixture was diluted with 80.0 g of chloroform, and 160.0 g of 5% aqueous sodium hydrogen carbonate solution was added to separate the layers. Furthermore, after separating the organic layer with 160.0 g of a 10% aqueous sodium bisulfite solution, 160.0 g of a 5% aqueous sodium bicarbonate solution, and 160.0 g of pure water, the solvent was distilled off from the organic layer at 30°C under reduced pressure. Thus, 4.36 g of the compound represented by the above formula (D) was obtained as a white solid (yield: 48.6%). The δ value in the ¹ H-NMR spectrum (500 MHz, DMSO-d6) of this compound was as follows.
4.65 (s, 4H), 4.52 (dd, 2H), 3.98 (dd, 2H), 3.24 (m, 2H), 2.81 (dd, 2H), 2.70 (dd , 2H)

２００ｍｌ四ッ口フラスコに、グリシドール４．５ｇ、塩化メチレン１１．５５ｇ、１－（３－ジメチルアミノプロピル）－３－エチルカルボジイミド塩酸塩２０ｇを仕込み、氷浴下、マグネチックスターラーで攪拌しながら、ジチオジグリコール酸５ｇをテトラヒドロフラン１０ｇに溶解させた溶液を３分間掛けて滴下した後、４－ジメチルアミノピリジン０．０３５ｇを添加し、室温にて、２時間攪拌した。次に、反応液を酢酸エチル約１００ｇで希釈し、有機層を純水約５０ｇで４回洗浄した後、有機層をエバポレータにて減圧濃縮した。続いて、濃縮物を酢酸エチル約２０ｇで希釈し、シリカゲルのショートカラムを行った後、溶出液をエバポレータにて減圧濃縮し、上記式（Ｅ）で表される化合物を３．２４ｇを得た（収率：４０％）。この化合物の^１Ｈ－ＮＭＲスペクトル（３００ＭＨｚ，ＤＭＳＯ－ｄ６）におけるδ値は下記のとおりであった。
^１Ｈ―ＮＭＲ（３００ＭＨｚ） ｉｎ ＤＭＳＯ―ｄ６：２．６６ｐｐｍ（ｍ，２Ｈ），２．７９ｐｐｍ（ｄｄ，Ｊ＝５．３Ｈｚ，Ｊ＝４．８Ｈｚ，２Ｈ），３．２１ｐｐｍ（ｍ，２Ｈ），３．８０ｐｐｍ（ｓ，４Ｈ），３．８９ｐｐｍ（ｄｄ，Ｊ＝１２．６Ｈｚ，Ｊ＝ ６．６Ｈｚ，２Ｈ），４．４３ｐｐｍ（ｄｄ，Ｊ＝１２．６Ｈｚ，Ｊ＝２．７Ｈｚ，２Ｈ）<Synthesis example 5>
(Synthesis of diglycidyl-2,2'-dithiodiacetate) (DG-DTDGA)

In a 200 ml four-necked flask, 4.5 g of glycidol, 11.55 g of methylene chloride, and 20 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride were charged, and while stirring with a magnetic stirrer under an ice bath, A solution of 5 g of dithiodiglycolic acid dissolved in 10 g of tetrahydrofuran was added dropwise over 3 minutes, and then 0.035 g of 4-dimethylaminopyridine was added and stirred at room temperature for 2 hours. Next, the reaction solution was diluted with about 100 g of ethyl acetate, the organic layer was washed four times with about 50 g of pure water, and then the organic layer was concentrated under reduced pressure using an evaporator. Subsequently, the concentrate was diluted with about 20 g of ethyl acetate and subjected to a short silica gel column, and the eluate was concentrated under reduced pressure using an evaporator to obtain 3.24 g of the compound represented by the above formula (E). (Yield: 40%). The δ value in the ¹ H-NMR spectrum (300 MHz, DMSO-d6) of this compound was as follows.
¹ H-NMR (300MHz) in DMSO-d6: 2.66ppm (m, 2H), 2.79ppm (dd, J = 5.3Hz, J = 4.8Hz, 2H), 3.21ppm (m, 2H) , 3.80ppm (s, 4H), 3.89ppm (dd, J = 12.6Hz, J = 6.6Hz, 2H), 4.43ppm (dd, J = 12.6Hz, J = 2.7Hz, 2H )

化合物２（ＤＧ－ＤＧＡ）２．５０ｇと３，３’－ジチオジプロピオン酸（堺化学工業（株）、商品名：ＤＴＤＰＡ）２．４０ｇ、及び触媒として第４級ホスホニウム塩であるテトラブチルホスホニウムブロミド０．１２ｇを、プロピレングリコールモノメチルエーテル２０．０７ｇに溶解させた後、１０５℃に加温し、窒素雰囲気下で２４時間撹拌し樹脂化合物の溶液を得た。得られた樹脂のＧＰＣ分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は約１７００であった。(Synthesis of polymer)
<Synthesis Example 6> (DG-DGA polymer)

