Composition for resist underlayer film formation

Abstract

Provided is a composition for forming an antiresist underlayer film, which is resistant to a solvent and has high sensitivity to an antiresist pattern. A composition for forming an antiresist underlayer film, which contains a polymer (A) and a solvent (B), the polymer (A) being a polymer having a sulfonic acid group.

Description

Technical Field

[0001] This invention relates to compositions for forming a photoresist underlayer, photoresist underlayers, laminates, methods for manufacturing semiconductor devices, and methods for patterning. Background Technology

[0002] For a long time, microfabrication has been carried out in the manufacture of semiconductor devices using photolithography with photoresist compositions. One such microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating an active light source such as ultraviolet light through a mask pattern depicting a device pattern, developing the image, and then etching the substrate with the resulting photoresist pattern as a protective film. This process forms a micro-unfold on the substrate surface corresponding to the photoresist pattern. In recent years, with the continuous development of high integration in semiconductor devices, in addition to the previously used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm) active light sources, the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) has been investigated in cutting-edge microfabrication. However, the influence of the semiconductor substrate and other factors can lead to poor photoresist pattern formation, which has become a serious problem. To address this issue, methods for providing a photoresist underlayer film between the photoresist and the semiconductor substrate have been extensively studied.

[0003] As a composition for forming a resist underlayer film, a composition for forming a resist underlayer film has been proposed, which comprises a reaction product of "a compound (A) of formula (1) (in formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring or a heterocyclic ring)," "a compound (B) having two functional groups that are reactive with an epoxy group" and "a compound (C) having one functional group that is reactive with an epoxy group" dissolved in a solvent (see Patent Document 1).

[0004] Existing technical documents

[0005] Patent documents

[0006] International Publication No. 2022 / 075339 Summary of the Invention

[0007] The problem to be solved by the present invention

[0008] As required properties of the underlying resist film, good resist patterns can be formed by improving the following properties: preventing miscibility with the resist film formed on the upper layer and being insoluble in the resist solvent (solvent resistance), reducing the exposure dose required for resist pattern formation (excellent sensitivity of the resist pattern), etc.

[0009] The present invention was made in view of the above circumstances, and its object is to provide a composition for forming a photoresist underlayer film that is resistant to solvents and has good sensitivity to photoresist patterns, as well as a method for manufacturing a photoresist underlayer film, a laminate, a semiconductor device, and a patterning method using the composition for forming a photoresist underlayer film.

[0010] Problem-solving methods

[0011] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned problems could be solved, thus completing the present invention with the following key points.

[0012] That is, the present invention includes the following solutions.

[0013] [1]. A composition for forming a resist underlayer film, comprising a polymer (A) and a solvent (B),

[0014] The polymer (A) is a polymer with sulfonic acid groups.

[0015] [2]. The composition for forming a resist underlayer film as described in [1], wherein the polymer (A) has a structure represented by the following formula (X),

[0016]

[0017] In formula (X), A represents a hydrogen atom, a methyl atom, or an ethyl atom.

[0018] Ta represents the following formula (X1), and * represents the connecting key.

[0019]

[0020] In formula (X1), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine and iodine atoms. * represents a connecting bond and n represents 0 or 1.

[0021] [3]. The composition for forming a resist underlayer film as described in [1], wherein the polymer (A) has a structure represented by the following formula (X2),

[0022]

[0023] In formula (X2), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine, and iodine atoms. * represents a connecting bond.

[0024] [4]. The composition for forming the lower layer film of the resist as described in [2], wherein the group represented by the formula (X1) is any one of the groups represented by the following formulas (X1-1) to (X1-5):

[0025]

[0026]

[0027] In equations (X1-1) to (X1-5), Rx is a halogen atom selected from fluorine, chlorine, bromine and iodine atoms, nx represents an integer from 0 to 4, and * represents a connecting bond.

[0028] [5]. The composition for forming a resist underlayer film as described in [1], wherein the polymer (A) is a polymer (Y) having repeating units represented by the following formula (Y),

[0029]

[0030] In formula (Y), A represents a hydrogen atom, a methyl atom, or an ethyl atom.

[0031] Qa and Qb represent the following equation (Y5) or the following equation (Y6), respectively.

[0032] T1 and T2 represent hydrogen atoms or the following formula (X1), respectively, wherein in the polymer (Y), either T1 or T2 in formula (Y) has a repeating unit represented by the following formula (X1).

[0033]

[0034] In formulas (Y5) and (Y6), Q1 represents an alkylene, phenylene, naphthylene, anthraceneylene, or the following formula (M1) having 1 to 10 carbon atoms, and the alkylene, phenylene, naphthylene, and anthraceneylene can be substituted by an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group formed by combinations thereof.

[0035] n1 and n2 represent 0 or 1 respectively.

[0036] Z1 and Z2 represent single bonds or groups represented by the following formula (Y6-1), respectively.

[0037] X1 represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0).

[0038] * indicates a connection key.

[0039]

[0040] In formula (M1), Y 101 This refers to an alkylene group with 1 to 10 carbon atoms in which at least one hydrogen atom can be replaced by a fluorine atom.

[0041] R 101 and R 102 These represent alkyl groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms.

[0042] n 10 and n 11 They represent integers from 0 to 4 respectively.

[0043] * indicates a connection key.

[0044]

[0045] In equation (Y6-1), m represents an integer from 1 to 4, n represents an integer from 0 to 4, p1 and p2 each independently represent 0 or 1, *3 represents the linking bond with the nitrogen atom in equation (Y6), and *4 represents the linking bond.

[0046]

[0047] In formulas (Y2), (Y3), (Y4), and (Y0), R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 3 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a benzyl group, or a phenyl group, respectively. The alkyl group with 1 to 6 carbon atoms, the alkenyl group with 3 to 6 carbon atoms, the alkynyl group with 2 to 6 carbon atoms, the benzyl group, and the phenyl group can be substituted with a group selected from alkyl groups with 1 to 6 carbon atoms, a halogen atom, an alkoxy group with 1 to 6 carbon atoms, an alkoxyalkyl group with 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group with 1 to 6 carbon atoms. Furthermore, R1 and R2 can combine with each other to form a ring with 3 to 6 carbon atoms.

[0048] R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, wherein the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms.

[0049] * indicates a linking bond; *1 indicates a linking bond with a carbon atom, and *2 indicates a linking bond with a nitrogen atom.

[0050]

[0051] In formula (X1), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine and iodine atoms. * represents a connecting bond and n represents 0 or 1.

[0052] [6]. The composition for forming a resist underlayer film as described in [5], wherein the formula (X1) is the following formula (X2),

[0053]

[0054] In formula (X2), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine, and iodine atoms. * represents a connecting bond, and n represents 0 or 1.

[0055] The composition for forming a resist underlayer film according to any one of [7]. [1] to [6] further comprises a crosslinking agent (C).

[0056] [8]. The composition for forming a resist underlayer film as described in [7], wherein the crosslinking agent (C) is at least one selected from amino plastic crosslinking agents and phenolic plastic crosslinking agents.

[0057] [9]. A resist underlayer film, which is a cured product of the resist underlayer film forming composition described in any one of [1] to [8].

[0058]

[10] . A laminate having a semiconductor substrate and a resist underlayer as described in [9].

[0059]

[11] . A method for manufacturing a semiconductor device, comprising:

[0060] The process of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film forming composition according to any one of [1] to [8], and

[0061] The process of forming a resist film on the resist underlayer film.

[0062]

[12] . A pattern forming method, comprising:

[0063] The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of [1] to [8]

[0064] The process of forming a resist film on the underlying resist film.

[0065] The process of irradiating the resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern, and...

