Resist underlayer film-forming composition containing reaction product of acid dianhydride

Abstract

The present invention provides: a composition for forming a resist underlayer film that enables the formation of a desired resist pattern; and a method for producing a resist pattern and a method for producing a semiconductor device, each of which uses said composition for forming a resist underlayer film. Provided is a resist underlayer film-forming composition including a solvent and a polymer having a unit structure represented by formula (I): (in formula (I), 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, R1 represents a tetravalent organic group including a C6-40 aromatic ring structure, and L1 and L2 each independently represent a hydrogen atom or a C1-10 alkyl group optionally substituted by a hydroxy group and optionally interrupted by an oxygen atom).

Description

[Technical Field]

[0001] The present invention relates to a composition used 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 with a resist pattern using the resist underlayer film, and a method for producing a semiconductor device. [Background technology]

[0002] In the manufacture of semiconductor devices, microfabrication by lithography using a resist composition has traditionally been performed. This microfabrication process 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 film, and then etching the substrate using the resulting photoresist pattern as a protective film, thereby forming 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 (extreme ultraviolet, wavelength 13.5 nm) or EB (electron beam) is being considered for cutting-edge microfabrication. As a result, the influence of semiconductor substrates on resists has become a major issue.

[0003] To solve this problem, methods for providing a resist underlayer film between a resist and a semiconductor substrate have been widely studied. Patent Document 1 discloses a resist underlayer film-forming composition containing a polymer obtained by reacting a tetracarboxylic acid dianhydride having an alicyclic structure or an aliphatic structure with a diepoxy-containing compound. Patent Document 2 discloses a resist underlayer film-forming composition containing a polymer obtained by reacting a specific heterocyclic compound with a diepoxy-containing compound. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2009 / 104685 [Patent Document 2] International Publication No. 2013 / 018802 Summary of the Invention [Problem to be solved by the invention]

[0005] The properties required for the resist underlayer film include, for example, that it does not intermix with the resist film formed on top (that is, it is insoluble in a resist solvent) and that it has a faster dry etching rate than the resist film.

[0006] 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 thinner than conventional films. When forming such a thin film, pinholes and aggregation are likely to occur due to the influence of the substrate surface and the polymer used, making it difficult to form a uniform film without defects.

[0007] On the other hand, when forming a resist pattern, a method is sometimes adopted in which the unexposed portions of the resist film are removed in the development step using a solvent capable of dissolving the resist film, usually an organic solvent, and the exposed portions of the resist film are left as a resist pattern. In such a negative development process, improving the adhesion of the resist pattern is a major challenge.

[0008] There is also a demand for suppressing deterioration of LWR (Line Width Roughness) during resist pattern formation, forming resist patterns with good rectangular shapes, and improving resist sensitivity.

[0009] 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. [Means for solving the problem]

[0010] The present invention encompasses the following.

[0011] [1] The following formula (I): [ka] (In formula (I), 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 R 1 represents a tetravalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms, and L 1 and L 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom. A resist underlayer film-forming composition comprising a polymer having a unit structure represented by the following formula:

[0012] [2] R 1 The resist underlayer film forming composition according to [1], wherein the compound (I) contains a biphenylene structure.

[0013] [3] The polymer is represented by the following formula (a-2): [ka] (In formula (a-2), Y 1represents 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; n1 T 1 and n2 T 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may be mutually bonded to bridge two benzene rings, n1 and n2 each independently represent an integer of 0 to 4; Q 1 , A 1 , A 2 , A 3 , A 4 , A 5 , A 6 , L 1 and L 2 is as defined in [1].) The resist underlayer film forming composition according to [1] or [2], which contains a repeating unit represented by the following formula:

[0014] [4] The resist underlayer film forming composition according to any one of [1] to [3], wherein the polymer further has a heterocyclic structure.

[0015] [5] The Y 1

[0022] The resist underlayer film forming composition according to any one of [1] to [4], wherein is a sulfonyl group.

[0016] [6] The resist underlayer film forming composition according to any one of [1] to [5], wherein the polymer is end-capped with a compound.

[0017] [7] The resist underlayer film forming composition according to [6], wherein the compound contains an aliphatic ring which may be substituted with a substituent.

