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

Abstract

The present application provides a resist underlayer film forming composition capable of forming a desired resist pattern, and a resist pattern manufacturing method and a semiconductor device manufacturing method using the same. The resist underlayer film forming composition comprises a polymer having a unit structure represented by the following formula (I), and a solvent, in the formula (I), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 each independently represent a hydrogen atom, a methyl group or an ethyl group, Q1 represents a divalent organic group, R 1 represents a 4-valent organic group comprising an aromatic ring structure having 6 to 40 carbon atoms, L 1 and L 2 each independently represent a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which can be substituted with a hydroxyl group or interrupted with an oxygen atom.

Description

[0001] This application is a divisional application of a patent application with an application date of January 26, 2022, application number 202280011840.0, and invention name “Composition for forming an anti-etching agent underlayer film comprising a reaction product of an acid dianhydride”. Technical Field

[0002] The present invention relates to a composition for use in photolithography processes in semiconductor manufacturing, particularly the most advanced photolithography processes (such as ArF, EUV, and EB), a method for manufacturing a substrate with a resist pattern using the resist underlayer film, and a method for manufacturing a semiconductor device. Background Art

[0003] All along, in the manufacture of semiconductor devices, micro-machining is carried out by using the photolithography of resist composition.Above-mentioned micro-machining is following processing method, i.e. forming the film of photoresist composition on semiconductor substrates such as silicon wafer, irradiating active light such as ultraviolet rays across the mask pattern depicting device pattern thereon, developing, using the photoresist pattern obtained as a protective film to etch substrate, thus forming the micro-concave-convex corresponding to the above-mentioned pattern on the substrate surface. In recent years, the integration level of semiconductor devices is more and more high, and the active light used is except the i-ray (wavelength 365nm), KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm) used in the past, also studying the practical application of EUV light (extreme ultraviolet light, wavelength 13.5nm) or EB (electron beam) in the most advanced micro-machining. Accompanied by this, the influence of semiconductor substrate on resist has become a big problem.

[0004] Therefore, to address this problem, methods for providing a resist underlayer film between the resist and the semiconductor substrate have been extensively studied. Patent Document 1 discloses a resist underlayer film-forming composition comprising a polymer obtained by reacting tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure with a compound containing a diepoxy group. Patent Document 2 discloses a resist underlayer film-forming composition comprising a polymer obtained by reacting a specific heterocyclic compound with a compound containing a diepoxy group.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2009 / 104685

[0008] Patent Document 2: International Publication No. 2013 / 018802 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] Examples of the properties required of the resist underlayer film include no mixing with the resist film formed overlying the resist film (insolubility in the resist solvent) and a faster dry etching rate than the resist film.

[0011] In photolithography with EUV exposure, the line width of the formed resist pattern is 32 nm or less, and the resist underlayer film for EUV exposure is thinner than before. Forming such a thin film is prone to pinholes and agglomeration due to the influence of the substrate surface and the polymer used, making it difficult to form a uniform film without defects.

[0012] On the other hand, when forming a resist pattern, a method is sometimes used in which, during the development step, the unexposed portions of the resist film are removed using a solvent capable of dissolving the resist film, typically an organic solvent, while the exposed portions of the resist film remain as the resist pattern. In such a negative-tone development process, improving the adhesion of the resist pattern becomes a major issue.

[0013] Furthermore, it is necessary to suppress deterioration of LWR (Line Width Roughness) during resist pattern formation, form a resist pattern having a good rectangular shape, and improve resist sensitivity.

[0014] An object of the present invention is to provide a resist underlayer film-forming composition that solves the above-mentioned problems and can form a desired resist pattern, and a resist pattern forming method using the resist underlayer film-forming composition.

[0015] Means of solving the problem

[0016] The present invention includes the following contents.

[0017] [1] A composition for forming a resist underlayer film, comprising a polymer having a unit structure represented by the following formula (I) and a solvent;

[0018]

[0019] 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, R 1 represents a tetravalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms, L 1 and L 2Each independently represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms which may be substituted by a hydroxy group or interrupted by an oxygen atom.

[0020] [2] The resist underlayer film-forming composition according to [1], wherein the R 1 Contains a biphenylene structure.

[0021] [3] The resist underlayer film-forming composition according to [1] or [2], wherein the polymer contains a repeating unit represented by the following formula (a-2);

[0022]

[0023] In formula (a-2), Y 1 represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with an oxygen atom, a sulfur atom, 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.

[0024] n1 and n2 each independently represent an integer from 0 to 4, Q 1 、A 1 、A 2 、A 3 、A 4 、A 5 、A 6 , L 1 and L 2 As defined in [1].

[0025] [4] The resist underlayer film-forming composition according to any one of [1] to [3], wherein the polymer further has a heterocyclic structure.

[0026] [5] The resist underlayer film-forming composition according to any one of [1] to [4], wherein the Y 1 It is a sulfonyl group.

[0027] [6] The resist underlayer film-forming composition according to any one of [1] to [5], wherein the terminal of the polymer is capped with a compound.

[0028] [7] The resist underlayer film-forming composition according to [6], wherein the compound contains an aliphatic ring which may be substituted with a substituent.

[0029] [8] The resist underlayer film-forming composition according to [6], wherein the compound is represented by the following formula (1) and formula (2).

[0030]

[0031] In formulas (1) and (2), R1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogen group or a hydroxyl group, R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen 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 hydroxyl group or a halogen 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 a heteroaromatic ring, t represents 0 or 1, and u represents 1 or 2.