[0066] The process of using the resist pattern as a mask to etch the underlying resist film.

[0067] Invention Effects

[0068] According to the present invention, a composition for forming a photoresist underlayer film with good solvent resistance and good sensitivity to photoresist patterning can be provided, as well as a method for manufacturing a photoresist underlayer film, a laminate, a semiconductor device, and a patterning method using the composition for forming a photoresist underlayer film. Detailed Implementation

[0069] (Composition for forming the lower layer film of the resist)

[0070] The composition for forming the resist underlayer film of the present invention contains a polymer (A) and a solvent (B).

[0071] Polymer (A) is a polymer containing sulfonic acid groups.

[0072] The composition for forming the resist underlayer film of the present invention may contain a crosslinking agent (C).

[0073] Furthermore, the composition for forming the lower layer of the resist film of the present invention may contain an acid catalyst (D) as a crosslinking agent catalyst, or it may not contain one.

[0074] In a composition for forming a photoresist underlayer film comprising a polymer (A) and a solvent (B), by using a polymer having sulfonic acid groups as polymer (A), the photoresist underlayer film formed by the composition exhibits good solvent resistance and is able to form a photoresist pattern on the photoresist underlayer film with low exposure (i.e., form a photoresist pattern with good sensitivity).

[0075] <Polymer (A)>

[0076] There are no particular limitations on polymer (A) as long as it is a polymer containing sulfonic acid groups. A preferred embodiment of polymer (A) is, for example, a polymer obtained by reacting a sulfonic anhydride with a hydroxyl group in the polymer. Furthermore, the hydroxyl groups that can react with the sulfonic anhydride do not include hydroxyl groups of carboxylic acids.

[0077] Polymer (A) is an organic polymer.

[0078] As a preferred embodiment of polymer (A), examples of first and second embodiments described later can be cited.

[0079] The polymer of the first embodiment is a polymer having a structure represented by the following formula (X).

[0080] Furthermore, the polymer in the second embodiment is a polymer having a structure represented by the following formula (X2).

[0081] <<First Implementation Method>>

[0082] As a preferred embodiment of polymer (A), examples of polymers having a structure represented by the following formula (X) can be cited.

[0083]

[0084] (In formula (X), A represents a hydrogen atom, a methyl group, or an ethyl group, respectively. Ta represents formula (X1) below. * indicates a connecting bond.)

[0085]

[0086] (In formula (X1), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. Substituents are halogen atoms selected from fluorine, chlorine, bromine, and iodine atoms. * indicates a linking bond. n represents 0 or 1.)

[0087] The aromatic hydrocarbon group of Ra can be a monocyclic aromatic hydrocarbon group or a fused-ring aromatic hydrocarbon group.

[0088] As an example of formula (X1), monovalent groups can be represented by formulas (X1-1) to (X1-5).

[0089]

[0090]

[0091] (In formulas (X1-1) to (X1-5), Rx is a halogen atom selected from fluorine, chlorine, bromine, and iodine atoms. nx represents an integer from 0 to 4. * indicates a linking bond.)

[0092] <<Second Implementation Method>>

[0093] As a preferred embodiment of polymer (A), examples of polymers having a structure represented by the following formula (X2) can be cited.

[0094]

[0095] (In formula (X2), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. Substituents are halogen atoms selected from fluorine, chlorine, bromine, and iodine atoms. * indicates a linking bond.)

[0096] In equation (X2), Ra has the same meaning as Ra in equation (X1).

[0097] Examples of (X2) include monovalent groups, such as those shown in (X1-1) above.

[0098] As a preferred embodiment of polymer (A), polymers (Y) having repeating units as shown in the following formula (Y) can be cited as an example.

[0099]

[0100] (In formula (Y), A represents a hydrogen atom, a methyl atom, or an ethyl atom.)

[0101] Qa and Qb represent the following formulas (Y5) and (Y6), respectively.

[0102] T1 and T2 represent hydrogen atoms or the above formula (X1), respectively. In the polymer (Y), either T1 or T2 in formula (Y) has a repeating unit represented by the above formula (X1).

[0103]

[0104] In formulas (Y5) and (Y6), Q1 represents an alkylene, phenylene, naphthylene, anthraceneylene, or the following formula (M1) having 1 to 10 carbon atoms, wherein the alkylene, phenylene, naphthylene, and anthraceneylene may be replaced by an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group formed by combinations thereof.

[0105] n1 and n2 represent 0 or 1, respectively.

[0106] Z1 and Z2 represent single bonds or groups represented by the following formula (Y6-1), respectively.

[0107] X1 represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0).

[0108] * indicates a connection key.

[0109]

[0110] (In formula (M1), Y 101 R represents an alkylene group having 1-10 carbon atoms, in which at least one hydrogen atom can be replaced by a fluorine atom. 101 and R 102 These represent alkyl groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms.

[0111] n 10 and n 11 They represent integers from 0 to 4.

[0112] * indicates a connection key.

[0113]

[0114] (In equation (Y6-1), m represents an integer from 1 to 4. n represents an integer from 0 to 4. p1 and p2 each independently represent 0 or 1. *3 represents the linking bond with the nitrogen atom in equation (Y6). *4 represents the linking bond.)

[0115]

[0116] In formulas (Y2), (Y3), (Y4), and (Y0), R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 3 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a benzyl group, or a phenyl group, respectively. The alkyl group with 1 to 6 carbon atoms, the alkenyl group with 3 to 6 carbon atoms, the alkynyl group with 2 to 6 carbon atoms, the benzyl group, and the phenyl group can be substituted with a group selected from alkyl groups with 1 to 6 carbon atoms, a halogen atom, an alkoxy group with 1 to 6 carbon atoms, an alkoxyalkyl group with 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group with 1 to 6 carbon atoms. Furthermore, R1 and R2 can be linked together to form a ring having 3 to 6 carbon atoms.

[0117] R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, wherein the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, or the phenyl group may be substituted with a group selected from the alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms.

[0118] * indicates a linking bond. *1 indicates a linking bond to a carbon atom. *2 indicates a linking bond to a nitrogen atom.

[0119] Among the repeating units represented by the above formula (Y), it is preferred that the above formula (X1) is the above formula (X2).

[0120] The following groups can be listed as the groups represented by the above formula (Y5).

[0121]

[0122]

[0123] (* indicates a connection key.)

[0124] The following groups can be listed as the groups represented by the above formula (Y6).

[0125]

[0126]

[0127]

[0128]

[0129]

[0130]

[0131] (* indicates a connection key.)

[0132] The following groups can be listed as groups represented by the above formula (M1).

[0133]

[0134] (* indicates a connection key.)

[0135] As repeating units represented by equation (Y), examples of repeating units represented by the following equations (Y-1) to (Y-21) can be listed.

[0136]

[0137]

[0138]

[0139]

[0140]

[0141] (In equations (Y-1) to (Y-20), T1 and T2 have the same meaning as T1 and T2 in equation (Y).)

[0142] As polymers (Y) in which T1 and T2 are hydrogen atoms, polymers described in International Publication No. 2013 / 018802 can be listed. The contents of International Publication No. 2013 / 018802 are incorporated herein in their entirety to the extent that they have been published.

[0143] The polymer (Y) of the present invention can be obtained by reacting a sulfonic anhydride with a polymer (Y') in which T1 and T2 are hydrogen atoms respectively. That is, the polymer (Y) is a reaction product obtained by reacting a sulfonic anhydride with the hydroxyl groups contained in the polymer (Y'). Here, a cyclic sulfonic anhydride is preferred as the sulfonic anhydride, and examples of cyclic sulfonic anhydrides represented by the following formulas (t-1) to (t-7) can be cited.

