JP2022132962A - Resist underlayer-forming composition - Google Patents

Abstract

To provide a resist underlayer-forming composition having dry etching resistance to a fluorocarbon-containing gas comparable to that of fullerene derivatives and further having excellent film hardness even when easily available cheep materials are used, and a production method of the same.SOLUTION: A resist underlayer, formed by using a resist underlayer-forming composition comprising a polymer of a 6-60C aromatic compound having at least one or more structures in which a formyl group and a hydroxy group are respectively bonded to two mutually adjacent carbons and a solvent, has high etching resistance close to a material using fullerene and a low film contraction coefficient and easily maintains in-surface uniformity of the underlayer, and thereby can suppress occurrence of any non-photosensitive region. In addition, the resist underlayer exhibits high hardness and therefore is advantageous to substrate processing with etching.SELECTED DRAWING: None

Description

The present invention relates to a resist underlayer film-forming composition for forming a resist underlayer film used in a lithography process, and a method for producing the same.

2. Description of the Related Art In a lithography process for manufacturing a semiconductor device, a technique is known in which a resist pattern having a desired shape is formed by providing a resist underlayer film prior to forming a photoresist film. Patent Document 1 below describes a composition for forming a resist underlayer film prepared using a fullerene derivative. A fullerene derivative is a compound with a high carbon content, and has high hardness when a resist underlayer film is formed. It has been used as a useful material due to its resistance.

WO2016/143436

However, since fullerene derivatives have a special chemical structure, they are not readily available, and they are expensive, so they are not necessarily useful materials for industrial use.
The present invention provides a composition for forming a resist underlayer film having dry etching resistance to a fluorocarbon-containing gas comparable to that of a fullerene derivative even when an easily available and inexpensive material is used, and having excellent film hardness, and its production. The purpose is to provide a method.

（式（１）中、Ａｒ_１は炭素数１乃至２０のアルキル基、炭素数２乃至１０のアルケニル基、炭素数２乃至１０のアルキニル基、、ハロゲン原子、ヒドロキシ基、エーテル基、アルコキシ基で置換されていても良い炭素数６～５９の芳香環を表す。）
３．式（１）において、Ａｒ_１が単環、縮合環、複素環またはこれらの環が単結合によりもしくはスペーサーを介して連結されている連結環である上記２に記載のレジスト下層膜
形成組成物に関する。
４．式（１）において、Ａｒ_１がベンゼン環、ナフタレン環、アントラセン環、ピレン環のいずれかである上記２に記載のレジスト下層膜形成組成物に関する。
５．更に架橋剤を含む、上記１乃至上記４のいずれか１つに記載のレジスト下層膜形成組成物に関する。
６．更に酸及び／又は酸発生剤を含む、上記１乃至上記５のいずれか１つに記載のレジスト下層膜形成組成物に関する。
７．前記溶剤の沸点が、１６０℃以上である上記１乃至上記６のいずれか１つに記載のレジスト下層膜形成組成物に関する。
８．上記１乃至上記７のいずれか１つ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に関する。
９．半導体基板上に塗布された上記１乃至上記８のいずれか１つに記載のレジスト下層膜形成組成物を焼成してレジスト下層膜を形成するレジスト下層膜の製造方法に関する。
１０.前記焼成を２段階でおこなう上記９に記載のレジスト下層膜の製造方法に関する。
１１．前記焼成における２段階目の焼成温度が４００℃以上である上記１０に記載のレジスト下層膜の製造方法に関する。
１２．前記焼成を不活性ガス雰囲気下で行う上記９乃至上記１１のいずれか１つに記載のレジスト下層膜レジスト下層膜の製造方法に関する。
１３．半導体基板上に上記１乃至上記８のいずれか１つに記載のレジスト下層膜形成組成物を用いてレジスト下層膜を形成する工程、
形成されたレジスト下層膜の上にレジスト膜を形成する工程、
形成されたレジスト膜に対する光又は電子線の照射と現像によりレジストパターンを形成する工程、
形成された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し、パターン化する工程、及び
パターン化されたレジスト下層膜を介して半導体基板を加工する工程
を含む半導体装置の製造方法に関する。 As a result of intensive studies, the inventors have found a composition for forming a resist underlayer film having high dry etching resistance and excellent film hardness, and completed the present invention.
That is, the present invention includes the following.
1. The present invention relates to a resist underlayer film-forming composition containing a polymer of an aromatic compound having 6 to 60 carbon atoms and having at least one structure in which a formyl group and a hydroxy group are bonded to two adjacent carbons, respectively, and a solvent.
2. 1. The composition for forming a resist underlayer film according to 1 above, wherein the aromatic compound is a compound represented by formula (1).

(wherein Ar ₁ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a halogen atom, a hydroxy group, an ether group, or an alkoxy group; represents an optionally substituted aromatic ring having 6 to 59 carbon atoms.)
3. 2. The composition for forming a resist underlayer film as described in 2 above, wherein in formula (1), Ar ₁ is a monocyclic ring, a condensed ring, a heterocyclic ring, or a linked ring in which these rings are linked via a single bond or via a spacer. .
4. 2. The composition for forming a resist underlayer film as described in 2 above, wherein in formula (1), Ar ₁ is any one of a benzene ring, a naphthalene ring, an anthracene ring and a pyrene ring.
5. 5. The composition for forming a resist underlayer film according to any one of 1 to 4 above, further comprising a cross-linking agent.
6. 6. The composition for forming a resist underlayer film according to any one of 1 to 5 above, further comprising an acid and/or an acid generator.
7. 7. The composition for forming a resist underlayer film according to any one of 1 to 6 above, wherein the solvent has a boiling point of 160° C. or higher.
8. 8. A resist underlayer film characterized by being a baked product of a coating film comprising the resist underlayer film-forming composition according to any one of 1 to 7 above.
9. The present invention relates to a method for producing a resist underlayer film, comprising baking the resist underlayer film-forming composition according to any one of 1 to 8 coated on a semiconductor substrate to form a resist underlayer film.
10. The method for producing a resist underlayer film according to 9 above, wherein the baking is performed in two stages.
11. 11. The method for producing a resist underlayer film as described in 10 above, wherein the baking temperature in the second step in the baking is 400° C. or higher.
12. 12. The method for producing a resist underlayer film according to any one of 9 to 11 above, wherein the baking is performed in an inert gas atmosphere.
13. forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of 1 to 8;
forming a resist film on the formed resist underlayer film;
forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing;
The present invention relates to a method of manufacturing a semiconductor device, including the steps of etching and patterning the resist underlayer film through a formed resist pattern, and processing a semiconductor substrate through the patterned resist underlayer film.

