Composition for resist underlayer film formation

Abstract

A composition for forming an underlayer film of a resist, comprising a polymer having a unit structure represented by the following formula (1) and a solvent. (In formula (1), each of A independently represents a hydrogen atom, a methyl group or an ethyl group, Q 1 and Q 2 each independently represents a divalent group having an aromatic hydrocarbon ring. X 1 and X 2 each independently represents a single bond or -C(=O)-.)

Description

Technical Field

[0001] This invention relates to a composition for forming a photoresist underlayer, a photoresist underlayer, a laminate, a method for manufacturing a semiconductor device, and a method for patterning. Background Technology

[0002] In the past, photolithography processes using resist compositions were employed in the manufacturing of semiconductor devices. Furthermore, with the increasing integration of semiconductor devices, there is a demand for miniaturized wiring and other patterns. This miniaturization utilizes short-wavelength light, such as KrF excimer lasers (wavelength 248nm) and ArF excimer lasers (wavelength 193nm). However, the effects of diffuse reflection and standing waves from the substrate become significant problems when using these short-wavelength lights. Therefore, the method of applying a bottom antireflective coating between the resist film and the substrate is widely adopted.

[0003] Generally speaking, increasing the refractive index of the anti-reflective coating is effective in terms of anti-reflection.

[0004] Therefore, in order to obtain a photoresist underlayer film with a high n-value (refractive index), a photoresist underlayer film forming composition comprising a polymer with disulfide bonds in the main chain and a solvent has been proposed (see Patent Document 1).

[0005] Existing technical documents Patent documents Patent Document 1: International Publication No. 2009 / 096340 Summary of the Invention

[0006] The problem that the invention aims to solve In the technology described in Patent Document 1, a resist lower layer film with a high refractive index of about 1.9 was obtained.

[0007] Furthermore, with the diversification of semiconductor devices, photolithography processes have also diversified. In this regard, a higher refractive index of the photoresist underlayer is not necessarily better. Depending on the photolithography process, the required refractive index varies, and sometimes a photoresist underlayer with a lower refractive index is required.

[0008] The object of the present invention is to provide a composition for forming a photoresist underlayer film that can obtain a photoresist underlayer film with a low refractive index, as well as a method for manufacturing a photoresist underlayer film, a laminate, a semiconductor device using the aforementioned composition for forming a photoresist underlayer film, and a method for patterning such a composition.

[0009] Solution for solving the problem In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that the above-mentioned technical problems could be solved, thereby completing the present invention with the following main purpose.

[0010] That is, the present invention includes the following.

[0011] [1] A composition for forming a resist underlayer film, comprising a polymer having a unit structure as shown in formula (1) and a solvent. (In formula (1), A independently represents a hydrogen atom, a methyl atom, or an ethyl atom, and Q...) 1 and Q 2 Each of these groups independently represents a divalent group having an aromatic hydrocarbon ring. X 1 and X 2 Each can independently represent a single bond or -C (=O)-. [2] The composition for forming a resist underlayer film according to [1], wherein Q in formula (1) 1 Q is expressed by the following equation (2). 2 It can be represented by any of the following equations (3-1) to (3-3). (In equation (2) and equations (3-1) to (3-3), R) a Each can be independently represented as an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms.

[0012] W represents a single bond, -CH2-, -C(CH3)2-, -C(CF3)2-, -CO-, -O-, -S-, or SO2-.

[0013] m independently represents an integer from 0 to 2.

[0014] n can represent an integer from 0 to 4 independently.

[0015] * indicates a bond. [3] The composition for forming a resist underlayer film according to [1] or [2], wherein the solvent comprises at least one selected from the group consisting of monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkylene glycol monoalkyl ethers.

[0016] [4] A composition for forming a resist underlayer film according to any one of [1] to [3], wherein the composition for forming a resist underlayer film further comprises a crosslinking agent.

[0017] [5] A composition for forming a resist underlayer film according to any one of [1] to [4], wherein the composition for forming a resist underlayer film further comprises a curing catalyst.

[0018] [6] A resist underlayer film, which is a cured product of the resist underlayer film forming composition as described in any one of [1] to [5].

[0019] [7] A laminate comprising: a semiconductor substrate; and a resist underlayer as described in [6].

[0020] [8] A method for manufacturing a semiconductor device includes the following steps: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition as described in any one of [1] to [5]; and forming a photoresist film on the photoresist underlayer film.

[0021] [9] A pattern forming method comprising the steps of: forming a photoresist underlayer film on a semiconductor substrate using a photoresist underlayer film forming composition as described in any one of [1] to [5]; forming a photoresist film on the photoresist underlayer film; irradiating the photoresist film with light; and then developing the photoresist film to obtain a photoresist pattern; and using the photoresist pattern as a mask to etch the photoresist underlayer film.

[0022] Invention Effects According to the present invention, a composition for forming a photoresist underlayer film that can obtain a photoresist underlayer film with a low refractive index, a method for manufacturing a photoresist underlayer film, a laminate, a semiconductor element using the composition for forming a photoresist underlayer film, and a patterning method are provided. Detailed Implementation

[0023] (Composition for forming the lower layer of the resist film) The composition for forming the resist underlayer film of the present invention comprises a polymer (hereinafter sometimes referred to as polymer (A)) and a solvent (hereinafter sometimes referred to as solvent (B)).

[0024] The composition for forming the underlayer film of the resist may also include a crosslinking agent (hereinafter sometimes referred to as crosslinking agent (C)), a curing catalyst (hereinafter sometimes referred to as curing catalyst (D)), etc.

[0025] <Polymer (A)> The polymer (A) has the unit structure shown in the following formula (1). (In formula (1), A independently represents a hydrogen atom, a methyl atom, or an ethyl atom, and Q...) 1 and Q 2 Each of these groups independently represents a divalent group having an aromatic hydrocarbon ring. X 1 and X 2 Each can independently represent a single bond or -C (=O)-. The polymer (A) contained in the composition for forming the lower layer film of the resist has the unit structure shown in formula (1), thereby, through Q 1 and Q 2 The aromatic hydrocarbon rings in the composition can reduce the refractive index of the resist underlayer film obtained from the resist underlayer film forming composition.

[0026] As Q 1 and Q 2 There is no particular restriction on the number of carbon atoms; for example, it can be 6 to 30 or 6 to 20.