[0018] [8] The compound is represented by the following formula (1) and formula (2): [ka] (In formulas (1) and (2), R1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group, a halogeno group, or a hydroxy group, which may have a substituent; R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a halogeno group, or an ester group represented by -C(=O)OX; X represents an alkyl group having 1 to 6 carbon atoms, which may have a substituent; R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a halogeno group; R4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms; R5 represents a divalent organic group having 1 to 8 carbon atoms; A represents an aromatic ring or an aromatic heterocycle; t represents 0 or 1; and u represents 1 or 2.) The resist underlayer film forming composition according to [6],

[0019] [9] The resist underlayer film-forming composition according to any one of [1] to [8], further comprising a curing catalyst.

[0020]

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

[0021]

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

[10] .

[0022]

[12] a step 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; a step of applying a resist onto the resist underlayer film and baking the resist to form a resist film; exposing the resist underlayer film and the semiconductor substrate covered with the resist; A step of developing and patterning the resist film after exposure. A method for manufacturing a patterned substrate, comprising:

[0023]

[13] forming a resist underlayer film on a semiconductor substrate, the resist underlayer film being composed of the resist underlayer film-forming composition according to any one of [1] to

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

[0024] The resist underlayer film formed from the resist underlayer film-forming composition exhibits excellent resistance to organic solvents used in the photoresist formed on top of the underlayer film, and can form a resist underlayer film that exhibits good film thickness uniformity even when it is very thin (10 nm or less in thickness). Furthermore, when a resist pattern is formed using the resist underlayer film-forming composition of the present invention, the limiting resolution size at which the resist pattern does not collapse after development is smaller than that of conventional resist underlayer films, making it possible to form finer resist patterns. Furthermore, bridging in line patterns can be suppressed, resulting in good pattern formation ability. DETAILED DESCRIPTION OF THE INVENTION

[0025] <Resist Underlayer Film-Forming Composition> The resist underlayer film-forming composition of the present invention includes a polymer and a solvent, and the polymer is represented by the following formula (I): [ka] (In formula (I), A 1 , A 2 , A 3 , A 4 , A 5 and A 6each independently represents a hydrogen atom, a methyl group, or an ethyl group; Q 1 represents a divalent organic group, and R 1 represents a tetravalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms, and L 1 and L 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom. It is a polymer having a unit structure represented by the following formula:

[0026] Examples of the aromatic ring structure having 6 to 40 carbon atoms include 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, and dibenzo[a,j]anthracene.

[0027] R 1 is represented by the following formula (III): [ka] (In formula (III), 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; n1 T 1 and n2 T 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may be bonded to each other to bridge two benzene rings; n1 and n2 each independently represent an integer of 0 to 4; * denotes R 1 is the bond to the carbon atom of the carbonyl group to which it is attached.) It may be expressed as:

[0028] The Y 1 is preferably a sulfonyl group.

[0029] Examples of the halogen atom include fluorine, chlorine, iodine, and bromine. 1 is a sulfonyl group, T 1 and T 2 is preferably a hydrogen atom.

[0030] Examples of the aryl group having 6 to 40 carbon atoms include a phenyl group, an o-methylphenyl group, a m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, a 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, a 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.

[0031] Examples of the alkylene group having 1 to 10 carbon atoms 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-methyl-cyclopropylene group, a 2-methyl-cyclopropylene group, an n-pentylene group, a 1-methyl-n-butylene group, a 2-methyl-n-butylene group, a 3-methyl-n-butylene group, a 1,1-dimethyl-n-propylene group, a 1,2-dimethyl-n-propylene group, a 2,2-dimethyl-n-propylene group, and a 1-ethyl-n-propylene group. propylene, cyclopentylene, 1-methylcyclobutylene, 2-methylcyclobutylene, 3-methylcyclobutylene, 1,2-dimethylcyclopropylene, 2,3-dimethylcyclopropylene, 1-ethylcyclopropylene, 2-ethylcyclopropylene, n-hexylene, 1-methyl-n-pentylene, 2-methyl-n-pentylene, 3-methyl-n-pentylene, 4-methyl-n-pentylene, 1,1-dimethyl-n-butylene, 1,2-dimethyl-n-butylene, 1,3-dimethyl-n-butylene , 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 cyclobutylene group, 3-ethylcyclobutylene group, 1,2-dimethylcyclobutylene group, 1,3-dimethylcyclobutylene group, 2,2-dimethylcyclobutylene group, 2,3-dimethylcyclobutylene group, 2,4-dimethylcyclobutylene group, 3,3-dimethylcyclobutylene group, 1-n-propylcyclopropylene group, 2-n-propylcyclopropylene group, 1-isopropylcyclopropylene group, 2-isopropylcyclopropylene group, 1,2,2-trimethylcyclopropylene group, 1,2,3-trimethylcyclopropylene group, 2,2,Examples of such alkyl groups include 3-trimethylcyclopropylene, 1-ethyl-2-methylcyclopropylene, 2-ethyl-1-methylcyclopropylene, 2-ethyl-2-methylcyclopropylene, 2-ethyl-3-methylcyclopropylene, n-heptylene, n-octylene, n-nonylene, and n-decanylene. Among these, alkyl groups having 1 to 4 carbon atoms are preferred, and are preferably selected from methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, and t-butyl groups, with methyl or ethyl being preferred.

