Resistor underlayer film formation composition, resistor underlayer film formed using the composition, and method for manufacturing semiconductor device.

Abstract

This invention provides a resist underlayer film forming composition that allows for good embedding even with stepped substrates, resulting in minimal film thickness variation and the formation of a flat film. Furthermore, this invention provides a polymer as a key component of this resist underlayer film forming composition, a resist underlayer film formed using this resist underlayer film forming composition, and a method for manufacturing a semiconductor device. An inhibitor underlayer film forming composition comprising a compound represented by formula (1) and a solvent. (In the formula, Ar1, Ar2, Ar3, and Ar4 each represent a monovalent aromatic hydrocarbon group that can be substituted, and a, b, c, and d are each 0 or 1, and a+b+c+d=1).

Description

Technical Field

[0001] This invention relates to exhibiting a good dry etching rate ratio and optical constants, that is, Even for stepped substrates, the coating is good, the thickness difference after embedding is small, and a flat film can be formed. The following are the components of the resistive underlayer film forming composition, including a polymer as an important component of the resistive underlayer film forming composition, the resistive underlayer film formed using the resistive underlayer film forming composition, and a method for manufacturing a semiconductor device. Prior Technology

[0002] In recent years, the requirements for the lower layer film material of the resist used in the multilayer resist process are particularly for short wavelength exposure. It is required to have appropriate optical constants as an anti-reflective film, while also having etch resistance in substrate processing. It is proposed to use polymers with repeating units containing benzene rings (Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2004-354554 Summary of the Invention

[0004] [The problem that the invention aims to solve]

[0005] As resist patterns become increasingly miniaturized, the required resist layer becomes thinner. Therefore, a photolithography process is known to form at least two resist underlayer films, using these resist underlayer films as masking materials. This involves forming at least one organic film (lower organic film) and at least one inorganic underlayer film on a semiconductor substrate. The resist pattern formed on the upper resist film is used as a mask to pattern the inorganic underlayer film, and then, using this pattern as a mask, the lower organic film is patterned. This method can form patterns with a high aspect ratio. Materials forming the aforementioned at least two resist underlayer films include combinations of organic resins (e.g., acrylic resins, phenolic varnish resins) and inorganic materials (e.g., silicone resins (e.g., organopolysiloxanes), inorganic silicon compounds (e.g., SiON, SiO2)). Furthermore, in recent years, double-patterning techniques, which involve two lithography and two etching processes to obtain a single pattern, have been widely used, employing the aforementioned multi-layer steps in each step. In this case, after the initial pattern is formed, the organic film must exhibit the characteristic of planarizing the step differences.

[0006] However, the above technologies also have the following problems: for substrates with varying heights or densities of resist patterns formed on the substrate being processed, the resistance pattern is still not sufficiently covered by the composition used to form the lower layer of the resist film, and the thickness difference of the film after embedding becomes larger, making it difficult to form a flat film.

[0007] This invention was made to solve this problem. It provides a resist underlayer film forming composition exhibiting high etch resistance, good dry etch rate ratio and optical constants, good coating even on so-called stepped substrates, small thickness variation after embedding, and the ability to form a flat film. Furthermore, this invention aims to provide a polymer as an important component of this resist underlayer film forming composition, a resist underlayer film formed using this resist underlayer film forming composition, and a method for manufacturing a semiconductor device. [Methods used to solve problems]

[0008] This invention includes the following. The first aspect of this invention relates to a resistive underlayer film forming composition, which comprises a compound represented by the following formula (1) and a solvent. (In the formula, Ar1, Ar2, Ar3, and Ar4 each represent a monovalent aromatic hydrocarbon group that can be substituted, a, b, c, and d are each 0 or 1, and a+b+c+d=1). The second aspect of this invention relates to the inhibitor lower film forming composition of the first aspect, wherein the aforementioned aromatic hydrocarbon group is phenyl, naphthyl, anthraceneyl, pyreneyl or a combination thereof. The third aspect of the invention relates to the inhibitor lower film formation composition of the first or second aspect, wherein the aforementioned aromatic hydrocarbon groups are unsubstituted. The fourth aspect of the invention relates to the inhibitor lower film forming composition of the first or second aspect, wherein the aforementioned aromatic hydrocarbon group is an aromatic hydrocarbon group bonded to an alkyl substituent, which may or may not be an oxygen represented by the following formula (2). (Ar represents an aromatic hydrocarbon group, n is 0 or 1, and R is an alkyl group with 1 to 19 carbon atoms). The fifth aspect of the invention relates to the composition of the inhibitor lower film formation of any one of the first to fourth aspects, wherein the aforementioned solvent is a solvent having a boiling point of 160°C or higher. The sixth aspect of the invention relates to a resistive underlayer film, which is a sintered product of a coating film composed of the resistive underlayer film forming composition of any one of the first to fifth aspects. The seventh aspect of this invention relates to a method for manufacturing a semiconductor device, which includes the following steps: The step of forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition as described in any of the first to fifth viewpoints. The step of forming a resist film on the formed lower resist film, The resist film is patterned by irradiating it with light or an electron beam and developing it. The process involves etching the aforementioned resist underlayer film using the formed resist pattern to perform a patterning step, and then processing the semiconductor substrate using the patterned resist underlayer film. [Invention Effects]

