Resist underlayer forming composition having protected basic organic groups

Abstract

Provides are: a composition for forming a resist underlayer film that enables the formation of a desired resist pattern; and a resist pattern production method and a semiconductor device manufacturing method, which use said composition for forming a resist underlayer film. The composition for forming a resist underlayer film has a basic organic group substituted with a protecting group in the repeating unit structure of a polymer containing a heterocycle, or at a terminal thereof, and further includes a solvent. The polymer may include a heterocycle containing an alkenyl group having 2-10 carbon atoms. The polymer may have, in a main chain thereof, at least one structural unit represented by formula (3). (In formula (3), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group, and Q1 represents a divalent organic group including a heterocycle, and m1 and m2 each independently represent 0 or 1.)

Description

[Technical Field]

[0001] This invention relates to compositions used in lithography processes in semiconductor manufacturing, particularly in state-of-the-art lithography processes (ArF, EUV, EB, etc.). It also relates to a method for manufacturing a substrate with a resist pattern to which the resist underlayer film is applied, and a method for manufacturing a semiconductor device. [Background technology]

[0002] Conventionally, microfabrication using lithography with resist compositions has been performed in the manufacturing of semiconductor devices. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate such as a silicon wafer, irradiating it with an active light such as ultraviolet light through a mask pattern on which the device pattern is drawn, developing the film, and then etching the substrate using the resulting photoresist pattern as a protective film to form fine irregularities on the substrate surface corresponding to the pattern. In recent years, semiconductor devices have become more highly integrated, and in addition to the conventionally used i-line (wavelength 365 nm), KrF excimer laser (wavelength 248 nm), and ArF excimer laser (wavelength 193 nm), the practical application of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, poor resist pattern formation due to influence from the semiconductor substrate has become a major problem. Therefore, in order to solve this problem, methods of providing a resist underlayer film between the resist and the semiconductor substrate are being widely investigated. Patent Document 1 discloses an additive for a resist underlayer film forming composition and a resist underlayer film forming composition containing the same. Patent Document 2 discloses a resist underlayer forming composition for EUV lithography having a condensation polymer. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2013 / 058189 [Patent Document 2] International Publication No. WO 2013 / 018802 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0004] As characteristics required for a resist underlayer film, for example, there can be mentioned that no intermixing occurs with a resist film formed on the upper layer (being insoluble in a resist solvent), and that the dry etching rate is higher than that of the resist film.

[0005] In the case of lithography involving EUV exposure, the line width of a formed resist pattern becomes 32 nm or less, and a resist underlayer film for EUV exposure is formed to have a thinner film thickness than before. When forming such a thin film, pinholes, aggregation, etc. are likely to occur due to the influence of the substrate surface, the polymer used, etc., and it has been difficult to form a uniform film without defects.

[0006] On the other hand, in the case of forming a resist pattern, in a development process, in a negative development process in which an unexposed portion of the resist film is removed using a solvent capable of dissolving the resist film, usually an organic solvent, and the exposed portion of the resist film is left as a resist pattern, or in a positive development process in which the exposed portion of the resist film is removed and the unexposed portion of the resist film is left as a resist pattern, improving the adhesion of the resist pattern has been a major issue.

[0007] In addition, suppressing the deterioration of LWR (Line Width Roughness, line width roughness, fluctuation of line width (roughness)) during resist pattern formation, forming a resist pattern having a good rectangular shape, and improving resist sensitivity are required. Also, improvement in the limit resolution (the minimum size at which a resist pattern does not collapse) is required.

[0008] The present invention aims to provide a composition for forming a resist underlayer film that can form a desired resist pattern, and a method for forming a resist pattern using the resist underlayer film forming composition, which solves the above problems. [Means for solving the problem]

[0009] This invention encompasses the following:

[0010] [1] It contains polymers and solvents, The polymer comprises a repeating unit structure including a heterocycle, At least a portion of the repeating unit structure has a basic organic group substituted with a protecting group. Resist underlayer film forming composition.

[0011] [2] It contains polymers and solvents, The polymer comprises a repeating unit structure including a heterocycle, The polymer has a basic organic group substituted with a protecting group at its terminus. Resist underlayer film forming composition.

[0012] [3] The resist underlayer forming composition according to [1] or [2], comprising a heterocycle containing an alkenyl group having 2 to 10 carbon atoms.

[0013] [4] The polymer comprises two or more of the heterocycles, and is a resist underlayer forming composition according to any one of [1] to [3].

[0014] [5] A resist underlayer forming composition according to any one of [1] to [4], wherein the polymer has at least one structural unit represented by the following formula (3) in its main chain.

[0015] [ka] (In formula (3), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group; Q1 represents a divalent organic group containing a heterocycle; and m1 and m2 each independently represent 0 or 1.)

