Composition for forming a resist underlayer film

Abstract

To provide a resist underlayer film formation composition that can form a good resist pattern while improving sensitivity. [Solution] A composition for forming a resist underlayer film, comprising a calixarene having a sulfonic acid group and a solvent. The calixarene having a sulfonic acid group is represented by formula (1). TIFF2026135588000034.tif61105 (R 1 (where n represents a sulfonic acid group, and n represents an integer between 4 and 8.)

Description

Technical Field

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

Background Art

[0002] Conventionally, in the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has been performed. The microfabrication involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with actinic rays such as ultraviolet light through a mask pattern on which a device pattern is drawn, developing it, and etching the substrate using the obtained photoresist pattern as a protective film to form fine irregularities corresponding to the photoresist pattern on the substrate surface. In recent years, as semiconductor devices have become more highly integrated, in addition to the i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm) that have been conventionally used as actinic rays, the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) has been studied for the most advanced microfabrication. Along with this, poor formation of resist patterns has become a major problem. Therefore, in order to solve this problem, a method of providing a resist underlayer film between the resist and the semiconductor substrate has been widely studied.

[0003] As a composition for forming a resist underlayer film, a composition for forming a resist underlayer film containing a polymer (A) having one or more polymerizable multiple bonds selected from the group consisting of carbon-carbon double bonds, carbon-carbon triple bonds, carbon-carbon double bonds, and carbon-carbon triple bonds in side chains and a solvent has been proposed (see Patent Document 1).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

[0005] The required properties for the resist underlayer include, for example, that it does not intermix with the resist film formed on top (i.e., it is insoluble in the resist solvent), and that it can improve the sensitivity and adhesion of the resist pattern to form a good resist pattern. The present invention has been made in view of the above circumstances, and aims to provide a resist underlayer film formation composition that can form a good resist pattern while improving sensitivity, and a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film formation composition. [Means for solving the problem]

[0006] The inventors of the present invention conducted diligent research to solve the above problems and, as a result, found that they could solve the above problems, and completed the present invention having the following gist.

[0007] In other words, the present invention encompasses the following aspects. [1] A composition for forming a resist underlayer film, comprising a calixarene having a sulfonic acid group and a solvent. [2] The resist underlayer film forming composition according to [1], wherein the calixarene having the sulfonic acid group is represented by the following formula (1). [ka] (In formula (1), R 1 R represents a sulfonic acid group. 2 n represents -CH2-, a sulfur atom, a sulfonyl group, or -CHR- (where R represents a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group with 6 to 20 carbon atoms). n represents an integer from 4 to 8. [3] The resist underlayer film forming composition according to [2], wherein n is 6. [4] The resist underlayer film forming composition according to any one of [1] to [3], wherein the solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers. [5] A composition for forming a resist underlayer film according to any one of [1] to [4], further comprising a crosslinking agent. [6] The resist underlayer film forming composition according to [5], wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents. [7] A composition for forming a resist underlayer film according to any one of [1] to [6], further comprising a curing catalyst. [8] A resist underlayer film formation composition according to any one of [1] to [7], used in EUV lithography. A resist underlayer film, which is a cured product of a resist underlayer film forming composition described in any of [9] [1] to [8].

[10] Semiconductor substrate and, [9] The resist underlayer film described above, A laminate comprising the following features.

[11] A step of forming a resist underlayer on a semiconductor substrate using a resist underlayer forming composition described in any of [1] to [8], The steps include forming a resist film on the resist underlayer film, A method for manufacturing semiconductor devices, including

[12] A step of forming a resist underlayer on a semiconductor substrate using a resist underlayer forming composition described in any of [1] to [8], The steps include forming a resist film on the resist underlayer film, The steps include irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern, A step of etching the resist underlayer film using the resist pattern as a mask, A pattern formation method, including the following.