[0009] Previously, when the polymer system of the resist underlayer film forming composition contained aromatic hydrocarbons at the ends of the backbone, the resist underlayer film forming composition had insufficient coverage of the substrate with a large coating step difference and poor planarization. However, the inventors discovered that only by using a large amount of aromatic hydrocarbons at the ends of the polymer backbone and using relatively low molecular weight compounds can the coating step difference be effectively suppressed, and thus the present invention was completed. The resist underlayer film composition of the present invention not only has a good dry etching rate ratio and optical constant, but also the resulting resist underlayer film has good coverage even for so-called stepped substrates, and the film thickness difference after embedding is small, forming a flat film, thus achieving finer substrate processing. In particular, the resist underlayer film forming composition of the present invention forms at least two resist underlayer films for the purpose of thinning the resist film thickness, which is effective for lithography processes that use the resist underlayer film as an etching mask. Furthermore, the resist lower layer film composition of the present invention has a suitable anti-reflection effect and a large dry etching speed for the resist film, so it can be used for substrate processing. [Forms of Invention Implementation]

[0010] [Inhibitor Lower Layer Film Formation Composition] The inhibitor underlayer film forming composition of the present invention comprises a compound represented by the following formula (1) and a solvent. (In the formula, Ar1, Ar2, Ar3, and Ar4 each represent a monovalent aromatic hydrocarbon group that can be substituted, a, b, c, and d are each 0 or 1, and a+b+c+d=1).

[0011] The aforementioned aromatic hydrocarbon groups may be phenyl, naphthyl, anthraceneyl, pyreneyl, or combinations thereof. Furthermore, the aforementioned aromatic hydrocarbon groups can be unsubstituted or bonded to alkyl substituents via oxygen or not via oxygen.

[0012] Aromatic hydrocarbon groups with alkyl substituents are as follows (2), where Ar represents an aromatic hydrocarbon group, n is 0 or 1, and R is a substituent.

[0013] Specifically, Ar can be phenyl, naphthyl, anthraceneyl, pyreneyl, or a combination thereof. R represents an alkyl group that may have a branched chain, and one of the hydrogen atoms may be replaced by a hydroxyl, nitro, cyano, or halogen atom (fluorine, chlorine, bromine, or iodine).

[0014] The alkyl groups mentioned above can be exemplified by alkyl groups having 1 to 19 carbon atoms, and examples include methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, s-butyl, t-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, n-Heptyl, 2-Ethyl-hexyl, n-Octyl, n-Nonyl, n-Decyl, n-Undecyl, n-Dodecyl, n-Tridecyl, n-Tetradecyl, n-Pentadedecyl, n-Hexadecyl, n-Heptadedecyl, 2-Heptyl-Undecyl, n-Octadedecyl, n-Nondecyl, 5,9-Dimethyl-2-(6-Methylheptyl)decyl, 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-i-propyl-cyclopropyl, 2-i-propyl-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, etc.

[0015] [solvent] The solvent for the resist lower film forming composition of this invention can be used as long as it can dissolve the above-mentioned reaction products, without any particular limitation. In particular, since the resist lower film forming composition of this invention is used in a uniform solution state, it is recommended to use it in conjunction with the solvents generally used in the lithography process when considering its coating performance.

[0016] Examples of such solvents include methylcellulose acetate, ethylcellulose acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl 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, ethyl 3-methoxypropionate, ethyl 3-ethoxy... Ethyl propionate, 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, methyl 3-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.

[0017] Alternatively, the following compounds described in WO2018 / 131562A1 may also be used. (In formula (i), R1, R2 and R3 each represent a hydrogen atom, an alkyl group with 1 to 20 carbon atoms that can be interrupted by an oxygen atom, a sulfur atom or a amide bond, and they can be the same or different from each other, and can bond together to form a ring structure).

[0018] Alkyl groups having 1 to 20 carbon atoms, including straight-chain or branched alkyl groups with or without substituents, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, cyclohexyl, 2-ethylhexyl, n-nonyl, isononyl, p-tert-butylcyclohexyl, n-decyl, n-dodecylnonyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, and eicosyl. Preferably, the alkyl group has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 4 carbon atoms.

[0019] Alkyl groups with 1 to 20 carbon atoms interrupted by oxygen, sulfur, or amide bonds can be exemplified by those containing the structural units -CH2-O-, -CH2-S-, -CH2-NHCO-, or -CH2-CONH-. -O-, -S-, -NHCO-, or -CONH- are one or more units in the aforementioned alkyl groups. Specific examples of alkyl groups with 1 to 20 carbon atoms interrupted by -O-, -S-, -NHCO-, or -CONH- units include methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, butylcarbonylamino, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, and butylaminocarbonyl. Other examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, or octadecyl, each substituted with methoxy, ethoxy, propoxy, butoxy, methylthio, ethylthio, propylthio, butylthio, methylcarbonylamino, ethylcarbonylamino, methylaminocarbonyl, and ethylaminocarbonyl. Methoxy, ethoxy, methylthio, and ethylthio are preferred, and methoxy and ethoxy are even more preferred.

