阅读说明：本技术 包含脂环式化合物末端的聚合物的抗蚀剂下层膜形成用组合物 (Resist underlayer film forming composition containing alicyclic compound terminal polymer ) 是由 若山浩之 水落龙太 清水祥 染谷安信 于 2020-05-01 设计创作，主要内容包括：提供用于形成能够形成所希望的抗蚀剂图案的抗蚀剂下层膜的组合物、和使用了该抗蚀剂下层膜形成用组合物的抗蚀剂图案制造方法、半导体装置的制造方法。一种抗蚀剂下层膜形成用组合物,其包含在末端含有脂肪族环的聚合物,且进一步包含有机溶剂,所述脂肪族环的碳-碳键可以被杂原子中断并且所述脂肪族环可以经取代基取代。上述脂肪族环为碳原子数3～10的单环式或多环式脂肪族环。上述多环式脂肪族环为二环或三环。(Provided are a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for producing a resist pattern using the composition for forming a resist underlayer film, and a method for producing a semiconductor device. A resist underlayer film forming composition comprising a polymer containing an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which aliphatic ring may be substituted with a substituent, and further comprising an organic solvent. The aliphatic ring is a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms. The polycyclic aliphatic ring is bicyclic or tricyclic.)

1. A resist underlayer film forming composition comprising a polymer containing an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which aliphatic ring may be substituted with a substituent, and further comprising an organic solvent.

2. The composition for forming a resist underlayer film according to claim 1, wherein the aliphatic ring is a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.

3. The composition for forming a resist underlayer film according to claim 2, wherein the polycyclic aliphatic ring is bicyclic or tricyclic.

4. The resist underlayer film forming composition according to any one of claims 1 to 3, wherein the aliphatic ring has at least 1 unsaturated bond.

5. The composition for forming a resist underlayer film according to any one of claims 1 to 4, wherein the substituent is selected from a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, and a carboxyl group.

6. The resist underlayer film forming composition according to any one of claims 1 to 5, wherein the polymer has at least 1 structural unit represented by the following formula (3) in a main chain,

in formula (3), A₁、A₂、A₃、A₄、A₅And A₆Each independently represents a hydrogen atom, a methyl group or an ethyl group, Q₁Represents a 2-valent organic group, m₁And m₂Each independently represents 0 or 1.

7. The composition for forming a resist underlayer film according to claim 6, wherein in formula (3), Q₁A 2-valent organic group represented by the following formula (5),

wherein Y represents a divalent group represented by the following formula (6) or (7);

in the formula, R₆And R₇Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, the phenyl group may be substituted with at least 1 selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group and an alkylthio group having 1 to 6 carbon atoms, or R₆And R₇Can be combined with each other to form the R₆And R₇The bonded carbon atoms together form a ring having 3 to 6 carbon atoms.

8. The resist underlayer film forming composition according to any one of claims 1 to 7, the polymer further comprising a disulfide bond in a main chain.

9. The resist underlayer film forming composition according to any one of claims 1 to 8, further comprising a curing catalyst.

10. The resist underlayer film forming composition according to any one of claims 1 to 9, further comprising a crosslinking agent.

11. A resist underlayer film, which is a fired product of a coating film formed from the resist underlayer film forming composition according to any one of claims 1 to 10.

12. A method for manufacturing a substrate having a pattern formed thereon, comprising the steps of: a step of forming a resist underlayer film by applying the resist underlayer film forming composition according to any one of claims 1 to 10 on a semiconductor substrate and baking the composition; a step of forming a resist film by applying a resist to the resist underlayer film and baking the resist; exposing the semiconductor substrate coated with the resist underlayer film and the resist to light; and developing the resist film after exposure to form a pattern.

13. A method for manufacturing a semiconductor device, comprising the steps of:

a step of forming a resist underlayer film formed from the resist underlayer film forming composition according to any one of claims 1 to 10 on a semiconductor substrate;

Forming a resist film on the resist underlayer film;

a step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing the resist film;

forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; and

and processing the semiconductor substrate using the patterned resist underlayer film.

Technical Field

The present invention relates to a composition that can be used in a lithography process in semiconductor manufacturing, particularly in the most advanced (ArF, EUV, EB, etc.) lithography process. The present invention also relates to a method for manufacturing a substrate with a resist pattern to which the resist underlayer film is applied, and a method for manufacturing a semiconductor device.

Background

In the manufacture of semiconductor devices, microfabrication has been conventionally performed by photolithography using a resist composition. The microfabrication is a processing method in which a thin film of a photoresist composition is formed on a semiconductor substrate such as a silicon wafer, an active ray such as ultraviolet light is irradiated through a mask pattern on which a device pattern is drawn, development is performed, and the substrate is etched using the obtained photoresist pattern as a protective film, thereby forming fine irregularities corresponding to the pattern on the surface of the substrate. In recent years, high integration of semiconductor devices has progressed, and practical use of EUV light (wavelength 13.5nm) or EB (electron beam) has been studied in most advanced microfabrication, in addition to conventionally used i-ray (wavelength 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm) as active light. Accordingly, the influence of the diffuse reflection and standing wave of the active light from the semiconductor substrate becomes a great problem. In order to solve this problem, a method of providing a Bottom Anti-Reflective Coating (BARC) between a resist and a semiconductor substrate has been widely studied. The antireflection film is also referred to as a resist underlayer film. As such an antireflection film, an organic antireflection film formed of a polymer having a light absorbing portion or the like has been studied in a large amount from the viewpoint of ease of use thereof and the like.