[0008] According to the present invention, it is possible to provide a resist underlayer film formation composition that can form a good resist pattern while improving sensitivity, as well as a method for manufacturing a resist underlayer film, a laminate, a semiconductor device, and a pattern formation method using the resist underlayer film formation composition. [Modes for carrying out the invention]

[0009] (Composition for forming a resist underlayer film) The present invention's composition for forming a resist underlayer film comprises a calixarene having a sulfonic acid group and a solvent. Calixarenes are cyclic oligomers that have a phenol skeleton. By using calixarenes having sulfonic acid groups in the resist underlayer film formation composition, a good resist pattern can be formed on the resist underlayer film formed from the resist underlayer film formation composition, while improving sensitivity and suppressing pattern collapse and bridging. The resist underlayer film formation composition may contain a crosslinking agent, a curing catalyst, and the like.

[0010] The calixarene of the present invention has one or more sulfonic acid groups in the oligomer. Preferably, the calixarene has two or more sulfonic acid groups in the oligomer, more preferably four or more sulfonic acid groups, and particularly preferably the same number or more sulfonic acid groups as the number of unit structures having a phenol skeleton. Calixarenes may have substituents other than sulfonic acid groups. The calixarene is preferably in the form of 4 to 8-mers, and more preferably in the form of 4-mers or 6-mers.

[0011] <Calyxarenes containing sulfonic acid groups> The composition for forming the resist underlayer preferably contains a calixarene having a sulfonic acid group.

[0012] Examples of calixarenes having a sulfonic acid group include those represented by (1) below. [ka]

[0013] In formula (1), R 1 R represents a sulfonic acid group (-SO3H). 2 n represents -CH2-, a sulfur atom (-S-), a sulfonyl group (-S(=O)2-), or -CHR- (where R represents a substituted or unsubstituted alkyl group with 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group with 6 to 20 carbon atoms). n represents an integer from 4 to 8.

[0014] The calixarene represented by equation (1) is R 1 It has a sulfonic acid group. The hydrogen atoms in the sulfonic acid group may be substituted to form a salt.

[0015] R 2 represents -CH2-, a sulfur atom, a sulfonyl group, or -CHR-. In -CHR-, R represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, isopropyl, isobutyl, tert-butyl, neopentyl, 2-hexyl, 2-octyl, 2-decyl, 2-dodecyl, 2-hexadecyl, and 2-octadecyl groups. The number of carbon atoms in the substituted or unsubstituted alkyl group is preferably 1 to 10. Examples of aryl groups with 6 to 20 carbon atoms include phenyl group, naphthyl group, 4-isopropylphenyl group, 4-cyclohexylphenyl group, 4-methylphenyl group, and 6-fluoronaphthyl group. The number of carbon atoms in the substituted or unsubstituted aryl group is preferably 6 to 10. "Substitution" refers to the substitution of one or more hydrogen atoms in a functional group with a halogen atom, a hydroxyl group, a cyano group, a nitro group, a heterocyclic group, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a combination thereof.

[0016] R 2 It is preferably -CH2-, a sulfur atom, or a sulfonyl group, and more preferably -CH2-.

[0017] n represents an integer between 4 and 8. n is preferably 4 or 6, and more preferably 6.

[0018] Examples of calixarenes represented by formula (1) include 4-sulfocalix[6]arene and 4-sulfocalix[4]arene.

[0019] Calixarenes having sulfonic acid groups may be commercially available products. An example of a commercially available product is S0470 (manufactured by Tokyo Chemical Industry Co., Ltd.). When a calixarene having a sulfonic acid group has geometric isomers, it may be the cis or trans isomer.

[0020] The lower limit of the weight-average molecular weight of calixarenes having a sulfonic acid group is, for example, 300, 500, 1,000, or 2,000. The upper limit of the weight-average molecular weight of calixarenes having a sulfonic acid group is, for example, 50,000, 20,000, or 10,000.

[0021] The content of calixarenes having sulfonic acid groups in the resist underlayer film forming composition is not particularly limited, but from the viewpoint of suitably obtaining the effects of the present invention, for example, 50 to 100% by mass and more preferably 60 to 95% by mass is preferred based on the film constituent components. In this invention, the term "film constituent component" refers to components other than the solvent contained in the resist underlayer film forming composition.