[0020] These solvents have relatively high boiling points, thus imparting high embeddability or high planarization to the inhibitor underlayer film forming composition.

[0021] The following shows specific examples of preferred compounds represented by formula (i).

[0022] Of the above, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamide, and... The following formula: The compounds represented by formula (i) are preferably 3-methoxy-N,N-dimethylpropionic acid and N,N-dimethylisobutylamide.

[0023] These solvents can be used alone or in combination of two or more. Among these solvents, those with a boiling point of 160°C or higher are preferred, including propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, cyclohexanone, 3-methoxy-N,N-dimethylpropionic acid, N,N-dimethylisobutylamide, 2,5-dimethylhexane-1,6-dimethyldiacetate (DAH; CAS, 89182-68-3), and 1,6-diethoxyhexane (CAS, 6222-17-9). Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and N,N-dimethylisobutylamide are particularly preferred.

[0024] [Cross-linking agent component] The inhibitor lower film forming composition of the present invention may include a crosslinking agent. The crosslinking agent may include melamine-based, substituted urea-based, or polymeric forms thereof. Preferably, it is a crosslinking agent having at least two crosslinking-forming substituents, and examples include compounds 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.

[0025] Furthermore, the aforementioned crosslinking agent can be a crosslinking agent with high heat resistance. Preferably, the crosslinking agent with high heat resistance is a compound containing a crosslinking substituent with an intramolecular aromatic ring (e.g., benzene ring, naphthalene ring).

[0026] Examples of compounds include compounds having a partial structure of formula (4) below or polymers or oligomers having repeating units of formula (5) below. R11, R12, R13, and R14 are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and the alkyl groups exemplified above may be used. n1 represents an integer satisfying 1 ≤ n1 ≤ 6 - n2, n2 represents an integer satisfying 1 ≤ n2 ≤ 5, n3 represents an integer satisfying 1 ≤ n3 ≤ 4 - n4, and n4 represents an integer satisfying 1 ≤ n4 ≤ 3.

[0027] Compounds having a partial structure of formula (4) are illustrated below.

[0028] The above-mentioned compounds can be obtained from products of Asahi Organic Materials Co., Ltd. and Honshu Chemical Co., Ltd. For example, among the above-mentioned crosslinking agents, the compound of formula (4-24) can be obtained from Asahi Organic Materials Co., Ltd. under the trade name TM-BIP-A. 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., and is 0.001 to 80% by mass relative to the total solids content, preferably 0.01 to 50% by mass, and even more preferably 0.05 to 40% by mass. These crosslinking agents generate crosslinking reactions through self-condensation. When crosslinking substituents are present in the reaction products of the present invention, crosslinking reactions can occur with those crosslinking substituents.

[0029] [Acids and / or acid-generating agents] The inhibitor lower film forming composition of the present invention may contain acid and / or acid generating agent. Examples of acids include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium p-toluenesulfonic acid, pyridinium phenolsulfonic 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 naphtholic acid. Acids may be used alone or in combination of two or more. The amount prepared relative to the total solids content is typically 0.0001 to 20% by mass, preferably 0.0005 to 10% by mass, and even more preferably 0.01 to 3% by mass.

[0030] Acid generating agents can be categorized as thermal acid generating agents or photoacid generating agents. Examples of heat-generating agents include 2,4,4,6-tetrabromocyclohexadienone, benzoin p-toluenesulfonate, 2-nitrobenzyltoluenesulfonate, K-PURE [registered trademark] CXC-1612, CXC-1614, TAG-2172, TAG-2179, TAG-2678, TAG2689, 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 other organic sulfonates and alkyl esters.

[0031] The photoacid generator produces acid during the exposure of the resist. Therefore, the acidity of the lower film can be adjusted. This is a method that combines the acidity of the lower film with the acidity of the upper resist. Furthermore, by adjusting the acidity of the lower film, the pattern shape of the resist formed on the upper layer can be adjusted. The photoacid generator contained in the lower layer film forming composition of the inhibitor of the present invention can be exemplified by onium salt compounds, sulfonium imine compounds, and disulfonyldiazomethane compounds.

[0032] Examples of onium salt compounds include diphenylmonium hexafluorophosphate, diphenylmonium trifluoromethane sulfonate, diphenylmonium nonafluoron-butane sulfonate, diphenylmonium perfluoron-octane sulfonate, diphenylmonium camphor sulfonate, bis(4-tert-butylphenyl)monium camphor sulfonate, and bis(4-tert-butylphenyl)monium trifluoromethane sulfonate as well as strontium salt compounds such as triphenylstrontium hexafluoroantimonate, triphenylstrontium nonafluoron-butane sulfonate, triphenylstrontium camphor sulfonate, and triphenylstrontium trifluoromethane sulfonate.