2.50 g of compound 2 (DG-DGA), 2.40 g of 3,3'-dithiodipropionic acid (Sakai Chemical Industries, Ltd., trade name: DTDPA), and tetrabutylphosphonium, which is a quaternary phosphonium salt, as a catalyst. After 0.12 g of bromide was dissolved in 20.07 g of propylene glycol monomethyl ether, it was heated to 105° C. and stirred for 24 hours under a nitrogen atmosphere to obtain a solution of the resin compound. GPC analysis of the obtained resin revealed that the weight average molecular weight was approximately 1700 in terms of standard polystyrene.

化合物３（ＤＧ－ＴＤＧＡ）２．３０ｇと３，３’－ジチオジプロピオン酸（堺化学工業（株）、商品名：ＤＴＤＰＡ）２．２６ｇ、及び触媒として第４級ホスホニウム塩であるテトラブチルホスホニウムブロミド０．１７ｇを、プロピレングリコールモノメチルエーテル１８．８９ｇに溶解させた後、１０５℃に加温し、窒素雰囲気下で２４時間撹拌し樹脂化合物の溶液を得た。得られた樹脂のＧＰＣ分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は約２３００であった。<Synthesis Example 7> (DG-TDGA polymer)

2.30 g of compound 3 (DG-TDGA), 2.26 g of 3,3'-dithiodipropionic acid (Sakai Chemical Industries, Ltd., trade name: DTDPA), and tetrabutylphosphonium, which is a quaternary phosphonium salt, as a catalyst. After 0.17 g of bromide was dissolved in 18.89 g of propylene glycol monomethyl ether, the solution was heated to 105° C. and stirred for 24 hours under a nitrogen atmosphere to obtain a solution of the resin compound. GPC analysis of the obtained resin revealed that the weight average molecular weight was approximately 2300 in terms of standard polystyrene.

化合物４（ＤＧ－ＳＤＧＡ）２．５０ｇと３，３’－ジチオジプロピオン酸（堺化学工業（株）、商品名：ＤＴＤＰＡ）２．１１ｇ、及び触媒として第４級ホスホニウム塩であるテトラブチルホスホニウムブロミド０．１６ｇを、プロピレングリコールモノメチルエーテル１９．０６ｇに溶解させた後、１０５℃に加温し、窒素雰囲気下で２４時間撹拌し樹脂化合物の溶液を得た。得られた樹脂のＧＰＣ分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は約１０００であった。<Synthesis Example 8> (DG-SDGA polymer)

2.50 g of compound 4 (DG-SDGA), 2.11 g of 3,3'-dithiodipropionic acid (Sakai Chemical Industry Co., Ltd., trade name: DTDPA), and tetrabutylphosphonium, which is a quaternary phosphonium salt, as a catalyst. After dissolving 0.16 g of bromide in 19.06 g of propylene glycol monomethyl ether, the solution was heated to 105° C. and stirred for 24 hours under a nitrogen atmosphere to obtain a solution of the resin compound. GPC analysis of the obtained resin revealed that the weight average molecular weight was approximately 1000 in terms of standard polystyrene.

化合物５（ＤＧ－ＤＴＤＧＡ）２．５０ｇと３，３’－ジチオジプロピオン酸（堺化学工業（株）、商品名：ＤＴＤＰＡ）１．７３ｇ、及び触媒として第４級ホスホニウム塩であるテトラブチルホスホニウムブロミド０．１３ｇを、プロピレングリコールモノメチルエーテル１７．３６ｇに溶解させた後、１０５℃に加温し、窒素雰囲気下で２４時間撹拌し樹脂化合物の溶液を得た。得られた樹脂のＧＰＣ分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は約２４００であった。<Synthesis Example 9> (DG-DTDGA polymer)

2.50 g of compound 5 (DG-DTDGA), 1.73 g of 3,3'-dithiodipropionic acid (Sakai Chemical Industry Co., Ltd., trade name: DTDPA), and tetrabutylphosphonium, which is a quaternary phosphonium salt, as a catalyst. After 0.13 g of bromide was dissolved in 17.36 g of propylene glycol monomethyl ether, it was heated to 105° C. and stirred for 24 hours under a nitrogen atmosphere to obtain a solution of the resin compound. GPC analysis of the obtained resin revealed that the weight average molecular weight was approximately 2400 in terms of standard polystyrene.

