Composition for resist underlayer film formation for nanoimprint

Abstract

A composition for forming a resist underlayer film for nanoimprinting exhibits exceptionally high hydrophobicity and good planarization even during high-temperature firing, and whose optical constants and etching rates can be adjusted to suit the process by changing the molecular skeleton. A composition for forming a resist underlayer film for nanoimprinting comprises a phenolic varnish resin having a repeating unit structure as shown in the following formula (1), [in formula (1), base A represents an organic group having an aromatic ring, a fused aromatic ring, or a fused aromatic heterocyclic ring, base B represents an organic group having an aromatic ring or a fused aromatic ring, base E represents a single bond, or a branched or straight-chain alkylene group having 1 to 10 carbon atoms that can be substituted and may contain ether bonds and / or carbonyl groups, base D represents an organic group having 1 to 15 carbon atoms as shown in formula (2), and n represents a number from 1 to 5. (in formula (2), R 1 R 2 R 3 Each is independently a fluorine atom, or a straight-chain, branched, or cyclic alkyl group, R 1 R 2 R 3 Any two elements can be combined to form a ring.

Description

Technical Field

[0001] The present invention relates to a composition for forming a resist underlayer film for nanoimprinting, a resist underlayer film as a cured product of a coating film formed from the composition, a method for manufacturing the resist underlayer film, a pattern forming method utilizing the resist underlayer film, and a method for manufacturing a semiconductor device. Background Technology

[0002] In the manufacturing of semiconductor devices, MEMS, and other applications requiring miniaturization, photoimprinting technology, which can form nanoscale structures on substrates, has attracted attention. This technology involves coating a curable composition (resist) onto a substrate (wafer), pressing a mold (mold) onto the substrate to form a finely patterned surface, directly curing the resist with heat or light, transferring the pattern from the mold onto the cured resist film, and then pulling the mold away to form the pattern on the substrate.

[0003] For typical photolithography, firstly, a liquid resist composition is dropped onto the patterning area of ​​a substrate using an inkjet printing method, spreading the droplets of the resist composition onto the substrate (pre-spreading). Next, the resist composition is molded using a mold (die) that is transparent to the light and has been patterned. At this time, the droplets of the resist composition spread throughout the gap between the substrate and the mold via capillary action (spreading). Furthermore, the resist composition also fills the interior of recesses on the mold via capillary action (filling). The time until spreading and filling are complete is called the filling time. After the resist composition is filled, it is cured by light, and then the two are separated. By performing these steps, a resist pattern with a predetermined shape is formed on the substrate.

[0004] In the demolding process of photo-nanoimaging technology, the adhesion between the resist composition and the substrate is crucial. If the adhesion is poor, defects such as pattern peeling can occur during demolding when the mold is separated, where a portion of the photocured material obtained by curing the resist composition remains attached to the mold. To improve the adhesion between the resist composition and the substrate, a technique has been proposed to form an adhesive layer between the resist composition and the substrate, serving as a layer for ensuring adhesion between them.

[0005] Furthermore, patterns formed in nanoimprinting sometimes utilize highly etch-resistant layers. Organic or silicone-based materials are commonly used as materials for these highly etch-resistant layers. Further, a Si-containing silicone layer can be formed on the lower layer of the nanoimprinting resist by coating or vapor deposition. When these silicone layers, containing Si, are hydrophobic and exhibit a high pure water contact angle, and the lower layer is also hydrophobic and exhibits a high pure water contact angle, improved adhesion between the films can be expected, making them less prone to peeling.

[0006] Since He, H2, N2, and air are known to be relatively hydrophobic at room temperature, high affinity for membranes with high contact angles and improved gas permeability are desirable. Therefore, materials with high water contact angles are preferred as the lower membrane material.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2019-36725 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] Therefore, the problem to be solved by the present invention is to provide a nanoimprint resist lower film forming composition that exhibits good planarization properties, obtains a highly hydrophobic film by firing, improves adhesion to a hydrophobic upper film, and can be adjusted to adapt the optical constants and etching speed to the process by changing the molecular skeleton of the resin.

[0012] Methods for solving problems

[0013] The present invention includes the following solutions.

[0014] [1] A composition for forming a resist underlayer film for nanoimprinting, comprising a phenolic varnish resin having a repeating unit structure as shown in formula (1).

[0015]

[0016] In equation (1),

[0017] The group A represents an organic group having an aromatic ring, a fused aromatic ring, or a fused aromatic heterocycle.

[0018] The group B represents an organic group having an aromatic ring or a fused aromatic ring.

[0019] The radical E represents a single bond, or a branched or straight-chain alkylene group having 1 to 10 carbon atoms that can be substituted and may contain ether bonds and / or carbonyl groups.

[0020] The group D represents an organic group with 1 to 15 carbon atoms, as shown in formula (2) below.

[0021] n represents a number from 1 to 5.

[0022]

[0023] (In equation (2), R) 1 R 2 R 3 Each is independently a fluorine atom, or a straight-chain, branched, or cyclic alkyl group, R 1 R 2 R 3 Any two elements can be combined to form a ring.

[0024] [2] The composition for forming a lower layer of resist for nanoimprinting according to [1], wherein base D is tert-butyl or trifluoromethyl.

[0025] [3] In the composition for forming a lower layer film of a resist for nanoimprinting as described in [1] or [2], the organic group in base A having an aromatic ring, a fused aromatic ring, or a fused aromatic heterocycle is an organic group having one or more benzene rings, naphthalene rings, anthracene rings, pyrene rings, or fused rings formed by benzene rings and heterocycles or aliphatic rings.

[0026] [4] In any one of [1] to [3], the organic group in base A having an aromatic ring, a fused aromatic ring, or a fused aromatic heterocycle is an organic group having 6 to 30 carbon atoms that may contain at least one heteroatom selected from N, S, and O on, inside, or between the rings.

[0027] [5] The composition for forming a resist underlayer film for nanoimprinting according to any one of [1] to [4], wherein base A is selected from at least one of the following groups.

[0028]

[0029] (In the formula, i, j, m, and n are each independently 1 or 2. G represents direct bonding or any of the following formulas.)

[0030] -CH2--CH(CH3)--C(CH3)2--C(CF3)2--C(CH3)(C2H5)--C(CH3)(C6H5)--C(C6H5)2--SO2-

[0031]

[0032] L and M each independently represent a hydrogen atom, a phenyl group, or a carbon atom. 1-3 alkyl.)

[0033] [6] The composition for forming a lower layer of resist for nanoimprinting according to any one of [1] to [5], wherein base B is phenylene, biphenylene, naphthylene, anthraceneylene, or phenanthrene.

[0034] [7] The composition for forming a resist lower layer film for nanoimprinting according to any one of [1] to [6], wherein the base E is a single bond or a straight-chain alkylene group having 1 to 6 carbon atoms.

[0035] [8] The composition for forming a resist underlayer film for nanoimprinting according to any one of [1] to [7], wherein the base E is a single bond.

[0036] [9] The composition for forming a lower layer of resist for nanoimprinting according to any one of [1] to [8] exhibits a contact angle of more than 76° to pure water when sintered at 240°C, and exhibits a contact angle of more than 70° to pure water when sintered at 350°C.

[0037]

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

[0038]

[11] The composition for forming a resist underlayer film for nanoimprinting according to any one of [1] to

[10] further comprises at least one selected from acids, their salts and acid-generating agents.

[0039]

[12] The composition for forming a lower layer of resist for nanoimprinting according to

[10] or

[11] shows a contact angle of more than 65° to pure water when sintered at 350°.

[0040]

[13] A resist underlayer film, which is a cured product of a coating film formed by any one of [1] to

[12] of the composition for forming a resist underlayer film for nanoimprinting.

[0041]

[14] A method for manufacturing a resist underlayer film, comprising: coating a nanoimprint resist underlayer film forming composition as described in any one of [1] to

[12] onto a semiconductor substrate and firing it.

[0042]

[15] A pattern forming method comprising the following steps:

[0043] A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film for nanoimprinting as described in any of [1] to

[12] ;

[0044] The process of applying a curable composition onto the aforementioned resist underlayer film;

[0045] The process of bringing the above-mentioned curable composition into contact with the mold;

[0046] The process of forming a cured film by irradiating the above-mentioned curable composition with light or electron beams; and

[0047] The process of separating the cured film from the mold.

[0048]

[16] According to the pattern forming method described in

[15] , the step of applying the curable composition to the above-mentioned resist underlayer film includes:

[0049] An adhesive layer and / or an organosilicon layer containing 99% by mass or less, or 50% by mass or less, of Si are formed on the lower layer of the above-mentioned resist film by coating or vapor deposition, and a curable composition is applied to the adhesive layer and / or the organosilicon layer containing 99% by mass or less, or 50% by mass or less, of Si.

