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

Abstract

To provide a resist underlayer film-forming composition and the like having improved heat resistance.SOLUTION: A resist underlayer film-forming composition contains a compound represented by formula (1) and a crosslinkable compound represented by formula (2'-1) or formula (2'-2).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 technology]

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a photoresist composition has traditionally been performed. This microfabrication process involves forming a thin film of the photoresist composition on a substrate to be processed, such as a silicon wafer, irradiating the thin film with actinic rays such as ultraviolet light through a mask pattern bearing a semiconductor device pattern, developing the thin film, and etching the substrate, such as a silicon wafer, using the resulting photoresist pattern as a protective film. However, with the recent trend toward higher integration of semiconductor devices, the wavelength of the actinic rays used has been shortened from KrF excimer lasers (248 nm) to ArF excimer lasers (193 nm). As a result, diffuse reflection and standing waves of actinic rays from the substrate have become major problems, leading to the widespread use of a resist underlayer called a bottom anti-reflective coating (BARC) between the photoresist and the substrate.

[0003] Furthermore, with the aim of achieving even finer processing, lithography technologies using extreme ultraviolet (EUV, 13.5 nm) and electron beam (EB) as actinic rays are also being developed. EUV lithography and EB lithography generally do not require specific anti-reflection coatings because diffuse reflection or standing waves do not occur from the substrate, but resist underlayer coatings are beginning to be widely considered as auxiliary coatings aimed at improving the resolution and adhesion of resist patterns.

[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 an underlayer film for lithography having excellent heat resistance and etching resistance has been disclosed (see, for example, Patent Document 1). However, the demand for heat resistance is increasing, and a composition for forming a resist underlayer film with improved heat resistance is desired. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2016 / 143635 Brochure Summary of the Invention [Problem to be solved by the invention]

[0006] Therefore, the present invention has been made in consideration of the above circumstances, and an object of the present invention is 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. [Means for solving the problem]

[0007] As a result of extensive research, the inventors have found that a resist underlayer film using a combination of a compound having a specific structure and a specific crosslinking agent reduces the amount of sublimation that occurs when a coating film made of a resist underlayer film-forming composition is baked to form a resist underlayer film, compared to conventional techniques, and have completed the present invention.

[0008] A first aspect of the present invention that achieves 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 (2-2):

[0009] [ka] (In formula (1), R 1are each independently a divalent group having 1 to 30 carbon atoms, and R 2 ~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 R 5 At least one of m is a hydroxyl group or a thiol group, 2 , m 3 and m 6 are each independently an integer of 0 to 9, and m 4 and m 7 are each independently an integer of 0 to 8, and m 5 is an integer from 1 to 9, n is an integer from 1 to 4, and p 2 ~p 7 are each independently an integer of 0 to 2.

[0010] [ka] (In formula (2-1) and formula (2-2), Q 1 is a single bond or m 12 is a 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 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms, and R 13 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 n19 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.)

[0011] A second aspect of the present invention that achieves the above object comprises (A) a compound represented by the following formula (1); (C) as a crosslinking compound, one or more compounds selected from a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an epoxy compound, a thioepoxy compound, an isocyanate compound, and an azide compound; 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 benzoate, or pyridinium benzoate. and a resist underlayer film-forming composition comprising one or more compounds selected from the group consisting of 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 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 hexafluorophosphate, and aromatic sulfonium hexafluoroantimonate.

[0012] [ka] (In formula (1), R 1 are each independently a divalent group having 1 to 30 carbon atoms, and R 2 ~R 7are 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 R 5 At least one of m is a hydroxyl group or a thiol group, 2 , m 3 and m 6 are each independently an integer of 0 to 9, and m 4 and m 7 are each independently an integer of 0 to 8, and m 5 is an integer from 1 to 9, n is an integer from 0 to 4, and p 2 ~p 7 are each independently an integer of 0 to 2.

[0013] A third aspect of the present invention that achieves the above object is the resist underlayer film-forming composition of the first aspect, further comprising (E) a crosslinking catalyst.

[0014] A fourth aspect of the present invention that achieves the above object is a resist underlayer film that is a baked product of a coating film made of the resist underlayer film-forming composition of any one of the first to third aspects.

[0015] A fifth aspect of the present invention that achieves the above object is a method for forming a resist pattern, characterized in that the method is used in the manufacture of a semiconductor, and includes a step of applying the resist underlayer film-forming composition of any one of the first to third aspects onto a semiconductor substrate and baking the composition to form a resist underlayer film.