[0016] [6] In formula (3) above, Q1 represents a divalent organic group represented by the following formula (5), the resist underlayer film forming composition according to [5]. [ka] (In formula (5), Y represents a divalent group represented by formula (6) or (7) below.) [ka] (In formulas (6) and (7), R6 and R7 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms, or R6 and R7 may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms bonded to R6 and R7.)

[0017] [7] The resist underlayer forming composition according to [5], wherein in formula (3), Q1 is a divalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms, which may contain a hydroxyl group.

[0018] [8] A resist underlayer forming composition according to any one of [1] to [7], wherein the polymer further comprises disulfide bonds in its main chain.

[0019] [9] The resist underlayer forming composition according to any one of [1] to [8], wherein the basic organic group substituted with the protecting group is an acyloxy group having an amino group substituted with the protecting group, or an acyloxy group having a nitrogen-containing heterocycle substituted with the protecting group.

[0020]

[10] The resist underlayer film forming composition according to [9], wherein the protecting group is selected from the group consisting of a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and an allyloxycarbonyl group.

[0021]

[11] A resist underlayer film forming composition according to any one of [1] to

[10] , further comprising an acid generator.

[0022]

[12] A resist underlayer film forming composition according to any one of [1] to

[11] , further comprising a crosslinking agent.

[0023]

[13] A resist underlayer film characterized by being a fired product of a coated film made from any one of the resist underlayer film forming compositions described in [1] to

[12] .

[0024]

[14] A step of forming a resist underlayer film by applying a resist underlayer film forming composition described in any one of items [1] to

[12] onto a semiconductor substrate and baking it, A step of forming a resist film by coating the resist on the resist underlayer film and baking it. A step of exposing the resist underlayer film and the semiconductor substrate coated with the resist, The process of developing and patterning the resist film after exposure. A method for manufacturing patterned substrates, including [the specified method].

[0025]

[15] A step of forming a resist underlayer on a semiconductor substrate, comprising a resist underlayer forming composition according to any one of items [1] to

[12] , A step of forming a resist film on the resist underlayer film, A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing it, A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, A process of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the following: [Effects of the Invention]

[0026] The resist underlayer film forming composition of the present invention has excellent coatability on semiconductor substrates to be processed and excellent adhesion between the resist and the resist underlayer film interface during resist pattern formation. This prevents peeling of the resist pattern, suppresses deterioration of LWR (Line Width Roughness) during resist pattern formation, enables minimization of the resist pattern size (minimum CD size), improves the limiting resolution, and allows for the formation of a good resist pattern with a rectangular shape. This effect is particularly noticeable when using EUV (wavelength 13.5 nm) or EB (electron beam). [Modes for carrying out the invention]

[0027] <Resist Underlayer Film Forming Composition> The resist underlayer forming composition of the present invention comprises a polymer and a solvent, wherein the polymer comprises a repeating unit structure containing a heterocyclic polymer, and at least a portion of the repeating unit structure has a basic organic group substituted with a protecting group.

[0028] A polymer containing a heterocyclic structure as used in this invention is a polymer that contains a heterocyclic structure within its repeating unit structure. All of the repeating unit structures in the polymer may have basic organic groups substituted with protecting groups, or some of the repeating unit structures in the polymer may have basic organic groups substituted with protecting groups. In this case, the molar ratio of "repeating unit structures having basic organic groups substituted with protecting groups" to "repeating unit structures not having basic organic groups substituted with protecting groups" is not particularly limited, but for example, it is in the range of 1:9 to 9:1, 2:8 to 8:2, 3:7 to 7:3, or 4:6 to 6:4.

[0029] The resist underlayer-forming composition of the present invention may have basic organic groups substituted with protecting groups at the polymer ends containing heterocyclic rings. The resist underlayer-forming composition of the present invention comprises a polymer and a solvent, wherein the polymer contains repeating unit structures containing heterocyclic rings, and the polymer may have basic organic groups substituted with protecting groups at its ends. For example, when the polymer is linear, the polymer may have basic organic groups substituted with protecting groups at both ends, or at only one end. The same applies when the polymer is branched. Repeating unit structures other than those at the ends of the polymer may or may not have basic organic groups substituted with protecting groups.

[0030] <Basic organic groups substituted with protecting groups> The basic organic group referred to in this invention is a monovalent saturated or unsaturated group comprising a carbon atom, a hydrogen atom, and a heteroatom (for example, at least one selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom), which exhibits basicity due to the uneven distribution of electrons in the molecular structure caused by the heteroatom. Preferably, the heteroatom is at least two selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom, or at least one selected from the group consisting of an oxygen atom and a nitrogen atom, and more preferably an oxygen atom and a nitrogen atom. It is preferable that the above organic group is an acyloxy group having an amino group substituted with a protecting group or an acyloxy group having a nitrogen-containing heterocycle substituted with a protecting group.