[0032] [9] The resist underlayer film-forming composition according to any one of [1] to [8], further comprising a curing catalyst.

[0033]

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

[0034]

[11] A resist underlayer film characterized by being a fired product of a coating film formed from the resist underlayer film-forming composition described in any one of [1] to

[10] .

[0035]

[12] A method for manufacturing a patterned substrate, comprising:

[0036] A process of coating the resist underlayer film-forming composition described in any one of [1] to

[10] on a semiconductor substrate and baking the composition to form a resist underlayer film,

[0037] a step of coating a resist on the resist underlayer film and baking the resist to form a resist film;

[0038] a step of exposing the semiconductor substrate covered with the resist underlayer film and the resist, and

[0039] The exposed resist film is developed and patterned.

[0040]

[13] A method for manufacturing a semiconductor device, comprising:

[0041] a step of forming a resist underlayer film formed from the resist underlayer film-forming composition described in any one of [1] to

[10] on a semiconductor substrate,

[0042] forming a resist film on the resist underlayer film;

[0043] A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing it.

[0044] a step of etching the resist underlayer film through the formed resist pattern to form a patterned resist underlayer film, and

[0045] A step of processing a semiconductor substrate using the patterned resist underlayer film.

[0046] Effects of the Invention

[0047] The resist underlayer film formed from the resist underlayer film-forming composition can form a resist underlayer film that exhibits excellent resistance to organic solvents used in the photoresist formed on top of the underlayer film and exhibits good film thickness uniformity even in extremely thin films (film thickness of 10 nm or less). Furthermore, when forming a resist pattern using the resist underlayer film-forming composition of the present invention, the critical resolution dimension at which no collapse of the resist pattern after development is observed is smaller than that of conventional resist underlayer films, enabling the formation of finer resist patterns. Furthermore, bridging in linear patterns can be suppressed, resulting in excellent pattern forming capabilities. DETAILED DESCRIPTION

[0048] <Resist Underlayer Film-Forming Composition>

[0049] The resist underlayer film-forming composition of the present invention contains a polymer and a solvent, wherein the polymer includes a unit structure represented by the following formula (I).

[0050]

[0051] 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, R 1 represents a tetravalent organic group containing an aromatic ring structure having 6 to 40 carbon atoms, 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 by a hydroxy group or interrupted by an oxygen atom.

[0052] Examples of the aromatic ring structure having 6 to 40 carbon atoms are benzene, naphthalene, anthracene, acenaphthene, fluorene, triphenylene, phenanthene, phenanthren, indene, indane, indacenes, pyrene, Aromatic ring structures derived from perylene, tetracene, pentacene, coronene, heptaacene, benz[a]anthracene, dibenzophenanthrene, and dibenzo[a,j]anthracene. 1It can be represented by the following formula (III):

[0053]

[0054] In formula (III), Y 1 represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with an oxygen atom, a sulfur atom, 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,

[0055] * is with R 1 The carbon atom of the bonded carbonyl group is bonded to the moiety.

[0056] The above Y 1 Preferred is a sulfonyl group.

[0057] Examples of the halogen atom include fluorine, chlorine, iodine and bromine.

[0058] Y 1 is sulfonyl, T 1 and T 2 Preferred is a hydrogen atom.

[0059] Examples of the aryl group having 6 to 40 carbon atoms include phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, and 9-phenanthrenyl.

[0060] Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, sec-butylene, tert-butylene, cyclobutylene, 1-methyl-cyclopropylene, 2-methyl-cyclopropylene, n-pentylene, 1-methyl-n-butylene, 2-methyl-n-butylene, 3-methyl-n-butylene, 1,1-dimethyl-n-propylene, 1,2-dimethyl-n-propylene, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene, cyclopentylene, 1-methyl-cyclobutylene, 2-methyl- Cyclobutylene, 3-methyl-cyclobutylene, 1,2-dimethyl-cyclopropylene, 2,3-dimethyl-cyclopropylene, 1-ethyl-cyclopropylene, 2-ethyl-cyclopropylene, 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, 2,3-dimethyl-n-butylene, 3,3-dimethyl-n-butylene, 1-ethyl-n-butylene Butyl, 2-ethyl-n-butylene, 1,1,2-trimethyl-n-propylene, 1,2,2-trimethyl-n-propylene, 1-ethyl-1-methyl-n-propylene, 1-ethyl-2-methyl-n-propylene, cyclohexylene, 1-methyl-cyclopentylene, 2-methyl-cyclopentylene, 3-methyl-cyclopentylene, 1-ethyl-cyclobutylene, 2-ethyl-cyclobutylene, 3-ethyl-cyclobutylene, 1,2-dimethyl-cyclobutylene, 1,3-dimethyl-cyclobutylene, 2,2-dimethyl-cyclobutylene, 2,3-dimethyl-cyclobutylene, 2,4- Dimethyl-cyclobutylene, 3,3-dimethyl-cyclobutylene, 1-n-propyl-cyclopropylene, 2-n-propyl-cyclopropylene, 1-isopropyl-cyclopropylene, 2-isopropyl-cyclopropylene, 1,2,2-trimethyl-cyclopropylene, 1,2,3-trimethyl-cyclopropylene, 2,2,3-trimethyl-cyclopropylene, 1-ethyl-2-methyl-cyclopropylene, 2-ethyl-1-methyl-cyclopropylene, 2-ethyl-2-methyl-cyclopropylene, 2-ethyl-3-methyl-cyclopropylene, n-heptylene, n-octylene, n-nonylene, or n-decylene. Among these, an alkyl group having 1 to 4 carbon atoms is preferred, preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and preferably methyl or ethyl.