Patent document 1 discloses a resist underlayer film forming composition for use in a photolithography step in the production of a semiconductor device, the composition containing a polymer having a repeating unit structure of a polycyclic aliphatic ring in the main chain of the polymer. Patent document 2 discloses a resist underlayer film forming composition for lithography, which contains a polymer having a specific structure at the end.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-093162

Patent document 2: international publication No. 2013/141015

Disclosure of Invention

Problems to be solved by the invention

Examples of the characteristics required for the resist underlayer film include that the film does not mix with a resist film formed on an upper layer (is insoluble in a resist solvent), and that the dry etching rate is higher than that of the resist film.

In the case of photolithography involving EUV exposure, the line width of the formed resist pattern is 32nm or less, and a resist underlayer film for EUV exposure is used by being formed thinner than a conventional film. When such a thin film is formed, pinholes, aggregation, and the like are likely to occur due to the influence of the substrate surface, the polymer used, and the like, and it is difficult to form a uniform film having no defects.

On the other hand, in the case of forming a resist pattern, in a developing step, a method may be employed in which an unexposed portion of the resist film is removed using a solvent capable of dissolving the resist film, usually an organic solvent, and an exposed portion of the resist film is left as a resist pattern. In such a negative development process, improvement of the adhesion of the resist pattern is a major problem.

Further, it is required to suppress deterioration of LWR (Line Width Roughness, Line Width fluctuation) at the time of resist pattern formation, formation of a resist pattern having a good rectangular shape, and improvement of resist sensitivity.

The present invention has an object to provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, which solves the above problems, and a resist pattern forming method using the composition for forming a resist underlayer film.

Means for solving the problems

The present invention includes the following aspects.

[1] A resist underlayer film forming composition comprising a polymer containing an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom and which aliphatic ring may be substituted with a substituent, and further comprising an organic solvent.

[2] The composition for forming a resist underlayer film according to [1], wherein the aliphatic ring is a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.

[3] The composition for forming a resist underlayer film according to [2], wherein the polycyclic aliphatic ring is bicyclic or tricyclic.

[4] The resist underlayer film forming composition according to any one of [1] to [3], wherein the aliphatic ring has at least 1 unsaturated bond.

[5] The composition for forming a resist underlayer film according to any one of [1] to [4], wherein the substituent is selected from the group consisting of a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms and a carboxyl group.

[6] The resist underlayer film forming composition according to any one of [1] to [5], wherein the polymer has at least 1 structural unit represented by the following formula (3) in a main chain.

(in the formula (3), A₁、A₂、A₃、A₄、A₅And A₆Each independently represents a hydrogen atom, a methyl group or an ethyl group, Q₁Represents a 2-valent organic group, m₁And m₂Each independently represents 0 or 1. )

[7]According to [6]The resist underlayer film forming composition described above,in the above formula (3), Q₁Represents a 2-valent organic group represented by the following formula (5).

(wherein Y represents a divalent group represented by the following formula (6) or (7))

(in the formula, R₆And R₇Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, the phenyl group may be substituted with at least 1 selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group and an alkylthio group having 1 to 6 carbon atoms, or R₆And R₇Can be combined with each other to form the R₆And R₇The bonded carbon atoms together form a ring having 3 to 6 carbon atoms. )

[8] The composition for forming a resist underlayer film according to any one of [1] to [7], wherein the polymer further contains a disulfide bond in a main chain.

[9] The resist underlayer film forming composition according to any one of [1] to [8], further comprising a curing catalyst.

[10] The resist underlayer film forming composition according to any one of [1] to [9], further comprising a crosslinking agent.

[11] A resist underlayer film, which is a fired product of a coating film formed from the resist underlayer film forming composition according to any one of [1] to [10 ].

[12] A method for manufacturing a substrate having a pattern formed thereon, comprising the steps of: a step of forming a resist underlayer film by applying the resist underlayer film forming composition according to any one of [1] to [10] onto a semiconductor substrate and baking the composition; a step of forming a resist film by applying a resist to the resist underlayer film and baking the resist; exposing the semiconductor substrate coated with the resist underlayer film and the resist to light; and developing the exposed resist film to form a pattern.

[13] A method for manufacturing a semiconductor device, comprising the steps of:

a step of forming a resist underlayer film formed from the resist underlayer film forming composition according to any one of [1] to [10] on a semiconductor substrate;

forming a resist film on the resist underlayer film;

a step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing the resist film;

forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; and

and processing the semiconductor substrate using the patterned resist underlayer film.

ADVANTAGEOUS EFFECTS OF INVENTION

The resist underlayer film forming composition for lithography of the present invention is characterized by being a composition comprising a polymer (or also referred to as a polymer) contained in the resist underlayer film forming composition, and an alicyclic ring whose terminal is interrupted by a carbon-carbon bond which may be interrupted by a heteroatom, and an alicyclic ring which may be substituted by a substituent, and containing such a polymer and an organic solvent, preferably further containing a crosslinking agent and/or a compound (curing catalyst) which promotes a crosslinking reaction. With such a configuration, the resist underlayer film forming composition for lithography according to the present application can realize formation of a resist pattern having a good rectangular shape (no pattern collapse), suppression of LWR deterioration at the time of resist pattern formation, and improvement of sensitivity.

Detailed Description

Description of terms

Terms used in the present invention have the following definitions unless otherwise specified.

