JPWO2020022086A1 - Resist underlayer film forming composition containing a hetero atom in the polymer main chain - Google Patents

Abstract

In particular, a resist underlayer film having a high dry etching rate, the resist underlayer film forming composition, a resist pattern forming method, and a method for manufacturing a semiconductor device are provided. The epoxy adduct-forming compound and the following formula (1): [In formula (1), A1 may have at least one hydrogen atom substituted with a halogen atom and an oxygen atom, a sulfur atom, a disulfide group, a sulfonyl group, Representing a linear or branched alkylene group having 2 to 10 carbon atoms interrupted by a carbonyl group or an imino group], and a resist underlayer film forming composition containing an epoxy addition product and a solvent. It is a thing.

Description

The present invention relates to a reaction product of 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 a method for producing a patterned substrate. The present invention relates to a method for manufacturing a semiconductor device.

Patent Document 1 describes a resist underlayer film forming composition for lithography containing a polymer which is a reaction product of at least one compound (diepoxy compound) containing two epoxy groups and at least one dicarboxylic acid containing a disulfide bond. A resist in which the selection ratio of the dry etching rate with respect to the resist film is large, the k value at a short wavelength such as ArF excimer laser is low, and the n value is high, and the resist pattern is formed in a desired shape. It is disclosed to form an underlayer film.

WO2009 / 0963340A1

However, it has been difficult to say that the conventional product has sufficiently high etching selectivity. Therefore, an object to be solved by the present invention is to provide a resist underlayer film forming composition that provides a resist underlayer film having higher etching selectivity than conventional products. Further, an object to be solved by the present invention is to provide a resist underlayer film capable of shortening the dry etching time and suppressing undesired 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):

[Equation (1), A ¹ is at least one hydrogen atom may and oxygen atoms optionally substituted by a halogen atom, a sulfur atom, a disulfide group, a sulfonyl group, carbon atoms which is interrupted by a carbonyl group or an imino group A resist underlayer film forming composition containing an epoxy addition product with a compound represented by [representing a linear or branched alkylene group of the number 2 to 10] and a solvent.
<2> The epoxy adduct forming compound is at least one selected from the group consisting of a carboxylic acid-containing compound, a carboxylic acid 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 compound of the species.
<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 cross-linking catalyst.
<7> The resist underlayer film forming composition according to any one of <1> to <6>, further comprising a cross-linking 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 to form a resist underlayer film, a step of forming a resist on the resist underlayer film. Patterned, including a step of applying and baking to form a resist film, a step of exposing the resist underlayer film and a semiconductor substrate coated with the resist, and a step of developing and patterning the resist film after exposure. Substrate manufacturing method.
<11> A step of forming a resist underlayer film composed of the resist underlayer film forming composition according to any one of <1> to <8> on the semiconductor substrate, and a step of forming the resist underlayer film.
The step of forming a resist film on the resist underlayer film and
A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing the resist film.
A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, and
The process of processing a semiconductor substrate with the patterned resist underlayer film and
A method for manufacturing a semiconductor device, which comprises.
<12> The following formula (1):

(In the formula (1), A ¹ may have at least one hydrogen atom substituted with a halogen atom and has 2 to 2 carbon atoms interrupted by a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group or an imino group. A compound represented by 10 (representing a linear or branched alkylene group).
<13> The following formula (1):

[In formula (1), A ¹ is at least one hydrogen atom may and sulfur atom optionally substituted by a halogen atom, a disulfide group, a sulfonyl group, a carbon atom number of 2 to 10 which is interrupted by a carbonyl group or an imino group Represents a linear or branched alkylene group]
Reaction formation with at least one epoxy adduct-forming compound selected from the group consisting of carboxylic acid-containing compounds, carboxylic acid 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 formed into a resist underlayer film forming composition. By applying it to a product, it has become possible to achieve a high etching rate as compared with the case where a heteroatomic compound having no glycidyl ester group is used.

［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 comprises an epoxy adduct forming compound and the following formula (1):

[Equation (1), A ¹ is at least one hydrogen atom may and oxygen atoms optionally substituted by a halogen atom, a sulfur atom, a disulfide group, a sulfonyl group, carbon atoms which is interrupted by a carbonyl group or an imino group It contains an epoxy addition product with a compound represented by [representing a linear or branched alkylene group of the number 2 to 10], and a solvent. Hereinafter, they will be described 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 linear or branched alkylene group having 2 to 10 carbon atoms.