[0027] From the viewpoint of properly obtaining the effects of the present invention, Q in equation (1) 1 The preferred expression is represented by the following formula (2).

[0028] From the viewpoint of properly obtaining the effects of the present invention, Q in equation (1) 2 It is preferred to be represented by any of the following formulas (3-1) to (3-3). (In equation (2) and equations (3-1) to (3-3), R) a Each can be independently represented as an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms.

[0029] W represents a single bond, -CH2-, -C(CH3)2-, -C(CF3)2-, -CO-, -O-, -S-, or SO2-.

[0030] m independently represents an integer from 0 to 2.

[0031] n can represent an integer from 0 to 4 independently.

[0032] * indicates a bond. Examples of alkyl groups having 1 to 10 carbon atoms include: methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl - Cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl 1,1,2-trimethyl-n-butyl, 2-ethyl-n-butyl, 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 Methyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl, etc.

[0033] Examples of alkoxy groups with 1 to 10 carbon atoms include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, 4-methyl-n-pentoxy Oxygen compounds, including 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, as well as 1-ethyl-2-methyl-n-propoxy, cyclopentoxy, cyclohexyloxy, norbornyloxy, adamantyloxy, etc.

[0034] Examples of alkenyl groups with 2 to 10 carbon atoms include: vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, 2-methyl-2-butenyl, 2-methyl-3-propenyl -Butenyl, 3-methyl-1-butenyl, 3-methyl-2-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-methyl-4-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-3-pentenyl alkenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl-1-pentenyl, 3-methyl-2-pentenyl, 3-methyl-3-pentenyl, 3-methyl-4-pentenyl, 3-ethyl-3-butenyl, 4-methyl-1-pentenyl, 4-methyl-2-pentenyl, 4-methyl-3-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1-methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3 -Dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 1-isobutylvinyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 2-isopropyl-2-propenyl, 3,3-dimethyl-1-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 1-n-propyl-1-propenyl, 1-n-propyl-2-propenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-Trimethyl-2-propenyl, 1-tert-butylvinyl, 1-Methyl-1-ethyl-2-propenyl, 1-Ethyl-2-methyl-1-propenyl, 1-Ethyl-2-methyl-2-propenyl, 1-Isopropyl-1-propenyl, 1-Isopropyl-2-propenyl, 1-Methyl-2-cyclopentenyl, 1-Methyl-3-cyclopentenyl, 2-Methyl-1-cyclopentenyl, 2-Methyl-2-cyclopentenyl 2-Methyl-3-cyclopentenyl, 2-methyl-4-cyclopentenyl, 2-methyl-5-cyclopentenyl, 2-methylene-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 3-methyl-4-cyclopentenyl, 3-methyl-5-cyclopentenyl, 3-methylene-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, and 3-cyclohexenyl, etc.

[0035] From the viewpoint of obtaining the effects of the present invention more appropriately, m in formula (2) is preferably 0 or 1, more preferably 0.

[0036] From the viewpoint of obtaining the effects of the present invention more appropriately, m in formula (3-1) is preferably 0 or 1.

[0037] From the viewpoint of obtaining the effects of the present invention more appropriately, n in equations (2) and (3-1) to (3-3) is preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 0.

[0038] As R a Preferably, it is an alkyl group or an alkoxy group with 1 to 4 carbon atoms.

[0039] As the structure shown in equation (1-a) below in equation (1), for example, the structures illustrated below can be listed. (In equation (1-a), Q) 1 Q in equation (1) 1 The meanings are the same. * indicates a bond. * indicates a bond.

[0040] As the structure shown in equation (1-b) below in equation (1), for example, the following exemplified structures can be listed. (In equation (1-b), Q) 2 X 1 and X 2 Q in equation (1) 2 X 1 and X 2They have the same meaning. * indicates a bond. * indicates a bond.

[0041] The polymer may further have a monovalent group as shown in formula (E). The monovalent group shown in formula (E) is located, for example, at the end of the polymer. (In formula (E), p represents 0 or 1. Z represents a monovalent group with 1 to 20 carbon atoms. * represents a bond.) The number of carbon atoms in Z is preferably 6 to 20.

[0042] Z, for example, has an aromatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include: benzene ring, naphthalene ring, anthracene ring, etc.

[0043] For example, in formula (E), Z has an aromatic hydrocarbon ring, and the carbon atoms constituting the aromatic hydrocarbon ring are bonded to the carbonyl carbon atoms in formula (E).

[0044] As Z in formula (E), for example, the group shown in the following formula (E-1) can be listed. In equation (E-1), q represents an integer from 0 to 2, and r represents an integer from 0 to 4. b Each element independently represents a halogen atom, a hydroxyl group, an alkyl group with 1 to 6 carbon atoms, or an alkoxy group with 1 to 6 carbon atoms. * indicates a bond. As a monovalent group represented by formula (E), the following groups can be listed as examples. * indicates a bond.

[0045] Polymers having the unit structure shown in formula (1) can be synthesized, for example, by the following method.

[0046] (I): The reaction of the compound shown in (1A) below with the compound shown in (1B) below.

[0047] (II): Reactions of the compound shown in (1A) below, the compound shown in (1B) below, and the compound shown in (EA) below. (In formula (1A), Q 1 Q in equation (1) 1 They have the same meaning.

[0048] In equation (1B), A and Q 2 X 1 and X 2 With A and Q in equation (1) 2 X 1 and X 2 They have the same meaning.

[0049] In equation (EA), p and Z have the same meanings as p and Z in equation (E). The above reaction can be carried out, for example, in the presence of a catalyst. The catalyst can be, for example, a quaternary phosphorus salt such as tetrabutylphosphine bromide or ethyltriphenylphosphine bromide; or a quaternary ammonium salt such as benzyltriethylammonium chloride. The amount of catalyst used can be selected from 0.1% to 10% by mass relative to the total mass of the reactants used in the reaction. The optimal conditions for the reaction can be selected, for example, from 50 to 160°C and 2 to 50 hours.

[0050] The mass ratio of the unit structure shown in formula (1) in polymer (A) is not particularly limited, but is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 80% by mass or more.

[0051] There are no particular limitations on the weight-average molecular weight of polymer (A), but it is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, and particularly preferably 2,500 to 15,000.