The resist underlayer film formed using the resist underlayer film-forming composition of the present invention has high etching resistance close to that of a material using fullerene, has a low film shrinkage rate, and easily maintains inner surface uniformity of the underlayer film. , the occurrence of non-photosensitive areas can be suppressed. In addition, since it exhibits high hardness, it is advantageous for substrate processing by etching.

The present invention provides a resist underlayer film-forming composition comprising a polymer of an aromatic compound having 6 to 60 carbon atoms and having at least one structure in which a formyl group and a hydroxy group are respectively bonded to two adjacent carbons, and a solvent. be.

（式（１）中、Ａｒ_１は炭素数１乃至２０のアルキル基、炭素数２乃至１０のアルケニル基、炭素数２乃至１０のアルキニル基、、ハロゲン原子、ヒドロキシ基、エーテル基、アルコキシ基で置換されていても良い炭素数６～５９の芳香環を表す。） [Aromatic compound having 6 to 60 carbon atoms]
An aromatic compound having 6 to 60 carbon atoms is a compound represented by formula (1).

(wherein Ar ₁ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a halogen atom, a hydroxy group, an ether group, or an alkoxy group; represents an optionally substituted aromatic ring having 6 to 59 carbon atoms.)

[Aromatic ring having 6 to 59 carbon atoms (Ar ₁ )]
The aromatic ring having 6 to 59 carbon atoms (Ar ₁ ) is a monocyclic ring, a condensed ring, a heterocyclic ring, or a linked ring in which these rings are linked via a single bond or via a spacer. Specifically, the aromatic ring having 6 to 59 carbon atoms (Ar ₁ ) is
(a) may be monocyclic such as benzene, phenol,
(b) may be condensed rings such as naphthalene, anthracene, pyrene, hydroxynaphthalene, naphthol, 9,10-anthraquinone, indenofluorenedione;
(c) may be a heterocycle such as furan, thiophene, pyridine, carbazole, phenothiazine, phenoxazine, indolocarbazole;
(d) biphenyl, phenylindole, 9,9-bis(4-hydroxyphenyl)fluorene, α,α,α',α'-tetrakis(4-hydroxyphenyl)-p-xylene, 9,9-fluorenylidene-bis It may be a ring in which the aromatic rings (a) to (c) are bonded with a single bond like naphthol,
(e) A ring in which the aromatic rings (a) to (d) are connected via a spacer, such as phenylnaphthylamine. The substituent R here can be exemplified by an alkyl group having 1 to 20 carbon atoms, which will be described later.
Examples of spacers include -(CH ₂ ) _n - (n=1-20), -CH=CH-, -C≡C-, -N=N-, -NH-, -NR-, -NHCO- , -NRCO-, -S-, -COO-, -OCO-, -O-, -CO-, -Ph-, -Ph-Ph-, -Ph-O-Ph- (Ph=C ₆ H ₄ ) , and —CH═N—, or a combination of two or more thereof. Two or more of these spacers may be linked.

In addition to the aromatic rings exemplified above, Ar ₁ further includes pyrimidine, pyrazine, pyrrole, oxazole, thiazole, imidazole, quinoline, fluorene, quinazoline, purine, indolizine, benzothiophene, benzofuran, indole, acridine, and the like. .

The hydrogen atom of the aromatic ring (Ar ₁ ) having 6 to 59 carbon atoms is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a halogen atom, and a hydroxy group. , an ether group, or an alkoxy group.

Examples of the alkyl group having 1 to 20 carbon atoms include a linear or branched alkyl group which may or may not have a substituent, such as 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, nonadecyl group and eicosyl group. An alkyl group having 1 to 12 carbon atoms is preferred, an alkyl group having 1 to 8 carbon atoms is more preferred, and an alkyl group having 1 to 4 carbon atoms is even more preferred.

Examples of alkenyl groups having 2 to 10 carbon atoms and alkynyl groups having 2 to 10 carbon atoms include linear or branched alkenyl groups and alkynyl groups which may or may not have substituents. vinyl group, ethynyl group, 2-propenyl group, 2-propynyl group, 2-butenyl group, 2-butynyl group, 3-butenyl group, 3-butynyl group and the like.

The alkyl group having 1 to 20 carbon atoms which may have a substituent, the alkenyl group having 2 to 10 carbon atoms which may have a substituent, and the alkynyl having 2 to 10 carbon atoms which may have a substituent Substituents for the groups include formyl groups, halogen atoms, hydroxy groups, ether groups, alkoxy groups and the like.

The aromatic ring (Ar ₁ ) is preferably a benzene ring, naphthalene ring, anthracene ring, or pyrene ring. Further, the aromatic ring (Ar ₁ ) may be a condensed ring in which two or more kinds of aromatic rings (Ar ₁ ) are condensed within a range not exceeding 59 carbon atoms.

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

Examples of such solvents 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, 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 Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, Methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate , Isopropyl Propionate, Butyl Propionate, Isobutyl Propionate, Methyl Butyrate, Ethyl Butyrate, Propyl Butyrate, Isopropyl Butyrate, Butyl Butyrate, Isobutyl Butyrate, Hydroxy Vinegar ethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, 3- Methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, N,N-dimethylformamide, N-methylacetamide , N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone. These solvents can be used alone or in combination of two or more.

（式（ｉ）中のＲ_４、Ｒ_５及びＲ_６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数１乃至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 WO2018/131562A1 can also be used.

(R ₄ , R ₅ and R ₆ in formula (i) each represent a hydrogen atom, an oxygen atom, a sulfur atom or an alkyl group having 1 to 20 carbon atoms which may be interrupted by an amide bond, and are the same as each other. may be different from each other, and may be combined with each other to form a ring structure.)

Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups which may or may not have substituents, such as methyl group, ethyl group, 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, Examples include heptadecyl, octadecyl, nonadecyl and eicosyl groups. It is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.

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

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

Specific examples of preferable compounds represented by formula (i) are shown below.

で表される化合物が好ましく、式（ｉ）で表される化合物として特に好ましいのは、３－メトキシ－Ｎ，Ｎ－ジメチルプロピオンアミド、及びＮ，Ｎ－ジメチルイソブチルアミドである。 Among the above, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylisobutyramide, and the formula:

are preferred, and particularly preferred compounds of formula (i) are 3-methoxy-N,N-dimethylpropionamide and N,N-dimethylisobutyramide.

These solvents can be used alone or in combination of two or more. Among these solvents, those having a boiling point of 160° C. or higher are preferred, and propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionamide, N, N-dimethylisobutyramide, 2,5-dimethylhexane-1,6-diyldiacetate (DAH; cas, 89182-68-3), and 1,6-diacetoxyhexane (cas, 6222-17-9), etc. is preferred. Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutyramide are particularly preferred.

