Composition for forming resist underlayer film including terminal-blocking polymer

Abstract

The present invention provides a composition for forming a resist underlayer film in which a desired resist pattern can be formed, a method for manufacturing a resist pattern using said composition for forming a resist underlayer film, and a method for manufacturing a semiconductor device. The present invention is a composition for forming a resist underlayer film, the composition including an organic solvent and a polymer, the polymer containing, at the terminal, a non-cyclic aliphatic hydrocarbon group that may be interrupted by a group including a heteroatom and that may be substituted by a substitution group.

Description

Resist underlayer film-forming composition containing end-capping polymer

[0001] The present invention relates to a composition for use in lithography processes in semiconductor manufacturing, particularly in cutting-edge lithography processes (ArF, EUV, EB, etc.), and also to a method for producing a substrate having a resist pattern using the resist underlayer film, and a method for producing a semiconductor device.

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has traditionally been performed. This microfabrication method involves forming a thin film of a photoresist composition on a semiconductor substrate, such as a silicon wafer, irradiating the substrate with actinic rays such as ultraviolet light through a mask pattern bearing a device pattern, developing the thin film, and 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, the integration density of semiconductor devices has increased, 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 use of EUV light (wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. As a result, diffuse reflection of actinic rays from semiconductor substrates and the effects of standing waves have become major problems. To solve this problem, a method of providing an antireflective film (Bottom Anti-Reflective Coating: BARC) between the resist and the semiconductor substrate has been widely studied. Such antireflective films are also called resist underlayer films. As such antireflective films, organic antireflective films made of polymers having light-absorbing moieties have been widely studied due to their ease of use. Patent Document 1 discloses a resist underlayer film-forming composition used in the lithography process of manufacturing a semiconductor device, which comprises a polymer containing a repeating unit structure having a polycyclic aliphatic ring in the main chain of the polymer. Patent Document 2 discloses a resist underlayer film-forming composition for lithography, which comprises a polymer having a specific structure at its terminal.

[0003] JP 2009-093162 A International Publication No. 2013 / 141015 A

[0004] The properties required for a resist underlayer film include, for example, no intermixing with the resist film formed on the upper layer (being insoluble in a resist solvent). In lithography involving EUV exposure, the line width of the formed resist pattern is 32 nm or less, and the resist underlayer film for EUV exposure is formed to a thinner film thickness than conventional films. 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., making it difficult to form a uniform film without defects. Furthermore, if the polymer itself can be given high photocurability, it would be advantageous from the perspectives of resources and the environment, for example, by eliminating the use of a photoacid generator, etc. Furthermore, there is a demand for suppressing deterioration of LWR (Line Width Roughness) during resist pattern formation, forming a resist pattern with a good rectangular shape, and improving resist sensitivity.

[0005] An object of the present invention is to provide a composition for forming a resist underlayer film that can solve the above-mentioned problems and that can form a desired resist pattern, and a method for forming a resist pattern that uses the resist underlayer film-forming composition.

[0006] The present invention includes the following: [1] A resist underlayer film-forming composition comprising an organic solvent and a polymer, wherein the polymer has an acyclic aliphatic hydrocarbon group at a terminal thereof, which may be interrupted by a group containing a heteroatom and which may be substituted with a substituent. [2] The resist underlayer film-forming composition according to [1], wherein the acyclic aliphatic hydrocarbon group is an acyclic aliphatic hydrocarbon group having fewer than 12 carbon atoms. [3] The resist underlayer film-forming composition according to [1] or [2], wherein the acyclic aliphatic hydrocarbon group contains at least one carbon-carbon unsaturated bond. [4] The resist underlayer film-forming composition according to any one of [1] to [3], wherein the group containing a heteroatom is at least one selected from the group consisting of an ether group, a thioether group, a carbonyl group, a thiocarbonyl group, an ester group, a thioester group, a thionoester group, an amide group, a urea group, and an oxysulfonyl group. [5] The resist underlayer film-forming composition according to any one of items [1] to [4], wherein the substituent is at least one selected from the group consisting of a hydroxy group, a carboxy group, and a linear or branched alkyl group, an alkoxy group, or an acyloxy group having 10 or less carbon atoms. [6] The resist underlayer film-forming composition according to any one of items [1] to [5], wherein the polymer has at least one structural unit represented by the following formula (3) in its main chain:

[0007] (In formula (3), A １ , A ２ , A ３ , A ４ , A ５ and A ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q １ represents a divalent organic group, m １ and m ２ each independently represents 0 or 1. [7] In the formula (3), Q １ represents a divalent organic group represented by the following formula (5):

[0008] (In the formula, Y represents a divalent group represented by the following formula (6) or formula (7).)

[0009]

[0010] (In the formula, R ６ and R ７ each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 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 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms, or R ６ and R ７ are bonded to each other to form the R ６ and R ７and the carbon atom bonded thereto may form a ring having 3 to 6 carbon atoms.) [8] The resist underlayer film-forming composition according to any one of items [1] to [7], wherein the polymer further contains a disulfide bond in the main chain. [9] The resist underlayer film-forming composition according to any one of items [1] to [8], further containing a curing catalyst.

[10] The resist underlayer film-forming composition according to any one of items [1] to [9], further containing a crosslinking agent.