[0032] R 1 However, the following formula (2-1): [ka] (In formula (2-1), 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; n1 T 1 and n2 T 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may be bonded to each other to bridge two benzene rings, and n1 and n2 each independently represent an integer of 0 to 4. It may be derived from a compound represented by the formula:

[0033] The polymer may have a heterocyclic structure. For example, it may be a reaction product of a compound represented by formula (2-1) and a compound containing a heterocyclic ring having two reactive groups reactive with the acid dianhydride contained in formula (2-1). In the case of the reaction product, the reaction product contains a heterocyclic ring structure as a repeating unit structure. Details of the heterocyclic ring will be described later.

[0034] Q 1 However, it may contain an alkenyl group or alkynyl group having 2 to 10 carbon atoms.

[0035] Q1 is not limited as long as it is a divalent organic group that exhibits the effects of the present invention, but is preferably derived from a diepoxy-containing compound containing two epoxy groups. Specific examples include structures derived from the compounds shown in the following (10-a) to (10-k). [ka]

[0036] Q 1 may contain a heterocyclic structure. Examples of the heterocyclic structure include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthrene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazineone, triazinedione, and triazinetrione, as well as the heterocyclic structures shown in formulas (10-h) to (10-k) above. Among these, triazinetrione is preferred, and specifically, the structures shown in formulas (10-h) to (10-k) above are preferred.

[0037] The polymer is represented by the following formula (a-1): [ka] (In formula (a-1), Y 1 , T 1 , T 2 , n1 and n2 are as defined above, and L 1 and L 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group and which may be interrupted with an oxygen atom, and * represents the bonding site to the polymer residue.

[0038] L 1 and L 2is preferably an alkyl group having 1 to 10 carbon atoms substituted with a hydroxy group and interrupted by an oxygen atom. The alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom refers to an alkyl group which contains an ether bond between one or more carbon-carbon bonds. 1 and L 2 The structure of may be produced, for example, as in the synthesis examples described in the Examples section, by reacting a solvent used in the reaction (for example, a solvent represented by the following (3d-1) or (3d-2)) with a carboxy group derived from the above compound (a).

[0039] [ka]

[0040] The polymer is represented by the following formula (a-2): [ka] (In formula (a-2), Y 1 , T 1 , T 2 , n1 and n2 are as defined above, and L 1 and L 2 is as defined above, and 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.

[0041] The weight-average molecular weight of the polymer is preferably 500 to 50,000, and more preferably 1,000 to 30,000. The weight-average molecular weight can be measured, for example, by gel permeation chromatography as described in the examples.

[0042] The content of the polymer in the entire resist underlayer film-forming composition of the present invention is usually 0.05 to 3.0% by mass, 0.08 to 2.0% by mass, or 0.1 to 1.0% by mass.

[0043] 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, 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 may be used alone or in combination of two or more.

[0044] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, etc. are preferred, with propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate being particularly preferred.

[0045] The polymer may be end-capped with a compound.

[0046] The compound may contain an aliphatic ring which may be substituted with a substituent.

[0047] The aliphatic ring is preferably a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms. Examples of the monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, tricyclo[3.2.1.0]octane, and cyclopentane-substituted cyclopentanes. 2,7 ]octane, spiro[3,4]octane, norbornane, norbornene, tricyclo[3.3.1.1 3,7 ] Decane (adamantane), etc.