[0061] The above R 1 It can be derived from the compound represented by the following formula (2-1):

[0062]

[0063] In formula (2-1), Y 1represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with an oxygen atom, a sulfur atom, 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.

[0064] The polymer may have a heterocyclic structure. For example, it may be a reaction product of a compound represented by the above formula (2-1) and a compound containing a heterocyclic ring, wherein the heterocyclic ring has two reactive groups that are reactive with the acid dianhydride contained in the formula (2-1). In the case of the above reaction product, the reaction product contains a heterocyclic structure as a repeating unit structure. The details of the above heterocyclic ring will be described later.

[0065] The above Q 1 It may also contain an alkenyl group or an alkynyl group having 2 to 10 carbon atoms.

[0066] The above Q 1 There is no limitation on the divalent organic group as long as it can achieve the effects of the present application, but it is preferably derived from a diepoxy-containing compound containing two epoxy groups. Specific examples include structures derived from compounds represented by the following (10-a) to (10-k).

[0067]

[0068] The above Q 1 Heterocyclic structures may be included. 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, triazone, triazinedione, and triazinetrione, or the heterocyclic structures shown in (10-h) to (10-k) above. Among them, triazinetrione is preferred, and specifically, the structures shown in formulas (10-h) to (10-k) above are preferred.

[0069] The above polymer may include a partial structure represented by the following formula (a-1):

[0070]

[0071] In formula (a-1), Y 1 、T 1 、T 2 , n1 and n2 are as defined above, L 1 and L 2Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted by a hydroxyl group and may be interrupted by an oxygen atom, and * represents a portion that bonds to the polymer residue.

[0072] L 1 and L 2 Preferably, it is an alkyl group having 1 to 10 carbon atoms substituted with a hydroxyl group and interrupted by an oxygen atom. The alkyl group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom means that an ether bond is contained between one or more carbon-carbon bonds of the alkyl group. 1 and L 2 The structure of is sometimes generated by the reaction of the solvent used in the reaction (for example, the solvent represented by the following (3d-1) or the following (3d-2)) with the carboxyl group derived from the above-mentioned compound (a), as in the synthesis examples described in the Examples.

[0073]

[0074] The above polymer may contain a repeating unit represented by the following formula (a-2):

[0075]

[0076] In formula (a-2), Y 1 、T 1 、T 2 , n1 and n2 are as defined above, L 1 and L 2 As defined above, 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 It represents a divalent organic group.

[0077] The weight average molecular weight of the polymer is preferably 500 to 50,000, more preferably 1,000 to 30,000. The weight average molecular weight can be measured, for example, by gel permeation chromatography as described in Examples.

[0078] The content of the polymer relative to the entire resist underlayer film-forming composition of the present invention is generally 0.05 to 3.0 mass%, 0.08 to 2.0 mass%, or 0.1 to 1.0 mass%.

[0079] As the organic solvent contained in the resist underlayer film-forming composition of the present application, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, 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 can be mentioned. These solvents can be used alone or in combination of two or more.

[0080] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone, etc. are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0081] The terminal of the above polymer can be capped with a compound.

[0082] The above compound can contain an aliphatic ring which can be substituted with a substituent.

[0083] The above aliphatic ring is preferably a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms. As the above monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms, 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 2,7 ]octane, spiro[3,4]octane, norbornane, norbornene, tricyclo[3.3.1.1 3,7 ]decane (adamantane), etc. can be mentioned.

[0084] The above polycyclic aliphatic ring is preferably a bicyclic or tricyclic ring.

[0085] As the above bicyclic ring, norbornane, norbornene, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, spiro[3,4]octane, etc. can be mentioned.

[0086] As the above tricyclic ring, tricyclo[3.2.1.0 2,7 ]octane, tricyclo[3.3.1.1 3,7 ]decane (adamantane) is preferred.

[0087] The aforementioned aliphatic ring which may be substituted by a substituent means that one or more hydrogen atoms of the aliphatic ring may be substituted by a substituent described below.

[0088] The substituent is preferably selected from a hydroxyl 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 carboxyl group.

[0089] Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pentoxy, 3-methyl-n-pentoxy, 4-methyl-n-pentoxy, 1,1-dimethyl-n-pentoxy, butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, and 1-ethyl-2-methyl-n-propoxy, cyclopentyloxy, cyclohexyloxy, norbornyloxy, adamantyloxy, adamantylmethoxy, adamantylethoxy, tetracyclodecyloxy, and tricyclodecyloxy.

[0090] 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.

[0091] Specific examples of the compound containing an aliphatic ring which may be substituted with a substituent include the following compounds. Specific examples include compounds in which the carboxyl group of the following specific examples is replaced with a hydroxyl group, an amino group, or a thiol group.

[0092]

[0093]

[0094] Regarding the polymer having an aliphatic ring which may be substituted with a substituent at the terminal, the entire disclosure of International Publication No. 2020 / 226141 is incorporated herein by reference.

[0095] The above compounds can be represented by the following formulas (1) and (2):

[0096]

[0097] In formulas (1) and (2), R1 represents an alkyl group having 1 to 6 carbon atoms which may have a substituent, a phenyl group, a pyridyl group, a halogen group or a hydroxyl group, R2 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, a halogen 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 hydroxyl group or a halogen 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 a heteroaromatic ring, t represents 0 or 1, and u represents 1 or 2.