[0022] <Solvent> The solvent is not particularly limited and may be water or an organic solvent. Examples of organic solvents include alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers.

[0023] Examples of alkylene groups in alkylene glycol monoalkyl ethers include alkylene groups having 2 to 4 carbon atoms. Examples of alkyl groups in alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms. Examples of the number of carbon atoms in alkylene glycol monoalkyl ethers include 3 to 8. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether.

[0024] Examples of alkylene groups in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkylene groups having 2 to 4 carbon atoms. Examples of alkyl groups in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include alkyl groups having 1 to 4 carbon atoms. Examples of monocarboxylic acids in the monocarboxylic acid esters of alkylene glycol monoalkyl ethers include saturated monocarboxylic acids having 2 to 4 carbon atoms. Examples of saturated monocarboxylic acids having 2 to 4 carbon atoms include acetic acid, propionic acid, and butyric acid. Examples of the number of carbon atoms in the monocarboxylic acid ester of alkylene glycol monoalkyl ether include 5 to 10. Examples of monocarboxylic acid esters of alkylene glycol monoalkyl ethers include methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol propyl ether acetate.

[0025] Other organic solvents include, for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 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.

[0026] Among these solvents, alkylene glycol monoalkyl ethers and monocarboxylic acid esters of alkylene glycol monoalkyl ethers are preferred.

[0027] These solvents can be used individually or in combination of two or more.

[0028] The mass percentage of the organic solvent in the solvent is not particularly limited, but 50% to 100% by mass is preferred.

[0029] The solvent content in the resist underlayer film forming composition is not particularly limited, but is preferably 50% to 99.99% by mass, more preferably 75% to 99.95% by mass, and particularly preferably 90% to 99.9% by mass.

[0030] <Crosslinking agent> The crosslinking agent is not particularly limited. As the crosslinking agent, aminoplast crosslinking agents and phenoplast crosslinking agents are preferred. The aminoplast crosslinking agent is an addition condensate of a compound having an amino group such as melamine or guanamine and formaldehyde. The phenoplast crosslinking agent is an addition condensate of a compound having a phenolic hydroxy group and formaldehyde.

[0031] Examples of the crosslinking agent include compounds having two or more of the following structures.

Chemical formula

[0032] R 101 is preferably a hydrogen atom, a methyl group, an ethyl group or a group represented by the following structure.

Chemical formula

[0033] As the crosslinking agent, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, and compounds having a phenolic hydroxy group are preferred. These can be used alone or in combination of two or more.

[0034] Examples of melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which one to six methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0035] Examples of guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are methoxymethylated or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which one to four methylol groups of tetramethylolguanamine are acyloxymethylated or mixtures thereof.

[0036] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, and compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof.

[0037] Furthermore, the glycoluryl compound may also be, for example, a glycoluryl derivative represented by the following formula (1E). [ka] (In formula (1E), each of the four R1s independently represents a methyl group or an ethyl group, and R2 and R3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.)

[0038] Examples of glycoluryl derivatives represented by formula (1E) include the compounds represented by the following formulas (1E-1) to (1E-6). [ka]

[0039] A glycoluryl derivative represented by formula (1E) can be obtained, for example, by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by the following formula (3d).

[0040] [ka] (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.)

[0041] [ka] (In formula (3d), R1 represents a methyl group or an ethyl group.)

[0042] Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below. [ka] [ka]

[0043] Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which one to four methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, and tetramethoxyethylurea.

[0044] Examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-1) or (G-2). [ka] (In equations (G-1) and (G-2), Q 1 This indicates a single bond or an m1 valent organic group. R 1 and R 4 Each of these represents an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms having an alkoxy group having 1 to 10 carbon atoms. R 2 and R 5 Each of these represents either a hydrogen atom or a methyl group. R 3 and R 6 Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. n1 is an integer between 1 and 3, n2 is an integer between 2 and 5, n3 is an integer between 0 and 3, n4 is an integer between 0 and 4, and 3 is an integer between 6 and 10 (n1 + n2 + n3 + n4). n5 is an integer between 1 and 5 (1 ≤ n5 ≤ 3), n6 is an integer between 1 and 6 (1 ≤ n6 ≤ 4), n7 is an integer between 0 and 7 (0 ≤ n7 ≤ 3), n8 is an integer between 0 and 8 (0 ≤ n8 ≤ 3), and 2 is an integer between 2 and (n5 + n6 + n7 + n8) ≤ 5. m1 represents an integer between 2 and 10.