[0033] Examples of sulfonamide compounds include N-(trifluoromethanesulfonoxy)butadieneimide, N-(nonafluoron-butanesulfonoxy)butadieneimide, N-(camphorsulfonoxy)butadieneimide, and N-(trifluoromethanesulfonoxy)naphthyleneimide.

[0034] Examples of disulfonyldiazomethane compounds include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0035] Acid-generating agents can be used alone or in combination of two or more. When using an acid-generating agent, its proportion is 0.01 to 5 parts by mass, or 0.1 to 3 parts by mass, or 0.5 to 1 part by mass relative to 100 parts by mass of the solid component of the lower layer film forming composition of the inhibitor.

[0036] [Other ingredients] To further improve the coating properties against surface unevenness and prevent pinholes or streaks in the lower film forming composition of the inhibitor of this invention, a surfactant can be formulated. Examples of surfactants include, but are not limited to, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octadecyl ether, polyoxyethylene hexadecyl ether, and polyoxyethylene oil ether; polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan monooleate, and sorbitan trioleate. Sorbitan fatty acid esters such as tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan tristearate, etc., nonionic surfactants such as EFTOPEF301, EF303, EF352 (TOHKEM Co., Ltd.) Fluoropolymer surfactants such as those manufactured by PRODUCTS (trade names), Megafac F171, F173, R-40, R-40N, R-40LM (manufactured by DIC Corporation, trade name), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Corporation, trade name), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Corporation, trade name), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) are used. The amount of these surfactants in the formulation is typically 2.0% by mass or less, preferably 1.0% by mass or less, relative to the total solids content of the underlayer membrane material. These surfactants can be used alone or in combination of two or more. When using surfactants, the proportion relative to 100 parts by weight of the solid components of the inhibitor underlayer film formation composition is 0.0001 to 5 parts by weight, or 0.001 to 1 part by weight, or 0.01 to 0.5 parts by weight.

[0037] The resist underlayer film forming composition of the present invention may include light absorbers, rheology modifiers, adhesion promoters, etc. Rheology modifiers can improve the flowability of the underlayer film forming composition. Adhesion promoters can improve the adhesion between the semiconductor substrate or the resist and the underlayer film.

[0038] As light absorbers, commercially available light absorbers listed in "Technology and Market of Industrial Pigments" (published by CMC) or "Dye Handbook" (edited by the Organic Synthetic Chemistry Society) are suitable, such as 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; CI Disperse Orange 1,5,13,25,29,30,31,44,57,72 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 Brightening 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, relative to the total solids content of the composition forming the lower layer film of the resist, are typically formulated at a ratio of 10% by mass or less, preferably 5% by mass or less.

[0039] Rheology modifiers primarily improve the flowability of the resist underlayer film-forming composition, especially during the baking process. They are added to improve the uniformity of the resist underlayer film thickness or to enhance the filling properties of the resist underlayer film-forming composition within 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 formulated at a ratio of less than 30% by mass relative to the all-solid component of the resistive underlayer film-forming composition.

[0040] Next, the additives are mainly added to improve the adhesion between the substrate or resist and the composition of the underlying resist film, especially during development, to prevent resist stripping. Specific examples include chlorosilanes such as trimethylchlorosilane, dimethylhydroxymethylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; alkoxysilanes such as trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylhydroxymethylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; hexamethyldisilazane; N,N'-bis(trimethylsilyl)urea; dimethyltrimethylsilylamine; and trimethylsilylimidazole. The additives include silanes such as hydroxymethyltrichlorosilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-epoxypropoxypropyltrimethoxysilane; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urea, thiouracil, mercaptoimidazole, and mercaptopyrimidine; and urea compounds such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds. These adhesion aids are the total solids component of the underlayer film-forming composition relative to the inhibitor, and are typically formulated at a ratio of less than 5% by mass, preferably less than 2% by mass.

[0041] The solid content of the inhibitor underlayer film-forming composition of 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 the total components of the inhibitor underlayer film-forming composition after solvent removal. The proportion of the above-mentioned reaction products in the solid content is preferably in the order of 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.

[0042] One of the criteria for evaluating whether the resistive underlayer membrane formation composition is a homogeneous solution is to observe the permeability of a specific microfilter. The resistive underlayer membrane formation composition of the present invention presents a homogeneous solution state when passing through a microfilter with a pore size of 0.1 μm.

[0043] The materials used for the microfilters mentioned above 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 (polyurethane), PES (polyether ether), and nylon, with PTFE (polytetrafluoroethylene) being the most preferred.

[0044] [Resistor underlayer film and semiconductor device manufacturing method] The following describes a method for manufacturing a resist underlayer film and a semiconductor device using the resist underlayer film formation composition of the present invention.