[0098] The polymer terminal structures represented by the above formulae (1) and (2) can be produced by reacting the above polymers with a compound represented by the following formula (1a) and / or a compound represented by the following formula (2a).

[0099]

[0100] The meanings of the symbols in the above formula (1a) and formula (2a) are the same as those described in the above formula (1) and formula (2).

[0101] Examples of the compound represented by the above formula (1a) include compounds represented by the following formulae.

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] Examples of the compound represented by the above formula (2a) include compounds represented by the following formulas.

[0108]

[0109] Regarding the contents related to the above formula (1) and formula (2), all the disclosure contents described in International Publication No. 2015 / 163195 are incorporated herein by reference.

[0110] <Curing Catalyst>

[0111] The curing catalyst included as an optional component in the resist underlayer film-forming composition of the present invention is preferably an acid generator. Examples of the acid generator include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium-p-hydroxybenzenesulfonic acid (pyridinium p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and other sulfonic acid compounds and carboxylic acid compounds. 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.

[0112] <Crosslinking Agent>

[0113] Examples of the crosslinking agent 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, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0114] The crosslinking agent of the present application may be a nitrogen-containing compound described in International Publication No. 2017 / 187969, which has 2 to 6 substituents represented by the following formula (1d) bonded to a nitrogen atom per molecule.

[0115]

[0116] In formula (1d), R1 represents a methyl group or an ethyl group.

[0117] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (1d) per molecule may be a glycoluril derivative represented by the following formula (1E).

[0118]

[0119] 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.

[0120] Examples of the glycoluril derivative represented by the above formula (1E) include compounds represented by the following formulas (1E-1) to (1E-6).

[0121]

[0122] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (Id) per molecule is obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) bonded to a nitrogen atom per molecule with at least one compound represented by the following formula (3d).

[0123]

[0124] In the formulae (2d) and (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.

[0125] The glycoluril derivative represented by the above formula (1E) is obtained by reacting a glycoluril derivative represented by the following formula (2E) with at least one compound represented by the above formula (3d).

[0126] The nitrogen-containing compound having 2 to 6 substituents represented by the above formula (2d) per molecule is, for example, a glycoluril derivative represented by the following formula (2E).

[0127]

[0128] In the formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms. As the glycoluril derivative represented by the above formula (2E), for example, compounds represented by the following formulae (2E-1) to (2E-4) can be mentioned. Further, as the compound represented by the above formula (3d), for example, compounds represented by the following formulae (3d-1) and (3d-2) can be mentioned.

[0129]

[0130] The content regarding the nitrogen-containing compound having 2 to 6 substituents represented by the above formula (Id) bonded to a nitrogen atom per molecule is incorporated herein by reference to the entire disclosure of WO 2017 / 187969.

[0131] Further, the crosslinking agent can be a crosslinkable compound represented by the following formula (G-1) or formula (G-2) described in International Publication No. 2014 / 208542.

[0132]

[0133] In the formula, Q 1 represents a single bond or an organic group having m1 valence, R 1 and R 4Each of them represents an alkyl group having 2 to 10 carbon atoms or an alkyl group having 2 to 10 carbon atoms and having an alkoxy group having 1 to 10 carbon atoms, and R 2 and R 5 Represents a hydrogen atom or a methyl group, R 3 and R 6 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0134] n1 represents an integer of 1≤n1≤3, n2 represents an integer of 2≤n2≤5, n3 represents an integer of 0≤n3≤3, n4 represents an integer of 0≤n4≤3, and 3≤(n1+n2+n3+n4)≤6.

[0135] n5 represents an integer of 1≤n5≤3, n6 represents an integer of 1≤n6≤4, n7 represents an integer of 0≤n7≤3, n8 represents an integer of 0≤n8≤3, and 2≤(n5+n6+n7+n8)≤5.

[0136] m1 represents an integer from 2 to 10.

[0137] The crosslinkable compound represented by the above formula (G-1) or (G-2) can be obtained by reacting a compound represented by the following formula (G-3) or (G-4) with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0138]

[0139] Where Q 2 Represents a single bond or an m2-valent organic group. 8 、R 9 、R 11 and R 12 Represents a hydrogen atom or a methyl group, R 7 and R 10 Each represents an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0140] 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, and 3≤(n9+n10+n11+n12)≤6.

[0141] 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, and 2≤(n13+n14+n15+n16)≤5.

[0142] m2 represents an integer from 2 to 10.

[0143] Examples of the compounds represented by the above formula (G-1) and formula (G-2) include the following.

[0144]

[0145]

[0146]

[0147]

[0148]

[0149] Examples of the compounds represented by formula (G-3) and formula (G-4) include the following.

[0150]

[0151]

[0152] In the formula, Me represents a methyl group.

[0153] The entire disclosure of International Publication No. 2014 / 208542 is incorporated herein by reference.

[0154] When the cross-linking agent is used, the content ratio of the cross-linking agent is, for example, 1 mass % to 50 mass %, or preferably 5 mass % to 30 mass % based on the reaction product.

