Resist underlayer forming composition containing a polymer with aryl group-encapsulated side chains

Abstract

To provide a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for producing a resist pattern using the resist underlayer film forming composition, and a method for producing a semiconductor device. [Solution] The following formula (1): TIFF2026140846000065.tif38165 (In formula (1), 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, and R 1 represents a tetravalent organic group, Q 1 represents a divalent organic group, L 1 represents a single bond or an alkylene group having 1 to 10 carbon atoms, Ar 1 represents an aryl group having 6 to 40 carbon atoms which may be substituted with a substituent.) The resist underlayer film forming composition contains a polymer having a unit structure represented by and a solvent.

Description

[Technical Field]

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

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

[0003] Patent Document 1 discloses a resist underlayer film forming composition that includes a polymer obtained by reacting a tetracarboxylic dianhydride having an alicyclic or aliphatic structure with a diexoyl compound. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] International Publication No. 2009 / 104685 [Overview of the project] [Problems that the invention aims to solve]

[0005] The required properties for the resist underlayer include, for example, that it does not intermix with the resist film formed on top (i.e., it is insoluble in the resist solvent) and that it has a faster dry etching rate compared to 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 and used with a thinner film thickness than conventional methods. When forming such thin films, 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, in the development process for forming resist patterns, a major challenge is improving the adhesion of the resist pattern in negative development processes, which use a solvent capable of dissolving the resist film, usually an organic solvent, to remove the unexposed parts of the resist film and leave the exposed parts as the resist pattern, and in positive development processes, which remove the exposed parts of the resist film and leave the unexposed parts as the resist pattern.

[0008] Furthermore, there is a need to suppress the deterioration of LWR (Line Width Roughness, fluctuations in line width (roughness)) during resist pattern formation, to form a resist pattern with a good rectangular shape, and to improve resist sensitivity.

[0009] The present invention aims to provide a composition for forming a resist underlayer film that can form a desired resist pattern, and a method for forming a resist pattern using the resist underlayer film forming composition, which solves the above problems. [Means for solving the problem]

[0010] The present invention includes the following.

[0011] [1] Formula (1) below:

Chemical Formula

[0012] [2] The R 1 comprises an aromatic ring structure having 6 to 40 carbon atoms or an alicyclic structure having 4 to 20 carbon atoms, the resist underlayer film-forming composition according to [1].

[0013] [3] The R 1 is formula (2), formula (3) or formula (4) below:

Chemical Formula

[0014] [4] The aforementioned Q 1 A resist underlayer forming composition according to any one of [1] to [3], comprising an alkenyl group or alkynyl group having 2 to 10 carbon atoms.

[0015] [5] The aforementioned Q 1 A resist underlayer film forming composition according to any one of [1] to [4], comprising a heterocycle.

[0016] [6] The resist underlayer forming composition according to any one of [1] to [5], wherein the polymer has aryl groups having 6 to 40 carbon atoms, which may be substituted with substituents, at its terminus.

[0017] [7] The resist underlayer forming composition according to [6], wherein an aryl group having 6 to 40 carbon atoms, which may be substituted with the substituent, is bonded to the polymer via an aliphatic ring, which may be substituted with the substituent, and a linking group.

[0018] [8] A resist underlayer film forming composition according to any one of [1] to [7], further comprising an acid generator.

[0019] [9] A resist underlayer film forming composition according to any one of [1] to [8], further comprising a crosslinking agent.

[0020]

[10] A resist underlayer film characterized by being a fired product of a coated film made from the resist underlayer film forming compositions described in [1] to [9].

[0021]

[11] A step of forming a resist underlayer film by applying a resist underlayer film forming composition described in any one of items [1] to [9] onto a semiconductor substrate and baking it, A step of forming a resist film by coating the resist on the resist underlayer film and baking it. A step of exposing the resist underlayer film and the semiconductor substrate coated with the resist, The process of developing and patterning the resist film after exposure. A method for manufacturing patterned substrates, including [the specified method].

[0022]

[12] A step of forming a resist underlayer on a semiconductor substrate, comprising a resist underlayer forming composition according to any one of items [1] to [9], A step of forming a resist film on the resist underlayer film, A process of forming a resist pattern by irradiating a resist film with light or an electron beam and then developing it, A step of forming a patterned resist underlayer film by etching the resist underlayer film through the formed resist pattern, A process of processing a semiconductor substrate with the patterned resist underlayer film, A method for manufacturing a semiconductor device, characterized by including the following: [Effects of the Invention]

[0023] The resist underlayer film forming composition of the present invention has excellent coatability on the semiconductor substrate to be processed and excellent adhesion between the resist and the resist underlayer film interface during resist pattern formation, enabling the formation of a good resist pattern with a rectangular shape without peeling of the resist pattern. This effect is particularly pronounced when using EUV (wavelength 13.5 nm) or EB (electron beam). [Modes for carrying out the invention]

[0024] <Resist Underlayer Film Forming Composition> The resist underlayer film forming composition of the present invention is defined by the following formula (1): [ka] (In formula (1), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 Each of these independently represents a hydrogen atom, a methyl group, or an ethyl group, and R 1 represents a tetravalent organic group, Q 1 represents a divalent organic group, L 1 represents a single bond or an alkylene group with 1 to 10 carbon atoms, Ar 1 The polymer has a unit structure represented by ) and a solvent.

