Film-forming composition having multiple bonds

Abstract

The present invention provides: a composition for forming a resist underlayer film that enables the formation of a desired resist pattern; and a method for producing a resist pattern and a method for producing a semiconductor device, each of which uses the composition for forming a resist underlayer film. (In formula (1), A1, A2, A3, A4, A5, and A6 each independently represent a hydrogen atom, methyl group, or ethyl group; Q1 represents a divalent organic group; R1 represents a tetravalent organic group; and R2 represents an alkenyl group or alkynyl group having 2-10 carbon atoms.) The film-forming composition contains a solvent and a polymer that has a unit structure given by formula (1).

Description

[Technical Field]

[0001] The present invention relates to a film-forming composition, preferably a resist underlayer film-forming composition used in lithography processes in semiconductor manufacturing, particularly in state-of-the-art lithography processes (ArF, EUV, EB, etc.). The invention 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 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 365nm), KrF excimer laser (wavelength 248nm), and ArF excimer laser (wavelength 193nm), the practical application of EUV light (extreme ultraviolet, wavelength 13.5nm) or EB (electron beam) is being considered for cutting-edge microfabrication. Consequently, the influence of the semiconductor substrate on the resist has become a major problem.

[0003] Therefore, in order to solve this problem, methods for providing an anti-reflective coating (Bottom Anti-Reflective Coating: BARC) or a resist underlayer film between the resist and the semiconductor substrate have been widely investigated. Patent Document 1 discloses a resist underlayer film forming composition that includes a polymer obtained by reacting at least a tetracarboxylic dianhydride having an alicyclic or aliphatic structure and a diepoxy compound having two epoxy groups with an organic solvent containing an alcohol-based 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 properties required of the film-forming composition of the present invention, preferably the resist underlayer film, include, for example, that intermixing with the resist film formed on top does not occur (i.e., it is insoluble in the resist solvent), and that the dry etching rate is faster than that of 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, during the development process for forming a resist pattern, a method is sometimes employed in which the unexposed areas of the resist film are removed using a solvent capable of dissolving the resist film, usually an organic solvent, leaving the exposed areas as the resist pattern. In such negative development processes, improving the adhesion of the resist pattern is a major challenge.

[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 capable of forming a desired resist pattern, which solves the above problems, and a resist pattern forming method using the resist underlayer film forming composition.

Means for Solving the Problems

[0010] The present invention includes the following. [1] The following formula (1):

Chemical formula

[0011] [2] The film-forming composition according to [1], wherein R 1 contains an aromatic ring structure having 6 to 40 carbon atoms or an alicyclic structure having 4 to 20 carbon atoms.

[0012] [3] The R 1 is represented by the following formula (2): <000!72>

Chemical formula

[0013] [4] The aforementioned Q 1 The film-forming composition according to any one of [1] to [3], comprising an alkenyl group or alkynyl group having 2 to 10 carbon atoms.

[0014] [5] The aforementioned Q 1 However, a film-forming composition according to any one of [1] to [4], comprising a heterocycle.

[0015] [6] A film-forming composition according to any one of [1] to [5], wherein the polymer has an alkenyl group or alkynyl group having 2 to 10 carbon atoms at its terminal end.

[0016] [7] A film-forming composition according to any one of [1] to [6], having an aliphatic ring, which may be substituted with substituents, at the end of the polymer.

[0017] [8] A film-forming composition according to any one of [1] to [7], further comprising an acid generator.

[0018] [9] A film-forming composition according to any one of [1] to [8], further comprising a crosslinking agent.

[0019]

[10] Use of a film-forming composition described in any one of items [1] to [9] for the formation of a resist underlayer film.