[0155] <Other ingredients>

[0156] The resist underlayer film-forming composition of the present invention may further contain a surfactant in order to prevent the generation of pinholes, streaks, and the like and to further improve coating properties with respect to surface unevenness. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, and sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate. Polyoxyethylene sorbitan fatty acid esters and other non-ionic surfactants such as sorbitol tristearate and other polyoxyethylene sorbitan fatty acid esters, EFT EF301, EF303, EF352 (Todo Co., Ltd. Made by ケムプロダクツ, brand name), Milk F171, F173, R-30 (made by Dainippon Co., Ltd., brand name), フロラード FC430, FC Fluorine-based surfactants such as 431 (trade name, manufactured by Sumitomo Soft-Em Co., Ltd.), Asahigard 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.) are also included. The amount of these surfactants added is usually 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solids 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.

[0157] 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 process and an EUV exposure process, and is preferably an EUV resist underlayer film-forming composition.

[0158] <Resist Underlayer Film>

[0159] The resist underlayer film according to the present invention can be produced by applying the above-mentioned resist underlayer film-forming composition on a semiconductor substrate and firing the composition.

[0160] The resist underlayer film according to the present invention is preferably an electron beam resist underlayer film or an EUV resist underlayer film.

[0161] Examples of the semiconductor substrate to which the resist underlayer film-forming composition of the present invention is applied include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0162] When using a semiconductor substrate having an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum evaporation, or spin coating (spin-on glass: SOG). Examples of the inorganic film include polycrystalline silicon film, silicon oxide film, silicon nitride film, BPSG (Boro-PhosphoSilicate Glass) film, titanium nitride film, titanium oxynitride film, tungsten film, gallium nitride film, and gallium arsenide film.

[0163] The resist underlayer film-forming composition of the present invention is applied to such a semiconductor substrate using an appropriate coating method such as a spin coater or a coater. The resist underlayer film is then baked using a heating means such as a hot plate to form the resist underlayer film. 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.

[0164] Examples of the thickness of the resist underlayer film to be formed include 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, and 0.006 μm (5 nm) to 0.05 μm. )~0.05μm(50nm), 0.003μm(3nm)~0.03μm(30nm), 0.003μm(3nm)~0.02μm(20nm), 0.005μm(5nm)~0.02μm(20nm), 0.002μm(2nm)~0.01μm(10nm), 0.003μm(3nm)~0.01μm(10nm), 0.002μm(2nm)~0.006μm(6nm), 0.004μm(4nm), 0.005μm(5nm). If the temperature during baking is lower than the above range, crosslinking becomes insufficient. On the other hand, if the temperature during baking is higher than the above range, the resist underlayer film may be decomposed by heat.

[0165] <Method for Manufacturing Patterned Substrate, Method for Manufacturing Semiconductor Device>

[0166] The method for manufacturing a patterned substrate involves the following steps. Typically, a photoresist layer is formed on a resist underlayer film. The photoresist, formed by coating and firing the resist underlayer film using a known method, is not particularly limited as long as it is sensitive to the light used for exposure. Both negative-type and positive-type photoresists can be used. Positive photoresists composed of a novolac resin and 1,2-naphthoquinonediazosulfonate, chemically amplified photoresists composed of a binder having a group whose alkali dissolution rate increases upon acid decomposition and a photoacid generator, chemically amplified photoresists composed of a low molecular weight compound whose alkali dissolution rate increases upon acid decomposition, an alkali-soluble binder, and a photoacid generator, chemically amplified photoresists composed of a binder having a group whose alkali dissolution rate increases upon acid decomposition, a low molecular weight compound whose alkali dissolution rate increases upon acid decomposition, and a photoacid generator, and resists containing metal elements, etc. Examples include V146G manufactured by JSR Corporation, APEX-E manufactured by Shipley Co., Ltd., PAR710 manufactured by Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 manufactured by Shin-Etsu Chemical Co., Ltd. In addition, 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) may be mentioned. Furthermore, so-called metal-containing resists (metal resists) containing metals may also be used.

[0167] As specific examples, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, Japanese Special Opening 2018-180525, WO2018 / 190088, Japanese Special Opening 2018-070596, Japanese Special Opening 2 018-028090, Japanese Special Opening 2016-153409, Japanese Special Opening 2016-130240, Japanese Special Opening 2016-108325, Japanese Special Opening 2016-047920, Japanese Special Opening 2016-035570, Japanese Special Opening 2016-035567, Japanese Special Opening 2016 -035565, Japan’s special opening 2019-101417, Japan’s special opening 2019-117373, Japan’s special opening 2019-052294, Japan’s special opening 2019-008280, Japan’s special opening 2019 -008279, Japan’s special opening 2019-003176, Japan’s special opening 2019-003175, Japan’s special opening 2018-197853, Japan’s special opening 2019-191298, Japan’s special opening 2019 -061217, Japan’s special opening 2018-045152, Japan’s special opening 2018-022039, Japan’s special opening 2016-090441, Japan’s special opening 2015-10878, Japan’s special opening 2012 -168279, Japanese Patent Application Laid-Open No. 2012-022261, Japanese Patent Application Laid-Open No. 2012-022258, Japanese Patent Application Laid-Open No. 2011-043749, Japanese Patent Application Laid-Open No. 2010-181857, Japanese Patent Application Laid-Open No. 2010-128369, WO2018 / 031896, Japanese Patent Application Laid-Open No. 2019-113855, WO2017 / 156388, WO2017 / 066319, Japanese Patent Application Laid-Open No. 2018-41099, WO2016 / 065120, WO2015 / 026482, Japanese Patent Application Laid-Open No. 2016-29498, Japanese Patent Application Laid-Open No. 2011-253185, etc., radiation-sensitive resin compositions, high-resolution patterning compositions based on organometallic solutions, so-called resist compositions, and metal-containing resist compositions are described, but are not limited thereto.