[0144]

[0145] When the cyclic sulfonic anhydride reacts with the polymer (Y'), as shown in the following formula (IL-1), the sulfonic acid group is introduced onto the hydroxyl group of the polymer (Y') to obtain the polymer (Y) of the present invention.

[0146] In formula (IL-1), the case where T1 and T2 in the above formula (Y-1) are hydrogen atoms is given as an example of polymer (Y'), and the case where example (t-1) is given as cyclic sulfonic anhydride is given as an example of cyclic sulfonic anhydride.

[0147] As previously stated, the polymer (Y) of the present invention is obtained by fixing sulfonic acid groups in the polymer using a ring-opening reaction of sulfonic acid anhydride.

[0148]

[0149] The polymer (Y') can be manufactured, for example, by the reaction described below.

[0150] For example, the following explanation will be given in the case where Qa in polymer (Y') is a group represented by formula (Y6).

[0151] The polymer (Y') can be manufactured, for example, by reacting the compound represented by formula (Y7) with the compound represented by formula (Y8).

[0152]

[0153] (In formula (Y7), X1 represents formula (Y2), formula (Y3), formula (Y4) or formula (Y0).

[0154] In formula (Y8), Qb represents either formula (Y5) or formula (Y6). A represents a hydrogen atom, a methyl group, or an ethyl group, respectively.

[0155] The reaction between the compound represented by formula (Y7) and the compound represented by formula (Y8) is preferably carried out in a solution state dissolved in organic solvents such as benzene, toluene, xylene, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N-methylpyrrolidone. Furthermore, quaternary ammonium salts such as benzyltriethylammonium chloride, tetrabutylammonium chloride, and tetraethylammonium bromide can also be used as catalysts in this reaction. There are no limitations on the reaction temperature and reaction time, which can be varied depending on the compounds used and their concentrations. A suitable range can be selected from a reaction time of 0.1 to 100 hours and a reaction temperature of 20°C to 200°C. When using a catalyst, it can be used in the range of 0.001% to 30% by mass relative to the total mass of the compounds used.

[0156] Furthermore, the ratio of the compounds represented by formula (Y7) and formula (Y8) used in the reaction can be any ratio. The molar ratio of the two compounds, "compound represented by formula (Y7):compound represented by formula (Y8)", is preferably 3:1 to 1:3, more preferably 3:2 to 2:3.

[0157] There is no particular limitation 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 3,000 to 15,000.

[0158] There is no particular limitation on the content of polymer (A) in the composition for forming the lower layer film of the etchant. However, from the viewpoint of obtaining the best results of the present invention, it is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and particularly preferably 50 to 80% by mass, relative to the film composition.

[0159] Furthermore, in this invention, the membrane constituents refer to components other than the solvent contained in the composition.

[0160] Solvent (B)

[0161] There are no particular restrictions on the solvent (B); it can be water or an organic solvent.

[0162] Examples of organic solvents include monoalkylene glycol ethers and monocarboxylic acid esters of monoalkylene glycol ethers.

[0163] Examples of alkylene groups that are monoalkylene glycol ethers include those with 2 to 4 carbon atoms.

[0164] Alkyl groups that are monoalkyl ethers of alkylene glycols can be exemplified by alkyl groups having 1 to 4 carbon atoms.

[0165] Examples of alkylene glycol monoalkyl ethers with 3 to 8 carbon atoms can be listed.

[0166] Examples of monoalkylene glycol ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0167] Alkylenes that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers can be exemplified by alkylenes having 2 to 4 carbon atoms.

[0168] Alkyl groups that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers can be exemplified by alkyl groups having 1 to 4 carbon atoms.

[0169] Monocarboxylic acids that are monocarboxylic acid esters of alkylene glycol monoalkyl ethers can be listed as saturated monocarboxylic acids with 2 to 4 carbon atoms.

[0170] Examples of saturated monocarboxylic acids with 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid.

[0171] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include, for example, 5 to 10 carbon atoms.

[0172] Examples of monocarboxylic acid esters that are monoalkylene glycol monoalkyl ethers include methyl cellolytic acetate, ethyl cellolytic acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0173] Other solvents that can be listed include: 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, and N,N-dimethylacetamide, etc.

[0174] Among these solvents (B), monoalkylene glycol monoalkyl ethers and monocarboxylic acid esters of monoalkylene glycol monoalkyl ethers are preferred.

[0175] These solvents (B) can be used alone or in combination of two or more.

[0176] There is no particular limitation on the mass ratio of the organic solvent in solvent (B), but it is preferably 50% to 100% by mass.

[0177] There is no particular limitation on the content of solvent (B) in the composition for forming the lower layer film of the photoresist, but it 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.

[0178] <Crosslinking agent (C)>

[0179] There are no particular restrictions on the crosslinking agent (C).

[0180] The crosslinking agent (C) has a different structure from the polymer (A).

[0181] The preferred crosslinking agent (C) is an amino plastic crosslinking agent or a phenolic plastic crosslinking agent.

[0182] Amino plastic crosslinking agents are addition condensation products of amino compounds such as melamine or guanidine with formaldehyde.

[0183] Phenolic plastic crosslinking agents are addition condensation compounds of compounds with phenolic hydroxyl groups and formaldehyde.

[0184] As crosslinking agents (C), examples include compounds having two or more of the following structures.

[0185]

[0186] (In the structure, R) 101 Indicates a hydrogen atom, an alkyl group with 1-4 carbon atoms, or an alkoxyalkyl group with 2-6 carbon atoms. * Indicates a linking bond.

[0187] Linking bonds, such as nitrogen atoms or carbon atoms that form aromatic hydrocarbon rings.

[0188] As R 101 Preferably, it is a hydrogen atom, methyl, ethyl or a group represented by the following structures.

[0189]

[0190] (In the structure, R) 102 * Represents a hydrogen atom, methyl group, or ethyl group. * Represents a connecting bond.

[0191] The preferred crosslinking agent (C) is a melamine compound, a guanidine compound, a glycourea compound, or a urea compound containing a phenolic hydroxyl group. They can be used alone or in combination of two or more.

[0192] Examples of melamine compounds include, for example, hexamethylolmelamine, hexamethoxymethylmelamine, compounds of hexamethylolmelamine in which 1 to 6 hydroxymethyl groups are methoxymethylated, or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds of hexamethylolmelamine in which 1 to 6 hydroxymethyl groups are acyloxymethylated, or mixtures thereof.

[0193] Examples of guanidine compounds include, for example, tetrahydroxymethylguanidine, tetramethoxymethylguanidine, compounds in which one to four hydroxymethyl groups of tetrahydroxymethylguanidine are methoxymethylated, or mixtures thereof; tetramethoxyethylguanidine, tetraacyloxyguanidine, compounds in which one to four hydroxymethyl groups of tetrahydroxymethylguanidine are acyloxymethylated, or mixtures thereof; and so on.

[0194] Examples of glycourea compounds include, for example, tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are methoxymethylated, and mixtures thereof, as well as compounds of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are acylmethylated.

[0195] Alternatively, the glycourea compound can be, for example, a glycourea derivative represented by the following formula (1E).

[0196]

[0197] (In formula (1E), each of the four R1s independently represents a methyl or ethyl group, and R2 and R3 independently represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group.)

[0198] Examples of glycourea derivatives represented by formula (1E) include compounds represented by formulas (1E-1) to (1E-6).

[0199]

[0200] The glycourea derivative represented by formula (1E) can be obtained, for example, by reacting the glycourea derivative represented by formula (2E) with at least one compound represented by formula (3d).

[0201]

[0202] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group with 1 to 4 carbon atoms.)