Examples of the linear or branched alkylene group having 2 to 10 carbon atoms include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an s-butylene group, an n-pentylene group and a 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-dimethylbutane-2-ylene group, 2,3-dimethylbutane-2-ylene group, 3-hexylene group, 2-ethylpentylene Group, 2-methylpentane-3-ylene group, heptylene group, octylene group, nonylene group, decylene group and the like.

"Interrupted" means an embodiment in which an oxygen atom, a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group or an imino group is inserted between the carbon-carbon bonds of the alkylene group.
Examples of the halogen atom include fluorine, chlorine, bromine, and iodine.
The at least one hydrogen atom may be substituted with a halogen atom, which 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 that. The number of halogen atom substitutions 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 halogen atoms).
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 - _{SC 3} H _6- , -CH ₂ - _{SC 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 interruptions by the group into which the alkylene group is inserted may be once, but may be two or more as long as the stability of the bond is maintained. In that case, the groups to be inserted may be the same or different.

Specific examples of the compound represented by the 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 capable of reacting with the compound represented by the above formula (1) to form a polymer or an oligomer. Usually, it is a compound having 1 to 4 functional groups having reactivity with an epoxy group per molecule. 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 the epoxy group occupies the majority of the mixture.

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

Specific examples of the epoxy adduct forming compound are as follows, but are not limited thereto.

[Epoxy addition product]
The epoxy adduct product is a reaction product of the compound represented by the formula (1) and an epoxy adduct-forming compound. That is, a catalyst for activating an epoxy group by dissolving a reaction product of a compound represented by the above formula (1), which is a raw material monomer, and an epoxy adduct forming compound in a solvent so as to have an appropriate molar ratio. Obtained by polymerization in the presence.

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, which is a raw material monomer (1). An appropriate amount can be selected and used from the range of 0.1% by mass to 10% by mass with respect to the total mass of the compound represented by and the epoxy adduct forming compound.

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

The above reaction is carried out without a solvent, but is usually carried out with a solvent. As the solvent, any solvent that does not inhibit the reaction can be used. Examples thereof 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, 1,000,000 or 500,000 or less.

[solvent]
The solvent for the resist underlayer film forming composition according to the present invention can be used without particular limitation as long as it is a solvent capable of dissolving the reaction product. In particular, since the resist underlayer film forming composition according to the present invention is used in a uniform solution state, it is recommended to use a solvent generally used in the lithography process in combination in consideration of its coating performance. ..

Examples of such a solvent include 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, and propylene glycol mono. 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 ethoxyacetate , 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 Diethyl 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, dairy Butyl acid, 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-methoxy Butyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N, Examples thereof include N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, γ-butyrolactone and the like. 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。）In addition, the following compounds described in Japanese Patent Application No. 2017-140193 can also be used.

^{(R 1} , R ² and R ³ in the formula (i) represent alkyl groups having 1 to 20 carbon atoms which may be interrupted by hydrogen atoms, oxygen atoms, sulfur atoms or amide bonds, respectively, and are identical to 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 a linear or branched alkyl group having or not having a substituent, for example, a methyl group, an ethyl group, and an n-propyl group. , 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, nonadecil group, eikosyl group and the like. An alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.

Oxygen atom, a sulfur atom or an amide interrupted by binding an alkyl group having 1 to 20 carbon atoms, for example, structural units _{-CH 2 -O -, - CH 2} -S -, - CH 2 -NHCO- or - Those containing CH _2- CONH- can be mentioned. -O-, -S-, -NHCO- or -CONH- may be one unit or two 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 group, ethoxy group, propoxy group, butoxy group, methylthio group and ethylthio. Group, propylthio group, butylthio group, methylcarbonylamino group, ethylcarbonylamino group, propylcarbonylamino group, butylcarbonylamino group, methylaminocarbonyl group, ethylaminocarbonyl group, propylaminocarbonyl group, butylaminocarbonyl group, etc. Furthermore, it is 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 or an ethoxy group. It is substituted with a group, a propoxy group, a butoxy group, a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a methylcarbonylamino group, an ethylcarbonylamino group, a methylaminocarbonyl group, an ethylaminocarbonyl group and the like. It is preferably a methoxy group, an ethoxy group, a methylthio group or an ethylthio group, and more preferably a methoxy group or an ethoxy group.