[0016] A sixth aspect of the present invention that achieves the above object is a method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of any one of the first to third aspects; a step of forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating with light or an electron beam and developing; a step of etching the resist underlayer film using the formed resist pattern; and a step of processing a semiconductor substrate using the patterned resist underlayer film.

[0017] A seventh aspect of the present invention that achieves the above object is a method for manufacturing a semiconductor device, comprising: a step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film-forming composition of 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 irradiating with light or an electron beam and developing; a step of etching the hard mask using the formed resist pattern; a step of etching the resist underlayer film using the patterned hard mask; and a step of processing a semiconductor substrate using the patterned resist underlayer film.

[0018] An eighth aspect of the present invention that achieves the above object is the method for manufacturing a semiconductor device according to the seventh aspect, characterized in that the hard mask is formed by coating or vapor deposition of an inorganic material. [Effects 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, all of which have improved heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0020] An embodiment of the present invention will be described in detail below, 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] [ka]

[0024] In the above formula (1), R 1 are each independently a divalent group having 1 to 30 carbon atoms. 1 The aromatic rings are bonded via R 2 ~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 R 5 At least one of m is a hydroxyl group or a thiol group. 2 , m 3 and m 6 are each independently an integer of 0 to 9, and m 4 and m 7 are each independently an integer of 0 to 8, and m 5 is an integer from 1 to 9. n is an integer from 0 to 4, and p 2 ~p 7 are each independently an integer of 0 to 2. The compound (A) of the present invention contains compounds where n=0 in an amount of 50% or more, preferably 60% or more.

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

[0026] Furthermore, the divalent group may have a double bond or a heteroatom. 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 formula (1), the resist underlayer film-forming composition containing compound (A) can be applied to a wet process and can achieve the effects of excellent heat resistance and etching resistance.

[0027] Although the compound (A) has a relatively low molecular weight, its rigid structure provides high heat resistance, allowing it to be used even under high-temperature baking conditions. Furthermore, because the compound (A) has a relatively low molecular weight and low viscosity, it can be easily and uniformly filled into every corner of a substrate having steps (particularly, fine spaces or hole patterns). As a result, a resist underlayer film-forming composition using the compound can advantageously have improved filling properties. Furthermore, the formed resist underlayer film has excellent flatness. Furthermore, high etching resistance is also imparted. The molecular weight of the compound (A) of this embodiment is preferably 500 to 5,000, more preferably 500 to 2,000.

[0028] From the viewpoint of ease of crosslinking and solubility in solvents, compound (A) is selected from R 6 Preferably, at least one of R is a hydroxyl group or a thiol group. 2 and / or R 3 More preferably, at least one of the groups is a hydroxyl group and / or a thiol group, and most preferably a hydroxyl group.

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

[0030] [ka]

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

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

[0033] [ka]

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

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

[0036] [ka]

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

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

[0039] [ka]

[0040] In the above formula (1-D), R 1 , R 4 and R 7has the same meaning as that explained in the above formula (1). 4’ and m 7’ has the same meaning as that explained in the above formula (1-A).

[0041] From the viewpoint of the supplyability 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] [ka]

[0043] In the above formula (1-E), R 4 and R 7 is the same as that explained 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. 4’ and m 7’ has the same meaning as that explained in the above formula (1-A).

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

[0045] [ka]

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

[0047] [ka]

[0048] Compound groups A to Q are shown below as specific examples of compound (A), but are not limited to these.

[0049] ≪Compound group A≫ [ka]

[0050] ≪Compound group B≫ [ka]

[0051] ≪Compound group C≫ [ka]

[0052] ≪Compound group D≫ [ka]

[0053] Among the above compound groups A to D, R 2 ~R 7 , m 2 ~m 7 and n have the same meanings as those explained in the above formula (1).

[0054] ≪Compound group E≫ [ka]

[0055] In the above compound group E, R 4 ~R 7 and m 4 ~m 7 has the same meaning as that explained in the above formula (1). n' is an integer of 0 to 3, and n" is an integer of 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. 8 ~m 11are each independently an integer of 0 to 6.

[0056] ≪Compound group F≫ [ka]

[0057] ≪Compound group G≫ [ka]

[0058] ≪Compound group H≫ [ka]

[0059] Among the above compound groups F to H, R 2 ~R 7 and n have the same meanings as those explained in the above formula (1). 2’ ~m 7’ has the same meaning as that explained in the above formula (1-A).