[0203]

[0204] (In formula (3d), R1 represents methyl or ethyl.)

[0205] Examples of compounds represented by formula (2E) and (2E-1) to (2E-4) can be cited as glycourea derivatives. Furthermore, examples of compounds represented by formula (3d) and (3d-1) can be cited as compounds represented by formula (3d).

[0206]

[0207]

[0208] Examples of urea compounds include tetrahydroxymethylurea, tetramethoxymethylurea, compounds of tetrahydroxymethylurea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, and tetramethoxyethylurea.

[0209] Examples of compounds having phenolic hydroxyl groups include those shown in formula (G-1) or formula (G-2) below.

[0210]

[0211] (In equations (G-1) and (G-2), Q) 1 This indicates a single bond or an organic group with an m1 valence.

[0212] R 1 and R 4 They respectively represent alkyl groups having 2 to 10 carbon atoms, or alkyl groups having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms.

[0213] R 2 and R 5 These represent hydrogen atoms or methyl groups, respectively.

[0214] R 3 and R 6 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0215] n1 represents an integer satisfying 1≤n1≤3, n2 represents an integer satisfying 2≤n2≤5, n3 represents an integer satisfying 0≤n3≤3, and n4 represents an integer satisfying 0≤n4≤3, and they are all integers satisfying 3≤(n1+n2+n3+n4)≤6.

[0216] n5 represents an integer satisfying 1≤n5≤3, n6 represents an integer satisfying 1≤n6≤4, n7 represents an integer satisfying 0≤n7≤3, and n8 represents an integer satisfying 0≤n8≤3, and they are all integers satisfying 2≤(n5+n6+n7+n8)≤5.

[0217] (m1 is an integer from 2 to 10.)

[0218] In addition, compounds having phenolic hydroxyl groups can be listed as examples of compounds represented by the following formula (G-3) or formula (G-4).

[0219] The compound represented by formula (G-1) or formula (G-2) can be obtained by reacting a compound represented by formula (G-3) or formula (G-4) with a hydroxyl-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0220]

[0221] (In equations (G-3) and (G-4), Q) 2 This indicates a single bond or an m2 valence organic group.

[0222] R 8 R 9 R 11 and R 12 These represent hydrogen atoms or methyl groups, respectively.

[0223] R 7 and R 10 They represent alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 40 carbon atoms, respectively.

[0224] n9 represents an integer satisfying 1 ≤ n9 ≤ 3, where n 10 This means that 2≤n 10 Integers ≤ 5, n 11 This means that 0 ≤ n 11 Integers ≤ 3, n 12 This means that 0 ≤ n 12 Integers ≤ 3, and they are integers satisfying 3 ≤ (n ≤ 9 + n). 10 +n 11 +n 12 Integers ≤ 6.

[0225] n 13 This means that 1 ≤ n 13 Integers ≤ 3, n 14 This means that 1 ≤ n 14 Integers ≤ 4, n 15 This means that 0 ≤ n 15 Integers ≤ 3, n 16 This means that 0 ≤ n 16 Integers ≤ 3, and they satisfy 2 ≤ (n - 3) / 2. 13 +n 14 +n 15 +n 16 Integers ≤ 5.

[0226] m2 represents an integer from 2 to 10.

[0227] Examples of organic groups with an m2 valence in Q2 include organic groups with 1 to 4 carbon atoms and an m2 valence.

[0228] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds.

[0229]

[0230]

[0231]

[0232]

[0233]

[0234] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds.

[0235]

[0236]

[0237] The aforementioned compounds can be obtained as products manufactured by Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. Examples of such products include, for instance, the trade name TMOM-BP from Asahi Organic Materials Co., Ltd.

[0238] Among these, glycourea compounds are preferred, specifically tetrahydroxymethylglycourea, tetramethoxyglycourea, tetramethoxymethylglycourea, compounds of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, compounds of tetrahydroxymethylglycourea in which 1 to 4 hydroxymethyl groups are methoxymethylated, or mixtures thereof, and more preferably tetramethoxymethylglycourea.

[0239] There is no particular limitation on the molecular weight of the crosslinking agent (C), but it is preferably below 1000.

[0240] The content of crosslinking agent (C) in the composition for forming the lower layer of the resist film is not particularly limited, but is, for example, 1 to 70% by mass relative to the polymer (A), preferably 5 to 60% by mass.

[0241] <Acid Catalyst (D)>

[0242] The composition for forming the lower layer of the resist film of the present invention may contain an acid catalyst (D) as a crosslinking agent catalyst, or it may not contain it, or both are acceptable.

[0243] The acid catalyst (D) contained as an arbitrary component in the composition for forming the lower layer film of the resist can be a thermally generated acid agent or a photo-generated acid agent, but a thermally generated acid agent is preferred.

[0244] Examples of heat-generating acid agents include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium salt of p-toluenesulfonic acid (pyridinium p-toluenesulfonate), pyridinium salt of phenolsulfonic acid, pyridinium p-hydroxybenzenesulfonate (pyridinium p-hydroxybenzenesulfonate), pyridinium salt of 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 compounds, as well as carboxylic acid compounds.

[0245] Examples of photoacid-generating agents include onium salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds.

[0246] Examples of ononium salt compounds include diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and other iodonium salt compounds; as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0247] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluorobutanyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0248] 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.

[0249] Acid catalyst (D) can be used in combination with one or more types.

[0250] When using an acid catalyst (D), the content of the acid catalyst (D) relative to the crosslinking agent (C) is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0251] <Other Ingredients>

[0252] To avoid pinholes and streaks and further improve the coating properties for uneven surfaces, a surfactant can be added to the composition for forming the lower layer of the resist film.

[0253] Examples of surfactants include linear or branched alkylbenzene sulfonic acids (such as dodecylbenzene sulfonic acid), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, and sorbitol monolaurate, sorbitol monopalmitate, and sorbitol monostearate. Nonionic surfactants including sorbitol fatty acid esters such as sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate, as well as polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate; Eftop Fluorinated surfactants such as EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., trade name), MEGAFACE F171, F173, R-30 (manufactured by DIC Co., Ltd., trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., trade name), AsahiGuard AG710, SURFLON S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0254] The amount of these surfactants mixed in 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 underlayer film of the resist.

[0255] These surfactants can be added individually or in combination of two or more.

[0256] The composition for forming the lower layer of the resist film may contain a polymerization inhibitor (free radical scavenger) as needed. Examples of polymerization inhibitors include 2,6-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-tert-butylcresol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, and 4-methoxy-1-naphthol.

[0257] The content of the polymerization inhibitor in the composition for forming the lower layer film of the etchant is not particularly limited, but it is preferably 1% by mass or less relative to the solid content.

[0258] The solid component contained in the resist lower film forming composition of the present invention, i.e. the component after removing the solvent, is, for example, 0.01% to 10% by mass.

[0259] The composition for forming the resist underlayer film can be well used in EUV lithography.

[0260] The composition for forming a resist underlayer film can be well used for forming an underlayer film containing a metal resist.

[0261] (Underlying film of the resist)

[0262] The resist underlayer film of the present invention is a cured product of the above-mentioned resist underlayer film forming composition.

[0263] The resist underlayer film can be manufactured, for example, by coating the above-mentioned resist underlayer film forming composition onto a semiconductor substrate and then firing it.

[0264] Examples of semiconductor substrates that can be coated with a composition for forming a resist underlayer include silicon wafers, germanium wafers, gallium arsenide, indium phosphide, gallium nitride, indium nitride, aluminum nitride, and other compound semiconductor wafers.