[0048] The polycyclic aliphatic ring is preferably a bicyclic ring or a tricyclic ring.

[0049] Examples of the bicyclo ring include norbornane, norbornene, spiro-bicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, and spiro[3,4]octane.

[0050] The tricyclo ring may be a tricyclo[3.2.1.0 2,7 ]octane, tricyclo[3.3.1.1 3,7 ] Decane (adamantane) is an example.

[0051] The aliphatic ring which may be substituted with the substituent means that one or more hydrogen atoms of the aliphatic ring may be substituted with the substituents described below.

[0052] The substituent is preferably selected from 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 which may be interrupted by an oxygen atom, and a carboxy group.

[0053] Examples of the alkoxy group having 1 to 20 carbon atoms 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, Examples of such groups include a 2-dimethyl-n-butoxy group, a 1,3-dimethyl-n-butoxy group, a 2,2-dimethyl-n-butoxy group, a 2,3-dimethyl-n-butoxy group, a 3,3-dimethyl-n-butoxy group, a 1-ethyl-n-butoxy group, a 2-ethyl-n-butoxy group, a 1,1,2-trimethyl-n-propoxy group, a 1,2,2-trimethyl-n-propoxy group, a 1-ethyl-1-methyl-n-propoxy group, a 1-ethyl-2-methyl-n-propoxy group, a cyclopentyloxy group, a cyclohexyloxy group, a norbornyoxy group, an adamantyloxy group, an adamantanemethyloxy group, an adamantaneethyloxy group, a tetracyclodecanyloxy group, and a tricyclodecanyloxy group.

[0054] The aliphatic ring preferably has at least one unsaturated bond (e.g., a double bond or a triple bond). The aliphatic ring preferably has one to three unsaturated bonds. The aliphatic ring preferably has one or two unsaturated bonds. The unsaturated bond is preferably a double bond.

[0055] Specific examples of the compound containing an aliphatic ring optionally substituted with the above-mentioned substituent include the compounds shown below. Specific examples also include compounds in which the carboxy group of the following specific examples is replaced with a hydroxy group, an amino group, or a thiol group.

[0056] [ka] [ka] [ka]

[0057] The entire disclosure of WO 2020 / 226141 regarding the polymer having an aliphatic ring optionally substituted at the end is incorporated herein by reference.

[0058] The compound is represented by the following formula (1) and formula (2): [ka] (In formulas (1) and (2), R1 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, a pyridyl group, a halogeno group, or a hydroxy group, which may have a substituent; R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a halogeno group, or an ester group represented by -C(=O)OX; X represents an alkyl group having 1 to 6 carbon atoms, which may have a substituent; R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a halogeno group; R4 represents a direct bond or a divalent organic group having 1 to 8 carbon atoms; R5 represents a divalent organic group having 1 to 8 carbon atoms; A represents an aromatic ring or an aromatic heterocycle; t represents 0 or 1; and u represents 1 or 2.) It may be expressed as:

[0059] The polymer terminal structures represented by the above formulas (1) and (2) can be produced by reacting the polymer with a compound represented by the following formula (1a) and / or a compound represented by the following formula (2a).

[0060] [ka] (The meanings of the symbols in the above formulas (1a) and (2a) are as explained in the above formulas (1) and (2).) Examples of the compound represented by the formula (1a) include compounds represented by the following formula:

[0061] [ka] [ka] [ka] [ka] [ka]

[0062] Examples of the compound represented by the formula (2a) include compounds represented by the following formula:

[0063] [ka]

[0064] The contents of the above formula (1) and formula (2) are disclosed in WO 2015 / 163195, the entire disclosure of which is incorporated herein by reference.

[0065] <Curing catalyst> The curing catalyst optionally contained in the resist underlayer film-forming composition of the present invention is preferably an acid generator. Examples of the acid generator 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 p-phenolsulfonate salt), 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. When the crosslinking catalyst is used, the content of the crosslinking catalyst is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass, relative to the crosslinking agent described below.

[0066] <Crosslinking agent> Examples of crosslinking agents that may be included 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, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0067] 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:

[0068] [ka] (In formula (1d), R1 represents a methyl group or an ethyl group.) 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).

