Resist underlayer film-forming composition containing a reaction product of a 3-functional compound

Abstract

Provided are a composition for forming an underlayer film for resist capable of forming a desired resist pattern, a resist pattern production method using the underlayer film for resist formation composition, and a semiconductor device production method. An underlayer film for resist formation composition includes a reaction product of a compound (A) and a compound (B) and a compound (C) dissolved in a solvent, the compound (A) is a compound represented by the following formula (1) (in formula (1), A represents an organic group including an aliphatic ring, an aromatic ring, or a heterocyclic ring), the compound (B) has two functional groups reactive with an epoxy group, and the compound (C) has one functional group reactive with an epoxy group.

Description

Technical Field

[0001] This invention relates to compositions used in photolithography processes in semiconductor manufacturing, particularly in the most advanced photolithography processes (ArF, EUV, EB, etc.). Furthermore, it relates to methods for manufacturing substrates with resist patterns on which the aforementioned resist underlayer film is applied, and methods for manufacturing semiconductor devices. Background Technology

[0002] In the manufacture of semiconductor devices, photolithography using photoresist compositions has long been used for microfabrication. This microfabrication process involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with active light such as ultraviolet light through a mask pattern depicting a device, developing the film to obtain a photoresist pattern, and then using this photoresist pattern as a protective film to etch the substrate, thereby forming micro-uneven surfaces corresponding to the pattern on the substrate surface. In recent years, with the advancement of high integration in semiconductor devices, the active light used has expanded beyond the previously used i-rays (wavelength 365nm), KrF excimer lasers (wavelength 248nm), and ArF excimer lasers (wavelength 193nm) to include the practical application of EUV light (wavelength 13.5nm) or EB (electron beam) in cutting-edge microfabrication. Along with this, poor photoresist pattern formation caused by influences from the semiconductor substrate has become a major problem. Therefore, to solve this problem, methods for setting a photoresist underlayer film between the photoresist and the semiconductor substrate have been extensively studied.

[0003] Patent Document 1 discloses a composition for forming a photoresist lower layer film having a disulfide structure. Patent Document 2 discloses a composition for forming an anti-reflective film for photolithography.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2019 / 151471

[0007] Patent Document 2: International Publication No. 02 / 086624 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] As required characteristics of the underlying resist film, examples include not mixing with the resist film formed on the upper layer (insoluble in resist solvent) and having a faster dry etching speed compared to the resist film.

[0010] In photolithography accompanied by EUV exposure, the linewidth of the formed resist pattern becomes less than 32nm, and the resist underlayer film used for EUV exposure is thinner than before. When forming such a thin film, pinholes and agglomeration are prone to occur due to the influence of the substrate surface and the polymer used, making it difficult to form a uniform film without defects.

[0011] On the other hand, during the formation of the resist pattern, in the development process, in the negative development process where the unexposed portion of the resist film is removed using a solvent that can dissolve the resist film, usually an organic solvent, leaving the exposed portion of the resist film as the resist pattern, and in the positive development process where the exposed portion of the resist film is removed and the unexposed portion of the resist film remains as the resist pattern, improving the adhesion of the resist pattern becomes a major challenge.

[0012] In addition, it is required to suppress the deterioration of LWR (Line Width Roughness, line width roughness, line width fluctuation (roughness)) during resist pattern formation, form resist patterns with good rectangular shape, and improve resist sensitivity.

[0013] The object of the present invention is to provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, which solves the above-mentioned problems, and a method for forming a resist pattern using the composition for forming the resist underlayer film.

[0014] Methods for solving problems

[0015] The present invention includes the following solutions. [1]

[0017] A composition for forming a resist underlayer film comprises a reaction product of compound (A), compound (B), and compound (C) dissolved in a solvent, wherein compound (A) is a compound represented by formula (1), compound (B) has two functional groups that are reactive with epoxy groups, and compound (C) has one functional group that is reactive with epoxy groups.

[0018]

[0019] (In formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring.) [2]

[0021] According to the composition for forming a resist underlayer film as described in [1], A in the above formula (1) is a heterocyclic ring. [3]

[0023] According to the composition for forming a lower layer film of the resist described in [2], the heterocyclic ring is a triazine. [4]

[0025] The composition for forming a resist underlayer film according to any one of [1] to [3], wherein the compound (B) is a compound having two functional groups that are reactive with epoxy groups, including an aliphatic ring, an aromatic ring, a heterocyclic ring, a fluorine atom, an iodine atom, or a sulfur atom. [5]

[0027] The composition for forming a resist underlayer film according to any one of [1] to [4], wherein the compound (C) is a compound having a functional group that is reactive with an epoxy group and comprising an aliphatic or aromatic ring that can be substituted by a substituent. [6]

[0029] A composition for forming a resist underlayer film comprises a reaction product (a) of compound (A) and compound (B) dissolved in a solvent, wherein compound (A) is a compound represented by formula (1) below, and compound (B) is a compound that does not contain disulfide bonds and has two functional groups that are reactive with epoxy groups.

[0030]

[0031] (In formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring.) [7]

[0033] The composition for forming a resist underlayer film according to any one of [1] to [6] further comprises an acid-generating agent. [8]

[0035] The composition for forming a resist underlayer film according to any one of [1] to [7] further comprises a crosslinking agent. [9]

[0037] A resist underlayer film, characterized in that it is a sintered product of a coating film formed by any one of the resist underlayer film forming compositions described in any one of [1] to [8].

[10]

[0039] A method for manufacturing a patterned substrate includes the following steps: coating a semiconductor substrate with a resist underlayer film forming composition according to any one of claims 1 to 8 and baking it to form a resist underlayer film; coating the resist underlayer film with a resist and baking it to form a resist film; exposing the semiconductor substrate covered with the resist underlayer film and the resist; and developing the exposed resist film to form a pattern.

[11]

[0041] A method for manufacturing a semiconductor device, characterized by comprising the following steps:

[0042] A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film as described in any one of [1] to [8];

[0043] The process of forming a resist film on the aforementioned lower resist film;

[0044] The process of forming a resist pattern by irradiating the resist film with light or electron beams and then developing it.

[0045] The process of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; and

[0046] The process of processing a semiconductor substrate using the patterned resist underlayer film described above.

[12]

[0048] A method for manufacturing reaction products, particularly reaction products for compositions used in the formation of resist underlayer films, comprising the step of reacting a mixture comprising compound (A), compound (B), and compound (C) in a solvent.