[0052] The content of polymer (A) in the composition for forming the lower layer of the resist film is not particularly limited. From the viewpoint of properly obtaining the effects of the present invention, it is preferably 40% to 100% by mass, more preferably 50% to 98% by mass, and particularly preferably 65% ​​to 95% by mass as a film component.

[0053] It should be noted that, in this invention, the membrane constituents refer to the components contained in the composition other than the solvent.

[0054] <Solvent (B)> As a solvent (B), there are no particular restrictions; it can be water or an organic solvent.

[0055] Examples of organic solvents include monoalkylene glycol ethers and monocarboxylic acid esters of monoalkylene glycol ethers.

[0056] Alkylenes that are monoalkylene glycol ethers include, for example, alkylenes with 2 to 4 carbon atoms.

[0057] Alkyl groups that are monoalkylene glycol ethers include, for example, alkyl groups with 1 to 4 carbon atoms.

[0058] Examples of alkylene glycol monoalkyl ethers with 3 to 8 carbon atoms can be listed, for example.

[0059] Examples of alkylene glycol monoalkyl ethers include: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.

[0060] Alkylenes that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers can be exemplified by alkylenes having 2 to 4 carbon atoms.

[0061] Alkyl groups that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers can be exemplified by alkyl groups having 1 to 4 carbon atoms.

[0062] Monocarboxylic acids that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers include saturated monocarboxylic acids with 2 to 4 carbon atoms.

[0063] Examples of saturated monocarboxylic acids with 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid.

[0064] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include, for example, 5 to 10 carbon atoms.

[0065] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include: methyl cellolytic acetate, ethyl cellolytic acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, etc.

[0066] Other organic solvents include, for example: diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxylate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0067] Among these solvents (B), monoalkylene glycol monoalkyl ethers and monocarboxylic acid esters of monoalkylene glycol monoalkyl ethers are preferred.

[0068] These solvents (B) can be used alone or in combination of two or more.

[0069] The mass percentage of the organic solvent in solvent (B) is not particularly limited, but is preferably 50% to 100% by mass.

[0070] The content of solvent (B) in the composition for forming the lower layer of the resist film is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0071] <Crosslinking agent (C)> There are no particular restrictions on its use as a crosslinking agent (C).

[0072] The crosslinking agent (C) has a different structure from the polymer (A).

[0073] As a crosslinking agent (C), amino plastic crosslinking agents and phenolic plastic crosslinking agents are preferred.

[0074] Amino plastic crosslinking agents are addition condensation products of amino compounds such as melamine and guanidine with formaldehyde.

[0075] Phenolic plastic crosslinking agents refer to the addition condensation products of compounds with phenolic hydroxyl groups and formaldehyde.

[0076] As a crosslinking agent (C), for example, compounds having two or more of the following structures can be listed. (In the structure, R) 101 This indicates a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxyalkyl group having 2 to 6 carbon atoms. * indicates a bond. Bonding bonds include those with nitrogen atoms, carbon atoms that form aromatic hydrocarbon rings, etc.

[0077] As R 101 Preferably, it contains hydrogen atoms, methyl, ethyl or groups represented by the following structures. (In the structure, R) 102 * indicates methyl or ethyl. * indicates a bonded bond. As a crosslinking agent (C), melamine compounds, guanidine compounds, glycourea compounds, urea compounds, and compounds with phenolic hydroxyl groups are preferred. They can be used alone or in combination of two or more.

[0078] Examples of melamine compounds include: hexahydroxymethyl melamine, hexamethoxymethyl melamine, compounds obtained by methoxymethylation of 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, compounds obtained by acyloxymethylation of 1 to 6 hydroxymethyl groups of hexahydroxymethyl melamine, and mixtures thereof.

[0079] Examples of guanidine compounds include: tetrahydroxymethylguanidine, tetramethoxymethylguanidine, compounds or mixtures thereof obtained by methoxymethylation of one to four hydroxymethyl groups of tetrahydroxymethylguanidine, tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds or mixtures thereof obtained by acyloxymethylation of one to four hydroxymethyl groups of tetrahydroxymethylguanidine, etc.

[0080] Examples of glycourea compounds include: tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds obtained by methoxymethylation of 1 to 4 of the hydroxymethyl groups of tetrahydroxymethylglycourea, or mixtures thereof, compounds obtained by acylmethylation of 1 to 4 of the hydroxymethyl groups of tetrahydroxymethylglycourea, or mixtures thereof.

[0081] Furthermore, as a glycourea compound, it can be, for example, a glycourea derivative as shown in the following formula (1E). (In formula (1E), each of the four R1s independently represents a methyl or ethyl group, and each of the R2 and R3 independently represents an alkyl or phenyl group with 1 to 4 carbon atoms.) Examples of compounds represented by formula (1E-1) to (1E-6) are examples of glycourea derivatives shown in formula (1E). The glycourea derivative shown in formula (1E) is obtained, for example, by reacting the glycourea derivative shown in formula (2E) with at least one compound shown in formula (3d). (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.) (In formula (3d), R1 represents methyl or ethyl.) Examples of compounds represented by formula (2E) as glycourea derivatives include those represented by formulas (2E-1) to (2E-4). Further examples of compounds represented by formula (3d) include those represented by formulas (3d-1) and (3d-2). Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds or mixtures thereof obtained by methoxymethylation of one to four hydroxymethyl groups of tetrahydroxymethylurea, and tetramethoxyethylurea.

[0082] Examples of compounds having phenolic hydroxyl groups include those represented by formula (G-1) or formula (G-2). (In equations (G-1) and (G-2), Q) 1 This indicates a single bond or an organic group with an m1 valence.

[0083] R 1 and R 4 Each represents 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.

[0084] R 2 and R 5 Each represents a hydrogen atom or a methyl group.

[0085] R 3 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0086] n1 represents an integer where 1 ≤ n1 ≤ 3, n2 represents an integer where 2 ≤ n2 ≤ 5, n3 represents an integer where 0 ≤ n3 ≤ 3, n4 represents an integer where 0 ≤ n4 ≤ 3, and also represents an integer where 3 ≤ (n1 + n2 + n3 + n4) ≤ 6.