[0060] ≪Compound group I≫ [ka]

[0061] In the above compound group I, R 4 ~R 7 has the same meaning as that explained in the above formula (1). 4’ ~m 7’ has the same meaning as that explained in the above formula (1-A). n' is an integer of 0 to 3, and n" is an integer of 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. 8’ ~m 11’ are each independently an integer of 0 to 4.

[0062] ≪Compound Group J≫

change

[0063] ≪Compound Group K≫

change

[0064] ≪Compound Group L≫

change

[0065] ≪Compound Group M≫

change

[0066] ≪Compound Group N≫

change

[0067] ≪Compound Group O≫

change

[0068] ≪Compound group P≫

change

[0069] ≪Compound Group Q≫

change

[0070] In the above compound group J to Q, n has the same meaning as explained in the above formula (1). n' is an integer of 0 to 3, and n'' is an integer of 1 to 4. The arrangement of each repeating unit is arbitrary.

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

[0072] In this embodiment, compound (A) can be appropriately synthesized by applying a known method, and the synthesis method is not particularly limited. For example, compound (A) can be obtained by polycondensation reaction of biphenols, bithiophenols, binaphthols, bithionaphthols, or bianthracenols with corresponding aldehydes or ketones in the presence of an acid catalyst under normal pressure. If necessary, the reaction can also be carried out under pressure.

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

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

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

[0076] Examples of bithionaphthols include, but are not limited to, bithionaphthol, methylbithionaphthol, and methoxybithionaphthol. These may be used alone or in combination of two or more. Among these, bithionaphthol is preferred from the viewpoint of increasing the carbon atom concentration and improving heat resistance.

[0077] Examples of bianthracenols include, but are not limited to, bianthracenol, methylbianthracenol, and methoxybianthracenol. These can be used alone or in combination of two or more. Among these, it is more preferable to use bianthracenol in order to increase the carbon atom concentration and improve heat resistance.

[0078] The aldehydes are not particularly limited, but examples thereof include formaldehyde, trioxane, paraformaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, hexylaldehyde, decylaldehyde, undecylaldehyde, phenylacetaldehyde, phenylpropylaldehyde, furfural, benzaldehyde, hydroxybenzaldehyde, fluorobenzaldehyde, chlorobenzaldehyde, nitrobenzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, ethylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde ...methylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, methylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, methylbenzaldehyde, propylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, methylbenzaldehyde, propylbenzaldehyde, propylbenzaldehyde, butylbenzaldehyde, cyclohexylbenzaldehyde, methylbenzaldehyde, propylbenzaldehyde From the viewpoint of providing high heat resistance, it is preferable to use benzophenone, 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.

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

[0080] The acid catalyst used in the polycondensation reaction when synthesizing compound (A) can be appropriately selected from known ones and is not particularly limited.As such acid catalyst, inorganic acid or organic acid is widely known, for example, hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, hydrofluoric acid etc. inorganic acid, 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 etc. organic acid, zinc chloride, aluminum chloride, iron chloride, boron trifluoride etc. Lewis acid, or silicotungstic acid, phosphotungstic acid, silicomolybdic acid, phosphomolybdic acid etc. solid acid etc., but not limited thereto. Among these, organic acids and solid acids are preferred from the viewpoint of production, and hydrochloric acid or sulfuric acid is more preferred from the viewpoint of production, such as ease of availability and ease of handling. The acid catalyst may be used alone or in combination of two or more. The amount of acid catalyst used can be appropriately determined depending on the types of raw materials and catalysts used, as well as reaction conditions, and is not particularly limited, but is preferably 0.01 to 100 parts by mass per 100 parts by mass of reaction raw materials.

[0081] A reaction solvent may be used during the polycondensation reaction. The reaction solvent is not particularly limited as long as it allows the reaction between the aldehydes or ketones used and the biphenols, bithiophenols, binaphthols, bithionaphthols, or bianthracenols to proceed, and can be appropriately selected from known solvents and used. Examples include water, methanol, ethanol, propanol, butanol, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and mixed solvents thereof. The solvent may be used alone or in combination of two or more.

[0082] The amount of reaction solvent used can be appropriately set depending on the types of raw materials and catalyst used, as well as the reaction conditions, and is not particularly limited, but is preferably in the range of 0 to 2000 parts by mass per 100 parts by mass of the reaction raw materials. Furthermore, the reaction temperature in the polycondensation reaction can be appropriately selected depending on the reactivity of the reaction raw materials, and is not particularly limited, but is usually in the range of 10°C to 200°C.