[0049] The above compound (A) is represented by the following formula (1),

[0050] The above compound (B) has two functional groups that are reactive with epoxy groups.

[0051] The above compound (C) has one functional group that is reactive with epoxy groups.

[0052]

[0053] (In formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring.)

[13]

[0055] A method for manufacturing a composition for forming a resist underlayer film includes the step of further mixing the same or different solvents into the reaction product described in

[12] .

[14]

[0057] A method for manufacturing reaction products, particularly reaction products for compositions used in the formation of resist underlayer films, comprising the step of reacting a mixture comprising compound (A) and compound (B) in a solvent.

[0058] The above compound (A) is represented by the following formula (1),

[0059] The above compound (B) is a compound that does not contain disulfide bonds and has two functional groups that are reactive with epoxy groups.

[0060]

[0061] (In formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring.)

[15]

[0063] A method for manufacturing a composition for forming a resist underlayer film includes the following step: further mixing the same or different solvents into the reaction product described in

[14] .

[0064] The effects of the invention

[0065] The resist underlayer film formation composition of the present invention exhibits excellent coating properties on the semiconductor substrate being processed, and can improve the adhesion and sensitivity of the resist-resist underlayer film interface during resist pattern formation. It is particularly effective during EUV (wavelength 13.5 nm) or EB (electron beam) exposure. Detailed Implementation

[0066] <Composition for forming a lower layer film of resist>

[0067] The composition for forming a resist underlayer film of the present invention comprises:

[0068] Solvent; and

[0069] A reaction product obtained by reacting a mixture containing compounds (A), (B), and (C) that is soluble in the solvent described above.

[0070] The above compound (A) is represented by the following formula (1),

[0071] The above compound (B) has two functional groups that are reactive with epoxy groups.

[0072] The above compound (C) has one functional group that is reactive with epoxy groups.

[0073]

[0074] (In formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring.)

[0075] The preferred molar ratio of the mixture of compounds (A) to (C) is 0.5 or more and 2 or less. By reacting the mixture of compounds (A) to (C) with a molar ratio of (C) to (A)+(B)) of 0.5 or more and 2 or less, excessive increase in the weight-average molecular weight of the reaction products can be suppressed, and a reaction product in which compound (C) is present at a certain proportion at each end of the reaction product molecules can be produced. By having compound (C) present at the ends, the solubility in the aforementioned solvent is improved.

[0076] The reaction products of compounds (A), (B), and (C) can be obtained, for example, by reacting them using the methods described in the examples.

[0077] The molar ratio of compounds (A), (B), and (C) during the reaction; (C) / ((A)+(B)) is 0.5 or more and 2 or less, can be 0.5 or more and 1.9 or less, can be 0.5 or more and 1.8 or less, can be 0.5 or more and 1.7 or less, can be 0.5 or more and 1.6 or less, can be 0.5 or more and 1.5 or less, can be 0.5 or more and 1.4 or less, can be 0.5 or more and 1.3 or less, can be 0.5 or more and 1.2 or less, can be 0.5 or more and 1.1 or less, can be 0.5 or more and 1.0 or less.

[0078] The term "able to dissolve in solvent" as used above refers to maintaining the state in which the reaction products are uniformly dissolved in the solvent described below. For example, it means that after storage under certain conditions (e.g., within the range of 5 to 40°C for 1 month), there are no visible precipitates (including gels) of the reaction products. The composition can be completely filtered within 30 minutes using a microfilter with a pore size of 0.05 μm to 0.1 μm.

[0079] Examples of functional groups that are reactive with epoxy groups include hydroxyl, acyl, acetyl, formyl, benzoyl, carboxyl, carbonyl, amino, imino, cyano, azo, azido, thiol, sulfonyl, allyl, and acid anhydride, but carboxyl is preferred.

[0080] The reaction products described above contain a portion of the structure shown in formula (1-1).

[0081]

[0082] (In formula (1-1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring, and R...) 1 The asterisk (*) indicates a residue derived from compound (B) above, and the asterisk (*) indicates a binding portion to compound (B) or compound (C) above.

[0083] The lower limit of the weight-average molecular weight of the above reaction products is, for example, 500, 1,000, 2,000, or 3,000, and the upper limit of the weight-average molecular weight of the above reaction products is, for example, 30,000, 20,000, or 10,000.

[0084] The above R 1 Preferably, it is a divalent organic group containing an aliphatic ring, an aromatic ring, a heterocyclic ring, or a sulfur atom, as described later.

[0085] The composition for forming the resist underlayer film of the present invention may include:

[0086] The reaction product (a) obtained by reacting a mixture containing compound (A) and compound (B), wherein compound (A) is represented by the following formula (1), and compound (B) is a compound that does not contain disulfide bonds and has two functional groups that are reactive with epoxy groups; and

[0087] Solvent.

[0088]

[0089] (In formula (1), A represents an organic group containing an aliphatic ring, an aromatic ring, or a heterocyclic ring.)

[0090] In the case of the above reaction product (a), the molar ratio of the above compound (A) to the above compound (B), which does not contain a single disulfide bond and has two functional groups that are reactive with an epoxy group, is, for example, 1:0.1 to 10. Preferably, it is 1:1 to 5, and more preferably, it is 1:3.

[0091] The lower limit of the weight-average molecular weight of the above reaction product (a) is, for example, 500, 1,000, 2,000, or 3,000, and the upper limit of the weight-average molecular weight of the above reaction product is, for example, 30,000, 20,000, or 10,000.

[0092] <Compound (A)>

[0093] The compound shown in formula (1) (compound (A)) is not limited as long as it contains an organic group including an aliphatic ring, an aromatic ring or a heterocyclic ring and performs the effects of this application, as exemplified below.

[0094]

[0095] Preferably, A in formula (1) above is a heterocycle. Preferably, the heterocycle is a triazine. Preferably, the heterocycle is a 1,2,3-triazine. Preferably, the heterocycle is a triazine trione.

[0096] <Compound (B)>

[0097] The compound (B) described above is not limited to any compound that achieves the effects of this application, but is preferably a compound containing two functional groups that are reactive with an epoxy group, including an aliphatic ring, an aromatic ring, a heterocyclic ring, a fluorine atom, an iodine atom, or a sulfur atom. The sulfur atom is preferably contained in the compound as a thioether bond, a disulfide bond, or a sulfonyl group.

[0098] The above compound (B) is exemplified below, for example.