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

[Crosslinking agent component]
The resist underlayer film forming composition of the present invention may contain a cross-linking agent component. Examples of the cross-linking agent include melamine-based, substituted urea-based, and polymers thereof. Preferably, it is a cross-linking agent having at least two cross-linking substituents, methoxymethylated glycol uryl, butoxymethylated glycol uryl, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzogwanamine, butoxymethylated benzogwanamine, It is a compound such as methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. Further, a condensate of these compounds can also be used.
Preferred examples thereof include tetramethoxymethyl glycol uryl (Nippon Cytec Industries, Ltd., trade name: POWDERLINK® 1174).

Further, as the cross-linking agent, a cross-linking agent having high heat resistance can be used. As the cross-linking agent having high heat resistance, a compound containing a cross-linking substituent having an aromatic ring (for example, a benzene ring or a 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 these alkyl groups can use the above-mentioned examples.

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

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

[Acid and / or acid generator]
The resist underlayer film forming composition of the present invention can contain an acid and / or an acid generator.
Examples of the acid include p-toluene sulfonic acid, trifluoromethane sulfonic acid, pyridinium p-toluene sulfonic acid, pyridinium trifluoromethane sulfonic acid, pyridinium-p-phenol sulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenol sulfonic acid, and the like. Examples thereof include camphor sulfonic acid, 4-chlorobenzene sulfonic acid, benzene di sulfonic acid, 1-naphthalene sulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalene carboxylic acid and the like.
Only one type of acid can be used, or two or more types 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 with respect to the total solid content.

Examples of the acid generator include a thermoacid generator and a photoacid generator.
Examples of the thermoacid generator include 2,4,4,6-tetrabromocyclohexadienone, benzointosylate, 2-nitrobenzyltosylate, and other organic sulfonic acid alkyl esters.

The photoacid generator produces an acid when the resist is exposed. Therefore, the acidity of the underlayer film can be adjusted. This is a method for adjusting 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 in 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, disulfonyldiazomethane compounds and the like.

As onium salt compounds, diphenyliodonium hexafluorosulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butane sulfonate, diphenyliodonium perfluoronormal octane sulfonate, diphenyliodonium camphor sulfonate, bis (4-tert-butylphenyl) iodonium sulfonium Iodonium salt compounds such as sulfonate and bis (4-tert-butylphenyl) iodonium trifluoromethane sulfonate, and triphenyl sulfonium hexafluoroantimonate, triphenyl sulfonium nonafluoronormal butane sulfonate, triphenyl sulfonium camphor sulfonate and triphenyl sulfonium trifluoromethane. Examples thereof include sulfonium salt compounds such as sulfonate.

Examples of the sulfoneimide compound include N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoronormal butanesulfonyloxy) succinimide, N- (kanfersulfonyloxy) succinimide and N- (trifluoromethanesulfonyloxy) naphthalimide. Can be mentioned.

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

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 ratio is 0.01 to 5 parts by mass, 0.1 to 3 parts by mass, or 0.% by mass with respect to 100 parts by mass of the solid content of the resist underlayer film forming composition. It is 5 to 1 part by mass.

[Other ingredients]
The resist underfilm forming composition of the present invention does not generate pinholes or stings, and a surfactant can be added in order to further improve the coatability against surface unevenness. Examples of the surfactant 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 alkylallyl ethers, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Solbitan 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), Megafuck F171, F173, R-40, R-40N, R-40LM (DIC) Made by Co., Ltd., trade name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), Asahi Guard AG710, Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) Fluorosurfactants such as (manufactured by, trade name), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned. 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 ratio thereof is 0.0001 to 5 parts by mass, 0.001 to 1 part by mass, or 0.01 with respect to 100 parts by mass of the solid content of the resist underlayer film forming composition. To 0.5 parts by mass.