[0045] Furthermore, examples of compounds having a phenolic hydroxyl group include compounds represented by the following formulas (G-3) or (G-4). The compound represented by formula (G-1) or formula (G-2) may be obtained by reacting the compound represented by formula (G-3) or formula (G-4) below with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms. [ka] (In equations (G-3) and (G-4), Q 2 This indicates a single bond or an m2 valent organic group. R 8 , R 9 , R 11 and R 12Each of these represents either a hydrogen atom or a methyl group. R 7 and R 10 Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. n9 is an integer 1 ≤ n9 ≤ 3, n 10 is 2≦n 10 An integer n ≤ 5 11 is 0≦n 11 n is an integer ≤ 3. 12 is 0≦n 12 Integers ≤ 3, 3 ≤ (n9 + n) 10 +n 11 +n 12 This shows integers ≤ 6. n 13 is 1≦n 13 n is an integer ≤ 3. 14 is 1≦n 14 n is an integer ≤ 4. 15 is 0≦n 15 n is an integer ≤ 3. 16 is 0≦n 16 Integers ≤ 3, 2 ≤ (n 13 +n 14 +n 15 +n 16 This shows integers for which ) ≤ 5. m² represents an integer between 2 and 10. Q 2 Examples of m2 valent organic groups in this context include m2 valent organic groups having 1 to 4 carbon atoms.

[0046] Examples of compounds represented by formula (G-1) or formula (G-2) include the following compounds. [ka] [ka] [ka] [ka] [ka]

[0047] Examples of compounds represented by formula (G-3) or formula (G-4) include the following compounds. [ka] [ka] The above compounds are available as products from Asahi Organic Chemicals Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, one such product is TMOM-BP, sold under the trade name of Asahi Organic Chemicals Co., Ltd.

[0048] Among these, glycoluryl compounds are preferred, specifically tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which one to four methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which one to four methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof, and tetramethoxymethyl glycoluryl is more preferred.

[0049] The molecular weight of the crosslinking agent is not particularly limited, but it is preferably 500 or less.

[0050] The content of the crosslinking agent in the resist underlayer film forming composition is not particularly limited, but is, for example, 5% to 90% by mass, preferably 10% to 70% by mass, relative to the calixarene having a sulfonic acid group of the present invention.

[0051] <Curing catalyst> The curing catalyst included as an optional component in the resist underlayer film formation composition can be either a thermal acid generator or a photoacid generator, but it is preferable to use a thermal acid generator. Examples of thermal acid generators include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0052] Examples of photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0053] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphor sulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0054] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0055] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0056] Only one type of curing catalyst may be used, or two or more types may be used in combination.

[0057] When a curing catalyst is used, the content of the curing catalyst is, for example, 0.1% to 50% by mass relative to the crosslinking agent, preferably 1% to 30% by mass.

[0058] <Other ingredients> The resist underlayer film formation composition does not produce pinholes or striations, and surfactants can be added to further improve the coatability against surface unevenness.

[0059] Examples of surfactants include linear or branched alkylbenzenesulfonic acids (e.g., dodecylbenzenesulfonic acid), polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and polyoxyethylene sorbitan monolaurate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorinated surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by DIC Corporation, product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants blended 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. These surfactants may be added individually or in combination of two or more types.

[0060] The resist underlayer film forming composition of the present invention preferably contains 5% by mass or less of polysiloxane, and more preferably 1% by mass or less. The lower limit of the polysiloxane content in the resist underlayer film forming composition is not limited, but it is particularly preferable that it is below the detection limit (i.e., polysiloxane-free).