[Crosslinking agent component]
The resist underlayer film-forming composition of the present invention can contain a cross-linking agent component. Examples of the cross-linking agent include melamine-based, substituted urea-based, or polymer-based thereof. Preferred are crosslinkers having at least two crosslink-forming substituents, methoxymethylated glycoluril (e.g., tetramethoxymethylglycoluril), butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxy Compounds such as methylated benzogwanamine, butoxymethylated benzogwanamine, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. Condensates of these compounds can also be used.

A cross-linking agent having high heat resistance can be used as the cross-linking agent. As a highly heat-resistant cross-linking agent, a compound containing a cross-linking substituent having an aromatic ring (eg, benzene ring, naphthalene ring) in the molecule can be preferably used.

上記Ｒ^１１、Ｒ^１２、Ｒ^１３、及びＲ^１４は水素原子又は炭素数１乃至１０のアルキル基であり、これらのアルキル基は上述の例示を用いることができる。ｎ３は１～４の整数であり、ｎ４は１～（５－ｎ３）の整数であり、（ｎ３＋ｎ４）は２～５の整数を示す。ｎ５は１～４の整数であり、ｎ６は０～（４－ｎ５）であり、（ｎ５＋ｎ６）は１～４の整数を示す。オリゴマー及びポリマーは繰り返し単位構造の数が２～１００、又は２～５０の範囲で用いることができる。 Examples of this compound include compounds having a partial structure of the following formula (4), and polymers or oligomers having repeating units of the following formula (5).

The above R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and the above examples can be used for these alkyl groups. n3 is an integer of 1-4, n4 is an integer of 1-(5-n3), and (n3+n4) is an integer of 2-5. n5 is an integer of 1-4, n6 is 0-(4-n5), and (n5+n6) is an integer of 1-4. Oligomers and polymers can be used in the range of 2 to 100 or 2 to 50 repeating unit structures.

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

The above compounds are available as products of Asahi Organic Chemical Industry Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, the compound of formula (4-24) among the above crosslinking agents is available from Asahi Organic Chemicals Industry Co., Ltd. under the trade name TM-BIP-A.
The amount of the cross-linking agent to be added varies depending on the coating solvent to be used, the underlying substrate to be used, the required solution viscosity, the required film shape, etc., but is preferably 0.001 to 80% by mass, based on the total solid content. 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 when cross-linkable substituents are present in the reaction product of the present invention, they can cause a cross-linking reaction with those cross-linkable 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 acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, pyridinium phenolsulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, and 4-chlorobenzenesulfonic acid. , benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid and the like.
Only one kind of acid can be used, or two or more kinds can be used in combination. The blending amount is usually 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, more preferably 0.01 to 3% by mass, based on the total solid content.

Examples of acid generators include thermal acid generators and photoacid generators.
Thermal acid generators include 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, K-PURE (registered trademark) CXC-1612, CXC-1614, and TAG. -2172, TAG-2179, TAG-2678, TAG2689, TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 ( manufactured by Sanshin Chemical Industry Co., Ltd.) and other organic sulfonic acid alkyl esters.

Photoacid generators generate acid when the resist is exposed to light. Therefore, the acidity of the underlayer film can be adjusted. This is one way to match the acidity of the underlayer film to that of the overlying resist. Also, the pattern shape of the resist formed on the upper layer can be adjusted by adjusting the acidity of the lower layer film.
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.

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

Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoro-normalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide and N-(trifluoromethanesulfonyloxy)naphthalimide. mentioned.

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

Only one kind of acid generator can be used, or two or more kinds can be used in combination.
When an acid generator is used, its proportion is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.1 to 3 parts by mass, per 100 parts by mass of the solid content of the resist underlayer film-forming composition. 5 to 1 part by mass.

[Other ingredients]
The composition for forming a resist underlayer film of the present invention can be blended with a surfactant in order to further improve coatability against surface unevenness without generating pinholes, striations, and the like. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and polyoxyethylene nonylphenol ether. Polyoxyethylene alkyl allyl ethers such as polyoxyethylene/polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. sorbitan fatty acid esters, polyoxyethylene sorbitan such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate Nonionic surfactants such as fatty acid esters, Ftop EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade names), Megaface F171, F173, R-40, R-40N, R-40LM (DIC stock company, product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product name) ), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. The blending amount of these surfactants is usually 2.0% by mass or less, preferably 1.0% by mass or less, based on the total solid content of the resist underlayer film material. These surfactants may be used alone or in combination of two or more. When a surfactant is used, its proportion is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01, per 100 parts by mass of the solid content of the resist underlayer film-forming composition. to 0.5 parts by mass.

The composition for forming a resist underlayer film of the present invention may contain a light absorber, a rheology modifier, an adhesion aid, and the like. Rheology modifiers are effective in improving the fluidity of the Underlayer film-forming composition. Adhesion aids are effective in improving the adhesion between the semiconductor substrate or resist and the underlying film.

Examples of light absorbing agents include commercially available light absorbing agents described in "Techniques and Markets of Industrial Dyes" (CMC Publishing) and "Handbook of Dyes" (Edited by Society of Organic Synthetic Chemistry), such as C.I. I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; 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; I. Disperse Blue 96; I. Fluorescent Brightening Agents 112, 135 and 163; I. Solvent Orange 2 and 45; C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; I. Pigment Green 10; C.I. I. Pigment Brown 2 and the like can be preferably used. The above light absorbing agent is usually blended in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solid content of the resist underlayer film-forming composition.

The rheology modifier mainly improves the fluidity of the resist underlayer film-forming composition, and particularly in the baking process, improves the film thickness uniformity of the resist underlayer film and improves the fillability of the resist underlayer film-forming composition into the holes. It is added for the purpose of enhancement. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; Maleic acid derivatives such as normal butyl maleate, diethyl maleate and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate and tetrahydrofurfuryl oleate; and stearic acid derivatives such as normal butyl stearate and glyceryl stearate. can. These rheology modifiers are usually blended in a ratio of less than 30% by mass based on the total solid content of the resist underlayer film-forming composition.

The adhesion adjuvant is added mainly for the purpose of improving the adhesion between the substrate or resist and the composition for forming a resist underlayer film, and especially for preventing the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylmethylolchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylmethylolethoxysilane, diphenyldimethoxysilane, Alkoxysilanes such as enyltriethoxysilane, silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole, methyloltrichlorosilane, γ-chloropropyltrimethoxysilane, γ -Aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane and other silanes, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole , thiouracil, mercaptoimidazole, and mercaptopyrimidine; ureas such as 1,1-dimethylurea and 1,3-dimethylurea; and thiourea compounds. These adhesion aids are blended at a ratio of usually less than 5% by mass, preferably less than 2% by mass, based on the total solid content of the resist underlayer film-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 components excluding the solvent from the resist underlayer film-forming composition. The proportion of the reaction product in the solid content is preferably in the order of 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

One measure for evaluating whether the resist underlayer film-forming composition is in a uniform solution state is to observe the permeability of a specific microfilter. , passes through a microfilter with a pore size of 0.1 μm, and presents a homogeneous solution state.