[0031] The protecting group referred to herein is a group that binds to the above-mentioned amino group or nitrogen-containing heterocycle, preventing changes during a predetermined chemical reaction, but is subsequently removed by predetermined means to restore the original amino group or nitrogen-containing heterocycle. Suitable protecting groups include carbamate protecting groups such as t-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, and allyloxycarbonyl group; sulfonamide protecting groups such as tosyl group and nosyl group; imide protecting groups such as phthaloyl group; and trifluoroacetyl group. For example, if the above-mentioned protecting group is a tert-butoxycarbonyl group, an acyloxy group having an amino group protected by a tert-butoxycarbonyl group or an acyloxy group having a nitrogen-containing heterocycle protected by a tert-butoxycarbonyl group can be represented, for example, by the following formulas (a) to (m). Here, the acyloxy group is represented as "-OC(=O)-R" (where R represents an organic group having an amino group protected by a tert-butoxycarbonyl group or an organic group having a nitrogen-containing heterocycle protected by a tert-butoxycarbonyl group), and the tert-butoxycarbonyl group may be abbreviated as "t-Boc" or "Boc".

[0032] [ka] The protecting group is preferably selected from tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, and allyloxycarbonyl group, but among these, tert-butoxycarbonyl group is preferred.

[0033] Examples of the above heterocycles include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazineone, triazinedione, and triazinetrione.

[0034] Furthermore, the above heterocycle may be a structure derived from a barbituric acid.

[0035] The polymer may contain a heterocycle having 2 to 10 carbon atoms and an alkenyl group.

[0036] The aforementioned alkenyl groups having 2 to 10 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2- Ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group , 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i Examples include the propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group. Among these, the 1-propenyl group is preferred.

[0037] The polymer may contain two or more of the heterocycles.

[0038] The polymer may have at least one structural unit represented by the following formula (3) as described in WO2020 / 226141 in its main chain. [ka] (In formula (3), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group; Q1 represents a divalent organic group containing a heterocycle; and m1 and m2 each independently represent 0 or 1.)

[0039] The aforementioned complex algebra is as described above.

[0040] In formula (3) above, Q1 may represent a divalent organic group represented by the following formula (5). [ka] (In formula (5), Y represents a divalent group represented by formula (6) or formula (7) below.) [ka] (In formulas (6) and (7), R6 and R7 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkoxy group having 1 to 10 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms, or R6 and R7 may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms bonded to R6 and R7.)

[0041] The alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. Group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2 -dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include 3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, 2-ethyl-3-methylcyclopropyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, and icodecyl group.

[0042] The alkoxy groups having 1 to 10 carbon atoms include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentyloxy, 2-methyl-n-pentyloxy, 3-methyl-n-pentyloxy, and 4-methyl-n - Examples include pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, and n-decanyloxy group.

[0043] Examples of alkylthio groups having 1 to 6 carbon atoms include methylthio, ethylthio, propylthio, butylthio, pentylthio, and hexylthio groups.

[0044] Examples of the halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0045] Examples of the ring having 3 to 6 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene, and cyclohexane.

[0046] The full disclosure of WO2020 / 226141 is incorporated herein by reference.

[0047] In formula (3) above, Q1 may be a divalent organic group containing an aromatic ring structure with 6 to 40 carbon atoms, which may also contain a hydroxyl group.

[0048] The aforementioned aromatic ring structures having 6 to 40 carbon atoms are aromatic ring structures derived from benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenalene, phenanthrene, indene, indane, indacene, pyrene, chrysene, perylene, naphthacene, pentacene, coronene, heptacene, benzo[a]anthracene, dibenzophenanthrene, dibenzo[a,j]anthracene, etc.

[0049] The polymer may further contain disulfide bonds in its main chain.

[0050] The weight-average molecular weight of the polymer is, for example, 2,000 to 50,000.

[0051] Examples of monomers that form structural units represented by formula (3) above, where m1 and m2 represent 1, include compounds having two epoxy groups represented by the following formulas (10-a) to (10-k), [ka] Specifically, examples include, but are not limited to, 1,4-terephthalate diglycidyl, 2,6-naphthalenedicarboxylate diglycidyl, 1,6-dihydroxynaphthalenediglycidyl, 1,2-cyclohexanedicarboxylate diglycidyl, 2,2-bis(4-hydroxyphenyl)propane diglycidyl, 2,2-bis(4-hydroxycyclohexane)propane diglycidyl, 1,4-butanediol diglycidyl, monoallyl isocyanurate diglycidyl, monomethyl isocyanurate diglycidyl, 5,5-diethylbarbiturate diglycidyl, and 5,5-dimethylhydantoin diglycidyl.