化合物５（ＤＧ－ＤＴＤＧＡ）２．００ｇとメチルジカルボキシメチルイソシアヌル酸（四国化成工業（株）、商品名：ＭｅＣＩＣ－１）２．３６ｇ、及び触媒として第４級ホスホニウム塩であるテトラブチルホスホニウムブロミド０．０７ｇを、プロピレングリコールモノメチルエーテル１７．７３ｇに溶解させた後、１０５℃に加温し、窒素雰囲気下で２４時間撹拌し樹脂化合物の溶液を得た。得られた樹脂のＧＰＣ分析を行ったところ、標準ポリスチレン換算にて重量平均分子量は約１６００であった。<Synthesis Example 10> (DG-DTDGA polymer (ii))

2.00 g of compound 5 (DG-DTDGA), 2.36 g of methyldicarboxymethylisocyanuric acid (Shikoku Kasei Kogyo Co., Ltd., trade name: MeCIC-1), and tetrabutylphosphonium bromide, which is a quaternary phosphonium salt, as a catalyst. After dissolving 0.07 g in 17.73 g of propylene glycol monomethyl ether, it was heated to 105° C. and stirred for 24 hours under a nitrogen atmosphere to obtain a solution of the resin compound. GPC analysis of the obtained resin revealed that the weight average molecular weight was approximately 1,600 in terms of standard polystyrene.

(Composition preparation)
[Example 1]
To 2.650 g of a solution containing 0.424 g of the reaction product (DG-DGA polymer) obtained in Synthesis Example 6, 7.334 g of propylene glycol monomethyl ether and 0.0 g of pyridinium trifluoromethanesulfonic acid (Tokyo Kasei Kogyo Co., Ltd.) were added. 016 g and 0.001 g of a surfactant (Dainippon Ink & Chemicals Co., Ltd., trade name: R-40) were added to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 2]
To 2.924 g of a solution containing 0.482 g of the reaction product (DG-TDGA polymer) obtained in Synthesis Example 7, 7.057 g of propylene glycol monomethyl ether and 0.0 g of pyridinium trifluoromethanesulfonic acid (Tokyo Kasei Kogyo Co., Ltd.) were added. 018 g and 0.001 g of a surfactant (Dainippon Ink & Chemicals Co., Ltd., trade name: R-40) were added to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 3]
To 2.486 g of a solution containing 0.482 g of the reaction product (DG-SDGA polymer) obtained in Synthesis Example 8, 7.496 g of propylene glycol monomethyl ether and 0.0 g of pyridinium trifluoromethanesulfonic acid (Tokyo Kasei Kogyo Co., Ltd.) were added. 018 g and 0.001 g of a surfactant (Dainippon Ink & Chemicals Co., Ltd., trade name: R-40) were added to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 4]
To 2.486 g of a solution containing 0.482 g of the reaction product (DG-DTDGA polymer) obtained in Synthesis Example 9, 7.496 g of propylene glycol monomethyl ether and 0.0 g of pyridinium trifluoromethanesulfonic acid (Tokyo Kasei Kogyo Co., Ltd.) were added. 018 g and 0.001 g of a surfactant (Dainippon Ink & Chemicals Co., Ltd., trade name: R-40) were added to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 5]
To 2.486 g of a solution containing 0.482 g of the reaction product (DG-DTDGA polymer (ii)) obtained in Synthesis Example 10, 7.496 g of propylene glycol monomethyl ether and pyridinium trifluoromethanesulfonic acid (Tokyo Kasei Kogyo Co., Ltd.) were added. ) and 0.001 g of a surfactant (Dainippon Ink & Chemicals Co., Ltd., trade name: R-40) were added to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 6]
To 2.211 g of a solution containing 0.357 g of the reaction product (DG-DTDGA polymer (ii)) obtained in Synthesis Example 10, 7.689 g of propylene glycol monomethyl ether and tetramethoxymethyl glycoluril (Japan Cytec Industries Co., Ltd.) were added. , trade name: POWDERLINK [registered trademark] 1174) 0.089 g, pyridinium-p-phenolsulfonic acid 0.013 g, and surfactant (Dainippon Ink & Chemicals Co., Ltd., trade name: R-40) 0.001 g was added to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Comparative example 1]
To 3.580 g of a solution containing 0.723 g of the reaction product obtained by the method described in Synthesis Example 1 of WO2009/096340, 88.431 g of propylene glycol monomethyl ether, 9.906 g of propylene glycol monomethyl ether acetate, and tetramethoxymethyl glycol were added. Uril (Japan Cytec Industries Co., Ltd., trade name: POWDERLINK [registered trademark] 1174) 0.181g, p-phenolsulfonic acid (Tokyo Kasei Kogyo Co., Ltd.), bisphenol S (Tokyo Kasei Kogyo Co., Ltd.) 0.011g , and 0.007 g of a surfactant (Dainippon Ink & Chemicals Co., Ltd., trade name: R-40) were added to form a solution. Thereafter, it was filtered using a polyethylene microfilter with a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