Examples of the microfilter material include fluorine-based resins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP ( polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, but PTFE (polytetrafluoroethylene) is preferred.

[Method for manufacturing resist underlayer film and semiconductor device]
Hereinafter, a method for producing 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, such as silicon wafer substrates, silicon/silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and 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 baked to form a resist underlayer film. The firing conditions are appropriately selected from a firing temperature of 80° C. to 800° C. and a firing time of 0.3 to 60 minutes. Air may be used as the atmosphere gas during firing, or an inert gas such as nitrogen or argon may be used. Preferably, after pre-baking in air at a baking temperature of 150° C. to 350° C. for a baking time of 0.5 to 2 minutes, baking in an inert gas at a temperature of 400° C. to 800° C., more preferably 450° C. to 700° C. More preferably, the main firing is carried out at 500°C to 600°C for a firing time of 0.5 to 2 minutes. The oxygen concentration under inert gas is less than 1% by volume, preferably 0.1% by volume or less, more preferably 0.01% by volume or less, further preferably 0.005% by volume or less, and 0.003% by volume. % or less is particularly preferred. If the oxygen concentration during heating is high, the oxidative decomposition of the resist underlayer film proceeds, and there is a risk that the characteristics required for the resist underlayer film cannot be exhibited. Here, the film thickness of the lower layer film to be formed is, for example, 10 to 1000 nm, 20 to 500 nm, 30 to 400 nm, or 50 to 300 nm.

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

Further, the composition for forming a resist underlayer film according to the present invention is applied onto a semiconductor substrate having a portion having a step and a portion having no step (so-called stepped substrate), and baked to obtain a portion having a step and a portion having a step. It is possible to form a resist underlayer film having a step in the range of 3 to 70 nm from a portion having no step.

A resist film, for example, a layer of photoresist is then formed on the resist underlayer film. The formation of the photoresist layer can be carried out by a well-known method, ie, applying a solution of the photoresist composition onto the underlying film and baking. The film thickness of the photoresist is, for example, 50 to 10000 nm, 100 to 2000 nm, or 200 to 1000 nm.

The photoresist to be formed on the resist underlayer film is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. positive photoresist composed of novolac resin and 1,2-naphthoquinonediazide sulfonic acid ester; A chemically amplified photoresist comprising a low-molecular 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 is a chemically amplified photoresist composed of a low-molecular-weight compound and a photoacid generator, which are decomposed by acid to increase the rate of alkali dissolution of the photoresist. Examples include APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Also, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

Next, a resist pattern is formed by irradiation with light or an electron beam and development. First, exposure is performed through a predetermined mask. Near-ultraviolet rays, far-ultraviolet rays, or extreme ultraviolet rays (for example, EUV (wavelength: 13.5 nm)) or the like are used for exposure. Specifically, KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength: 193 nm), F2 excimer laser ₍ wavelength: 157 nm), and the like can be used. Among these, ArF excimer laser (wavelength 193 nm) and EUV (wavelength 13.5 nm) are preferable. After exposure, a post exposure bake can be performed if necessary. The post-exposure heating is performed under conditions appropriately selected from a heating temperature of 70° C. to 150° C. and a heating time of 0.3 to 10 minutes.

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

Development is then performed with a developer. This removes the exposed portions of the photoresist and forms a pattern of the photoresist, for example, if a positive photoresist is used.
Examples of the developer include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, quaternary ammonium hydroxides such as choline, ethanolamine, propylamine, Examples include aqueous alkaline solutions such as aqueous solutions of amines such as ethylenediamine. Furthermore, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5° C. to 50° C. and a time of 10 to 600 seconds.

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

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

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

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

Moreover, an organic antireflection film can be formed on the upper layer of the resist underlayer film before forming the photoresist. The antireflection coating composition used there is not particularly limited, and can be used by arbitrarily selecting from those commonly used in the lithography process. The antireflection film can be formed by coating with a coater and baking.

In the present invention, an organic underlayer film is formed on a substrate, an inorganic underlayer film is formed thereon, and a photoresist can be further coated thereon. As a result, the pattern width of the photoresist is narrowed, and even if the photoresist is thinly coated to prevent pattern collapse, the substrate can be processed by selecting an appropriate etching gas. For example, it is possible to process the resist underlayer film by using a fluorine-based gas, which has a sufficiently high etching rate for the photoresist, as an etching gas, and etch the fluorine-based gas, which has a sufficiently high etching rate for the inorganic underlayer film. The substrate can be processed by using the gas, and furthermore, the substrate can be processed by using the oxygen-based gas as the etching gas, which has a sufficiently high etching rate for the organic underlayer film.

Depending on the wavelength of the light used in the lithography process, the resist underlayer film formed from the resist underlayer film-forming composition may also absorb light. In such a case, it can function as an antireflection film having an effect of preventing reflected light from the substrate. Furthermore, the underlayer film formed from the composition for forming a resist underlayer film of the present invention can also function as a hard mask. The underlayer film of the present invention has a layer for preventing interaction between the substrate and the photoresist, and a function for preventing adverse effects on the substrate of materials used for the photoresist or substances generated when the photoresist is exposed to light. 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 baking into the upper photoresist layer, and a barrier layer for reducing the poisoning effect of the photoresist layer by the dielectric layer of the semiconductor substrate. It is possible.

In addition, the underlayer film formed from the resist underlayer film-forming composition can be applied to a substrate having via holes formed therein for use in a dual damascene process, and can be used as a filling material capable of filling the holes without gaps. It can also be used as a planarizing material for planarizing the uneven surface of a semiconductor substrate.