[0025] The alkylene groups having 1 to 10 carbon atoms include methylene, ethylene, n-propylene, isopropylene, cyclopropylene, n-butylene, isobutylene, s-butylene, t-butylene, cyclobutylene, 1-methylcyclopropylene, 2-methylcyclopropylene, 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, and 1-ethyl-n-propylene. Polyethylene group, cyclopentylene group, 1-methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1,1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group , 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n-butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2,2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2-methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene n group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1,2,3-trimethyl-cyclopropylene group, 2,2,Examples include 3-trimethylcyclopropylene group, 1-ethyl-2-methylcyclopropylene group, 2-ethyl-1-methylcyclopropylene group, 2-ethyl-2-methylcyclopropylene group, 2-ethyl-3-methylcyclopropylene group, n-heptylene group, n-octylene group, n-nonylene group, or n-decanylene group.

[0026] Examples of the aryl group having 6 to 40 carbon atoms include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-fluorophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-nitrophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.

[0027] An aryl group having 6 to 40 carbon atoms substituted with the aforementioned substituent means that one or more hydrogen atoms of the aryl group are substituted with a group selected from the following: hydroxyl group, epoxy group, acyl group, acetyl group, formyl group, benzoyl group, carboxyl group, carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, and allyl group.

[0028] The aforementioned R 1 However, it may include an aromatic ring structure with 6 to 40 carbon atoms or an alicyclic structure with 4 to 20 carbon atoms.

[0029] The aforementioned R 1 However, equation (2), equation (3), or equation (4) below: [ka] (In equations (2), (3), and (4), Y 1T represents a single bond, an oxygen atom, a sulfur atom, a halogen atom, or an alkylene group or sulfonyl group having 1 to 10 carbon atoms which may be substituted with an aryl group having 6 to 40 carbon atoms. 1 and T 2 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L 2 * represents a single bond, a methylene group, or an ethylene group; n1 and n2 each independently represent integers from 0 to 4; m1 represents an integer from 0 to 2; and * represents R in equation (1). 1 This is the bond portion between the carbonyl group and the carbon atom to which it is bonded. ) This can be represented as ).

[0030] Specific examples of alkylene groups having 1 to 10 carbon atoms that may be substituted with aryl groups having 6 to 40 carbon atoms in the above formula are as described above.

[0031] The alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, i-propyl group, cyclopropyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, and 1-ethyl-n-propyl group. Group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2 -dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,Examples include the 3-trimethylcyclopropyl group, the 1-ethyl-2-methylcyclopropyl group, the 2-ethyl-1-methylcyclopropyl group, the 2-ethyl-2-methylcyclopropyl group, the 2-ethyl-3-methylcyclopropyl group, and the decyl group.

[0032] The aforementioned Q 1 However, it may contain an alkenyl group or alkynyl group having 2 to 10 carbon atoms.

[0033] The aforementioned alkenyl groups having 2 to 10 carbon atoms include ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2- Ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group , 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group, 2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i Examples include the propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, and 3-cyclohexenyl group.

[0034] Examples of the alkynyl groups having 2 to 10 carbon atoms include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 4-methyl-1-pentynyl group, and 3-methyl-1-pentynyl group.

[0035] The aforementioned Q 1 However, it may include complex algebras.

[0036] Examples of the aforementioned heterocycles include furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, morpholine, indole, purine, quinoline, isoquinoline, quinuclidine, chromene, thianthlene, phenothiazine, phenoxazine, xanthene, acridine, phenazine, carbazole, triazineone, triazinedione, and triazinetrione.

[0037] The aforementioned R 1 The tetravalent organic group represented by may be derived from the following compounds.

[0038] [ka]

[0039] The aforementioned Q 1 The divalent organic group represented by may be derived from the following compounds.

[0040] [ka]

[0041] (R 0 (This represents an alkylene group with 2 to 6 carbon atoms.) [ka]

[0042] The polymer of the present invention is R 1 A compound for inducing Q 1 The reaction product may be obtained by polymerizing a compound for inducing the reaction using a known method, for example, as described in the examples.

[0043] The lower limit of the weight-average molecular weight of the polymer is, for example, 500, 1,000, 2,000, or 3,000, and the upper limit of the weight-average molecular weight of the reaction product is, for example, 30,000, 20,000, or 10,000.

[0044] <Solvent> The solvent used in the resist underlayer film forming composition of the present invention is not particularly limited as long as it is a solvent that can uniformly dissolve solid components such as the polymer at room temperature, but organic solvents commonly used in semiconductor lithography process chemicals are preferred. Specifically, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cyclo Examples include heptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl ethoxyacetate, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents can be used individually or in combination of two or more.

[0045] Among these solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, and cyclohexanone are preferred. Propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are particularly preferred.

[0046] The polymer may have aryl groups having 6 to 40 carbon atoms at its termini, which may be substituted with substituents.

[0047] The substituents and aryl groups having 6 to 40 carbon atoms are as described above.

[0048] The aryl group having 6 to 40 carbon atoms, which may be substituted with the substituents, may be bonded to the polymer via an aliphatic ring, which may also be substituted with substituents, and a linking group.

[0049] Examples of the linking groups include single bonds, ether bonds, sulfide bonds, amide bonds, and ester bonds.

[0050] The aliphatic ring may be a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms.

[0051] Examples of monocyclic or polycyclic aliphatic rings 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[3.2.1.02,7]octane, spiro[3,4]octane, norbornane, norbornene, and tricyclo[3.3.1.13,7]decane (adamantane).

[0052] The polycyclic aliphatic ring is preferably a bicyclo ring or a tricyclo ring. Examples of bicyclo rings include norbornane, norbornene, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, and spiro[3,4]octane. Examples of tricyclo rings include tricyclo[3.2.1.02,7]octane and tricyclo[3.3.1.13,7]decane (adamantane).

[0053] The aliphatic ring which may be substituted with the substituents mentioned above means that one or more hydrogen atoms of the aliphatic ring may be replaced with the substituents described below.