[0050]

[17] A method for manufacturing a semiconductor device, comprising the following steps:

[0051] A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film for nanoimprinting as described in any of [1] to

[12] ;

[0052] The process of forming a resist film on the lower layer of the resist film;

[0053] The process of forming a resist pattern by irradiation and development with light or electron beams;

[0054] The process of etching the underlying film using the formed resist pattern; and

[0055] The process of processing a semiconductor substrate using a patterned lower film.

[0056]

[18] A method for manufacturing a semiconductor device, comprising the following steps:

[0057] A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film for nanoimprinting as described in any of [1] to

[12] ;

[0058] The process of forming a hard mask on the lower layer of the resist film;

[0059] The next step is to form a resist film on the hard mask.

[0060] The process of forming a resist pattern by irradiation and development with light or electron beams;

[0061] The process of etching a hard mask using the resulting resist pattern;

[0062] The process of etching the underlying film using a patterned hard mask; and

[0063] The process of processing a semiconductor substrate using a patterned resist underlayer film.

[0064] The effects of the invention

[0065] The phenolic varnish resin of this invention is not limited to low-temperature firing; it also exhibits an exceptionally high pure water contact angle (= hydrophobicity) during high-temperature firing. Furthermore, the phenolic varnish resin of this invention also exhibits an exceptionally high pure water contact angle (= hydrophobicity) during high-temperature firing when a crosslinking agent, acid catalyst, and surfactant are mixed and prepared into a material. This improves adhesion to the hydrophobic upper film and also allows for good permeability to hydrophobic gases. Furthermore, the phenolic varnish resin of this invention exhibits good planarization properties, which can be adjusted to suit the optical constants and etching rate of the process by modifying the molecular skeleton. Detailed Implementation

[0066] [Composition for forming the lower layer of resist for nanoimprinting]

[0067] The composition for forming a resist underlayer film for nanoimprinting according to the present invention comprises a phenolic varnish resin having a repeating unit structure as shown in formula (1) below, and optionally includes a solvent and other components.

[0068] The following will explain in sequence.

[0069]

[0070] In equation (1),

[0071] The group A represents an organic group having an aromatic ring, a fused aromatic ring, or a fused aromatic heterocycle.

[0072] The group B represents an organic group having an aromatic ring or a fused aromatic ring.

[0073] The radical E represents a single bond, or a branched or straight-chain alkylene group having 1 to 10 carbon atoms that can be substituted and may contain ether bonds and / or carbonyl groups.

[0074] The group D represents an organic group with 1 to 15 carbon atoms, as shown in formula (2) below.

[0075] n represents a number from 1 to 5.

[0076]

[0077] (where R is in the formula) 1 R 2 R 3 Each is independently a fluorine atom, or a straight-chain, branched, or cyclic alkyl group, R 1 R 2 R3 Any two elements can be combined to form a ring.

[0078] [Phenolic varnish resin having the repeating unit structure shown in formula (1)]

[0079] The term "organogroup with an aromatic ring" in groups A and B refers to a group of a hydrocarbon exhibiting aromaticity in a monocyclic form. Examples include groups derived from benzene, cyclooctatetraene, and toluene, xylene, mesitylene, isopropylbenzene, and styrene with any substituents. Furthermore, it also includes organic groups with fused rings formed by an aromatic ring like benzene and an aliphatic ring such as cyclohexane, cyclohexene, methylcyclohexane, or methylcyclohexene, as well as organic groups with fused rings formed by an aromatic ring like benzene and a heterocyclic ring such as furan, thiophene, pyrrole, imidazole, pyran, pyridine, pyrimidine, pyrazine, pyrrolidine, piperidine, piperazine, or morpholine.

[0080] The term "organogroup with a fused aromatic ring" in groups A and B refers to a group of a hydrocarbon exhibiting aromaticity through a fused ring. Examples include those derived from indene, naphthalene, azurite, anthracene, phenanthrene, tetraphenylene, benzo[9,10]phenanthrene, pyrene, etc. . group.

[0081] The term "organogroup with fused aromatic heterocycles" in group A refers to a group that exhibits aromaticity through a fused ring and contains heteroatoms from hydrocarbons. Examples include groups derived from indole, purine, quinoline, isoquinoline, chromene, thiathracene, phenothiazine, and phenanthrene. The groups of azines, xanthannes, acridine, phenazine, and carbazole.

[0082] The aforementioned aromatic rings, fused aromatic rings, and fused aromatic heterocycles can be linked to each other via alkylene groups, etc.

[0083] Preferably, the organic group in base A that has an aromatic ring, a fused aromatic ring, or a fused aromatic heterocycle is an organic group with 6 to 30 carbon atoms.

[0084] Preferably, the organogroup A having an aromatic ring, a fused aromatic ring, or a fused aromatic heterocycle is an organogroup having one or more benzene rings, naphthalene rings, or fused rings formed by benzene rings and heterocycles or aliphatic rings.

[0085] Preferably, the organic group in group A having an aromatic ring, a fused aromatic ring, or a fused aromatic heterocycle is an organic group with 6 to 30 carbon atoms that may contain at least one heteroatom selected from N, S, and O on, within, or between the rings. Examples of heteroatoms contained on the ring include, for example, nitrogen atoms contained in amino groups (e.g., propargylamino), cyano groups, formyl groups, hydroxyl groups, carboxyl groups, oxygen atoms contained in alkoxy groups (e.g., propargyloxy), and nitrogen and oxygen atoms contained in nitro groups. Examples of heteroatoms contained within the ring include, for example, oxygen atoms contained in thallium and nitrogen atoms contained in carbazole. Examples of heteroatoms contained between the rings include nitrogen atoms, oxygen atoms, and sulfur atoms contained in -NH- bonds, -NHCO- bonds, -O- bonds, -COO- bonds, -CO- bonds, -S- bonds, -SS- bonds, and -SO2- bonds.

[0086] Preferably, group A is selected from at least one of the following groups.

[0087]

[0088] (In the formula, i, j, m, and n are each independently 1 or 2. G represents direct bonding or any of the following formulas.)

[0089] -CH2--CH(CH3)--C(CH3)2--C(CF3)2--C(CH3)(C2H5)--C(CH3)(C6H5)--C(C6H5)2--SO2-

[0090]

[0091] L and M each independently represent a hydrogen atom, a phenyl group, or a carbon atom. 1-3 alkyl.)

[0092] Preferably, group A is selected from at least one of the following groups.

[0093]

[0094] Preferably, base B is phenylene, biphenylene, naphthylene, anthraceneylene, or phenanthrene.

[0095] The base D represents an organic group with 1 to 15 carbon atoms as shown in formula (2) above, preferably an organic group with 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 5 carbon atoms, or 1 to 4 carbon atoms.

[0096] As R 1 R 2 R 3The term "straight-chain, branched, or cyclic alkyl" can be exemplified by, for example, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl, 2- Methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1 -Ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-Ethyl-1-methyl-n-propyl, 1-Ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3- Dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, and 2-ethyl-3-methyl-cyclopropyl. Further, R 1 R 2 R 3 Any two elements can be combined to form a ring.

[0097] Preferably, base D is tert-butyl or trifluoromethyl.

[0098] The base E is a single bond or a straight-chain alkylene group having 1 to 6 carbon atoms. Examples of straight-chain alkylene groups include methylene, ethylene, propylene, butylene, pentylene, and hexylene. Preferably, the base E is a single bond.

[0099] n is a number from 1 to 5, 1 to 4, or 1 to 3, preferably 1, 2, 3, 4, or 5, more preferably 1, 2, 3, or 4, and most preferably 1, 2, or 3.

[0100] [Synthesis Method]

[0101] Phenolic varnish resin having the repeating unit structure shown in formula (1) can be prepared by known methods. For example, it can be prepared by condensing the cyclic compound shown in HAH with the aldehyde compound shown in OHC-BED (where A, B, E, and D have the same meaning as described above). One type of cyclic compound and one type of aldehyde compound can be used, or two or more types can be used in combination. In this condensation reaction, the aldehyde compound can be used in a ratio of 0.1 to 10 moles, preferably 0.1 to 2 moles, relative to 1 mole of the cyclic compound.

[0102] As catalysts used in condensation reactions, inorganic acids such as sulfuric acid, phosphoric acid, and perchloric acid, organic sulfonic acids such as p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, and methanesulfonic acid, and carboxylic acids such as formic acid and oxalic acid can be used. The amount of catalyst used varies depending on the type of catalyst used, but is generally 0.001 to 10,000 parts by mass relative to 100 parts by mass of the cyclic compound (in the case of multiple compounds, their totality), preferably 0.01 to 1,000 parts by mass, and more preferably 0.05 to 100 parts by mass.

[0103] Condensation reactions can occur even in solvent-free conditions, but are usually carried out using a solvent. There are no particular limitations on the solvent, as long as it can dissolve the reaction substrate and does not hinder the reaction. Examples include 1,2-dimethoxyethane, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofuran, and dimethyl ether. Alkane, etc. The condensation reaction temperature is usually 40℃ to 200℃, preferably 100℃ to 180℃. The reaction time varies depending on the reaction temperature, but is usually 5 minutes to 50 hours, preferably 5 minutes to 24 hours.