[0087] n5 represents an integer where 1 ≤ n5 ≤ 3, n6 represents an integer where 1 ≤ n6 ≤ 4, n7 represents an integer where 0 ≤ n7 ≤ 3, n8 represents an integer where 0 ≤ n8 ≤ 3, and also represents an integer where 2 ≤ (n5 + n6 + n7 + n8) ≤ 5.

[0088] m1 represents an integer from 2 to 10. In addition, compounds having phenolic hydroxyl groups can be listed, for example, as compounds represented by the following formula (G-3) or formula (G-4).

[0089] The compound represented by formula (G-1) or (G-2) can be obtained by reacting the compound represented by formula (G-3) or (G-4) with a hydroxyl-containing ether compound or an alcohol having 2 to 10 carbon atoms. (In equations (G-3) and (G-4), Q) 2 This indicates a single bond or an m2 valence organic group.

[0090] R 8 R 9 R 11 and R 12 Each represents a hydrogen atom or a methyl group.

[0091] R 7 and R10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0092] n9 represents an integer where 1 ≤ n9 ≤ 3, n 10 It means 2≤n 10 Integers ≤ 5, n 11 It means 0≤n 11 Integers ≤ 3, n 12 It means 0≤n 12 Integers ≤ 3, and represent 3 ≤ (n ≤ 9 + n). 10 +n 11 +n 12 Integers ≤ 6.

[0093] n 13 This means 1 ≤ n 13 Integers ≤ 3, n 14 It means 1≤n 14 Integers ≤ 4, n 15 It means 0≤n 15 Integers ≤ 3, n 16 It means 0≤n 16 Integers ≤ 3, and represent 2 ≤ (n 13 +n 14 +n 15 +n 16 Integers ≤ 5.

[0094] m2 represents an integer from 2 to 10. As Q 2 The m2 valence organic groups in the text can be exemplified by, for example, m2 valence organic groups with 1 to 4 carbon atoms.

[0095] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds. Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds. The aforementioned compounds can be obtained in the form of products from Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, the trade name TMOM-BP from Asahi Organic Materials Co., Ltd. can be cited as an example of such a product.

[0096] Among them, glycourea compounds are preferred, specifically tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds obtained by methoxymethylation of 1 to 4 of the hydroxymethyl groups of tetrahydroxymethylglycourea, or mixtures thereof, compounds obtained by acylmethylation of 1 to 4 of the hydroxymethyl groups of tetrahydroxymethylglycourea, or mixtures thereof, and more preferably tetramethoxymethylglycourea.

[0097] The molecular weight of the crosslinking agent (C) is not particularly limited, but is preferably 500 or less.

[0098] The content of the crosslinking agent (C) in the composition for forming the lower layer of the resist film is not particularly limited, and is, for example, 1% to 70% by mass relative to the polymer (A), preferably 5% to 60% by mass.

[0099] <Cure Catalyst (D)> The curing catalyst (D) included as an optional component in the composition for forming the lower layer film of the resist can be any of a thermally generated acid agent or a photo-generated acid agent, but a thermally generated acid agent is preferred.

[0100] Examples of heat-generating acid agents include: p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, N-methylmorpholine-5-sulfosalicylic acid, and other sulfonic acid and carboxylic acid compounds.

[0101] Examples of photoacid-generating agents include: onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0102] Examples of onionium salt compounds include: diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate; as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0103] Examples of sulfonylimide compounds include: N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0104] Examples of disulfonyl diazonium compounds include: bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium, etc.

[0105] The curing catalyst (D) can be used alone or in combination of two or more.

[0106] When using a curing catalyst (D), the content of the curing catalyst (D) relative to the crosslinking agent (C) is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0107] <Other Ingredients> To prevent pinholes, streaks, and other defects, and to further improve the coating properties against surface unevenness, a surfactant may be added to the composition for forming the resist underlayer film.

[0108] Examples of surfactants include: linear or branched alkylbenzene sulfonic acids (e.g., dodecylbenzene sulfonic acid), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oil-based ether, and other polyoxyethylene alkyl ethers; polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, and other polyoxyethylene alkyl aryl ethers; polyoxyethylene-polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, and sorbitol. Sorbitan anhydride fatty acid esters such as sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; nonionic surfactants such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EFTOP Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS, trade name), MEGAFACE F171, F173, R-30 (manufactured by DIC Corporation, trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Corporation, trade name), AsahiGuard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation, trade name); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0109] The amount of these surfactants is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the composition for forming the resist underlayer film.

[0110] These surfactants can be added individually or in combination of two or more.

[0111] The solid components contained in the resist underlayer film forming composition of the present invention, i.e., components excluding the solvent, are, for example, 0.01% to 10% by mass.

[0112] (Underlying film of the resist) The resist underlayer film of the present invention is a cured product of the above-mentioned resist underlayer film forming composition.

[0113] The photoresist underlayer film can be manufactured, for example, by coating the above-mentioned photoresist underlayer film forming composition onto a semiconductor substrate and then firing it.

[0114] Examples of semiconductor substrates for coating with compositions for forming a resist underlayer include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0115] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed, for example, by ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (spin-coated glass: SOG). Examples of such inorganic films include: polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (boro-phosphorus silicon glass) films, titanium nitride films, titanium oxynitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0116] On such a semiconductor substrate, the resist underlayer film formation composition of the present invention is coated using a suitable coating method such as a spin coater or a coating machine. Then, the resist underlayer film is formed by baking using a heating unit such as a heating plate. Baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 minutes to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 minutes to 30 minutes; more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 minutes to 10 minutes.

[0117] There are no particular restrictions on the refractive index (n value) at a wavelength of 193 nm for the lower layer of the resist film; for example, it can be 1.30 to 1.50 or 1.30 to 1.45.

[0118] There are no particular restrictions on the attenuation coefficient (k value) at a wavelength of 193nm for the lower layer of the resist film. For example, it can be 0.23 to 0.50 or 0.25 to 0.45.

[0119] These optical constants can be determined, for example, by using a spectroscopic ellipsometer (JAWoollam, VUV-VASEVU-302) to measure the n-value (refractive index) and k-value (attenuation coefficient or extinction coefficient) at a wavelength of 193 nm for the coating.

[0120] For example, the coating can be formed by applying the composition to be tested onto a silicon wafer using a spin coater at a speed of 1500 rpm and baking it on a hot plate at 205°C for 1 minute.