(Measurement of dry etching speed)
The resist underlayer film forming compositions prepared in Examples 1 to 6 and Comparative Example 1 were each applied onto a silicon wafer using a spinner, and baked on a hot plate at 205° C. for 1 minute to give a film thickness of 100 nm. A resist underlayer film was formed. The dry etching rate (amount of decrease in film thickness per unit time) was measured using a dry etching apparatus (RIE-10NR) manufactured by Samco Co., Ltd. under the conditions of using CF ₄ and N ₂ as dry etching gases. . Tables 1 and 2 show the etching selectivity of each underlayer film, assuming that the etching selectivity of the resist underlayer film obtained from Comparative Example 1 is 1.00.

From the above results, it can be seen that Examples 1 to 6 have sufficiently higher etching selectivity than Comparative Example 1. As a result, the composition for forming a resist underlayer film obtained by the present invention can shorten the etching time during dry etching of the resist underlayer film, and the resist film thickness can be reduced when the resist underlayer film is removed by dry etching. Undesirable phenomena that occur can be suppressed. Furthermore, being able to shorten the dry etching time is particularly useful as a resist underlayer film, since undesirable etching damage to the underlying substrate of the resist underlayer film can be suppressed.

The resist underlayer film forming composition according to the present invention provides a resist underlayer film having a particularly high dry etching rate.

Claims (13)

An epoxy adduct-forming compound and the following formula (1):

[In formula (1), A ¹ is a carbon atom in which at least one hydrogen atom may be substituted with a halogen atom and is interrupted by an oxygen atom, a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group, or an imino group representing a linear or branched alkylene group of numbers 2 to 10, and a solvent, and the epoxy adduct-forming compound is a carboxylic acid-containing compound, a carboxylic acid anhydride, and a solvent. 1. A resist underlayer film-forming composition, which is at least one compound selected from the group consisting of compounds containing compounds, compounds containing hydroxy groups, compounds containing thiol groups, and compounds containing amino groups. The resist underlayer film forming composition according to claim 1, wherein the epoxy adduct-forming compound is a carboxylic acid-containing compound or a thiol group-containing compound. The resist underlayer film forming composition according to claim 2, wherein the carboxylic acid-containing compound is a dicarboxylic acid containing at least one sulfur atom. The resist underlayer film forming composition according to claim 3, wherein the dicarboxylic acid containing at least one sulfur atom is an aliphatic dicarboxylic acid containing at least one sulfur atom. The resist underlayer film forming composition according to any one of claims 1 to 4, further comprising a crosslinking catalyst. The resist underlayer film forming composition according to any one of claims 1 to 5, further comprising a crosslinking agent. The resist underlayer film forming composition according to any one of claims 1 to 6, further comprising a surfactant. A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film forming composition according to any one of claims 1 to 7. a step of applying the resist underlayer film forming composition according to any one of claims 1 to 7 on a semiconductor substrate and baking it to form a resist underlayer film; applying a resist on the resist underlayer film; Manufacturing a patterned substrate, including a step of baking to form a resist film, a step of exposing the resist underlayer film and the semiconductor substrate covered with the resist, and a step of developing and patterning the resist film after exposure. Method. forming a resist underlayer film comprising the resist underlayer film forming composition according to any one of claims 1 to 7 on a semiconductor substrate;
forming a resist film on the resist underlayer film;
forming a resist pattern by irradiating the resist film with light or electron beam and subsequent development;
forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern;
processing a semiconductor substrate using the patterned resist underlayer film;
A method for manufacturing a semiconductor device, the method comprising: The following formula (1):

(In formula (1), A ¹ represents a straight chain or branched alkylene group having 2 to 10 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom and is interrupted by a disulfide group, carbonyl group, or imino group. Compound. The following formula (1):

[In formula (1), A ¹ represents a straight chain or branched alkylene group having 2 to 10 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom and is interrupted by a disulfide group, carbonyl group, or imino group] and,
Reaction product with at least one epoxy adduct-forming compound selected from the group consisting of carboxylic acid-containing compounds, carboxylic anhydride-containing compounds, hydroxy group-containing compounds, thiol group-containing compounds, amino group-containing compounds, and imide group-containing compounds. thing. The following formula (1):

[In formula (1), A ¹ represents a straight chain or branched alkylene group having 2 to 10 carbon atoms, in which at least one hydrogen atom may be substituted with a halogen atom and is interrupted by a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group or an imino group. ] and a compound represented by
A reaction product with at least one epoxy adduct-forming compound selected from the group consisting of carboxylic acid-containing compounds, carboxylic anhydride-containing compounds, hydroxy group-containing compounds, thiol group-containing compounds, and imide group-containing compounds.