[0052] Examples of monomers that form a structural unit represented by formula (3) above, in which m1 and m2 are 0, include compounds having two carboxyl groups, hydroxyphenyl groups, or imide groups, represented by the following formulas (11-a) to (11-s), and acid dianhydrides. [ka] Specifically, examples include, but are not limited to, isophthalic acid, 5-hydroxyisophthalic acid, 2,4-dihydroxybenzoic acid, 2,2-bis(4-hydroxyphenyl)sulfone, succinic acid, fumaric acid, tartaric acid, 3,3'-dithiodipropionic acid, 1,4-cyclohexanedicarboxylic acid, cyclobutanoic acid dianhydride, cyclopentanoic acid dianhydride, monoallyl isocyanuric acid, 5,5-diethylbarbituric acid, diglycolic acid, acetonedicarboxylic acid, 2,2'-thiodiglycolic acid, 4-hydroxybenzoic acid-4-hydroxyphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,3-bis(carboxymethyl)-5-methylisocyanurate, and 1,3-bis(carboxymethyl)-5-allyl isocyanurate.

[0053] <Solvent> The solvent used in the resist underlayer film forming composition of the present invention is not particularly limited as long as it is a solvent that can uniformly dissolve solid components such as the polymer at room temperature, but organic solvents commonly used in semiconductor lithography process chemicals are preferred. Specifically, 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, cyclo Examples include heptanone, 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. These solvents can be used individually or in combination of two or more.

[0054] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0055] <Acid Generator> As an optional component in the resist underlayer film forming composition of the present invention, either a thermal acid generator or a photoacid generator can be used, but the use of a thermal acid generator is preferred. 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, and hydroxybenzoic acid.

[0056] Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0057] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0058] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0059] 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.

[0060] The aforementioned acid generating agent can be used by one type only, or by a combination of two or more types.

[0061] When the aforementioned acid generator is used, the content of the acid generator is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass, relative to the crosslinking agent described below.

[0062] <Crosslinking agent> Examples of crosslinking agents that may be included as optional components in the resist underlayer film forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (tetramethoxymethylglycoluryl) (POWDERLINK® 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0063] Furthermore, the crosslinking agent of this application may be a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) that bond to a nitrogen atom in one molecule, as described in International Publication No. 2017 / 187969.

[0064] [ka] (In formula (1d), R1 represents a methyl group or an ethyl group.) A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule may be a glycoluryl derivative represented by the following formula (1E).

[0065] [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.) Examples of glycoluryl derivatives represented by formula (1E) include the compounds represented by the following formulas (1E-1) to (1E-6).

[0066] [ka]

[0067] A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) that bond to a nitrogen atom in one molecule with at least one compound represented by the following formula (3d).

[0068] [ka] (In formulas (2d) and (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.) The glycoluryl derivative represented by formula (1E) is obtained by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by formula (3d).

[0069] A nitrogen-containing compound having 2 to 6 substituents represented by formula (2d) in one molecule is, for example, a glycoluryl derivative represented by the following formula (2E).

[0070] [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.) 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.

[0071] [ka] [ka]

[0072] With regard to nitrogen-containing compounds having 2 to 6 substituents represented by the following formula (1d) bonded to the aforementioned nitrogen atom in one molecule, the full disclosure in WO2017 / 187969 is incorporated herein by reference.

[0073] Furthermore, the above-mentioned crosslinking agent may be a crosslinkable compound represented by the following formula (G-1) or formula (G-2) as described in International Publication No. 2014 / 208542.

[0074] [ka] (where Q 1 represents a single bond or a m1-valent organic group, R 1 and R 4 each represent an alkyl group having 2 to 10 carbon atoms, or an alkyl group having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms, R 2 and R 5 each represent a hydrogen atom or a methyl group, R 3 and R 6 each represent an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms.) n1 represents an integer of 1 ≦ n1 ≦ 3, n2 represents an integer of 2 ≦ n2 ≦ 5, n3 represents an integer of 0 ≦ n3 ≦ 3, n4 represents an integer of 0 ≦ n4 ≦ 3, and 3 ≦ (n1 + n2 + n3 + n4) ≦ 6 represents an integer.) n5 represents an integer of 1 ≦ n5 ≦ 3, n6 represents an integer of 1 ≦ n6 ≦ 4, n7 represents an integer of 0 ≦ n7 ≦ 3, n8 represents an integer of 0 ≦ n8 ≦ 3, and 2 ≦ (n5 + n6 + n7 + n8) ≦ 5 represents an integer.) m1 represents an integer of 2 to 10.)