[0020]

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

[0021]

[12] A step of forming a resist underlayer film by applying a 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]

[13] A step of forming a resist underlayer film on a semiconductor substrate, comprising a film-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 formed from the film-forming composition of the present invention, preferably the resist underlayer film-forming composition, exhibits excellent resistance to organic solvents used in the photoresist formed on top of the underlayer film, and can form a film with high film hardness. Furthermore, when a resist pattern is formed using the resist underlayer film-forming composition of the present invention, the critical resolution size at which the resist pattern collapse is not observed after development is smaller compared to conventional resist underlayer films, enabling the formation of finer resist patterns. In addition, the range of resist pattern sizes that exhibit good patterns is increased compared to the prior art. [Modes for carrying out the invention]

[0024] <Film forming composition> The film-forming composition of the present invention is of 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, Q 1 represents a divalent organic group, R 1 represents a tetravalent organic group, R 2 (This represents an alkenyl or alkynyl group with 2 to 10 carbon atoms.) The material comprises a polymer having a unit structure represented by [formula] and a solvent.

[0025] The film-forming composition of the present invention may be a resist underlayer film used in the lithography process in the semiconductor manufacturing process described later.

[0026] The above 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.

[0027] Examples of 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.

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

[0030] Examples of the alicyclic structures having 4 to 20 carbon atoms include cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, and tricyclo[3.2.1.0]. 2,7 Examples include alicyclic structures derived from octane and spiro[3,4]octane.

[0031] The aforementioned R 1 However, see equation (2) below: [ka] (In formula (2), Y 1 T 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. n1 and n2 each independently represent integers from 0 to 4. * is R 1 This is the bond portion to the carbonyl group that is bonded to it. It can be expressed as follows.

[0032] Examples of the halogen atoms include fluorine, chlorine, iodine, and bromine. 1 is a sulfonyl group, T 1 and T 2 It is preferable that it is a hydrogen atom.

[0033] Examples of the aryl group having 6 to 40 carbon atoms include a benzyl group, a naphthyl group, anthracenyl group, a phenantrenyl group, or a pyrenyl group.

[0034] 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.

[0035] The aforementioned R 1 However, see equation (2-1): [ka] (In formula (2-1), Y 1 T 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. n1 and n2 each independently represent integers between 0 and 4. It may be derived from the compound represented by .

[0036] The aforementioned Q 1 However, it may contain an alkenyl group or alkynyl group having 2 to 10 carbon atoms. Specific examples are as described above. The aforementioned Q 1 However, it may contain a heterocycle. Examples of the heterocycle 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 Q 1 However, it may be derived from a compound represented by the following formula. [ka]

[0038] The polymer having the unit structure of formula (1) of this application is, for example, a compound represented by formula (2-1), and, when polymer end encapsulation is performed, an aliphatic ring compound containing two carboxyl groups, and a compound represented by the following formula 3 or formula (3-1). [ka] The reaction product may be obtained by reacting (wherein n3 represents an integer from 1 to 8) with the above formulas (10-a) to (10-k).

[0039] The polymer may have an alkenyl group or alkynyl group having 2 to 10 carbon atoms at its terminus. Preferably, the carbon-carbon double bond of the alkenyl group or the carbon-carbon triple bond of the alkynyl group is present at the terminus of the polymer. The polymer may also have an aliphatic ring at its terminus, which may be substituted with substituents.

[0040] The end-binding compound preferably contains an aliphatic ring which may be substituted with substituents. The aliphatic ring is preferably a monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms. Examples of the monocyclic or polycyclic aliphatic ring having 3 to 10 carbon atoms include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohexene, cycloheptane, cyclooctane, cyclononane, cyclodecane, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, and tricyclo[3.2.1.0] 2,7 ]Octane, spiro[3,4]Octane, norbornane, norbornene, tricyclo[3.3.1.1 3,7 Examples include decane (adamantane).

[0041] The polycyclic aliphatic ring is preferably a bicyclo ring or a tricyclo ring. Examples of the bicyclo ring include norbornane, norbornene, spirobicyclopentane, bicyclo[2.1.0]pentane, bicyclo[3.2.1]octane, and spiro[3,4]octane. The aforementioned tricyclo ring is tricyclo[3.2.1.0 2,7 Octane, tricyclo[3.3.1.1 3,7 Deccan (adamantane) is one example.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] Specific examples of compounds containing an aliphatic ring which may be substituted with the aforementioned substituents include the compounds listed below. Compounds in which the carboxyl group of the following specific examples is replaced with a hydroxyl group, an amino group, and a thiol group are also examples. [ka] [ka] [ka]

[0047] The weight-average molecular weight of the above 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 the gel permeation chromatography method described in the examples.