[0054] 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 aryl group having 6 to 40 carbon atoms, an acyloxy group having 1 to 10 carbon atoms which may be interrupted by an oxygen atom, and a carboxyl group.

[0055] The alkoxy groups having 1 to 20 carbon atoms include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1, Examples include 2-dimethyl-n-butoxy group, 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, and 1-ethyl-2-methyl-n-propoxy group, cyclopentyloxy group, cyclohexyloxy group, norbornioxy group, adamantyloxy group, adamantanemethyloxy group, adamantaneethyloxy group, tetracyclodecanyloxy group, and tricyclodecanyloxy group.

[0056] Examples of the aryl group having 6 to 40 carbon atoms include benzyl, naphthyl, anthracenyl, phenantrenyl, or pyrenyl groups, but among these, the phenyl group is preferred.

[0057] The acyloxy group having 1 to 10 carbon atoms is defined by the following formula (4): [ka] (In formula (4), Z is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms from among the alkyl groups having 1 to 10 carbon atoms, and the alkyl group may be substituted with the substituent, interrupted by an oxygen atom or an ester bond, or have an allyl group or a propagyl group. * represents the bond with the "aliphatic ring".)

[0058] It is preferable that the aliphatic ring has at least one unsaturated bond (e.g., a double bond or a triple bond). It is preferable that the aliphatic ring has one to three unsaturated bonds. It is preferable that the aliphatic ring has one or two unsaturated bonds. It is preferable that the unsaturated bonds are double bonds.

[0059] Specific examples of compounds containing an aliphatic ring which may be substituted with the aforementioned substituents include the compounds listed below. Specific examples also include compounds in which the carboxyl group of the following specific examples is replaced with a hydroxyl group, acyl group, acetyl group, formyl group, benzoyl group, carboxyl group, carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, and allyl group.

[0060] [ka] [ka] [ka] [ka]

[0061] The ends of the polymer of the present invention may be sealed with compound (C) described below. The compound (C) is not limited to any compound that exhibits the effects of the present invention, but it is preferably a compound having one functional group that is reactive with an epoxy group containing an aliphatic ring or aromatic ring, which may be substituted with substituents.

[0062] The aforementioned compound (C) is given by the following formulas (11) and (12): [ka] (In formulas (11) and (12), R1 represents an alkyl group having 1 to 6 carbon atoms which may have substituents, 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 which may have substituents, 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 substituents; R3 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have substituents, 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 an aromatic heterocycle; t represents 0 or 1; and u represents 1 or 2.)

[0063] The contents relating to formulas (11) and (12) above are fully disclosed in International Publication No. 2015 / 163195, which is incorporated herein by reference.

[0064] The polymer terminal structures represented by formulas (11) and (12) above 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).

[0065] [ka] (The meanings of the symbols in equations (1a) and (2a) above are as explained in equations (11) and (12) above.) Examples of compounds represented by formula (1a) include those represented by the following formula. Specific examples also include compounds in which the carboxyl group or hydroxyl group of the following compound is replaced by an acyl group, acetyl group, formyl group, benzoyl group, carboxyl group, carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, and allyl group.

[0066] [ka] [ka] [ka] [ka] [ka]

[0067] Examples of compounds represented by formula (2a) include those represented by the following formula.

[0068] [ka]

[0069] The aforementioned compound (C) may be a compound represented by the following formula (1-1) as described in International Publication No. 2020 / 071361.

[0070] [ka] (In formula (1-1) above, X is a divalent organic group, A is an aryl group having 6 to 40 carbon atoms, R1 is a halogen atom, an alkyl group having 1 to 40 carbon atoms, or an alkoxy group having 1 to 40 carbon atoms, n1 is an integer from 1 to 12, and n2 is an integer from 0 to 11.) The carboxyl group in formula (1-1) may be replaced with a hydroxyl group, acyl group, acetyl group, formyl group, benzoyl group, carboxyl group, carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, or allyl group.

[0071] Specific examples of X mentioned above include ester bonds, ether bonds, amide bonds, urethane bonds, or urea bonds, with ester bonds or ether bonds being preferred among these.

[0072] Specific examples of A above include groups derived from benzene, naphthalene, anthracene, phenanthrene, or pyrene, with groups derived from benzene, naphthalene, or anthracene being preferred among these.

[0073] Examples of the halogen atoms mentioned above include fluorine, chlorine, bromine, and iodine atoms.

[0074] Specific examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, hexyl, or pentyl groups, with methyl being preferred among these.

[0075] Specific examples of the alkoxy group having 1 to 10 carbon atoms mentioned above include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexoxy group, or a pentoxy group, with the methoxy group being preferred among these.

[0076] The phrase "may be substituted" means that some or all of the hydrogen atoms of the alkyl group having 1 to 10 carbon atoms may be substituted with, for example, a fluoro group or a hydroxyl group.

[0077] Specific examples of the alkyl group having 1 to 10 carbon atoms include the methyl group, ethyl group, propyl group, butyl group, hexyl group, or pentyl group, but the methyl group is preferred.

[0078] As mentioned above, the aryl group having 6 to 40 carbon atoms is as described, but among these, the phenyl group is preferred.

[0079] n1 and n3 are each independent integers between 1 and 12, but integers between 1 and 6 are preferred.

[0080] n² can be an integer between 0 and 11, but an integer between 0 and 2 is preferred.

[0081] In the above formula (1-1), it is preferable that n2 is 0.

[0082] Specific examples of compounds represented by formula (1-1) include the compounds listed below. The carboxyl group of the compounds listed below may be replaced with a hydroxyl group, acyl group, acetyl group, formyl group, benzoyl group, carboxyl group, carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, and allyl group.