[11] A resist underlayer film, which is a baked product of a coating film comprising the resist underlayer film-forming composition according to any one of items [1] to

[10] .

[12] A method for producing a patterned substrate, comprising the steps of: applying the resist underlayer film-forming composition according to any one of items [1] to

[10] onto a semiconductor substrate and baking the composition to form a resist underlayer film; applying a resist onto the resist underlayer film and baking the composition to form a resist film; exposing the resist underlayer film and the semiconductor substrate covered with the resist; and developing and patterning the exposed resist film.

[13] A method for producing a semiconductor device, comprising the steps of: forming a resist underlayer film composed of the resist underlayer film-forming composition according to any one of items [1] to

[10] onto a semiconductor substrate; forming a resist film on the resist underlayer film; irradiating the resist film with light or an electron beam and then developing it to form a resist pattern; etching the resist underlayer film through the formed resist pattern to form a patterned resist underlayer film; and processing a semiconductor substrate using the patterned resist underlayer film.

[0011] The resist underlayer film-forming composition for lithography of the present invention is characterized in that the polymer (also referred to as a polymer) contained in the resist underlayer film-forming composition has, at its terminal, an acyclic aliphatic hydrocarbon group which may be interrupted by a group containing a heteroatom and which may be substituted with a substituent, and is a composition containing such a polymer and an organic solvent, and preferably further a crosslinking agent and / or a compound (curing catalyst) that promotes the crosslinking reaction. By having such a constitution, the resist underlayer film-forming composition for lithography of the present application can achieve the formation of a resist pattern having a good rectangular shape (without pattern collapse), the suppression of deterioration of LWR during resist pattern formation, and the improvement of sensitivity.

[0012] <Resist Underlayer Film Forming Composition> The resist underlayer film forming composition of the present application comprises an organic solvent and a polymer, and the polymer has an acyclic aliphatic hydrocarbon group at its terminal which may be interrupted by a group containing a heteroatom and which may be substituted with a substituent.

[0013] The acyclic aliphatic hydrocarbon group refers to a linear or branched alkyl group, a linear or branched alkenyl group, a linear or branched alkynyl group, or any combination thereof. The number of carbon atoms in the acyclic aliphatic hydrocarbon group is preferably less than 12, more preferably less than 10.

[0014] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, 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- 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 of such groups include a 3-trimethyl-cyclopropyl group, a 1-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-1-methyl-cyclopropyl group, a 2-ethyl-2-methyl-cyclopropyl group, a 2-ethyl-3-methyl-cyclopropyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an icodecyl group.

[0015] Examples of the alkenyl group include 1-propenyl, 2-propenyl, 1-methyl-1-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylethenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-n-propylethenyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 1-methyl-3-butenyl, 2-ethyl-2-propenyl, 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-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-propyl-2-propenyl group Examples of such alkyl groups include cyclopentyl groups, 1-methyl-2-cyclopentenyl groups, 1-methyl-3-cyclopentenyl groups, 2-methyl-1-cyclopentenyl groups, 2-methyl-2-cyclopentenyl groups, 2-methyl-3-cyclopentenyl groups, 2-methyl-4-cyclopentenyl groups, 2-methyl-5-cyclopentenyl groups, 2-methylene-cyclopentyl groups, 3-methyl-1-cyclopentenyl groups, 3-methyl-2-cyclopentenyl groups, 3-methyl-3-cyclopentenyl groups, 3-methyl-4-cyclopentenyl groups, 3-methyl-5-cyclopentenyl groups, 3-methylene-cyclopentyl groups, 1-cyclohexenyl groups, 2-cyclohexenyl groups, and 3-cyclohexenyl groups.

[0016] Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, and a 2-propynyl group.

[0017] The heteroatom is not particularly limited, but is usually an oxygen atom, a sulfur atom, or a nitrogen atom.

[0018] Examples of the group containing a hetero atom include an ether group, a thioether group, a carbonyl group, a thiocarbonyl group, an ester group, a thioester group, a thionoester group, an amide group, a urea group, and an oxysulfonyl group.

[0019] The phrase "optionally interrupted by a group containing a hetero atom" means that the acyclic aliphatic hydrocarbon group according to the present application may contain, between its carbon-carbon bonds, one or more ether bonds, thioether bonds, carbonyl bonds, thiocarbonyl bonds, ester bonds, thioester bonds, thionoester bonds, amide bonds, urea bonds, oxysulfonyl bonds, etc. When two or more bonds are contained, the type of bond may be one or two or more.

[0020] Some specific examples of groups containing a heteroatom that interrupts an acyclic aliphatic hydrocarbon group include the following formulae: wherein * represents a bond.

[0021] The phrase "optionally substituted with a substituent" means that all or part of the hydrogen atoms of the acyclic aliphatic hydrocarbon group according to the present application may be substituted with at least one substituent selected from the group consisting of, for example, a hydroxy group, a linear or branched alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, and a carboxy group.

[0022] The alkyl group is as described above.

[0023] Examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n-pentyloxy group, a 1,1-dimethyl-n-butoxy group, a 1,2-dimethyl Examples of the alkyl group include a cyclohexyloxy group, a cyclopentyloxy group, ...