[0075] The crosslinkable compound represented by the above formula (G-1) or formula (G-2) may be obtained by reacting a compound represented by the following formula (G-3) or formula (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.)

[0076]

Chemical formula

[0077] The compounds represented by formulas (G-1) and (G-2) above can be exemplified as follows.

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083] The compounds represented by formulas (G-3) and (G-4) can be exemplified below.

[0084] [ka]

[0085] [ka] In the formula, Me represents a methyl group.

[0086] The full disclosure of International Publication No. 2014 / 208542 is incorporated herein by reference.

[0087] When the crosslinking agent is used, the content of the crosslinking agent is, for example, 1% to 50% by mass, preferably 5% to 30% by mass, relative to the reaction product.

[0088] <Other ingredients> The resist underlayer film-forming composition of the present invention does not produce pinholes or striations, and a surfactant can be added to further improve the coatability against surface unevenness. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl 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 and polyoxyethylene sorbitan monopalmitate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by Dainippon Ink, Inc., 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 Asahi Glass Co., Ltd., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added 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 may be added individually or in combination of two or more types.

[0089] 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.

[0090] <Underlying resist film> The resist underlayer film according to the present invention can be manufactured by applying the aforementioned resist underlayer film forming composition onto a semiconductor substrate and firing it.

[0091] Examples of semiconductor substrates to which the resist underlayer film forming composition of the present invention is coated include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0092] 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.

[0093] 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.

[0094] The thickness of the resist underlayer film formed 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), or 0.005 μm (5 nm). The thicknesses are as follows: 0.003μm(3nm)~0.03μm(30nm), 0.003μm(3nm)~0.02μm(20nm), 0.005μm(5nm)~0.02μm(20nm), 0.002μm(2nm)~0.01μm(10nm), 0.003μm(3nm)~0.01μm(10nm), 0.002μm(2nm)~0.006μm(6nm), 0.004μm(4nm), and 0.005μm(5nm). If the baking temperature is lower than the above range, crosslinking will be insufficient. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may decompose due to heat.

[0095] <Manufacturing method for patterned substrates, manufacturing method for semiconductor devices> The manufacturing process for patterned substrates involves the following steps. Typically, a photoresist layer is formed on a resist underlayer film. The photoresist formed by coating and firing on the resist underlayer film using a known method is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. Examples include positive 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 V146G from JSR Corporation, APEX-E from Cyprey Corporation, PAR710 from Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 from Shin-Etsu Chemical Co., Ltd. Additionally, examples include fluorine-containing polymer 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).

[0096] 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.

[0097] Examples of resist compositions include the following compositions.

[0098] 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 general formula (21).

[0099] [ka] In general formula (21), m represents an integer from 1 to 6.

[0100] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0101] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0102] L2 represents an alkylene group or single bond which may have substituents.

[0103] W1 represents a cyclic organic group which may have substituents.

[0104] M + This represents a cation.

[0105] 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.

[0106] 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.

[0107] [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 groups are used. 1 They are the same or different. R 2 R 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.)

[0108] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by formula (II), and structural units having acid-unstable groups, and an acid generator.

[0109] [ka] [In formula (II), 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.

[0110] Examples of resist films include the following:

[0111] 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.

[0112] [ka] (In equations (a1) and (a2), R A Each of these is independently either a hydrogen atom or a methyl group. 1 and R 2 Each 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 This 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.)

[0113] Examples of resist materials include the following:

[0114] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0115] [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 ~Rf4 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 5 Each 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.

[0116] A resist material comprising a base resin containing a polymer containing repeating units represented by the following formula (a).

[0117] [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 This 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 (where m is -O-, -O-CH2-, or -NH-; where m is an integer from 1 to 4, and n is an integer from 0 to 3.) 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 resist composition is characterized in that 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).

[0118] [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.

[0119] 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).

[0120] [ka] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. 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.

[0121] Examples of coatings, coating solutions, and coating compositions include the following:

[0122] A coating comprising a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond.

[0123] Inorganic oxo / hydroxyl-based composition.

[0124] A coating solution comprising 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, the first organometallic composition; and a hydrolyzable metal compound represented by the formula MX’ v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X’ is a ligand having a hydrolyzable M-X bond or a combination thereof), the coating solution comprising the hydrolyzable metal compound.

[0125] A coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (where 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, and R is an alkyl group or a 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.

[0126] An inorganic pattern-forming precursor aqueous solution comprising water, a metal oxide cation, a polyatomic inorganic anion, and a mixture with a radiation-sensitive ligand containing a peroxide group.