[0083] [ka] [ka] [ka] [ka] [ka] [ka]

[0084] The aforementioned compound (C) may be a compound represented by the following formula (2-1) as described in International Publication No. 2020 / 071361.

[0085] [ka] (In formula (2-1) above, X is a divalent organic group, A is an aryl group having 6 to 40 carbon atoms, R2 and R3 are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 40 carbon atoms, or a halogen atom, and n3 is an integer from 1 to 12.) In the above formula (2-1), the preferred X, A, R2, R3, and n3 in the present invention are as described above. In the above formula (2-1), it is preferable that R2 and R3 are hydrogen atoms.

[0086] Specific examples of compounds represented by formula (1-1) include the compounds listed below. The carboxyl group of the compounds listed below may be replaced with a hydroxyl group, acyl group, acetyl group, formyl group, benzoyl group, carboxyl group, carbonyl group, amino group, imino group, cyano group, azo group, azi group, thiol group, sulfo group, and allyl group.

[0087] [ka]

[0088] The full disclosure contained in International Publication No. 2020 / 071361 is incorporated herein by reference.

[0089] <Acid Generator> As an optional component in the resist underlayer film forming composition of the present invention, either a thermal acid generator or a photoacid generator can be used, but the use of a thermal acid generator is preferred. Examples of thermal acid generators include sulfonic acid compounds and carboxylic acid compounds such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate (pyridinium-p-toluenesulfonic acid), pyridinium phenolsulfonic acid, pyridinium-p-hydroxybenzenesulfonic acid (pyridinium salt of p-phenolsulfonic acid), pyridinium-trifluoromethanesulfonic acid, salicylic acid, camphorsulfonic acid, 5-sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0090] Examples of the photoacid generator include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0091] Examples of iodonium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoron-butanesulfonate, diphenyliodonium perfluoron-octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butanesulfonate, triphenylsulfonium camphorsulfonate and triphenylsulfonium trifluoromethanesulfonate.

[0092] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0093] Examples of disulfonyl diazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0094] The aforementioned acid generating agent can be used by one type only, or by a combination of two or more types.

[0095] When the aforementioned acid generator is used, the content of the acid generator is, for example, 0.1% to 50% by mass, preferably 1% to 30% by mass, relative to the crosslinking agent described below.

[0096] <Crosslinking agent> Examples of crosslinking agents that may be included as optional components in the resist underlayer film forming composition of the present invention include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (tetramethoxymethylglycoluryl) (POWDERLINK® 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, and 1,1,3,3-tetrakis(methoxymethyl)urea.

[0097] Furthermore, the crosslinking agent of this application may be a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (1d) that bond to a nitrogen atom in one molecule, as described in International Publication No. 2017 / 187969.

[0098] [ka] (In formula (1d), R1 represents a methyl group or an ethyl group.) A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule may be a glycoluryl derivative represented by the following formula (1E).

[0099] [ka] (In formula (1E), each of the four R1s independently represents a methyl group or an ethyl group, and R2 and R3 independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group.) Examples of glycoluryl derivatives represented by formula (1E) include the compounds represented by the following formulas (1E-1) to (1E-6).

[0100] [ka]

[0101] A nitrogen-containing compound having 2 to 6 substituents represented by formula (1d) in one molecule can be obtained by reacting a nitrogen-containing compound having 2 to 6 substituents represented by the following formula (2d) that bond to a nitrogen atom in one molecule with at least one compound represented by the following formula (3d).

[0102] [ka] (In formulas (2d) and (3d), R1 represents a methyl group or an ethyl group, and R4 represents an alkyl group having 1 to 4 carbon atoms.) The glycoluryl derivative represented by formula (1E) is obtained by reacting a glycoluryl derivative represented by the following formula (2E) with at least one compound represented by formula (3d).

[0103] A nitrogen-containing compound having 2 to 6 substituents represented by formula (2d) in one molecule is, for example, a glycoluryl derivative represented by the following formula (2E).

[0104] [ka] (In formula (2E), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and R4 each independently represents an alkyl group having 1 to 4 carbon atoms.) Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0105] [ka] [ka]

[0106] With regard to nitrogen-containing compounds having 2 to 6 substituents represented by the following formula (1d) bonded to the aforementioned nitrogen atom in one molecule, the full disclosure in WO2017 / 187969 is incorporated herein by reference.

[0107] Furthermore, the above-mentioned crosslinking agent may be a crosslinkable compound represented by the following formula (G-1) or formula (G-2) as described in International Publication No. 2014 / 208542.

[0108] [ka] (In the formula, Q 1 R indicates a single bond or an m1 valent organic group. 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 having an alkoxy group having 1 to 10 carbon atoms, R 2 and R 5 Each represents either a hydrogen atom or a methyl group, and R 3 and R 6 Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. n1 is an integer between 1 and 3, n2 is an integer between 2 and 5, n3 is an integer between 0 and 3, n4 is an integer between 0 and 4, and 3 is an integer between 6 and 10 (n1 + n2 + n3 + n4). n5 is an integer between 1 and 5 (1 ≤ n5 ≤ 3), n6 is an integer between 1 and 6 (1 ≤ n6 ≤ 4), n7 is an integer between 0 and 7 (0 ≤ n7 ≤ 3), n8 is an integer between 0 and 8 (0 ≤ n8 ≤ 3), and 2 is an integer between 2 and (n5 + n6 + n7 + n8) ≤ 5. m1 represents an integer between 2 and 10.

[0109] The crosslinkable compound represented by formula (G-1) or formula (G-2) above may be obtained by reacting a compound represented by formula (G-3) or formula (G-4) below with a hydroxyl group-containing ether compound or an alcohol having 2 to 10 carbon atoms.