[0083] The reaction temperature for obtaining Compound (A) is preferably high, specifically, preferably 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, biphenols, bithiophenols, binaphthols, bithionaphthols, or bianthracenols, aldehydes or ketones, and a catalyst can be charged all at once, or biphenols, bithiophenols, binaphthols, bithionaphthols, or bianthracenols, and aldehydes or ketones can be added dropwise in the presence of a catalyst. After the polycondensation reaction is completed, the resulting compound can be isolated by a conventional method and is not particularly limited. For example, to remove unreacted raw materials and catalysts present in the system, the temperature of the reaction vessel can be increased to 130°C to 230°C, and volatiles can be removed at approximately 1 mmHg to 50 mmHg. This can be done by a common method to obtain the target compound (A).

[0084] The preferred reaction conditions are to use 1.0 mole to an excess of biphenols, bithiophenols, binaphthols, bithionaphthols or bianthracenols and 0.001 mole to 1 mole of an acid catalyst per mole of aldehydes or ketones, and to carry out the reaction at normal pressure, 50°C to 150°C, for about 20 minutes to 100 hours.

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

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

[0087] [ka]

[0088] In the above formula (2-1) and the above formula (2-2), Q 1 is a single bond or m 12 is a 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 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms, and R 13 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≦(n12 +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.

[0089] For more information, see Q 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 Here, examples of the chain hydrocarbon group include the alkyl group described below, and examples of the aromatic group include the aryl group described below.

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

[0091] Furthermore, examples of the alkyl group having 1 to 10 carbon atoms include the above alkyl groups having 2 to 10 carbon atoms and further include a methyl group.

[0092] Examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-butoxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 2-methyl-n-but ... Examples of such groups include 1-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, and 1-ethyl-2-methyl-n-propoxy group.

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

[0094] Specific examples of the crosslinking agent (B) include compounds represented by the following formulae (3-1) to (3-40), but are not limited to these.

[0095] [ka]

[0096] [ka]

[0097] [ka]

[0098] [ka]

[0099] [ka]

[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 this embodiment, the crosslinking agent (B) can be appropriately synthesized by applying a known method, 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 (2'-2) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. Note that a crosslinking agent (B) in which 1 mole of a compound represented by the following formula (2'-1) or (2'-2) is substituted with 1 mole of a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms is called a mono-substituted crosslinking agent, a crosslinking agent (B) in which 2 moles of a crosslinking agent (B) are similarly substituted with 2 moles of a crosslinking agent (B) is called a di-substituted crosslinking agent, a crosslinking agent (B) in which 3 moles of a crosslinking agent (B) are similarly substituted with 3 moles of a crosslinking agent (B) is called a tri-substituted crosslinking agent, and a crosslinking agent (B) in which 4 moles of a crosslinking agent (B) are similarly substituted with 4 moles of a crosslinking agent (B) is called a tetra-substituted crosslinking agent.

[0102] [ka]

[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 compound (A) and crosslinking agent (B), the resist underlayer film-forming composition of this embodiment may contain, as needed, solvents and known additives, as described below. The resist underlayer film-forming composition has a solids content of 0.1% to 70% by mass, preferably 0.1% to 60% by mass. The solids content refers to the content of all components in the resist underlayer film-forming composition excluding the solvent. The resist underlayer film-forming composition may contain, based on the solids content, the compound (A) in an amount of 1% to 99.9% by mass, preferably 50% to 99.9% by mass, particularly preferably 50% to 95% by mass, and most preferably 50% to 90% by mass. The resist underlayer film-forming composition may also contain, based on the solids content, the crosslinking agent (B) in an amount of 0.01% to 50% by mass, preferably 0.01% to 40% by mass, and particularly preferably 0.1% to 30% by mass.