[0127] Exposure is performed through a mask (reticle) to form a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) lasers are used, but the resist underlayer forming composition of this application is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and more preferably for EUV (extreme ultraviolet) exposure. An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C and the development time from 10 seconds to 300 seconds. As the alkaline developer, for example, aqueous solutions of alkalis such as inorganic alkalis like sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines like ethylamine and n-propylamine; secondary amines like diethylamine and di-n-butylamine; tertiary amines like triethylamine and methyldiethylamine; alcohol amines like dimethylethanolamine and triethanolamine; quaternary ammonium salts like tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines like 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 quaternary ammonium salts, and more preferably 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 to develop the parts of the photoresist where the alkali dissolution rate has not improved. Through the above process, a substrate with the resist patterned can be manufactured.

[0128] Next, the resist underlayer film is dry-etched using the formed resist pattern as a mask. At this time, 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. After that, the substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device. [Examples]

[0129] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0130] The weight-average molecular weights of the polymers shown in the synthesis examples of this specification were obtained by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurements, and the measurement conditions were as follows.

[0131] GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801 [registered trademark] (Showa Denko K.K.) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 1.0ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0132] <Synthesis Example 1> Polymer 1 was synthesized as follows: 5.67 g of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 3.40 g of monoallyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 0.58 g of N-(tert-butoxycarbonyl)-L-glutamic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.35 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 40.0 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 5,500 on a standard polystyrene basis and a dispersion degree of 4.3. The repeating unit structure present in Polymer 1 is shown by the following formula. [ka]

[0133] <Synthesis Example 2> Polymer 2 was synthesized as follows: 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.41 g of diethyl barbituric acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.71 g of N-(tert-butoxycarbonyl)-glutamic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.42 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 20.9 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 6,500 on a standard polystyrene basis and a dispersion degree of 4.1. The repeating unit structure present in Polymer 2 is shown by the following formula. [ka]

[0134] <Synthesis Example 3> Polymer 3 was synthesized as follows: 8.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 5.41 g of diethyl barbituric acid (manufactured by Tokyo Chemical Industries, Ltd.), 0.71 g of N-[(9H-fluoren-9-ylmethoxy)carbonyl]-aspartic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.42 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 20.9 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 6,000 on a standard polystyrene basis and a dispersion degree of 4.5. The repeating unit structure present in Polymer 3 is shown by the following formula. [ka]

[0135] <Synthesis Example 4> Polymer 4 was synthesized as follows: 11.29 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 6.32 g of diethyl barbituric acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.29 g of N-(tert-butoxycarbonyl)-β-alanine (manufactured by Tokyo Chemical Industries, Ltd.), and 0.60 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 21.5 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 4,000 on a standard polystyrene basis and a dispersion degree of 3.7. The repeating unit structure and terminal structure present in polymer 4 are shown in the following formula. [ka] (In the formula, * indicates a binding site with the polymer end.)

[0136] <Synthesis Example 5> Polymer 5 was synthesized as follows: 110.04 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 6.41 g of 3,3'-dithiodipropionic acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.04 g of N-(tert-butoxycarbonyl)-β-alanine (manufactured by Tokyo Chemical Industries, Ltd.), and 0.53 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 20.9 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 4,000 on a standard polystyrene basis and a dispersion degree of 3.7. The repeating unit structure and terminal structure present in polymer 5 are shown in the following formula. [ka] (In the formula, * indicates a binding site with the polymer end.)

[0137] <Synthesis Example 6> Polymer 6 was synthesized as follows: 11.80 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 6.60 g of diethyl barbituric acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.72 g of 4-(tert-butoxycarbonylamino)benzoic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.63 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 23.5 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 4,500 on a standard polystyrene basis and a dispersion degree of 3.9. The repeating unit structure and terminal structure present in polymer 6 are shown in the following formula. [ka] (In the formula, * indicates a binding site with the polymer end.)

[0138] <Synthesis Example 7> Polymer 7 was synthesized as follows: 11.80 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 6.60 g of diethyl barbituric acid (manufactured by Tokyo Chemical Industries, Ltd.), 2.72 g of N-(tert-butoxycarbonyl)-proline (manufactured by Tokyo Chemical Industries, Ltd.), and 0.63 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 23.5 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 4,500 on a standard polystyrene basis and a dispersion degree of 3.9. The repeating unit structure and terminal structure present in polymer 7 are shown in the following formula. [ka] (In the formula, * indicates a binding site with the polymer end.)

[0139] <Synthesis Example 8> Polymer 8 was synthesized as follows: 5.21 g of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemicals, Inc.), 3.12 g of monoallyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 1.35 g of N-[(9H-fluoren-9-ylmethoxy)carbonyl]-alanine (manufactured by Tokyo Chemical Industries, Ltd.), and 0.32 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 40.0 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 4,500 on a standard polystyrene basis and a dispersion degree of 3.9. The repeating unit structure and terminal structure present in polymer 8 are shown in the following formula. [ka] (In the formula, * indicates a binding site with the polymer end.)