Examples of the "alkyl group having 1 to 10 carbon atoms" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1, 1-dimethyl-n-propyl group, a 1, 2-dimethyl-n-propyl group, a 2, 2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1, 2-dimethyl-cyclopropyl group, a 2, 3-dimethyl-cyclopropyl group, a, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1-dimethyl-n-butyl, 1, 2-dimethyl-n-butyl, 1, 3-dimethyl-n-butyl, 2, 2-dimethyl-n-butyl, 2, 3-dimethyl-n-butyl, 3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, n-pentyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-dimethyl-n-butyl, 3, 1, 3-dimethyl-n-butyl, 1, 2-ethyl-n-butyl, 1, 2-trimethyl-n-propyl, 1,2, 2-methyl-n-pentyl, 2-pentyl, 3, 2-pentyl, 2-dimethyl-n-butyl, 3, 2, 2-butyl, 2-methyl-butyl, 2-n-butyl, 2-n-butyl, 2-propyl, 2-butyl, 2-propyl, 2-butyl, 2-n-butyl, 2-butyl, or a, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1, 2-dimethyl-cyclobutyl, 1, 3-dimethyl-cyclobutyl, 2-dimethyl-cyclobutyl, 2, 3-dimethyl-cyclobutyl, 2, 4-dimethyl-cyclobutyl, 3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2, 2-trimethyl-cyclopropyl, 1,2, 3-trimethyl-cyclopropyl, 2, 3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and the like.

Examples of the "alkoxy group having 1 to 20 carbon atoms" include a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1, 1-dimethyl-n-propoxy group, a 1, 2-dimethyl-n-propoxy group, a 2, 2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, a n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1, 1-dimethyl-n-butoxy group, a 1, 2-dimethyl-n-butyloxy group, a, 1, 3-dimethyl-n-butoxy group, 2, 2-dimethyl-n-butoxy group, 2, 3-dimethyl-n-butoxy group, 3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1, 2-trimethyl-n-propoxy group, 1,2, 2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group, cyclopentyloxy group, cyclohexyloxy group, norbornanyloxy group, adamantyloxy group, adamantylmethyloxy group, adamantylethyloxy group, tetracyclodecyloxy group, tricyclodecyloxy group, and the like.

The "acyloxy group having 1 to 10 carbon atoms" is a group represented by the following formula (20).

Z-COO-type (20)

(in the formula (20), Z represents a hydrogen atom or an "alkyl group having 1 to 9 carbon atoms" of the "alkyl group having 1 to 10 carbon atoms", and Z represents a bonding moiety to the "alicyclic ring")

Examples of the "alkenyl group having 3 to 6 carbon atoms" include a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-vinyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-ethylvinyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-n-propylvinyl group, a 1-methyl-1-butenyl group, a 1-methyl-2-butenyl group, a 1-methyl-3-butenyl group, a 2-ethyl-2-propenyl group, a substituted aryl group, a substituted heteroaryl group, a substituted or a substituted heteroaryl group, a substituted or a substituted heteroaryl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1-dimethyl-2-propenyl, 1-isopropylvinyl, 1, 2-dimethyl-1-propenyl, 1, 2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, methyl-3-pentenyl, methyl-4-pentenyl, methyl-2-pentenyl, methyl-3-pentenyl, methyl-2-pentenyl, methyl-pentenyl, ethyl-2-pentenyl, ethyl-2-pentenyl, and ethyl-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1-dimethyl-2-butenyl, 1-dimethyl-3-butenyl, 1, 2-dimethyl-1-butenyl, 1, 2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1, 3-dimethyl-1-butenyl, 1, 3-dimethyl-2-butenyl, 1, 3-dimethyl-3-butenyl, 1-isobutyl vinyl, 2-dimethyl-3-butenyl, 4-methyl-3-butenyl, 1-dimethyl-2-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1, 3-dimethyl-1-butenyl, 1-isobutyl vinyl, 2-dimethyl-3-butenyl, 1-isobutyl vinyl, 2-butyl-3-butenyl, 1-butyl, 2-butyl-ethyl-2-butyl-2-3-butenyl, 1-butyl, 2-butyl, 3-butenyl, 1, 2-butyl, 3, 2-butyl, 2-butyl, 3, 2-butyl, 3, 2-butyl, 2,3, 2,3, 2, or 2,3, 2,3, or 2,3, 2,3, or 2,3, 2, or 2, or 3, 2, or, 2, 3-dimethyl-1-butenyl, 2, 3-dimethyl-2-butenyl, 2, 3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3-dimethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 2-trimethyl-2-propenyl, 2-ethyl-3-butenyl, 2-methyl-2-propenyl, 2-methyl-butenyl, 2-ethyl-3-butenyl, 2-methyl-propenyl, 2-methyl-ethyl-2-butenyl, 2-methyl-ethyl-3-butenyl, 2-methyl-1-butenyl, 2-methyl-ethyl-1-methyl-2-methyl-2-methyl-ethyl-3-butenyl, 1-methyl-ethyl-methyl-2-methyl-ethyl-methyl-2-ethyl-methyl-ethyl-methyl-2-methyl-ethyl-methyl-2-ethyl-2-methyl-ethyl-methyl-2-ethyl-methyl-ethyl-methyl-ethyl-2-methyl-ethyl-2-methyl-2-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-methyl-ethyl-2-ethyl-2-ethyl-methyl-ethyl-methyl-ethyl-, 1-tert-butylvinyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-isopropyl-1-propenyl group, 1-isopropyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, methyl-2-propenyl group, methyl-1-propenyl group, 1-ethyl-2-methyl-1-cyclopentenyl group, 1-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, and mixtures thereof, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl and the like.

Examples of the "alkylthio group having 1 to 6 carbon atoms" include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, and a hexylthio group.