[0099]

[0100] When the above compound (B) is an acid dianhydride, the above epoxy group and unreacted carboxyl group can be free or react with at least one of the compounds shown in the following formula (3d).

[0101]

[0102] (In formula (3-d), R1 represents methyl or ethyl.)

[0103] <Compound (C)>

[0104] The above-mentioned compound (C) is not limited as long as it is a compound that can exert the effects of this application, but it is preferred to be a compound containing an aliphatic or aromatic ring that can be substituted by a substituent and having a functional group that is reactive with an epoxy group.

[0105] The above compound (C) may contain an aliphatic ring that can be substituted by a substituent.

[0106] Preferably, the aforementioned aliphatic ring is a monocyclic or polycyclic aliphatic ring with 3 to 10 carbon atoms. Examples of monocyclic or polycyclic aliphatic rings with 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, and tricyclo[3.2.1.0]octane. 2,7 Octane, spiro[3,4]octane, norbornane, norbornene, tricyclic[3.3.1.1] 3,7 Decane (adamantane), etc.

[0107] Preferably, the aforementioned polycyclic aliphatic ring is a bicyclic or tricyclic ring.

[0108] Examples of the aforementioned bicyclic rings include norbornane, norbornene, spirobycyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, and spiroby[3,4]octane.

[0109] As an example of the aforementioned three rings, three rings can be cited [3.2.1.0]. 2,7 Octane, tricyclic [3.3.1.1]3,7 Decane (adamantane).

[0110] The aforementioned aliphatic ring that can be substituted by a substituent refers to a ring in which one or more hydrogen atoms can be replaced by the substituents described below.

[0111] The substituents mentioned above are preferably selected from hydroxyl groups, linear or branched alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, aryl groups having 6 to 40 carbon atoms, acyloxy groups having 1 to 10 carbon atoms that can be interrupted by oxygen atoms, and carboxyl groups.

[0112] Examples of alkoxy groups with 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, 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-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, 4-methyl-n-pentyloxy, and 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, and 1-ethyl-2-methyl-n-propoxy, cyclopentyloxy, cyclohexyloxy, norbornyloxy, adamantylalkyloxy, adamantanemethyloxy, adamantaneethyloxy, tetracyclodecyloxy, tricyclodecyloxy.

[0113] Examples of aryl groups with 6 to 40 carbon atoms include benzyl, naphthyl, anthraceneyl, phenanthryl, or pyrene, but phenyl is preferred among them.

[0114] As the acyloxy group with 1 to 10 carbon atoms mentioned above, it refers to the group shown in the following formula (4).

[0115] Z-COO-* formula (4)

[0116] (In formula (4), Z is a hydrogen atom, and the alkyl group having 1 to 9 carbon atoms among the alkyl groups having 1 to 10 carbon atoms mentioned above can be substituted by the substituents mentioned above, can be interrupted by an oxygen atom or an ester bond, and can have an allyl or propytyl group. * indicates the part that is bonded to the "aliphatic ring" mentioned above.)

[0117] Preferably, the aliphatic ring has at least one unsaturated bond (e.g., a double or triple bond). Preferably, the aliphatic ring has one to three unsaturated bonds. Preferably, the aliphatic ring has one or two unsaturated bonds. The unsaturated bond is preferably a double bond.

[0118] Specific examples of compounds containing aliphatic rings that can be substituted by substituents include the compounds described below. Specific examples of the compounds described below in which the carboxyl group is replaced by a hydroxyl, acyl, acetyl, formyl, benzoyl, carboxyl, carbonyl, amino, imino, cyano, azo, azido, thiol, sulfonyl, or allyl group may also be given.

[0119]

[0120]

[0121]

[0122] Preferably, the above compound (C) is represented by the following formulas (11) and (12).

[0123]

[0124] (In formulas (11) and (12), R1 represents an alkyl, phenyl, pyridyl, halogroup or hydroxyl group with 1 to 6 carbon atoms that may have substituents; R2 represents a hydrogen atom, an alkyl, hydroxyl, halogroup or ester group represented by -C(=O)OX; X represents an alkyl group with 1 to 6 carbon atoms that may have substituents; R3 represents a hydrogen atom, an alkyl, hydroxyl or halogroup with 1 to 6 carbon atoms; R4 represents a directly bonded or divalent organic group with 1 to 8 carbon atoms; R5 represents a divalent organic group with 1 to 8 carbon atoms; A represents an aromatic ring or aromatic heterocycle; t represents 0 or 1; u represents 1 or 2.)

[0125] Regarding the contents of equations (11) and (12) above, all the disclosures recorded in International Publication No. 2015 / 163195 are incorporated herein by reference.

[0126] The polymer end structures shown in formulas (11) and (12) above can be manufactured by reacting the polymer with the compound shown in formula (1a) and / or the compound shown in formula (2a).

[0127]

[0128] (The symbols in equations (1a) and (2a) above have the same meaning as explained in equations (11) and (12) above.)

[0129] Examples of compounds represented by formula (1a) above include compounds represented by the following formulas. Specific examples also include compounds obtained by substituting the carboxyl or hydroxyl group of the following compounds with acyl, acetyl, formyl, benzoyl, carboxyl, carbonyl, amino, imino, cyano, azo, azido, thiol, sulfonyl, and allyl groups.

[0130]

[0131]

[0132]

[0133]

[0134]

[0135] Examples of compounds represented by formula (2a) above include compounds represented by the following formula.

[0136]

[0137] The above compound (C) can be the compound shown in formula (1-1) as described in International Publication No. 2020 / 071361.

[0138]

[0139] (In the above formula (1-1), X is a divalent organic group, A is an aryl group with 6 to 40 carbon atoms, R1 is a halogen atom, an alkyl group with 1 to 40 carbon atoms, or an alkoxy group with 1 to 40 carbon atoms, n1 is an integer from 1 to 12, and n2 is an integer from 0 to 11.)

[0140] The carboxyl group in formula (1-1) can be replaced by hydroxyl, acyl, acetyl, formyl, benzoyl, carboxyl, carbonyl, amino, imino, cyano, azo, azido, thiol, sulfonyl, and allyl.

[0141] As a specific example of X above, it is an ester bond, ether bond, amide bond, carbamate bond or urea bond, preferably an ester bond or ether bond.

[0142] As a specific example of A above, it is a group derived from benzene, naphthalene, anthracene, phenanthrene or pyrene, preferably a group derived from benzene, naphthalene or anthracene.

