Resist underlayer film, method for forming resist pattern, and method for manufacturing semiconductor device

Abstract

To provide a composition for forming a resist underlayer film improved in heat resistance, a resist underlayer film, a method for forming a resist pattern, and a method for producing a semiconductor device.SOLUTION: A composition for forming a resist underlayer film comprises (A) a compound represented by formula (1) in the figure, (C) cross-linkable compounds that are one or more compounds selected from among melamine compounds, guanamine compounds, glycoluryl compounds, urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, and azide compounds, and (D) cross-linking catalysts that are one or more compounds selected from among 5-sulfosalicylic acid, pyridinium trifluoromethanesulfonate, pyridinium p-phenolsulfonate, and trifluoromethanesulfonic acid partially or totally blocked with a quaternary element.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resist underlayer film forming composition, a resist underlayer film, a method for forming a resist pattern, and a method for manufacturing a semiconductor device.

Background Art

[0002] Conventionally, in the manufacture of semiconductor devices, microfabrication by lithography using a photoresist composition has been performed. The microfabrication involves forming a thin film of a photoresist composition on a substrate to be processed such as a silicon wafer, irradiating it with actinic rays such as ultraviolet rays through a mask pattern on which a pattern of a semiconductor device is drawn, developing it, and etching the substrate to be processed such as a silicon wafer using the obtained photoresist pattern as a protective film. However, in recent years, as the degree of integration of semiconductor devices has increased, the actinic rays used have also been shifted to shorter wavelengths from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). Along with this, the effects of specular reflection and standing waves from the substrate of the actinic rays have become major problems, and a method of providing a resist underlayer film called a bottom anti-reflective coating (BARC) between the photoresist and the substrate to be processed has come to be widely applied.

[0003] Also, for the purpose of further microfabrication, development of lithography techniques using extreme ultraviolet rays (EUV, 13.5 nm) or electron beams (EB) as actinic rays has been carried out. In EUV lithography and EB lithography, generally, specular reflection and standing waves from the substrate do not occur, so a specific anti-reflection film is not required. However, as an auxiliary film for improving the resolution and adhesion of the resist pattern, the resist underlayer film has begun to be widely studied.

[0004] As a material for forming a resist underlayer film formed between such a photoresist and a substrate to be processed, for example, a material for forming a lower layer film for lithography excellent in heat resistance and etching resistance is disclosed (see, for example, Patent Document 1). However, the requirement for heat resistance has been further increased, and a composition for forming a resist underlayer film with improved heat resistance is desired.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, the present invention has been made in view of the above circumstances, and an object thereof is to provide a resist underlayer film forming composition having improved heat resistance, a resist underlayer film, a method for forming a resist pattern, and a method for manufacturing a semiconductor device.

Means for Solving the Problems

[0007] As a result of intensive studies by the inventors, it has been found that a resist underlayer film formed by combining a compound having a specific structure and a specific crosslinking agent reduces the amount of sublimates generated when forming a resist underlayer film by baking a coating film composed of a resist underlayer film forming composition, and the present invention has been completed.

[0008] The first aspect of the present invention for achieving the above object is a resist underlayer film forming composition comprising (A) a compound represented by the following formula (1) and (B) a crosslinkable compound represented by the following formula (2-1) or the following formula (2-2).

[0009]

Chemical Formula

[0010]

Chemical formula

[0011] A second aspect of the present invention for achieving the above object is (A) a compound represented by the following formula (1), (C) as a crosslinkable compound, one or more compounds selected from melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds and azide compounds, and (D) as a crosslinking catalyst, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, pyridinium trifluoromethanesulfonic acid, pyridinium p-phenolsulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, pyridinium p-toluenesulfonic acid, trifluoromethanesulfonic acid partially or entirely blocked by a quaternary element, hexafluoroantimonic acid partially or entirely blocked by a quaternary element, dodecylbenzenesulfonic acid partially or entirely blocked by an amine, an aromatic sulfonium hexafluorophosphate and an aromatic sulfonium hexafluoroantimonate, and a resist underlayer film forming composition characterized by containing one or more compounds selected from the group consisting of:

[0012] [Chemical formula] (In formula (1), R 1 is each independently a divalent group having 1 to 30 carbon atoms, and R 2 ~ R 7is, independently of each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group or a hydroxyl group, and R 5 at least one of which is a hydroxyl group or a thiol group, and m 2 , m 3 and m 6 are each independently an integer from 0 to 9, and m 4 and m 7 are each independently an integer from 0 to 8, and m 5 is an integer from 1 to 9, n is an integer from 0 to 4, and p 2 to p 7 are each independently an integer from 0 to 2.)

[0013] A third aspect of the present invention for achieving the above object is further characterized in that it contains (E) a crosslinking catalyst in the resist underlayer film forming composition of the first aspect.

[0014] A fourth aspect of the present invention for achieving the above object is a resist underlayer film characterized in that it is a fired product of a coating film composed of the resist underlayer film forming composition according to any one of the first aspect to the third aspect.

[0015] A fifth aspect of the present invention for achieving the above object is a method for forming a resist pattern, which includes a step of applying and firing the resist underlayer film forming composition according to any one of the first aspect to the third aspect on a semiconductor substrate to form a resist underlayer film, and is characterized in that it is used in the manufacture of a semiconductor.

[0016] A sixth aspect of the present invention for achieving the above object is a method for manufacturing a semiconductor device, which includes a step of forming a resist underlayer film on a semiconductor substrate with the resist underlayer film forming composition according to any one of the first aspect to the third aspect, a step of forming a resist film on the resist underlayer film, a step of forming a resist pattern by irradiation with light or an electron beam and development, a step of etching the resist underlayer film with the formed resist pattern, and a step of processing the semiconductor substrate with the patterned resist underlayer film.

[0017] The seventh aspect of the present invention for achieving the above object is a method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a semiconductor substrate with a resist underlayer film forming composition according to any one of the first to third aspects; a step of forming a hard mask on the resist underlayer film; a step of forming a resist film on the hard mask; a step of forming a resist pattern by irradiation with light or an electron beam and development; a step of etching the hard mask with the formed resist pattern; a step of etching the resist underlayer film with the patterned hard mask; and a step of processing the semiconductor substrate with the patterned resist underlayer film.

[0018] The eighth aspect of the present invention for achieving the above object is a method for manufacturing a semiconductor device according to the seventh aspect, wherein the hard mask is formed by coating an inorganic substance or depositing an inorganic substance.

Advantages of the Invention

[0019] According to the present invention, it is possible to provide a resist underlayer film forming composition, a resist underlayer film, a method for forming a resist pattern, and a method for manufacturing a semiconductor device, which have improved heat resistance.

Embodiments for Carrying Out the Invention

[0020] Hereinafter, an embodiment of the present invention will be described in detail, but the present invention is not limited thereto.

[0021] (Resist Underlayer Film Forming Composition) The resist underlayer film forming composition of the present embodiment contains (A) a compound having a specific structure and (B) a crosslinkable compound having a specific structure.

[0022] The compound (A) having a specific structure contained in the resist underlayer film forming composition is a compound represented by the following formula (1) (hereinafter referred to as "compound (A)").