[0069] [ka] (In formula (1E), four R1s each independently represent a methyl group or an ethyl group, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) Examples of the glycoluril derivative represented by the formula (1E) include compounds represented by the following formulae (1E-1) to (1E-6).

[0070] [ka]

[0071] 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):

[0072] [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 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).

[0073] 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).

[0074] [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 represent an alkyl group having 1 to 4 carbon atoms.) Examples of glycoluril derivatives represented by the formula (2E) include compounds represented by the following formulae (2E-1) to (2E-4): Furthermore, examples of compounds represented by the formula (3d) include compounds represented by the following formulae (3d-1) and (3d-2):

[0075] [ka] [ka]

[0076] The entire disclosure of WO2017 / 187969 is incorporated herein by reference with respect to the content of the nitrogen-containing compound having 2 to 6 substituents bonded to the nitrogen atom and represented by the following formula (1d) per molecule.

[0077] 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.

[0078] [ka] (In the formula, Q 1 represents a single bond or 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 3and R 6 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n1 is an integer satisfying 1≦n1≦3, n2 is an integer satisfying 2≦n2≦5, n3 is an integer satisfying 0≦n3≦3, n4 is an integer satisfying 0≦n4≦3, and 3≦(n1+n2+n3+n4)≦6. n5 is an integer in the range of 1≦n5≦3, n6 is an integer in the range of 1≦n6≦4, n7 is an integer in the range of 0≦n7≦3, n8 is an integer in the range of 0≦n8≦3, and 2≦(n5+n6+n7+n8)≦5. m1 represents an integer of 2 to 10.

[0079] 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.

[0080] [ka] (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 R 10 represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms. n9 is an integer in the range of 1≦n9≦3, n10 is an integer in the range of 2≦n10≦5, n11 is an integer in the range of 0≦n11≦3, n12 is an integer in the range of 0≦n12≦3, and 3≦(n9+n10+n11+n12)≦6. n13 is an integer satisfying 1≦n13≦3, n14 is an integer satisfying 1≦n14≦4, n15 is an integer satisfying 0≦n15≦3, n16 is an integer satisfying 0≦n16≦3, and 2≦(n13+n14+n15+n16)≦5. m2 represents an integer from 2 to 10.

[0081] Examples of the compounds represented by the above formula (G-1) and formula (G-2) include the following.

[0082] [ka]

[0083] [ka]

[0084] [ka]

[0085] [ka]

[0086] [ka]

[0087] Examples of the compounds represented by formula (G-3) and formula (G-4) include the following.

[0088] [ka]

[0089] [ka] In the formula, Me represents a methyl group.

[0090] The entire disclosure of WO 2014 / 208542 is incorporated herein by reference.

[0091] 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 reaction product.

[0092] <Other ingredients> The resist underlayer film-forming composition of the present invention may further contain a surfactant to prevent pinholes, striations, etc., and further improve coating properties against surface irregularities. Examples of surfactants 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; nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-containing surfactants such as F-TOP 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.

[0093] The resist underlayer film-forming composition of the present invention is preferably an electron beam resist underlayer film-forming composition or an EUV resist underlayer film-forming composition used in an electron beam (EB) writing step and an EUV exposure step, and is preferably an EUV resist underlayer film-forming composition.

[0094] <Resist Underlayer Film> The resist underlayer film according to the present invention can be produced by applying the above-described resist underlayer film-forming composition onto a semiconductor substrate and baking it.

[0095] The resist underlayer film according to the present invention is preferably an electron beam resist underlayer film or an EUV resist underlayer film.

[0096] Examples of semiconductor substrates to which the resist underlayer film-forming composition of the present invention can be applied include silicon wafers, germanium wafers, and wafers of compound semiconductors such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0097] When a semiconductor substrate having an inorganic film formed on its surface is used, 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 film, silicon oxide film, silicon nitride film, BPSG (Boro-Phospho Silicate Glass) film, titanium nitride film, titanium nitride oxide film, tungsten film, gallium nitride film, and gallium arsenide film.

[0098] The resist underlayer film-forming composition of the present invention is applied onto 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.

[0099] 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, 0.003 μm (3 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 (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), 0.002 μm (2 nm) to 0.01 μm (10 nm), 0.003 μm (3 nm) to 0.01 μm (10 nm), 0.002 μm (2 nm) to 0.006 μm (6 nm), 0.004 μm (4 nm), 0.005 μm (5 nm). 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 be decomposed by heat.