[0104] The weight-average molecular weight of phenolic varnish resin having the repeating unit structure shown in formula (1) is typically 500-100,000, preferably 600-80,000, 800-60,000, or 1,000-50,000.

[0105] The phenolic varnish resin of the present invention having a repeating unit structure as shown in formula (1) is coated on a substrate (silicon wafer) without the addition of crosslinking agents or other additives and dissolved in a solvent. When fired at 240°C, it shows a contact angle of more than 76° to pure water, and when fired at 350°C, it shows a contact angle of more than 70° to pure water.

[0106] [solvent]

[0107] The composition for forming the lower layer of the resist for nanoimprinting according to the present invention may contain a solvent. The solvent is not particularly limited as long as it can dissolve a phenolic varnish resin having the repeating unit structure shown in formula (1) and any other components added as needed. In particular, since the composition for forming the lower layer of the resist for nanoimprinting according to the present invention is used in a uniform solution state, it is recommended to use a solvent commonly used in photolithography processes, taking into account its coating performance.

[0108] Examples of such solvents include, for instance, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl isobutyl methanol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, 3-methyl... Ethyl oxypropionate, 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate Isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyethyl acetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyethyl acetate, ethyl ethoxyethyl acetate, 3 Methyl methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutylacetate, 3-methoxypropylacetate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, 3-methyl-3-methoxybutylbutyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone, etc. These solvents can be used alone or in combination of two or more.

[0109] Among them, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate are more preferred, and propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are even more preferred.

[0110] [Cross-linking agent]

[0111] The composition for forming the lower layer of a resist for nanoimprinting according to the present invention may include a crosslinking agent. Examples of such crosslinking agents include melamine-based, substituted urea-based, or polymeric forms thereof. Preferably, the crosslinking agent has at least two crosslinking-forming substituents, such as methoxymethylated glycourea (e.g., tetramethoxymethylated glycourea), butoxymethylated glycourea, methoxymethylated melamine, butoxymethylated melamine, methoxymethylated benzoguanamine, butoxymethylated benzoguanamine, methoxymethylated urea, butoxymethylated urea, or methoxymethylated thiourea. Condensates of these compounds may also be used.

[0112] Furthermore, as the aforementioned crosslinking agent, a crosslinking agent with high heat resistance can be used. Preferably, a compound containing crosslinking-forming substituents with aromatic rings (e.g., benzene rings, naphthalene rings) within its molecule is used as a crosslinking agent with high heat resistance.

[0113] Examples of such compounds include compounds having a partial structure of formula (4), polymers or oligomers having repeating units of formula (5).

[0114]

[0115] The above R 11 R 12 R 13 and R 14 The alkyl group consists of 1 to 10 hydrogen or carbon atoms, as illustrated above. n1 is an integer from 1 to 4, n2 is an integer from 1 to (5-n1), and (n1+n2) represents an integer from 2 to 5. n3 is an integer from 1 to 4, n4 is an integer from 0 to (4-n3), and (n3+n4) represents an integer from 1 to 4. Oligomers and polymers can be used in the range of 2 to 100 or 2 to 50 repeating unit structures.

[0116] The following examples illustrate compounds, polymers, and oligomers of formulas (4) and (5).

[0117]

[0118]

[0119] The above-mentioned compounds can be obtained as products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Industry Co., Ltd. For example, among the above-mentioned crosslinking agents, the compound of formula (4-23) can be obtained by Honshu Chemical Industry Co., Ltd. under the trade name TMOM-BP, the compound of formula (4-24) can be obtained by Asahi Organic Materials Co., Ltd. under the trade name TM-BIP-A, and the compound of formula (4-28) can be obtained under the trade name PGME-BIP-A.

[0120] The amount of crosslinking agent added varies depending on the coating solvent used, the substrate used, the required solution viscosity, the required film shape, etc., but is 0.001% by mass or more, 0.01% by mass or more, 0.05% by mass or more, 0.5% by mass or more, or 1.0% by mass or more relative to the total solid content, and is less than 80% by mass, less than 50% by mass, less than 40% by mass, less than 20% by mass, or less than 10% by mass. These crosslinking agents sometimes undergo crosslinking reactions caused by self-condensation, but when crosslinking substituents are present in the polymers of the present invention, crosslinking reactions can occur with these crosslinking substituents.

[0121] [Acids and / or their salts and / or acid-producing agents]

[0122] The composition for forming a resist underlayer film for nanoimprinting according to the present invention may contain an acid and / or its salt and / or an acid-generating agent.

[0123] Examples of acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, salicylic acid, 5-sulfosalicylic acid, 4-phenolsulfonic acid, camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, citric acid, benzoic acid, hydroxybenzoic acid, and naphthoic acid.

[0124] Salts of the aforementioned acids can also be used as salts. There are no limitations on the salt composition; salts of ammonia derivatives such as trimethylamine and triethylamine, pyridine derivatives, and morpholine derivatives are suitable.

[0125] The acid and / or its salt may be used alone, or two or more may be used in combination. The mixing amount relative to the total solids content is typically 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and more preferably 0.01 to 5% by mass.

[0126] Examples of acid-producing agents include thermal acid-producing agents and photo-producing acid-producing agents.

[0127] Examples of heat-generating acid agents include 2,4,4,6-tetrabromocyclohexadienone, benzoin toluene sulfonate, 2-nitrobenzyl toluene sulfonate, K-PURE (registered trademark) CXC-1612, K-PURE CXC-1614, K-PURE TAG-2172, K-PURE TAG-2179, K-PURE TAG-2678, K-PURE TAG2689, K-PURE TAG2700 (manufactured by King Industries), and SI-45, SI-60, SI-80, SI-100, SI-110, SI-150 (manufactured by Sanshin Chemical Industry Co., Ltd.), as well as alkyl sulfonic acid esters.

[0128] Photoacid-generating agents produce acid during the exposure of the photoresist. Therefore, the acidity of the lower film can be adjusted. This is a method to match the acidity of the lower film with that of the upper photoresist. Furthermore, by adjusting the acidity of the lower film, the pattern shape of the photoresist formed on the upper layer can be adjusted.

[0129] Examples of photoacid generators included in the composition for forming the lower layer film of the resist for nanoimprinting of the present invention include: Salt compounds, sulfonylimide compounds, and disulfonyldiazomethane compounds, etc.

[0130] As Salt compounds, such as diphenyliodine, can be cited as an example. Hexafluorophosphate, diphenyliodine Trifluoromethanesulfonate, diphenyliodine Nonafluoro-n-butane sulfonate, diphenyl iodide Perfluorooctane sulfonate, diphenyl iodide Camphor sulfonate, bis(4-tert-butylphenyl)iodine Camphor sulfonate and bis(4-tert-butylphenyl)iodine Iodine, such as trifluoromethanesulfonate Salt compounds, as well as sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoron-butane sulfonate, triphenylsulfonium camphor sulfonate, and triphenylsulfonium trifluoromethane sulfonate.

[0131] Examples of sulfonylimide compounds include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoron-butanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalenediformimide.

[0132] Examples of disulfonyl diazonium compounds include, for example, bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyl diazonium.

[0133] Acid-producing agents can be used alone, or two or more can be used in combination.

[0134] When using an acid-generating agent, its proportion is 0.01 to 10 parts by mass, or 0.1 to 8 parts by mass, or 0.5 to 5 parts by mass relative to 100 parts by mass of the solid component of the composition for forming the lower layer film of the resist for nanoimprinting.

[0135] The composition for forming the lower layer of a resist for nanoimprinting according to the present invention may contain any components other than those described above. The components are described below.

[0136] [Other ingredients]

[0137] In the composition for forming the lower layer film of the resist for nanoimprinting of the present invention, in order to avoid the generation of pinholes, streaks, etc., and to further improve the coating performance on uneven surfaces, a surfactant can be mixed in. Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil-based ether; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene / polyoxypropylene block copolymers; sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monooleate, sorbitol monooleate, sorbitol trioleate, and sorbitol tristearate; and polyoxyethylene sorbitol monolaurate, polyoxyethylene sorbitol monopalmitate, polyoxyethylene sorbitol monostearate, polyoxyethylene sorbitol trioleate, and polyoxyethylene sorbitol tristearate. Polyoxyethylene sorbitan fatty acid esters and other non-ionic surfactants, such as acid esters, Etotron EF301, EF303, EF352 (manufactured by Toto Co., Ltd. , trade name), メガファック F171, F173, R-40, R-40N, R-40LM (made by DIC Co., Ltd., trade name), フロラード FC430, F Fluoropolymer surfactants such as C431 (manufactured by Sumitomo Silem Co., Ltd., trade name), Asahigard AG710, Servolon S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd., trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) are used. The amount of these surfactants mixed in the formulation is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solid content of the composition for forming the resist underlayer. These surfactants can be used alone or in combination of two or more. When using a surfactant, the proportion of the surfactant is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass relative to 100 parts by mass of the solid component of the composition for forming the lower layer film of the nanoimprint resist.