A light absorbing agent, a rheology adjusting agent, an adhesion auxiliary agent, or the like can be added to the resist underfilm forming composition of the present invention. Rheology modifiers are effective in improving the fluidity of the underlayer film forming composition. Adhesive aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

Examples of the light-absorbing agent include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Handbook of Dyes" (edited by the Society of Synthetic Organic Chemistry), for example, 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. I. Disperse Orange 1,5,13,25,29,30,31,44,57,72 and 73; C.I. I. Disperse Red 1,5,7,13,17,19,43,50,54,58,65,72,73,88,117,137,143,199 and 210; I. Disperse Violet 43; C.I. I. Disperse Blue 96; C.I. I. Fluorescent Fluorescence Agents 112, 135 and 163; C.I. I. Solvent Orange 2 and 45; C.I. I. Sudan Red 1,3,8,23,24,25,27 and 49; C.I. I. Pigment Green 10; C.I. I. Pigment Brown 2 and the like can be preferably used. The above-mentioned absorbent 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 underfilm forming composition.

The rheology adjuster mainly improves the fluidity of the resist underlayer film forming composition, and particularly improves the film thickness uniformity of the resist underlayer film and the filling property of the resist underlayer film forming composition into the hole in the baking step. It is added for the purpose of enhancing. Specific examples include phthalic acid derivatives such as dimethylphthalate, diethylphthalate, diisobutylphthalate, dihexylphthalate and butylisodecylphthalate, adipic acid derivatives such as dinormal butyl adipate, diisobutyl adipate, diisooctyl adipate and octyldecyl adipate, and didi. Maleic acid derivatives such as normal butylmalate, diethylmalate, and dinonylmalate, oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate, or stearic acid derivatives such as normal butyl stearate and glyceryl stearate can be mentioned. can. These rheology adjusters 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 mainly added 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, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, silazans such as trimethylsilylimidazole, methyloltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyl Silanes such as triethoxysilane and γ-glycidoxypropyltrimethoxysilane, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazol, thiouracil, Examples thereof include heterocyclic compounds such as mercaptoimidazole and mercaptopyrimidine, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, and thiourea compounds. These adhesive aids are usually blended in a proportion 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 usually 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content is the content ratio of all the components excluding the solvent from the resist underlayer film forming composition. The proportion of the reaction product in the solid content is preferably 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 in this order.

One of the scales for evaluating whether or not the resist underlayer film forming composition is in a uniform solution state is to observe the passability of a specific microfilter, but the resist underlayer film forming composition according to the present invention has. , Passes through a microfilter having a pore size of 0.1 μm and exhibits a uniform solution state.

Examples of the microfilter material include fluororesins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra high molecular weight polyethylene), and PP ( Examples thereof include polypropylene), PSF (polysulphon), PES (polyether sulfone), and nylon, but it is preferably made of PTFE (polytetrafluoroethylene).

[Manufacturing method of resist underlayer 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 (eg, 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 an appropriate coating method such as a spinner or a coater, and then the resist underlayer film is formed by firing. The firing conditions are appropriately selected from 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 film thickness of the underlayer film formed is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 300 nm, or 50 to 200 nm.

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

Further, the resist underlayer film forming composition according to the present invention is applied onto a semiconductor substrate (so-called stepped substrate) having a portion having a step and a portion having no step, and fired to obtain the portion having the step. It is possible to form a resist underlayer film in which the step with the portion having no step is in the range of 3 to 50 nm.

Next, a resist film, for example, a photoresist layer is formed on the resist underlayer film. The layer of the photoresist can be formed by a well-known method, that is, by applying and firing the photoresist composition solution on the underlayer film. The film thickness of the photoresist is, for example, 50 to 10000 nm, 100 to 2000 nm, or 200 to 1000 nm.

The photoresist formed on the resist underlayer film is not particularly limited as long as it is sensitive to light used for exposure. Both negative photoresists and positive photoresists can be used. A positive photoresist consisting of a novolak resin and a 1,2-naphthoquinonediazide sulfonic acid ester, a chemically amplified photoresist consisting of a binder having a group that decomposes with an acid to increase the alkali dissolution rate and a photoacid generator, and an acid. A chemically amplified photoresist composed of 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 composed of low molecular weight compounds and photoacid generators that are decomposed by an acid to increase the alkali dissolution rate of the photoresist. For example, the product name APEX-E manufactured by Chypre, the product name PAR710 manufactured by Sumitomo Chemical Co., Ltd., and the product name SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999,357-364 (2000), and Proc. SPIE, Vol. Fluorine-containing atomic polymer-based photoresists as described in 3999,365-374 (2000) can be mentioned.