[0024] The acyloxy group is represented by the following formula (20):

[0025] (in formula (20), Z represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms among the above alkyl groups, and * represents the bonding site to the above non-cyclic aliphatic hydrocarbon group).

[0026] Acyclic aliphatic hydrocarbon groups containing a heteroatom and having less than 12 carbon atoms are preferred, acyclic aliphatic hydrocarbon groups containing an oxygen atom and having less than 12 carbon atoms are more preferred, acyclic aliphatic hydrocarbon groups containing less than 12 carbon atoms and interrupted by at least two groups selected from the group consisting of ether groups, carbonyl groups, and ester groups are even more preferred, and acyclic aliphatic hydrocarbon groups containing less than 12 carbon atoms and interrupted by ether groups and ester groups are most preferred.

[0027] The acyclic aliphatic hydrocarbon group preferably has at least one unsaturated bond (e.g., a double bond or a triple bond). The acyclic aliphatic hydrocarbon group preferably has 1 to 3 unsaturated bonds. The unsaturated bond is preferably a double bond.

[0028] The "acyclic aliphatic hydrocarbon group which may be interrupted by a group containing a hetero atom and which may be substituted with a substituent" can be derived by reacting a saturated or unsaturated dicarboxylic acid anhydride such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, methylmaleic acid, ethylmaleic acid, dimethylmaleic acid, or citraconic acid with the terminal of a polymer by a method known per se.

[0029] The polymer preferably has at least one structural unit represented by the following formula (3) in the main chain:

[0030]

[0031] (In formula (3), A １ , A ２ , A ３ , A ４ , A ５ and A ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q １ represents a divalent organic group, m １ and m ２ Each independently represents 0 or 1. In the formula (3), Q １ preferably represents a divalent organic group represented by the following formula (5).

[0032]

[0033] (In the formula, Y represents a divalent group represented by the following formula (6) or formula (7).)

[0034]

[0035] (In the formula, R ６ and R ７each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 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 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, and an alkylthio group having 1 to 6 carbon atoms, or R ６ and R ７ are bonded to each other to form the R ６ and R ７ may form a ring having 3 to 6 carbon atoms together with the carbon atom bonded to

[0036] The alkyl group, alkenyl group, and alkoxy group are as described above.

[0037] "Halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0038] Examples of the "ring having 3 to 6 carbon atoms" include cyclopropane, cyclobutane, cyclopentane, cyclopentadiene, and cyclohexane.

[0039] Examples of the "alkylthio group having 1 to 6 carbon atoms" include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, and a hexylthio group.

[0040] It is preferable that the polymer further contains a disulfide bond in the main chain.

[0041] The polymer preferably contains an arylene group having 6 to 40 carbon atoms which may be substituted with a substituent, the meaning of which is the same as described above.

[0042] Examples of the "arylene group having 6 to 40 carbon atoms" include a phenylene group, an o-methylphenylene group, an m-methylphenylene group, a p-methylphenylene group, an o-chlorophenylene group, an m-chlorophenylene group, a p-chlorophenylene group, an o-fluorophenylene group, a p-fluorophenylene group, an o-methoxyphenylene group, a p-methoxyphenylene group, a p-nitrophenylene group, a p-cyanophenylene group, an α-naphthylene group, a β-naphthylene group, an o-biphenylylene group, an m-biphenylylene group, a p-biphenylylene group, a 1-anthrylene group, a 2-anthrylene group, a 9-anthrylene group, a 1-phenanthrylene group, a 2-phenanthrylene group, a 3-phenanthrylene group, a 4-phenanthrylene group, and a 9-phenanthrylene group.

[0043] The weight average molecular weight of the polymer is, for example, 2,000 to 50,000.

[0044] Represented by the formula (3), m １ and m ２ Examples of the monomer forming the structural unit in which R represents 1 include compounds having two epoxy groups represented by the following formulas (10-a) to (10-k):

[0045]

[0046] Examples include, but are not limited to, 1,4-terephthalic acid 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.

[0047] Represented by the formula (3), m １ and m ２Examples of the monomer forming the structural unit represented by 0 include compounds having two carboxyl groups, hydroxyphenyl groups or imide groups, and acid dianhydrides, which are represented by the following formulas (11-a) to (11-s):

[0048]

[0049] That is, 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 dianhydride, cyclopentanoic dianhydride, monoallyl isocyanuric acid, 5,5-diethylbarbituric acid, diglycolic acid, acetonedicarboxylic acid, 2,2'-thiodiglycolic acid, 4-hydroxybenzoate-4-hydroxyphenyl, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 1,3-bis(carboxymethyl)-5-methylisocyanurate, 1,3-bis(carboxymethyl)-5-allyl isocyanurate, but are not limited to these examples.