[0143] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0144] Specific examples of the alkyl groups having 1 to 10 carbon atoms are methyl, ethyl, propyl, butyl, hexyl, or pentyl, with methyl being the most preferred.

[0145] Specific examples of the aforementioned alkoxy groups with 1 to 10 carbon atoms are methoxy, ethoxy, propoxy, butoxy, hexoxy, or pentoxy, with methoxy being the preferred one.

[0146] The term "can be replaced" means that some or all of the hydrogen atoms in the alkyl group with 1 to 10 carbon atoms can be replaced, for example, by a fluorine group or a hydroxyl group.

[0147] Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, hexyl, or pentyl, but methyl is preferred.

[0148] As described above, the aryl groups with 6 to 40 carbon atoms are, but phenyl is preferred among them.

[0149] n1 and n3 are each an integer from 1 to 12, but preferably an integer from 1 to 6.

[0150] n2 is an integer from 0 to 11, but preferably an integer from 0 to 2.

[0151] In the above formula (1-1), n2 is preferably 0.

[0152] As specific examples of the compounds shown in formula (1-1) above, the compounds described below can be cited. The carboxyl group of the compounds described below may be replaced by hydroxyl, acyl, acetyl, formyl, benzoyl, carboxyl, carbonyl, amino, imino, cyano, azo, azido, thiol, sulfonyl, and allyl.

[0153]

[0154]

[0155]

[0156] The above compound (C) can be the compound shown in formula (2-1) as described in International Publication No. 2020 / 071361.

[0157]

[0158] (In the above formula (2-1), X is a divalent organic group, A is an aryl group with 6 to 40 carbon atoms, R2 and R3 are each independently a hydrogen atom, an alkyl group with 1 to 10 carbon atoms that can be substituted, an aryl group with 6 to 40 carbon atoms that can be substituted, or a halogen atom, and n3 is an integer from 1 to 12.)

[0159] In formula (2-1) above, in this invention, X, A, R2, R3 and n3 are preferably as described above. In formula (2-1) above, R2 and R3 are preferably hydrogen atoms.

[0160] As specific examples of the compounds shown in formula (1-1) above, the compounds described below can be cited. The carboxyl group of the compounds described below may be replaced by hydroxyl, acyl, acetyl, formyl, benzoyl, carboxyl, carbonyl, amino, imino, cyano, azo, azido, thiol, sulfonyl, and allyl.

[0161]

[0162] The entire contents of International Publication No. 2020 / 071361 are incorporated herein by reference.

[0163] <Solvent>

[0164] The solvent used in the resist underlayer film forming composition of this application is not particularly limited as long as it can uniformly dissolve the components such as the reaction products that are solid at room temperature. However, organic solvents used in semiconductor photolithography processes are generally preferred. Specifically, examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 2 Ethyl 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. These solvents can be used alone or in combination of two or more.

[0165] Preferred solvents include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0166] <Acid-producing agent>

[0167] As an acid-generating agent optionally included in the resist lower film forming composition of the present invention, both thermal acid-generating agents and photo-acid-generating agents can be used, but thermal acid-generating agents are preferred. Examples of thermal acid-generating agents include, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, and pyridine. - p-Toluenesulfonate (pyridine) -p-Toluenesulfonic acid), pyridine Phenolsulfonic acid, pyridine - p-Hydroxybenzenesulfonic acid (p-phenolsulfonic acid pyridine) salt), pyridine - Sulfonic acid compounds and carboxylic acid compounds such as trifluoromethanesulfonic acid, salicylic acid, camphor sulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzene disulfonic acid, 1-naphthalene sulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0168] Examples of photoacid-producing agents mentioned above include: Salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds, etc.

[0169] As Salt compounds, such as diphenyliodine, can be cited as an example. Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate and bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Sulfonate compounds, and sulfonate compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoro n-butane sulfonate, triphenylsulfonium camphor sulfonate, and triphenylsulfonium trifluoromethane sulfonate.

[0170] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0171] Examples of disulfonyl diazonium compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium.

[0172] The above-mentioned acid-producing agents can be used alone, or two or more can be used in combination.

[0173] When using the above-mentioned acid-producing agent, the proportion of the acid-producing agent relative to the crosslinking agent is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass.

[0174] <Cross-linking agent>

[0175] Examples of crosslinking agents that may be included as optional components in the resist underlayer film forming composition of the present invention include, for example, hexamethoxymethyl melamine, tetramethoxymethyl guanidine, 1,3,4,6-tetra(methoxymethyl)glyurea (tetramethoxymethylglyurea) (POWDERLINK [registered trademark] 1174), 1,3,4,6-tetra(butoxymethyl)glyurea, 1,3,4,6-tetra(hydroxymethyl)glyurea, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetra(butoxymethyl)urea, and 1,1,3,3-tetra(methoxymethyl)urea.

[0176] Furthermore, the crosslinking agent of this application can be a nitrogen-containing compound as described in International Publication No. 2017 / 187969, having 2 to 6 substituents of the following formula (1d) bonded to a nitrogen atom in one molecule.

[0177]

[0178] (In formula (1d), R1 represents methyl or ethyl.)

[0179] A nitrogen-containing compound having 2 to 6 substituents as shown in the above formula (1d) in one molecule can be a glycourea derivative as shown in the following formula (1E).

[0180]

[0181] (In formula (1E), each of the four R1s independently represents a methyl or ethyl group, and each of the R2 and R3 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0182] Examples of glycourea derivatives represented by the above formula (1E) include compounds represented by formulas (1E-1) to (1E-6).

[0183]

[0184] A nitrogen-containing compound having 2 to 6 substituents as shown in formula (1d) in one molecule is obtained by reacting a nitrogen-containing compound having 2 to 6 substituents as shown in formula (2d) in one molecule that are bonded to a nitrogen atom with at least one compound as shown in formula (3d).

[0185]

[0186] (In formulas (2d) and (3d), R1 represents methyl or ethyl, and R4 represents an alkyl group having 1 to 4 carbon atoms.)

[0187] The glycourea derivative shown in formula (1E) above is obtained by reacting the glycourea derivative shown in formula (2E) below with at least one compound shown in formula (3d) above.

[0188] A nitrogen-containing compound having 2 to 6 substituents as shown in the above formula (2d) in one molecule is, for example, a glycourea derivative as shown in the following formula (2E).

[0189]

[0190] (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.)