[0110] [ka] (In the formula, Q 2 R indicates a single bond or an m2 valent organic group. 8 , R 9 , R 11 and R 12 Each represents either a hydrogen atom or a methyl group, and R 7 and R 10 Each of these represents an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 40 carbon atoms. n9 represents an integer between 1 ≤ n9 ≤ 3, n10 represents an integer between 2 ≤ n10 ≤ 5, n11 represents an integer between 0 ≤ n11 ≤ 3, n12 represents an integer between 0 ≤ n12 ≤ 3, and 3 represents an integer between 3 ≤ (n9 + n10 + n11 + n12) ≤ 6. n13 represents an integer between 1 ≤ n13 ≤ 3, n14 represents an integer between 1 ≤ n14 ≤ 4, n15 represents an integer between 0 ≤ n15 ≤ 3, n16 represents an integer between 0 ≤ n16 ≤ 3, and 2 represents an integer between 2 ≤ (n13 + n14 + n15 + n16) ≤ 5. m² represents an integer between 2 and 10.

[0111] The compounds represented by formulas (G-1) and (G-2) above can be exemplified as follows.

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115] [ka]

[0116] [ka]

[0117] The compounds represented by formulas (G-3) and (G-4) can be exemplified below.

[0118] [ka]

[0119] [ka] In the formula, Me represents a methyl group.

[0120] The full disclosure of International Publication No. 2014 / 208542 is incorporated herein by reference.

[0121] When the crosslinking agent is used, the content of the crosslinking agent is, for example, 1% to 50% by mass, preferably 5% to 30% by mass, relative to the reaction product.

[0122] <Other ingredients> The resist underlayer film-forming composition of the present invention does not produce pinholes or striations, and a surfactant can be added to further improve the coatability against surface unevenness. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by Dainippon Ink, Inc., product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added individually or in combination of two or more types.

[0123] The solid content of the resist underlayer film forming composition of the present invention, i.e., the components excluding the solvent, is, for example, 0.01% to 10% by mass.

[0124] <Underlying resist film> The resist underlayer film according to the present invention can be manufactured by applying the aforementioned resist underlayer film forming composition onto a semiconductor substrate and firing it.

[0125] Examples of semiconductor substrates to which the resist underlayer film forming composition of the present invention is coated include silicon wafers, germanium wafers, and compound semiconductor wafers such as gallium arsenide, indium phosphide, gallium nitride, indium nitride, and aluminum nitride.

[0126] When using a semiconductor substrate with an inorganic film formed on its surface, the inorganic film is formed by, for example, ALD (atomic layer deposition), CVD (chemical vapor deposition), reactive sputtering, ion plating, vacuum deposition, or spin coating (spin-on-glass: SOG). Examples of the inorganic film include polysilicon films, silicon oxide films, silicon nitride films, BPSG (Boro-Phospho-Silicate Glass) films, titanium nitride films, titanium oxide nitride films, tungsten films, gallium nitride films, and gallium arsenide films.

[0127] The resist underlayer film forming composition of the present invention is applied to such a semiconductor substrate by an appropriate coating method such as a spinner or coater. Subsequently, the resist underlayer film is formed by baking using a heating means such as a hot plate. The baking conditions are appropriately selected from a bake temperature of 100°C to 400°C and a bake time of 0.3 minutes to 60 minutes. Preferably, the bake temperature is 120°C to 350°C and the bake time is 0.5 minutes to 30 minutes, and more preferably, the bake temperature is 150°C to 300°C and the bake time is 0.8 minutes to 10 minutes.

[0128] The thickness of the resist underlayer film formed can be, for example, 0.001 μm (1 nm) to 10 μm, 0.002 μm (2 nm) to 1 μm, 0.005 μm (5 nm) to 0.5 μm (500 nm), 0.001 μm (1 nm) to 0.05 μm (50 nm), 0.002 μm (2 nm) to 0.05 μm (50 nm), 0.003 μm (3 nm) to 0.05 μm (50 nm), 0.004 μm (4 nm) to 0.05 μm (50 nm), or 0.005 μm (5 nm). The thicknesses are as follows: 0.003μm(3nm)~0.03μm(30nm), 0.003μm(3nm)~0.02μm(20nm), 0.005μm(5nm)~0.02μm(20nm), 0.002μm(2nm)~0.01μm(10nm), 0.003μm(3nm)~0.01μm(10nm), 0.002μm(2nm)~0.006μm(6nm), 0.004μm(4nm), and 0.005μm(5nm). If the baking temperature is lower than the above range, crosslinking will be insufficient. On the other hand, if the baking temperature is higher than the above range, the resist underlayer film may decompose due to heat.

[0129] <Manufacturing method for patterned substrates, manufacturing method for semiconductor devices> The manufacturing process for patterned substrates involves the following steps. Typically, a photoresist layer is formed on a resist underlayer film. The photoresist formed by coating and firing on the resist underlayer film using a known method is not particularly limited as long as it is sensitive to the light used for exposure. Both negative and positive photoresists can be used. Examples include positive photoresists consisting of novolac resin and 1,2-naphthoquinone diazide sulfonic acid ester, chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a photoacid generator, chemically amplified photoresists consisting of a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist, an alkali-soluble binder and a photoacid generator, and chemically amplified photoresists consisting of a binder having a group that decomposes with acid to increase the alkali dissolution rate and a low-molecular-weight compound that decomposes with acid to increase the alkali dissolution rate of the photoresist and a photoacid generator, as well as resists containing metal elements. Examples include V146G from JSR Corporation, APEX-E from Cyprey Corporation, PAR710 from Sumitomo Chemical Co., Ltd., and AR2772 and SEPR430 from Shin-Etsu Chemical Co., Ltd. Additionally, examples include fluorine-containing polymer photoresists, such as those described in Proc.SPIE, Vol.3999, 330-334 (2000), Proc.SPIE, Vol.3999, 357-364 (2000), and Proc.SPIE, Vol.3999, 365-374 (2000).