[0050] Furthermore, examples of the monomer forming the structural unit represented by formula (3) in which m1 and m2 are 0 include those represented by the following formula (11): (In formula (11), Y １ represents a single bond, an oxygen atom, a sulfur atom, an alkylene group having 1 to 10 carbon atoms which may be substituted with a halogen atom or an aryl group having 6 to 40 carbon atoms, or a sulfonyl group; T １ and T ２represents an alkyl group having 1 to 10 carbon atoms, and n1 and n2 each independently represent an integer of 0 to 4. The alkyl group is as described above. Examples of the aryl group include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, and a 9-phenanthryl group. Examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, a cyclopropylene group, an n-butylene group, an isobutylene group, an s-butylene group, a t-butylene group, a cyclobutylene group, a 1-methylcyclopropylene group, a 2-methylcyclopropylene group, an n-pentylene group, a 1-methyln-butylene group, a 2-methyln-butylene group, a 3-methyln-butylene group, a 1,1-dimethyln-propylene group, a 1,2-dimethyln-propylene group, a 2,2-dimethyln-propylene group, a 1-ethyln-propylene group, a cyclopentylene group, a 1-methylcyclobutylene group, a 2-methylcyclobutylene group, a 3-methylcyclobutylene group, cyclopropylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1 Examples of Y include an n-propyl-cyclopropylene group, a 2-n-propyl-cyclopropylene group, a 1-isopropyl-cyclopropylene group, a 2-isopropyl-cyclopropylene group, a 1,2,2-trimethyl-cyclopropylene group, a 1,2,3-trimethyl-cyclopropylene group, a 2,2,3-trimethyl-cyclopropylene group, a 1-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-1-methyl-cyclopropylene group, a 2-ethyl-2-methyl-cyclopropylene group, a 2-ethyl-3-methyl-cyclopropylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, and an n-decanylene group. １ is preferably a sulfonyl group.

[0051] m represented by the formula (3) １ and m ２ a monomer (bifunctional) forming a structural unit represented by the formula (3), １ and m ２The copolymerization ratio (feed weight ratio) of the monomer (bifunctional) forming the structural unit represented by formula (3) is, for example, 1:2 to 2:1. Furthermore, the feed weight ratio of the monomer (monofunctional at the site that primarily reacts with the polymer) for deriving the acyclic aliphatic hydrocarbon group bonded to the polymer terminal of the present application to the total of the above-mentioned monomers is, for example, 20:1 to 5:1. The term "functionality" refers to a concept that focuses on the chemical attributes and chemical reactivity of a substance. While functional groups are assumed to have their own unique physical properties and chemical reactivity, in the present application, they refer to reactive substituents that can bond with other compounds. The repeating number of the structural unit represented by formula (3) is, for example, in the range of 5 to 10,000.

[0052] Examples of the organic solvent contained in the resist underlayer film forming composition of the present invention include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cyclopentanone. Examples of suitable solvents include cyclohexane, 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. These solvents can be used alone or in combination of two or more. 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. The ratio of the organic solvent to the resist underlayer film-forming composition of the present invention is, for example, 50% by mass or more and 99.9% by mass or less. The content of the polymer contained in the resist underlayer film-forming composition of the present invention is, for example, 0.1% by mass to 50% by mass relative to the resist underlayer film-forming composition.

[0053] The resist underlayer film-forming composition of the present invention may contain, in addition to the polymer and organic solvent, a crosslinking agent and a crosslinking catalyst (curing catalyst), which is a compound that promotes a crosslinking reaction. When the components excluding the organic solvent from the resist underlayer film-forming composition of the present invention are defined as the solid content, the solid content includes the polymer and additives, such as the crosslinking agent and crosslinking catalyst, that are added as needed. The proportion of the additives is, for example, 0.1% by mass to 50% by mass, preferably 1% by mass to 30% by mass, relative to the solid content of the resist underlayer film-forming composition of the present invention.

[0054] Examples of crosslinking agents that may be contained as an optional component in the resist underlayer film-forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (tetramethoxymethylglycoluril) (POWDERLINK (registered trademark) 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, and 3,3',5,5'-tetrakis(methoxymethyl)4,4'-biphenol.

[0055] The crosslinking agent of the present application may also be a nitrogen-containing compound having, per molecule, 2 to 6 substituents bonded to nitrogen atoms and represented by the following formula (1d), as described in WO 2017 / 187969:

[0056] (In formula (1d), R １ represents a methyl group or an ethyl group.

[0057] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule may be a glycoluril derivative represented by the following formula (1E).

[0058] (In formula (1E), four R １ each independently represents a methyl group or an ethyl group, R ２ and R ３each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.

[0059] Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0060]

[0061] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents bonded to a nitrogen atom in one molecule, represented by the following formula (2d), with at least one compound represented by the following formula (3d):

[0062] (In formula (3d), R １ represents a methyl group or an ethyl group, and in formula (2d), R ４ represents an alkyl group having 1 to 4 carbon atoms.

[0063] The glycoluril derivative represented by the formula (1E) can be obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the formula (3d).

[0064] The nitrogen-containing compound having 2 to 6 substituents represented by the formula (2d) in one molecule is, for example, a glycoluril derivative represented by the following formula (2E).

[0065] (In formula (2E), R ２ and R ３ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group; R ４ each independently represents an alkyl group having 1 to 4 carbon atoms.

[0066] Examples of glycoluril derivatives represented by formula (2E) include compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include compounds represented by formulas (3d-1) and (3d-2) below.

[0067]

[0068] The entire disclosure of WO 2017 / 187969 is incorporated herein by reference with respect to the content of the nitrogen-containing compound having, per molecule, 2 to 6 substituents bonded to the nitrogen atom and represented by the following formula (1d):

[0069] The crosslinking agent may be a crosslinkable compound represented by the following formula (G-1) or formula (G-2), which is described in WO 2014 / 208542.