[0048] The proportion of the above polymer in the total resist underlayer film forming composition of the present invention is typically 0.05% to 3.0% by mass, 0.08% to 2.0% by mass, and 0.1% to 1.0% by mass.

[0049] The solvent included in the resist underlayer film forming composition of the present invention is preferably an organic solvent commonly used in semiconductor lithography processes. 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.

[0050] 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.

[0051] <Acid Generator> As an optional component of the 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-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, hydroxybenzoic acid, N-methylmorpholine-p-toluenesulfonic acid, N-methylmorpholine-p-hydroxybenzenesulfonic acid, and N-methylmorpholine-5-sulfosalicylic acid.

[0052] Examples of the photoacid generators include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds.

[0053] 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.

[0054] Examples of sulfonimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0055] 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.

[0056] The aforementioned acid generating agent can be used by one type only, or by a combination of two or more types.

[0057] When the above-mentioned 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.

[0058] <Crosslinking agent> Examples of crosslinking agents that may be included as optional components in the 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.

[0059] 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.

[0060] [ka] (In formula (1d), R1 represents a methyl group or an ethyl group.)

[0061] 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).

[0062] [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.)

[0063] Examples of glycoluryl derivatives represented by formula (1E) include the compounds represented by the following formulas (1E-1) to (1E-6).

[0064] [ka]

[0065] 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).

[0066] [ka] (In formula (3d), R1 represents a methyl group or an ethyl group, and in formula (2d), R4 represents an alkyl group having 1 to 4 carbon atoms.)

[0067] 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).

[0068] 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).

[0069] [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.)

[0070] Examples of glycoluryl derivatives represented by formula (2E) include the compounds represented by formulas (2E-1) to (2E-4) below. Furthermore, examples of compounds represented by formula (3d) include the compounds represented by formulas (3d-1) and (3d-2) below.

[0071] [ka] [ka]

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

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

[0074] [ka] (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.

[0075] 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.

[0076] [ka] (In the formula, Q 2 R indicates a single bond or an m2 valent organic group. 8 , R 9 , R 11 and R 12Each 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.

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

[0078] [ka]

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

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

[0084] [ka]

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

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

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

[0088] <Other ingredients> The film-forming composition of the present invention does not produce pinholes or striations, and a surfactant can be added to further improve the coatability against surface unevenness. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monopalmitate. Examples include nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters like polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; fluorine-based surfactants such as F-Top EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd., product name), Megafac F171, F173, R-30 (manufactured by Dainippon Ink, Inc., product name), Florard FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd., product name), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd., product name); and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). The amount of these surfactants added is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the resist underlayer film-forming composition of the present invention. These surfactants may be added individually or in combination of two or more types.

[0089] The 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) lithography process and an EUV exposure process, and is preferably an EUV resist underlayer film-forming composition.

[0090] <Underlying resist film> The resist underlayer film according to the present invention can be manufactured by coating the above-described film-forming composition onto a semiconductor substrate and firing it. The resist underlayer film according to the present invention is preferably an electron beam resist underlayer film or an EUV resist underlayer film. 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. 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. 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. 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), or 0.003 μm (1 nm). The thickness ranges are 0.005μm (50nm), 0.004μm (4nm) to 0.05μm (50nm), 0.005μm (5nm) to 0.05μm (50nm), 0.003μm (3nm) to 0.03μm (30nm), 0.003μm (3nm) to 0.02μm (20nm), and 0.005μm (5nm) to 0.02μm (20nm). 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.