[0265] When using a semiconductor substrate on which an inorganic film is formed on its surface, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (SOG). Examples of such inorganic films include polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho Silicate Glass) films, titanium nitride films, titanium oxynitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0266] The resist underlayer film forming composition of the present invention can be coated onto such a semiconductor substrate using a suitable coating method such as a spin coater or a coating machine. Then, the composition is baked using a heating means such as a heating plate to form a resist underlayer film. The 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 to 30 minutes; more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 to 10 minutes.

[0267] The thickness of the underlying resist film is, for example, 0.001 μm (1 nm) ~ 10 μm, 0.002 μm (2 nm) ~ 1 μm, 0.005 μm (5 nm) ~ 0.5 μm (500 nm), 0.001 μm (1 nm) ~ 0.05 μm (50 nm), 0.002 μm (2 nm) ~ 0.05 μm (50 nm), 0.003 μm (3 nm) ~ 0.05 μm (50 nm), 0.004 μm (4 nm) ~ 0.05 μm (50 nm), 0.005 μm (5 nm) ~ 0.05 μm (500 nm). 0nm), 0.003μm (3nm)~0.03μm (30nm), 0.003μm (3nm)~0.02μm (20nm), 0.005μm (5nm)~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).

[0268] The method for determining the thickness of the resist underlayer film in this specification is as follows.

[0269] Name of measuring device: Ellipso film thickness measuring device RE-3100 (SCREEN Co., Ltd.)

[0270] SWE (Single Wavelength Elliptometry) mode

[0271] The arithmetic mean of 8 points (e.g., 8 points measured at 1 cm intervals along the X direction of the wafer).

[0272] (Layered structure)

[0273] The laminate of the present invention has a semiconductor substrate and a photoresist underlayer film of the present invention.

[0274] Examples of semiconductor substrates include those described above.

[0275] The photoresist underlayer film is disposed, for example, on a semiconductor substrate.

[0276] (Semiconductor device manufacturing methods, patterning methods)

[0277] The method for manufacturing the semiconductor device of the present invention includes at least the following steps:

[0278] The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition of the present invention, and

[0279] The process of forming a resist film on the resist underlayer film.

[0280] The pattern forming method of the present invention includes at least the following steps.

[0281] The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition of the present invention.

[0282] The process of forming a resist film on the underlying resist film.

[0283] The process of irradiating a resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern, and...

[0284] The process of using a resist pattern as a mask to etch the underlying resist film.

[0285] The resist layer is usually formed on the underlying resist film.

[0286] The thickness of the resist layer is, for example, below 3000 nm, below 2000 nm, below 1800 nm, below 1500 nm, or below 1000 nm. The lower limit is 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, or 10 nm.

[0287] As a photoresist film formed on a photoresist underlayer by known methods (e.g., coating and firing of the photoresist composition), there are no particular limitations as long as the film is responsive to the light or electron beam (EB) used for irradiation. Either negative or positive photoresists can be used.

[0288] In addition, in this specification, resists that respond to EB are also referred to as photoresists.

[0289] Photoresists include: positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazonium sulfonate; chemically amplified photoresists composed of binders and photoacid generators that increase the rate of alkali dissolution by acid decomposition; chemically amplified photoresists composed of low-molecular-weight compounds that increase the rate of alkali dissolution by acid decomposition; alkali-soluble binders and photoacid generators; and photoresists containing metal elements. Examples include JSR Corporation's V146G, Shipley's APEX-E, Sumitomo Chemical's PAR710, and Shin-Etsu Chemical Co., Ltd.'s AR2772 and SEPR430. In addition, examples of 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) can be cited.

[0290] Alternatively, you can use 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, Japanese Patent Application 2018-180525, WO2018 / 190088, Japan Patent Application 2018-070596, Japan Patent Application 2018-028090, Japan Patent Application 2016-153409, Japan Patent 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, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions, as described in Japanese Patent Application Publications (JP2010-043749, 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.

[0291] The following compositions can be listed as resist compositions.

[0292] An active light-sensitive or radiation-sensitive resin composition comprising a resin A having repeating units and a compound represented by the following general formula (121), wherein the repeating units have acid-degradable groups whose polar groups are protected by protecting groups that can be removed by acid action.

[0293]

[0294] In general formula (121), m represents an integer from 1 to 6. R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0295] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0296] L2 indicates an alkylene group or a single bond that may have substituents.

[0297] W1 represents a cyclic organic group that may have substituents.

[0298] M + It represents a cation.

[0299] A composition for forming a metal-containing film for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to period 3-7 of group 3-15 of the periodic table.

[0300] A radiation-sensitive resin composition comprising a polymer and an acid-generating agent, said polymer having a first structural unit represented by formula (31) and a second structural unit containing an acid-dissociating group represented by formula (32).

[0301]

[0302] 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, thioalkyl, or monovalent organic group with 1 to 20 carbon atoms. n represents an integer from 0 to 11. When n is 2 or more, multiple R... 1 They can be the same or different. R 2 Represents 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 of the aforementioned acid-dissociable groups. Z represents a single bond, an oxygen atom, or a sulfur atom. R 4 (It could be a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0303] An anti-corrosion composition comprising a resin (A1) and an acid-generating agent, said resin (A1) comprising structural units having a cyclic carbonate structure, structural units represented by the following formula, and structural units having acid-instable groups.

[0304]

[0305] [In the formula, R] 2 X represents an alkyl group, hydrogen atom, or halogen atom with 1 to 6 carbon atoms that may have halogen atoms. 1 Indicates a single bond, -CO-O-*, or -CO-NR 4 -* indicates a connection key with -Ar, R 4 [This indicates an alkyl group having 1 to 4 hydrogen atoms or carbon atoms; Ar indicates an aromatic hydrocarbon group having 6 to 20 carbon atoms and possibly having one or more groups selected from hydroxyl and carboxyl groups.]

[0306] Examples of resist films include the following.

[0307] A photoresist film comprising a base resin comprising "repeating units represented by formula (a1) and / or repeating units represented by formula (a2)", and "repeating units that generate an acid bonded to the polymer backbone upon exposure".

[0308]

[0309] In formulas (a1) and (a2), RA is independently a hydrogen atom or a methyl group. 1 and R 2 Independently, it is a 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 group, a naphthylene group, or a linker group containing at least one carbon atom selected from ester bonds, lactone rings, phenylene groups, and naphthylene groups. X 2 (Single bond, ester bond, or amide bond).

[0310] Examples of materials that can be used as corrosion resists include the following.

[0311] A corrosion-resistant material comprising a polymer having repeating units represented by formula (b1) or (b2).

[0312]

[0313] (In equations (b1) and (b2), R) A Represents a hydrogen atom or a methyl group. X 1 Indicates a single bond or ester group. X 2This indicates a linear, branched, or cyclic alkylene group with 1 to 12 carbon atoms or an aryl group with 6 to 10 carbon atoms, wherein a portion of the methylene group constituting the alkylene group may be substituted with an ether group, an ester group, or a group containing an lactone ring. Additionally, X... 2 At least one hydrogen atom in X is replaced by a bromine atom. 3 Represents a single bond, ether group, ester group, or a straight-chain, branched, or cyclic alkylene group with 1 to 12 carbon atoms, wherein a portion of the methylene group constituting the alkylene group may be substituted with an ether group or an ester group. Rf 1 ~Rf 4 Each of these can be independently represented by a hydrogen atom, a fluorine atom, or a trifluoromethyl group, at least one of which is a fluorine atom or a trifluoromethyl group. Rf 1 and Rf 2 They can form a carbonyl group together. R 1 ~R 5 Each group is independently a straight-chain, branched, or cyclic alkyl group with 1 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aralkyl group with 7 to 12 carbon atoms, or an aryloxyalkyl group with 7 to 12 carbon atoms. Some or all of the hydrogen atoms in these groups may be substituted with hydroxyl, carboxyl, halogen, oxo, cyano, amide, nitro, sulopentalide, sulfone, or sulfonate groups. Some methylene groups constituting these groups may be substituted with ether, ester, carbonyl, carbonate, or sulfonate groups. Furthermore, R... 1 and R 2 They can also combine and form rings together with the sulfur atoms they are bound to.