[0121] The thickness of the underlying resist film is, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm (5nm)~0.05μm (50nm), 0.003μm (3nm)~0.03μm (30nm), 0.003μm (3nm)~0.02μm (20nm), 0.005μm (5nm)~0.02μm (20nm), 0.003μm (3nm)~0.01μm (10nm), 0.005μm (5nm)~0.01μm (10nm), 0.003μm (3nm)~0.006μm (6nm) or 0.005μm (5nm).

[0122] (Layered structure) The laminate of the present invention comprises a semiconductor substrate and a photoresist underlayer film of the present invention.

[0123] Examples of semiconductor substrates include the semiconductor substrates described above.

[0124] The photoresist underlayer film is disposed, for example, on a semiconductor substrate.

[0125] (Semiconductor device manufacturing methods and patterning methods) The method for manufacturing the semiconductor element of the present invention includes at least the following steps.

[0126] • A process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition of the present invention; and • The process of forming a resist film on the resist underlayer film.

[0127] The pattern forming method of the present invention includes at least the following steps.

[0128] • A process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition of the present invention; • The process of forming a resist film on the underlying resist film; • The process of irradiating the resist film with light, followed by developing the resist film to obtain the resist pattern; and • The process of using a resist pattern as a mask to etch the underlying resist film.

[0129] A resist film is usually formed on the underlying resist film.

[0130] The thickness of the resist film is, for example, below 3000 nm, below 2000 nm, below 1800 nm, below 1500 nm, and below 1000 nm. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, and 10 nm.

[0131] As a photoresist film formed on a resist underlayer by a known method (e.g., coating and firing of the photoresist composition), there are no particular limitations as long as it responds to light used for irradiation. Either negative or positive photoresists can be used.

[0132] As photoresists, there are: positive photoresists containing phenolic varnish resin and 1,2-naphthoquinone didiazosulfonate; chemically amplified photoresists containing binders and photoacid generators that increase the rate of alkali dissolution by utilizing acid decomposition; chemically amplified photoresists containing low-molecular-weight compounds, alkali-soluble binders, and photoacid generators that increase the rate of alkali dissolution by utilizing acid decomposition; and chemically amplified photoresists containing binders, low-molecular-weight compounds, and photoacid generators that increase the rate of alkali dissolution by utilizing acid decomposition; and photoresists containing metal elements, etc. Examples include: JSR Corporation's product V146G, Shipley's product APEX-E, Sumitomo Chemical Co., Ltd.'s product PAR710, and Shin-Etsu Chemical Co., Ltd.'s products AR2772 and SEPR430, etc. In addition, examples include fluorinated atom polymer photoresists described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0133] In addition, the following codes can be used: WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, and WO2019 / 172054. WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japan Special Application 2018-180525, WO2018 / 190088, Japan Special Application 2018-070596, Japan Special Application 2018-028090, Japan Special Application 2016-153409, Japan Special Application Open 2016-130240, Japan Special Open 2016-108325, Japan Special Open 2016-047920, Japan Special Open 2016-035570, Japan Special Opening 2016-035567, Japanese Special Opening 2016-035565, Japanese Special Opening 2019-101417, Japanese Special Opening 2019-11737 3. Japan Special Opening 2019-052294, Japanese Special Opening 2019-008280, Japanese Special Opening 2019-008279, Japanese Special Opening 2019-003176, Japanese Special Opening 2019-003175, Japanese Special Opening 2018-197853, Japanese Special Opening 2019-191298, Japanese Special Opening 2019- 061217, Japanese Special Opening 2018-045152, Japanese Special Opening 2018-022039, Japanese Special Opening 2016-090441, Japanese Special Opening 2015-10878, Japanese Special Opening 2012-168279, Japanese Special Opening 2012-022261, Japanese Special Opening 2012-022258, Japanese Special Opening 2 The so-called resist compositions, such as resist compositions, radiosensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions, as described in Japanese Patent Application Publications (JP2011-043749, JP2010-181857, JP2010-128369, WO2018 / 031896, JP2019-113855, WO2017 / 156388, WO2017 / 066319, JP2018-41099, WO2016 / 065120, WO2015 / 026482, JP2016-29498, and JP2011-253185, are not limited to these.

[0134] Examples of resist compositions include the following.

[0135] An active light-sensitive or radiation-sensitive resin composition comprising resin A and a compound represented by the following general formula (121), wherein resin A comprises repeating units having acid-degradable groups protected by a protecting group whose polar groups are removed by the action of an acid. In general formula (121), m represents an integer from 1 to 6.

[0136] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0137] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0138] L2 represents an alkylene group or a single bond that may optionally have substituents.

[0139] W1 represents a cyclic organic group that optionally has substituents.

[0140] M ＋ It represents a cation.

[0141] A radiation-sensitive resin composition containing a polymer and an acid-producing agent, wherein the polymer has a first structural unit as shown in formula (31) and a second structural unit containing an acid-dissociating group as shown in formula (32). (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon with 6 to 20 carbon atoms. R 1 It is a hydroxyl, mercapto, or monovalent organic group with 1 to 20 carbon atoms. n is an integer from 0 to 11. When n is 2 or more, multiple R... 1 Same or different. R 2 It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 It is a monovalent group containing 1 to 20 carbon atoms, comprising the aforementioned acid-dissociable groups. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 (It can be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.) A photoresist composition containing a resin (A1) and an acid-producing agent, wherein the resin (A1) comprises structural units having a cyclic carbonate structure, structural units shown in the following formula, and structural units having acid-instable groups. [In the formula,] R 2X represents an alkyl group, hydrogen atom, or halogen atom having 1 to 6 carbon atoms, optionally containing halogen atoms. 1 Indicates a single bond, -CO-O-*, or -CO-NR. 4 —, * indicates a bond with -Ar, R 4 [Ar represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms, and optionally an aromatic hydrocarbon group having 6 to 20 carbon atoms having one or more groups selected from the group consisting of hydroxyl and carboxyl groups.] Examples of resist films include the following.