[0045] On 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.), the resist lower layer film forming composition of the present invention is coated by a suitable coating method such as a spin coater or a coating machine, and then the resist lower layer film is formed by firing. The firing conditions can be 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 thickness of the formed lower layer film is, for example, 10 to 1000 nm, or 20 to 500 nm, or 30 to 400 nm, or 50 to 300 nm.

[0046] Alternatively, an inorganic resist lower layer film (hard mask) can also be formed on the organic resist lower layer film of the present invention. For example, the silicon-containing resist lower layer film (inorganic resist lower layer film) composition described in WO2009 / 104552A1 can be formed by spin coating, and Si-based inorganic material films can be formed by CVD or other methods.

[0047] Furthermore, the resist lower layer film forming composition of the present invention is coated on a semiconductor substrate (so-called a step substrate) containing a step portion and a non-step portion, and by firing, a resist lower layer film with a step difference in the range of 3 to 70 nm between the step portion and the non-step portion can be formed.

[0048] Next, a resist film, such as a photoresist layer, is formed on the lower resist film. The photoresist layer is formed by a conventional method, namely, by coating a photoresist composition solution onto the lower film and then firing it. The thickness of the photoresist film is, for example, 50 to 10000 nm, or 100 to 2000 nm, or 200 to 1000 nm.

[0049] Photoresist formed on the underlayer of the resist is not particularly limited as long as it is photosensitive to the light used for exposure. Both negative and positive photoresist can be used. Positive photoresist is composed of phenolic varnish resin and 1,2-naphthoquinone diazidesulfonate; chemically reinforced photoresist is composed of a binder with a group that increases the alkali dissolution rate through acid decomposition and a photoacid generator; chemically reinforced photoresist is composed of a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition, an alkali-soluble binder, and a photoacid generator; and chemically reinforced photoresist is composed of a binder with a group that increases the alkali dissolution rate of the photoresist through acid decomposition, a low-molecular-weight compound that increases the alkali dissolution rate of the photoresist through acid decomposition, and a photoacid generator. Examples include Shipley's APEX-E, Sumitomo Chemical Industries Co., Ltd.'s PAR710, and Shin-Etsu Chemical Industries Co., Ltd.'s SEPR430. Furthermore, examples of fluorine-containing polymer photoresists can be cited, such as those described in Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), or Proc. SPIE, Vol. 3999, 365-374 (2000).

[0050] Next, a resist pattern is formed by irradiation and development using light or electron beams. First, exposure is performed through a specific mask. Exposure is performed using near-ultraviolet, far-ultraviolet, or extreme ultraviolet light (e.g., EUV (wavelength 13.5 nm)). Specifically, KrF excimer lasers (wavelength 248 nm), ArF excimer lasers (wavelength 193 nm), and F2 excimer lasers (wavelength 157 nm) can be used. Among these, ArF excimer lasers (wavelength 193 nm) and EUV (wavelength 13.5 nm) are preferred. After exposure, post-exposure baking may be performed if necessary. Post-exposure baking can be performed under suitable conditions ranging from a heating temperature of 70°C to 150°C and a heating time of 0.3 to 10 minutes.

[0051] Furthermore, in this invention, photoresist can be used instead of photoresist, and an electron beam lithography resist can be used instead. Negative or positive electron beam resists can be used. These resists include chemically reinforced resists composed of binders having groups that alter the alkali dissolution rate through acid generation and acid decomposition; chemically reinforced resists composed of alkali-soluble binders and low-molecular-weight compounds that alter the alkali dissolution rate of the resist through acid generation and acid decomposition; chemically reinforced resists composed of binders having groups that alter the alkali dissolution rate through acid generation and acid decomposition and low-molecular-weight compounds that alter the alkali dissolution rate of the resist through acid decomposition; non-chemically reinforced resists composed of binders having groups that alter the alkali dissolution rate through electron beam decomposition; and non-chemically reinforced resists composed of binders having portions that alter the alkali dissolution rate when cut by an electron beam. When using these electron beam resists, the resist pattern can be formed in the same way as when the irradiation source is an electron beam and photoresist is used.

[0052] Next, development is performed using a developing solution. In this way, for example when using positive photoresist, the exposed portion of the photoresist is removed, forming a photoresist pattern. Examples of suitable developing solutions include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, aqueous solutions of tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetraammonium hydroxide such as choline, and alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants may be added to these developing solutions. Suitable developing conditions are selected from temperatures ranging from 5 to 50°C and development times ranging from 10 to 600 seconds.

[0053] Then, the patterned photoresist (upper layer) is used as a protective film, and the inorganic lower layer (intermediate layer) is removed. Next, the film composed of the patterned photoresist and the inorganic lower layer (intermediate layer) is used as a protective film, and the organic lower layer (lower layer) is removed. Finally, the patterned inorganic lower layer (intermediate layer) and organic lower layer (lower layer) are used as protective films for semiconductor substrate processing.