Examples of the "halogen atom" include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the "arylene group having 6 to 40 carbon atoms" include a phenylene group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenylene group, an m-chlorophenylene group, a p-chlorophenylene group, an o-fluorophenylene group, a p-fluorophenylene group, an o-methoxyphenylene group, a p-nitrophenylene group, a p-cyanophenylene group, an α -naphthylene group, a β -naphthylene group, an o-biphenylene group, an m-biphenylene group, a p-biphenylene group, a 1-anthrylene group, a 2-anthrylene group, a 9-anthrylene group, a 1-phenanthrylene group, a 2-phenanthrylene group, a 3-phenanthrylene group, a 4-phenanthrylene group and a 9-phenanthrylene group.

< composition for forming resist underlayer film >

With regard to the resist underlayer film forming composition of the present application, the terminal of the polymer contained in the resist underlayer film forming composition contains an aliphatic ring whose carbon-carbon bond may be interrupted by a heteroatom, an aliphatic ring which may be further substituted with a substituent, and further contains an organic solvent.

By carbon-carbon bond may be interrupted by heteroatoms, it is meant that the aliphatic rings herein contain-O-, -S-linkages between carbon-carbon bonds.

The term "optionally substituted aliphatic ring" as used herein means that all or a part of the hydrogen atoms of the aliphatic ring is substituted with, for example, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms or a carboxyl group.

The aliphatic ring is preferably a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.

Examples of the "monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms" include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, and bicyclo [2.1.0]]Pentane, bicyclo [3.2.1]Octane, tricyclo [3.2.1.0^2,7]Octane, spiro [3,4]]Octane, norbornane, norbornene, tricyclo [3.3.1.1^3,7]Decane (adamantane), and the like.

The polycyclic aliphatic ring is preferably bicyclic or tricyclic.

Among them, examples of the bicyclo ring include norbornane, norbornene, spirobicyclopentane, bicyclo [2.1.0] pentane, bicyclo [3.2.1] octane, spiro [3,4] octane and the like.

Among them, as the tricyclic ring, a tricyclic ring [3.2.1.0 ] is mentioned^2,7]Octane, tricyclo [3.3.1.1^3,7]Decane (adamantane).

The above aliphatic ring preferably has at least 1 unsaturated bond (e.g., double bond, triple bond). The alicyclic ring preferably has 1 to 3 unsaturated bonds. The above aliphatic ring preferably has 1 or 2 unsaturated bonds. The unsaturated bond is preferably a double bond.

As a specific example of the "aliphatic ring whose carbon-carbon bond may be interrupted by a hetero atom and which may be substituted with a substituent", a compound described below is derived by reacting with the terminal of the polymer by a method known per se.

The polymer preferably has at least 1 structural unit represented by the following formula (3) in the main chain.

(in the formula (3), A₁、A₂、A₃、A₄、A₅And A₆Each independently represents a hydrogen atom, a methyl group or an ethyl group, Q₁Represents a 2-valent organic group, m₁And m₂Each independently represents 0 or 1. )

In the above formula (3), Q₁Preferably, the compound represents a 2-valent organic group represented by the following formula (5).

(wherein Y represents a divalent group represented by the following formula (6) or (7))

(in the formula, R₆And R₇Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, the phenyl group may be substituted with at least 1 selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group and an alkylthio group having 1 to 6 carbon atoms, or R ₆And R₇Can be combined with each other to form the R₆And R₇The bonded carbon atoms together form a ring having 3 to 6 carbon atoms. )

Examples of the "ring having 3 to 6 carbon atoms" include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene and cyclohexane.

The above polymer preferably further contains disulfide bonds in the main chain.

The polymer preferably contains an arylene group having 6 to 40 carbon atoms which may be substituted with a substituent. The substituents have the same meanings as described above.

The weight average molecular weight of the polymer is, for example, 2000 to 50000.

Is represented by the above formula (3), and m₁And m₂Examples of the monomer having a structural unit of 1 include compounds having 2 epoxy groups represented by the following formulae (10-a) to (10-k),

that is, 1, 4-diglycidyl terephthalate, 2,6 diglycidyl naphthalenedicarboxylate, 1,6 diglycidyl dihydroxynaphthalene, 1,2 diglycidyl cyclohexanedicarboxylate, 2 diglycidyl bis (4-hydroxyphenyl) propane, 2 diglycidyl bis (4-hydroxycyclohexane) propane, 1,4 diglycidyl butanediol, monoallyl diglycidyl isocyanurate, monomethyl diglycidyl isocyanurate, 5 diglycidyl diethyl barbiturate, and 5 diglycidyl dimethylhydantoin, but the present invention is not limited to these examples.

Is represented by the above formula (3), and m₁And m₂Examples of the monomer having a structural unit represented by 0 include compounds having 2 carboxyl groups, hydroxyphenyl groups or imide groups represented by the following formulae (11-a) to (11-s), and acid dianhydrides,

i.e., isophthalic acid, 5-hydroxyisophthalic acid, 2, 4-dihydroxybenzoic acid, 2-bis (4-hydroxyphenyl) sulfone, succinic acid, fumaric acid, tartaric acid, 3 '-dithiodipropionic acid, 1, 4-cyclohexanedicarboxylic acid, cyclobutyric dianhydride, cyclopentanoic dianhydride, monoallyl isocyanuric acid, 5-diethylbarbituric acid, diglycolic acid, acetonedicarboxylic acid, 2' -thiodiglycolic acid, 4-hydroxyphenyl 4-hydroxybenzoate, 2-bis (4-hydroxyphenyl) propane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 1, 3-bis (carboxymethyl) -5-methylisocyanate, 1, 3-bis (carboxymethyl) -5-allylisocyanurate, but is not limited to these examples.