[0023]

Chemical formula

[0024] In the above formula (1), R 1 is, independently of each other, a divalent group having 1 to 30 carbon atoms. Compound (A) has a structure in which each aromatic ring is bonded via this R 1 . R 2 ~R 7 are, independently of each other, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group or a hydroxyl group, and at least one of R 5 is a hydroxyl group or a thiol group. m 2 , m 3 and m 6 are, independently of each other, integers from 0 to 9, m 4 and m 7 are, independently of each other, integers from 0 to 8, m 5 is an integer from 1 to 9. n is an integer from 0 to 4, and p 2 ~p 7 are, independently of each other, integers from 0 to 2. The compound (A) of the present application contains 50% or more, preferably 60% or more, of the compound with n = 0.

[0025] The divalent group is not particularly limited, and examples thereof include an alkylene group having 1 to 30 carbon atoms. Examples of the alkylene group having 1 to 30 carbon atoms include those having a linear hydrocarbon group, a branched hydrocarbon group, etc. Further, the divalent group may have an aromatic group having 6 to 30 carbon atoms.

[0026] Further, the divalent group may have a double bond or may have a hetero atom. Note that the structure of the divalent group does not affect the desired effects of the resist underlayer film forming composition containing compound (A), and as long as it has the structure of the above formula (1), the resist underlayer film forming composition containing compound (A) is applicable to a wet process and can obtain the effects of excellent heat resistance and etching resistance.

[0027] Compound (A) has relatively low molecular weight but high heat resistance due to the rigidity of its structure, so it can be used even under high-temperature baking conditions. Also, since it has relatively low molecular weight and low viscosity, it is easy to uniformly fill every corner of the steps of a substrate (especially in a fine space, hole pattern, etc.). As a result, the resist underlayer film-forming composition using this can have relatively advantageous enhanced embedding properties. Also, the flatness of the formed resist underlayer film is excellent. Furthermore, high etching resistance is also imparted. Here, the molecular weight of compound (A) in this embodiment is preferably 500 to 5000, more preferably 500 to 2000.

[0028] From the viewpoints of ease of crosslinking and solubility in solvents, it is preferable that at least one of R 6 is a hydroxyl group or a thiol group. Also, from the same viewpoints, it is more preferable that at least one of R 2 and / or at least one of R 3 is a hydroxyl group and / or a thiol group, and most preferably a hydroxyl group.

[0029] Also, from the viewpoint of the supplyability of raw materials, compound (A) is more preferably a compound represented by the following formula (1-A).

[0030]

Chemical formula

[0031] In the above formula (1-A), R 1 ~R 7 and n have the same meanings as those described in the above formula (1). m 2’ , m 3’ and m 6’ are each independently an integer from 0 to 5, m 4’ and m 7’ are each independently an integer from 0 to 4, and m 5’ is an integer from 1 to 5.

[0032] From the viewpoint of solubility in a solvent, the compound represented by the above formula (1-A) is more preferably a compound represented by the following formula (1-B).

[0033]

Chemical formula

[0034] In the above formula (1-B), R 1 ~R 4 , R 7 and n have the same meanings as those described in the above formula (1). m 2’ ~m 4’ and m 7’ have the same meanings as those described in the above formula (1-A).

[0035] From the viewpoint of further solubility in a solvent, the compound represented by the above formula (1-B) is more preferably a compound represented by the following formula (1-C).

[0036]

Chemical formula

[0037] In the above formula (1-C), R 1 , R 4 , R 7 and n have the same meanings as those described in the above formula (1). m 4’ and m 7’ have the same meanings as those described in the above formula (1-A).

[0038] From the viewpoint of simplicity of synthesis, the compound represented by the above formula (1-C) is more preferably a compound represented by the following formula (1-D).

[0039]

Chemical formula

[0040] In the above formula (1-D), R 1 , R 4 and R 7is synonymous with that described in the above formula (1). m 4’ and m 7’ is synonymous with that described in the above formula (1-A).

[0041] From the viewpoint of the availability of raw materials, the compound represented by the above formula (1-D) is more preferably a compound represented by the following formula (1-E).

[0042]

Chemical formula

[0043] In the above formula (1-E), R 4 and R 7 are synonymous with those described in the above formula (1), and R 8 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. m 4’ and m 7’ are synonymous with those described in the above formula (1-A).

[0044] From the viewpoint of solubility in a further solvent, the compound represented by the above formula (1-E) is particularly preferably a compound represented by the following formula (1-F).

[0045]

Chemical formula

[0046] From the viewpoint of solubility in a further solvent, the compound represented by the above formula (1-C) is particularly preferably a compound represented by the following formula (1-G).

[0047]

Chemical formula

[0048] Hereinafter, as specific examples of the compound (A), compound groups A to Q are shown, but it is not limited to those listed here.

[0049] <<Compound Group A>> [Chem.]

[0050] <<Compound Group B>> [Chem.]

[0051] <<Compound Group C>> [Chem.]

[0052] <<Compound Group D>> [Chem.]

[0053] Among the above Compound Groups A to D, R 2 ~R 7 , m 2 ~m 7 and n are synonymous with those described in the above formula (1).

[0054] <<Compound Group E>> [Chem.]

[0055] Among the above Compound Group E, R 4 ~R 7 and m 4 ~m 7 are synonymous with those described in the above formula (1). n' is an integer from 0 to 3, and n'' is an integer from 1 to 4. The arrangement of each repeating unit is arbitrary. R 8 ~R 11 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group or a hydroxyl group. m 8 ~m 11is independently an integer from 0 to 6.

[0056] ≪Compound Group F≫

Chem.

[0057] ≪Compound Group G≫

Chem.

[0058] ≪Compound Group H≫

Chem.

[0059] Among the above Compound Groups F to H, R 2 ~R 7 and n are synonymous with those described in the above formula (1). m 2’ ~m 7’ is synonymous with those described in the above formula (1-A).

[0060] ≪Compound Group I≫

Chem.

[0061] Among the above Compound Group I, R 4 ~R 7 is synonymous with those described in the above formula (1). m 4’ ~m 7’ is synonymous with those described in the above formula (1-A). n' is an integer from 0 to 3, and n'' is an integer from 1 to 4. The arrangement of each repeating unit is arbitrary. R 8 ~R 11 are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group or a hydroxyl group. m 8’ ~m 11’ are each independently an integer from 0 to 4.

[0062] <<Compound Group J>> [Chemistry]

[0063] <<Compound Group K>> [Chemistry]

[0064] <<Compound Group L>> [Chemistry]

[0065] <<Compound Group M>> [Chemistry]

[0066] <<Compound Group N>> [Chemistry]

[0067] <<Compound Group O>> [Chemistry]

[0068] <<Compound Group P>> [Chemistry]

[0069] <<Compound Group Q>> [Chemistry]

[0070] Among the above compound groups J to Q, n has the same meaning as that described in the above formula (1). n' is an integer from 0 to 3, and n'' is an integer from 1 to 4. The sequence of each repeating unit is arbitrary.

[0071] In the resist underlayer film-forming composition of this embodiment, these compounds (A) may be used alone or in combination of two or more.

[0072] In this embodiment, the compound (A) can be appropriately synthesized by applying known methods, and the synthesis method is not particularly limited. For example, under normal pressure, biphenols, bithiophenols, binaphthols, bithionaphthols or bianthracenols and the corresponding aldehydes or ketones are subjected to a polycondensation reaction under an acid catalyst to obtain the compound (A). Also, if necessary, it can be carried out under pressure.