[0168] As the resist composition, for example, the following can be mentioned.

[0169] (i) A photosensitive or radiation-sensitive resin composition comprising a resin A and a compound represented by the general formula (11), wherein the resin A has a repeating unit of an acid-decomposable group, wherein the acid-decomposable group is a polar group protected by a protecting group that is detached by the action of an acid.

[0170]

[0171] In the general formula (11), m represents an integer of 1 to 6.

[0172] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0173] L1 represents -O-, -S-, -COO-, -SO2- or -SO3-.

[0174] L2 represents an alkylene group which may have a substituent or a single bond.

[0175] W1 represents a cyclic organic group which may have a substituent.

[0176] M + Represents a cation.

[0177] (ii) A composition for forming a metal-containing film 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.

[0178] (iii) A radiation-sensitive resin composition comprising a polymer and an acid generator, wherein the polymer has a first structural unit represented by the following formula (21) and a second structural unit containing an acid-dissociable group represented by the following formula (22).

[0179]

[0180] In formula (21), Ar is a group obtained by removing (n+1) hydrogen atoms from an aromatic hydrocarbon having 6 to 20 carbon atoms. 1 is a hydroxyl group, a sulfanyl group or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. When n is 2 or more, multiple R 1 Same or different. 2 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0181] In formula (22), R 3 It is a monovalent group having 1 to 20 carbon atoms and containing the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom or a sulfur atom. 4is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

[0182] (iv) A resist composition comprising a resin (A1) and an acid generator, wherein the resin (A1) has a structural unit containing a cyclic carbonate structure, a structural unit represented by formula (II), and a structural unit containing an acid-labile group.

[0183]

[0184] 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, and X 1 is a single bond, -CO-O-* or -CO-NR 4 -** represents the bond with -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 a hydroxyl group and a carboxyl group.

[0185] (v) A resist composition that generates acid upon exposure and changes its solubility in a developer under the action of the acid, characterized in that:

[0186] The invention comprises a base component (A) whose solubility in a developer changes under the action of an acid and a fluorine additive component (F) which is decomposable in an alkaline developer.

[0187] The fluorine additive component (F) contains a fluororesin component (F1) having a structural unit (f1) containing an alkali-dissociable group and a structural unit (f2) containing a group represented by the following general formula (f2-r-1).

[0188]

[0189] In formula (f2-r-1), Rf 21 Each is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group or a cyano group. n" is an integer from 0 to 2. * is a connecting bond.

[0190] (vi) The resist composition according to the above-mentioned (v), wherein the structural unit (f1) contains a structural unit represented by the following general formula (f1-1) or a structural unit represented by the following general formula (f1-2).

[0191]

[0192] In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms. X is a divalent linking group having no acid-dissociable site. arylX is a divalent aromatic ring group which may have a substituent. 01 is a single bond or a divalent linking group. 2 Each is independently an organic group having a fluorine atom.

[0193] Examples of metal-containing resist compositions include coatings comprising a metal oxy-hydroxy network having organic ligands via metal-carbon bonds and / or metal carboxylate bonds.

[0194] (vii) Inorganic oxygen / hydroxyl based compositions.

[0195] Examples of the resist film include the following.

[0196] (i) A resist film comprising a base resin having 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 a polymer main chain upon exposure.

[0197]

[0198] In formula (a1) and (a2), R A R are each independently a hydrogen atom or a methyl group. 1 and R 2 Each independently represents a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each independently represents a fluorine atom or a methyl group. m represents an integer from 0 to 4. 1 X is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms and comprising at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. 2 It is a single bond, an ester bond or an amide bond.

[0199] Examples of resist materials include the following.

[0200] (i) A resist material comprising a polymer having a repeating unit represented by the following formula (a1) or (a2).

[0201]

[0202] In formula (a1) and (a2), R A X 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, wherein a portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group or a group containing a lactone ring, and further, X 2 At least one hydrogen atom is replaced by a bromine atom. 3is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and a part of the methylene group constituting the alkylene group can be replaced with an ether group or an ester group. Rf 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. In addition, Rf 1 and Rf 2 may also combine to form a carbonyl group. R 1 ~R 5 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, a part or all of the hydrogen atoms of which are optionally substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amido group, a nitro group, a sultine group, a sulfo group, or a sulfonium salt-containing group, and a part of the methylene group constituting these groups is optionally replaced with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonate group. In addition, R 1 and R 2 may also combine to form a ring together with the sulfur atom to which they are bonded.

[0203] (ii) a resist material comprising a base resin comprising a polymer having a repeating unit represented by the following formula (a).

[0204]

[0205] In formula (a), R A is a hydrogen atom or a methyl group. R 1 is a hydrogen atom or an acid-labile group. R 2 is a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, or a halogen atom other than bromine. X 1 is a single bond, a phenylene group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms which can contain an ester group or a lactone ring. X 2 is -O-, -O-CH2-, or -NH-. m is an integer of 1 to 4. n is an integer of 0 to 3.

[0206] As the coating solution, for example, the following can be cited.

[0207] (i) a coating solution comprising an organic solvent, a first organometallic composition, and a hydrolyzable metal compound. The first organometallic composition is represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (wherein 0 < z ≤ 2 and 0 < (z + x) ≤ 4), the formula R'n SnX 4-n (wherein n = 1 or 2), or a mixture thereof, wherein R and R' are independently a hydrocarbon group having 1 to 31 carbon atoms, and X is a ligand having a hydrolysable bond to Sn or a combination thereof; the hydrolysable metal compound is represented by the formula MX' v (wherein, M is a metal selected from Groups 2 to 16 of the Periodic Table, v is a number from 2 to 6, and X' is a ligand having a hydrolysable M-X bond or a combination thereof).