[0091] <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 (manufactured by JSR Corporation), APEX-E (manufactured by Cyprey Corporation), PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), and AR2772 and SEPR430 (manufactured by 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). Furthermore, metal-containing resists (metal resists) are also acceptable.Specific examples include WO2019 / 188595, WO2019 / 187881, WO2019 / 187803, WO2019 / 167737, WO2019 / 167725, WO2019 / 187445, WO2019 / 167419, WO2019 / 123842, WO2019 / 054282, WO2019 / 058945, WO2019 / 058890, WO2019 / 039290, WO2019 / 044259, WO2019 / 044231, WO2019 / 026549, WO2018 / 193954, W O2019 / 172054, WO2019 / 021975, WO2018 / 230334, WO2018 / 194123, JP 2018-180525, WO2018 / 190088, JP 2018-070596, JP 2018-028090, JP 2016-153409, JP 2016-130240, JP 2016-108325, JP 2016-047920, JP 2016-035570, JP 2016-035567, JP 2016-035565, JP 2019-101417, JP 2019-1173 73, JP 2019-052294, JP 2019-008280, JP 2019-008279, JP 2019-003176, JP 2019-003175, JP 2018-197853, JP 2019-191298, JP 2019-061217, JP 2018-045152, JP 2018-022039, JP 2016-090441, JP 2015-10878, JP 2012-168279, JP 2012-022261, JP 2012-022258, JP 2011-043749, JP 2010-1 While so-called resist compositions and metal-containing resist compositions such as resist compositions, radiation-sensitive resin compositions, and high-resolution patterning compositions based on organometallic solutions described in JP 81857, JP 2010-128369, WO2018 / 031896, JP 2019-113855, WO2017 / 156388, WO2017 / 066319, JP 2018-41099, WO2016 / 065120, WO2015 / 026482, JP 2016-29498, JP 2011-253185, etc., can be used, they are not limited to these.

[0092] Examples of resist compositions include the following: A photosensitive or radiation-sensitive resin composition comprising resin A having repeating units with acid-degradable groups whose polar groups are protected by protective groups that are removed by the action of an acid, and a compound represented by general formula (1).

[0093] [ka] In general formula (1), m represents an integer from 1 to 6.

[0094] R1 and R2 each independently represent a fluorine atom or a perfluoroalkyl group.

[0095] L1 represents -O-, -S-, -COO-, -SO2-, or -SO3-.

[0096] L2 represents an alkylene group or single bond which may have substituents.

[0097] W1 represents a cyclic organic group which may have substituents.

[0098] M + This represents a cation.

[0099] 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.

[0100] A radiation-sensitive resin composition comprising a polymer having a first structural unit represented by the following formula (1) and a second structural unit represented by the following formula (2) that contains an acid-dissociable group, and an acid generator.

[0101] [ka] (In formula (1), Ar is a group obtained by removing (n+1) hydrogen atoms from an arene with 6 to 20 carbon atoms. 1R 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 These are a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

[0102] In formula (2), 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.)

[0103] 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.

[0104] [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. A resist composition that generates acid upon exposure, and whose solubility in a developer changes due to the action of the acid, It contains a base component (A) whose solubility in the developer changes due to the action of acid, and a fluorine additive component (F) that is degradable in alkaline developer. The resist composition is characterized in that the fluorine additive component (F) contains a fluororesin component (F1) having a constituent unit (f1) containing a base-dissociable group and a constituent unit (f2) containing a group represented by the following general formula (f2-r-1).

[0105] [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.

[0106] The resist composition comprises a constituent unit (f1) represented by the following general formula (f1-1) or a constituent unit represented by the following general formula (f1-2).

[0107] [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.

[0108] Examples of resist materials include the following:

[0109] A resist material comprising a polymer having repeating units represented by the following formula (a1) or (a2).

[0110] [ka] (In equations (a1) and (a2), RA 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 ~Rf 4 Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one is a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 They may combine to form a carbonyl group. 1 ~R 5 Each of these is independently a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, a linear, branched, or cyclic alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryloxyalkyl group having 7 to 12 carbon atoms, and some or all of the hydrogen atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, a halogen atom, an oxo group, a cyano group, an amide group, a nitro group, a sultone group, a sulfone group, or a sulfonium salt-containing group, and some of the methylene groups constituting these groups may be substituted with an ether group, an ester group, a carbonyl group, a carbonate group, or a sulfonic acid ester group. 1 and R 2 These may combine to form a ring with the sulfur atom to which they are bonded.