[0073] Examples of biphenols include, but are not limited to, biphenol, methylbiphenol, etc. These can be used alone or in combination of two or more. Among these, using biphenol is preferable from the viewpoint of stable supply of raw materials.

[0074] Examples of bithiophenols include, but are not limited to, bithiophenol, methylbithiophenol, methoxybithiophenol, etc. These can be used alone or in combination of two or more. Among these, using bithiophenol is preferable from the viewpoint of stable supply of raw materials.

[0075] Examples of binaphthols include, but are not limited to, binaphthol, methylbinaphthol, methoxybinaphthol, etc. These can be used alone or in combination of two or more. Among these, using binaphthol is preferable from the viewpoint of increasing the carbon atom concentration and improving heat resistance.

[0076] Examples of bithionaphthols include, but are not limited to, bithionaphthol, methyl bithionaphthol, methoxy bithionaphthol, etc. These can be used alone or in combination of two or more. Among these, using bithionaphthol is preferable from the viewpoint of increasing the carbon atom concentration and improving heat resistance.

[0077] Examples of bianthracenols include, but are not particularly limited to, bianthracenol, methyl bianthracenol, and methoxy bianthracenol, etc. These can be used alone or in combination of two or more. Among these, using bianthracenol is more preferable in terms of increasing the carbon atom concentration and improving heat resistance.

[0078] Although the aldehydes are not particularly limited, for example, formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propyl aldehyde, butyl aldehyde, hexyl aldehyde, decyl aldehyde, undecyl aldehyde, phenylacetaldehyde, phenylpropyl aldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, fluorobenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, benzaldehyde, hydroxybenzaldehyde, fluorobenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, biphenylaldehyde, naphthaldehyde, anthracenecarboxaldehyde, phenanthrenecarboxaldehyde, pyrenecarboxaldehyde, glyoxal, glutaraldehyde, phthalaldehyde, naphthalenedicarboxaldehyde, biphenyldicarboxaldehyde, anthracenedicarboxaldehyde, bis(diformylphenyl)methane, bis(diformylphenyl)propane, or benzenetricarboxaldehyde is preferably used from the viewpoint of imparting high heat resistance.

[0079] Examples of the ketones include, but are not limited to, acetone, methyl ethyl ketone, cyclobutanone, cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone, etc. These can be used alone or in combination of two or more. Among these, from the viewpoint of imparting high heat resistance, it is preferable to use cyclopentanone, cyclohexanone, norbornanone, tricyclohexanone, tricyclodecanone, adamantanone, fluorenone, benzofluorenone, acenaphthenequinone, acenaphthenone, anthraquinone.

[0080] The acid catalyst used in the polycondensation reaction during the synthesis of the compound (A) can be appropriately selected from known ones and is not particularly limited. Such acid catalysts are widely known, including inorganic acids and organic acids. For example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid, and organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, and Lewis acids such as zinc chloride, aluminum chloride, iron chloride, boron trifluoride, or solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, phosphomolybdic acid, etc. are included, but not limited thereto. Among these, from the viewpoint of production, organic acids and solid acids are preferable, and from the viewpoints of production such as easy availability and easy handling, it is more preferable to use hydrochloric acid or sulfuric acid. Note that the acid catalyst can be used alone or in combination of two or more. Also, the usage amount of the acid catalyst can be appropriately set according to the raw materials used, the type of catalyst used, and further reaction conditions, etc., and is not particularly limited, but it is preferably 0.01 parts by mass to 100 parts by mass with respect to 100 parts by mass of the reaction raw materials.

[0081] In the polycondensation reaction, a reaction solvent may be used. The reaction solvent is not particularly limited as long as the reaction between the aldehydes or ketones to be used and biphenols, bithiophenols, binaphthols, bithionaphthols or bianthracenols proceeds, and it can be appropriately selected from known ones and used. For example, water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether or a mixed solvent thereof, etc. are exemplified. Note that the solvent can be used alone or in combination of two or more.

[0082] The amount of the reaction solvent used can be appropriately set according to the types of raw materials and catalysts used, and further reaction conditions, etc., and is not particularly limited, but it is preferably in the range of 0 parts by mass to 2000 parts by mass with respect to 100 parts by mass of the reaction raw materials. Furthermore, the reaction temperature in the polycondensation reaction can be appropriately selected according to the reactivity of the reaction raw materials and is not particularly limited, but it is usually in the range of 10°C to 200°C.

[0083] The reaction temperature for obtaining the compound (A) is preferably higher, specifically in the range of 60°C to 200°C. The reaction method can be appropriately selected from known methods and is not particularly limited. For example, there are methods such as charging biphenols, bithiophenols, binaphthols, bithionaphthols or bianthracenols, aldehydes or ketones, and a catalyst all at once, or methods of dropping biphenols, bithiophenols, binaphthols, bithionaphthols or bianthracenols, aldehydes or ketones in the presence of a catalyst. After the polycondensation reaction is completed, the isolation of the obtained compound can be carried out according to a conventional method and is not particularly limited. For example, in order to remove unreacted raw materials and catalysts present in the system, the temperature of the reaction kettle is raised to 130°C to 230°C, and general methods such as removing volatile components at about 1 mmHg to 50 mmHg are adopted to obtain the target compound (A).

[0084] As preferable reaction conditions, 1.0 mol to an excessive amount of biphenols, bithiophenols, binaphthols, bithionaphthols or bianthracenols, and 0.001 mol to 1 mol of an acid catalyst are used with respect to 1 mol of aldehydes or ketones, and the reaction proceeds by reacting at normal pressure at 50°C to 150°C for about 20 minutes to 100 hours.

[0085] After completion of the reaction, the target product can be isolated by a known method. For example, the reaction solution is concentrated, pure water is added to precipitate the reaction product, cooled to room temperature, then filtered and separated, the obtained solid is filtered and dried, and then separated and purified from by-products by column chromatography, and the solvent is distilled off, filtered and dried to obtain the target compound (A).

[0086] The crosslinkable compound (B) contained in the resist underlayer film-forming composition is a compound represented by the following formula (2-1) or the following formula (2-2) (hereinafter referred to as "crosslinking agent (B)").

[0087]

Chemical formula

[0088] In the above formula (2-1) and the above formula (2-2), Q 1 is a single bond or an m 12 valent organic group, R 12 and R 15 are each independently an alkyl group having 2 to 10 carbon atoms or an alkyl group having carbon atoms 2 to 10 having an alkoxy group having 1 to 10 carbon atoms, R 13 and R 16 are each independently a hydrogen atom or a methyl group, R 14 and R 17 are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n 12 is an integer of 1 to 3, n 13 is an integer of 2 to 5, n 14 is an integer of 0 to 3, n 15 is an integer of 0 to 3, and these satisfy 3 ≤ (n12 +n 13 +n 14 +n 15 ) has a relationship of ≤ 6. n 16 is an integer from 1 to 3, and n 17 is an integer from 1 to 4, and n 18 is an integer from 0 to 3, and n 19 is an integer from 0 to 3, and they satisfy 2 ≤ (n 16 +n 17 +n 18 +n 19 ) has a relationship of ≤ 5. m 12 is an integer from 2 to 10.