The weight average molecular weights shown in the synthesis examples below in this specification are the results of measurement by gel permeation chromatography (hereinafter abbreviated as GPC in this specification). A GPC apparatus (HLC-8320GPC) manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions and the like were as follows.
GPC column: TSKgelSuperH-RC, TSKgelSuperMultipore HZ-N, TSKgelSuperMultipore HZ-N (manufactured by Tosoh Corporation)
Column temperature: 40°C
Solvent: Tetrahydrofuran (Kanto Kagaku, for high performance liquid chromatography)
Standard sample: polystyrene (manufactured by Shodex)

In addition, the abbreviations described in the synthesis examples below have the following meanings.
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

窒素下、３００ミリリットル容量の四口フラスコに、２－ヒドロキシ－１－ナフトアルデヒド（東京化成工業（株）製）７０．００ｇ（４０６．６ｍｍｏｌ）、メタンスルホン酸（東京化成工業（株）製）３９．１ｇ（４０６．６ｍｍｏｌ）、Ｎ－メチル－２－ピロリジノン（関東化学、鹿１級）４９．１ｇ、ＰＧＭＥＡ１１４．５ｇを入れて１５０℃に昇温し、１５０℃で１８時間攪拌した。得られた反応混合物を１６００ｍｌのメタノール（関東化学，特級）／水（５／５）混合溶媒に滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、真空乾燥したのち再度シクロヘキサノンで固形分３０％に溶解し、８００ｍｌのメタノール（関東化学，特級）／水（５／５）混合溶媒に滴下してポリマーを再度沈殿させた。得られた沈殿物を濾別し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は５２４であり、収率は３０．１％であった。得られたポリマーをシクロヘキサノンで固形分濃度３０％に希釈し、固形分量と同量の陽イオン交換樹脂と陰イオン交換樹脂をそれぞれ加え、４時間撹拌した。イオン交換樹脂をろ過してポリマー溶液を得た。 <Synthesis Example 1> (Synthesis of Polymer (1))

Under nitrogen, 70.00 g (406.6 mmol) of 2-hydroxy-1-naphthaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 300-mL four-necked flask. 39.1 g (406.6 mmol), 49.1 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, Shika 1st grade) and 114.5 g of PGMEA were added, heated to 150° C., and stirred at 150° C. for 18 hours. The resulting reaction mixture was added dropwise to 1600 ml of methanol (Kanto Kagaku, special grade)/water (5/5) mixed solvent to precipitate the polymer. The resulting precipitate was separated by filtration, dried in vacuo, dissolved again with cyclohexanone to a solid content of 30%, and added dropwise to 800 ml of a mixed solvent of methanol (Kanto Kagaku, special grade)/water (5/5) to recover the polymer. precipitated. The resulting precipitate was filtered off and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 524 and the yield was 30.1%. The obtained polymer was diluted with cyclohexanone to a solid content concentration of 30%, and the same amount of cation exchange resin and anion exchange resin as the solid content were added and stirred for 4 hours. The ion exchange resin was filtered to obtain a polymer solution.

窒素下、１００ミリリットル容量の二口フラスコに、サリチルアルデヒド（東京化成工業（株）製）８．００ｇ（６５．５ｍｍｏｌ）、メタンスルホン酸（東京化成工業（株）製）６．３ｇ（６５．５ｍｍｏｌ）、Ｎ－メチル－２－ピロリジノン（関東化学、鹿１級）６．４ｇ、ＰＧＭＥＡ１５．０ｇを入れて１５０℃に昇温し、１５０℃で１８時間攪拌した。得られた反応混合物を３５０ｍｌのメタノール（関東化学，特級）／水（５／５）
混合溶媒に滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は３２００であった。得られたポリマーをシクロヘキサノンで固形分濃度３０％に希釈し、固形分量と同量の陽イオン交換樹脂と陰イオン交換樹脂をそれぞれ加え、４時間撹拌した。イオン交換樹脂をろ過してポリマー溶液を得た。 <Synthesis Example 2> (Synthesis of polymer (2))

Under nitrogen, 8.00 g (65.5 mmol) of salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.3 g (65.5 mmol) of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100-ml two-necked flask. 5 mmol), 6.4 g of N-methyl-2-pyrrolidinone (Kanto Kagaku Co., Ltd., Shika 1st grade), and 15.0 g of PGMEA were added, the temperature was raised to 150° C., and the mixture was stirred at 150° C. for 18 hours. The resulting reaction mixture was added to 350 ml of methanol (Kanto Kagaku, special grade)/water (5/5).
The polymer was precipitated by dropping into the mixed solvent. The resulting precipitate was filtered off and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 3,200. The obtained polymer was diluted with cyclohexanone to a solid content concentration of 30%, and the same amount of cation exchange resin and anion exchange resin as the solid content were added and stirred for 4 hours. The ion exchange resin was filtered to obtain a polymer solution.

窒素下、１００ミリリットル容量の二口フラスコに、３－メチルサリチルアルデヒド（東京化成工業（株）製）８．００ｇ（５８．８ｍｍｏｌ）、メタンスルホン酸（東京化成工業（株）製）５．６ｇ（５８．８ｍｍｏｌ）、Ｎ－メチル－２－ピロリジノン（関東化学、鹿１級）６．１ｇ、ＰＧＭＥＡ１４．３ｇを入れて１５０℃に昇温し、１５０℃で１８時間攪拌した。得られた反応混合物を３５０ｍｌのメタノール（関東化学，特級）／水（５／５）混合溶媒に滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は１０００であった。得られたポリマーをＰＧＭＥで固形分濃度３０％に希釈し、固形分量と同量の陽イオン交換樹脂と陰イオン交換樹脂をそれぞれ加え、４時間撹拌した。イオン交換樹脂をろ過してポリマー溶液を得た。 <Synthesis Example 3> (Synthesis of Polymer (3))

Under nitrogen, 8.00 g (58.8 mmol) of 3-methylsalicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.6 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 100-ml two-necked flask. (58.8 mmol), 6.1 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, Shika 1st class) and 14.3 g of PGMEA were added, heated to 150° C., and stirred at 150° C. for 18 hours. The resulting reaction mixture was added dropwise to 350 ml of methanol (Kanto Kagaku, special grade)/water (5/5) mixed solvent to precipitate the polymer. The resulting precipitate was filtered off and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 1,000. The obtained polymer was diluted with PGME to a solid content concentration of 30%, and the same amount of cation exchange resin and anion exchange resin as the solid content were added and stirred for 4 hours. The ion exchange resin was filtered to obtain a polymer solution.