[0070] (In the formula, Q １ represents a single bond or m represents a monovalent organic group, and R １ and R ４ each represents an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms and an alkoxy group having 1 to 10 carbon atoms; R ２ and R ５ each represents a hydrogen atom or a methyl group, and R ３ and R ６ respectively 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, or an integer of 3≦(n1+n2+n3+n4)≦6. 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, or an integer of 2≦(n5+n6+n7+n8)≦5. m1 represents an integer of 2 to 10.

[0071] 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.

[0072] (In the formula, Q ２ represents a single bond or a divalent organic group. ８ , R ９ , R １１ and R １２ each represents a hydrogen atom or a methyl group, and R ７ and R１０ respectively represent an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n9 represents an integer of 1≦n9≦3, n10 represents an integer of 2≦n10≦5, n11 represents an integer of 0≦n11≦3, n12 represents an integer of 0≦n12≦3, or an integer of 3≦(n9+n10+n11+n12)≦6. n13 represents an integer of 1≦n13≦3, n14 represents an integer of 1≦n14≦4, n15 represents an integer of 0≦n15≦3, n16 represents an integer of 0≦n16≦3, or an integer of 2≦(n13+n14+n15+n16)≦5. m2 represents an integer of 2 to 10.

[0073] Examples of the compounds represented by the above formula (G-1) and formula (G-2) include the following.

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] Examples of the compounds represented by formula (G-3) and formula (G-4) are as follows.

[0080]

[0081] In the formula, Me represents a methyl group.

[0082] The entire disclosure of WO 2014 / 208542 is incorporated herein by reference. When the crosslinking agent is used, the content of the crosslinking agent is, for example, 1% by mass to 50% by mass, and preferably 5% by mass to 30% by mass, relative to the polymer.

[0083] Examples of the curing catalyst (crosslinking catalyst) that may be included as an optional component in the resist underlayer film-forming composition of the present invention include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonate (pyridinium p-toluenesulfonic acid), pyridinium p-hydroxybenzenesulfonic acid, pyridinium trifluoromethanesulfonic acid, cyclohexyl p-toluenesulfonate, morpholine, p-toluenesulfonate, 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. When the above-mentioned crosslinking catalyst is used, the content of the crosslinking catalyst is, for example, 0.1% by mass to 50% by mass, and preferably 1% by mass to 30% by mass, relative to the crosslinking agent.

[0084] The resist underlayer film-forming composition of the present invention can further contain a surfactant in order to prevent pinholes, striations, etc., and further improve coating properties against surface irregularities. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl 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, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and the like. nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as Eftop EF301, EF303, and EF352 (trade names, manufactured by Tochem Products Co., Ltd.), Megafac F171, F173, and R-30 (trade names, manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430 and FC431 (trade names, manufactured by Sumitomo 3M Limited), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (trade names, manufactured by Asahi Glass Co., Ltd.); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants to be added is usually 2.0 mass % or less, and preferably 1.0 mass % or less, based on the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added alone or in combination of two or more.

[0085] <Resist Underlayer Film> The resist underlayer film according to the present invention can be produced by applying the resist underlayer film-forming composition described above to a semiconductor substrate and baking the applied composition. Examples of semiconductor substrates onto which the resist underlayer film-forming composition of the present invention can be applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride. When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film can be formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon films, silicon oxide films, silicon nitride films, BPSG (boro-phosphosilicate glass) films, titanium nitride films, titanium nitride oxide films, tungsten films, gallium nitride films, and gallium arsenide films. The resist underlayer film-forming composition of the present invention is applied to such a semiconductor substrate by a suitable application method such as a spinner or coater. The composition is then baked using a heating means such as a hot plate to form a resist underlayer film. The baking conditions are appropriately selected from a baking temperature of 100°C to 400°C and a baking time of 0.3 to 60 minutes. Preferably, the baking temperature is 120°C to 350°C and the baking time is 0.5 to 30 minutes, and more preferably, the baking temperature is 150°C to 300°C and the baking time is 0.8 to 10 minutes.The thickness of the resist underlayer film to be formed may 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 (5 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.03 μm (30 nm), 0.003 μm (3 nm) to 0.02 μm (20 nm), 0.005 μm (5 nm) to 0.02 μm (20 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.005 μm (5 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.006 μm (6 nm), 0.005 μm (5 nm). If the baking temperature is lower than the above range, crosslinking may be insufficient. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may be decomposed by heat.

[0086] <Method for Manufacturing Patterned Substrate, Method for Manufacturing Semiconductor Device> A patterned substrate is manufactured through the following steps. Typically, a photoresist layer is formed on a resist underlayer film. The photoresist formed on the resist underlayer film by coating and baking using a method known per se 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 of suitable photoresists include positive photoresists composed of a novolak resin and a 1,2-naphthoquinone diazide sulfonic acid ester; chemically amplified photoresists composed of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator; chemically amplified photoresists composed of a binder having a group that decomposes in an acid to increase the alkaline dissolution rate, a low-molecular-weight compound that decomposes in an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and resists containing metal elements. Examples of such photoresists include V146G (trade name) manufactured by JSR Corporation, APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 (trade names) manufactured by Shin-Etsu Chemical Co., Ltd. Further 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).