[0089] Specifically, Q 1 can be a single bond or an m-valent organic group selected from a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic group having 6 to 40 carbon atoms, or a combination thereof. Here, the chain hydrocarbon group can include an alkyl group described later. The aromatic group can include an aryl group described later. 12

[0090] Examples of the alkyl group having 2 to 10 carbon atoms include ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include 3 - trimethyl - cyclopropyl group, 1 - ethyl - 2 - methyl - cyclopropyl group, 2 - ethyl - 1 - methyl - cyclopropyl group, 2 - ethyl - 2 - methyl - cyclopropyl group, 2 - ethyl - 3 - methyl - cyclopropyl group, etc.

[0091] In addition, as the alkyl group having 1 to 10 carbon atoms, in addition to the above alkyl group having 2 to 10 carbon atoms, a methyl group is further exemplified.

[0092] Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n - propoxy group, i - propoxy group, n - butoxy group, i - butoxy group, s - butoxy group, t - butoxy group, n - pentoxy group, 1 - methyl - n - butoxy group, 2 - methyl - n - butoxy group, 3 - methyl - n - butoxy group, 1,1 - dimethyl - n - propoxy group, 1,2 - dimethyl - n - propoxy group, 2,2 - dimethyl - n - propoxy group, 1 - ethyl - n - propoxy group, n - hexyloxy group, 1 - methyl - n - pentyloxy group, 2 - methyl - n - pentyloxy group, 3 - methyl - n - pentyloxy group, 4 - methyl - n - pentyloxy group, 1,1 - dimethyl - n - butoxy group, 1,2 - dimethyl - n - butoxy group, 1,3 - dimethyl - n - butoxy group, 2,2 - dimethyl - n - butoxy group, 2,3 - dimethyl - n - butoxy group, 3,3 - dimethyl - n - butoxy group, 1 - ethyl - n - butoxy group, 2 - ethyl - n - butoxy group, 1,1,2 - trimethyl - n - propoxy group, 1,2,2, - trimethyl - n - propoxy group, 1 - ethyl - 1 - methyl - n - propoxy group, 1 - ethyl - 2 - methyl - n - propoxy group, etc.

[0093] Examples of the aryl group having 6 to 40 carbon atoms include phenyl group, naphthyl group, anthryl group, etc.

[0094] Hereinafter, as specific examples of the cross - linking agent (B), compounds represented by the following formulas (3 - 1) to (3 - 40) are shown, but it is not limited to those listed here.

[0095]

Chemical formula

[0096]

Chem.

[0097]

Chem.

[0098]

Chem.

[0099]

Chem.

[0100] In the resist underlayer film forming composition of the present embodiment, these crosslinking agents (B) may be used alone or in combination of two or more.

[0101] In the present embodiment, the crosslinking agent (B) can be appropriately synthesized by applying known methods, and the synthesis method is not particularly limited. For example, it can be obtained by reacting a compound represented by the following formula (2'-1) or the following formula (2'-2) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. Note that, for 1 mol of the compound represented by the following formula (2'-1) or the following formula (2'-2), the crosslinking agent (B) in which a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms is substituted at a ratio of 1 mol is a monosubstituted product, similarly, the crosslinking agent (B) substituted with 2 mol is a disubstituted product, similarly, the crosslinking agent (B) substituted with 3 mol is a trisubstituted product, and similarly, the crosslinking agent (B) substituted with 4 mol is a tetrasubstituted product.

[0102]

Chem.

[0103] In the above formula (2'-1) or (2'-2), Q 1’ is a single bond or m 12’ That is, Q is an organic group having a valence of 1. 1’ is a single bond or a group selected from a chain hydrocarbon group having 1 to 10 carbon atoms, an aromatic group having 6 to 40 carbon atoms, or a combination thereof; 12’ The chain hydrocarbon group may be the alkyl group described above, and the aromatic group may be the aryl group described above.

[0104] Also, R 12’ , R 13’ , R 15’ and R 16’ are each independently a hydrogen atom or a methyl group, and R 14’ and R 17’ are each independently an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. 12’ is an integer from 1 to 3, and n 13’ is an integer from 2 to 5, and n 14’ is an integer from 0 to 3, and n 15’ are integers from 0 to 3, and 3≦(n 12’ +n 13’ +n 14’ +n 15’ )≦6. 16’ is an integer from 1 to 3, and n 17’ is an integer from 1 to 4, and n 18’ is an integer from 0 to 3, and n 19’ are integers from 0 to 3, and these are 2≦(n 16’ +n 17’ +n 18’ +n 19’ )≦5. 12’ is an integer between 2 and 10.

[0105] Specific examples of the compound represented by the above formula (2'-1) or (2'-2) include compounds represented by the following formulas (4-1) to (4-27), but are not limited to these.

[0106] [ka]

[0107] [ka]

[0108] Specifically, the crosslinking agent (B) can be obtained by reacting a compound represented by the above formula (2'-1) or (2'-2) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms in the presence of an acid catalyst.

[0109] The acid catalyst can be appropriately selected from known ones and is not particularly limited.As such an acid catalyst, the above-mentioned inorganic acid or organic acid can be used, and for example, an acidic compound such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, or naphthalenecarboxylic acid can be used.

[0110] In order to prevent unreacted acid from remaining in the reaction system, a catalyst ion exchange resin can be used, such as a strong acid ion exchange resin of the sulfonic acid type.

[0111] Examples of hydroxyl group-containing ether compounds include propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc. Examples of alcohols having 2 to 10 carbon atoms include ethanol, 1-propanol, 2-methyl-1-propanol, butanol, 2-methoxyethanol, and 2-ethoxyethanol.

[0112] In addition to the above-described compound (A) and crosslinking agent (B), the resist underlayer film-forming composition of this embodiment can use a solvent and known additives described later as needed. The solid content of the resist underlayer film-forming composition is 0.1% by mass to 70% by mass, preferably 0.1% by mass 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 resist underlayer film-forming composition can contain compound (A) in a proportion of 1% by mass to 99.9% by mass, preferably 50% by mass to 99.9% by mass, particularly preferably 50% by mass to 95% by mass, and most preferably 50% by mass to 90% by mass in the solid content. Further, the crosslinking agent (B) can be contained in the solid content in a proportion of 0.01% by mass to 50% by mass, preferably 0.01% by mass to 40% by mass, particularly preferably 0.1% by mass to 30% by mass.

[0113] Note that the resist underlayer film-forming composition can use a crosslinking agent other than the crosslinking agent (B) as needed. Examples of these crosslinking agents include melamine-based, substituted urea-based, or their polymer-based, etc. Preferably, it is a crosslinking agent having at least two crosslink-forming substituents, and compounds such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Further, condensates of these compounds can also be used.

[0114] Examples of solvents that dissolve various components in the resist underlayer film-forming composition of this embodiment 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, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, and propylene glycol. Examples of such an alkyl propyl ether acetate include ethanol, 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, ethyl acetate, butyl acetate, ethyl lactate, and butyl lactate.

[0115] These solvents can be used alone or in combination of two or more. Alternatively, high-boiling point solvents such as propylene glycol monobutyl ether and propylene glycol monobutyl ether acetate may be mixed and used. Among these solvents, from the viewpoint of safety, it is preferable to use propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, etc. alone or in combination of two or more.

[0116] The resist underlayer film-forming composition may contain known additives such as a crosslinking catalyst, a surfactant, a light absorber, a rheology adjuster, and an adhesion aid.