[0138] In the composition for forming the lower layer film of the nanoimprint resist of the present invention, light absorbers, rheology modifiers, adhesive additives, etc., may be added. Rheology modifiers are effective in improving the flowability of the composition for forming the lower layer film. Adhesive additives are effective in improving the adhesion between the semiconductor substrate or the resist and the lower layer film.

[0139] As light absorbers, commercially available light absorbers listed in publications such as "Technology and Market of Industrial Pigments" (CMC Publishing) and "Dye Handbook" (Organic Synthetic Chemistry Society) are suitable, including CI Disperse Yellow 1, 3, 4, 5, 7, 8, 13, 23, 31, 49, 50, 51, 54, 60, 64, 66, 68, 79, 82, 88, 90, 93, 102, 114, and 124; and CI Disperse Orange 1, 5, and 13. 25, 29, 30, 31, 44, 57, 72 and 73; CI Disperse Red 1, 5, 7, 13, 17, 19, 43, 50, 54, 58, 65, 72, 73, 88, 117, 137, 143, 199 and 210; CI Disperse Violet 43; CI Disperse Blue 96; CI Fluorescent Whitening Agent 112, 135 and 163; CI Solvent Orange 2 and 45; CI Solvent Red 1, 3, 8, 23, 24, 25, 27 and 49; CI Pigment Green 10; CI Pigment Brown 2, etc. The above-mentioned light absorbers are generally mixed in a proportion of 10% by mass or less, preferably 5% by mass or less, relative to the total solid components of the composition for forming the lower layer film of the resist for nanoimprinting.

[0140] Rheology modifiers are primarily added to improve the flowability of the composition for forming the lower layer of the resist film for nanoimprinting, especially during the baking process, to improve the uniformity of the film thickness of the lower layer of the resist film and to improve the filling ability of the composition for forming the lower layer of the resist film for nanoimprinting into the pores. Specific examples include phthalic acid derivatives such as dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dihexyl phthalate, and butyl isodecyl phthalate; adipic acid derivatives such as di-n-butyl adipate, diisobutyl adipate, diisooctyl adipate, and octyl decyl adipate; maleic acid derivatives such as di-n-butyl maleate, diethyl maleate, and dinonyl maleate; oleic acid derivatives such as methyl oleate, butyl oleate, and tetrahydrofurfuryl oleate; or stearic acid derivatives such as n-butyl stearate and glyceryl stearate. These rheology modifiers are typically blended in proportions of less than 30% by mass relative to the total solid components of the composition for forming the lower layer of the resist for nanoimprinting.

[0141] Adhesion aids are mainly added to improve the adhesion between the substrate or resist and the composition for forming the lower layer film of the nanoimprint resist, especially to prevent the resist from peeling off during development. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylhydroxymethylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylhydroxymethylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilylimidazolium; silanes such as hydroxymethyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-epoxypropoxypropyltrimethoxysilane; and benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, and 2-mercaptobenzo[]. Heterocyclic compounds such as azoles, urazoles, thiouracil, mercaptoimidazoles, and mercaptopyrimidines, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesive aids are typically formulated in proportions of less than 5% by mass, preferably less than 2% by mass, relative to the total solid content of the composition for forming the lower layer of the resist for nanoimprinting.

[0142] The solid content of the composition for forming the lower layer of the resist for nanoimprinting according to the present invention is typically 0.1 to 70% by mass, preferably 0.1 to 60% by mass. The solid content refers to the percentage of all components remaining after removing the solvent from the composition for forming the lower layer of the resist for nanoimprinting. The proportion of the aforementioned polymer in the solid content is preferably in the following order: 1 to 100% by mass, 1 to 99.9% by mass, 50 to 99.9% by mass, 50 to 95% by mass, and 50 to 90% by mass.

[0143] One criterion for evaluating whether a nanoimprint resist underlayer film forming composition is a homogeneous solution is to observe the permeability of a specific microfilter. The nanoimprint resist underlayer film forming composition of the present invention can pass through a microfilter with a pore size of 0.1 μm and presents a homogeneous solution.

[0144] Examples of materials for the aforementioned microfilters include fluorinated resins such as PTFE (polytetrafluoroethylene) and PFA (tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer), PE (polyethylene), UPE (ultra-high molecular weight polyethylene), PP (polypropylene), PSF (polysulfone), PES (polyethersulfone), and nylon, but PTFE (polytetrafluoroethylene) is preferred.

[0145] The present invention relates to a composition for forming a resist lower layer film for nanoimprinting, which is prepared by mixing a phenolic varnish resin with a repeating unit structure as shown in Formula (1) with a solvent and other arbitrary components, and is coated on a substrate (silicon wafer). When fired at 350°C, it exhibits a contact angle of more than 65° to pure water.

[0146] Hereinafter, methods for manufacturing a resist underlayer film, a patterning method, and a semiconductor device using the resist underlayer film forming composition for nanoimprinting according to the present invention will be described.

[0147] [Method for manufacturing the lower layer of resist for nanoimprint lithography]

[0148] The nanoimprint resist underlayer film forming composition of the present invention is applied to a substrate used in the manufacture of semiconductor devices (e.g., silicon wafer substrate, silicon / silicon dioxide coated substrate, silicon nitride substrate, glass substrate, ITO substrate, polyimide substrate, and low-k material coated substrate, etc.) using a suitable coating method such as a spin coater or a coating machine, and then fired to form a resist underlayer film. The firing conditions are appropriately selected from a firing temperature of 80°C to 400°C and a firing time of 0.3 to 60 minutes. Preferably, the firing temperature is 150°C to 350°C and the firing time is 0.5 to 2 minutes. Here, the film thickness of the formed underlayer film is, for example, 10 to 1000 nm, or 20 to 500 nm, or 30 to 400 nm, or 50 to 300 nm. Furthermore, if a quartz substrate is used as the substrate, a replica of the quartz imprinting mold (mold replica) can be fabricated.

[0149] Furthermore, an adhesive layer and / or an organosilicon layer containing 99% by mass or less, or 50% by mass or less, of Si can also be formed on the nanoimprint resist underlayer film of the present invention by coating or vapor deposition. For example, in addition to the method of forming the adhesive layer described in Japanese Patent Application Publication No. 2013-202982, Japanese Patent No. 5827180, and the composition for forming a silicon-containing resist underlayer film (inorganic resist underlayer film) described in WO2009 / 104552A1 by spin coating, Si-based inorganic material films can be formed by CVD or the like.

[0150] Furthermore, by coating the nanoimprint resist lower layer film forming composition of the present invention onto a semiconductor substrate (so-called high-low difference substrate) having a portion having a height difference and a portion not having a height difference, and then firing it, a resist lower layer film with a height difference between the portion having a height difference and the portion not having a height difference can be formed in the range of 3 to 70 nm.

[0151] [Pattern Formation Method]

[0152] The pattern forming method of the present invention includes the following steps:

[0153] The process of applying a curable composition to a photoresist underlayer film formed by the photoresist underlayer film manufacturing method of the present invention;

[0154] The process of bringing the above-mentioned curable composition into contact with the mold;

[0155] The process of forming a cured film by irradiating the above-mentioned curable composition with light or electron beams; and

[0156] The process of separating the cured film from the mold.

[0157] [Curing composition]

[0158] As a photoresist formed on the underlying resist film, there are no particular limitations as long as it is a photosensitive substance used for exposure. Both negative and positive photoresists can be used. Examples include positive photoresists composed of phenolic varnish resin and 1,2-naphthoquinone diazonyl sulfonate; chemically amplified photoresists composed of a binder and a photoacid-generating agent having groups that increase the rate of alkali dissolution through acid decomposition; chemically amplified photoresists composed of low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition, alkali-soluble binders, and photoacid-generating agents; and chemically amplified photoresists composed of binders that increase the rate of alkali dissolution through acid decomposition, low-molecular-weight compounds that increase the rate of alkali dissolution through acid decomposition, and photoacid-generating agents, etc. Examples include APEX-E manufactured by Sprint, PAR710 manufactured by Sumitomo Chemical Industries, Ltd., and SEPR430 manufactured by Shin-Etsu Chemical Industries, Ltd. Furthermore, examples include fluorinated polymer photoresists as described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0159] [Process for applying curable compositions]

[0160] This process involves applying a curable composition to a photoresist underlayer film formed by the method for manufacturing the photoresist underlayer film according to the present invention. Methods for applying the curable composition include, for example, inkjet printing, dip coating, air knife coating, curtain coating, wire rod coating, gravure coating, extrusion coating, spin coating, and slot scanning. Inkjet printing is suitable for applying the curable composition as droplets, while spin coating is suitable for coating the curable composition. In this process, a bonding layer and / or an organosilicon layer containing 99% by mass or less, or 50% by mass or less, of Si can also be formed on the photoresist underlayer film by coating or vapor deposition, and the curable composition can then be applied thereon.