[0111] A resist material comprising a base resin containing a polymer containing repeating units represented by the following formula (a).

[0112] [Chemical formula] (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 may 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.)

[0113] Examples of the resist film include the following.

[0114] (i) A resist film containing a base resin including a repeating unit represented by the following formula (a1) and / or a repeating unit represented by the following formula (a2), and a repeating unit that generates an acid bonded to the polymer main chain upon exposure.

[0115] [Chemical formula] (In formulas (a1) and (a2), R A is each independently a hydrogen atom or a methyl group. R 1 and R 2 are each independently a tertiary alkyl group having 4 to 6 carbon atoms. R 3 is each independently a fluorine atom or a methyl group. m is an integer of 0 to 4. X 1 is a single bond, a phenylene group, a naphthylene group, or a linking group having 1 to 12 carbon atoms containing at least one selected from an ester bond, a lactone ring, a phenylene group and a naphthylene group. X 2 is a single bond, an ester bond or an amide bond.)

[0116] Examples of the coating solution include the following.

[0117] Examples of the metal-containing resist composition include a coating containing a metal oxo-hydroxone network having an organic ligand by a metal-carbon bond and / or a metal carboxylate bond.

[0118] Inorganic oxo / hydroxyl-based composition.

[0119] A coating solution comprising an organic solvent; a first organometallic composition represented by the formula R z SnO (2-(z / 2)-(x / 2)) (OH) x (where 0 < z ≦ 2 and 0 < (z + x) ≦ 4), the formula R' n SnX 4-n (where n = 1 or 2), or a mixture thereof, where R and R' are independently hydrocarbyl groups having 1 to 31 carbon atoms, and X is a ligand having a hydrolyzable bond to Sn or a combination thereof, the first organometallic composition; and a hydrolyzable metal compound represented by the formula MX' v (where M is a metal selected from Groups 2 to 16 of the Periodic Table of the Elements, v is a number from 2 to 6, and X' is a ligand having a hydrolyzable M-X bond or a combination thereof), the coating solution containing the hydrolyzable metal compound.

[0120] A coating solution comprising an organic solvent and a first organometallic compound represented by the formula RSnO (3 / 2-x / 2) (OH) x (where 0 < x < 3), wherein the solution contains about 0.0025 M to about 1.5 M of tin, R is an alkyl group or a cycloalkyl group having 3 to 31 carbon atoms, and the alkyl group or cycloalkyl group is bonded to tin at a secondary or tertiary carbon atom, the coating solution.

[0121] An aqueous solution of an inorganic pattern-forming precursor comprising a mixture of water, a metal oxide cation, a polyatomic inorganic anion, and a radiation-sensitive ligand containing a peroxide group.

[0122] 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) are used, but the resist underlayer film forming composition of the present invention is preferably applied for EUV (extreme ultraviolet) exposure. For development, an alkaline developer is used, 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, aqueous solutions of alkalis such as inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, primary amines such as ethylamine and n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline, and cyclic amines such as pyrrole and piperidine can be used. Furthermore, an appropriate amount of alcohol such as isopropyl alcohol and a nonionic surfactant can be added to the aqueous solution 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, and the parts of the photoresist whose alkali dissolution rate has not improved are developed. Through the above process, a substrate with the resist patterned can be manufactured.