[0113] The resist underlayer film-forming composition may contain a crosslinking agent other than the crosslinking agent (B) as needed. Examples of such crosslinking agents include melamine-based crosslinkers, substituted urea-based crosslinkers, and polymers thereof. A crosslinking agent having at least two crosslink-forming substituents is preferred, such as methoxymethylated glycoluril, butoxymethylated glycoluril, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguwanamine, butoxymethylated benzoguwanamine, methoxymethylated urea, butoxymethylated urea, methoxymethylated thiourea, or methoxymethylated thiourea. Condensates of these compounds may 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 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-phenolsulfonic acid (PyPSA), pyridinium p-toluenesulfonic acid (PyPTS), pyridinium trifluoromethanesulfonic acid (PyTFMS), pyridinium p-phenolsulfonic acid (PyPSA), pyridinium p-toluenesulfonic acid (PyPTS), 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthalenecarboxylic acid; Thermal acid generators such as 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 and triphenylsulfonium trifluoromethanesulfonate; halogen-containing compound-based photoacid generators such as phenyl-bis(trichloromethyl)-s-triazine; and sulfonic acid-based photoacid generators such as benzoin tosylate, N-hydroxysuccinimide trifluoromethanesulfonate, and ditertiarybutyldiphenyliodonium nonafluoromethanesulfonate (for example, trade name: DTDPI, manufactured by Midori Chemical Co., Ltd.), 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 completely blocked with a quaternary element (e.g., K-PURE TAG-2689 (manufactured by King Industries)).The content of the crosslinking catalyst is 0.0001% by mass to 20% by mass, preferably 0.0005% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, based on the total solid content.

[0118] The resist underlayer film-forming composition may contain a surfactant to further improve coating properties against surface irregularities without generating pinholes, striations, etc. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octyl phenol ether and polyoxyethylene nonyl phenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and the like. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorosurfactants such as EFTOP EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more. The content of the surfactant is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition.

[0119] Examples of the light-absorbing agent used in the resist underlayer film-forming composition include commercially available light-absorbing agents described in "Technology and Market of Industrial Dyes" (CMC Publishing) and "Dye Handbook" (edited by the Society of Organic Synthetic Chemistry), such as CI 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; ... Examples of the light-absorbing agent include CI DisperseOrange 1, 5, 13, 25, 29, 30, 31, 44, 57, 72, and 73; CI DisperseRed 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199, and 210; CI DisperseViolet 43; CI DisperseBlue 96; CI Fluorescent Brightening Agent 112, 135, and 163; CI SolventOrange 2 and 45; CI SolventRed 1, 3, 8, 23, 24, 25, 27, and 49; CI PigmentGreen 10; and CI PigmentBrown 2. The content of these light-absorbing agents is usually 10% by mass or less, and 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] The adhesion promoter is added mainly for the purpose of improving the adhesion between the substrate or 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, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazole; vinyltrichlorosilane; Examples of the adhesion promoter include silanes such as silane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-glycidoxypropyltrimethoxysilane; heterocyclic compounds such as 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. The content of these adhesion promoters is usually less than 5% by mass, and preferably less than 2% by mass, based on the total solids content of the resist underlayer film-forming composition.

[0122] The resist underlayer film-forming composition of the present embodiment may use another crosslinkable compound (hereinafter referred to as “crosslinking agent (C)”) instead of the crosslinking agent (B), and may use a crosslinking catalyst (D) described below as a crosslinking catalyst.

[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 has 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 melamine compound include, but are not limited to, hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated or a mixture thereof, etc. Specific examples of the epoxy compound include tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, triethylolethane triglycidyl ether, etc.

[0125] Specific examples of the guanamine compound include, but are not limited to, tetramethylolguanamine, tetramethoxymethylguanamine, a compound of tetramethylolguanamine in which one to four methylol groups have been methoxymethylated, or a mixture thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound of tetramethylolguanamine in which one to four methylol groups have been acyloxymethylated, or a mixture thereof. Specific examples of glycoluril compounds include tetramethylolglycoluril, tetramethoxyglycoluril, tetramethoxymethylglycoluril, a compound of tetramethylolglycoluril in which one to four methylol groups have been methoxymethylated, or a mixture thereof, and a compound of tetramethylolglycoluril in which one to four methylol groups have been acyloxymethylated, or a mixture thereof. Specific examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, a compound of tetramethylolurea in which one to four methylol groups have been methoxymethylated, or a mixture thereof, and tetramethoxyethylurea.

[0126] Specific examples of the compound containing the 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, and trimethylolpropane trivinyl ether.

[0127] Among these, glycoluril compounds are preferred, specifically tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, tetramethylol glycoluril compounds in which 1 to 4 methylol groups have been methoxymethylated or mixtures thereof, and tetramethylol glycoluril compounds in which 1 to 4 methylol groups have been acyloxymethylated or mixtures thereof, with tetramethoxymethyl glycoluril being preferred.