[0130] Also, WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, WO201 9 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-117373, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-18 While so-called resist compositions and metal-containing resist compositions such as those described in JP 1857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0131] Examples of resist compositions include the following compositions.

[0132] A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protecting groups that are removed by the action of an acid, and a compound represented by general formula (21).

[0133] [ka] In general formula (21), m represents an integer from 1 to 6.

[0134] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0135] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0136] L2 represents an alkylene group or single bond which may have substituents.

[0137] W1 represents a cyclic organic group which may have substituents.

[0138] M + This represents a cation.

[0139] A metal-containing film-forming composition for extreme ultraviolet or electron beam lithography, comprising a compound having a metal-oxygen covalent bond and a solvent, wherein the metal element constituting the compound belongs to the 3rd to 7th periods of groups 3 to 15 of the periodic table.

[0140] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (31) and a second structural unit represented by the following formula (32) that includes an acid-dissociable group, and an acid generator.

[0141] [ka] (In formula (31), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene with 6 to 20 carbon atoms. 1 R is a hydroxyl group, a sulfanyl group, or a monovalent organic group having 1 to 20 carbon atoms. n is an integer from 0 to 11. If n is 2 or greater, multiple R groups are used. 1 They are the same or different. 2 R is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. In formula (32), R 3 This is a monovalent group having 1 to 20 carbon atoms that contains the above-mentioned acid-dissociable group. Z is a single bond, an oxygen atom, or a sulfur atom. R 4 (This is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.)

[0142] A resist composition containing a resin (A1) comprising structural units having a cyclic carbonate ester structure, structural units represented by formula (II), and structural units having acid-unstable groups, and an acid generator.

[0143] [ka] [In formula (II), R 2 X represents an alkyl group having 1 to 6 carbon atoms, a hydrogen atom, or a halogen atom, which may have a halogen atom. 1 These are single bonds, -CO-O-*, or -CO-NR 4 -* represents a bond with -Ar, and R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may have one or more groups selected from the group consisting of hydroxyl groups and carboxyl groups.

[0144] Examples of resist films include the following:

[0145] A resist film comprising a base resin containing repeating units represented by the following formula (a1) and / or repeating units represented by the following formula (a2), and repeating units that generate acid bonded to the polymer main chain upon exposure.

[0146] [ka] (In equations (a1) and (a2), R A Each of these is independently either a hydrogen atom or a methyl group. 1 and R 2 Each of these is independently a tertiary alkyl group having 4 to 6 carbon atoms. 3 Each of these is independently either a fluorine atom or a methyl group. m is an integer from 0 to 4. 1 This is a linking group having 1 to 12 carbon atoms, containing a single bond, a phenylene group or a naphthylene group, or at least one selected from an ester bond, a lactone ring, a phenylene group, and a naphthylene group. 2 (These are single bonds, ester bonds, or amide bonds.)

[0147] Examples of resist materials include the following:

[0148] A resist material comprising a polymer having repeating units represented by the following formula (b1) or formula (b2).

[0149] [ka] (In equations (b1) and (b2), R A X is a hydrogen atom or a methyl group. 1 X is a single bond or an ester group. 2 X is a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms or an arylene group having 6 to 10 carbon atoms, and a portion of the methylene groups constituting the alkylene group may be substituted with an ether group, an ester group, or a lactone ring-containing group, and X 2 At least one hydrogen atom in X is replaced by a bromine atom. 3 Rf is a single bond, an ether group, an ester group, or a linear, branched, or cyclic alkylene group having 1 to 12 carbon atoms, and some of the methylene groups constituting the alkylene group may be substituted with an ether group or an ester group. 1 ~Rf4 each independently represent a hydrogen atom, a fluorine atom or a trifluoromethyl group, provided that at least one of said groups is a fluorine atom or a trifluoromethyl group; and Rf 1 and Rf 2 may together form a carbonyl group. R 1 to R 5 each independently represent 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; some or all hydrogen atoms in these groups may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group or a sulfonium salt-containing group, and some methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group or a sulfonic acid ester group. In addition, R 1 and R 2 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded.)

[0150] A resist material comprising a base resin comprising a polymer comprising a repeating unit represented by the following formula (a).

[0151]

Chemical Formula

[0152] [ka] [In formula (f2-r-1), Rf 21 Each of these is independently a hydrogen atom, an alkyl group, an alkoxy group, a hydroxyl group, a hydroxyalkyl group, or a cyano group. n'' is an integer from 0 to 2. * represents a bond.

[0153] The aforementioned constituent unit (f1) includes a constituent unit represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0154] [ka] [In formulas (f1-1) and (f1-2), R is independently a hydrogen atom, a C1-C5 alkyl group, or a C1-C5 halogenated alkyl group. X is a divalent linking group that does not have an acid-dissociable site. A aryl X is a divalent aromatic cyclic group which may have substituents. 01 R is a single bond or a divalent linking group. 2 These are, independently, organic groups that contain a fluorine atom.

[0155] Examples of coatings, coating solutions, and coating compositions include the following:

[0156] A coating comprising a metal oxo-hydroxo network having organic ligands via metal-carbon bonds and / or metal carboxylate bonds.

[0157] An inorganic oxo / hydroxo-based composition.