[0100] <Method for manufacturing a patterned substrate, and method for manufacturing a semiconductor device> The manufacturing method of a patterned substrate involves 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 acid to increase the alkaline dissolution rate and a photoacid generator; chemically amplified photoresists composed of a low-molecular-weight compound that decomposes in 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 acid to increase the alkaline dissolution rate, a low-molecular-weight compound that decomposes in acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator; and resists containing metal elements. Examples of such photoresists include those manufactured by JSR Corporation under the trade name V146G, those manufactured by Shipley Chemical Co., Ltd. under the trade name APEX-E, those manufactured by Sumitomo Chemical Co., Ltd. under the trade name PAR710, and those manufactured by Shin-Etsu Chemical Co., Ltd. under the trade names AR2772 and SEPR430. Other 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) containing metals may also be used.

[0101] 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., radiation-sensitive resin compositions, so-called resist compositions such as high-resolution patterning compositions based on organometallic solutions, and metal-containing resist compositions can be used, but are not limited to these.

[0102] Examples of the resist composition include the following. (i) An actinic ray-sensitive or radiation-sensitive resin composition comprising: 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 (11): [ka] In the general formula (11), m represents an integer of 1 to 6. R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group. L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-. L2 represents an alkylene group which may have a substituent or a single bond. W1 represents a cyclic organic group which may have a substituent. M + represents a cation.

[0103] (ii) 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.

[0104] (iii) A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (21) and a second structural unit represented by the following formula (22) containing an acid-dissociable group, and an acid generator: [ka]

[0105] In formula (21), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene having 6 to 20 carbon atoms. 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. R 2 is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0106] In formula (22), 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.

[0107] (iv) 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. [ka] [In formula (II), R 2 represents an alkyl group having 1 to 6 carbon atoms which may have one or more halogen atoms, a hydrogen atom, or a halogen atom; X 1 is 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.]

[0108] (v) A resist composition that generates an acid upon exposure and whose solubility in a developer changes due to the action of the acid, The composition contains a base component (A) whose solubility in a developer changes under the action of an acid, and a fluorine additive component (F) that is decomposable in an alkaline developer, The resist composition is characterized in that the fluorine additive component (F) contains a fluorine resin component (F1) having a structural unit (f1) containing a base dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1): [ka] [In formula (f2-r-1), Rf 21are 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.

[0109] (vi) The resist composition according to (v) above, 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): [ka] [In formulas (f1-1) and (f1-2), each R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid-dissociable site. A aryl X is a divalent aromatic cyclic group which may have a substituent. 01 R is a single bond or a divalent linking group. 2 are each independently an organic group having a fluorine atom.

[0110] Metal-containing resist compositions include, for example, coatings comprising metal oxo-hydroxo networks with organic ligands through metal carbon bonds and / or metal carboxylate bonds.

[0111] (vii) Inorganic oxo / hydroxo-based compositions. Examples of the resist film include the following. (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: [ka] (In formulas (a1) and (a2), R A are each independently a hydrogen atom or a methyl group. 1 and R 2are 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. X 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 resist materials include the following: (i) A resist material containing a polymer having a repeating unit represented by the following formula (a1) or (a2):

[0113] [ka] (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 a part 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 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 ~R 5are 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 amido 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.

[0114] (ii) A resist material comprising a base resin containing a polymer containing a repeating unit represented by the following formula (a): [ka] (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-CH2- or -NH-. m is an integer of 1 to 4. n is an integer of 0 to 3.

[0115] Examples of coating solutions include: (i) 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 (where n = 1 or 2), or a mixture thereof, where R and R’ are, independently, hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof, a first organometallic composition; and a hydrolyzable metal compound represented by the formula MX’ v (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), a coating solution containing the hydrolyzable metal compound. (ii) A coating solution containing 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, 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, a coating solution. (iii) An inorganic pattern-forming precursor aqueous solution comprising a mixture of water, metal oxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand containing a peroxide group. Examples include the like.