[0208] (ii) a coating solution comprising an organic solvent, a formula RSnO (3 / 2-x / 2) (OH) x a first organometallic compound represented by the formula RSnO (OH) (x) (in the formula, 0 < x < 3). The solution contains tin in an amount of about 0.0025 M to about 1.5 M, and R is an alkyl group or a cycloalkyl group having 3 to 31 carbon atoms, the alkyl group or the cycloalkyl group being bonded to tin at a secondary carbon atom or a tertiary carbon atom.

[0209] (iii) an aqueous inorganic pattern-forming precursor solution comprising a mixture of water, metal suboxide cations, polyatomic inorganic anions, and a radiation-sensitive ligand comprising a peroxide group.

[0210] Exposure is performed through a mask (intermediate mask) for forming a prescribed pattern using, for example, i-ray, a KrF excimer laser, an ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam), and the resist underlayer film-forming composition of the present application is preferably used for EUV (extreme ultraviolet) exposure. An alkaline developer is used in development, and the development temperature and the development time are appropriately selected from a range of 5°C to 50°C and a range of 10 seconds to 300 seconds, respectively. As the alkaline developer, for example, an aqueous solution of an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, a primary amine such as ethylamine, n-propylamine, a secondary amine such as diethylamine, di-n-butylamine, a tertiary amine such as triethylamine, methyldiethylamine, an alcohol amine such as dimethyl ethanolamine, triethanolamine, a quaternary ammonium salt such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, a cyclic amine such as pyrrole, piperidine, or the like can be used. Further, an appropriate amount of an alcohol such as isopropyl alcohol, a surfactant such as a nonionic surfactant, or the like can be added to the above-described aqueous solution of an alkali and used. Among them, the preferred developer is a quaternary ammonium salt, and further preferred are tetramethylammonium hydroxide and choline. Further, a surfactant or the like can be added to these developers. A method in which an organic solvent such as butyl acetate is used instead of the alkaline developer to perform development on a portion of the photoresist for which the alkali dissolution rate is not increased can also be used. Through the above-described process, a substrate on which the above-described resist is patterned can be produced.

[0211] Next, the formed resist pattern is used as a mask to perform dry etching on the above-mentioned resist underlayer film. At this time, in the case where the above-mentioned inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed, and in the case where the above-mentioned inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. Then, by going through a process of processing the substrate by a publicly known method (dry etching method, etc.), a semiconductor device can be manufactured.

[0212] Example

[0213] The weight average molecular weight of the polymers shown in the following Synthesis Example 1 to Synthesis Example 3 and Comparative Synthesis Example 1 to Comparative Synthesis Example 3 of the present specification is based on the measurement results of gel permeation chromatography (hereinafter, abbreviated as GPC). The GPC device manufactured by Tosoh Corporation was used in the measurement, and the measurement conditions, etc. are as described below.

[0214] GPC column: Shodex KF803L, Shodex KF802, Shodex KF801 (registered trademark) (Showa Denko Co., Ltd.)

[0215] Column temperature: 40°C

[0216] Solvent: N,N-dimethylformamide (DMF)

[0217] Flow rate: 0.6 ml / minute

[0218] Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0219] < Synthesis Example 1 >

[0220] A monallyl diglycidyl isocyanurate (manufactured by Shikoku Chemicals Corporation) 3.00 g, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.27 g, 4-(methylsulfonyl)benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.64 g, tetrabutylphosphonium bromide (manufactured by Kitagawa Chemical Industry Co., Ltd.) 0.27 g were added to propylene glycol monomethyl ether 21.83 g and dissolved. After nitrogen substitution was performed on the reaction vessel, the reaction was performed at 105°C for 24 hours to obtain a polymer solution. Even if the polymer solution was cooled to room temperature, no turbidity, etc. was generated, and the solubility in propylene glycol monomethyl ether was good. GPC analysis was performed, and as a result, the weight average molecular weight of the polymer in the obtained solution was 8,300 in terms of standard polystyrene. The polymer obtained in the present synthesis example had the structural units represented by the following formulae (XX), (XY), (XZ).

[0221]

[0222] < Synthesis Example 2 >

[0223] 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 3.27 g of 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.53 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.27 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were added to 21.49 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction vessel, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. Even when the polymer solution was cooled to room temperature, it did not become turbid, etc., and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the weight average molecular weight of the polymer in the obtained solution was 12,300 in terms of standard polystyrene. The polymer obtained in this synthesis example has structural units represented by the following formulas (XX), (XY), and (Xa).

[0224]

[0225] <Synthesis Example 3>

[0226] 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 3.27 g of 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.27 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were added to 19.90 g of propylene glycol monomethyl ether and dissolved. After nitrogen replacement of the reaction vessel, the reaction was carried out at 105°C for 24 hours to obtain a polymer solution. Even when the polymer solution was cooled to room temperature, it did not become turbid, etc., and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the result showed that the weight average molecular weight of the polymer in the obtained solution was 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).