[0158] A coating solution, comprising: an organic solvent; a first organometallic composition represented by formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (wherein 0<z≤2 and 0<(z+x)≤4), formula R' n SnX 4-n (wherein n=1 or 2), or a mixture thereof, wherein R and R' are each independently a hydrocarbyl group having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof; and a hydrolyzable metal compound represented by formula MX' v (wherein M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof), the coating solution comprising the hydrolyzable metal compound.

[0159] A coating solution comprising an organic solvent and a first organometallic compound represented by formula RSnO (3 / 2-x / 2) (OH) x (wherein 0<x<3), wherein about 0.0025 M to about 1.5 M of tin is contained in the solution, R is an alkyl group or cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom.

[0160] An aqueous inorganic patterning precursor solution comprising a mixture of water, a metal suboxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand comprising a peroxide group.

[0161] Exposure is performed through a mask (reticle) to form a predetermined pattern, and for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) lasers are used, but the resist underlayer forming composition of this application is preferably applied for EB (electron beam) or EUV (extreme ultraviolet) exposure, and more preferably for EUV (extreme ultraviolet) exposure. An alkaline developer is used for development, and the development temperature is appropriately selected from 5°C to 50°C and the development time from 10 seconds to 300 seconds. As the alkaline developer, for example, aqueous solutions of alkalis such as inorganic alkalis like sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines like ethylamine and n-propylamine; secondary amines like diethylamine and di-n-butylamine; tertiary amines like triethylamine and methyldiethylamine; alcohol amines like dimethylethanolamine and triethanolamine; quaternary ammonium salts like tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and cyclic amines like pyrrole and piperidine can be used. Furthermore, appropriate amounts of alcohols such as isopropyl alcohol and nonionic surfactants can be added to the aqueous solutions of the above alkalis. Among these, preferred developers are quaternary ammonium salts, and more preferably tetramethylammonium hydroxide and choline. Furthermore, surfactants can also be added to these developers. Instead of an alkaline developer, a method can be used in which development is performed with an organic solvent such as butyl acetate to develop the parts of the photoresist where the alkali dissolution rate has not improved. Through the above process, a substrate with the resist patterned can be manufactured.

[0162] Next, the resist underlayer film is dry-etched using the formed resist pattern as a mask. At this time, if the inorganic film is formed on the surface of the semiconductor substrate used, the surface of the inorganic film is exposed; if the inorganic film is not formed on the surface of the semiconductor substrate used, the surface of the semiconductor substrate is exposed. After that, the substrate is processed by a known method (such as dry etching) to manufacture a semiconductor device. [Examples]

[0163] The present invention will be described in detail next with reference to examples and comparative examples, but the present invention is not limited to these.

[0164] The weight-average molecular weights of the polymers shown in Synthesis Example 1 and Comparative Synthesis Example 1 in this specification were obtained by measurement using gel permeation chromatography (hereinafter abbreviated as GPC). A GPC instrument manufactured by Tosoh Corporation was used for the measurement, and the measurement conditions were as follows.

[0165] GPC columns: Shodex KF803L, Shodex KF802, Shodex KF801 [registered trademark] (Showa Denko K.K.) Column temperature: 40℃ Solvent: Tetrahydrofuran (THF) Flow rate: 1.0ml / min Standard sample: Polystyrene (manufactured by Tosoh Corporation)

[0166] <Synthesis Example 1> 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 6.53 g of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin-Nippon Rika Co., Ltd.), 1.06 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.09 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 56.19 g of benzyl alcohol. The reaction vessel was then purged with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer-containing solution. After cooling to room temperature, the obtained solution was added dropwise to 2-propanol and reprecipitation occurred. Subsequently, the mixture was filtered by suction using a Buchner funnel, washed twice with 2-propanol, and the resulting solid was dried in a vacuum dryer for 12 hours to obtain the polymer. GPC analysis revealed that the obtained polymer 1 had a weight-average molecular weight of 3,000 on a standard polystyrene basis and a dispersion degree of 2.6. The structure present in Synthesis Example 1 is shown by the following formula.

[0167] [ka]

[0168] <Synthesis Example 2> 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 3.98 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.06 g of 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.09 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 46.07 g of benzyl alcohol and dissolved. The reaction vessel was then purged with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer-containing solution. After cooling to room temperature, the obtained solution was added dropwise to 2-propanol and reprecipitation occurred. Subsequently, the mixture was filtered by suction using a Buchner funnel, washed twice with 2-propanol, and the resulting solid was dried in a vacuum dryer for 12 hours to obtain polymer 2. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 4,600 on a standard polystyrene basis and a dispersion degree of 2.2. The structure present in Synthesis Example 2 is shown by the following formula.

[0169] [ka]

[0170] <Synthesis Example 3> 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 3.58 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.06 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.09 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 44.36 g of benzyl alcohol. The reaction vessel was then purged with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer-containing solution. After cooling to room temperature, the obtained solution was added dropwise to 2-propanol and reprecipitation occurred. Subsequently, the mixture was filtered by suction using a Buchner funnel, washed twice with 2-propanol, and the resulting solid was dried in a vacuum dryer for 12 hours to obtain polymer 3. GPC analysis revealed that the obtained polymer 3 had a weight-average molecular weight of 3,800 on a standard polystyrene basis and a dispersion degree of 1.7. The structure present in synthesis example 3 is shown by the following formula.

[0171] [ka]

[0172] <Synthesis Example 4> 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 6.73 g of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin-Nippon Rika Co., Ltd.), 0.08 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.30 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 48.54 g of benzyl alcohol. The reaction vessel was purged with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a solution containing the polymer. After cooling to room temperature, the obtained solution was added dropwise to 2-propanol and reprecipitation occurred. Subsequently, the mixture was filtered by suction using a Buchner funnel, washed twice with 2-propanol, and the resulting solid was dried in a vacuum dryer for 12 hours to obtain the polymer. GPC analysis revealed that the obtained polymer 4 had a weight-average molecular weight of 3,400 on a standard polystyrene basis and a dispersion degree of 2.8. The structure present in synthesis example 4 is shown by the following formula.