[0116] Exposure is performed through a mask (reticle) to form a predetermined pattern. For example, i-line, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) can be used. However, the resist underlayer film-forming composition of the present invention is preferably used for EUV (extreme ultraviolet) exposure. An alkaline developer is used for development, with the development temperature selected from 5°C to 50°C and the development time selected from 10 seconds to 300 seconds. Examples of alkaline developers that can be used 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, an appropriate amount of alcohols such as isopropyl alcohol or a nonionic surfactant can be added to the aqueous alkali solution. Among these, preferred developers are quaternary ammonium salts, more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can be added to these developers. Instead of using an alkaline developer, development can be performed with an organic solvent such as butyl acetate to develop the portions of the photoresist where the alkaline dissolution rate is not improved. Through the above steps, a substrate with the resist patterned thereon can be produced.

[0117] 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. [Example]

[0118] The weight-average molecular weights of the polymers shown in the following Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 3 in this specification are the results of measurements by gel permeation chromatography (hereinafter abbreviated as GPC). The measurements were performed using a GPC device manufactured by Tosoh Corporation, and the measurement conditions were as follows:

[0119] GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko K.K.) Column temperature: 40℃ Solvent: N,N-dimethylformamide (DMF) Flow rate: 0.6ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0120] <Synthesis Example 1> 3.00 g of monoallyldiglycidyl isocyanuric acid (Shikoku Chemical Industry Co., Ltd.), 3.27 g of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (Tokyo Chemical Industry Co., Ltd.), 0.64 g of 4-(methylsulfonyl)benzoic acid (Tokyo Chemical Industry Co., Ltd.), and 0.27 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added to and dissolved in 21.83 g of propylene glycol monomethyl ether. The atmosphere in the reaction vessel was replaced with nitrogen, and the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, indicating good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the polymer in the resulting solution had a weight-average molecular weight of 8,300 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulae (XX), (XY), and (XZ).

[0121] [ka]

[0122] <Synthesis Example 2> 3.00 g of monoallyl diglycidyl isocyanuric acid (Shikoku Chemical Industry Co., Ltd.), 3.27 g of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (Tokyo Chemical Industry Co., Ltd.), 0.53 g of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.), and 0.27 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added to and dissolved in 21.49 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, indicating good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the polymer in the resulting solution had a weight-average molecular weight of 12,300 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulae (XX), (XY), and (Xa).

[0123] [ka]

[0124] <Synthesis Example 3> 3.00 g of monoallyl diglycidyl isocyanuric acid (Shikoku Chemical Industry Co., Ltd.), 3.27 g of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (Tokyo Chemical Industry Co., Ltd.), and 0.27 g of tetrabutylphosphonium bromide (Hokuko Chemical Industry Co., Ltd.) were added to and dissolved in 19.90 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, indicating good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 7,900 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (XX) and (XY).

[0125] [ka]

[0126] <Comparative Synthesis Example 1> 3.00 g of monoallyl diglycidyl isocyanurate (manufactured by Shikoku Chemical Industry Co., Ltd.), 1.91 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 0.57 g of adamantanecarboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.14 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to and dissolved in 6.87 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 8 hours to obtain a polymer solution. The polymer solution did not become cloudy even when cooled to room temperature, indicating good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 5,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (XX), (Xb), and (Xc).

[0127] [ka]

[0128] <Comparative Synthesis Example 2> 2.50 g of monoallyl diglycidyl isocyanuric acid (Shikoku Chemical Industry Co., Ltd.), 1.47 g of diethylbarbituric acid (Tokyo Chemical Industry Co., Ltd.), 0.29 g of 5-norbornene-2,3-dicarboxylic anhydride (Tokyo Chemical Industry Co., Ltd.), and 0.16 g of ethyltriphenylphosphonium bromide (Tokyo Chemical Industry Co., Ltd.) were added to and dissolved in 8.97 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. The polymer solution did not become cloudy even when cooled to room temperature, indicating good solubility in propylene glycol monomethyl ether. GPC analysis revealed that the polymer in the obtained solution had a weight-average molecular weight of 3,000 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (XX), (Xd), and (Xa).

[0129] [ka]

[0130] <Examples 1-3, Comparative Examples 1-2> The polymers, crosslinking agents, curing catalysts, and solvents of Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2 were mixed in the proportions shown in Tables 1 and 2, and the mixture was filtered through a 0.1 μm fluororesin filter to prepare solutions of compositions for forming resist underlayer films.