[0161] [The process of bringing the curable composition into contact with the mold]

[0162] In this process, the curable composition is brought into contact with the mold. For example, if the curable composition, which is a liquid, is brought into contact with a mold having a prototype pattern for transferring the pattern shape, a liquid film is formed in which the curable composition fills the recesses of the fine pattern on the surface of the mold.

[0163] Considering the processes involving irradiation with light or electron beams, as described later, it is recommended to use molds with light-transmitting materials as the substrate. Specifically, the mold substrate is preferably made of light-transmitting resins such as glass, quartz, PMMA, and polycarbonate resin, transparent metal vapor-deposited films, flexible films such as polydimethylsiloxane, photocurable films, and metal films. Considering the low coefficient of thermal expansion and minimal pattern skew, quartz is more preferably used as the mold substrate.

[0164] The micro-patterns on the surface of the mold preferably have a pattern height of 4 nm or more and 200 nm or less. To improve the processing accuracy of the substrate, a certain pattern height is required. A lower pattern height results in less force required to peel the mold from the cured film during the process of separating the cured film from the mold (described later). Furthermore, it reduces the number of defects remaining on the mask side due to the resist pattern being broken up. Considering these factors, it is recommended to select an appropriate, balanced pattern height.

[0165] In addition, sometimes the elastic deformation of the resist pattern caused by the impact when peeling off the mold can cause adjacent resist patterns to come into contact with each other, resulting in the resist patterns sticking together or breaking. This can sometimes be avoided by keeping the pattern height to be about twice or less than the pattern width (length-to-width ratio less than 2).

[0166] To improve the peelability of the cured composition from the mold surface, the mold can be pre-treated. One method of surface treatment is to apply a release agent to the mold surface to form a release agent layer. Examples of release agents include silicone-based, fluorine-based, hydrocarbon-based, polyethylene-based, polypropylene-based, paraffin-based, lignite-based, and carnauba-based release agents. Fluorine-based and hydrocarbon-based release agents are preferred. Commercially available examples include, for instance, DSX (registered trademark) manufactured by Daikin Kogyo Co., Ltd. A single release agent or two or more can be used together.

[0167] In this process, there is no particular limitation on the pressure applied to the curable composition when the mold comes into contact with it. A pressure of 0 MPa or more and 100 MPa or less is recommended. The pressure is preferably 0 MPa or more, and 50 MPa or less, 30 MPa or less, or 20 MPa or less.

[0168] In the case where the pre-expansion of the droplets of the curable composition is performed in the preceding process (the process of applying the curable composition), the expansion of the curable composition in this process is completed rapidly. As a result, the time for the mold to contact the curable composition can be shortened. There is no particular limitation on the contact time, but it is preferably 0.1 seconds or more, and less than 600 seconds, less than 3 seconds, or less than 1 second. If the contact time is too short, the expansion and filling become insufficient, and a defect known as an unfilled defect may occur.

[0169] This process can be carried out under any conditions, including atmospheric, reduced pressure, and inert gas atmospheres, but is preferably carried out at a pressure above 0.0001 atm and below 10 atm. To prevent the influence of oxygen and moisture on the curing reaction, it is recommended to carry out the process under reduced pressure or inert gas atmospheres. Specific examples of inert gases that can be used to form an inert gas atmosphere include nitrogen, carbon dioxide, helium, argon, CFCs, HCFCs, HFCs, or mixtures thereof.

[0170] This process can be performed in an atmosphere containing a condensable gas (hereinafter referred to as a "condensable gas atmosphere"). In this specification, a condensable gas refers to a gas that condenses and liquefies due to capillary pressure generated during filling when it is filled, along with the curable composition, into the recesses of the fine pattern formed on the mold and into the gap between the mold and the substrate. Furthermore, the condensable gas exists as a gas in the atmosphere before the curable composition comes into contact with the mold in this process. If this process is performed in a condensable gas atmosphere, the gas filled into the recesses of the fine pattern liquefies due to the capillary pressure generated by the curable composition, thereby eliminating bubbles and resulting in excellent filling performance. The condensable gas is soluble in the curable composition.

[0171] There is no limitation on the boiling point of the condensable gas as long as it is below the atmosphere temperature of this process, but it is preferred to be above -10°C, or above +10°C and below +23°C.

[0172] In this process, the vapor pressure of the condensable gas at the ambient temperature is not particularly limited as long as it is below the mold pressure. It is preferably in the range of 0.1 MPa to 0.4 MPa.

[0173] Specifically, condensable gases include chlorofluorocarbons (CFCs) such as trichlorofluoromethane, fluorocarbons (FCs), hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs) such as 1,1,1,3,3-pentafluoropropane (CHF2CH2CF3, HFC-245fa, PFP), and hydrofluoroethers (HFEs) such as pentafluoroethyl methyl ether (CF3CF2OCH3, HFE-245mc).

[0174] The condensable gas can be used alone or in combination with two or more other gases. Furthermore, these condensable gases can be mixed with non-condensable gases such as air, nitrogen, carbon dioxide, helium, and argon. Air and helium are preferred as non-condensable gases to be mixed with the condensable gas.

[0175] [The process of forming a cured film by irradiating a curable composition with light or electron beams]

[0176] In this process, a cured film is formed by irradiating the curable composition with light or electron beams. That is, the curable composition with a fine pattern filled in the mold is irradiated with light or electron beams through the mold, so that the curable composition with the fine pattern filled in the mold is directly cured in this state, thereby forming a cured film with a patterned shape.

[0177] The wavelength of light or electron beam is selected based on the sensitivity of the curable composition. Specifically, ultraviolet light, X-rays, electron beams, etc., with wavelengths above 150 nm and below 400 nm can be appropriately selected. Examples of light or electron beam sources include high-pressure mercury lamps, ultra-high-pressure mercury lamps, low-pressure mercury lamps, Deep-UV lamps, carbon arc lamps, chemical lamps, metal halide lamps, xenon lamps, KrF stimulated excimer lasers, ArF stimulated excimer lasers, and F2 stimulated excimer lasers. There can be one or more light sources. Irradiation can be performed on the entire curable composition filled with a fine pattern in the mold, or only on a portion of the area. Light irradiation can be performed intermittently multiple times on the entire area of ​​the substrate, or continuously on the entire area. Alternatively, a portion of the substrate can be irradiated first, and a different area can be irradiated a second time.

[0178] The cured film obtained by this operation preferably has a pattern with a size of 1 nm or more, or 10 nm or more and 10 mm or less, or 100 μm or less.

[0179] [The process of separating the cured film from the mold]

[0180] In this process, the cured film is separated from the mold. The cured film with a patterned shape is separated from the mold, and the cured film with a patterned shape that is a reversed pattern of the micro-pattern formed on the mold is obtained in a free-standing state.

[0181] As a method for separating a patterned cured film from a mold, there are no particular limitations as long as the means of moving the cured film and the mold in a direction that is relatively far apart, and as long as a portion of the patterned cured film is not physically damaged. There are also no particular limitations on various conditions. For example, the substrate can be fixed while the mold is moved away from the substrate for peeling, or the mold can be fixed while the substrate is moved away from the mold for peeling. Alternatively, the substrate and the mold can be stretched in opposite directions to move them for peeling.

[0182] Furthermore, when the process of bringing the aforementioned curable composition into contact with the mold is performed in a condensing gas atmosphere, the condensing gas vaporizes as the pressure at the interface between the cured film and the mold decreases during the separation of the cured film from the mold in this process. This reduces the demolding force required to separate the cured film from the mold.

[0183] Through the above process, a cured film with the desired raised and recessed pattern shape derived from the mold can be prepared at the desired location.

[0184] [Semiconductor device manufacturing method]

[0185] The inorganic lower layer (intermediate layer) is removed using the pattern of photoresist (upper layer) formed by the patterning method of the present invention as a protective film. Then, the organic lower layer (lower layer) is removed using a film composed of the patterned photoresist and the inorganic lower layer (intermediate layer) as a protective film. Finally, a semiconductor substrate is processed using the patterned inorganic lower layer (intermediate layer) and the organic lower layer (lower layer) as protective films.

[0186] First, the inorganic lower layer (intermediate layer), to which the photoresist has been removed, is removed by dry etching, exposing the semiconductor substrate. Gases that can be used in the dry etching of the inorganic lower layer include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride and chlorine trifluoride, chlorine, trichloroborane, and dichloroborane. Halogen-based gases are preferred for the dry etching of the inorganic lower layer, and fluorine-based gases are more preferred. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0187] Then, the organic underlayer is removed using a film consisting of patterned photoresist and an inorganic underlayer as a protective film. The organic underlayer (underlayer) is preferably removed by dry etching with an oxygen-based gas. This is because the inorganic underlayer, which contains a large number of silicon atoms, is difficult to remove by dry etching with an oxygen-based gas.

[0188] Finally, the semiconductor substrate is processed. The semiconductor substrate is preferably processed by dry etching using a fluorine-based gas.