[0227]

[0228] <Comparative Synthesis Example 1>

[0229] 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 1.91 g of 3,3'-dithiodipropionic acid (manufactured by Sakai Chemical Industry Co., Ltd., trade name: DTDPA), 0.57 g of adamantane carboxylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.14 g of tetrabutylphosphonium bromide (manufactured by Hokuko Chemical Industry Co., Ltd.) were added to 6.87 g of propylene glycol monomethyl ether and dissolved. After nitrogen replacement of the reaction vessel, the reaction was carried out at 105°C for 8 hours to obtain a polymer solution. Even when the polymer solution was cooled to room temperature, it did not produce white turbidity, etc., and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the result showed that the weight average molecular weight of the polymer in the obtained solution was 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).

[0230]

[0231] <Comparative Synthesis Example 2>

[0232] 2.50 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 1.47 g of diethylbarbituric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.29 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.16 g of ethyltriphenylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 8.97 g of propylene glycol monomethyl ether and dissolved. After nitrogen substitution in the reaction vessel, the reaction was carried out at 110°C for 24 hours to obtain a polymer solution. The polymer solution did not become turbid even when cooled to room temperature and had good solubility in propylene glycol monomethyl ether. GPC analysis was performed, and the weight average molecular weight of the polymer in the obtained solution was 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).

[0233]

[0234] <Examples 1-3, Comparative Examples 1-2>

[0235] The polymers, crosslinking agents, curing catalysts, and solvents of Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 2 were mixed in the proportions shown in Tables 1 and 2, and filtered through a 0.1 μm fluororesin filter to prepare solutions of resist underlayer film-forming compositions.

[0236] In Tables 1 and 2, tetramethoxymethyl glycoluril (manufactured by Japan Science Instruments 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 added are expressed in parts by mass.

[0237] Table 1

[0238]

[0239] Table 2

[0240]

[0241] (Dissolution test in photoresist solvent)

[0242] The resist underlayer film-forming compositions of Examples 1, 2, and 3 and Comparative Examples 1 and 2 were each applied using a spin coater onto a silicon wafer serving as a semiconductor substrate. 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 for photoresists, and were confirmed to be insoluble in these solvents.

[0243] (Forming a positive resist pattern using EUV exposure equipment)

[0244] The compositions for forming a resist underlayer film of Examples 1, 2, and 3 and Comparative Examples 1 and 2 were applied to silicon wafers using a spin coater. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer film having a thickness of 4 nm. A positive resist solution for EUV (containing a methacrylic polymer) was spin-coated on 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 drawing apparatus (NXE-3400). After exposure, the film was baked (PEB) at 100°C for 60 seconds, cooled to room temperature on a cooling plate, and developed with an alkaline developer (2.38% TMAH) to form a resist pattern with a 19 nm linear pattern and a 32 nm pitch. The length of the resist pattern was measured using a scanning electron microscope (CG4100, manufactured by Hitachi High-Tech Norodomics). In the resist pattern formation described above, formation of a linear pattern with a CD size of 19 nm was considered "good," while observation of bridging of the linear pattern was considered "poor." The results are shown in Table 3.

[0245] Table 3

[0246] CD size 19 nm linear pattern Example 1 Good Example 2 Good Example 3 Good Comparative Example 1 Poor Comparative Example 2 Poor

[0247] Compared with Comparative Examples 1 and 2, Examples 1, 2, and 3 can suppress bridging in the linear pattern, demonstrating good pattern forming ability.

[0248] Industrial applicability

[0249] The resist underlayer film-forming composition of the present invention can provide a resist underlayer film-forming composition capable of forming a desired resist pattern, and a method for manufacturing a substrate with a resist pattern and a method for manufacturing a semiconductor device using the resist underlayer film-forming composition.

Claims

1. A resist underlayer film-forming composition comprising a polymer having a repeating unit represented by the following formula (a-2) and a solvent; In formula (a-2), Y 1 represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted by an oxygen atom, a sulfur atom or a halogen atom, 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, 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 structure derived from the compounds represented by the following (10-h) to (10-k), 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 by a hydroxy group or interrupted by an oxygen atom.

2. The resist underlayer film-forming composition according to claim 1, wherein the Y 1 It is a sulfonyl group.

3. The resist underlayer film-forming composition according to claim 1, wherein the terminal of the polymer is capped with a compound selected from the following compounds and compounds in which the carboxyl group of the following compounds is replaced by a hydroxyl group, an amino group, and a thiol group; 4. The resist underlayer film-forming composition according to claim 1, wherein the terminal of the polymer is capped with a compound selected from the following compounds: The resist underlayer film-forming composition according to claim 1 , further comprising a curing catalyst. The resist underlayer film-forming composition according to claim 1 , further comprising a cross-linking agent.

7. A resist underlayer film, characterized in that: A fired product of a coating film formed from the resist underlayer film-forming composition according to any one of claims 1 to 6.

8. A method for manufacturing a patterned substrate, comprising: A step of applying the resist underlayer film-forming composition according to any one of claims 1 to 6 on a semiconductor substrate and baking the composition to form a resist underlayer film, a step of coating a resist on the resist underlayer film and baking the resist to form a resist film; exposing the semiconductor substrate covered with the resist underlayer film and the resist, and The exposed resist film is developed and patterned.

9. A method for manufacturing a semiconductor device, characterized in that: Include: a step of forming a resist underlayer film formed from the resist underlayer film-forming composition according to any one of claims 1 to 6 on a semiconductor substrate, 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 etching the resist underlayer film through the formed resist pattern to form a patterned resist underlayer film, and A step of processing a semiconductor substrate using the patterned resist underlayer film.

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