[0191] Examples of glycourea derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4). Further examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2).

[0192]

[0193] The entire disclosure of WO2017 / 187969 is incorporated herein by reference to the above-mentioned nitrogen-containing compounds having 2 to 6 substituents of the following formula (1d) bonded to a nitrogen atom in one molecule.

[0194] When using the above-mentioned crosslinking agent, the proportion of the crosslinking agent relative to the above-mentioned reaction product is, for example, 1% to 50% by mass, preferably 5% to 30% by mass.

[0195] <Other Ingredients>

[0196] In the resist lower film forming composition of the present invention, in order to avoid the generation of pinholes, streaks, etc., and to further improve the coating performance on uneven surfaces, a surfactant may be added. Examples of surfactants include 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; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol monostearate. Non-ionic surfactants such as sorbitol tristearate and other polyoxyethylene sorbitan fatty acid esters, EFT EF301, EF303, EF352 (Technology Co., Ltd. Made by ケムプロダクツ, brand name), Milk F171, F173, R-30 (made by Dainippon Co., Ltd., brand name), フロラード FC430, FC Fluoropolymer surfactants such as 431 (manufactured by Sumitomo Silem Co., Ltd., trade name), Asahigard AG710, Servolon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) are used. The amount of these surfactants mixed is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the resist underlayer film forming composition of the present invention. These surfactants can be added individually or in combination of two or more.

[0197] The composition for forming the lower layer of the resist film of the present invention contains solid components, that is, components other than the solvent mentioned above, in an amount of, for example, 0.01% to 10% by mass.

[0198] <Resist Underlayer>

[0199] The resist underlayer film of the present invention can be manufactured by coating the above-mentioned resist underlayer film forming composition onto a semiconductor substrate and then firing it.

[0200] Examples of semiconductor substrates for coating the resist underlayer film formation composition of the present invention include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0201] When using a semiconductor substrate on which an inorganic film is formed on its surface, this inorganic film is formed, for example, by ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (SOG). Examples of such inorganic films include, for instance, polycrystalline silicon films, silicon oxide films, silicon nitride films, BPSG (boro-phosphorus silicon glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0202] 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 means such as a hot plate. 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 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.

[0203] The thickness of the underlying resist film formed 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), or 0.003 μm (1 nm). The thicknesses are as follows: ~0.05μm (50nm), 0.004μm (4nm) ~0.05μm (50nm), 0.005μm (5nm) ~0.05μm (50nm), 0.003μm (3nm) ~0.03μm (30nm), 0.003μm (3nm) ~0.02μm (20nm), 0.005μm (5nm) ~0.02μm (20nm). When the baking temperature is below these ranges, cross-linking becomes insufficient. On the other hand, when the baking temperature is above these ranges, the resist underlayer film sometimes decomposes due to heat.

[0204] <Method for manufacturing a substrate with patterned substrate, method for manufacturing a semiconductor device>

[0205] The method for manufacturing a patterned substrate involves the following steps. Typically, a photoresist layer is formed on a photoresist underlayer film. As for the photoresist formed by coating and firing on the photoresist underlayer film using methods known to the public, there are no particular limitations as long as it is a photosensitive substance used for exposure. Both negative and positive photoresists can be used. There are positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazonyl sulfonate; chemically amplified photoresists composed of binders and photoacid generators having groups that increase the rate of alkali dissolution through acid decomposition; chemically amplified photoresists composed of low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition, alkali-soluble binders, and photoacid generators; chemically amplified photoresists composed of binders that increase the rate of alkali dissolution through acid decomposition, low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition, and photoacid generators; and photoresists containing metal elements. Examples include JSR Co., Ltd.'s product V146G, Shiplay Co., Ltd.'s product APEX-E, Sumitomo Chemical Co., Ltd.'s product PAR710, and Shin-Etsu Chemical Co., Ltd.'s products AR2772 and SEPR430. In addition, examples of fluorinated polymer photoresists can be cited, such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0206] In addition, the following 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, WO2019 / 172054, W O2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Special Opening 2018-180525, WO2018 / 190088, Japanese Special Opening 2018-070596, Japanese Special Opening 2018-028090, Japanese Special Opening 2016-153409, Japanese Special Opening 2016-130240, Japanese Special Opening 2016-108325, Japanese Special Opening 2016-047920, Japanese Special Opening 2016-035570, Japan Special opening 2016-035567, Japanese special opening 2016-035565, Japanese special opening 2019-101417, Japanese special opening 2019-117373, 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 2019-06 1217, Japan’s special opening 2018-045152, Japan’s special opening 2018-022039, Japan’s special opening 2016-090441, Japan’s special opening 2015- 10878, Japan’s special opening 2012-168279, Japan’s special opening 2012-022261, Japan’s special opening 2012-022258, Japan’s special opening 2011 The resist compositions described in Japanese Patent Application Publication Nos. -043749, 2010-181857, 2010-128369, WO2018 / 031896, 2019-113855, WO2017 / 156388, WO2017 / 066319, 2018-41099, WO2016 / 065120, WO2015 / 026482, 2016-29498, and 2011-253185 are called resist compositions, radiation-sensitive resin compositions, and compositions for high-resolution patterning based on organometallic solutions, and are metal-containing resist compositions, but are not limited to these.

[0207] Examples of resist compositions include, for example, the following compositions.

[0208] An active light-sensitive or radiation-sensitive resin composition comprising resin A and a compound of general formula (21), wherein resin A has repeating units having acid-degradable groups of polar groups protected by protecting groups that are deactivated by acid.

[0209]

[0210] In general formula (21), m represents an integer from 1 to 6.

[0211] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0212] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0213] L2 indicates that it can have alkylene groups or single bonds that have substituents.

[0214] W1 represents a cyclic organic group that can have substituents.

[0215] M + It represents a cation.

[0216] A metal-containing film-forming composition for 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 the 3rd to 7th periods of Groups IIIB to VA (Groups 3 to 15 of the Japanese Periodic Table).

[0217] A radiation-sensitive resin composition comprising: a polymer having a first structural unit represented by formula (31) and a second structural unit represented by formula (32) and containing an acid-dissociating group; and an acid-generating agent.

[0218]

[0219] (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 group, a mercapto group, or a 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-dissociating group. 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.)

[0220] A photoresist composition comprising a resin (A1) and an acid-generating agent, wherein the resin (A1) comprises structural units having a cyclic carbonate structure, structural units represented by formula (II), and structural units having acid-instantaneous groups.