[0189] Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0190] Furthermore, an organic antireflective film can be formed on top of the photoresist underlayer before the formation of the photoresist. There are no particular limitations on the antireflective film composition used herein; any material conventionally used in photolithography processes can be selected. Furthermore, the antireflective film can be formed using conventional methods, such as coating and firing with a spin coater or coater.

[0191] In this invention, an organic underlayer film can be formed on a substrate, followed by an inorganic underlayer film, and then a photoresist can be coated onto it. This narrows the pattern width of the photoresist, allowing substrate processing even when the photoresist is thinly coated to prevent pattern collapse, by selecting an appropriate etching gas. For example, a fluorine-based gas with a sufficiently fast etching rate relative to the photoresist can be used as the etching gas to process the photoresist underlayer film. Furthermore, a fluorine-based gas with a sufficiently fast etching rate relative to the inorganic underlayer film can be used as the etching gas to process the substrate. Even further, an oxygen-based gas with a sufficiently fast etching rate relative to the organic underlayer film can be used as the etching gas to process the substrate.

[0192] Furthermore, the photoresist underlayer film formed by the composition for forming the photoresist underlayer sometimes absorbs light depending on the wavelength of the light used in the photolithography process. In such cases, it can function as an anti-reflective film that prevents reflected light from the substrate. Furthermore, the underlayer film formed by the composition for forming the photoresist underlayer of the present invention can also function as a hard mask. The underlayer film of the present invention can also be used as a layer for preventing interaction between the substrate and the photoresist, a layer that prevents the adverse effects of the material used in the photoresist or substances generated during exposure to the photoresist on the substrate, a layer that prevents the diffusion of substances generated from the substrate during heating and firing onto the upper photoresist layer, and a barrier layer that reduces the poisoning effect of the photoresist layer caused by the dielectric layer of the semiconductor substrate, etc.

[0193] Furthermore, the lower film formed from the resist lower film forming composition is applied to a substrate with through-holes used in a dual damascene process, and can be used as an embedding material capable of filling the cavities without gaps. Additionally, it can also be used as a planarizing material for planarizing the surface of a semiconductor substrate with unevenness.

[0194] Example

[0195] The following examples illustrate the content of the present invention in detail, but the present invention is not limited to them.

[0196] The weight-average molecular weight of the resin (polymer) obtained in Synthesis Example 1 below was determined by gel permeation chromatography (hereinafter referred to as GPC). The determination was performed using a GPC apparatus manufactured by Higashi Sou Corporation, and the determination conditions are as follows.

[0197] GPC pillars: Shodex KF803L, Shodex KF802, Shodex KF801 [Registered Trademark] (Showa Denko Co., Ltd.)

[0198] Column temperature: 40℃

[0199] Solvent: Tetrahydrofuran (THF)

[0200] Flow rate: 1.0 ml / minute

[0201] Standard sample: Polystyrene (manufactured by Higashi Sou Co., Ltd.)

[0202] The following substances were used in the etcher and etching gas used to determine the dry etching rate.

[0203] RIE-10NR (manufactured by SAMU): CF4

[0204] [Synthesis example 1]

[0205] In a 100 mL two-necked flask, 9.71 g of 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 48.68 g of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA), and 1.15 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for 30 minutes. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (2-1). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 4,900.

[0206]

[0207] [Synthesis example 2]

[0208] In a 100 mL two-necked flask, add 10.42 g of 4-(trifluoromethyl)-benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 50.34 g of PGMEA, and 1.15 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). Heat to 150 °C and reflux with stirring for 3.5 hours. After the reaction is complete, add the solution dropwise to methanol to allow reprecipitation. Filter the resulting precipitate and dry the filter under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (2-2).

[0209] The weight-average molecular weight (Mw) determined by GPC in polystyrene form is 4,200.

[0210]

[0211] [Synthesis example 3]

[0212] In a 100 mL two-necked flask, 8.39 g of 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 2-phenylindole (manufactured by Tokyo Chemical Industry Co., Ltd.), 45.24 g of PGMEA, and 0.99 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for 17 hours. After the reaction was complete, the solution was added dropwise to a methanol / water mixture to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer is equivalent to formula (2-3). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 1,200.

[0213]

[0214] [Synthesis Example 4]

[0215] 9.01 g of 4-(trifluoromethyl)-benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 2-phenylindole (manufactured by Tokyo Chemical Industry Co., Ltd.), 46.68 g of PGMEA, and 0.99 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL two-necked flask. The mixture was then heated to 150 °C and stirred under reflux for 17 hours. After the reaction was complete, the solution was added dropwise to a methanol / water mixture to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer is equivalent to formula (2-4). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 2,200.

[0216]

[0217] [Synthesis example 5]

[0218] In a 100 mL two-necked flask, 7.40 g of 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 18.50 g of PGMEA, and 1.10 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for 10 minutes. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer is equivalent to formula (2-5). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 6,000.

[0219]

[0220] [Synthesis example 6]

[0221] In a 100 mL two-necked flask, 7.95 g of 4-(trifluoromethyl)-benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 18.50 g of PGMEA, and 0.55 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for 10 minutes. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer is equivalent to formula (2-6). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 30,000.

[0222]

[0223] [Synthesis Example 7]

[0224] In a 100 mL two-necked flask, 4.63 g of 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.77 g of PGMEA, and 0.55 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for 5.5 hours. After the reaction was complete, the solution was added dropwise to a methanol / water mixture to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (2-7). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 2,000.

[0225]

[0226] [Synthesis example 8]

[0227] In a 100 mL two-necked flask, 4.97 g of 4-(trifluoromethyl)-benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 23.28 g of PGMEA, and 0.55 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for 5.5 hours. After the reaction was complete, the solution was added dropwise to a methanol / water mixture to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (2-8). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 10,000.

[0228]

[0229] [Synthesis Example 9]

[0230] 10.13 g of 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 49.77 g of PGMEA, and 1.20 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL two-necked flask. The mixture was then heated to 150 °C and stirred under reflux for 1 hour and 45 minutes. After the reaction was complete, the solution was added dropwise to a methanol / water mixture to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer is equivalent to formula (2-9). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 5,200.

[0231]

[0232] [Synthesis Example 10]

[0233] 10.87 g of 4-(trifluoromethyl)-benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.50 g of PGMEA, and 1.20 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL two-necked flask. The mixture was then heated to 150 °C and stirred under reflux for 2 hours and 15 minutes. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer is equivalent to formula (2-10). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 8,300.

[0234]

[0235] [Synthesis Example 11]

[0236] 4.69 g of 4-tert-butylbenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of bisphenol M (manufactured by Tokyo Chemical Industry Co., Ltd.), 35.56 g of PGMEA, and 0.56 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL two-necked flask. The mixture was then heated to 150 °C and stirred under reflux for 16 hours. After the reaction was complete, the solution was added dropwise to a methanol / water mixture to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer is equivalent to formula (2-11). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 8,000.

[0237]

[0238] [Synthesis Example 12]

[0239] Add 5.03 g of 4-(trifluoromethyl)-benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of bisphenol M (manufactured by Tokyo Chemical Industry Co., Ltd.), 36.36 g of PGMEA, and 0.56 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) to a 100 mL two-necked flask. Heat to 150 °C and reflux with stirring for 5 hours. After the reaction is complete, add the solution dropwise to a methanol / water mixture to allow for reprecipitation. Filter the resulting precipitate and dry the filter under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (2-12). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene is 6,500.

[0240]

[0241] [Comparative Synthesis Example 1]

[0242] In a 100 mL two-necked flask, add 6.35 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 40.84 g of PGMEA, and 1.15 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). Heat to 150 °C and reflux with stirring for approximately 30 minutes. After the reaction is complete, add the solution dropwise to methanol to allow for reprecipitation. Filter the resulting precipitate and dry the filter under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (1-1). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene is 52,300.

[0243]

[0244] [Comparative Synthesis Example 2]

[0245] 5.49 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 2-phenylindole (manufactured by Tokyo Chemical Industry Co., Ltd.), 16.49 g of PGMEA, and 0.99 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a 100 mL two-necked flask. The mixture was then heated to 150 °C and stirred under reflux for approximately 5 hours. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (1-2). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 1,600.

[0246]

[0247] [Comparative Synthesis Example 3]

[0248] In a 100 mL two-necked flask, 4.84 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of N-phenyl-1-naphthylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 36.67 g of PGMEA, and 0.88 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for approximately 15 minutes. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (1-3). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 5,900.

[0249]

[0250] [Comparative Synthesis Example 4]

[0251] In a 100 mL two-necked flask, 3.03 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 9,9-bis(4-hydroxyphenyl)fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.), 32.68 g of PGMEA, and 0.55 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for approximately 17.5 hours. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (1-4). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 10,300.

[0252]

[0253] [Comparative Synthesis Example 5]

[0254] In a 100 mL two-necked flask, 6.62 g of benzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of 1,5-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.), 41.58 g of PGMEA, and 1.20 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for approximately 1.5 hours. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (1-5). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 5,300.