M is represented by the above formula (3)₁And m₂A monomer (2-functional group) which is a structural unit represented by the formula (1), and m which is represented by the formula (3)₁And m₂The copolymerization ratio (addition weight ratio) of the monomer (2-functional) of the structural unit represented by 0 is, for example, 1: 2-2: 1.

the monomer further used for deriving an alicyclic ring bound to the end of the polymer of the present application (the site mainly reacting with the polymer is 1 functional), and the above-mentioned monomers are added in a weight ratio of, for example, 20: 1-5: 1.

The term "functional group" is a concept focusing on chemical properties and chemical reactivity of a substance, and when it is referred to as a functional group, its inherent physical properties and chemical reactivity are assumed, but in the present application, it means a reactive substituent capable of binding to another compound.

The number of repetitions of the structural unit represented by formula (3) is, for example, in the range of 5 to 10000.

Examples of the organic solvent contained in the resist underlayer film forming composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, ethyl acetate, methyl 3-ethoxypropionate, ethyl acetate, ethyl 3-ethoxypropionate, ethyl acetate, methyl acetate, ethyl acetate, methyl acetate, ethyl acetate, and methyl acetate, Methyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, gamma-butyrolactone, N-methylpyrrolidone, N-dimethylformamide, and N, N-dimethylacetamide. These solvents may be used alone or in combination of 2 or more.

Among these solvents, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, and the like are preferable. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

The ratio of the organic solvent to the resist underlayer film forming composition of the present invention is, for example, 50 mass% or more and 99.9 mass% or less.

The polymer contained in the resist underlayer film forming composition of the present invention is, for example, 0.1 to 50% by mass of the resist underlayer film forming composition.

The resist underlayer film forming composition of the present invention may contain a crosslinking agent and a crosslinking catalyst (curing catalyst) as a compound that promotes a crosslinking reaction, in addition to the polymer and the organic solvent. If the component obtained by removing the organic solvent from the resist underlayer film forming composition of the present invention is defined as a solid component, the solid component contains a polymer and, if necessary, additives such as a crosslinking agent and a crosslinking catalyst. The proportion of the additive is, for example, 0.1 to 50% by mass, preferably 1 to 30% by mass, based on the solid content of the resist underlayer film forming composition of the present invention.

Examples of the crosslinking agent contained as an optional component in the resist underlayer film forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4, 6-tetrakis (methoxymethyl) glycoluril (tetramethoxymethyl glycoluril) (POWDERLINK [ registered trademark ] 1174), 1,3,4, 6-tetrakis (butoxymethyl) glycoluril, 1,3,4, 6-tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1,3, 3-tetrakis (butoxymethyl) urea, 1,3, 3-tetrakis (methoxymethyl) urea, and 3,3 ', 5,5 ' -tetrakis (methoxymethyl) 4,4 ' -biphenol. When the crosslinking agent is used, the content of the crosslinking agent is, for example, 1 to 50% by mass, preferably 5 to 30% by mass, based on the polymer.

Examples of the curing catalyst (crosslinking catalyst) contained as an optional component in the resist underlayer film forming composition of the present invention include p-toluenesulfonic acid, trifluoromethanesulfonic acid, and pyridine-p-toluenesulfonate salt (pyridine)-p-toluenesulfonic acid), pyridine-p-hydroxybenzenesulfonic acid, pyridineSulfonic acid compounds and carboxylic acid compounds such as trifluoromethanesulfonic acid, cyclohexylp-toluenesulfonate, morpholine, p-toluenesulfonate, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid and the like. In the presence of the above-mentioned crosslinking catalyst In the case of the agent, the content of the crosslinking catalyst is, for example, 0.1 to 50% by mass, preferably 1 to 30% by mass, based on the crosslinking agent.

In the resist underlayer film forming composition of the present invention, a surfactant may be further added in order to further improve coatability to uneven surfaces without causing pinholes, streaks, and the like. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether and polyoxyethylene oleyl ether, polyoxyethylene alkylallyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene/polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate and other polyoxyethylene sorbitan fatty acid esters A surfactant エフトップ EF301, EF303, EF352 (trade name, manufactured by Tokuai chemical Co., Ltd.), (trade name, manufactured by Tokuai トーケムプロダクツ), メガファック F171, F173, R-30 (trade name, manufactured by Tokuai インキ Co., Ltd.), フロラード FC430, FC431 (trade name, manufactured by Sumitomo スリーエム Co., Ltd.), アサヒガード AG710, サーフロン S-382, SC101, SC102, SC103, SC104, SC105, SC106 (trade name, manufactured by Asahi Nitro Co., Ltd.), a fluorine-based surfactant, and an organosiloxane polymer KP341 (manufactured by shin-Etsu chemical Co., Ltd.). The amount of these surfactants to be mixed 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 forming composition of the present invention. These surfactants may be added alone or in combination of 2 or more.

< resist underlayer film >

The resist underlayer film according to the present invention can be produced by applying the resist underlayer film forming composition to a semiconductor substrate and baking the composition.

Examples of the semiconductor substrate to which the resist underlayer film forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers of gallium arsenide, indium phosphide, gallium nitride, indium nitride, aluminum nitride, and the like.

When a semiconductor substrate having an inorganic film formed on the surface thereof is used, the inorganic film is formed by, for example, an ALD (atomic layer deposition) method, a CVD (chemical vapor deposition) method, a reactive sputtering method, an ion plating method, a vacuum evaporation method, or a spin-on-glass (SOG) method. Examples of the inorganic film include a polycrystalline silicon film, a silicon oxide film, a silicon nitride film, a BPSG (borophosphosilicate Glass) film, a titanium nitride oxide film, a tungsten film, a gallium nitride film, and a gallium arsenide film.