[0140] <Synthesis Example 9> Polymer 9 was synthesized as follows: 15.01 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 8.28 g of 5-hydroxyisophthalic acid (manufactured by Tokyo Chemical Industries, Ltd.), 3.03 g of N-(tert-butoxycarbonyl)-β-alanine (manufactured by Tokyo Chemical Industries, Ltd.), and 0.68 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 21.5 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 4,800 on a standard polystyrene basis and a dispersion degree of 3.5. The repeating unit structure and terminal structure present in polymer 9 are shown in the following formula. [ka] (In the formula, * indicates a binding site with the polymer end.)

[0141] <Comparative Synthesis Example 1> Polymer 10 was synthesized as follows: 14.82 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 9.76 g of diethyl barbituric acid (manufactured by Tokyo Chemical Industries, Ltd.), and 0.79 g of ethyl triphenylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 24.63 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 9,000 on a standard polystyrene basis and a dispersion degree of 4.5. The repeating unit structure present in polymer 10 is shown by the following formula. [ka]

[0142] <Comparative Synthesis Example 2> Polymer 11 was synthesized as follows: 25.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 15.86 g of dithiodipropanoic acid (manufactured by Tokyo Chemical Industries, Ltd.), and 1.13 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industries, Ltd.) were dissolved in 57.12 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 6,000 on a standard polystyrene basis and a dispersion degree of 4.3. The repeating unit structure present in polymer 11 is shown by the following formula. [ka]

[0143] (Preparation of the resist underlayer film) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1-9 and Comparative Synthesis Examples 1-2 were mixed in the proportions shown in Table 1, and the mixtures were filtered through a 0.1 μm fluororesin filter to prepare solutions for resist underlayer film formation compositions.

[0144] In Table 1, tetramethoxymethyl glycoluryl (manufactured by Nippon Scitec Industries Co., Ltd.) is abbreviated as PL-LI, pyridinium-p-toluenesulfonic acid as PyPTS, pyridinium-p-hydroxybenzenesulfonic acid as PyPSA, propylene glycol monomethyl ether acetate as PGMEA, and propylene glycol monomethyl ether as PGME. The amount of each additive is shown in parts by mass.

[0145] [Table 1] [Table 2]

[0146] [Elution test into photoresist solvent] The resist underlayer compositions of Examples 1-9, Comparative Example 1, and Comparative Example 2 were coated onto silicon wafers using a spinner. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain films 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 a solvent used for photoresists, to confirm their insolubility in the solvent.

[0147] [Formation of resist patterns by KrF exposure] A KrF exposure anti-reflective coating DUV-30J (manufactured by Nissan Chemical Corporation) was applied to a silicon wafer using a spinner and baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 18 nm. On this film, the resist underlayer formation compositions of Examples 1 to 9 and Comparative Examples 1 to 2 were applied to the silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer with a thickness of 5 nm. SEPR-430 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a positive-type resist solution for KrF excimer lasers was spin-coated onto the resist underlayer and heated at 100°C for 60 seconds to form a KrF resist film. The resist film was exposed to a KrF excimer laser exposure apparatus (Nikon Corporation, NSR S205C) under predetermined conditions. After exposure, the photoresist was subjected to post-exposure baking (PEB) at 110°C for 60 seconds. Then, paddle development was performed for 60 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as the photoresist developer. The resulting photoresist patterns were evaluated as good if no significant pattern peeling occurred.

[0148] [Table 3]

[0149] [Formation of positive resist patterns using an electron beam lithography system] The resist underlayer-forming compositions of Examples 1-10 and Comparative Example 1 were applied to silicon wafers using a spinner. The silicon wafers were baked on a hot plate at 215°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 100°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 110°C for 60 seconds, cooled to room temperature on a cooling plate, developed with an alkaline developer (2.38% TMHA), and then a resist pattern with 20 nm lines / 40 nm pitch was formed. A scanning electron microscope (Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern. In forming the above resist pattern, the exposure amount used to form a 20nm line / 40nm pitch (line and space (L / S=1 / 1)) was considered the optimal exposure amount.

[0150] The photoresist pattern obtained in this way was observed from above, and the minimum line width at which no pattern distortion was observed was expressed as the limiting resolution.

[0151] [Table 4] [Industrial applicability]

[0152] The resist underlayer film forming composition according to the present invention provides a composition for forming a resist underlayer film capable of forming 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. It contains polymers and solvents, The polymer comprises a repeating unit structure including a heterocycle, At least a portion of the repeating unit structure has a basic organic group substituted with a protecting group, A resist underlayer film forming composition wherein the protecting group is selected from the group consisting of a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and an allyloxycarbonyl group.