[0117] Examples of the crosslinking catalyst (E) for promoting the crosslinking reaction between the above-described compound (A) and the crosslinking agent (B) include acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid (5-SSA), pyridinium p-phenolsulfonate (PyPSA), pyridinium p-toluenesulfonate (PyPTS), pyridinium trifluoromethanesulfonate (PyTFMS), pyridinium p-phenolsulfonate (PyPSA), pyridinium p-toluenesulfonate (PyPTS), 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid; thermal acid generators such as 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, and other organic sulfonic acid alkyl esters; onium salt-based photoacid generators such as bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate; halogen-containing compound-based photoacid generators such as phenyl-bis(trichloromethyl)-s-triazine; sulfonic acid-based photoacid generators such as benzoin tosylate, N-hydroxysuccinimide trifluoromethanesulfonate, ditertiary butyldiphenyliodonium nonafluoromethanesulfonate (e.g., trade name: DTDPI, manufactured by Midori Chemical Co., Ltd.), etc. These can be used alone or in combination. Among these crosslinking catalysts, it is preferable to use ditertiary butyldiphenyliodonium nonafluoromethanesulfonate (e.g., trade name: DTDPI, manufactured by Midori Chemical Co., Ltd.), 5-sulfosalicylic acid (5-SSA), pyridinium p-phenolsulfonate (PyPSA), pyridinium p-toluenesulfonate (PyPTS), pyridinium trifluoromethanesulfonate (PyTFMS), and trifluoromethanesulfonic acid partially or entirely blocked with a quaternary element (e.g., K-PURE TAG-2689, manufactured by King Industries).The content ratio of the crosslinking catalyst is 0.0001% by weight to 20% by weight, preferably 0.0005% by weight to 10% by weight, and more preferably 0.01% by weight to 3% by weight based on the total solid content.

[0118] In order to form a resist underlayer film composition without the occurrence of pinholes, streaks, etc. and further improve the coatability with respect to surface unevenness, a surfactant can be blended. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., nonionic surfactants; fluorine-based surfactants such as EFtop EF301, EF303, EF352 (manufactured by Tocem Products Co., Ltd., trade name), Megafac F171, F173, R-30 (manufactured by Dainippon Ink and Chemicals, Inc., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Limited, trade name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., trade name), etc.; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. These surfactants may be used alone or in combination of two or more. The content ratio of the surfactant is usually 2.0% by weight or less, preferably 1.0% by weight or less based on the total solid content of the resist underlayer film forming composition.

[0119] Examples of the light absorbent used in the resist underlayer film forming composition include commercially available light absorbents described in, for example, "Technology and Market of Industrial Dyes" (published by CMC) and "Dye Handbook" (edited by the Society of Synthetic Organic Chemistry, Japan), such as C.I. Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114 and 124; C.I. Disperse Orange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72 and 73; C.I. Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; C.I. Disperse Violet 43; C.I. Disperse Blue 96; C.I. Fluorescent Brightening Agent 112, 135 and 163; C.I. Solvent Orange 2 and 45; C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; C.I. Pigment Green 10; C.I. Pigment Brown 2, etc. The content ratio of these light absorbents is usually 10% by mass or less, preferably 5% by mass or less, based on the total solid content of the resist underlayer film forming composition.

[0120] The rheology modifier is added mainly to improve the fluidity of the resist underlayer film-forming composition, particularly in the baking process, to improve the film thickness uniformity of the resist underlayer film and the ability of the resist underlayer film-forming composition to fill holes. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyldecyl adipate; maleic acid derivatives such as di-n-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 n-butyl stearate and glyceryl stearate. The content of these rheology modifiers is usually less than 30% by mass based on the total solids content of the resist underlayer film-forming composition.

[0121] Subsequently, the auxiliary agent is mainly added for the purpose of improving the adhesion between the substrate or the resist and the resist underlayer film forming composition, and particularly to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, trimethylsilylimidazole; silanes such as vinyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine; ureas such as 1,1-dimethylurea, 1,3-dimethylurea; thiourea compounds and the like. The content ratio of these adhesion auxiliary agents is 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.

[0122] For the resist underlayer film forming composition of this embodiment, instead of the crosslinking agent (B), another crosslinkable compound (hereinafter referred to as "crosslinking agent (C)") may be used, and as the crosslinking catalyst, a crosslinking catalyst (D) described later may be used.

[0123] Examples of the crosslinking agent (C) contained in the resist underlayer film-forming composition include melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, epoxy compounds, thioepoxy compounds, isocyanate compounds, azide compounds, and compounds containing a double bond such as an alkenyl ether group, which have at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group as a substituent (crosslinkable group). These crosslinking agents (C) may be used alone or in combination of two or more.

[0124] Specific examples of the above melamine compounds include, but are not limited to, hexamethylol melamine, hexamethoxymethyl melamine, compounds or mixtures thereof in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds or mixtures thereof in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated, and the like. Specific examples of the epoxy compound include, for example, tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, and the like.

[0125] Specific examples of the above guanamine compound include, but are not limited to, tetramethylol guanamine, tetramethoxymethyl guanamine, a compound or a mixture thereof in which 1 to 4 methylol groups of tetramethylol guanamine are methoxymethylated, tetramethoxyethyl guanamine, tetraacyloxy guanamine, a compound or a mixture thereof in which 1 to 4 methylol groups of tetramethylol guanamine are acyloxymethylated, and the like. Specific examples of the glycoluril compound include, for example, tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound or a mixture thereof in which 1 to 4 methylol groups of tetramethylol glycoluril are methoxymethylated, a compound or a mixture thereof in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated, and the like. Specific examples of the urea compound include, for example, tetramethylol urea, tetramethoxymethyl urea, a compound or a mixture thereof in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated, tetramethoxyethyl urea, and the like.

[0126] Specific examples of the compound containing the above alkenyl ether group include, but are not limited to, ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, trimethylolpropane trivinyl ether, and the like.

[0127] Among these, glycoluril compounds are preferred. Specifically, tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, compounds in which 1 to 4 of the methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, compounds in which 1 to 4 of the methylol groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof are preferred, and tetramethoxymethyl glycoluril is preferred.

[0128] In addition, examples of the crosslinking catalyst (D) contained in the resist underlayer film-forming composition include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, pyridinium trifluoromethanesulfonic acid, pyridinium p-phenolsulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, 2,4,4,6-tetrabromocyclohexadienone, benzoin tosylate, 2-nitrobenzyl tosylate, pyridinium p-phenolsulfonic acid, pyridinium p-toluenesulfonic acid, pyridinium trifluoromethanesulfonic acid, trifluoromethanesulfonic acid partially or wholly blocked with a quaternary element, hexafluorotantalic acid partially or wholly blocked with a quaternary element, dodecylbenzenesulfonic acid partially or wholly blocked with an amine, hexafluorophosphate of aromatic sulfonium, hexafluoroantimonate of aromatic sulfonium, and the like. Examples of the quaternary element include a quaternary ammonium cation.

[0129] Among these, 5-sulfosalicylic acid, pyridinium trifluoromethanesulfonate, pyridinium p-phenolsulfonate, trifluoromethanesulfonate, pyridinium p-toluenesulfonate, trifluoromethanesulfonate partially or fully blocked with a quaternary element, hexafluoroantimonic acid partially or fully blocked with a quaternary element, dodecylbenzenesulfonic acid partially or fully blocked with an amine, aromatic sulfonium hexafluorophosphates, and aromatic sulfonium hexafluoroantimonates are preferred, and from the viewpoint of particularly high heat resistance, 5-sulfosalicylic acid (5-SSA), pyridinium p-phenolsulfonate (PyPSA), pyridinium p-toluenesulfonate (PyPTS), pyridinium trifluoromethanesulfonate (PyTFMS), and trifluoromethanesulfonate partially or fully blocked with a quaternary element (e.g., K-PURE TAG-2689 (King Industries)) are preferred.