[0142] A photoresist film comprising a base resin comprising repeating units as shown in formula (a1) and / or repeating units as shown in formula (a2) and repeating units of acid bonded to the polymer backbone by exposure. (In equations (a1) and (a2), R) A Each can be independently a hydrogen atom or a methyl group. R 1 and R 2 Each is an independent tertiary alkyl group having 4 to 6 carbon atoms. R 3 Each atom can be independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. X 1 It is a single bond, a phenylene or naphthylene group, or a linking group having 1 to 12 carbon atoms selected from at least one of ester bonds, lactone rings, phenylene, and naphthylene. X 2 (These can be single bonds, ester bonds, or amide bonds.) Examples of corrosion-resistant materials include the following.

[0143] A resist material comprising a polymer having repeating units as shown in formula (b1) or formula (b2). (In equations (b1) and (b2), R) A It can be a hydrogen atom or a methyl group. X 1 It is a single bond or an ester group. X 2 It is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms, wherein a portion of the methylene group constituting the alkylene group is optionally substituted with an ether group, an ester group, or a group containing an lactone ring; furthermore, X 2 At least one hydrogen atom is replaced by a bromine atom. X 3 It is a single bond, an ether group, an ester group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, wherein a portion of the methylene group constituting the alkylene group is optionally substituted with an ether group or an ester group. Rf 1 ~Rf 4Each is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Furthermore, Rf 1 and Rf 2 Optionally, they can be combined to form a carbonyl group. R 1 ~R 5 Each group is independently composed of a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkyne group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms. Some or all of the hydrogen atoms in these groups are optionally substituted with hydroxyl, carboxyl, halogen, oxo, cyano, amide, nitro, sulopentalide, sulfone, or sulfonate groups. A portion of the methylene group constituting these groups is optionally substituted with an ether, ester, carbonyl, carbonate, or sulfonate group. Alternatively, R may also be... 1 With R 2 (They bond together, forming a ring with the sulfur atoms they are bonded to.) A resist material comprising a base resin, wherein the base resin comprises a polymer containing repeating units as shown in formula (a). (In formula (a), R) A It can be a hydrogen atom or a methyl group. R 1 It is a hydrogen atom or an acid-labile group. R 2 It is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 It is a single bond or phenylene, or optionally a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, comprising an ester group or lactone ring. X 2 It can be -O-, -O-CH2-, or -NH-. m is an integer from 1 to 4. u is an integer from 0 to 3. Where m + u is an integer from 1 to 4. A photoresist composition comprising a photoresist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid. The resist composition contains a substrate component (A) whose solubility in the developer changes due to the action of acid, and a fluorine additive component (F) that exhibits decomposition properties in alkaline developers. The fluorinated additive component (F) contains a fluoropolymer component (F1), which has a structural unit (f1) containing a base-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1). In the formula (f2-r-1), Rf 21Each atom is independently a hydrogen atom, alkyl group, alkoxy group, hydroxy group, hydroxyalkyl group, or cyano group. n" is an integer from 0 to 2. * represents a bond. The structural unit (f1) includes the structural unit shown in the following general formula (f1-1) or the structural unit shown in the following general formula (f1-2). In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. X is a divalent linking group without an acid-dissociating site. A aryl X is a divalent aromatic cyclic group optionally having substituents. 01 It is a single bond or a divalent linker. R 2 Each is an organic group that independently possesses a fluorine atom. Irradiation is performed, for example, by using a mask (intermediate mask) to form a predetermined pattern. Examples include i-rays (365 nm), KrF excimer lasers (248 nm), and ArF excimer lasers (193 nm). The resist underlayer film formation composition of the present invention is preferably used for irradiation with KrF excimer lasers (248 nm) and ArF excimer lasers (193 nm), and more preferably for irradiation with ArF excimer lasers (193 nm).

[0144] There are no particular restrictions on the amount of light exposure.

[0145] It can also be baked after exposure to light and before development (PEB: Post Exposure Bake).

[0146] There are no particular limitations on the baking temperature, but it is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C.

[0147] There are no particular restrictions on the baking time, but 1 second to 10 minutes is preferred, 10 seconds to 5 minutes is more preferred, and 30 seconds to 3 minutes is particularly preferred.

[0148] For example, developing can be done using an alkaline developing solution.

[0149] Examples of developing temperatures include 5°C to 50°C.

[0150] For example, development time can range from 10 seconds to 300 seconds.

[0151] As an alkaline developer, examples of suitable alkaline developers include: inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; alkanolamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines such as pyrrole and piperidine. Furthermore, appropriate amounts of alcohols such as isopropanol and nonionic surfactants can be added to the aforementioned alkaline aqueous solutions. Preferably, the developer is an aqueous solution of a quaternary ammonium salt, and more preferably, an aqueous solution of tetramethylammonium hydroxide and an aqueous solution of choline. Surfactants can also be added to these developers. Alternatively, an organic solvent such as butyl acetate can be used instead of the alkaline developer for development, developing the portion where the alkaline dissolution rate of the photoresist is not improved.

[0152] Next, using the formed resist pattern as a mask, the underlying resist film is etched. The etching can be dry etching or wet etching, but dry etching is preferred.

[0153] When the inorganic film is formed on the surface of the semiconductor substrate, the surface of the inorganic film is exposed; when the inorganic film is not formed on the surface of the semiconductor substrate, the surface of the semiconductor substrate is exposed. Then, by processing the semiconductor substrate using a known method (dry etching, etc.), a semiconductor device can be manufactured.

[0154] Example The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to the embodiments described below. It should be noted that the apparatus used is as described below.

[0155] The weight-average molecular weights of the polymers shown in the following examples are the results obtained using gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus manufactured by TOSOH Corporation, and the determination conditions are as follows.

[0156] Column temperature: 40℃.

[0157] Flow rate: 0.35 ml / min.

[0158] Eluent: Tetrahydrofuran (THF).

[0159] Standard sample: polystyrene (TOSOH Corporation).

[0160] <Synthesis example 1> A reaction flask containing 20.00 g of a propylene glycol monomethyl ether solution (manufactured by DIC Corporation, trade name: WR-400), 1.27 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.09 g of tetrabutylsulfonium bromide (manufactured by HOKKO CHEMICAL INDUSTRY Co., Ltd.), and 1.05 g of propylene glycol monomethyl ether was heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere. The resulting reaction product corresponds to formula (X1), and the weight-average molecular weight (Mw) determined by GPC to be 7300 converted to polystyrene.