[0054] First, the inorganic lower layer (intermediate layer) where the photoresist is removed is removed by dry etching, exposing the semiconductor substrate. Dry etching of the inorganic lower layer can use gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane. Halogen-based gases are preferred for dry etching of the inorganic lower layer, and fluorine-based gases are even more preferred. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0055] Then, the organic underlayer is removed using a protective film consisting of patterned photoresist and an inorganic underlayer. The organic underlayer (underlayer) is preferably removed by dry etching with an oxygen-based gas. Inorganic underlayers containing many silicon atoms are difficult to remove by dry etching with an oxygen-based gas.

[0056] Finally, the semiconductor substrate is processed. The semiconductor substrate is preferably processed using dry etching with fluorine-based gases. Fluorine-based gases include, for example, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0057] Furthermore, an organic antireflective film can be formed on the upper layer of the resist film before the formation of the photoresist. The composition of the antireflective film used at this time is not particularly limited and can be selected from those currently used in lithography processes. Also, conventional methods, such as coating and firing by a spin coater, can be used to form the antireflective film.

[0058] In this invention, after an organic lower layer film is formed on the substrate, an inorganic lower layer film is formed on top of it, and then photoresist can be coated on top of it. This narrows the pattern width of the photoresist. To prevent pattern collapse, even when coating the photoresist thin layer, substrate processing can be performed by selecting an appropriate etching gas. For example, a fluorine-based gas with a very fast etching rate for photoresist can be used to process the photoresist lower layer film; a fluorine-based gas with a very fast etching rate for inorganic lower layers can be used to process the substrate; and an oxygen-based gas with a very fast etching rate for organic lower layers can be used to process the substrate.

[0059] The resist underlayer film formed by the resist underlayer film forming composition sometimes absorbs the wavelength of light used in the photolithography process. In such cases, it functions as an antireflective film that prevents light reflected from the substrate. Furthermore, the underlayer film formed by the resist underlayer film forming composition 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 to prevent interaction between the substrate and the photoresist, a layer that prevents adverse effects on the substrate from the photoresist material or substances generated during photoresist exposure, a layer that prevents the diffusion of substances generated from the substrate onto the upper photoresist layer during heating and firing, and a barrier layer that reduces the poisoning effect of the photoresist layer caused by the dielectric layer of the semiconductor substrate.

[0060] Furthermore, the lower layer film formed by the resist lower layer film composition is used on substrates with vias used in dual damascene processes, and can be used as an embedded material for filling gapless vias. It can also be used as a planarization material to planarize the surface of semiconductor substrates with uneven surfaces. Implementation

[0061] [Example]

[0062] The following examples illustrate specific examples of the inhibitor lower film formation composition of the present invention, but the present invention is not limited thereto.

[0063] This refers to an apparatus used to determine the weight-average molecular weight of the reaction products obtained in the following synthetic examples. Device: Tosoh (Co., Ltd.) HLC-8320GPC GPC tubing: TSKgel Super-MultiporeHZ-N (2 tubes) Column temperature: 40℃ Flow rate: 0.35 ml / min Dissolution solution: THF Standard sample: polystyrene

[0064] <Synthesis example 1> To 45.54 g of propylene glycol monomethyl ether (hereinafter referred to as PGME), 80.00 g of a 29.9 wt% PGME solution (manufactured by DAICEL, Ltd., under the trade name EPOLEAD GT401), 7.47 g of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 11.12 g of 9-anthracarboxylic acid (manufactured by Midori Chemical Co., Ltd.), and 1.03 g of ethyltriphenylphosphonium bromide as a catalyst were added, and the mixture was reacted at 140°C for 24 hours to obtain a solution containing the reaction products. Then, 43.55 g of anion exchange resin (manufactured by Dowex MONOSPHERE 550A, MUROMACHI TECHNOS, Ltd.) and 43.55 g of cation exchange resin (manufactured by Amberlyst 15JWET, organo, Ltd.) were added, and the mixture was stirred at 25°C to 30°C for 4 hours, followed by filtration. The resulting reaction product was subjected to GPC analysis, and the weight-average molecular weight converted to standard polystyrene was 1400. The resulting reaction product was determined to be a copolymer having structural units represented by the following formula (A). (a, b, c, and d are each 0 or 1, and a + b + c + d = 1).

[0065] <Synthesis example 2> To 7.57g of PGME, 17.67g of PGMEA (trade name: EHPE-3150, manufactured by DAICEL AG), 5.00g of 9-anthracarboxylic acid, 2.09g of benzoic acid, and 0.62g of ethyltriphenylphosphonium bromide as a catalyst were added. The mixture was heated under nitrogen and refluxed for 13 hours. The resulting solution was then mixed with 16g of cation exchange resin (product name: Amberlyst 15JWET, Organo AG) and 16g of anion exchange resin (product name: Dowex MONOSPHERE 550A, MUROMACHI TECHNOS AG). The mixture was stirred at 25°C to 30°C for 4 hours and then filtered. The resulting reaction product was subjected to GPC analysis, and the weight-average molecular weight converted to standard polystyrene was 4,700. The resulting reaction product was determined to be a copolymer having structural units represented by the following formula (B).