[0221]

[0222] In equation (II),

[0223] R 2 X represents an alkyl group, hydrogen atom, or halogen atom that can have 1 to 6 carbon atoms and may contain 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 an aromatic hydrocarbon group having 6 to 20 carbon atoms that may have one or more groups selected from hydroxyl and carboxyl groups.]

[0224] Examples of resist films include the following.

[0225] A photoresist film comprising a base resin comprising: repeating units as shown in formula (a1) and / or repeating units as shown in formula (a2) below, and repeating units of acid bonded to the polymer backbone by exposure.

[0226]

[0227] (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 linker group containing 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.)

[0228] Examples of corrosion-resistant materials include the following.

[0229] A resist material comprising a polymer having repeating units as shown in formula (b1) or formula (b2).

[0230]

[0231] (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 with 1 to 12 carbon atoms or an aryl group with 6 to 10 carbon atoms. 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. 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 may be substituted with an ether group or an ester group. Rf 1 ~Rf 4 Each atom is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl atom, but at least one of them is a fluorine atom or a trifluoromethyl atom. Furthermore, Rf 1 and Rf 2 They can combine to form a carbonyl group. R 1 ~R 5 Each group is independently a linear, branched, or cyclic alkyl group with 1 to 12 carbon atoms, an alkenyl group with 2 to 12 carbon atoms, an alkynyl 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 group, cyano, amide, nitro, sulopentalide, sulfone, or a group containing a sulfonium salt. A portion of the methylene group constituting these groups may be substituted with ether, ester, carbonyl, carbonate, or sulfonate groups. Furthermore, R... 1 With R 2 They can combine with the sulfur atoms they are bonded to to form rings.

[0232] A photoresist material comprising a base resin comprising a polymer comprising repeating units as shown in formula (a) below.

[0233]

[0234] (In equation (a), R) A It can be a hydrogen atom or a methyl group. R 1 It is a hydrogen atom or an acid-instable 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 a phenylene group, or a straight-chain, branched, or cyclic alkylene group having 1 to 12 carbon atoms that 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. n is an integer from 0 to 3.

[0235] A photoresist composition characterized by being a photoresist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid.

[0236] It contains a substrate component (A) whose solubility in the developer changes due to the action of acid, and a fluorinated additive component (F) that exhibits decomposition properties in alkaline developers.

[0237] The aforementioned fluorinated additive component (F) contains a fluoropolymer component (F1) having a constituent unit (f1) and a constituent unit (f2), wherein the constituent unit (f1) contains a base-dissociable group and the constituent unit (f2) contains a group represented by the following general formula (f2-r-1).

[0238]

[0239] [In the formula, Rf] 21 Each group can be 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 bonding bond.

[0240] The aforementioned constituent unit (f1) includes the constituent unit shown in the following general formula (f1-1) or the constituent unit shown in the following general formula (f1-2).

[0241]

[0242] [In the formula, R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. X is a divalent linker without an acid-dissociating site. A] aryl It is a divalent aromatic cyclic group that can have substituents. X 01 It is a single bond or a divalent linker. R 2 Each is an organic group containing a fluorine atom.

[0243] Examples of substances that can be used as coatings, coating solutions, and coating compositions include the following.

[0244] Coatings comprising a network of metal oxygen-hydroxyl groups having organic ligands via metal carbon bonds and / or metal carboxylate bonds.

[0245] Compositions of inorganic oxo / hydroxo bases.

[0246] The coating solution comprises: an organic solvent; and a first organometallic composition of formula R. z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≤ 2 and 0 < (z + x) ≤ 4), Equation R' n SnX4-n (where n = 1 or 2), or mixtures thereof, wherein R and R' are independently hydrocarbon groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolytic bond to Sn or a combination thereof; and a hydrolytic metal compound, which is expressed by formula MX' v (where M is a metal selected from Groups IIA to VIA of the periodic table (Groups 2 to 16 of the Japanese periodic table), v is a number of 2 to 6, and X' is a ligand of an MX bond with hydrolytic properties or a combination thereof.)

[0247] The coating solution contains organic solvents and the formula RSnO. (3 / 2-x / 2) (OH) x The coating solution of the first organometallic compound shown in the formula (where 0 < x < 3) contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl or cycloalkyl group having 3 to 31 carbon atoms, wherein the alkyl or cycloalkyl group has tin bonded to a secondary or tertiary carbon atom.

[0248] An aqueous solution of inorganic pattern forming precursor contains water, metal suboxide cations, polyatomic inorganic anions, and a mixture of radiation-sensitive ligands containing peroxide groups.

[0249] Exposure is performed using a mask (intermediate mask) to form a prescribed pattern, employing, for example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (ultraviolet light) or EB (electron beam), but the resist underlayer film forming composition of this application is preferably used for EB (electron beam) or EUV (ultraviolet light) exposure, and more preferably for EUV (ultraviolet light) exposure. Development is performed using an alkaline developer, appropriately selected from a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds. As an alkaline developer, aqueous solutions of, for example, 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 and tetraethylammonium hydroxide; and cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of surfactants such as isopropanol or nonionic surfactants can be added to the above-mentioned alkaline aqueous solution. Among these, quaternary ammonium salts are preferred, and tetramethylammonium hydroxide and choline are more preferred. Furthermore, surfactants can also be added to these developers. Alternatively, an organic solvent such as butyl acetate can be used instead of an alkaline developer to develop the portion of the photoresist whose alkaline dissolution rate has not been increased. Through the above processes, a substrate with the above-mentioned photoresist patterned can be manufactured.

[0250] Next, using the formed resist pattern as a mask, the underlying resist film is dry-etched. At this time, if the inorganic film is formed on the surface of the semiconductor substrate, the surface of the inorganic film is exposed; if 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 substrate using methods known in the art (such as dry etching), a semiconductor device can be manufactured.

[0251] Example

[0252] The following examples illustrate the content of the present invention in detail, but the present invention is not limited to them.

[0253] The weight-average molecular weights of the polymers shown in Synthesis Example 1 and Comparative Synthesis Example 1 in this specification are determined by gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus manufactured by Higashi Sou Corporation, and the determination conditions are as follows.

[0254] GPC pillars: Shodex KF803L, Shodex KF802, Shodex KF801 [Registered Trademark] (Showa Denko Co., Ltd.)