Next, a resist pattern is formed by irradiation and development with light or an electron beam. First, exposure is performed through a predetermined mask. Near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (for example, EUV (wavelength 13.5 nm)) and the like are used for exposure. Specifically, KrF excimer laser (wavelength 248 nm), it is possible to use an ArF excimer laser (wavelength 193 nm) and _{F 2} excimer laser (wavelength 157 nm) or the like. Among these, ArF excimer laser (wavelength 193 nm) and EUV (wavelength 13.5 nm) are preferable. After the exposure, if necessary, post-exposure heating (post exposure break) can be performed. Post-exposure heating is performed under appropriately selected conditions 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 the photoresist. As the electron beam resist, either a negative type or a positive type can be used. A chemically amplified resist consisting of an acid generator and a binder having a group that decomposes with an acid to change the alkali dissolution rate, and a low molecular weight compound that decomposes with an alkali-soluble binder, an acid generator and an acid to change the alkali dissolution rate of the resist. A chemically amplified resist composed of an acid generator, a binder having a group that decomposes with an acid to change the alkali dissolution rate, and a chemically amplified resist composed of a low molecular weight compound that decomposes with an acid to change the alkali dissolution rate of the resist. There are non-chemically amplified resists composed of binders having a group that is decomposed by an electron beam to change the alkali dissolution rate, non-chemically amplified resists composed of a binder that is cut by an electron beam and has a site that changes the alkali dissolution rate, and the like. 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 the irradiation source as an electron beam.

Then, development is performed with a developer. As a result, for example, when a positive photoresist is used, the photoresist in the exposed portion is removed and a photoresist pattern is formed.
The developing solution includes an aqueous solution of alkali metal hydroxide such as potassium hydroxide and sodium hydroxide, an aqueous solution of quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline, ethanolamine and propylamine. An alkaline aqueous solution such as an amine aqueous solution such as ethylenediamine can be mentioned as an example. Further, a surfactant or the like can be added to these developers. The developing conditions 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) thus formed as a protective film, and then the patterned photoresist and the inorganic lower layer film (intermediate layer) are formed. The organic lower layer 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 the organic lower layer film (lower layer) as protective films.

First, the inorganic underlayer film (intermediate layer) of the portion from which 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, 6 Gases such as sulfur fluorofluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane and dichloroborane can be used. A halogen-based gas is preferably used for dry etching of the inorganic underlayer film, and a fluorine-based gas is more preferable. Examples of the fluorine-based gas include tetrafluoromethane (CF ₄ ), perfluorocyclobutane (C ₄ F ₈ ), perfluoropropane (C ₃ F ₈ ), trifluoromethane, and difluoromethane (CH ₂ F ₂ ). Can be mentioned.

After that, the organic underlayer film is removed using a film composed of a patterned photoresist and an inorganic underlayer film as a protective film. The organic lower layer film (lower layer) is preferably performed by dry etching with an oxygen-based gas. This is because the inorganic underlayer film containing a large amount of silicon atoms is difficult to be removed by dry etching with an oxygen-based gas.

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

Further, an organic antireflection film can be formed on the upper layer of the resist lower layer film before the photoresist is formed. The antireflection film composition used there is not particularly limited, and can be arbitrarily selected and used from those conventionally used in the lithography process, and a commonly used method such as a spinner can be used. The antireflection film can be formed by coating and firing with a coater.

In the present invention, an organic underlayer film can be formed on a substrate, an inorganic underlayer film can be formed on the film, and a photoresist can be further coated on the film. As a result, the pattern width of the photoresist becomes narrower, and even when the photoresist is thinly coated to prevent the pattern from collapsing, the substrate can be processed by selecting an appropriate etching gas. For example, a fluorine-based gas having a sufficiently fast etching rate for a photoresist can be used as an etching gas to process a resist underlayer film, and a fluorine-based gas having a sufficiently fast etching rate for an inorganic underlayer film can be etched. The substrate can be processed as a gas, and the substrate can be processed using an oxygen-based gas having a sufficiently high etching rate for the organic underlayer film as an etching gas.

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

Further, the underlayer film formed from the resist underlayer film forming composition is applied to the substrate on which the via holes are formed used in the dual damascene process, and can be used as an embedding material capable of filling the holes without gaps. It can also be used as a flattening material for flattening the surface of a semiconductor substrate having irregularities.