[0128] Examples of the crosslinking catalyst (D) contained in the resist underlayer film-forming composition include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, pyridinium trifluoromethanesulfonate, pyridinium p-phenolsulfonate, citric acid, benzoic acid, hydroxybenzoic acid, naphthalenecarboxylic acid, and 2,4,4,6-tetrabromocyclohexane. Examples of such an acid include hexafluoroisopropyl ether, benzoin tosylate, 2-nitrobenzyl tosylate, pyridinium p-phenolsulfonate, pyridinium p-toluenesulfonate, pyridinium trifluoromethanesulfonate, trifluoromethanesulfonic acid partially or completely blocked with a quaternary element, hexafluoroantimonic acid partially or completely blocked with a quaternary element, dodecylbenzenesulfonic acid partially or completely blocked with an amine, aromatic sulfonium hexafluorophosphates, and aromatic sulfonium hexafluoroantimonates. An example of a quaternary element is 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] The resist underlayer film-forming composition of this embodiment contains a compound (A) having a specific structure, so that a wet process can be applied when forming a photoresist underlayer film, and the composition has excellent heat resistance and etching resistance. It also has high solvent solubility. Therefore, by using these compounds, film deterioration during high-temperature baking is suppressed, and an underlayer film having excellent etching resistance to oxygen plasma etching and the like can be formed. Furthermore, the composition has excellent adhesion to the resist layer, so that an excellent resist pattern can be formed.

[0133] Furthermore, since the resist underlayer film-forming composition contains a crosslinker (B) having a specific structure, when considering its effectiveness as an anti-reflective film, the light-absorbing moiety is incorporated into the backbone, so that no material diffuses into the resist during heating and drying. Furthermore, the light-absorbing moiety has sufficiently high light-absorbing properties, resulting in a high anti-reflection effect. In addition, the composition has high thermal stability, preventing contamination of the upper layer film by decomposition products during baking and allowing for a sufficient temperature margin during baking. Furthermore, depending on the process conditions, the composition can be used as a film that not only prevents light reflection but also prevents interactions between the substrate and the resist, or prevents adverse effects on the substrate of materials used in the resist or substances generated during exposure to the resist.

[0134] The resist underlayer film-forming composition can obtain the effects of the compound (A) having a specific structure even when it is a composition that uses the crosslinking agent (C) instead of the crosslinking agent (B). That is, when forming a resist underlayer film, a wet process can be applied, and since the composition has excellent heat resistance and etching resistance, film deterioration during high-temperature baking is suppressed, and an underlayer film that also has excellent etching resistance to oxygen plasma etching and the like can be formed. Furthermore, since the composition has excellent adhesion to the resist layer, 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 used for lithography in the semiconductor manufacturing process. The photoresist applied on top of the resist underlayer film can be either negative or positive, and examples thereof include a positive photoresist composed of a novolac resin and a 1,2-naphthoquinone diazide sulfonic acid ester; a chemically amplified photoresist composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate and a photoacid generator; a chemically amplified photoresist composed of an alkali-soluble binder, a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; a chemically amplified photoresist composed of a binder having a group that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, a low-molecular-weight compound that decomposes in the presence of an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and a photoresist having silicon (Si) atoms in its skeleton. Examples of commercially available photoresists include APEX-E, a product of Rohm and Hertz.

[0137] Examples of electron beam resists that are applied on top of the resist underlayer film include a composition consisting of a resin containing Si-Si bonds in its main chain and aromatic rings at its terminals, and an acid generator that generates acid upon irradiation with an electron beam, and a composition consisting of poly(p-hydroxystyrene) in which the hydroxyl groups are substituted with organic groups containing N-carboxyamine, and an acid generator that generates acid upon irradiation with an electron beam. In the latter electron beam resist composition, the acid generated from the acid generator upon irradiation with an electron beam reacts with the N-carboxyaminooxy groups in the polymer side chains, decomposing the polymer side chains into hydroxyl groups, making them alkali-soluble and dissolving them in an alkaline developer, thereby forming 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 to a substrate (e.g., a transparent substrate such as a silicon / silicon dioxide-coated substrate, a glass substrate, or an ITO substrate) used in the manufacture of precision integrated circuit devices by a suitable application method such as a spinner or coater to form a coating film, which is then baked and cured to form a resist underlayer film (baked product). The thickness of the resist underlayer film is preferably 0.01 μm to 3.0 μm. The baking conditions after application are 80° C. to 350° C. for 0.5 to 120 minutes.