[0255] Column temperature: 40℃

[0256] Solvent: Tetrahydrofuran (THF)

[0257] Flow rate: 1.0 ml / minute

[0258] Standard sample: Polystyrene (manufactured by Tosoo Corporation)

[0259] <Synthesis example 1>

[0260] The following ingredients were added: 8.00 g of triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd.), 4.75 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 6.69 g of adamantane carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutyl bromide. 0.31 g of (manufactured by ACROSS) was added to 79.00 g of propylene glycol monomethyl ether to dissolve it. After purging the reaction vessel with nitrogen, the reaction was carried out at 80°C for 24 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the polymer in the obtained solution had a weight-average molecular weight of 6,000 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural units shown in formulas (1a), (2a), and (3a) below.

[0261]

[0262] <Synthesis example 2>

[0263] Triglycidyl isocyanurate (manufactured by Nissan Chemical Co., Ltd.) 8.00g, 1,3-adamantanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.73g, adamantanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.69g, tetrabutyl bromide 0.31 g of (manufactured by ACROSS) was dissolved in 46.08 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the polymer in the obtained solution had a weight-average molecular weight of 8,000 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural units shown in formulas (1a), (4a), and (3a) below.

[0264]

[0265] <Synthesis Example 3>

[0266] Triglycidyl isocyanurate (Nissan Chemical Co., Ltd.) 3.00 g, 2,2',6,6'-Tetramethylbisphenol S (Tokyo Chemical Industry Co., Ltd.) 2.44 g, 4-(methylsulfonyl)benzoic acid (Tokyo Chemical Industry Co., Ltd.) 2.78 g, tetrabutyl bromide 0.12 g of (manufactured by ACROSS) was dissolved in 75.03 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the polymer in the obtained solution had a weight-average molecular weight of 3,000 converted to standard polystyrene. The polymer obtained in this synthetic example has the structural units shown in formulas (1a), (6a), and (7a) below.

[0267]

[0268] <Synthesis example 4>

[0269] Triglycidyl isocyanurate (Nissan Chemical Co., Ltd.) 4.00 g, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (Tokyo Chemical Industry Co., Ltd.) 4.72 g, 4-(methylsulfonyl)benzoic acid (Tokyo Chemical Industry Co., Ltd.) 2.63 g, tetrabutyl bromide 0.16 g of (manufactured by ACROSS) was dissolved in 75.03 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 120°C for 24 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the polymer in the obtained solution had a weight-average molecular weight of 7,000 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural units shown in formulas (1a), (8a), and (7a) below.

[0270]

[0271] <Comparative Synthesis Example 1>

[0272] The following ingredients were added: 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 1.91 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 0.57 g of adamantane carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutyl bromide. 0.14 g of (manufactured by ACROSS) was dissolved in 6.87 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 8 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the polymer in the obtained solution had a weight-average molecular weight of 5,000 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural units shown in formulas (1b), (2a), and (3a) below.

[0273]

[0274] <Comparative Synthesis Example 2>

[0275] 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 2.04 g of 1,3-adamantanedicarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.57 g of adamantanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutyl bromide were added. 0.04 g of (manufactured by ACROSS) was dissolved in 15.08 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the weight-average molecular weight of the polymer in the obtained solution was 8,300 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural units shown in formulas (1b), (4a), and (3a) below.

[0276]

[0277] <Reference Synthesis Example 3>

[0278] The following ingredients were added: 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 4.64 g of 2,2',6,6'-tetramethylbisphenol S (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.07 g of 4-(methylsulfonyl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutyl bromide. 0.06 g of (manufactured by ACROSS) was dissolved in 25.03 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the weight-average molecular weight of the polymer in the obtained solution was 6,200 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural units shown in formulas (1b), (6a), and (7a) below.

[0279]

[0280] <Comparative Synthesis Example 4>

[0281] The following ingredients were added: 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 3.27 g of 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.64 g of 4-(methylsulfonyl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and tetrabutyl bromide. 0.03 g of (manufactured by ACROSS) was dissolved in 27.66 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. This polymer solution did not turn cloudy even when cooled to room temperature and showed good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the weight-average molecular weight of the polymer in the obtained solution was 8,300 converted to standard polystyrene. The polymer obtained in this synthesis example has the structural units shown in formulas (1b), (8a), and (7a) below.

[0282]

[0283] <Example 1>

[0284] To the polymer solution obtained in Synthesis Example 1 above (solid content: 16.4% by weight), 0.02g of tetramethoxymethyl urea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 44.5 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0285] <Example 2>

[0286] To the polymer solution obtained in Synthesis Example 2 above (solid content: 17.8% by weight), 0.02g of tetramethoxymethyl glycourea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 44.6 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0287] <Example 3>

[0288] To the polymer solution obtained in Synthesis Example 3 above (solid content: 18.3% by weight), 0.02g of tetramethoxymethyl glycourea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 44.6 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0289] <Example 4>

[0290] To the polymer solution obtained in Synthesis Example 4 above (solid content: 17.7% by weight), 0.02g of tetramethoxymethyl urea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 44.4 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved in the solution. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0291] <Comparative Example 1>

[0292] To the polymer solution obtained in Comparative Synthesis Example 1 above, 0.47 g (solid content: 18.0 wt%) of tetramethoxymethyl glycourea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 44.6 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0293] <Comparative Example 2>

[0294] To the polymer solution obtained in Comparative Synthesis Example 2 above (solid content: 18.0% by weight) of 0.47 g, 0.02 g of tetramethoxymethyl glycourea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 44.6 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0295] <Reference Example 3>

[0296] To the polymer solution obtained in Reference Synthesis Example 3 above (solid content: 18.1% by weight) of 0.43 g, 0.02 g of tetramethoxymethyl glycourea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 43.0 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0297] <Comparative Example 4>

[0298] To the polymer solution obtained in the comparative synthesis example 4 above (solid content: 26.7% by weight) of 0.29 g, 0.02 g of tetramethoxymethyl urea (manufactured by Cytec Industries Co., Ltd., Japan) and pyridine were added. 0.003 g of phenolsulfonic acid, 44.0 g of propylene glycol monomethyl ether, and 4.99 g of propylene glycol monomethyl ether acetate were dissolved. The solution was then filtered using a polyethylene microfilter with a pore size of 0.05 μm to prepare a composition for forming the lower layer of a photoresist film.