The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate application method such as a spin coater or a coater. Then, a resist underlayer film is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from the baking temperature of 100 ℃ to 400 ℃ and the baking time of 0.3 minute to 60 minutes. Preferably, the baking temperature is 120-350 ℃, the baking time is 0.5-30 minutes, more preferably, the baking temperature is 150-300 ℃, and the baking time is 0.8-10 minutes.

The film thickness of the resist underlayer film to be formed is, for example, 0.001 μm (1nm) to 10 μm, 0.002 μm (2nm) to 1 μm, 0.005 μm (5nm) to 0.5 μm (500nm), 0.001 μm (1nm) to 0.05 μm (50nm), 0.002 μm (2nm) to 0.05 μm (50nm), 0.003 μm (1nm) to 0.05 μm (50nm), 0.004 μm (4nm) to 0.05 μm (50nm), 0.005 μm (5nm) to 0.05 μm (50nm), 0.003 μm (3nm) to 0.03 μm (30nm), 0.003 μm (3nm) to 0.02 μm (20nm), and 0.005 μm (5nm) to 0.02 μm (20 nm). When the temperature during baking is lower than the above range, crosslinking may be insufficient. On the other hand, when the temperature during baking is higher than the above range, the resist underlayer film may be thermally decomposed.

< method for manufacturing substrate having pattern formed thereon, method for manufacturing semiconductor device >

The method for manufacturing a substrate having a pattern formed thereon includes the following steps. In general, a photoresist layer is formed on a resist underlayer film. The photoresist formed on the resist underlayer film by coating and baking by a method known per se is not particularly limited as long as it is sensitive to light used for exposure. Both negative and positive photoresists may be used. There are positive photoresists comprising novolak resins and 1, 2-naphthoquinone diazosulfonate, chemically amplified photoresists comprising a binder having a group which increases the alkali dissolution rate by acid decomposition and a photoacid generator, chemically amplified photoresists comprising a low-molecular compound which increases the alkali dissolution rate of the photoresist by acid decomposition, an alkali-soluble binder and a photoacid generator, chemically amplified photoresists comprising a binder having a group which increases the alkali dissolution rate by acid decomposition, a low-molecular compound which increases the alkali dissolution rate of the photoresist by acid decomposition and a photoacid generator, and metal element-containing resists. Examples thereof include trade name V146G manufactured by JSR, trade name APEX-E manufactured by シプレー, trade name PAR710 manufactured by Sumitomo chemical industry, trade name AR2772 manufactured by shin-Etsu chemical industry, and SEPR 430. Further, examples of the fluorine atom-containing polymer-based photoresist include those described in Proc.SPIE, Vol.3999, 330-.

The exposure is performed through a mask (reticle) for forming a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet) or EB (electron beam) is used, but the resist underlayer film forming composition of the present invention is preferably applied to EUV (extreme ultraviolet) exposure. The developing is carried out by using an alkaline developing solution, and the developing temperature is 5-50 ℃ and the developing time is properly selected from 10 seconds to 300 seconds. Examples of the alkali developer include aqueous solutions of bases such as inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, ethanolamines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine. Further, an appropriate amount of an alcohol such as isopropyl alcohol, a nonionic surfactant, or the like may be added to the alkali aqueous solution. Among them, the preferred developer is a quaternary ammonium salt, and tetramethylammonium hydroxide and choline are more preferred. Further, a surfactant or the like may be added to these developer solutions. Instead of the alkali developer, a method of developing a portion of the photoresist where the alkali dissolution rate is not increased by developing with an organic solvent such as butyl acetate may be used. Through the above steps, a substrate on which the resist is patterned can be manufactured.

Then, the resist underlayer film is dry-etched using the formed resist pattern as a mask. In this case, the surface of the inorganic film is exposed when the inorganic film is formed on the surface of the semiconductor substrate to be used, and the surface of the semiconductor substrate is exposed when the inorganic film is not formed on the surface of the semiconductor substrate to be used. Then, the substrate is processed by a method known per se (dry etching method, etc.) to manufacture a semiconductor device.

Examples

The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

The weight average molecular weight of the polymers shown in synthetic examples 1 to 8 and comparative synthetic examples 1 to 2 described below in the present specification was measured by gel permeation chromatography (hereinafter, abbreviated as GPC). GPC equipment manufactured by DONG ソー (Inc.) was used for the measurement, and the measurement conditions were as follows.

GPC column: shodex KF803L, Shodex KF802, Shodex KF801 [ registered trademark ] (Shorey electrician strain)

Column temperature: 40 deg.C

Solvent: tetrahydrofuran (THF)

Flow rate: 1.0 ml/min

Standard sample: polystyrene (manufactured by imperial Chinese imperial ceramics ソー)

< Synthesis example 1 >

As the polymer 1, 7.88g of N, N-diglycidyl-5, 5-dimethylhydantoin (manufactured by Shikoku Kogyo Co., Ltd.), 5.03g of monoallyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), 1.45g of 5-norbornene-2-carboxylic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and ethyl triphenyl brominate were added0.65g of propylene glycol monomethyl ether (66.60 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 3000 in terms of standard polystyrene and a dispersity of 2.8. The structure present in the polymer 1 is shown in the following formula.