[0130] Specific examples of hexafluoroantimonic acids partially or fully blocked with a quaternary element include K-PURE (registered trademark) CXC-1612 and CXC-1733; specific examples of trifluoromethanesulfonic acids partially or fully blocked with a quaternary element include K-PURE (registered trademark) CXC-1614, TAG-2678, and TAG-2689; specific examples of dodecylbenzenesulfonic acids partially or fully blocked with an amine include TAG-2172 and TAG-2179 (all manufactured by King Industries); specific examples of aromatic sulfonium hexafluoroantimonates include SI-45, SI-60, SI-80, SI-100, and SI-150 (all manufactured by Sanshin Chemical Industry Co., Ltd.); and a specific example of aromatic sulfonium hexafluorophosphate is SI-110 (manufactured by Sanshin Chemical Industry Co., Ltd.).

[0131] These crosslinking catalysts (D) may be used alone or in combination of two or more.

[0132] Since the resist underlayer film forming composition of this embodiment is composed of a compound (A) having a specific structure, a wet process can be applied when forming a photoresist underlayer film, and it has excellent heat resistance and etching resistance. In addition, it also has high solvent solubility. Therefore, by using these compounds, deterioration of the film during high-temperature baking can be suppressed, and an underlayer film with excellent etching resistance against oxygen plasma etching or the like can be formed. Furthermore, since the adhesion to the resist layer is also excellent, an excellent resist pattern can be formed.

[0133] In addition, since the resist underlayer film forming composition is composed of a crosslinking agent (B) having a specific structure, considering the effect as an antireflection film, since the light absorption site is incorporated into the skeleton, there is no diffusate into the resist during heat drying, and since the light absorption site has sufficiently large light absorption performance, the antireflection effect is high. In addition, it has high thermal stability, can prevent contamination of the upper layer film by decomposition products during baking, and can have a margin in the temperature margin during baking. Furthermore, depending on the process conditions, it can be used as a film having a function of preventing light reflection, and further a function of preventing the interaction between the substrate and the resist, or preventing the adverse effect of substances generated during exposure to the material used for the resist or the resist on the substrate.

[0134] Note that even if the resist underlayer film forming composition is a composition using a crosslinking agent (C) instead of the crosslinking agent (B), the effect of the compound (A) having a specific structure can be obtained. That is, when forming a resist underlayer film, a wet process can be applied, and since it has excellent heat resistance and etching resistance, deterioration of the film during high-temperature baking can be suppressed, and an underlayer film with excellent etching resistance against oxygen plasma etching or the like can be formed. Furthermore, since the adhesion to the resist layer is also excellent, an excellent resist pattern can be formed.

[0135] (Resist underlayer film) The resist used in this embodiment is a photoresist or an electron beam resist.

[0136] The resist underlayer film in this embodiment is for lithography in the semiconductor manufacturing process. As the photoresist applied on the upper part of the resist underlayer film, either a negative type or a positive type can be used. Examples of positive type photoresists include those composed of a novolak resin and 1,2-naphthoquinonediazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes by an acid to increase the alkali dissolution rate and a photoacid generator; chemically amplified photoresists composed of an alkali-soluble binder, a low molecular compound that decomposes by an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator; chemically amplified photoresists composed of a binder having a group that decomposes by an acid to increase the alkali dissolution rate, a low molecular compound that decomposes by an acid to increase the alkali dissolution rate of the photoresist, and a photoacid generator; photoresists having silicon (Si) atoms in the skeleton, etc. Examples of commercially available photoresists include those with the trade name APEX-E manufactured by Rohm and Haas Co., etc.

[0137] As the electron beam resist applied on the upper part of the resist underlayer film, for example, there are compositions composed of a resin containing Si-Si bonds in the main chain and an aromatic ring at the end and an acid generator that generates an acid upon irradiation with an electron beam, and compositions composed of poly(p-hydroxystyrene) in which the hydroxyl groups are substituted with organic groups containing N-carboxyamine and an acid generator that generates an acid upon irradiation with an electron beam. In the latter composition of the electron beam resist, the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminoxy groups on the polymer side chains, the polymer side chains decompose into hydroxyl groups, show alkali solubility, and dissolve in an alkali developer to form a resist pattern.

[0138] Examples of acid generators that generate acid upon irradiation with an electron beam include halogenated organic compounds such as 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, and 2-chloro-6-(trichloromethyl)pyridine; onium salts such as triphenylsulfonium salts and diphenyliodonium salts; and sulfonic acid esters such as nitrobenzyl tosylate and dinitrobenzyl tosylate.

[0139] Examples of developers for resists having a resist underlayer film formed using a resist underlayer film-forming composition include aqueous solutions of alkalis such as inorganic alkalis (e.g., sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia); primary amines (e.g., ethylamine and n-propylamine); secondary amines (e.g., diethylamine and di-n-butylamine); tertiary amines (e.g., triethylamine and methyldiethylamine); alcohol amines (e.g., dimethylethanolamine and triethanolamine); quaternary ammonium salts (e.g., tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline); and cyclic amines (e.g., pyrrole and piperidine). Furthermore, aqueous solutions of alkalis can be used by adding an appropriate amount of alcohols (e.g., isopropyl alcohol) or a nonionic surfactant. Among these, preferred developers are quaternary ammonium salts, and more preferred are tetramethylammonium hydroxide and choline.

[0140] (Method for forming a resist pattern) Next, a method for forming a resist pattern according to this embodiment will be described. A resist underlayer film forming composition is applied onto a substrate (e.g., a transparent substrate such as a silicon / silicon dioxide coating, a glass substrate, an ITO substrate, etc.) used for manufacturing a highly integrated circuit element by an appropriate coating method such as a spinner or a coater to form a coating film, and then baked and cured to form a resist underlayer film (a fired product). Here, the film thickness of the resist underlayer film is preferably 0.01 μm to 3.0 μm. Further, the baking conditions after coating are 80°C to 350°C for 0.5 minutes to 120 minutes.

[0141] Thereafter, a resist is directly applied onto the resist underlayer film, or, if necessary, one to several layers of the resist underlayer film forming composition are formed on the first-layer resist underlayer film and then a resist is applied. Light or an electron beam is irradiated through a predetermined mask, and development, rinsing, and drying are performed to obtain a good resist pattern. After irradiating with light or an electron beam if necessary, heating (PEB: PostExposure Bake) can also be performed. Then, the resist underlayer film in the portion where the resist has been developed and removed is removed by dry etching, and a desired pattern can be formed on the substrate.

[0142] The exposure light in the exposure of the resist is actinic rays such as near ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays (e.g., EUV, wavelength 13.5 nm), and light having wavelengths such as 248 nm (KrF laser light), 193 nm (ArF laser light), 157 nm (F2 laser light), etc. is used. For light irradiation, any method that can generate an acid from a photoacid generator can be used without particular limitation, and preferably 1 mJ / cm 2 ~2000 mJ / cm 2 , more preferably 10 mJ / cm 2 ~1500 mJ / cm 2 , particularly preferably 50 mJ / cm 2 ~1000 mJ / cm 2 is based on the exposure dose. Also, the irradiation of the electron beam on the electron beam resist can be performed using, for example, an electron beam irradiation apparatus.