[0061] The solid content of the resist underlayer film forming composition of the present invention, i.e., the components excluding the solvent, is, for example, 0.01% to 10% by mass.

[0062] The resist underlayer film formation composition is preferably used in EUV lithography.

[0063] (Underlying resist film) The resist underlayer film of the present invention is a cured product of the resist underlayer film forming composition described above. The resist underlayer film can be manufactured, for example, by coating the aforementioned resist underlayer film forming composition onto a semiconductor substrate and firing it.

[0064] Examples of semiconductor substrates to which the resist underlayer film formation composition is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0065] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho-Silicate Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0066] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Subsequently, 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 bake temperature of 100°C to 400°C and a bake time of 0.3 minutes to 60 minutes. Preferably, the bake temperature is 120°C to 350°C and the bake time is 0.5 minutes to 30 minutes, and more preferably, the bake temperature is 150°C to 300°C and the bake time is 0.8 minutes to 10 minutes.

[0067] The thickness of the resist underlayer film can be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), 0.005 μm ( The ranges are 5nm to 0.05μm (50nm), 0.003μm (3nm) to 0.03μm (30nm), 0.003μm (3nm) to 0.02μm (20nm), 0.005μm (5nm) to 0.02μm (20nm), 0.003μm (3nm) to 0.01μm (10nm), 0.005μm (5nm) to 0.01μm (10nm), 0.003μm (3nm) to 0.006μm (6nm), or 0.005μm (5nm).

[0068] The method for measuring the thickness of the resist underlayer film in this specification is as follows: • Measurement device name: Ellipso-type film thickness gauge RE-3100 (SCREEN Co., Ltd.) • SWE (Single-Wavelength Ellipsometer) Mode • Arithmetic mean of 8 points (for example, 8 measurements taken at 1cm intervals in the X direction of the wafer)

[0069] (Laminated structure) The laminate of the present invention comprises a semiconductor substrate and a resist underlayer film of the present invention. Examples of semiconductor substrates include the aforementioned semiconductor substrates. The resist underlayer film is, for example, placed on a semiconductor substrate.

[0070] (Method for manufacturing semiconductor devices, method for forming patterns) The method for manufacturing a semiconductor device of the present invention includes at least the following steps. The process of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition of the present invention, and • A process of forming a resist film on top of the resist underlayer film.

[0071] The pattern forming method of the present invention includes at least the following steps. • A step of forming a resist underlayer film on a semiconductor substrate using the resist underlayer film formation composition of the present invention. • A process of forming a resist film on top of the resist underlayer film. The process of irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern, and • A process of etching the underlying resist layer using a resist pattern as a mask.

[0072] Typically, a resist film is formed on top of the underlying resist film. The thickness of the resist film can be, for example, 3,000 nm or less, 2,000 nm or less, 1,800 nm or less, 1,500 nm or less, and 1,000 nm or less. The lower limits are 100 nm, 80 nm, 50 nm, 30 nm, 20 nm, and 10 nm.

[0073] The resist film formed on the resist underlayer by known methods (e.g., coating and firing of a resist composition) is not particularly limited as long as it responds to light or electron beam (EB) used for irradiation. Both negative and positive photoresists can be used. In this specification, resists that respond to EB are also referred to as photoresists. Examples of photoresists include positive-type photoresists consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, as well as resists containing metal elements. Examples include JSR Corporation's product name V146G, Cyprey Corporation's product name APEX-E, Sumitomo Chemical Co., Ltd.'s product name PAR710, and Shin-Etsu Chemical Co., Ltd.'s product names AR2772 and SEPR430. Furthermore, examples include fluorine-containing polymer-based photoresists, 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).

[0074] Also, 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, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 While so-called resist compositions and metal-containing resist compositions such as those described in JP 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0075] Examples of resist compositions include the following compositions.

[0076] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by the following general formula (121).

[0077] [ka] 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. L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-. L2 represents an alkylene group or single bond which may have substituents. W1 represents a cyclic organic group which may have substituents. M + This represents a cation.