[0123] 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]

[0124] The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples. 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. 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)

[0125] <Synthesis Example 1> 6.72 g of 4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin-Nippon Rika Co., Ltd.), 15.01 g of 3-buty-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.08 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel. After purging with nitrogen, the mixture was heated and stirred at 80°C for 18 hours. After cooling to room temperature, 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals Co., Ltd.), 0.30 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 36.50 g of propylene glycol monomethyl ether were added. After purging with nitrogen, 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 was performed. The mixture was then 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 form a polymer. 1 GPC analysis was performed, and the obtained polymer was found. 1 The polymer had a weight-average molecular weight of 3,400 and a dispersion degree of 2.8, based on standard polystyrene. 1 The internal structure is shown by the following formula. [ka]

[0126] <Synthesis Example 2> 5.44 g of 4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin-Nippon Rika Co., Ltd.), 0.88 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.00 g of 3-buty-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 0.08 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel. After purging with nitrogen, the mixture was heated and stirred at 80°C for 18 hours. After cooling to room temperature, 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals Co., Ltd.), 0.30 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 35.12 g of propylene glycol monomethyl ether were added. After purging with nitrogen, the mixture was reacted at 105°C for 24 hours to obtain a solution containing the polymer. After cooling to room temperature, the resulting solution was added dropwise to 2-propanol and reprecipitation was performed. Then, it 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 form a polymer. 2 GPC analysis was performed, and the obtained polymer was found. 2 The polymer had a weight-average molecular weight of 5,000 and a dispersion degree of 2.6, based on standard polystyrene. 2 The internal structure is shown by the following formula. [ka]

[0127] <Synthesis Example 3> 5.44 g of 4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin-Nippon Rika Co., Ltd.), 0.88 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.00 g of 2-propyne-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.00 g of N-methyl-2-pyrrolidinone, and 0.08 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel. After purging with nitrogen, the mixture was heated and stirred at 80°C for 18 hours. After cooling to room temperature, 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Ltd.), 0.30 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 20.12 g of propylene glycol monomethyl ether were added. After purging with nitrogen, the mixture was reacted at 105°C for 24 hours to obtain a solution containing the polymer. After cooling to room temperature, the resulting solution was added dropwise to 2-propanol and reprecipitation was performed. Then, it 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 form a polymer. 3 GPC analysis was performed, and the obtained polymer was found. 3 The polymer had a weight-average molecular weight of 4,800 and a dispersion degree of 2.0, based on standard polystyrene. 3 The internal structure is shown by the following formula. [ka]

[0128] <Synthesis Example 4> 5.44 g of 4,4'-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin-Nippon Rika Co., Ltd.), 0.88 g of 5-norbornene-2,3-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.00 g of 2-hydroxyethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.00 g of N-methyl-2-pyrrolidinone, and 0.08 g of 2,6-di-tert-butyl-p-cresol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a reaction vessel. After purging with nitrogen, the mixture was heated and stirred at 80°C for 18 hours. After cooling to room temperature, 5.00 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Ltd.), 0.30 g of tetrabutylphosphonium bromide (manufactured by Hokko Chemical Industry Co., Ltd.), and 20.12 g of propylene glycol monomethyl ether were added. After purging with nitrogen, the mixture was reacted at 105°C for 24 hours to obtain a solution containing the polymer. After cooling to room temperature, the resulting solution was added dropwise to 2-propanol and reprecipitation was performed. Then, it 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 form a polymer. 4 GPC analysis was performed, and the obtained polymer was found. 4 The polymer had a weight-average molecular weight of 5,500 and a dispersion degree of 2.1, based on standard polystyrene. 4 The internal structure is shown by the following formula. [ka]

[0129] <Comparative Synthesis Example 1> As raw materials for comparative polymer 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 dissolved in 21.49 g of propylene glycol monomethyl ether. After purging the reaction vessel with nitrogen, the reaction was carried out at 105°C for 24 hours to obtain a 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 polymer 1 is shown by the following formula. [ka]

[0130] (Preparation of the resist underlayer film) (Examples, Comparative Examples) The polymers, crosslinking agents, curing catalysts, and solvents obtained in Synthesis Examples 1-4 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, 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 as PyPSA, propylene glycol monomethyl ether acetate as PGMEA, and propylene glycol monomethyl ether as PGME. The amount of each additive is shown in parts by mass.

[0131] [Table 1]

[0132] [Table 2]

[0133] (Elution test into photoresist solvent) Each of the resist underlayer forming compositions from Examples 1-4 and Comparative Example 1 was coated onto a silicon wafer using a spinner. The silicon wafer was then baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 5 nm. These resist underlayer films were immersed in a mixed solution of propylene glycol monomethyl ether / propylene glycol monomethyl ether = 70 / 30, which is the solvent used for photoresists. A film thickness change of 1 Å or less was considered good, and a change of 1 Å or more was considered poor. The results are shown in Table 3.