Next, the contents of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

The weight average molecular weight of the polymer shown in the following synthetic example of the present specification is a measurement result by gel permeation chromatography (hereinafter, abbreviated as GPC). A GPC device manufactured by Tosoh Corporation is used for the measurement, and the measurement conditions and the like are as follows.
GPC column: Shodex [registered trademark], Asahipak [registered trademark] (Showa Denko (Showa Denko)
stock))
Column temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow rate: 0.35 ml / 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)

50.01 g of diglycolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 128.81 g of potassium carbonate (0.89 mol, Kanto Chemical Co., Inc., special grade), 350.0 g of acetone in a 1 L flask equipped with a cooling tube, a thermometer and a stirrer. The mixture was added and cooled to 5 ° C. or lower, and 135.33 g (1.12 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) of allyl bromide was added dropwise. Then, the temperature was raised to 55 ° C., the mixture was stirred for 23 hours, cooled to room temperature, the insoluble material was filtered, and the mixture was washed twice with 50.0 g of acetone. The solvent was distilled off from the filtrate 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 filtrates. Further, the organic layer was washed twice with 250.0 g of pure water, and then the solvent was distilled off from the organic layer at 40 ° C. under reduced pressure to make the compound represented by the above formula (A) a pale yellow liquid. Obtained at 47 g (yield 30.6%). The δ value of this compound in the ¹ H-NMR spectrum (500 MHz, Deuterated-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 and 230.0 g of chloroform obtained in Synthesis Example 1 were placed in a 500 mL flask equipped with a thermometer and a stirrer, and cooled to 5 ° C. or lower. 68.41 g of 3-chloroperbenzoic acid (0.26 mol, manufactured by Tokyo Chemical Industry Co., Ltd., 35% hydrous product) was gradually added. Then, the temperature was raised to 25 ° C. and the mixture was stirred for 91.5 hours. The reaction mixture was diluted with 230.0 g of chloroform, 460.0 g of a 5% aqueous sodium hydrogen carbonate solution was added, and the mixture was separated. Further, the organic layer was separated by 460.0 g of a 10% sodium hydrogen sulfite aqueous solution, 460.0 g of a 5% sodium hydrogen carbonate aqueous solution, and 460.0 g of pure water, and then the solvent was distilled off from the organic layer at 40 ° C. under reduced pressure. The diglycidyl-2,2'-oxydiacetate represented by the above formula (B) was obtained as a white solid in 17.63 g (yield 66.7%). The δ value of this compound in the ¹ H-NMR spectrum (500 MHz, DMSO-d6) 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)

Put 30.01 g of 2,2'-thiodiglycolic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 90.0 g of tetrahydrofuran (Kanto Chemical Co., Inc.) in a 500 mL flask equipped with a thermometer and a stirrer, and cool to 5 ° C. Then, 32.40 g of pyridine (0.41 mol, Kanto Chemical Co., Inc., dehydration) was added. A solution prepared by dissolving 82.44 g of dicyclohexylcarbodiimide (0.40 mol, Kanto Chemical Co., Inc., special grade deer) in 60.0 g of THF was added dropwise thereto, and the mixture was stirred for 1 hour. Then, a solution prepared by dissolving glycidol (0.40 mol, manufactured by Aldrich) 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, the insoluble material was filtered and washed twice with 30.0 g of THF. The solvent was distilled off from the filtrate under reduced pressure at 30 ° C., 300.0 g of ethyl acetate was added to the concentrate, the insoluble material was filtered, and the mixture was washed twice with 15.0 g of ethyl acetate. 300.0 g of pure water was added thereto to separate the liquids, 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)), and the compound represented by the above formula (C) was used as a white solid. It was obtained at 20.67 g (yield 39.4%). The δ value of this compound in the ¹ H-NMR spectrum (500 MHz, DMSO-d6) 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)