[0143] (Method of manufacturing a semiconductor device) In this embodiment, a semiconductor device can be manufactured through the steps of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of the present embodiment, forming a resist film on the resist underlayer film, forming a resist pattern by irradiating with light or an electron beam and developing, etching the resist underlayer film using the formed resist pattern, and processing a semiconductor substrate using the patterned resist underlayer film.

[0144] As resist patterns become increasingly finer, resolution issues and problems such as resist pattern collapse after development will arise, necessitating thinner resists. Therefore, it is difficult to obtain resist patterns thick enough for substrate processing. This has led to the need for processes in which not only the resist pattern but also the resist underlayer film formed between the resist and the semiconductor substrate to be processed functions as a mask during substrate processing. For resist underlayer films for such processes, unlike conventional high-etch-rate resist underlayer films, there is a growing demand for resist underlayer films with dry etching selectivities similar to those of resists, resist underlayer films with dry etching selectivities lower than those of resists, and resist underlayer films with dry etching selectivities lower than those of the semiconductor substrate. Furthermore, such resist underlayer films can be imparted with antireflective properties, thereby combining the functions of conventional antireflective films.

[0145] On the other hand, in order to obtain fine resist patterns, a process has begun to be used in which, during dry etching of the resist underlayer film, the resist pattern and the resist underlayer film are made narrower than the pattern width during resist development. For the resist underlayer film used in such a process, there is a growing demand for a resist underlayer film that has a dry etching rate selectivity similar to that of the resist, unlike conventional antireflective films with high etch rates. Furthermore, such resist underlayer films can also be imparted with antireflective properties, allowing them to possess the functions of conventional antireflective films.

[0146] In this embodiment, after forming the resist underlayer film of this embodiment on a substrate, a resist can be applied directly onto the resist underlayer film, or, if necessary, one to several layers of the resist underlayer film-forming composition can be formed on the first layer of the resist underlayer film, and then a resist can be applied. This narrows the resist pattern width, and even if the resist is thinly coated to prevent pattern collapse, by selecting an appropriate etching gas, it becomes possible to process the substrate.

[0147] That is, a semiconductor device can be manufactured through the following steps: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film-forming composition; forming a hard mask on the resist underlayer film using a coating material (inorganic material) containing a silicon component or the like, or a hard mask by vapor deposition (for example, forming a silicon-containing resist underlayer film (inorganic resist underlayer film)-forming composition described in WO2009 / 104552A1 by spin coating, or forming a film of an inorganic material such as silicon nitride oxide by a CVD method or the like); forming a resist film on the hard mask; forming a resist pattern by irradiating with light or an electron beam and developing; etching the hard mask with a halogen-based gas using the formed resist pattern; etching the resist underlayer film with an oxygen-based gas or a hydrogen-based gas using the patterned hard mask; and processing the semiconductor substrate with a halogen-based gas using the patterned resist underlayer film. [Example]

[0148] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0149] ( Reference Example 1) As the compound (A) represented by the following formula (5), 3.33 g of a resin (NeoFARIT7177C-30A) for a resist underlayer film-forming composition (a mixture measured by GPC (standard substance: polystyrene): n = 0 (61%), n = 1 (25%), n = 2 (9%), n = 4 (5%)), 0.10 g of 3,3’,5,5’-tetramethoxymethyl-4,4’-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as the crosslinking agent (B) represented by the following formula (4-23), 0.01 g of ditertiary butyldiphenyliodonium nonafluoromethanesulfonate (trade name: DTDPI, manufactured by Midori Chemical Co., Ltd.) as a crosslinking catalyst, and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant were dissolved in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate to prepare a resist underlayer film-forming composition.

[0150]

Chemical formula

[0151]

Chemical formula

[0152] ( Reference Example 2) A resist underlayer film-forming composition was prepared by dissolving 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) as the compound (A) represented by the above formula (5), 0.10 g of a crosslinking agent (B) (trade name: PGME-BIP-A, manufactured by Finechem Co., Ltd.), 0.01 g of di-tert-butyldiphenyliodonium nonafluoromethanesulfonate (trade name: DTDPI, manufactured by Midori Chemical Co., Ltd.) as a crosslinking catalyst, and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate. The PGME-BIP-A used as the crosslinker (B) is a mixture of the compounds represented by the following formula (3-36), the compounds represented by the following formulas (3-33), (3-34), and (3-35).

[0153] [ka]

[0154] ( Reference Example 3) A resist underlayer film-forming composition was prepared by dissolving 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) as the compound (A) represented by the above formula (5), 0.10 g of 3,3′,5,5′-tetramethoxymethyl-4,4′-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as the crosslinking agent (B), 0.01 g of 5-sulfosalicylic acid as a crosslinking catalyst, and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0155] ( Reference Example 4) A resist underlayer film-forming composition was prepared by dissolving 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) as the compound (A) represented by the above formula (5), 0.10 g of 3,3′,5,5′-tetramethoxymethyl-4,4′-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as the crosslinking agent (B), 0.01 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst, and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0156] ( Reference Example 5) A resist underlayer film-forming composition was prepared by dissolving 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) as the compound (A) represented by the above formula (5), 0.10 g of 3,3′,5,5′-tetramethoxymethyl-4,4′-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as the crosslinking agent (B), 0.01 g of pyridinium p-phenolsulfonate as a crosslinking catalyst, and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0157] ( Reference Example 6) A resist underlayer film-forming composition was prepared by dissolving 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) as the compound (A) represented by the above formula (5), 0.10 g of 3,3′,5,5′-tetramethoxymethyl-4,4′-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as the crosslinking agent (B), 0.01 g of trifluoromethanesulfonic acid partially or fully blocked with a quaternary element (trade name: K-PURE TAG-2689, manufactured by King Industries) as a crosslinking catalyst, and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0158] Example 7 As the compound (A) represented by the above formula (5), 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) and 3.33 g of a compound represented by the following formula (6) were used. Compound A resist underlayer film-forming composition was prepared by dissolving 0.10 g of 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent (C) having the basic skeleton of the above, 0.01 g of 5-sulfosalicylic acid as a crosslinking catalyst (D), and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0159] [ka]

[0160] Example 8 As the compound (A) represented by the above formula (5), 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) and CompoundA resist underlayer film-forming composition was prepared by dissolving 0.10 g of 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent (C) having the basic skeleton of the above, 0.01 g of pyridinium trifluoromethanesulfonate as a crosslinking catalyst (D), and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0161] Example 9 As the compound (A) represented by the above formula (5), 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) and Compound A resist underlayer film-forming composition was prepared by dissolving 0.10 g of 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as a crosslinking agent (C) having the basic skeleton shown below, 0.01 g of pyridinium p-phenolsulfonate represented by the following formula (7) as a crosslinking catalyst (D), and 0.001 g of a fluorine-based surfactant (trade name: R-30N, product name: Megafac, manufactured by DIC Corporation) as a surfactant in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0162] [ka]

[0163] Example 10 As the compound (A) represented by the above formula (5), 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) and CompoundAs a crosslinking agent (C) having the basic skeleton, 0.10 g of 1,3,4,6 - tetrakis(methoxymethyl) glycoluril (trade name: Nikalac MX - 270, manufactured by Sanwa Chemical Co., Ltd.), as a crosslinking catalyst (D), 0.01 g of trifluoromethanesulfonic acid partially or entirely blocked with a quaternary element (trade name: K - PURE TAG - 2689, manufactured by King Industries), and as a surfactant, 0.001 g of a fluorosurfactant (trade name: R - 30N, product name: Megafac, manufactured by DIC Corporation) were dissolved in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate to prepare a resist underlayer film forming composition.