[0087] Further 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). Metal-containing resists (metal resists) may also be used.Specific examples include 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, W WO2019 / 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 2019-1173 73, 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 2010-1 81857, 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. Resist compositions described in, for example, radiation-sensitive resin compositions, high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

[0088] Examples of resist compositions include the following: An actinic ray-sensitive or radiation-sensitive resin composition containing a resin A having a repeating unit having an acid-decomposable group in which a polar group is protected with a protecting group that is cleaved by the action of an acid, and a compound represented by general formula (1):

[0089] In the general formula (1), m represents an integer of 1 to 6.

[0090] R １ and R ２ each independently represents a fluorine atom or a perfluoroalkyl group.

[0091] L １ is -O-, -S-, -COO-, -SO ２ - or -SO ３ Represents -.

[0092] L ２ represents an alkylene group which may have a substituent or a single bond.

[0093] W １ represents a cyclic organic group which may have a substituent.

[0094] M ＋ represents a cation.

[0095] 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 Periods 3 to 7 of Groups 3 to 15 of the periodic table.

[0096] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2) containing an acid-dissociable group, and an acid generator:

[0097] (In formula (1), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. R １ is a hydroxy group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer of 0 to 11. When n is 2 or more, multiple R １ are the same or different. ２is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0098] In formula (2), R ３ is a monovalent group having 1 to 20 carbon atoms and containing the above acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R ４ is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0099] A resist composition comprising: a resin (A1) containing a structural unit having a cyclic carbonate structure, a structural unit represented by formula (II), and a structural unit having an acid labile group; and an acid generator.

[0100] [In formula (II), R ２ represents an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, a hydrogen atom or a halogen atom; X １ represents a single bond, —CO—O—*, or —CO—NR ４ -*, * represents a bond to -Ar, 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 a hydroxy group and a carboxyl group.] A resist composition that generates an acid upon exposure, and whose solubility in a developer changes due to the action of the acid, comprising: a base component (A) whose solubility in a developer changes due to the action of the acid, and a fluorine additive component (F) that exhibits decomposition in an alkaline developer, wherein the fluorine additive component (F) contains a fluororesin component (F1) that has a structural unit (f1) that contains a base dissociable group, and a structural unit (f2) that contains a group represented by the following general formula (f2-r-1):

[0101] [In formula (f2-r-1), Rf ２１ are each independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group; n" is an integer of 0 to 2; * is a bond.

[0102] The resist composition, wherein the structural unit (f1) includes a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2):

[0103] [In formulas (f1-1) and (f1-2), each R independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X represents a divalent linking group that does not have an acid-dissociable site. A ａｒｙｌ represents a divalent aromatic cyclic group which may have a substituent. ０１ is a single bond or a divalent linking group. ２ are each independently an organic group having a fluorine atom.

[0104] Examples of resist materials include the following:

[0105] A resist material comprising a polymer having a repeating unit represented by the following formula (a1) or (a2):

[0106] (In formulas (a1) and (a2), R Ａ is a hydrogen atom or a methyl group. １ is a single bond or an ester group. ２ 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 some 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 contained in X is substituted with 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 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. １ and Rf ２ may combine to form a carbonyl group. １ ~R５ are each 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, in which some or all of the hydrogen atoms may be substituted with a hydroxy group, a carboxy 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 in which 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 sulfonate ester group. １ and R ２ may be bonded to form a ring together with the sulfur atom to which they are attached.

[0107] A resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a):

[0108] (In formula (a), R Ａ is a hydrogen atom or a methyl group. １ is a hydrogen atom or an acid labile group. ２ is a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. １ X is a single bond, a phenylene group, or a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms which may contain an ester group or a lactone ring. ２ is -O-, -O-CH ２ - or -NH-. m is an integer of 1 to 4. n is an integer of 0 to 3.

[0109] Examples of the resist film include the following.

[0110] (i) A resist film comprising a base resin containing a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to the polymer main chain upon exposure:

[0111] (In formulas (a1) and (a2), R Ａ are each independently a hydrogen atom or a methyl group. １ and R ２ are each independently a tertiary alkyl group having 4 to 6 carbon atoms. ３ are each independently a fluorine atom or a methyl group, and m is an integer of 0 to 4. １ X is a single bond, a phenylene group, or a naphthylene group, or a linking group having 1 to 12 carbon atoms and containing at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. ２ is a single bond, an ester bond, or an amide bond.

[0112] Examples of coating solutions include:

[0113] Metal-containing resist compositions include, for example, coatings containing metal oxo-hydroxo networks with organic ligands through metal carbon bonds and / or metal carboxylate bonds.

[0114] Inorganic oxo / hydroxo-based compositions.

[0115] a coating solution comprising an organic solvent; a first organometallic composition having the formula R ｚ SnO （２－（ｚ／２）－（ｘ／２）） (OH) ｘ (where 0<z≦2 and 0<(z+x)≦4), formula R′ ｎ SnX ４－ｎ wherein n=1 or 2, or mixtures 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; and a hydrolyzable metal compound having the formula MX′ ｖ wherein M is a metal selected from groups 2 to 16 of the periodic table of the elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof.