In a 200 mL flask equipped with a thermometer and a stirrer, 8.01 g of diglycidyl-2,2'-thiodiacetate and 80.0 g of chloroform obtained in Synthesis Example 3 were placed and cooled to 5 ° C. or lower, and 3-chloroperbenzoic acid was added. 19.43 g (0.26 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was gradually added. Then, the temperature was raised to 23 ° C. and the mixture was stirred for 4.5 hours. The reaction mixture was diluted with 80.0 g of chloroform, 160.0 g of a 5% aqueous sodium hydrogen carbonate solution was added, and the mixture was separated. Further, the organic layer was separated by 160.0 g of a 10% sodium hydrogen sulfite aqueous solution, 160.0 g of a 5% sodium hydrogen carbonate aqueous solution, and 160.0 g of pure water, and then the solvent was distilled off from the organic layer at 30 ° C. under reduced pressure. The compound represented by the above formula (D) was obtained as a white solid in an amount of 4.36 g (yield 48.6%). The δ value of this compound in the ¹ H-NMR spectrum (500 MHz, DMSO-d6) 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 the mixture was stirred in an ice bath with a magnetic stirrer. A solution prepared by dissolving 5 g of dithiodiglycolic acid in 10 g of tetrahydrofuran was added dropwise over 3 minutes, 0.035 g of 4-dimethylaminopyridine was added, and the mixture was 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 4 times with about 50 g of pure water, and then the organic layer was concentrated under reduced pressure with an evaporator. Subsequently, the concentrate was diluted with about 20 g of ethyl acetate, a short column of silica gel was performed, and then the eluate was concentrated under reduced pressure with an evaporator to obtain 3.24 g of the compound represented by the above formula (E). (Yield: 40%). The δ value of this compound in the ¹ H-NMR spectrum (300 MHz, DMSO-d6) was as follows.
^{1 1} H-NMR (300 MHz) in DMSO-d6: 2.66 ppm (m, 2H), 2.79 ppm (dd, J = 5.3 Hz, J = 4.8 Hz, 2H), 3.21 ppm (m, 2H) , 3.80 ppm (s, 4H), 3.89 ppm (dd, J = 12.6 Hz, J = 6.6 Hz, 2H), 4.43 ppm (dd, J = 12.6 Hz, J = 2.7 Hz, 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) and 2.40 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 0.12 g of bromide in 20.07 g of propylene glycol monomethyl ether, the mixture was heated to 105 ° C. and stirred under a nitrogen atmosphere for 24 hours to obtain a solution of the resin compound. When GPC analysis of the obtained resin was performed, the weight average molecular weight was about 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) and 2.26 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 0.17 g of bromide in 18.89 g of propylene glycol monomethyl ether, the mixture was heated to 105 ° C. and stirred under a nitrogen atmosphere for 24 hours to obtain a solution of the resin compound. When GPC analysis of the obtained resin was performed, the weight average molecular weight was about 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) and 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 mixture was heated to 105 ° C. and stirred under a nitrogen atmosphere for 24 hours to obtain a solution of the resin compound. When GPC analysis of the obtained resin was performed, the weight average molecular weight was about 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) and 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 dissolving 0.13 g of bromide in 17.36 g of propylene glycol monomethyl ether, the mixture was heated to 105 ° C. and stirred under a nitrogen atmosphere for 24 hours to obtain a solution of the resin compound. When GPC analysis of the obtained resin was performed, the weight average molecular weight was about 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))

Compound 5 (DG-DTDGA) 2.00 g, methyldicarboxymethyl isocyanuric acid (Shikoku Kasei Kogyo Co., Ltd., trade name: MeCIC-1) 2.36 g, 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, the mixture was heated to 105 ° C. and stirred under a nitrogen atmosphere for 24 hours to obtain a solution of the resin compound. When GPC analysis of the obtained resin was performed, the weight average molecular weight was about 1600 in terms of standard polystyrene.

(Composition preparation)
[Example 1]
7.334 g of propylene glycol monomethyl ether and pyridinium trifluoromethanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) 0. 016 g and 0.001 g of a surfactant (Dainippon Ink and Chemical Industry Co., Ltd., trade name: R-40) were added to prepare a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 2]
In 2.924 g of the 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 pyridinium trifluoromethanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) 0. 018 g and 0.001 g of a surfactant (Dainippon Ink and Chemical Industry Co., Ltd., trade name: R-40) were added to prepare a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 3]
In 2.486 g of the 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 pyridinium trifluoromethanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) 0. 018 g and 0.001 g of a surfactant (Dainippon Ink and Chemical Industry Co., Ltd., trade name: R-40) were added to prepare a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 4]
In addition to 2.486 g of the 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 pyridinium trifluoromethanesulfonic acid (Tokyo Chemical Industry Co., Ltd.) 0. 018 g and 0.001 g of a surfactant (Dainippon Ink and Chemical Industry Co., Ltd., trade name: R-40) were added to prepare a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 5]
In addition 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 Chemical Industry Co., Ltd.) ) 0.018 g and 0.001 g of a surfactant (Dainippon Ink and Chemical Industry Co., Ltd., trade name: R-40) were added to prepare a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Example 6]
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 glycol uryl (Nippon Cytec Industries Co., Ltd.) , Trade name: POWDERLINK (registered trademark) 1174) 0.089 g, pyridinium-p-phenolsulfonic acid 0.013 g, and surfactant (Dainippon Ink and Chemicals Co., Ltd., trade name: R-40) 0.001 g Was added to prepare a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