[0164] (Comparative Example 1) As the compound (A) represented by the above formula (5), 3.33 g of a resin for resist underlayer film forming composition (NeoFARIT7177C - 30A), as a crosslinking agent (C) having the basic skeleton of the urea compound represented by the above formula (6), 0.10 g of 1,3,4,6 - tetrakis(methoxymethyl) glycoluril (trade name: Nikalac MX - 270, manufactured by Sanwa Chemical Co., Ltd.), as a crosslinking catalyst, 0.01 g of ditertiary butyl diphenyliodonium nonafluoromethanesulfonate (trade name: DTDPI, manufactured by Midori Chemical Co., Ltd.), and as a surfactant, 0.001 g of a fluorosurfactant (trade name: R - 30N, product name: Megafac, manufactured by DIC Corporation) were dissolved in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate to prepare a resist underlayer film forming composition.

[0165] (Measurement of the amount of sublimated substance) The measurement of the amount of sublimated substance was carried out using the sublimated substance measuring device described in Pamphlet of International Publication No. 2007 / 111147. First, on a 4 - inch - diameter silicon wafer substrate, Reference Examples 1 to 6 , Example 7The resist underlayer film-forming compositions prepared in Examples 10 and 10 and Comparative Example 1 were applied to a film thickness of 50 nm using a spin coater. The wafer coated with the resist underlayer film was placed in the sublimation amount measuring device with an integrated hot plate and baked for 120 seconds, and the sublimation product was collected in a QCM (Quartz Crystal Microbalance) sensor, i.e., a quartz crystal oscillator with electrodes. The QCM sensor is capable of measuring minute changes in mass by utilizing the property that when sublimation product adheres to the surface (electrode) of the quartz crystal oscillator, the frequency of the quartz crystal oscillator changes (decreases) depending on the mass of the product.

[0166] The detailed measurement procedure is as follows: The hot plate of the sublimation amount measurement device was heated to the measurement temperature shown in Table 1, and the pump flow rate was set to 1 m 3 The flow rate was set to / s and the device was left to stabilize for the first 60 seconds. Immediately afterwards, the wafer coated with the resist underlayer film was quickly placed on the hot plate through the slide port, and sublimate collection was performed from 60 seconds to 180 seconds (120 seconds). The flow attachment (detection part) connecting the QCM sensor and collection funnel of the sublimate amount measurement device was used without a nozzle. Therefore, the airflow was unrestricted from the flow path (diameter: 32 mm) of the chamber unit, which was 30 mm away from the sensor (quartz crystal oscillator). The QCM sensor used electrodes made of a material primarily composed of silicon and aluminum (AlSi), with a quartz crystal oscillator diameter (sensor diameter) of 14 mm, an electrode diameter on the quartz crystal oscillator surface of 5 mm, and a resonant frequency of 9 MHz.

[0167] The obtained frequency change was converted into grams from the characteristic value of the quartz crystal oscillator used in the measurement, and the relationship between the amount of sublimation per wafer coated with the resist underlayer film and the baking temperature was clarified. Note that the first 60 seconds was a time period during which the apparatus was left to stabilize (no wafer was set), and the measurement values from 60 seconds after the wafer was placed on the hot plate to 180 seconds were the measurement values for the amount of sublimation per wafer. The amount of sublimation per resist underlayer film quantified by the apparatus is shown in Table 1 below as the sublimation amount ratio. Note that the sublimation amount ratio is expressed as a value normalized with the amount of sublimation generated from the resist underlayer film of Comparative Example 1 set to 1.00.

[0168] [Table 1]

[0169] (summary) Results and Examples 7 The ratio of the amount of sublimation of the resist underlayer film obtained from the resist underlayer film composition prepared in Example 10 is smaller than the ratio of the amount of sublimation of the resist underlayer film-forming composition of Comparative Example 1. 7 The crosslinking agent and crosslinking catalyst used in Example 10 can effectively suppress the amount of sublimate generated. [Industrial Applicability]

[0170] INDUSTRIAL APPLICABILITY The present invention provides a resist underlayer film-forming composition that has good coatability and gives a resist underlayer film that is excellent in etching resistance, heat resistance, etc., and is therefore industrially useful.

Claims

1. (A) A compound represented by the following formula (1), and the compound represented by the formula (1) is at least one selected from the group consisting of the following compound group B, compound group J, compound group M, and compound group R, (C) At least one compound selected from glycoluril compounds as a crosslinkable compound, and (D) As a crosslinking catalyst, one or more compounds selected from 5-sulfosalicylic acid, pyridinium trifluoromethanesulfonate, pyridinium p-phenolsulfonate, and trifluoromethanesulfonate in which part or all of the quaternary element is blocked A resist underlayer film, characterized in that it is a fired product of a coating film composed of a resist underlayer film forming composition containing the same. 【Chemical 1】 (In formula (1), R １ is each independently a divalent group having 1 to 30 carbon atoms, and R ２ to R ７ are each independently a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a thiol group or a hydroxyl group, and at least one of R ５ is a hydroxyl group or a thiol group, m ２ to m ７ each represent the number of substituents in parentheses, m ２ , m ３ and m ６ are each independently an integer from 0 to 9, m ４ and m ７ are each independently an integer from 0 to 8, m ５ is an integer from 1 to 9, n is an integer from 1 to 4, and p ２ to p ７ are each independently an integer from 0 to 2. ) [Chemical 2] Among the above compound group B, R ２ ~R ７ , m ２ ~m ７ and n have the same meanings as those described in the above formula (1). 【Chemical Formula 3】 【Chemical Formula 4】 In the above compound groups J and M, n has the same meaning as that described in the above formula (1). n' is an integer of 0 to 3, and n" is an integer of 1 to 4. The sequence of each repeating unit is arbitrary. 【Chemical Formula 5】 In the above compound group R, n has the same meaning as that described in the above formula (1).

2. A method for forming a resist pattern, comprising the step of applying and firing the resist underlayer film forming composition according to claim 1 on a semiconductor substrate to form a resist underlayer film, and using the same in the manufacture of a semiconductor.

3. A step of forming a resist underlayer film on a semiconductor substrate with the resist underlayer film forming composition according to claim 1; A step of forming a resist film on the resist underlayer film; A step of forming a resist pattern by irradiation with light or an electron beam and development; A step of etching the resist underlayer film with the formed resist pattern; A step of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the same.

4. A step of forming a resist underlayer film on a semiconductor substrate with the resist underlayer film forming composition according to claim 1; A step of forming a hard mask on the resist underlayer film; [[ID= nineteen]] A step of forming a resist film on the hard mask; A step of forming a resist pattern by irradiation with light or an electron beam and development; A step of etching the hard mask with the formed resist pattern; A step of etching the resist underlayer film with the patterned hard mask; A step of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the same.

5. The hard mask is formed by applying an inorganic substance or depositing an inorganic substance. The method of manufacturing a semiconductor device according to claim 4, characterized by the above.

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