[0255]

[0256] [Comparative Synthesis Example 6]

[0257] In a 100 mL two-necked flask, 7.19 g of p-tolualdehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.00 g of carbazole (manufactured by Tokyo Chemical Industry Co., Ltd.), 42.80 g of PGMEA, and 1.15 g of methanesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The mixture was then heated to 150 °C and stirred under reflux for approximately 30 minutes. After the reaction was complete, the solution was added dropwise to methanol to allow for reprecipitation. The resulting precipitate was filtered, and the filter was dried under reduced pressure at 60 °C overnight. The resulting polymer corresponds to formula (1-6). The weight-average molecular weight (Mw) determined by GPC to be equivalent to polystyrene was 5,900.

[0258]

[0259] The chemical structures (illustrated) and abbreviations of the raw materials used in the examples are described below.

[0260]

[0261] [Example 1]

[0262] The resin obtained in Synthesis Example 1 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0263] [Example 2]

[0264] The resin obtained in Synthesis Example 2 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0265] [Example 3]

[0266] The resin obtained in Synthesis Example 3 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0267] [Example 4]

[0268] The resin obtained in Synthesis Example 4 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0269] [Example 5]

[0270] The resin obtained in Synthesis Example 5 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0271] [Example 6]

[0272] The resin obtained in Synthesis Example 6 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0273] [Example 7]

[0274] The resin obtained in Synthesis Example 7 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0275] [Example 8]

[0276] The resin obtained in Synthesis Example 8 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0277] [Example 9]

[0278] The resin obtained in Synthesis Example 9 was dissolved in propylene glycol monomethyl ether (hereinafter referred to as PGME), and a resin solution (solid content of 22.6% by mass) was obtained by ion exchange. PGME was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the lower layer of the resist film.

[0279] [Example 10]

[0280] The resin obtained in Synthesis Example 10 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0281] [Example 11]

[0282] The resin obtained in Synthesis Example 11 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0283] [Example 12]

[0284] The resin obtained in Synthesis Example 12 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.6% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0285] [Example 13]

[0286] The resin obtained in Synthesis Example 1 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 22.6% by mass). To 2.65 g of this resin solution, 0.12 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megfack R-40), 0.09 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.45g of p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.34g of PGMEA, and 2.35g of PGME in the solution, and filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a composition for forming a photoresist lower film.

[0287] [Example 14]

[0288] The resin obtained in Synthesis Example 2 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 20.1% by mass). To 3.00 g of this resin solution, 0.12 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.09 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.34 g of PGME, 4.00 g of PGMEA, and 2.49 g of PGME from p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm, and prepare a composition for forming the lower layer film of the resist.

[0289] [Example 15]

[0290] The resin obtained in Synthesis Example 3 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 19.0% by mass). To 1.94 g of this resin solution, 0.07 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Co., Ltd., MegaFake R-40), 0.18 g of PGMEA-BIP-A (manufactured by Fankenke Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.46 g of PGME, 2.91 g of PGMEA, and 1.43 g of PGME from p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), filter the solution using a micro-filter made of polytetrafluoroethylene with a pore size of 0.1 μm, and prepare a composition for forming the lower layer film of the resist.

[0291] [Example 16]

[0292] The resin obtained in Synthesis Example 4 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 20.8% by mass). To 2.02 g of this resin solution, 0.08 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, MegaFake R-40), 0.06 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.31 g of PGME, 2.88 g of PGMEA, and 1.64 g of PGME from p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm, and prepare a composition for forming the lower layer film of the resist.

[0293] [Example 17]

[0294] The resin obtained in Synthesis Example 5 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 19.1% by mass). To 3.01 g of this resin solution, 0.12 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Co., Ltd., MegaFake R-40), 0.19 g of PGME-BIP-A (manufactured by Fankenke Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.43 g of PGME, 3.96 g of PGMEA, and 2.29 g of PGME from p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm, and prepare a composition for forming the lower layer film of the resist.

[0295] [Example 18]

[0296] The resin obtained in Synthesis Example 6 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 20.5% by mass). To 2.92 g of this resin solution, 0.12 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.09 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and pyridine containing 2% by mass were added. Dissolve 0.45g of p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.07g of PGMEA, and 2.35g of PGME in the solution, and filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of a composition for forming a lower layer film of the resist.

[0297] [Example 19]

[0298] The resin obtained in Synthesis Example 7 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 22.2% by mass). To 2.56 g of this resin solution, 0.11 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.11 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.85g of p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.41g of PGMEA, and 1.95g of PGME in the solution, and filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of a composition for forming a photoresist lower film.

[0299] [Example 20]

[0300] The resin obtained in Synthesis Example 8 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 22.8% by mass). To 2.49 g of this resin solution, 0.11 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.11 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.85g of p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.47g of PGMEA, and 1.95g of PGME in the solution, and filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a composition for forming a photoresist lower film.

[0301] [Example 21]

[0302] The resin obtained in Synthesis Example 9 was dissolved in PGME and then subjected to ion exchange to obtain a resin solution (solid content 19.7% by mass). To 2.88 g of this resin solution, 0.11 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.11 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.85g, 2.68g, and 3.36g of PGME (Tokyo Chemical Industry Co., Ltd.) in p-hydroxybenzenesulfonate, filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1μm, and prepare a composition for forming the lower layer film of the resist.

[0303] [Example 22]

[0304] The resin obtained in Synthesis Example 10 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 22.9% by mass). To 2.48 g of this resin solution, 0.11 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.11 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.85g of p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.48g of PGMEA, and 1.95g of PGME in the solution, and filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1μm to prepare a solution of a composition for forming a lower layer film of the resist.

[0305] [Example 23]

[0306] The resin obtained in Synthesis Example 11 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 17.9% by mass). To 1.93 g of this resin solution, 0.07 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.07 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.26 g of PGME, 2.25 g of PGMEA, and 1.42 g of PGME from p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm, and prepare a composition for forming the lower layer film of the photoresist.

[0307] [Example 24]

[0308] The resin obtained in Synthesis Example 12 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 17.8% by mass). To 3.24 g of this resin solution, 0.12 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.12 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.43 g of p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 3.73 g of PGMEA, and 2.37 g of PGME in the solution, and filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of a composition for forming a lower layer film of the resist.

[0309] [Comparative Example 1]

[0310] The resin obtained in Comparative Synthesis Example 1 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 18.4% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0311] [Comparative Example 2]

[0312] The resin obtained in Comparative Synthesis Example 2 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 22.5% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0313] [Comparative Example 3]

[0314] The resin obtained in Comparative Synthesis Example 3 was dissolved in cyclohexanone and then subjected to ion exchange to obtain a resin solution (solid content of 17.7% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0315] [Comparative Example 4]

[0316] The resin obtained in Comparative Synthesis Example 4 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 15.9% by mass). PGMEA was added to the resin at a solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0317] [Comparative Example 5]

[0318] The resin obtained in Comparative Synthesis Example 5 was dissolved in PGME and then subjected to ion exchange to obtain a resin solution (solid content of 18.2% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The mixture was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0319] [Comparative Example 6]

[0320] The resin obtained in Comparative Synthesis Example 6 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content of 26.0% by mass). PGMEA was added to the solution at a resin solid content of 5% and mixed. The solution was then filtered using a polytetrafluoroethylene microfilter with a pore size of 0.1 μm to prepare a solution of the composition for forming the resist underlayer film.

[0321] [Comparative Example 7]

[0322] The resin obtained in Comparative Synthesis Example 6 was dissolved in PGMEA and then subjected to ion exchange to obtain a resin solution (solid content 22.6% by mass). To 2.19 g of this resin solution, 0.11 g of PGMEA containing 1% by mass surfactant (manufactured by DIC Corporation, Megafack R-40), 0.11 g of TMOM-BP (manufactured by Honshu Chemical Industry Co., Ltd.), and 2% by mass pyridine were added. Dissolve 0.85g of p-hydroxybenzenesulfonate (Tokyo Chemical Industry Co., Ltd.), 4.78g of PGMEA, and 1.95g of PGME in the solution, filter the solution using a polytetrafluoroethylene microfilter with a pore size of 0.1μm, and prepare a composition for forming the lower layer film of the resist.

[0323] (Measuring the contact angle of polymers)

[0324] Solutions of the resist underlayer film forming compositions prepared in Examples 1-12 and Comparative Examples 1-6 were respectively coated onto silicon wafers using a spin coater and then fired on a hot plate at 240°C for 60 seconds or 350°C for 60 seconds to form polymer films. The contact angle of the polymer with pure water was then measured using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.

[0325] [Table 1]

[0326] Table 1. Contact angle (°) with pure water

[0327]

[0328] As stated above, phenolic varnish resins containing tert-butyl or trifluoromethyl groups exhibit exceptionally high pure water contact angles (i.e., hydrophobicity) not only at low temperatures but also at high temperatures compared to similar skeletons, demonstrating a clear advantage. The next project will present the evaluation results of the physical properties of the materials prepared by mixing crosslinking agents, acid catalysts, and surfactants with phenolic varnish resins containing tert-butyl or trifluoromethyl groups.