[Comparative Example 1]
In 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 (Nippon Cytec Industries Co., Ltd., trade name: POWDERLINK (registered trademark) 1174) 0.181 g, p-phenolsulfonic acid (Tokyo Kasei Kogyo Co., Ltd.), Bisphenol S (Tokyo Kasei Kogyo Co., Ltd.) 0.011 g And 0.007 g of a surfactant (Dainippon Ink and Chemicals Co., Ltd., trade name: R-40) were added to prepare a solution. Then, it was filtered using a polyethylene microfilter having a pore size of 0.02 μm to prepare a composition for forming a resist underlayer film.

(Measurement of dry etching rate)
The resist underlayer film forming compositions prepared in Examples 1 to 6 and Comparative Example 1 were each applied on a silicon wafer by a spinner, baked on a hot plate at 205 ° C. for 1 minute, and each had a film thickness of 100 nm. A resist underlayer film was formed. Using a dry etching apparatus (RIE-10NR) manufactured by SAMCO Corporation, the dry etching rate (decrease in film thickness per unit time) was measured under the condition that _{CF 4} and N _{2 were used as the dry etching gas.} .. Tables 1 and 2 show the etching selectivity of each underlayer film when 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 resist underlayer film forming composition obtained by the present invention can shorten the etching time during dry etching of the resist underlayer film, and the resist film thickness is reduced when the resist underlayer film is removed by dry etching. It is possible to suppress an unfavorable phenomenon. Further, being able to shorten the dry etching time is particularly useful as a resist underlayer film because it can suppress undesired etching damage to the underlying substrate of the resist underlayer film.

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)

Epoxy adduct forming compound and the following formula (1):

[Equation (1), A ¹ is at least one hydrogen atom may and oxygen atoms optionally substituted by a halogen atom, a sulfur atom, a disulfide group, a sulfonyl group, carbon atoms which is interrupted by a carbonyl group or an imino group A resist underlayer film forming composition containing an epoxy addition product with a compound represented by [representing a linear or branched alkylene group of the number 2 to 10] and a solvent. At least one compound selected from the group consisting of a carboxylic acid-containing compound, a carboxylic acid 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 claim 1. The resist underlayer film forming composition according to claim 1 or 2, 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 or 3, 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 4, 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 5, further comprising a cross-linking catalyst. The resist underlayer film forming composition according to any one of claims 1 to 6, further comprising a cross-linking agent. The resist underlayer film forming composition according to any one of claims 1 to 7, 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 8. A step of applying the resist underlayer film forming composition according to any one of claims 1 to 8 on a semiconductor substrate and baking to form a resist underlayer film, and applying a resist on the resist underlayer film. Manufacture of a patterned substrate including a step of baking to form a resist film, a step of exposing the resist underlayer film and a semiconductor substrate coated with the resist, and a step of developing and patterning the resist film after exposure. Method. A step of forming a resist underlayer film composed of the resist underlayer film forming composition according to any one of claims 1 to 8 on a semiconductor substrate, and a step of forming the resist underlayer film.
The step of forming a resist film on the resist underlayer film and
A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing the resist film.
A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, and
The process of processing a semiconductor substrate with the patterned resist underlayer film and
A method for manufacturing a semiconductor device, which comprises. The following formula (1):

(In the formula (1), A ¹ may have at least one hydrogen atom substituted with a halogen atom and has 2 to 2 carbon atoms interrupted by a sulfur atom, a disulfide group, a sulfonyl group, a carbonyl group or an imino group. A compound represented by 10 (representing a linear or branched alkylene group). The following formula (1):

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