[0134] (Hardness test) Each of the resist underlayer film-forming compositions from Examples 1-4 and Comparative Example 1 was coated onto a silicon wafer using a spinner. The silicon wafer was then baked on a hot plate at 205°C for 60 seconds to obtain a film with a thickness of 200 nm. These resist underlayer films were measured using a nanoindenter, and the film hardness was set to 1 for Comparative Example 1. The results are shown in Table 3.

[0135] [Table 3]

[0136] (Resistance patterning evaluation) [Test of resist pattern formation using electron beam lithography equipment] A resist underlayer-forming composition was applied to a silicon wafer using a spinner. The silicon wafer was baked on a hot plate at 205°C for 60 seconds to obtain a resist underlayer with a thickness of 5 nm. An EUV positive-type resist solution 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 electron beam lithography (ELS-G130) under predetermined conditions. After exposure, it was baked (PEB) at 90°C for 60 seconds, cooled to room temperature on a cooling plate, and paddle developed for 30 seconds using a 2.38% tetramethylammonium hydroxide aqueous solution (manufactured by Tokyo Ohka Kogyo Co., Ltd., trade name NMD-3) as a photoresist developer. A resist pattern with a line size of 16 nm to 28 nm was formed. A scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, CG4100) was used to measure the length of the resist pattern. The photoresist patterns obtained in this manner were then evaluated for the possibility of forming 22 nm line-and-space (L / S) patterns. In all cases of Examples 1-4, the formation of 22 nm L / S patterns was confirmed. Furthermore, the optimal irradiation energy was determined by the charge amount required to form 22 nm lines / 44 nm pitch (line-and-space (L / S=1 / 1)), and the irradiation energy at that time (μC / cm²) was also determined. 2 Table 4 shows the minimum CD size and LWR at which no collapse is observed within the resist pattern shot.

[0137] [Table 4] [Industrial applicability]

[0138] The resist underlayer film forming composition according to the present invention provides a composition for forming a resist underlayer film capable of forming a desired resist pattern, a method for manufacturing a substrate with a resist pattern using the resist underlayer film forming composition, and a method for manufacturing a semiconductor device.

Claims

1. The following formula (1): 【Chemistry 40】 (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, Q １ represents a divalent organic group containing a heterocyclic ring on the main chain, R １ represents a tetravalent organic group, and R ２ represents an alkenyl group or an alkynyl group having 2 to 10 carbon atoms.) A polymer having a unit structure represented by and a solvent, The aforementioned R １ However, see formula (2) below: 【Chemistry 41】 (In formula (2), Y １ represents a sulfonyl group, T １ and T ２ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. n1 and n2 each independently represent integers from 0 to 4. * is R １ (This is the bond portion to the carbonyl group that is bonded to it.) A resist underlayer film forming composition represented by the following:

2. The aforementioned Q １ The resist underlayer film forming composition according to claim 1, wherein the composition comprises an alkenyl group or alkynyl group having 2 to 10 carbon atoms.

3. The resist underlayer forming composition according to claim 1 or 2, wherein the polymer has an alkenyl group or alkynyl group having 2 to 10 carbon atoms at its terminal end.

4. A resist underlayer forming composition according to any one of claims 1 to 3, wherein the polymer has an aliphatic ring at its terminus, which may be substituted with a substituent.

5. A resist underlayer film forming composition according to any one of claims 1 to 4, further comprising an acid generator.

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

7. Use of the resist underlayer forming composition according to any one of claims 1 to 6 for forming a resist underlayer.

8. A resist underlayer film characterized by being a fired product of a coated film made from the resist underlayer film forming composition described in any one of claims 1 to 6.

9. A step of forming a resist underlayer film by applying a resist underlayer film forming composition according to any one of claims 1 to 6 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].

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

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