[0314] A corrosion-resistant material comprising a base resin containing a polymer, said polymer containing repeating units represented by the following formula (a).

[0315]

[0316] (In equation (a), R) A It can be a hydrogen atom or a methyl group. R 1 It is a hydrogen atom or an unstable group in acids. R 2 It is a linear, branched, or cyclic alkyl group with 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 It is a single bond, a phenylene group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain an ester group or an 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.

[0317] A photoresist composition that generates acid upon exposure and whose solubility relative to a developer changes with the action of the acid, the photoresist composition comprising: a substrate component (A) whose solubility relative to a developer changes with the action of the acid, and a fluorinated additive component (F) that exhibits decomposability relative to an alkaline developer, said fluorinated additive component (F) containing a fluoropolymer component (F1), said fluoropolymer component (F) having a structural unit (f1) containing a base-dissociating group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0318]

[0319] [In formula (f2-r-1), Rf21 independently represent a hydrogen atom, alkyl group, alkoxy group, hydroxyl group, hydroxyalkyl group, or cyano group. n” represents an integer from 0 to 2. * represents a connecting bond.]

[0320] The above 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).

[0321]

[0322] In formulas (f1-1) and (f1-2), R independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. X represents a divalent linking group without an acid-dissociating site. A aryl This indicates a divalent aromatic cyclic group that may have substituents. X 01 Indicates a single bond or a divalent linker. R 2 Each can be used independently to represent an organic group containing a fluorine atom.

[0323] As a corrosion resist composition, it can also be a metal-containing corrosion resist.

[0324] Metal-containing photoresists are also called metal oxide photoresists (MOR), and tin oxide photoresists are a representative example.

[0325] As a metal oxide resist material, examples include the coating composition containing a metal oxide-hydroxyl network disclosed in Japanese Patent Application Publication No. 2019-113855, which has organic ligands via metal carbon bonds and / or metal carboxylate bonds.

[0326] As an example of a metal-containing resist, a peroxy ligand is used as a radiation-sensitive stabilizing ligand. Metal oxo-hydroxy compounds containing peroxy groups are described in detail in the patent literature mentioned, for example, in paragraph

[0011] of Japanese Patent Publication No. 2019-532489. Examples of such patent documents include the specification of U.S. Patent No. 9,176,377B2, the specification of U.S. Patent Application Publication No. 2013 / 0224652A1, the specification of U.S. Patent No. 9,310,684B2, the specification of U.S. Patent Application Publication No. 2016 / 0116839 A1, and the specification of U.S. Patent Application Serial No. 15 / 291738.

[0327] A coating comprising a metal oxo-hydroxy network, wherein the metal oxo-hydroxy network has an organic ligand via a metal-carbon bond and / or a metal carboxylate bond.

[0328] An inorganic oxo / hydroxy-based composition.

[0329] A coating solution comprising an organic solvent, a first organometallic composition, and a hydrolyzable metal compound, wherein the first organometallic composition is represented by formula R z SnO (2-(z / 2)-(x / 2)) (OH) x wherein 0 < z ≤ 2 and 0 < (z+x) ≤ 4, or represented by formula R' n SnX 4-n wherein n = 1 or 2, or represented by a mixture thereof, wherein R and R' are each independently a hydrocarbyl group having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn, or a combination thereof; and the hydrolyzable metal compound is represented by formula MX' v wherein M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond, or a combination thereof.

[0330] A coating solution comprising an organic solvent and a first organometallic compound represented by formula RSnO (3 / 2-x / 2) (OH) x wherein 0 < x < 3, the solution contains from about 0.0025 M to about 1.5 M tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, said alkyl or cycloalkyl group being bonded to said tin at a secondary or tertiary carbon atom.

[0331] An aqueous inorganic patterning precursor comprising a mixture of "water", "metal lower oxide cations", "polyatomic inorganic anions", and "radiation-sensitive ligands containing peroxide groups".

[0332] Other examples of metal-containing corrosion resists include the compositions described in Japanese Patent Application Publication No. 2011-253185 A, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, Japanese Patent Application Publication No. 2020-122959 A, Japanese Patent Application Publication No. 2020-122960 A, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367 and WO2021 / 016229.

[0333] Their contents are incorporated in their entirety into this specification to the same extent as they are disclosed.

[0334] There are no particular limitations on the method of forming a metal-containing resist film from a metal-containing resist. For example, a method can be described by coating a coating type resist material (a composition for forming a metal-containing resist film) as a metal-containing resist and then firing it.

[0335] Alternatively, metal-containing resist films can also be formed by vapor deposition. As a method for forming metal-containing resist films using vapor deposition, the method described in Japanese Patent Application Publication No. 2017-116923 can be cited as an example. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein by reference in their entirety to the extent disclosed. Furthermore, in Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film of the present invention is referred to as a metal oxide film.

[0336] Irradiation with light or electron beams, for example, is performed via a mask used to form a predetermined pattern. For example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) lasers can be used. The resist underlayer film formation composition of the present invention is preferably used for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation applications, and more preferably for EUV (extreme ultraviolet) exposure applications.

[0337] There are no particular restrictions on the irradiation energy of the electron beam and the exposure dose of the light.

[0338] Baking (PEB: Post-exposure baking) can be performed after irradiation with light or an electron beam and before development.

[0339] There is no particular limitation on the baking temperature, but it is preferably 60℃~150℃, more preferably 70℃~120℃, and particularly preferably 75℃~110℃. There is no particular limitation on the baking time, but it is preferably 1 second~10 minutes, more preferably 10 seconds~5 minutes, and particularly preferably 30 seconds~3 minutes.

[0340] Regarding development, for example, alkaline developing solutions or organic solvents may be used.

[0341] Examples of developing temperatures include 5°C to 50°C.

[0342] For example, development time can range from 10 seconds to 300 seconds.

[0343] As an alkaline developer, aqueous solutions of inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia can be used; 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 can also be used. Furthermore, an appropriate amount of an alcohol such as isopropanol or a nonionic surfactant can be added to the above-mentioned alkaline aqueous solutions. Among these, aqueous solutions of quaternary ammonium salts are preferred, and aqueous solutions of tetramethylammonium hydroxide and choline are more preferred. Furthermore, surfactants can also be added to these developers. Alternatively, the following method can be used: developing is performed using an organic solvent such as butyl acetate instead of an alkaline developer, developing the portion where the alkaline dissolution rate of the photoresist is not improved.

[0344] Examples of organic solvents that can be used as developers include, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethyl 4-Propoxybutylacetic acid, 2-Methoxypentylacetic acid, 3-Methoxypentylacetic acid, 4-Methoxypentylacetic acid, 2-Methyl-3-Methoxypentylacetic acid, 3-Methyl-3-Methoxypentylacetic acid, 3-Methyl-4-Methoxypentylacetic acid, 4-Methyl-4-Methoxypentylacetic acid, Propylene glycol diacetate, Methyl formate, Ethyl formate, Butyl formate, Propyl formate, Lactic acid Ethyl acetate, butyl lactate, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl 3-methoxypropionate, etc. Furthermore, surfactants can be added to the developing solution.

[0345] Next, using the formed resist pattern as a mask, the underlying resist film is etched. Etching can be dry etching or wet etching, but dry etching is preferred.