< Synthesis example 2 >

As the polymer 2, 7.88g of N, N-diglycidyl-5, 5-dimethylhydantoin (manufactured by Shikoku Kogyo Co., Ltd.), 5.07g of monoallyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), 1.34g of 3-cyclohexene-1-carboxylic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and ethyltriphenylphosphonium bromide were added0.66g of propylene glycol monomethyl ether (66.60 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 2500 in terms of standard polystyrene and a dispersity of 2.2. The structure present in polymer 2 is shown in the following formula.

< Synthesis example 3 >

As the polymer 3, 7.95g of N, N-diglycidyl-5, 5-dimethylhydantoin (manufactured by Shikoku Kogyo Co., Ltd.), 5.07g of monoallyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), 1.74g of 5-norbornene-2, 3-dicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and ethyltriphenylbromohydantoin were added0.66g of propylene glycol monomethyl ether (66.60 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 2500 in terms of standard polystyrene and a dispersity of 2.2. The structure present in polymer 3 is shown in the following formula.

< Synthesis example 4 >

As the polymer 4, 7.88g of N, N-diglycidyl-5, 5-dimethylhydantoin (manufactured by Shikoku Kogyo Co., Ltd.), 5.07g of monoallyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), 1.73g of cyclohexane-1-carboxylic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and ethyltriphenylphosphonium bromide were added0.63g of propylene glycol monomethyl ether (66.60 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 2500 in terms of standard polystyrene and a dispersity of 2.2. The structure present in polymer 4 is shown in the following formula.

< Synthesis example 5 >

As the polymer 5, 7.73g of N, N-diglycidyl-5, 5-dimethylhydantoin (manufactured by Shikoku Kogyo Co., Ltd.), 4.94g of monoallyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), and 7-oxabicyclo [2.2.1]1.71g of hept-5-ene-2, 3-dicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and ethyltriphenylphosphonium bromide0.64g of propylene glycol monomethyl ether (66.60 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 2500 in terms of standard polystyrene and a dispersity of 2.0. The structure present in the polymer 5 is shown in the following formula.

< Synthesis example 6 >

As the polymer 6, 7.20g of N, N-diglycidyl-5, 5-dimethylhydantoin (manufactured by Sikko chemical Co., Ltd.), 4.95g of 5-hydroxyisophthalic acid (manufactured by Tokyo chemical Co., Ltd.), 1.33g of 5-norbornene-2-carboxylic acid (manufactured by Tokyo chemical Co., Ltd.) and ethyltriphenylphosphonium bromide were added0.54g of propylene glycol monomethyl ether (39.19 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 2500 in terms of standard polystyrene and a dispersity of 2.2.

The structure present in polymer 6 is shown in the following formula.

< Synthesis example 7 >

As the polymer 7, 25.00g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), 14.72g of diethyl barbituric acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 2.91g of 5-norbornene-2, 3-dicarboxylic anhydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and ethyltriphenylphosphonium bromide were used1.64g of propylene glycol monomethyl ether (89.73 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 3000 in terms of standard polystyrene and a dispersity of 2.3. The structure present in polymer 7 is shown in the following formula.

< Synthesis example 8 >

As the polymer 8, 25.00g of monoallyl diglycidyl isocyanuric acid (manufactured by Sikko chemical industry Co., Ltd.), 15.86g of dithiodipropionic acid (manufactured by Tokyo chemical industry Co., Ltd.), 4.80g of adamantanecarboxylic acid (manufactured by Tokyo chemical industry Co., Ltd.), and tetrabutyl bromide1.13g of propylene glycol monomethyl ether (57.12 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the weight average molecular weight of the resulting polymer was 5000 in terms of standard polystyrene and the degree of dispersion was 2.3. The structure present in the polymer 8 is shown in the following formula.

< synthetic example 9 >

Polymer 9 contained 25.00g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), 15.86g of dithiodipropionic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), 3.68g of 5-norbornene-2-carboxylic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and tetrabutyl bromide1.13g of propylene glycol monomethyl ether (57.12 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the weight average molecular weight of the resulting polymer was 5000 in terms of standard polystyrene and the degree of dispersion was 2.5.

The structure present in the polymer 9 is shown in the following formula.

Comparative Synthesis example 1

As the polymer 10, 21.90g of monoallyl diglycidyl isocyanuric acid (manufactured by Sikko chemical industry Co., Ltd.), 12.17g of diethyl barbituric acid (manufactured by Tokyo chemical industry Co., Ltd.), 4.67g of lauric acid (manufactured by Tokyo chemical industry Co., Ltd.), and ethyltriphenylphosphonium bromide were added0.56g of propylene glycol monomethyl ether (89.73 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 3000 in terms of standard polystyrene and a dispersity of 2.2. The structure present in the polymer 10 is shown in the following formula.

Comparative Synthesis example 2

Polymer 11 contained 25.00g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Kogyo Co., Ltd.), 15.86g of dithiodipropionic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and tetrabutyl bromide1.13g of propylene glycol monomethyl ether (57.12 g) was added and dissolved. After the reaction vessel was purged with nitrogen, the reaction was carried out at 110 ℃ for 24 hours to obtain a polymer solution. GPC analysis showed that the weight average molecular weight of the resulting polymer was 5000 in terms of standard polystyrene and the degree of dispersion was 4.3. The structure present in the polymer 11 is shown in the following formula.

(preparation of resist underlayer film)

(example 1)

Each of the above synthetic examples 1 to 9 and comparative synthetic examples 1 to 2 was mixed with the polymer, the crosslinking agent, the curing catalyst and the solvent at the ratio shown in Table 1, and filtered through a 0.1 μm fluororesin filter to prepare a solution of the resist underlayer film forming composition.