[0078] A metal-containing film-forming composition 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 the 3rd to 7th periods of groups 3 to 15 of the periodic table.

[0079] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) that includes an acid-dissociable group, and an acid generator.

[0080] [ka] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene with 6 to 20 carbon atoms. 1 R is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R 1 They are the same or different. 2R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 This is a monovalent group having 1 to 20 carbon atoms that contains the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 (This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0081] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by the following formula, and structural units having an acid-unstable group, and an acid generator.

[0082] [ka] [In the formula, R 2 X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. 1 These are single bonds, -CO-O-*, or -CO-NR 4 -* represents a bond with -Ar, and R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0083] Examples of resist films include the following:

[0084] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0085] [ka] (In equations (a1) and (a2), R A Each of these is independently either a hydrogen atom or a methyl group. 1 and R 2Each of these is independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. 1 X is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. 2 (These are single bonds, ester bonds, or amide bonds.)

[0086] Examples of resist materials include the following:

[0087] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0088] [ka] (In equations (b1) and (b2), R A X is a hydrogen atom or a methyl group. 1 X is a single bond or an ester group. 2 X is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and X 2 At least one hydrogen atom in X is replaced by a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf 4 Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 They may combine to form a carbonyl group. 1 ~R 5Each of these is independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonic acid ester group. 1 and R 2 These may combine to form a ring with the sulfur atom to which they are bonded.

[0089] A resist material comprising a base resin containing a polymer containing repeating units represented by the following formula (a).

[0090] [ka] (In formula (a), R A R is a hydrogen atom or a methyl group. 1 R is a hydrogen atom or an acid-unstable group. 2 X is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. 1 This is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, which may contain a single bond or a phenylene group, or an ester group or a lactone ring. 2 is -O-, -O-CH2-, or -NH-. m is an integer between 1 and 4. u is an integer between 0 and 3. However, m+u is an integer between 1 and 4.

[0091] A resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, It contains a base component (A) whose solubility in the developer changes due to the action of acid, and a fluorine additive component (F) that is degradable in alkaline developer. The fluorine additive component (F) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1), wherein the fluorine additive component (F) contains a fluororesin component (F1).

[0092] [ka] [In formula (f2-r-1), Rf 21 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n'' is an integer from 0 to 2. * represents a bond.

[0093] The aforementioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0094] [ka] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group that does not have an acid-dissociable site. A aryl X is a divalent aromatic cyclic group which may have substituents. 01 R is a single bond or a divalent linking group. 2 These are, independently, organic groups that contain a fluorine atom.

[0095] The resist composition may be a metal-containing resist. Metal-containing resists are also called metal oxide resists (MORs), and a typical example is tin oxide-based resists. As a metal oxide resist material, for example, a coating composition containing a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond described in JP-A-2019-113855 can be mentioned. An example of a metal-containing resist uses a peroxo ligand as a radiation-sensitive stabilizing ligand. The details of peroxo-based metal oxo-hydroxo compounds are described in, for example, the patent documents described in paragraph

[0011] of JP-A-2019-532489. Examples of such patent documents include, for example, US Patent No. 9,176,377 B2, US Patent Application Publication No. 2013 / 0224652 A1, US Patent No. 9,310,684 B2, US Patent Application Publication No. 2016 / 0116839 A1, and US Patent Application Publication No. 15 / 291738.

[0096] A coating containing a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond.

[0097] An inorganic oxo / hydroxo-based composition.

[0098] A coating solution, an organic solvent; a first organometallic composition represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≦ 2 and 0 < (z + x) ≦ 4), the formula R' n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof, a first organometallic composition; and a hydrolyzable metal compound represented by the formula MX' v(Here, M is a metal selected from Groups 2 to 16 of the periodic table, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof), a coating solution containing a hydrolyzable metal compound represented by

[0099] an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (where 0 < x < 3), a coating solution in which about 0.0025 M to about 1.5 M of tin is contained in the solution, R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom

[0100] an inorganic pattern-forming precursor aqueous solution comprising a mixture of water, a metal oxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group

[0101] Another example of the metal-containing resist includes the compositions described in JP-A-2011-253185, WO2015 / 026482, WO2016 / 065120, WO2017 / 066319, WO2017 / 156388, WO2018 / 031896, JP-A-2020-122959, JP-A-2020-122960, WO2019 / 099981, WO2019 / 199467, WO2019 / 195522, WO2019 / 195522, WO2020 / 210660, WO2021 / 011367, and WO2021 / 016229. All of these contents are incorporated herein to the same extent as if fully set forth.