[0161] Equation (X1) <Synthesis example 2> A reaction flask containing 2.00 g of resorcinol diglycidyl ether (product name: DENACOL EX-201-IM, manufactured by NagaseChemteX Co., Ltd.), 1.44 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.11 g of tetrabutylsulfonium bromide (manufactured by HOKKO CHEMICAL INDUSTRY Co., Ltd.), and 20.12 g of propylene glycol monomethyl ether was heated and stirred at 105°C for 24 hours under a nitrogen atmosphere. The resulting reaction product corresponds to formula (X2), and the weight-average molecular weight (Mw) determined by GPC using polystyrene conversion is 9100.

[0162] Equation (X2) <Synthesis Example 3> A reaction flask containing 15.00 g of a propylene glycol monomethyl ether solution (manufactured by DIC Corporation, trade name: WR-400), 5.65 g of resorcinol diglycidyl ether (product name: DENACOL EX-201-IM, manufactured by Nagase ChemteX Corporation), 1.31 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.10 g of tetrabutylsulfonium bromide (manufactured by HOKKO CHEMICAL INDUSTRY Co., Ltd.), and 1.39 g of propylene glycol monomethyl ether was heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere. The resulting reaction product corresponds to formula (X3), and the weight-average molecular weight (Mw) determined by GPC using polystyrene conversion is 6600.

[0163] Equation (X3) <Synthesis example 4> A reaction flask containing 3.00 g of 1,4-dihydroanthracene-9,10-dimethylbis(glycidyl ether) (product name: YX8800, manufactured by MITSUBISHI CHEMICAL Co., Ltd.), 3.61 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.39 g of tetrabutylsulfonium bromide (manufactured by HOKKO CHEMICAL INDUSTRY Co., Ltd.), and 38.17 g of propylene glycol monomethyl ether was heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere. The resulting reaction product corresponds to formula (X4), and the weight-average molecular weight (Mw) determined by GPC using polystyrene conversion is 6500.

[0164] Equation (X4) <Synthesis example 5> A reaction flask containing 40.00 g of a propylene glycol monomethyl ether solution (manufactured by DIC Corporation, trade name: WR-400), 2.18 g of isophthalic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.32 g of 9-anthracarboxylic acid, 0.18 g of tetrabutylsulfonium bromide (manufactured by HOKKO CHEMICAL INDUSTRY Co., Ltd.), and 2.06 g of propylene glycol monomethyl ether was heated and stirred at 105 °C for 24 hours under a nitrogen atmosphere. The resulting reaction product corresponds to formula (X5), and the weight-average molecular weight (Mw) determined by GPC using polystyrene conversion is 7300.

[0165] Equation (X5) <Comparative Synthesis Example 1> A reaction flask containing 10.00 g of monoallyl diglycidyl isocyanuric acid (product name: MA-DGICA, manufactured by Shikoku Chemical Industry Co., Ltd.), 8.96 g of 3,3'-dithiopropionic acid, 0.66 g of ethyltriphenylphosphine bromide, and 78.47 g of propylene glycol monomethyl ether was heated and stirred at 100°C for 23 hours under a nitrogen atmosphere. The resulting reaction product corresponds to formula (X6), and its weight-average molecular weight (Mw) determined by GPC using polystyrene conversion is 2800.

[0166] Equation (X6) (Example 1) To 11.53 g of a solution containing the polymer obtained in Synthesis Example 1 (solid content concentration 15.12% by mass), 0.17 g of tetramethoxymethyl urea (manufactured by Nihon Cytec Industries, Ltd., trade name: POWDERLINK [registered trademark] 1174) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Corporation) as a surfactant were mixed. The resulting mixture was dissolved in 78.42 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a photoresist lower film.

[0167] (Example 2) To 10.60 g of a solution containing the polymer obtained in Synthesis Example 1 (solid content concentration 15.12% by mass), 0.16 g of tetramethoxymethyl urea (manufactured by Nihon Cytec Industries, Ltd., trade name: POWDERLINK [registered trademark] 1174) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, 0.17 g of VP-2500 (manufactured by Nippon Soda, Ltd.) as an additive, and 0.002 g of a fluorinated surfactant (product name: MEGAFACER-40, manufactured by DIC, Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 79.20 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a resist lower film.

[0168] (Example 3) To 11.53 g of a solution containing the polymer obtained in Synthesis Example 1 (solid content concentration 15.12% by mass), 0.17 g of NIKALAC (registered trademark) MW-390 (manufactured by SANWA CHEMICAL Co., Ltd.) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Co., Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 78.42 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a photoresist lower film.

[0169] (Example 4) To 10.60 g of a solution containing the polymer obtained in Synthesis Example 1 (solid content concentration 15.12% by mass), 0.16 g of NIKALAC (registered trademark) MW-390 (manufactured by SANWA CHEMICAL Co., Ltd.) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, 0.17 g of VP-2500 (manufactured by Nippon Soda Co., Ltd.) as an additive, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Co., Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 79.20 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a photoresist lower film.

[0170] (Example 5) To 11.53 g of a solution containing the polymer obtained in Synthesis Example 1 (solid content concentration 15.12% by mass), 0.17 g of 3,3',5,5'-tetratetra(methoxymethyl)-4,4'-dihydroxybiphenyl (product name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Co., Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 78.42 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a resist lower film.

[0171] (Example 6) To 12.18 g of a solution containing the polymer obtained in Synthesis Example 2 (solid content concentration 14.31% by mass), 0.17 g of tetramethoxymethyl urea (manufactured by Nihon Cytec Industries, Ltd., trade name: POWDERLINK [registered trademark] 1174) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Corporation) as a surfactant were mixed. The resulting mixture was dissolved in 78.75 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the solution was filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a photoresist lower film.

[0172] (Example 7) To 11.91 g of a solution containing the polymer obtained in Synthesis Example 3 (solid content concentration 15.57% by mass), 0.17 g of tetramethoxymethyl urea (manufactured by Nihon Cytec Industries, Ltd., trade name: POWDERLINK [registered trademark] 1174) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Corporation) as a surfactant were mixed. The resulting mixture was dissolved in 78.42 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a photoresist lower film.

[0173] (Example 8) To 11.91 g of a solution containing the polymer obtained in Synthesis Example 3 (solid content concentration 15.57% by mass), 0.17 g of NIKALAC (registered trademark) MW-390 (manufactured by SANWA CHEMICAL Co., Ltd.) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Co., Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 78.42 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a photoresist lower film.