[0329] (Contact angle measurement of materials)

[0330] Solutions of the resist underlayer film forming compositions prepared in Examples 13-24 and Comparative Example 7 were respectively coated onto silicon wafers using a spin coater and fired on a hot plate at 350°C for 60 seconds to form a 200 nm resist underlayer film. The contact angle with pure water was then measured using a contact angle meter manufactured by Kyowa Interface Science Co., Ltd.

[0331] [Table 2]

[0332] Table 2 Contact angles (°) with pure water

[0333]

[0334] As mentioned above, phenolic varnish resins containing tert-butyl or trifluoromethyl groups exhibit an exceptionally high pure water contact angle (= hydrophobicity) during high-temperature firing when the material is manufactured. This improves adhesion to the hydrophobic upper film and also provides good permeability to hydrophobic gases.

[0335] (Dissolution test in resist solvent)

[0336] Solutions of the resist underlayer film forming compositions prepared in Examples 13-24 and Comparative Example 7 were respectively coated onto silicon wafers using a spin coater and fired at 350°C for 60 seconds on a hot plate to form resist underlayer films (film thickness 0.20 μm). These resist underlayer films were then immersed in ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone, which were used as solvents for resisting. These resist underlayer films were insoluble in these solvents.

[0337] (Optical constant measurement)

[0338] Solutions of the resist underlayer film forming compositions prepared in Examples 13-24 and Comparative Example 7 were respectively coated onto silicon wafers using a spin coater. The wafers were then fired at 350°C for 60 seconds on a hot plate to form resist underlayer films (film thickness 0.05 μm). The refractive index (n-value) and optical absorptivity (also known as k-value or attenuation coefficient) of these resist underlayer films at a wavelength of 193 nm were measured using a spectroscopic ellipsometry (Table 3).

[0339] [Table 3]

[0340] Table 3 Refractive index n and optical absorption coefficient k

[0341]

[0342] As mentioned above, phenolic varnish resins containing tert-butyl or trifluoromethyl groups can be modified to adapt their optical constants to suit the process by changing the molecular skeleton.

[0343] [Determination of dry etching rate]

[0344] Solutions of the resist underlayer film formation compositions prepared in Examples 13-24 and Comparative Example 7 were respectively coated onto silicon wafers using a spin coater. The wafers were then fired at 350°C for 60 seconds on a hot plate to form a resist underlayer film (film thickness 0.20 μm). The dry etching rate was measured using CF4 gas as the etching gas, and the dry etching rate ratios for Examples 13-24 and Comparative Example 7 were determined. The dry etching rate ratio is the dry etching rate ratio of (resist underlayer film) / (KrF photoresist) (Table 4).

[0345] [Table 4]

[0346] Table 4 Dry Etching Rate Ratio

[0347]

[0348] As mentioned above, phenolic varnish resins containing tert-butyl or trifluoromethyl groups can be modified to adjust the etching rate to suit the process by changing the molecular skeleton.

[0349] (Coating test on substrates with uneven surfaces)

[0350] As a coating test on substrates with varying heights, the coating thickness of the 800 nm trench region (TRENCH) and the unpatterned open region (OPEN) was compared using a 200 nm thick SiO2 substrate. The resist underlayer film forming compositions prepared in Examples 13-24 and Comparative Example 7 were coated onto the aforementioned substrates and then fired at 350°C for 60 seconds to form a resist underlayer film of approximately 200 nm. The planarization of the substrate was observed using a scanning electron microscope (S-4800) manufactured by Hitachi Hightech Noroges Co., Ltd., and the film thickness difference between the trench region (patterned area) and the open region (unpatterned area) of the substrate with varying heights was measured (the difference in coating height between the trench region and the open region is referred to as deviation), thereby evaluating the planarization. Here, planarization refers to the small difference in film thickness (Iso-TRENCH deviation) between the patterned area (TRENCH area) and the unpatterned area (open area, unpatterned area) on top of the coated material (Table 5). Furthermore, embodiments showing an improvement of less than 10 nm compared to the comparative examples are evaluated as △, embodiments showing an improvement of 10 nm or more are evaluated as ○, and embodiments showing an improvement of 20 nm or more compared to the comparative examples are evaluated as ◎.

[0351] [Table 5]

[0352] Table 5 Flatness Evaluation

[0353]

[0354] As mentioned above, phenolic varnish resins containing tert-butyl or trifluoromethyl groups exhibit good planarization properties.

[0355] Industry availability

[0356] The phenolic varnish resin of this invention is not limited to low-temperature firing; it also exhibits an exceptionally high pure water contact angle (= hydrophobicity) during high-temperature firing. Furthermore, when the phenolic varnish resin of this invention is formulated by mixing a crosslinking agent, an acid catalyst, and a surfactant, it also exhibits an exceptionally high pure water contact angle (= hydrophobicity) during high-temperature firing. Moreover, the phenolic varnish resin of this invention exhibits good planarization properties, and its optical constants and etching rates can be adjusted to suit the process by modifying the molecular skeleton.

Claims

1. A composition for forming a resist underlayer film for nanoimprinting, comprising a phenolic varnish resin having a repeating unit structure as shown in formula (1), In equation (1), Group A is selected from at least one of the following groups: In the formula, G represents the following expression, L and M represent hydrogen atoms. The group B represents an organic group having an aromatic ring or a fused aromatic ring. The radical E represents a single bond, or a branched or straight-chain alkylene group having 1 to 10 carbon atoms that can be substituted and may contain ether bonds and / or carbonyl groups. The group D represents an organic group with 1 to 15 carbon atoms, as shown in formula (2) below. n represents a number from 1 to 5. In equation (2), R 1 R 2 R 3 Each is independently a fluorine atom, or a straight-chain, branched, or cyclic alkyl group, R 1 R 2 R 3 Any two elements can be combined to form a ring.

2. The composition for forming the lower layer of resist for nanoimprinting according to claim 1, wherein base D is tert-butyl or trifluoromethyl.

3. The composition for forming the lower layer film of the resist for nanoimprinting according to claim 1 or 2, wherein base B is phenylene, biphenylene, naphthylene, anthraceneylene, or phenanthrene.

4. The composition for forming a lower layer of resist for nanoimprinting according to claim 1 or 2, wherein the base E is a single bond or a straight-chain alkylene group having 1 to 6 carbon atoms.

5. The composition for forming a lower layer of resist for nanoimprinting according to claim 1 or 2 exhibits a contact angle of 76° or more with pure water when calcined at 240°C, and exhibits a contact angle of 70° or more with pure water when calcined at 350°C.

6. The composition for forming a resist underlayer film for nanoimprinting according to claim 1 or 2, further comprising a crosslinking agent.

7. The composition for forming a resist underlayer film for nanoimprinting according to claim 1 or 2, further comprising at least one selected from acids, their salts, and acid-generating agents.

8. The composition for forming a resist underlayer film for nanoimprinting according to claim 6, when fired at 350°C, exhibits a contact angle of more than 65° to pure water.

9. A resist underlayer film, which is a cured product of a coating film formed by the composition for forming a resist underlayer film for nanoimprinting according to any one of claims 1 to 8.

10. A method for manufacturing a resist underlayer film, comprising: coating a nanoimprint resist underlayer film forming composition according to any one of claims 1 to 8 onto a semiconductor substrate and firing it.

11. A pattern forming method, comprising the following steps: A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film for nanoimprinting as described in any one of claims 1 to 8; The process of applying a curable composition onto the resist underlayer film; The process of bringing the curable composition into contact with the mold; The process of forming a cured film by irradiating the curable composition with light or electron beams; and The process of separating the cured film from the mold.

12. The pattern forming method according to claim 11, wherein the step of applying a curable composition on the photoresist underlayer film comprises: forming an adhesive layer and / or an organosilicon layer containing less than 99% by mass of Si on the photoresist underlayer film by coating or vapor deposition, and applying the curable composition on the adhesive layer and / or the organosilicon layer containing less than 99% by mass of Si.

13. A method for manufacturing a semiconductor device, comprising the following steps: A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film for nanoimprinting as described in any one of claims 1 to 8; The process of forming a resist film on the lower layer of the resist film; The process of forming a resist pattern by irradiation and development with light or electron beams; The process of etching the underlying film using the formed resist pattern; and The process of processing a semiconductor substrate using a patterned lower film.

14. A method for manufacturing a semiconductor device, comprising the following steps: A process of forming a photoresist underlayer film on a semiconductor substrate using the composition for forming a photoresist underlayer film for nanoimprinting as described in any one of claims 1 to 8; The process of forming a hard mask on the lower layer of the resist film; The next step is to form a resist film on the hard mask. The process of forming a resist pattern by irradiation and development with light or electron beams; The process of etching a hard mask using the resulting resist pattern; The process of etching the underlying film using a patterned hard mask; and The process of processing a semiconductor substrate using a patterned resist underlayer film.

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