[0173]

Chem.

[0174] <Synthesis Example 5> 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals Corporation), 4.42 g of pyromellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.09 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 43.52 g of benzyl alcohol and dissolved. Then, the reaction vessel was replaced with nitrogen, and reacted at 105°C for 24 hours to obtain a polymer-containing solution. After cooling to room temperature, the obtained solution was added dropwise to 2-propanol for reprecipitation. Thereafter, suction filtration was performed with a Buchner funnel, washing was carried out twice with 2-propanol, and the obtained solid was dried in a vacuum dryer for 12 hours to obtain a polymer. GPC analysis revealed that the obtained polymer 5 had a weight average molecular weight of 2,600 in terms of standard polystyrene, and a dispersity of 2.6. The structure present in Synthesis Example 5 is shown in the following formula.

[0175]

Chem.

[0176] <Synthesis Example 6> 6.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 4.42 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.08 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.36 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were dissolved in 43.52 g of benzyl alcohol. The reaction vessel was then purged with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a polymer-containing solution. After cooling to room temperature, the obtained solution was added dropwise to 2-propanol and reprecipitation occurred. Subsequently, the solution was filtered by suction using a Buchner funnel, washed twice with 2-propanol, and the resulting solid was dried in a vacuum dryer for 12 hours to obtain polymer 6. GPC analysis revealed that the obtained polymer had a weight-average molecular weight of 3,500 on a standard polystyrene basis and a dispersion degree of 2.5. The structure present in synthesis example 6 is shown by the following formula.

[0177] [ka]

[0178] <Comparative Synthesis Example 1> 3.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 3.27 g of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin-Nippon Rika Co., Ltd.), 0.53 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.10 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.27 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.) were added to 21.49 g of propylene glycol monomethyl ether and dissolved. The reaction vessel was then purged with nitrogen, and the mixture was reacted at 105°C for 24 hours to obtain a solution containing comparative polymer 1. GPC analysis revealed that the obtained comparative polymer 1 had a weight-average molecular weight of 12,600 on a standard polystyrene basis and a dispersion degree of 4.2. The structure present in comparative synthesis example 1 is shown by the following formula.

[0179] [ka]

[0180] <Preparation of resist underlayer film forming composition> (Examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1-6 and Comparative Synthesis Example 1 were mixed in the proportions shown in Tables 1 and 2, and the mixtures were filtered through a 0.1 μm fluororesin filter to prepare solutions of the resist underlayer film forming compositions. In Tables 1 and 2, tetramethoxymethyl glycol uryl (manufactured by Nippon Scitec Industries Co., Ltd.) is abbreviated as PL-LI, pyridinium-p-hydroxybenzenesulfonic acid as PyPSA, propylene glycol monomethyl ether acetate as PGMEA, and propylene glycol monomethyl ether as PGME. The unit of each additive amount is parts by mass.

[0181] [Table 1] [Table 2]

[0182] [Elution test into photoresist solvent] The resist underlayer-forming compositions of Examples 1, 2, 3, 4, 5, 6, and Comparative Example 1 were each coated onto a silicon wafer, which is a semiconductor substrate, using a spinner. The silicon wafer was then placed on a hot plate and baked at 205°C for 1 minute to form a resist underlayer (thickness 4 nm). These resist underlayers were immersed in ethyl lactate and propylene glycol monomethyl ether, which are solvents used in photoresists, and it was confirmed that they were insoluble in these solvents.

[0183] [Formation of positive resist patterns using EUV exposure equipment] The resist underlayer-forming compositions of Example 1, Example 3, and Comparative Example 1 were applied to silicon wafers using a spinner. The silicon wafers were baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer with a thickness of 4 nm. An EUV positive-type resist solution (containing methacrylic polymer) was spin-coated onto the resist underlayer and heated at 130°C for 60 seconds to form an EUV resist film. The resist film was exposed to EUV lithography using an EUV exposure apparatus (NXE-3400) under predetermined conditions. After exposure, it was baked at 100°C for 60 seconds (PEB), cooled to room temperature on a cooling plate, developed with an alkaline developer (2.38% TMAH), and then a resist pattern with a 16 nm line pattern / 32 nm pitch was formed. A scanning electron microscope (Hitachi High-Technologies Corporation, CG6300) was used to measure the length of the resist pattern. In forming the resist pattern described above, as a comparison between Example 1 and Comparative Example 1, a line-and-space pattern with a CD size of 15 nm was formed, which was considered "good," while any collapse or peeling of the line-and-space pattern was indicated as "poor."

[0184] [Table 3] Examples 1 and 3, compared to Comparative Example 1, showed that line and space collapse and peeling could be suppressed, suggesting that they had good pattern-forming ability. [Industrial applicability]

[0185] The resist underlayer film forming composition according to the present invention provides a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for manufacturing a substrate with a resist pattern using the resist underlayer film forming composition, and a method for manufacturing a semiconductor device.

Claims

[Claim 1] The following formula (1): 【Chemistry 61】 (In Formula (1), 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, and R １ represents a tetravalent organic group, Q １ represents a divalent organic group, L １ represents a single bond or an alkylene group having 1 to 10 carbon atoms, and Ar １ represents an aryl group having 6 to 40 carbon atoms which may be substituted with a substituent.) A resist underlayer film forming composition comprising a polymer having a unit structure represented by and a solvent.

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