[0346] 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. The semiconductor substrate is then processed using a known method (e.g., dry etching) to manufacture a semiconductor device.

[0347] Example

[0348] The present invention will now be described in detail with examples, but the present invention is not limited thereto.

[0349] The weight-average molecular weights of the polymers shown in the following synthesis examples were determined by gel permeation chromatography (GPC). A GPC apparatus manufactured by Tosoh Corporation was used in the determination, and the determination conditions are as follows.

[0350] GPC pillars: Shodex KF803L, Shodex KF802, Shodex KF801 [Registered Trademark] (Showa Denko Co., Ltd.)

[0351] Column temperature: 40℃

[0352] Solvent: N,N-dimethylformamide (DMF)

[0353] Flow rate: 0.6 ml / min

[0354] Standard sample: Polystyrene (manufactured by Tosoh Corporation).

[0355] <Synthesis example 1-1>

[0356] 100g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 66.4g of 5,5-diethylbarbituric acid, and 4.1g of benzyltriethylammonium chloride were dissolved in 682g of propylene glycol monomethyl ether and reacted at 130°C for 24 hours to obtain a solution containing the polymer.

[0357] The results of GPC analysis on the obtained polymer showed that its weight-average molecular weight, converted to standard polystyrene, was 6800. Furthermore, the obtained polymer had the following structure (1a) as a repeating structural unit.

[0358]

[0359] <Synthesis example 1-2>

[0360] The polymer solution obtained in Synthesis Example 1-1 was evaporated to dryness, and the precipitated powder was dried under reduced pressure. 2.0 g of the resulting polymer powder and 0.05 g of 2-sulfobenzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 10.25 g of PGMEA (propylene glycol monomethyl ether acetate), and refluxed at 130°C for 24 hours.

[0361] GPC analysis of the obtained polymer showed that its weight-average molecular weight, converted to standard polystyrene, was 10,000. Furthermore, the obtained polymer had the following formula (1b) as a repeating structural unit.

[0362]

[0363] <Synthesis example 2-1>

[0364] 9.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 12.93 g of bisphenol AF (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.30 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were dissolved in 58.08 g of propylene glycol monomethyl ether and reacted at 105 °C for 24 hours to obtain a solution containing the polymer.

[0365] The results of GPC analysis on the obtained polymer showed that its weight-average molecular weight, converted to standard polystyrene, was 8500. Furthermore, the obtained polymer had the following formula (2a) as a repeating structural unit.

[0366]

[0367] <Synthesis example 2-2>

[0368] The polymer solution obtained in Synthesis Example 2-1 was evaporated to dryness, and the precipitated powder was dried under reduced pressure. 2.0 g of the resulting polymer powder and 0.05 g of 2-sulfobenzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 0.25 g of PGMEA and refluxed at 130°C for 24 hours.

[0369] GPC analysis of the obtained polymer showed that its weight-average molecular weight, converted to standard polystyrene, was 8900. Furthermore, the obtained polymer is a polymer with the structure of formula (2b) as a repeating structural unit.

[0370]

[0371] <Synthesis example 3-1>

[0372] 10.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 7.44 g of phenobarbital (manufactured by Shikoku Chemical Industry Co., Ltd.), 0.9834 g of 4-hydroxybenzoic acid, and 1.45 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were dissolved in 29.81 g of propylene glycol monomethyl ether and reacted at 105°C for 24 hours to obtain a solution containing the polymer.

[0373] GPC analysis of the obtained polymer showed that its weight-average molecular weight, converted to standard polystyrene, was 9000. Furthermore, the obtained polymer was a polymer with the structure of formula (3a) as a repeating structural unit.

[0374]

[0375] <Synthesis example 3-2>

[0376] The polymer solution obtained in Synthesis Example 3-1 was evaporated to dryness, and the precipitated powder was dried under reduced pressure. 2.0 g of the resulting polymer powder and 0.2 g of 2-sulfobenzoic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were dissolved in 0.25 g of PGMEA, and refluxed at 130°C for 24 hours.

[0377] GPC analysis of the obtained polymer showed that its weight-average molecular weight, converted to standard polystyrene, was 9300. Furthermore, the obtained polymer was a polymer with the structure of formula (3b) as a repeating structural unit.

[0378]

[0379] <Example 1>

[0380] 0.40 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Ltd., Japan), 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to 0.580 g of the polymer solution (solid content 13.88% by mass) obtained in Synthesis Examples 1-2, and the solutions were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer of a photoresist film.

[0381] <Example 2>

[0382] 0.400 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Japan), 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to 0.580 g of the polymer solution (solid content 13.80% by mass) obtained in Synthesis Example 2-2, and the solutions were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer of a photoresist film.

[0383] <Example 3>

[0384] 0.40 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Ltd., Japan), 34.13 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to 0.498 g of the polymer solution (solid content 16.05% by mass) obtained in Synthesis Example 3-2, and the solutions were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer of a photoresist film.

[0385] <Comparative Example 1>

[0386] To 0.580 g of the polymer solution (4.86% by mass of solids) obtained in Synthesis Example 1-1, 0.362 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Japan), 0.165 g of a 1% by mass propylene glycol monomethyl ether solution of pyridinium toluenesulfonate, 32.98 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer of a photoresist film.

[0387] <Comparative Example 2>

[0388] To 0.415 g of the polymer solution (18.88% by mass of solids) obtained in Synthesis Example 2-1, 0.391 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Ltd., Japan), 0.178 g of a 1% by mass propylene glycol monomethyl ether solution of pyridinium toluenesulfonate, 33.85 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer of a photoresist film.

[0389] <Comparative Example 3>

[0390] To 0.443 g of the polymer solution (17.65% by mass of solids) obtained in Synthesis Example 3-1, 0.391 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Ltd., Japan), 0.178 g of a 1% by mass propylene glycol monomethyl ether solution of pyridinium toluenesulfonate, 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added and dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer of a photoresist film.

[0391] <Comparative Example 4>

[0392] 0.362 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Ltd., Japan), 32.98 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to 0.580 g of the polymer solution (solid content 4.86 by mass) obtained in Synthesis Example 1-1 and dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer of a photoresist film.

[0393] <Comparative Example 5>

[0394] 0.391 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Japan), 33.85 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to 0.415 g of the polymer solution (solid content 18.88% by mass) obtained in Synthesis Example 2-1, and the solutions were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer film of photoresist.

[0395] <Comparative Example 6>

[0396] 0.391 g of tetramethoxymethyl urea (manufactured by Cytec Industries, Japan), 34.05 g of propylene glycol monomethyl ether, and 14.97 g of propylene glycol monomethyl ether acetate were added to 0.443 g of the polymer solution (solid content 17.65% by mass) obtained in Synthesis Example 3-1, and the solutions were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to obtain a composition for forming the lower layer film of photoresist.

[0397] (Dissolution test of photoresist solvent)

[0398] The photoresist underlayer film formation compositions of Examples 1-3 and Comparative Examples 1-6 were coated onto a silicon wafer, which served as a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 215°C for 1 minute to form a photoresist underlayer film (film thickness 5 nm). These photoresist underlayer films were immersed in a mixture of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate = 7 / 3 (mass ratio), which served as the solvent for photoresist. Solvent resistance was evaluated based on the change in film thickness before and after immersion. Film thickness reduction of 2 Å or less was considered acceptable, while reduction greater than 2 Å was considered unacceptable.