2. It contains polymers and solvents, The polymer comprises a repeating unit structure including a heterocycle, The polymer has at least one structural unit represented by the following formula (3) in its main chain, 【Chemistry 1】 (In formula (3), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group; Q1 represents a divalent organic group represented by formula (5) below; and m1 and m2 each independently represent 0 or 1.) 【Chemistry 2】 (In formula (5), Y represents a divalent group represented by formula (6) or (7) below.) 【Transformation 3】 (In formulas (6) and (7), R6 and R7 each independently represent a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one selected from the group consisting of a C1-C10 alkyl group, a halogen atom, a C1-C10 alkoxy group, a nitro group, a cyano group, and a C1-C6 alkylthio group, or R6 and R7 may be bonded to each other to form a C3-C6 ring together with the carbon atoms bonded to R6 and R7.) The aforementioned polymer has a basic organic group substituted with a protecting group at its terminus. The protecting group is selected from the group consisting of tert-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, and allyloxycarbonyl group. When the protecting group is a tert-butoxycarbonyl group, an acyloxy group having an amino group protected by a tert-butoxycarbonyl group or an acyloxy group having a nitrogen-containing heterocycle protected by a tert-butoxycarbonyl group is represented by the following formulas (a) to (h) or (j) to (n): Resist underlayer film forming composition. 【Chemistry 4】

3. The resist underlayer forming composition according to claim 1, wherein the polymer has at least one structural unit represented by the following formula (3) in its main chain. 【Transformation 5】 (In formula (3), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, a methyl group, or an ethyl group; Q1 represents a divalent organic group containing a heterocycle; and m1 and m2 each independently represent 0 or 1.)

4. The resist underlayer film forming composition according to claim 3, wherein in formula (3), Q1 represents a divalent organic group represented by the following formula (5). 【Transformation 6】 (In formula (5), Y represents a divalent group represented by formula (6) or (7) below.) 【Transformation 7】 (In formulas (6) and (7), R6 and R7 each independently represent a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a benzyl group, or a phenyl group, and the phenyl group may be substituted with at least one selected from the group consisting of a C1-C10 alkyl group, a halogen atom, a C1-C10 alkoxy group, a nitro group, a cyano group, and a C1-C6 alkylthio group, or R6 and R7 may be bonded to each other to form a C3-C6 ring together with the carbon atoms bonded to R6 and R7.)

5. The resist underlayer forming composition according to claim 1, 3, or 4, wherein the polymer comprises a heterocycle containing an alkenyl group having 2 to 10 carbon atoms.

6. The resist underlayer film forming composition according to claim 1, 3, 4, or 5, wherein the polymer comprises two or more of the heterocycles.

7. The polymer is, in formula (3), Q １ The resist underlayer forming composition according to claim 3, further comprising a structural unit in the main chain which is a divalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms that may contain a hydroxyl group.

8. The resist underlayer forming composition according to any one of claims 1 to 7, wherein the polymer further comprises disulfide bonds in its main chain.

9. The resist underlayer forming composition according to any one of claims 1 to 8, wherein the basic organic group substituted with the protecting group is an acyloxy group having an amino group substituted with the protecting group, or an acyloxy group having a nitrogen-containing heterocycle substituted with the protecting group.

10. The resist underlayer film forming composition according to any one of claims 1 to 9, wherein the basic organic group substituted with the protecting group is an acyloxy group having an amino group substituted with a protecting group selected from the group consisting of a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and an allyloxycarbonyl group, or an acyloxy group having a nitrogen-containing heterocycle substituted with a protecting group selected from the group consisting of a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, a 2,2,2-trichloroethoxycarbonyl group, and an allyloxycarbonyl group.

11. A resist underlayer film forming composition according to any one of claims 1 to 10, further comprising an acid generator.

12. A resist underlayer film forming composition according to any one of claims 1 to 11, further comprising a crosslinking agent.

13. A resist underlayer film characterized by being a fired product of a coated film made from the resist underlayer film forming composition according to any one of claims 1 to 12.

14. A step of forming a resist underlayer film by applying a resist underlayer film forming composition according to any one of claims 1 to 12 onto a semiconductor substrate and baking it, A step of forming a resist film by coating the resist on the resist underlayer film and baking it. A step of exposing the resist underlayer film and the semiconductor substrate coated with the resist, The process of developing and patterning the resist film after exposure. A method for manufacturing patterned substrates, including [the specified method].

15. A step of forming a resist underlayer on a semiconductor substrate, comprising the resist underlayer forming composition according to any one of claims 1 to 12, A step of forming a resist film on the resist underlayer film, A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing it, A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, A process of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the following:

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