[0116] an organic solvent and a solution of the formula RSnO（３／２－ｘ／２） (OH) ｘ and a first organometallic compound of the formula: wherein 0<x<3, wherein the solution contains from about 0.0025M to about 1.5M tin, and R is an alkyl or cycloalkyl group having from 3 to 31 carbon atoms, the alkyl or cycloalkyl group being bonded to the tin at a secondary or tertiary carbon atom.

[0117] An aqueous inorganic patterning precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and radiation-sensitive ligands comprising peroxide groups.

[0118] The exposure / irradiation is carried out through a mask (reticle) for forming a predetermined pattern, and for example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used, but the resist underlayer film-forming composition of the present application is preferably applied for EB (electron beam) irradiation and EUV (extreme ultraviolet) exposure. An alkaline developer is used for development, and the development temperature is appropriately selected from the range of 5°C to 50°C, and the development time is appropriately selected from the range of 10 seconds to 300 seconds. Examples of alkaline developers include 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. Furthermore, aqueous solutions of the above alkalis can be used by adding an appropriate amount of alcohols such as isopropyl alcohol or a nonionic surfactant. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of using an alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate to develop portions of the photoresist where the alkaline dissolution rate is not improved. Through the above steps, a substrate having the resist patterned thereon can be produced.

[0119] 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, and if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Thereafter, the substrate is processed by a method known per se (e.g., dry etching), thereby manufacturing a semiconductor device.

[0120] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these. The weight-average molecular weights of the polymers shown in Synthesis Examples 1 to 4 and Comparative Synthesis Example 1 below in this specification are the results of measurements by gel permeation chromatography (hereinafter abbreviated as GPC). A GPC device manufactured by Tosoh Corporation was used for the measurements, and the measurement conditions are as follows:

[0121] GPC column: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko K.K.) Column temperature: 40°C Solvent: N,N-dimethylformamide (DMF) Flow rate: 0.6 ml / min Standard sample: polystyrene (manufactured by Tosoh Corporation)

[0122] Synthesis Example 1 To prepare Polymer 1, 6.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 3.36 g of diethyl barbital (manufactured by Yatsushiro Pharmaceutical Co., Ltd.), 0.72 g of citraconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.19 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.55 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved in 32.44 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 4,900 and a polydispersity of 3.0, calculated as standard polystyrene. The structure present in Polymer 1 is shown in the following formula.

[0123]

[0124] Synthesis Example 2 To prepare Polymer 2, 6.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 3.36 g of diethyl barbital (manufactured by Yatsushiro Pharmaceutical Co., Ltd.), 0.63 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.19 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.55 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved in 32.17 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 5,500 and a polydispersity of 3.0, calculated as standard polystyrene. The structure present in Polymer 2 is shown in the following formula.

[0125]

[0126] Synthesis Example 3 To prepare Polymer 3, 6.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 5.59 g of bis(4-hydroxy-3,5-dimethylphenyl)sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.72 g of citraconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.19 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.55 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved in 39.13 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 7,900 and a polydispersity of 3.2, calculated as standard polystyrene. The structure present in Polymer 3 is shown in the following formula.

[0127]

[0128] Synthesis Example 4 To prepare Polymer 4, 6.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 5.59 g of bis(4-hydroxy-3,5-dimethylphenyl)sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.63 g of maleic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.19 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.55 g of tetrabutylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved in 38.86 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 7,600 and a polydispersity of 4.4, calculated as standard polystyrene. The structure present in Polymer 4 is shown in the following formula.

[0129]

[0130] Comparative Synthesis Example 1 To prepare polymer 5, 10.00 g of N,N-diglycidyl-5,5-dimethylhydantoin (manufactured by Shikoku Chemical Industry Co., Ltd.), 3.04 g of monoallyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), and 0.63 g of 7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and dissolved in 14.41 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer solution. GPC analysis showed that the resulting polymer had a weight average molecular weight of 3,200 and a polydispersity of 1.6, calculated as standard polystyrene. The structure present in polymer 5 is shown in the following formula.

[0131]

[0132] (Preparation of Resist Underlayer Film) (Examples and Comparative Examples) The polymers obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Example 1 above, crosslinking agents, curing catalysts, surfactants, and solvents were mixed in the proportions shown in Table 1, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare solutions of compositions for forming resist underlayer films. In Tables 1 and 2, tetramethoxymethyl glycoluril (manufactured by Nippon Cytec Industries Co., Ltd.) is abbreviated as PL-LI, imidazo[4,5-d]imidazole-2,5(1H,3H)-dione,tetrahydro-1,3,4,6-tetrakis[(2-methoxy-1-methylethoxy)methyl]- is abbreviated as PGME-PL, pyridinium-p-hydroxybenzenesulfonic acid is abbreviated as PyPSA, surfactant is abbreviated as R-30N, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, and propylene glycol monomethyl ether is abbreviated as PGME. The amounts of each additive are shown in parts by mass.

[0133]

[0134]

[0135] (Elution test into photoresist solvent) The resist underlayer film-forming compositions of Examples 1 to 4 and Comparative Example 1 were applied 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 in photoresists. A change in film thickness of 1 Å or less was rated as good, and a change in film thickness of 1 Å or more was rated as bad. The results are shown in Table 3.