[0131] 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, 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.

[0132] [Table 1] [Table 2]

[0133] [Photoresist solvent elution test] Each of the resist underlayer film-forming compositions of Examples 1, 2, and 3 and Comparative Examples 1 and 2 was applied to a silicon wafer, which was a semiconductor substrate, using a spinner. The silicon wafer was placed on a hot plate and baked at 205°C for 1 minute to form a resist underlayer film (film thickness: 4 nm). These resist underlayer films were immersed in ethyl lactate and propylene glycol monomethyl ether, solvents used in photoresists, and were confirmed to be insoluble in these solvents.

[0134] [Positive resist pattern formation using EUV exposure equipment] The resist underlayer film-forming compositions of Examples 1, 2, and 3 and Comparative Examples 1 and 2 were each 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 4-nm-thick resist underlayer film. A positive EUV resist solution (containing a methacrylic polymer) 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 EUV exposure lithography system (NXE-3400). After exposure, the resist was baked at 100°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38% TMAH), forming a 19-nm line pattern / 32-nm pitch resist pattern. A scanning electron microscope (CG4100, manufactured by Hitachi High-Technologies Corporation) was used to measure the resist pattern. In forming the resist pattern, if a line pattern with a CD size of 19 nm was formed, it was rated as "good," and if bridging of the line pattern was observed, it was rated as "poor." The results are shown in Table 3.

[0135] [Table 3] In comparison with Comparative Examples 1 and 2, Examples 1, 2 and 3 all showed that bridging in the line pattern could be suppressed, and that they had good pattern forming capabilities. [Industrial Applicability]

[0136] The resist underlayer film-forming composition according to the present invention can provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, as well as a method for producing a substrate having a resist pattern and a method for producing a semiconductor device using the resist underlayer film-forming composition.

Claims

1. The following formula (a-2): 【Chemistry 52】 In formula (a-2), Y １ represents a sulfonyl group, 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 having a heterocyclic structure in the main chain selected from the group consisting of triazineone, triazinedione, and triazinetrione; L １ and L ２ each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted with a hydroxy group and which may be interrupted by an oxygen atom. and a solvent.

2. The resist underlayer film forming composition according to claim 1 , wherein the polymer is end-capped with a compound.

3. The resist underlayer film forming composition according to claim 2 , wherein the compound contains an aliphatic ring which may be substituted with a substituent.

4. The compound is represented by the following formula (1) and formula (2): 【Chemistry 53】 (In formulas (1) and (2), R １ represents an alkyl group having 1 to 6 carbon atoms, which may have a substituent, a phenyl group, a pyridyl group, a halogeno group, or a hydroxy group; R ２ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, a halogeno group, or an ester group represented by -C(=O)O-X, where X represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, R ３ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxy group, or a halogeno group; R ４ represents a direct bond or a divalent organic group having 1 to 8 carbon atoms; R ５ represents a divalent organic group having 1 to 8 carbon atoms, A represents an aromatic ring or an aromatic heterocycle, t represents 0 or 1, and u represents 1 or 2. The resist underlayer film forming composition according to claim 2 , represented by the formula:

5. The resist underlayer film forming composition according to any one of claims 1 to 4, further comprising a curing catalyst.

6. The resist underlayer film forming composition according to any one of claims 1 to 5, further comprising a crosslinking agent.

7. A resist underlayer film, which is a fired product of a coating film comprising the resist underlayer film-forming composition according to any one of claims 1 to 6.

8. A step of applying the resist underlayer film-forming composition according to any one of claims 1 to 6 onto a semiconductor substrate and baking the composition to form a resist underlayer film; a step of applying a resist onto the resist underlayer film and baking the resist to form a resist film; exposing the resist underlayer film and the semiconductor substrate covered with the resist; A step of developing and patterning the resist film after exposure. A method for manufacturing a patterned substrate, comprising:

9. forming a resist underlayer film on a semiconductor substrate, the resist underlayer film being composed of the resist underlayer film-forming composition according to any one of claims 1 to 6; forming a resist film on the resist underlayer film; a step of forming a resist pattern by irradiating the resist film with light or an electron beam and then developing it; forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern; processing a semiconductor substrate using the patterned resist underlayer film; A method for manufacturing a semiconductor device, comprising:

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