窒素下、１００ミリリットル容量の二口フラスコに、４－メチルサリチルアルデヒド（東京化成工業（株）製）８．００ｇ（５８．８ｍｍｏｌ）、メタンスルホン酸（東京化成工業（株）製）５．６ｇ（５８．８ｍｍｏｌ）、Ｎ－メチル－２－ピロリジノン（関東化学、鹿１級）６．１ｇ、ＰＧＭＥＡ１４．３ｇを入れて１５０℃に昇温し、１５０℃で１８時間攪拌した。得られた反応混合物を３５０ｍｌのメタノール（関東化学，特級）／水
（５／５）混合溶媒に滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は１５００であった。得られたポリマーをＰＧＭＥで固形分濃度３０％に希釈し、固形分量と同量の陽イオン交換樹脂と陰イオン交換樹脂をそれぞれ加え、４時間撹拌した。イオン交換樹脂をろ過してポリマー溶液を得た。 <Synthesis Example 4> (Synthesis of polymer (4))

Under nitrogen, 8.00 g (58.8 mmol) of 4-methylsalicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.6 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 100-ml two-necked flask. (58.8 mmol), 6.1 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, Shika 1st class) and 14.3 g of PGMEA were added, heated to 150° C., and stirred at 150° C. for 18 hours. The resulting reaction mixture was added dropwise to 350 ml of methanol (Kanto Kagaku, special grade)/water (5/5) mixed solvent to precipitate the polymer. The resulting precipitate was filtered off and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 1,500. The obtained polymer was diluted with PGME to a solid content concentration of 30%, and the same amount of cation exchange resin and anion exchange resin as the solid content were added and stirred for 4 hours. The ion exchange resin was filtered to obtain a polymer solution.

窒素下、１００ミリリットル容量の二口フラスコに、５－メチルサリチルアルデヒド（東京化成工業（株）製）８．００ｇ（５８．８ｍｍｏｌ）、メタンスルホン酸（東京化成工業（株）製）５．６ｇ（５８．８ｍｍｏｌ）、Ｎ－メチル－２－ピロリジノン（関東化学、鹿１級）６．１ｇ、ＰＧＭＥＡ１４．３ｇを入れて１５０℃に昇温し、１５０℃で１８時間攪拌した。得られた反応混合物を３５０ｍｌのメタノール（関東化学，特級）／水（５／５）混合溶媒に滴下してポリマーを沈殿させた。得られた沈殿物を濾別し、真空乾燥してポリマーを得た。このポリマーの分子量をＧＰＣ（標準ポリスチレン換算）で測定したところ、重量平均分子量（Ｍｗ）は８００であった。得られたポリマーをＰＧＭＥで固形分濃度３０％に希釈し、固形分量と同量の陽イオン交換樹脂と陰イオン交換樹脂をそれぞれ加え、４時間撹拌した。イオン交換樹脂をろ過してポリマー溶液を得た。 <Synthesis Example 5> (Synthesis of polymer (5))

Under nitrogen, 8.00 g (58.8 mmol) of 5-methylsalicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.6 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 100-ml two-necked flask. (58.8 mmol), 6.1 g of N-methyl-2-pyrrolidinone (Kanto Kagaku, Shika 1st class) and 14.3 g of PGMEA were added, heated to 150° C., and stirred at 150° C. for 18 hours. The resulting reaction mixture was added dropwise to 350 ml of methanol (Kanto Kagaku, special grade)/water (5/5) mixed solvent to precipitate the polymer. The resulting precipitate was filtered off and vacuum dried to obtain a polymer. When the molecular weight of this polymer was measured by GPC (converted to standard polystyrene), the weight average molecular weight (Mw) was 800. The obtained polymer was diluted with PGME to a solid content concentration of 30%, and the same amount of cation exchange resin and anion exchange resin as the solid content were added and stirred for 4 hours. The ion exchange resin was filtered to obtain a polymer solution.

窒素下、１００ｍＬ容量の二口フラスコに２,２’－ビフェノール(東京化成工業（株）製）２５．００ｇ、１－ナフトアルデヒド(東京化成工業（株）製）１０．５ｇ、１－ピレンカルボキシアルデヒド(アルドリッチ製）１５．５ｇ及びメタンスルホン酸(東京化成工業（株）製）３．８７ｇを入れた。その後、１２０℃まで加熱し、約２４時間後室温まで放冷し、メタノールで沈殿させて、得られた沈殿物を乾燥させた。ＧＰＣによりポリスチレン換算で測定される重量平均分子量Ｍｗは２,０００であった。得られたポリマーをＰＧＭＥＡで固形分濃度３０％に希釈し、固形分量と同量の陽イオン交換樹脂と陰イオン交換樹脂をそれぞれ加え、４時間撹拌した。イオン交換樹脂をろ過してポリマー溶液を得た。 <Comparative Synthesis Example 1> (Synthesis of polymer (7))

Under nitrogen, 2,2′-biphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 25.00 g, 1-naphthaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.5 g, 1-pyrenecarboxy 15.5 g of aldehyde (manufactured by Aldrich) and 3.87 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. After that, the mixture was heated to 120° C., allowed to cool to room temperature after about 24 hours, precipitated with methanol, and dried. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 2,000. The obtained polymer was diluted with PGMEA to a solid content concentration of 30%, and the same amount of cation exchange resin and anion exchange resin as the solid content were added and stirred for 4 hours. The ion exchange resin was filtered to obtain a polymer solution.

窒素下、３リットル容量の四口フラスコにマロン酸－ジ－ｔｅｒｔ－ブチル（Ａｌｄｒｉｃｈ社製）９．８０ｇを入れ、さらに１，２，４－トリメチルベンゼン１５０ｃｍ^３とジアザビシクロ［５．４．０］－７－ウンデセン（１，８－ｄｉａｚａｂｉｃｙｃｌｏ［５．４．０］ｕｎｄｅｃ－７－ｅｎｅ、東京化成工業株式会社製）６．５０ｇを加えて撹拌しながら、温度を４℃に調整した。得られた温度調整後の反応液に、ヨウ素（和光純薬工業株式会社製）１０．９ｇを１３０ｃｍ^３の１，２，４－トリメチルベンゼンに溶解させた黒紫色の溶液をゆっくり滴下した。滴下中は氷浴を用いてフラスコ内温を１１℃になるよう制御した。滴下終了後、反応液の温度を室温まで戻し、その後、上記反応容器内の反応液に、フラーレン混合物（Ｃ６０、Ｃ７０及びその他高次フラーレン類を含む、フロンティアカーボン株式会社製）５．００ｇを１，２，４－トリメチルベンゼン３５０ｃｍ^３に溶解させた溶液を撹拌しながら加えた。その後、フラスコ内の反応液に、ジアザビシクロ［５．４．０］－７－ウンデセン（１，８－ｄｉａｚａｂｉｃｙｃｌｏ［５．４．０］ｕｎｄｅｃ－７－ｅｎｅ、東京化成工業株式会社製）６．９０ｇを５ｃｍ^３の１，２，４－トリメチルベンゼンで希釈した溶液を撹拌しながらゆっくり滴下した。室温で６．５時間撹拌して反応させた。得られた反応液について、反応層（有機相）を飽和亜硫酸ナトリウム水溶液で４回洗浄した。得られた有機相を、１Ｎ硫酸水溶液１００ｃｍ^３を用いて２回洗浄した後、純水２００ｃｍ^３を用いて３回洗浄した。溶剤（１，２，４－トリメチルベンゼン）を減圧下留去し、赤茶色の固体９．５０ｇを得た。 得られた固体をシリカゲルクロマトグラフでｎ－ヘキサンと酢酸エチルの混合溶媒にて分別して、フラーレン誘導体（マロン酸－ジ－ｔｅｒｔ－ブチルエステル付加体）を得た。 <Comparative Synthesis Example 2> (Synthesis of Polymer (8))