[0066] <Synthesis example 3> To PGME 164.47g, 35.00g of EPPN-501H (manufactured by Nippon Kayaku Co., Ltd.), 34.25g of 2-hexyldecanoic acid (manufactured by Tokyo Kasei Corporation), and 1.24g of ethyltriphenylphosphonium bromide as a catalyst were added, and the mixture was reacted at 140°C for 24 hours to obtain a solution containing the reaction products. 70.50g of anion exchange resin (manufactured by Dowex MONOSPHERE 550A, MUROMACHI TECHNOS) and 70.50g of cation exchange resin (manufactured by Amberlyst 15JWET, organo) were added, and the mixture was stirred at 25°C to 30°C for 4 hours, followed by filtration. The resulting reaction product was subjected to GPC analysis, and the weight-average molecular weight converted to standard polystyrene was 2,200. The resulting reaction product was determined to be a copolymer having structural units represented by the following formula (C).

[0067] <Synthesis example 4> To PGME 86.52g, 15.00g of EPICLON HP-4700 (manufactured by DIC Corporation), 9.32g of 9-anthracarboxylic acid, 11.99g of 4-(heptoxy)benzoic acid (manufactured by Sanuki Chemical Industry Co., Ltd.), and 0.86g of ethyltriphenylphosphonium bromide as a catalyst were added, and the mixture was reacted at 140°C for 24 hours to obtain a solution containing the reaction products. Then, 37.08g of anion exchange resin (product name: AMBERJET [registered trademark] ESG4002(OH), organo [company name]) and 37.08g of cation exchange resin (product name: Amberlyst [registered trademark] 15JWET, organo [company name]) were added, and the mixture was stirred at 25°C to 30°C for 4 hours, followed by filtration. The resulting reaction product was subjected to GPC analysis, and the weight-average molecular weight converted to standard polystyrene was 1,600. The resulting reaction product was determined to be a copolymer having structural units represented by the following formula (D).

[0068] [Modulation of the composition of the lower layer film forming inhibitor] <Example 1> In a solution containing 16.97 g of the copolymer obtained in the aforementioned Synthesis Example 1 (solvent being PGME used in the synthesis, with a solid content of 25.59% by mass), 4.24 g of tetramethoxymethyl glycourea (product name: POWDERLINK [registered trademark] 1174, manufactured by Cytec Industries Co., Ltd., Japan), 12.73 g of 1% by mass PGME solution of pyridinium p-toluenesulfonate, 65.45 g of PGME2, and 1.27 g of 1% by mass PGME solution of surfactant (manufactured by DIC Co., Ltd., trade name: R-30N) were mixed to form a 6.10% by mass solution. This solution was filtered using a microfilter made of polytetrafluoroethylene with a pore size of 0.2 μm to form the inhibitor lower membrane composition.

[0069] <Comparative Example 1> In a solution containing 4.51 g of the copolymer obtained in the aforementioned Synthesis Example 2 (the solvent was a PGME / PGMEA mixed solvent used in the synthesis, with a solid content of 23.26% by mass), 1.14 g of tetramethoxymethyl glycourea (product name: POWDERLINK [registered trademark] 1174, manufactured by Cytec Industries Co., Ltd., Japan), 3.41 g of 1% by mass PGME solution of p-toluenesulfonic acid pyridinium salt, 0.68 g of PGME5, 14.80 g of PGMEA, and 0.45 g of 1% by mass PGME solution of surfactant (manufactured by DIC Co., Ltd., trade name: R-30) was prepared as a 6.35% by mass solution. The solution was filtered using a microfilter made of polytetrafluoroethylene with a pore size of 0.2 μm to form the inhibitor lower membrane composition.

[0070] <Comparative Example 2> In a solution containing 19.48 g of the copolymer obtained in the aforementioned Synthesis Example 3 (solvent being PGME used in the synthesis, solid content 26.30% by mass), 4.87 g of tetramethoxymethyl glycourea (product name: POWDERLINK [registered trademark] 1174, manufactured by Cytec Industries Co., Ltd., Japan), 14.60 g of a 1% by mass PGME solution of p-toluenesulfonic acid pyridinium salt, 156.91 g of PGME, 97.65 g of PGMEA, and 1.95 g of a 1% by mass PGME solution of surfactant (manufactured by DIC Co., Ltd., trade name: R-30N) were mixed to form a 7.00% by mass solution. The solution was filtered using a fine polytetrafluoroethylene filter with a pore size of 0.2 μm to modulate the lower membrane formation composition.

[0071] <Comparative Example 3> In a solution containing 3.58 g of the copolymer obtained in the aforementioned Synthesis Example 4 (solvent being PGME used in the synthesis, solid content 28.27% by mass), 0.89 g of tetramethoxymethyl glycourea (product name: POWDERLINK [registered trademark] 1174, manufactured by Cytec Industries Co., Ltd., Japan), 2.68 g of a 1% by mass PGME solution of p-toluenesulfonic acid pyridinium salt, 3.50 g of PGME, and 0.27 g of a 1% by mass PGME solution of surfactant (manufactured by DIC Co., Ltd., trade name: R-30N) were mixed to form a 6.21% by mass solution. The solution was filtered using a microfilter made of polytetrafluoroethylene with a pore size of 0.2 μm to modulate the lower membrane formation composition.