[0174] (Example 9) To 11.60 g of a solution containing the polymer obtained in Synthesis Example 4 (solid content concentration 15.02% by mass), 0.17 g of 3,3',5,5'-tetratetra(methoxymethyl)-4,4'-dihydroxybiphenyl (product name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Co., Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 78.34 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a photoresist lower film.

[0175] (Example 10) To 11.91 g of a solution containing the polymer obtained in Synthesis Example 5 (solid content concentration 14.64% by mass), 0.17 g of 3,3',5,5'-tetra(methoxymethyl)-4,4'-dihydroxybiphenyl (product name: TMOM-BP, manufactured by Honshu Chemical Industry Co., Ltd.) as a crosslinking agent, 0.06 g of pyridinium-p-toluenesulfonic acid as a crosslinking catalyst, and 0.002 g of a fluorinated surfactant (product name: MEGAFACE R-40, manufactured by DIC Co., Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 78.04 g of propylene glycol monomethyl ether and 9.80 g of propylene glycol monomethyl ether acetate to prepare a solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming a resist lower film.

[0176] (Comparative Example 1) To a solution containing the polymer obtained in Comparative Synthesis Example 1 (solid content concentration 17.76% by mass), 0.18g of tetramethoxymethyl urea (manufactured by Nihon Cytec Industries, Ltd., trade name: POWDERLINK [registered trademark] 1174) as a crosslinking agent, 0.06g of 4-hydroxybenzenesulfonic acid as a crosslinking catalyst, 0.01g of bis(4-hydroxyphenyl) sulfone as an additive, and 0.007g of a fluorinated surfactant (product name: MEGAFACER-40, manufactured by DIC Co., Ltd.) as a surfactant were mixed. The resulting mixture was dissolved in 85.76g of propylene glycol monomethyl ether and 9.91g of propylene glycol monomethyl ether acetate to prepare a solution. Then, the solution was filtered using a polyethylene microfilter with a pore size of 0.05μm to prepare a composition for forming a resist lower film.

[0177] [Resist Solvent Resistance Test] The resist underlayer film forming compositions prepared in Examples 1 to 10 and Comparative Example 1 were each spin-coated onto silicon wafers using a spin coater. The coated silicon wafers were then heated on a hot plate at 215°C for 1 minute to form a resist underlayer film. Next, to confirm the resist solvent resistance of the resist underlayer film, the silicon wafers with the resist underlayer film formed were immersed in a solvent composed of propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 7:3 (PGME:PGMEA = 7:3) for 1 minute, then spin-dried and baked at 100°C for 30 seconds. The film thickness of the resist underlayer film before and after immersion in the mixed solvent was measured using an optical interferometer (product name: NanoSpec 6100, manufactured by Nanometrics Japan Co., Ltd.).

[0178] Regarding the evaluation of resist solvent resistance, the film thickness reduction rate (%) of the resist underlayer removed by solvent impregnation was calculated according to the following formula, and the evaluation was carried out. The results are shown in Table 1. It should be noted that if the film thickness reduction rate is less than approximately 2%, it is considered to have sufficient resist solvent resistance and is evaluated as "good". The results are shown in Table 1.

[0179] Film thickness reduction rate (%) = [(A-B)÷A]×100 A: Film thickness before solvent impregnation.

[0180] B: Film thickness after solvent impregnation. [Determination of optical constants] The resist underlayer film forming compositions prepared in Examples 1 to 10 and Comparative Example 1 were respectively coated onto silicon wafers using a spin coater at a speed of 1500 rpm. The wafers were then baked on a hot plate at 215°C for 1 minute to form the resist underlayer film. For these resist underlayer films, the n-value (refractive index) and k-value (attenuation coefficient or extinction coefficient) at a wavelength of 193 nm were measured using a spectroscopic ellipsometry (JAWoollam, VUV-VASE VU-302). The results are shown in Table 2. According to the results in Table 2, the resist film obtained by the resist film forming composition of the present invention has a sufficiently low n value for light with a wavelength of 193 nm compared with the resist film obtained by the known resist film forming composition.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer having a unit structure as shown in formula (1) and a solvent, In formula (1), A independently represents a hydrogen atom, a methyl atom, or an ethyl atom, and Q... 1 and Q 2 Each independently represents a divalent group having an aromatic hydrocarbon ring; X 1 and X 2 Each can independently represent a single bond or -C (=O)-.

2. The composition for forming a resist underlayer film according to claim 1, wherein, Q in equation (1) 1 Q is expressed by the following equation (2). 2 Expressed by any of the following equations (3-1) to (3-3), In equations (2) and (3-1) to (3-3), R a Each can independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. W represents a single bond, -CH2-, -C(CH3)2-, -C(CF3)2-, -CO-, -O-, -S-, or SO2-. m independently represents an integer from 0 to 2. n independently represents an integer from 0 to 4. * indicates a bond.

3. The composition for forming a resist underlayer film according to claim 1, wherein, The solvent comprises at least one selected from the group consisting of monocarboxylic acid esters of alkylene glycol monoalkyl ethers and alkylene glycol monoalkyl ethers.

4. The composition for forming a resist underlayer film according to claim 1, wherein, The composition for forming the resist underlayer film further comprises a crosslinking agent.

5. The composition for forming a resist underlayer film according to claim 1, wherein, The composition for forming the resist underlayer film further comprises a curing catalyst.

6. A resist underlayer film, which is a cured product of the resist underlayer film forming composition as described in any one of claims 1 to 5.

7. A laminated body, comprising: Semiconductor substrates; and The resist underlayer film as described in claim 6.

8. A method for manufacturing a semiconductor device, comprising the following steps: Using the composition for forming a photoresist underlayer as described in any one of claims 1 to 5, a photoresist underlayer film is formed on a semiconductor substrate; and A resist film is formed on the lower resist film.

9. A method for forming a pattern, comprising the following steps: A photoresist underlayer film is formed on a semiconductor substrate using the composition for forming a photoresist underlayer film as described in any one of claims 1 to 5; A resist film is formed on the lower resist film; The resist film is irradiated with light, and then the resist film is developed to obtain a resist pattern; as well as The resist pattern is used as a mask to etch the underlying resist film.

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