[0399] Regarding the resist underlayer films of Examples 1-3 and Comparative Examples 1-6, in Table 1, "whether or not acid is immobilized in the polymer contained in the resist underlayer film forming composition that forms the resist underlayer film" is recorded as "whether or not acid is immobilized in the polymer". Additionally, in Table 1, "whether or not an acid catalyst is added to the resist underlayer film forming composition that forms the resist underlayer film" is recorded as "whether or not an acid catalyst is added to the underlayer film forming composition". Furthermore, in Table 1, "the solvent resistance test results of the resist underlayer film" is recorded as "solvent resistance test results".

[0400]

[0401] As can be seen from the results in Table 1, in Examples 1-3, even without the addition of an acid catalyst, a resist film exhibiting solvent resistance can be formed.

[0402] (Formation of positive resist pattern using an electron beam tracing device)

[0403] The resist underlayer film formation compositions of Example 1 and Comparative Example 1 were respectively coated onto a silicon wafer using a spinner. The silicon wafer was baked at 215°C for 60 seconds on a hot plate to obtain a resist underlayer film with a thickness of 5 nm. An EUV positive resist solution (containing methacrylic polymer) was spin-coated onto the resist underlayer film, and heated at 110°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam tracing apparatus (ELS-G130). After exposure, it was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38%) to form a line / spacer pattern with a CD size of 20 nm and a spacing of 40 nm. The length of the resist pattern was measured using a scanning electron microscope (Hitachi High Technology Co., Ltd., CG4100). In the above resist pattern formation, the exposure dose required to form a line pattern with a CD size of 20 nm was defined as sensitivity and compared.

[0404] The results of the exposure dose required to form a line pattern with a CD size of 20 nm in Example 1 and Comparative Example 1 are shown in Table 2 below.

[0405]

[0406] As shown in Table 2, Example 1, compared to Comparative Example 1, requires a lower exposure dose for pattern formation and exhibits superior sensitivity. These results demonstrate that Example 1 can form a resist underlayer film with excellent pattern formation capability and high sensitivity.

[0407] Therefore, according to the present invention, a composition for forming a resist underlayer film can be provided, which is capable of forming a resist underlayer film that is resistant to solvents and has good sensitivity to resist patterns.

Claims

1. A composition for forming a resist underlayer film, comprising a polymer (A) and a solvent (B), The polymer (A) is a polymer with sulfonic acid groups.

2. The composition for forming a resist underlayer film as claimed in claim 1, wherein the polymer (A) has a structure represented by the following formula (X), In formula (X), A represents a hydrogen atom, a methyl atom, or an ethyl atom. Ta represents the following formula (X1), and * represents the connecting key. In formula (X1), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine and iodine atoms. * represents a connecting bond and n represents 0 or 1.

3. The composition for forming a resist underlayer film as claimed in claim 1, wherein the polymer (A) has a structure represented by the following formula (X2). In formula (X2), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine, and iodine atoms. * represents a connecting bond.

4. The composition for forming a resist underlayer film as described in claim 2, wherein the group represented by formula (X1) is selected from any one of the groups represented by the following formulas (X1-1) to (X1-5): In equations (X1-1) to (X1-5), Rx is a halogen atom selected from fluorine, chlorine, bromine and iodine atoms, nx represents an integer from 0 to 4, and * represents a connecting bond.

5. The composition for forming a resist underlayer film as claimed in claim 1, wherein the polymer (A) is a polymer (Y) having repeating units represented by the following formula (Y). In formula (Y), A represents a hydrogen atom, a methyl atom, or an ethyl atom. Qa and Qb represent the following equation (Y5) or the following equation (Y6), respectively. T1 and T2 represent hydrogen atoms or the following formula (X1), respectively, where, In polymer (Y), either T1 or T2 in formula (Y) has a repeating unit represented by the following formula (X1). In formulas (Y5) and (Y6), Q1 represents an alkylene, phenylene, naphthylene, anthraceneylene, or the following formula (M1) having 1 to 10 carbon atoms, and the alkylene, phenylene, naphthylene, and anthraceneylene can be substituted by an alkyl group having 1 to 6 carbon atoms, a carbonyloxyalkyl group having 2 to 7 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a nitro group, a cyano group, a hydroxyl group, an alkylthio group having 1 to 6 carbon atoms, a group having a disulfide group, a carboxyl group, or a group formed by combinations thereof. n1 and n2 represent 0 or 1 respectively. Z1 and Z2 represent single bonds or groups represented by the following formula (Y6-1), respectively. X1 represents the following formula (Y2), the following formula (Y3), the following formula (Y4), or the following formula (Y0). * indicates a connection key. In formula (M1), Y 101 An alkylene group consisting of 1 to 10 carbon atoms, in which at least one hydrogen atom can be replaced by a fluorine atom. R 101 and R 102 These represent alkyl groups with 1 to 10 carbon atoms that can be replaced by fluorine atoms. n 10 and n 11 They represent integers from 0 to 4 respectively. * indicates a connection key. In equation (Y6-1), m represents an integer from 1 to 4, n represents an integer from 0 to 4, p1 and p2 each independently represent 0 or 1, *3 represents the linking bond with the nitrogen atom in equation (Y6), and *4 represents the linking bond. In formulas (Y2), (Y3), (Y4), and (Y0), R1 and R2 represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 3 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a benzyl group, or a phenyl group, respectively. The alkyl group with 1 to 6 carbon atoms, the alkenyl group with 3 to 6 carbon atoms, the alkynyl group with 2 to 6 carbon atoms, the benzyl group, and the phenyl group can be substituted with a group selected from alkyl groups with 1 to 6 carbon atoms, a halogen atom, an alkoxy group with 1 to 6 carbon atoms, an alkoxyalkyl group with 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, and an alkylthio group with 1 to 6 carbon atoms. Furthermore, R1 and R2 can combine with each other to form a ring with 3 to 6 carbon atoms. R3 represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a benzyl group, or a phenyl group, wherein the alkyl group having 1 to 6 carbon atoms, the alkenyl group having 3 to 6 carbon atoms, the alkynyl group having 2 to 6 carbon atoms, the benzyl group, and the phenyl group may be substituted with a group selected from the alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, an alkoxyalkyl group having 2 to 6 carbon atoms, a nitro group, a cyano group, a hydroxyl group, and an alkylthio group having 1 to 6 carbon atoms. * indicates a linking bond; *1 indicates a linking bond with a carbon atom, and *2 indicates a linking bond with a nitrogen atom. In formula (X1), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine and iodine atoms. * represents a connecting bond and n represents 0 or 1.

6. The composition for forming a resist underlayer film as described in claim 5, wherein formula (X1) is the following formula (X2). In formula (X2), Ra represents an aromatic hydrocarbon group, an alkylene group with 1 to 10 carbon atoms, or an alkenyl group with 2 to 10 carbon atoms that may have substituents. The substituents are halogen atoms selected from fluorine, chlorine, bromine, and iodine atoms. * represents a connecting bond, and n represents 0 or 1.

7. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent (C).

8. The composition for forming a resist underlayer film as claimed in claim 7, wherein the crosslinking agent (C) is at least one selected from amino plastic crosslinking agents and phenolic plastic crosslinking agents.

9. A resist underlayer film, which is a cured product of the resist underlayer film forming composition according to any one of claims 1 to 8.

10. A laminate having a semiconductor substrate and a resist underlayer as claimed in claim 9.

11. A method for manufacturing a semiconductor device, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of claims 1 to 8, and The process of forming a resist film on the resist underlayer film.

12. A method for forming a pattern, comprising: The process of forming a photoresist underlayer film on a semiconductor substrate using the photoresist underlayer film forming composition according to any one of claims 1 to 8. The process of forming a resist film on the underlying resist film. The process of irradiating the resist film with light or an electron beam, followed by developing the resist film to obtain a resist pattern, and... The process of using the resist pattern as a mask to etch the underlying resist film.

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