[0299] [Dissolution test of photoresist solvent]

[0300] The resist underlayer film formation compositions of Examples 1, 2, 3, 4, and Comparative Examples 1, 2, 3, and 4 were respectively coated onto a silicon wafer serving as a semiconductor substrate using a spin coater. The silicon wafer was placed on a hot plate and baked at 205°C for 1 minute to form a resist underlayer film (film thickness 5 nm). These resist underlayer films were immersed in ethyl lactate and propylene glycol monomethyl ether, solvents used as photoresists, and it was confirmed that they were insoluble in these solvents.

[0301] [Formation of positive resist patterns using an electron beam tracing device]

[0302] The resist underlayer film formation compositions of Examples 1, 2, and Comparative Examples 1 and 2 were respectively coated onto silicon wafers using a spin coater. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film with a thickness of 5 nm. An EUV positive resist solution (containing a methacrylic polymer) was spin-coated onto this resist underlayer film, and heated at 130°C for 60 seconds to form an EUV resist film. This resist film was exposed under specified conditions using an electron beam tracing apparatus (ELS-G130). After exposure, it was baked at 100°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38% TMAH) to form a resist pattern with a 26 nm column pattern and a 52 nm spacing. The length of the resist pattern was measured using a scanning electron microscope (manufactured by Hitachi High Tech Noroze Co., Ltd., CG4100). In the formation of the resist pattern described above, a pillar pattern with a CD size of 31 nm was considered "good," while a pillar pattern collapse or peeling was observed and was considered "poor." Furthermore, the necessary exposure for forming a pillar pattern with a CD size of 31 nm was compared with standard exposure values ​​based on Comparative Example 1.

[0303] [Table 1]

[0304] (Table 1)

[0305] CD size 31nm column pattern Standard value of exposure Example 1 good 0.97 Example 2 good 0.97 Comparative Example 1 bad 1.00 Comparative Example 2 bad 0.99

[0306] In Examples 1 and 2, compared with Comparative Examples 1 and 2, it was confirmed that the collapse and peeling of the column pattern could be suppressed, demonstrating good pattern forming ability. Furthermore, regarding the necessary exposure amount, in Examples 1 and 2, compared with Comparative Examples 1 and 2, it was confirmed that pattern forming could be performed with less exposure.

[0307] [Formation of negative resist patterns using an electron beam tracing device]

[0308] The resist underlayer film formation compositions of Examples 3, 4, and Comparative Example 4 were spin-coated onto silicon wafers. The silicon wafers were baked at 205°C for 60 seconds on a hot plate to obtain a resist underlayer film with a thickness of 5 nm. An EUV negative resist solution was spin-coated onto this resist underlayer film, and the film was heated at 100°C for 60 seconds to form an EUV resist film. This resist film was exposed under specified conditions using an electron beam tracing apparatus (ELS-G130). After exposure, it was baked at 100°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with butyl acetate to form a resist pattern with a 23 nm column pattern and a 46 nm spacing. The length of the resist pattern was measured using a scanning electron microscope (Hitachi High Tech Noroze Co., Ltd., CG4100). The photoresist pattern obtained through this operation was evaluated by observing it from the top. In the formation of the aforementioned photoresist pattern, a pillar pattern with a CD size of 20 nm was considered "good," while a pillar pattern exhibiting collapse or peeling was considered "poor." Furthermore, the necessary exposure for forming a pillar pattern with a CD size of 31 nm was compared.

[0309] [Table 2]

[0310] (Table 2)

[0311] CD-sized 20nm column pattern Example 3 good Example 4 good Comparative Example 4 bad

[0312] In Examples 3 and 4, compared with Comparative Example 4, it was confirmed that the collapse and peeling of the column pattern could be suppressed, and that the pattern forming ability was good.

[0313] The results above show that the composition for forming the resist underlayer film of the present invention exhibits good photolithography performance compared with the prior art.

[0314] Industry availability

[0315] The resist underlayer film forming composition of the present invention can provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, and a method for manufacturing a substrate with a resist pattern using the resist underlayer film forming composition, and a method for manufacturing a semiconductor device.

Claims

1. A composition for forming a resist underlayer film, comprising a reaction product of compound (A) and compound (B) and compound (C) dissolved in a solvent, wherein compound (A) is a compound represented by the following formula (1), In equation (1), A is a heterocyclic ring. The compound (B) does not contain disulfide bonds and has two functional groups that are reactive with epoxy groups. The compound (C) is a compound containing an aliphatic or aromatic ring that can be substituted by a substituent, and having one functional group selected from hydroxyl, carboxyl, amino, imino, azide, thiol, sulfonyl, and acid anhydride that is reactive with an epoxy group. The reaction product comprises a portion of the structure shown in formula (1-1) below. In equation (1-1), A is a heterocyclic ring, and R... 1 The symbol indicates a residue derived from the compound (B) described above, and the asterisk (*) indicates a portion that is bound to the compound (B) or the compound (C) described above.

2. The composition for forming a resist underlayer film according to claim 1, wherein the heterocyclic ring is a triazine.

3. The composition for forming a resist underlayer film according to claim 1 or 2, wherein the compound (B) is a compound containing an aliphatic ring, an aromatic ring, a heterocyclic ring, a fluorine atom or an iodine atom, and having two functional groups that are reactive with an epoxy group.

4. The composition for forming a resist underlayer film according to claim 1 or 2, The compound (B) is selected from the following compounds, 。 5. The composition for forming a resist underlayer film according to claim 1, further comprising an acid-generating agent.

6. The composition for forming a resist underlayer film according to claim 1, further comprising a crosslinking agent.

7. A resist underlayer film, characterized in that, It is a sintered product of a coating film formed by the composition for forming a resist underlayer film according to any one of claims 1 to 6.

8. A method for manufacturing a patterned substrate, comprising the steps of: coating a resist underlayer film forming composition according to any one of claims 1 to 6 onto a semiconductor substrate and baking it to form a resist underlayer film; coating a resist onto the resist underlayer film and baking it to form a resist film; exposing the semiconductor substrate covered with the resist underlayer film and the resist; and developing the exposed resist film to form a pattern.

9. A method for manufacturing a semiconductor device, characterized in that, Includes the following processes: A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film according to any one of claims 1 to 6; The process of forming a resist film on the lower resist film; The process of forming a resist pattern by irradiating the resist film with light or electron beams and then developing it. The process of forming a patterned resist underlayer film by etching the resist underlayer film via the formed resist pattern; and A process of processing a semiconductor substrate using the patterned resist underlayer film.

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