[0072] [Dissolution test of photoresist solvent] The resist underlayer film formation compositions prepared in Examples 1 and Comparative Examples 1 to 3 were coated onto silicon wafers using a spin coater. Then, they were baked on a hot plate at the temperatures shown in Table 1 below for 1 minute to form a resist underlayer film (film thickness 0.2 μm). These resist underlayer films were immersed in a PGME / PGMEA mixed solvent (mixing ratio of PGME / PGMEA 70 / 30) used in the photoresist solution, and it was confirmed that they were insoluble in the solvent. The results are indicated by “○” in Table 1 below.

[0073] [Optical Parameter Testing] The resist underlayer film formation compositions prepared in Examples 1 and Comparative Examples 1 to 3 were respectively coated onto silicon wafers using a spin coater. Then, they were baked on a hot plate at the temperatures shown in Table 1 below for 1 minute to form a resist underlayer film (film thickness 0.2 μm). The refractive index (n value) and attenuation coefficient (k value) at a wavelength of 193 nm were then measured using an optical ellipsometry (JAWoollam, VUV-VASE VU-302). The results are shown in Table 1 below. To ensure sufficient anti-reflection performance of the above resist underlayer film, the k value at a wavelength of 193 nm is preferably 0.1 or higher and 0.5 or lower.

[0074]

[0075] [Coating Test on Stepped Substrate] For the evaluation of planarization, the film thickness of the trench patterned area (TRENCH) with a trench width of 10 nm and a spacing of 100 nm was compared with that of the isolation trench patterned area (ISO) with a trench width of 100 nm and a spacing of 10 μm on a SiO2 substrate with a film thickness of 100 nm. The resist underlayer film forming compositions of Examples 1, 1 to 3 were coated onto the above substrate with a film thickness of 240 nm, and then baked on a hot plate at the temperature shown in Table 1 for 1 minute to form a resist underlayer film (film thickness 0.24 μm). The step coverage of this substrate was observed using a Hitachi High Technologies scanning electron microscope (S-4800). The planarization was evaluated by measuring the film thickness difference between the trench area (patterned area) and the isolation area (unpatterned area) of the step substrate (the coating step difference between the trench area and the isolation area is called bias). The film thickness and coating step difference values ​​for each area are shown in Table 2. The smaller the Bias value in the flatness evaluation system, the higher the flatness.

[0076] When comparing planarization, the results of Example 1 show that the coating step difference between the patterned area and the low-density area is smaller than that of Comparative Examples 1 to 3. Therefore, the resist underlayer film obtained from the resist underlayer film formation composition of Example 1 has better planarization. Furthermore, the resist underlayer film formation composition of Example 1 exhibits excellent storage stability, and the resist underlayer film obtained from this composition displays good etch resistance and good heat resistance during baking. Additionally, it has the advantage of producing less sublimation during baking. [Industrial Applicability]

[0077] The resist underlayer film forming composition of this invention, when coated onto a substrate, can be evenly coated to form a flat film, even on a substrate with stepped surfaces. Furthermore, it possesses suitable anti-reflective properties, and therefore can be used as a resist underlayer film forming composition.

Claims

1. A barrier underlayer film forming composition comprising a compound represented by the following formula (1) and a solvent, wherein the aromatic hydrocarbon group is phenyl, naphthyl, anthracene, pyrene or a combination thereof, and the solvent comprises at least one of propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (where Ar1, Ar2, Ar3, and Ar4 each independently represent a substituted monovalent aromatic hydrocarbon group, a, b, c, and d are each 0 or 1, and a+b+c+d=1), wherein the aforementioned aromatic hydrocarbon group is unsubstituted, or the aforementioned aromatic hydrocarbon group is an aromatic hydrocarbon group bonded to an alkyl substituent between or not between an oxygen represented by the following formula (2) (Ar represents an aromatic hydrocarbon group, n is 0 or 1, and R is an alkyl group with 1 to 19 carbon atoms).

2. The composition of the inhibitor lower film forming component as claimed in claim 1, wherein the aforementioned solvent is a solvent having a boiling point of 160°C or higher.

3. A resistive underlayer film, which is a sintered product of a coated film composed of a resistive underlayer film forming composition as claimed in claim 1 or 2.

4. A method for manufacturing a semiconductor device, comprising the following steps: forming a resist underlayer film on a semiconductor substrate using a resist underlayer film forming composition as described in any one of claims 1 to 3; forming a resist film on the formed resist underlayer film; forming a resist pattern by irradiating the formed resist film with light or an electron beam and developing it; etching the aforementioned resist underlayer film using the formed resist pattern to perform patterning; and processing the semiconductor substrate using the patterned resist underlayer film.