[0136] (Film-Forming Property Test) The resist underlayer film-forming compositions of Examples 1 to 4 and Comparative Example 1 were applied 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. The surface roughness (Sa) of these resist underlayer films was measured using an atomic force microscope (AFM). Coatability was rated as good when it was 3 Å or less, and poor when it was 3 Å or more, and the results are shown in Table 3.

[0137]

[0138] (Evaluation of Photocrosslinkability of Polymer) The polymers of Synthesis Examples 1 to 4 and Comparative Synthesis Example 1 were applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a polymer monolayer film with a thickness of 50 nm. The film was then irradiated with light using a 172 nm light irradiation device (manufactured by Ushio Inc.). The film was immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30, which is a solvent used in photoresists, and the remaining film thickness was measured to calculate the remaining film ratio. The results are shown in Table 4.

[0139]

[0140] (Resist Patterning Evaluation) [Resist Pattern Formation Test Using Electron Beam Lithography Apparatus] Each resist underlayer film-forming composition was applied to a 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 film with a film thickness of 5 nm. An EUV positive resist solution was spin-coated onto the resist underlayer film and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed under specified conditions using an electron beam lithography apparatus (ELS-G130). After exposure, the resist film was baked at 90°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and then puddle developed for 30 seconds using a 2.38% aqueous solution of tetramethylammonium hydroxide (manufactured by Tokyo Ohka Kogyo Co., Ltd., product name NMD-3) as a photoresist developer. Resist patterns with line sizes of 15 nm to 27 nm were formed. A scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation) was used to measure the resist pattern. The photoresist patterns thus obtained were examined to determine whether or not 22 nm lines and spaces (L / S) could be formed. Formation of a 22 nm L / S pattern was confirmed in all cases of Examples 1 to 4 and Comparative Example 1. The amount of charge required to form a 22 nm line / 44 nm pitch (line and space (L / S = 1 / 1)) was defined as the optimal irradiation energy, and the irradiation energy (μC / cm ２) and pattern line width roughness (LWR) are shown in Table 5.

[0141]

[0142] The resist underlayer film-forming composition for lithography of the present invention is characterized in that the polymer (also referred to as a polymer) contained in the resist underlayer film-forming composition has, at its terminal, an acyclic aliphatic hydrocarbon group which may be interrupted by a group containing a heteroatom and which may be substituted with a substituent, and is a composition containing such a polymer and an organic solvent, and preferably further a crosslinking agent and / or a compound (curing catalyst) that promotes the crosslinking reaction. By having such a constitution, the resist underlayer film-forming composition for lithography of the present application can achieve the formation of a resist pattern having a good rectangular shape (without pattern collapse), the suppression of deterioration of LWR during resist pattern formation, and the improvement of sensitivity.

Claims

1. It contains organic solvents and polymers, The polymer may have a cyclic aliphatic hydrocarbon group at its terminus that is interrupted by a group containing a heteroatom and may be substituted with a substituent. Resist underlayer film forming composition.

2. The resist underlayer film forming composition according to claim 1, wherein the acyclic aliphatic hydrocarbon group is an acyclic aliphatic hydrocarbon group having less than 12 carbon atoms.

3. The resist underlayer forming composition according to claim 1, wherein the acyclic aliphatic hydrocarbon group comprises at least one carbon-carbon unsaturated bond.

4. The resist underlayer film forming composition according to claim 1, wherein the group containing the heteroatom is at least one selected from the group consisting of an ether group, a thioether group, a carbonyl group, a thiocarbonyl group, an ester group, a thioester group, a thionoester group, an amide group, a urea group, and an oxysulfonyl group.

5. The resist underlayer film forming composition according to claim 1, wherein the substituent is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and a linear or branched alkyl group, alkoxy group, or acyloxy group having 10 or fewer carbon atoms.

6. 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. 【Chemistry 41】 (In formula (3), A １ , A ２ , A ３ , A ４ , A ５ , and A ６ each independently represents a hydrogen atom, a methyl group, or an ethyl group, Q １ represents a divalent organic group, and m １ and m ２ each independently represents 0 or 1.)

7. In the above formula (3), Q １ The resist underlayer film forming composition according to claim 6, wherein is a divalent organic group represented by the following formula (5). 【Chemistry 42】 (In the formula, Y represents a divalent group represented by formula (6) or formula (7) below.) 【Chemistry 43】 (In the formula, R ６ and R ７ Each of these independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 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 alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, and alkylthio groups having 1 to 6 carbon atoms, or R ６ and R ７ They are joined together, and the R ６ and R ７ (It may also form a ring with 3 to 6 carbon atoms together with the bonded carbon atom.)

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

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

10. 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 9.

11. A method for manufacturing a patterned substrate, comprising the steps of: applying a resist underlayer forming composition according to any one of claims 1 to 9 onto a semiconductor substrate and baking it to form a resist underlayer; applying a resist onto the resist underlayer and baking it to form a resist film; exposing the semiconductor substrate covered with the resist underlayer and the resist; and developing and patterning the resist film after exposure.

12. A step of forming a resist underlayer film on a semiconductor substrate, comprising the resist underlayer film forming composition according to any one of claims 1 to 9, 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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