[0141] Thereafter, a resist is applied directly onto the resist underlayer film, or, if necessary, one to several layers of the resist underlayer film-forming composition are formed on the first resist underlayer film, followed by application of the resist, followed by irradiation with light or an electron beam through a predetermined mask, followed by development, rinsing, and drying, thereby obtaining a good resist pattern. If necessary, after irradiation with light or an electron beam, heating (PEB: Post-Exposure Bake) may also be performed. The resist underlayer film in the area where the resist was developed and removed is then removed by dry etching, allowing the desired pattern to be formed on the substrate.

[0142] The exposure light for exposing the resist is actinic radiation such as near ultraviolet, far ultraviolet, or extreme ultraviolet (e.g., EUV, wavelength 13.5 nm), and light with wavelengths of, for example, 248 nm (KrF laser light), 193 nm (ArF laser light), or 157 nm (F2 laser light) is used. The light irradiation can be carried out by any method that can generate acid from a photoacid generator, without particular limitation, and preferably at a dose of 1 mJ / cm. 2 ~2000mJ / cm 2 , and more preferably 10 mJ / cm 2 ~1500mJ / cm 2 , particularly preferably 50 mJ / cm 2 ~1000mJ / cm 2 The electron beam resist can be irradiated with electron beams using, for example, an electron beam irradiation device.

[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] Example 1 3.33 g of a resin for a resist underlayer film-forming composition (NeoFARIT7177C-30A) (mixture of n = 0 (61%), n = 1 (25%), n = 2 (9%), and n = 4 (5%) measured by GPC (standard substance: polystyrene)) as compound (A) represented by the following formula (5), 0.1 g of 3,3',5,5'-tetramethoxymethyl-4,4'-bisphenol (trade name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as crosslinking agent (B) represented by the following formula (4-23) A resist underlayer film-forming composition was prepared by dissolving 0.01 g of propylene glycol monomethyl ether, 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 in 6.67 g of propylene glycol monomethyl ether and 15.55 g of propylene glycol monomethyl ether acetate.

[0150] [ka]

[0151] [ka]

[0152] 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] 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] 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] 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] 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 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 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as the crosslinking agent (C) having a basic skeleton of a urea compound represented by the following formula (6), 0.01 g of 5-sulfosalicylic acid as the 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 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 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as the crosslinking agent (C) having a basic skeleton of the urea compound represented by the above formula (6), 0.01 g of pyridinium trifluoromethanesulfonate as the 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 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 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as the crosslinking agent (C) having a basic skeleton of the urea compound represented by the above formula (6), 0.01 g of pyridinium p-phenolsulfonate represented by the following formula (7) as the 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 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 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as the crosslinking agent (C) having the urea compound represented by the above formula (6) as a basic skeleton, 0.01 g of trifluoromethanesulfonic acid partially or completely blocked with a quaternary element (trade name: K-PURE TAG-2689, manufactured by King Industries) as the 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.

[0164] (Comparative Example 1) 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 1,3,4,6-tetrakis(methoxymethyl)glycoluril (trade name: Nikalac MX-270, manufactured by Sanwa Chemical Co., Ltd.) as the crosslinking agent (C) having a basic skeleton of the urea compound represented by the above formula (6), 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.

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

[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) As a result, the ratio of the amount of sublimation product in the resist underlayer films obtained from the resist underlayer film compositions prepared in Examples 1 to 10 was lower than the ratio of the amount of sublimation product generated from the resist underlayer film-forming composition of Comparative Example 1. That is, the crosslinking agents and crosslinking catalysts used in Examples 1 to 10 can effectively suppress the amount of sublimation product 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

[Claim 1] 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 (2'-2): 【Chemistry 1】 (In formula (1), each R1 is independently a divalent group having 1 to 30 carbon atoms, and the divalent group is represented by the following formula: 【Chemistry 2】 R ２ ~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 R ５ At least one of 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 of 0 to 8, ５ is an integer from 1 to 9, n is an integer from 0 to 4, and p ２ ~p ７ are each independently an integer of 0 to 2. 【Transformation 3】 (In formula (2'-1) and formula (2'-2), Q １’ is a single bond or m １２’ is a valent organic group, and 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 such that 2≦(n １６’ +n １７’ +n １８’ +n １９’ )≦5. １２’ is an integer from 2 to 10.

Images