[0102] The method for forming a metal-containing resist film from a metal-containing resist is not particularly limited, and examples include a method of applying and baking a coating-type resist material (composition for forming a metal-containing resist film) that is a metal-containing resist.

[0103] Furthermore, the metal-containing resist film may be formed by vapor deposition. An example of a method for forming a metal-containing resist film by vapor deposition is the method described in Japanese Patent Application Publication No. 2017-116923. The contents of Japanese Patent Application Publication No. 2017-116923 are incorporated herein to the same extent as if they were fully explicit. In Japanese Patent Application Publication No. 2017-116923, the metal-containing resist film in this invention is referred to as a metal oxide-containing film.

[0104] Irradiation with light or an electron beam is performed, for example, through a mask (reticle) for forming a predetermined pattern. For example, i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet) or EB (electron beam) lasers are used. The resist underlayer film forming composition of the present invention is preferably applied for EB (electron beam) or EUV (extreme ultraviolet: 13.5 nm) irradiation, and more preferably for EUV (extreme ultraviolet) exposure. There are no particular limitations on the electron beam irradiation energy and the amount of light exposure.

[0105] Post-exposure baking (PEB) may be performed after irradiation with light or electron beam and before development. The baking temperature is not particularly limited, but is preferably 60°C to 150°C, more preferably 70°C to 120°C, and particularly preferably 75°C to 110°C. The baking time is not particularly limited, but is preferably 1 second to 10 minutes, more preferably 10 seconds to 5 minutes, and especially preferably 30 seconds to 3 minutes.

[0106] For developing film, for example, alkaline developers and organic solvents are used. For example, a development temperature of 5°C to 50°C is recommended. Development times can range from, for example, 10 to 300 seconds. As alkaline developers, for example, aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous 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; alcohol amines 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 be used. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are aqueous solutions of quaternary ammonium salts, and more preferably aqueous solutions of tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of an alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate, and the parts of the photoresist where the alkali dissolution rate has not improved are developed.

[0107] Organic solvents can be used as the developer for metal-containing resists, and development is performed with the developer (solvent) after irradiation with light or electron beam. As a result, for example, when a negative-type metal-containing resist film is used, the unexposed areas of the metal-containing resist film are removed, and a pattern of the metal-containing resist film is formed. Examples of developers (organic solvents) include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, 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 monoethyl 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-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, propyl lactate Examples include methyl 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 and other substances can be added to these developing solutions.

[0108] Next, the resist underlayer is etched using the formed resist pattern as a mask. The etching may be dry etching or wet etching, but dry etching is preferred. If the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed. If the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Subsequently, the semiconductor substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device. [Examples]

[0109] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. The weight-average molecular weight of the polymers shown in Comparative Synthesis Example 1 of this specification was obtained by measurement using gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows. GPC column: TSKgel Super-MultiporeHZ-N (2 tubes) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 0.35ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0110] <Comparative Synthesis Example 1> 100.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride were added to 682.00 g of propylene glycol monomethyl ether in a reaction vessel and dissolved. After purging the reaction vessel with nitrogen, the mixture was reacted at 130°C for 24 hours to obtain a solution containing comparative polymer 1. GPC analysis revealed that the obtained comparative polymer 1 had a weight-average molecular weight of 6800 on a standard polystyrene basis and a dispersion degree of 4.8. The structure present in comparative polymer 1 is shown by the following formula. [ka]

[0111] (Preparation of composition for forming a resist underlayer film) The polymer obtained in Comparative Synthesis Example 1, a commercially available reagent, a crosslinking agent, a curing catalyst, a surfactant, and a solvent were mixed in the proportions shown in Tables 1 and 2 below, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare solutions of the resist underlayer film forming compositions for Example 1 and Comparative Example 1, respectively. The amounts of each additive are shown in parts by mass, and the solvent is shown in composition ratio.