Under nitrogen, 9.80 g of di-tert-butyl malonate (manufactured by Aldrich) was placed in a 3-liter four-necked flask, and 150 cm ³ of 1,2,4-trimethylbenzene and diazabicyclo[5.4.0] were added. 6.50 g of -7-undecene (1,8-diazabicyclo[5.4.0]undec-7-ene, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and the temperature was adjusted to 4° C. while stirring. To the resulting temperature-controlled reaction solution was slowly added dropwise a black purple solution of 10.9 g of iodine (manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in 130 cm ³ of 1,2,4-trimethylbenzene. During the dropwise addition, an ice bath was used to control the internal temperature of the flask to 11°C. After the completion of dropping, the temperature of the reaction solution is returned to room temperature, and then 5.00 g of a fullerene mixture (containing C60, C70 and other higher fullerenes, manufactured by Frontier Carbon Co., Ltd.) is added to the reaction solution in the reaction vessel. , 2,4-trimethylbenzene in 350 cm ³ was added with stirring. After that, 6.90 g of diazabicyclo[5.4.0]-7-undecene (1,8-diazabicyclo[5.4.0]undec-7-ene, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution in the flask. was slowly added dropwise with stirring to a solution diluted with 5 cm ³ of 1,2,4-trimethylbenzene. The reaction was allowed to stir at room temperature for 6.5 hours. The reaction layer (organic phase) of the resulting reaction solution was washed four times with a saturated sodium sulfite aqueous solution. The obtained organic phase was washed twice with 100 cm ³ of a 1N aqueous sulfuric acid solution, and then washed three times with 200 cm ³ of pure water. The solvent (1,2,4-trimethylbenzene) was distilled off under reduced pressure to obtain 9.50 g of a reddish brown solid. The resulting solid was fractionated by silica gel chromatography using a mixed solvent of n-hexane and ethyl acetate to obtain a fullerene derivative (malonic acid-di-tert-butyl ester adduct).

窒素下、３００ｍＬ容量の四口フラスコに１，５－ジヒドロキシナフタレン(東京化成工業（株）製）１２．５ｇ（７６．５ｍｍｏｌ）、パラトルエンスルホン酸一水和物（東京化成工業（株）製）３．５５ｇ（２．１ｍｍｏｌ）、ＰＧＭＥ７４．４ｇを入れて８５℃に昇温し、３７％ホルムアルデヒド液(東京化成工業（株）製）５．８６ｇを反応液に滴下した。その後、約５時間後室温まで放冷し、ヘプタンで沈殿させて、得られた沈殿物を乾燥させた。ＧＰＣによりポリスチレン換算で測定される重量平均分子量Ｍｗは１，４００であった。 <Comparative Synthesis Example 3> (Synthesis of Polymer (9))

Under nitrogen, 12.5 g (76.5 mmol) of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) and paratoluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 300 mL four-necked flask. ) and 74.4 g of PGME were added, the temperature was raised to 85° C., and 5.86 g of a 37% formaldehyde solution (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise to the reaction solution. After about 5 hours, the mixture was allowed to cool to room temperature, precipitated with heptane, and dried. The weight average molecular weight Mw measured by GPC in terms of polystyrene was 1,400.

窒素下、１００ミリリットル容量の二口フラスコに、６－ヒドロキシ－１－ナフトアルデヒド（東京化成工業（株）製）４．００ｇ（２３．２ｍｍｏｌ）、メタンスルホン酸（東京化成工業（株）製）２．２３ｇ（２３．２ｍｍｏｌ）、Ｎ－メチル－２－ピロリジノン（関東化学、鹿１級）７．４１ｇ、ＰＧＭＥＡ１７．４ｇを入れて１５０℃に昇温したところ、１時間程度でゲル化した。 <Comparative Synthesis Example 4> (Synthesis of polymer (10))

Under nitrogen, 4.00 g (23.2 mmol) of 6-hydroxy-1-naphthaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) are placed in a 100-mL two-necked flask. 2.23 g (23.2 mmol), 7.41 g of N-methyl-2-pyrrolidinone (Kanto Kagaku Co., Ltd., Shika 1st grade), and 17.4 g of PGMEA were added, and when the temperature was raised to 150° C., gelation occurred in about 1 hour.

<Example 1>
0.14 g of PGMEA containing 1% surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-40, fluorine-based surfactant) in 5.31 g of the resin solution obtained in Synthesis Example 1, PGMEA2 .40 g and 2.13 g of cyclohexanone were mixed. Thereafter, the solution was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 μm to prepare a solution of the composition for forming a resist underlayer film.

<Example 2>
0.10 g of PGMEA containing 1% surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-40, fluorine-based surfactant) in 3.98 g of the resin solution obtained in Synthesis Example 2, PGME1 .80 g, 3.50 g PGMEA and 0.61 g cyclohexanone were mixed. Thereafter, the solution was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 μm to prepare a solution of the composition for forming a resist underlayer film.

<Example 3>
0.21 g of PGMEA containing 1% surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-40, fluorine-based surfactant) in 10.59 g of the resin solution obtained in Synthesis Example 3, PGME0 .53 g and 3.66 g of PGMEA were mixed. Thereafter, the solution was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 μm to prepare a solution of the composition for forming a resist underlayer film.

<Example 4>
0.21 g of PGMEA containing 1% surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-40, fluorine-based surfactant) in 8.78 g of the resin solution obtained in Synthesis Example 4, PGME2 .34 g and 3.66 g of PGMEA were mixed. Thereafter, the solution was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 μm to prepare a solution of the composition for forming a resist underlayer film.

<Example 5>
0.21 g of PGMEA containing 1% surfactant (manufactured by DIC Corporation, product name: Megafac [trade name] R-40, fluorine-based surfactant) in 9.79 g of the resin solution obtained in Synthesis Example 5, PGME1 .32 g and 3.66 g of PGMEA were mixed. Thereafter, the solution was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 μm to prepare a solution of the composition for forming a resist underlayer film.