In Table 1, tetramethoxymethyl glycoluril (manufactured by Japan サイテックインダストリーズ Co., Ltd.) is abbreviated as PL-LI, and pyridine is addedP-toluenesulfonic acid abbreviated PyPTS, pyridineP-hydroxybenzene sulfonic acid is abbreviated as PyPSA, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, and propylene glycol monomethyl ether is abbreviated as PGME. The respective addition amounts are expressed by parts by mass.

[ Table 1]

TABLE 1

[ Table 2]

TABLE 2

(dissolution test into Photoresist solvent)

The resist underlayer film forming compositions of examples 1 to 11, comparative example 1 and comparative example 2 were applied to a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205 ℃ for 60 seconds to obtain a film having a film thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether/propylene glycol monomethyl ether (70/30) as a solvent used for a photoresist, and the film thickness was changed toThe following is preferable, andthe above cases were regarded as defects, and the results are shown in table 3. Only comparative example 1 showed a failure.

(measurement of Water contact Angle)

The resist underlayer film forming compositions of examples 1 to 11, comparative example 1 and comparative example 2 were applied to a silicon wafer using a spin coater. The silicon wafer was baked on a hot plate at 205 ℃ for 60 seconds to obtain a film having a film thickness of 5 nm. The resist underlayer films were measured for the contact angle of water by the liquid drop method using a full-automatic contact angle meter DM-701 (manufactured by kyowa interface science corporation).

[ Table 3]

TABLE 3

(evaluation of resist Pattern formation)

[ formation of resist Pattern by KrF Exposure ]

A silicon wafer was coated with DUV-30J (manufactured by Nissan chemical Co., Ltd.) as an antireflection film by using a spin coater. The silicon wafer was baked on a hot plate at 205 ℃ for 60 seconds to obtain a film having a film thickness of 18 nm. On the film, the resist underlayer film forming compositions of examples 1 to 6, example 8 and comparative examples 1 to 2 were applied to silicon wafers using a spin coater. The silicon wafer was baked on a hot plate at 205 ℃ for 60 seconds to obtain a resist underlayer film having a film thickness of 5 nm. On the resist underlayer film, SEPR-430 (manufactured by shin-Etsu chemical Co., Ltd.) as a positive resist solution for KrF excimer laser was spin-coated, and heated at 100 ℃ for 60 seconds to form a KrF resist film. The resist film was exposed to light under predetermined conditions using a KrF excimer laser exposure apparatus (NSR S205C, manufactured by ltd. ニコン). After exposure, the resist was exposed to light at 110 ℃ for 60 seconds and then heated, and then subjected to paddle development for 60 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (NMD-3, product name, manufactured by tokyo chemical industries, ltd.) as a developing solution for a photoresist. With respect to the obtained photoresist pattern, the case where large pattern peeling did not occur was evaluated as good.

[ Table 4]

TABLE 4

[ EUV exposure test ]

The resist underlayer film forming compositions of example 9, example 10 and comparative example 2 of the present invention were spin-coated on a silicon wafer, and heated at 215 ℃ for 1 minute to form a resist underlayer film (film thickness 5 nm). A resist solution for EUV (methacrylate resin-based resist) was spin-coated on the resist underlayer film, heated, and exposed to light under an NA of 0.33Dipole using an EUV exposure apparatus (manufactured by ASML corporation, NXE 3300). After exposure, post-exposure heating (PEB, 100 ℃ for 60 seconds) was performed, cooling was performed on a cooling plate until room temperature, and alkali development and rinsing treatments were performed to form a resist pattern on a silicon wafer. Evaluation was performed by determining whether a 16nm line and a gap (L/S) could be formed. In all cases of example 9, example 10 and comparative example 2, 16nmL/S pattern formation was confirmed. The exposure amount at the time when the 16nm line/32 nm pitch (line and space (L/S) 1/1) was formed was set as the optimum exposure amount, and the exposure amount (EOP) at the time was displayed, the roughness (LWR) of the line width at the time was further shown in table 5, and the improvement in LWR was observed in examples 9 and 10 as compared with comparative example 2.

[ Table 5]

TABLE 5

[ EUV exposure test ]

The resist underlayer film forming composition of example 1 of the present invention was spin-coated on a silicon wafer and heated at 215 ℃ for 1 minute to form a resist underlayer film (film thickness 5 nm). Further, an EUV resist solution (methacrylate resin-based resist) was spin-coated thereon, heated at 130 ℃ for 1 minute to form an EUV resist film, and exposed to light under an NA of 0.33 and Dipole using an EUV exposure apparatus (NXE3300B) manufactured by ASML. After exposure, heating after exposure (PEB, 110 ℃ for 1 minute), cooling on a cooling plate to room temperature, developing with an organic solvent developer (butyl acetate) for 60 seconds, and rinsing treatment were performed to form a resist pattern.

Resist patterns were formed in the same manner using the compositions obtained in examples 3, 6 to 8 and comparative example 2.

For the evaluation, whether lines and spaces of 44nm pitch and 22nm could be formed was evaluated by confirming the pattern shape by pattern cross-section observation.

In the observation of the pattern shape, a state between the footing (footing) and the undercut (undercut) and no significant residue in the gap portion was evaluated as "good", an undesired state in which the resist pattern was peeled off and collapsed was evaluated as "collapse", and an undesired state in which the upper portion or the lower portion of the resist pattern was in contact with each other was evaluated as "bridge". The obtained results are shown in table 6.

[ Table 6]

TABLE 6

Industrial applicability

The resist underlayer film forming composition according to the present invention can provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for producing a substrate with a resist pattern using the resist underlayer film forming composition, and a method for producing a semiconductor device.