[0112] The meanings of the abbreviations in Tables 1 and 2 are as follows: SCA:4-Sulfocalix[6]arene (manufactured by Tokyo Chemical Industry Co., Ltd., model number S0470) <Crosslinking agent> PL-LI: Tetramethoxymethylglycoluryl TMOM-BP:3,3',5,5'-Tetrakis(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol <Curing catalyst> PyPSA: Pyridinium-p-hydroxybenzenesulfonic acid <Surfactants> R-30N: Surfactant <Solvent> PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether DIW: Ultrapure water

[0113] [Table 1]

[0114] [Table 2]

[0115] (Elution test into photoresist solvent) Each of the resist underlayer formation compositions from Example 1 and Comparative Example 1 was coated onto a silicon wafer using a spinner. The silicon wafer was then baked on a hot plate at 205°C or 240°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30, which is the solvent used for photoresists, and evaluated as "good" if the film thickness change was less than 0.5 nm (5 Å), and "poor" if it was 0.5 nm or more. The results are shown in Table 3.

[0116] [Table 3]

[0117] (Resistance patterning evaluation) [Test of resist pattern formation using electron beam lithography equipment] A resist underlayer formation composition was applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C or 240°C for 60 seconds to obtain a resist underlayer with a thickness of 5 nm. An EUV positive-type resist solution was spin-coated onto the resist underlayer and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed using an electron beam lithography system (ELS-G130) under predetermined conditions. After exposure, it was baked (PEB) at 100°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle developed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as a photoresist developer. A resist pattern with hole sizes of 16 nm to 26 nm was formed. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern.

[0118] The photoresist patterns obtained in this way were evaluated based on whether or not 23nm contact holes (C / H) could be formed. In Example 1, the formation of a 23nm C / H pattern was confirmed. Furthermore, the optimal irradiation energy was set to the amount of charge required to form a 23nm contact hole, and the irradiation energy (μC / cm²) was set to 1.00 for Comparative Example 1. 2 The results are shown in Table 4. In Example 1, a reduction in the optimal irradiation energy was confirmed compared to Comparative Example 1.

[0119] [Table 4] [Industrial applicability]

[0120] The present invention provides a composition for forming a resist underlayer film that can form a desired resist pattern, 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 calixarene having a sulfonic acid group and a solvent.

2. The resist underlayer film forming composition according to claim 1, wherein the calixarene having the sulfonic acid group is represented by the following formula (1). 【Chemistry 1】 (In formula (1), R １ R represents a sulfonic acid group. ２ is, -CH ２ - represents a sulfur atom, a sulfonyl group, or -CHR- (where R represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms). n represents an integer from 4 to 8.

3. The resist underlayer film forming composition according to claim 2, wherein n is 6.

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

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

6. The resist underlayer film forming composition according to claim 5, wherein the crosslinking agent is at least one selected from the group consisting of aminoplast crosslinking agents and phenoplast crosslinking agents.

7. The resist underlayer film forming composition according to claim 1, further comprising a curing catalyst.

8. A resist underlayer film formation composition according to claim 1, used in EUV lithography.

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

10. Semiconductor substrate and The resist underlayer film according to claim 9, A laminate comprising the following features.

11. A step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film formation composition according to any one of claims 1 to 8, The steps include forming a resist film on the aforementioned resist underlayer film, A method for manufacturing semiconductor devices, including

12. A step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film formation composition according to any one of claims 1 to 8, The steps include forming a resist film on the aforementioned resist underlayer film, The steps include irradiating the resist film with light or an electron beam, then developing the resist film to obtain a resist pattern, A step of etching the resist underlayer film using the resist pattern as a mask, A pattern formation method, including the following.

Images