<Example 6>
To 7.82 g of the resin obtained in Synthesis Example 1, 2.54 g of PGME containing 2% pyridinium p-hydroxybenzenesulfonate, TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd., cross-linking agent) 0.51 g, 1% 0.20 g of PGMEA, 4.35 g of PGME, 4.15 g of PGMEA and 0.42 g of cyclohexanone containing a surfactant (manufactured by DIC Corporation, product name: MEGAFACE [trade name] R-40, fluorosurfactant) were mixed. Thereafter, the solution was filtered through a polytetrafluoroethylene microfilter having a diameter of 0.1 μm to prepare a solution of the composition for forming a resist underlayer film.

<Comparative Example 1>
The resin solution obtained in Comparative Synthesis Example 1 (solid content: 29.9% by mass) was obtained. 0.10 g of PGMEA, 3.68 g of PGMEA, and 2.68 g of PGME containing 1% by mass of a surfactant (manufactured by DIC Corporation, Megafac R-40) were added to 3.02 g of this resin solution and dissolved. The solution was filtered through a tetrafluoroethylene microfilter to prepare a solution of the composition for forming a resist underlayer film.

<Comparative Example 2>
To 1.0 g of the fullerene derivative obtained in Comparative Synthesis Example 2, 0.15 g of an epoxy compound represented by the following formula (6) (manufactured by Toto Kasei Co., Ltd., trade name: YH434L), Megafac [registered trademark] as a surfactant ] 0.001 g of R-30 (DIC Corporation) was mixed and dissolved in 7.0 g of PGMEA to prepare a solution. Thereafter, the solution was filtered using a polyethylene microfilter with a pore size of 0.10 μm and then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a resist underlayer film-forming composition solution.

<Comparative Example 3>
To 1.29 g of the resin obtained in Comparative Synthesis Example 3, 0.25 g of PGMEA containing 1% by mass of surfactant (manufactured by DIC Corporation, Megafac R-40), 6.09 g of PGME, and 2.35 g of PGMEA were added and dissolved. The solution was filtered through a 0.1 μm polytetrafluoroethylene microfilter to prepare a solution of the composition for forming a resist underlayer film.

[Measurement of film shrinkage]
Each of the resist underlayer film-forming compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spinner. Then, it was baked on a hot plate in the atmosphere at 350° C. for 1 minute to form a resist underlayer film (thickness: about 0.25 μm), and the film thickness A was measured. This substrate was further baked at 500° C. or 600° C. for 5 minutes in a nitrogen atmosphere, and the film thickness B was measured. The film shrinkage ratio was defined as film thickness B/film thickness A×100.
In addition, when the firing temperature is 500 ° C., it is listed as "symbol -1" in Table 1, and the firing temperature is 600
°C is described in Table 1 as “symbol-2”.
The film shrinkage ratio of the resist underlayer film composition prepared in Comparative Example 1 is as high as 50%, whereas the film shrinkage ratio of the compositions of Examples 1 to 6 is as small as 25% or less. This has the advantage of less sublimate and less contamination of the device, and a smaller shrinkage rate is also advantageous for the in-plane uniformity of the film.

[Measurement of dry etching rate]
Each of the resist underlayer film-forming compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was applied onto a silicon wafer using a spinner. After that, it was baked on a hot plate at 350° C. for 1 minute, and then baked at 500° C. and 600° C. for 5 minutes in a nitrogen atmosphere to form a resist underlayer film (thickness: 0.2 μm). Then, the dry etching rate of these resist underlayer films was measured using an RIE system manufactured by Samco Corporation under the condition of using _CF4 as a dry etching gas.
Taking the dry etching rate (ER) of Comparative Example 2-1 (fullerene) as 1.00, the dry etching rate of each resist underlayer film was calculated. The results are shown in Table 1 below as "Relative Dry Etching Rate". The resist underlayer film formed in Comparative Example 2-1 has a dry etching rate that can substitute for the amorphous carbon layer formed by vapor deposition. On the other hand, the resist underlayer films formed in Examples 1 to 6 have high etching resistance close to that of the material using fullerene (Comparative Example 2).

[Measurement of hardness]
Using the resist underlayer film-forming compositions prepared in Examples 1 to 6 and Comparative Examples 1 to 3, resist underlayer films were formed on silicon wafers in the same manner as described above. A nanoindentation test was performed using a nanoindenter manufactured by Toyo Technica Co., Ltd. to measure the hardness of the resist underlayer film. Examples 1 to 6 showed a hardness of 1.40 GPa or more and had a denser structure, which was shown to be advantageous for substrate processing by etching.

Claims (13)

A resist underlayer film-forming composition comprising a polymer of an aromatic compound having 6 to 60 carbon atoms and having at least one structure in which a formyl group and a hydroxy group are bonded to two adjacent carbons, respectively, and a solvent. 2. The composition for forming a resist underlayer film according to claim 1, wherein the aromatic compound is a compound represented by formula (1).

(In formula (1), Ar ₁ is substituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, a halogen atom, a hydroxy group, an ether group, or an alkoxy group. represents an aromatic ring having 6 to 59 carbon atoms which may be substituted.) 3. The composition for forming a resist underlayer film according to claim 2, wherein in formula (1), Ar ₁ is a monocyclic ring, a condensed ring, a heterocyclic ring, or a linking ring in which these rings are linked via a single bond or via a spacer. . 3. The composition for forming a resist underlayer film according to claim 2, wherein in formula (1), Ar ₁ is any one of a benzene ring, naphthalene ring, anthracene ring and pyrene ring. 5. The composition for forming a resist underlayer film according to claim 1, further comprising a cross-linking agent. 6. The resist underlayer film-forming composition according to any one of claims 1 to 5, further comprising an acid and/or an acid generator. 7. The composition for forming a resist underlayer film according to claim 1, wherein the solvent has a boiling point of 160[deg.] C. or higher. A resist underlayer film characterized by being a baked product of a coating film comprising the resist underlayer film-forming composition according to any one of claims 1 to 7. A method for producing a resist underlayer film, comprising baking the resist underlayer film-forming composition according to any one of claims 1 to 8 coated on a semiconductor substrate to form a resist underlayer film. 10. The method for producing a resist underlayer film according to claim 9, wherein the baking is performed in two steps. 11. The method for producing a resist underlayer film according to claim 10, wherein the baking temperature in the second stage of the baking is 400[deg.] C. or higher. 12. The method for producing a resist underlayer film according to claim 9, wherein the baking is performed in an inert gas atmosphere. forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition according to any one of claims 1 to 8;
forming a resist film on the formed resist underlayer film;
forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing;
A method of manufacturing a semiconductor device, comprising: etching the resist underlayer film through a formed resist pattern to form a pattern; and processing a semiconductor substrate through the patterned resist underlayer film.