Composition for semiconductor production

Abstract

The present invention provides a composition for semiconductor production, which contains a solvent (B) that contains a compound (B1) represented by general formula (b-1). (In the formula, R1, R2, R3 and R4 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group.)

Description

Composition for semiconductor manufacturing

[0001] The present invention relates to a composition for manufacturing a semiconductor.

[0002] In the manufacture of semiconductors, microfabrication is carried out by lithography using photoresist materials. Lithography typically involves forming a resist on a wafer, followed by exposure and development, followed by etching or other processes to form a circuit pattern on the wafer, and finally peeling and removing the resist.

[0003] In recent years, semiconductors have become more sophisticated and smaller in size, resulting in a demand for even finer pattern dimensions. To accommodate such finer pattern dimensions, short-wavelength light sources have been used as exposure light sources, including ultraviolet rays such as the g-line (wavelength 436 nm) and i-line (wavelength 365 nm) of a high-pressure mercury lamp, far ultraviolet rays such as KrF excimer lasers (wavelength 248 nm) and ArF excimer lasers (wavelength 193 nm), and extreme ultraviolet rays (EUV).

[0004] However, when a short-wavelength exposure light source is used, the resolution performance of the resist may be reduced due to the influence of reflection of the exposure light source from the wafer or standing waves. To address this problem, a technique is known in which a bottom anti-reflective coating (BRAC) is formed between the resist and the wafer as a resist auxiliary film (see, for example, Patent Document 1).

[0005] Furthermore, when a short-wavelength exposure light source is used, the exposure light source is sensitive to contamination sources. Therefore, a technique is known in which a process of removing residues and contaminants from a resist film, an anti-reflective coating (BRAC), and the like using a thinner composition before the exposure process, known as an EBR (edge ​​bead removing) process, is performed (see, for example, Patent Document 2).

[0006] On the other hand, instead of miniaturizing the pattern dimensions as described above, a technology relating to three-dimensional packaging is also known in which semiconductor elements are integrated three-dimensionally using minute electrodes (bumps) to increase memory capacity (for example, Patent Document 3). Note that Patent Document 3 describes that in three-dimensional packaging, minute electrodes (bumps) are formed using a thick resist film to maintain the distance between semiconductor elements.

[0007] International Publication No. 2004 / 034148 Japanese Patent Application Laid-Open No. 2015-232708 Japanese Patent Application Laid-Open No. 2019-137612

[0008] Here, resist films, resist auxiliary films, etc. are generally formed by applying a solution and heating. Furthermore, thinner compositions are solutions, and by applying them, residues, contaminants, etc. are removed. That is, these semiconductor manufacturing compositions are solutions, and conventional liquid semiconductor manufacturing compositions have room for improvement in terms of handleability. Therefore, an object of the present invention is to provide a semiconductor manufacturing composition that is easy to handle and a novel compound that is suitable for use in the composition.

[0009] The present invention provides, for example, the following composition for manufacturing a semiconductor and a novel compound suitable for use in the composition: <1> A compound represented by the following formula (1): <2> A composition for manufacturing a semiconductor, comprising a solvent (B) containing a compound (B1) represented by the following general formula (b-1): (In the formula, R １ , R ２、 R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. １ , R ２、 R ３ and R ４each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. <4> The composition for manufacturing a semiconductor according to the above item <2>, wherein the compound (B1) is 5,5-dimethyl-1,3-dioxolan-4-one (DDO), 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (TDO), 5-methyl-1,3-dioxolan-4-one, 1,3-dioxolan-4-one, 2,5,5-trimethyl-1,3-dioxolan-4-one, 2,5-dimethyl-1,3-dioxolan-4-one, 2-methyl-1,3-dioxolan-4 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO), 2-ethyl-5-methyl-1,3-dioxolan-4-one, 2-ethyl-1,3-dioxolan-4-one, 2,2,5-trimethyl-1,3-dioxolan-4-one, and 2,2-dimethyl-1,3-dioxolan-4-one. <5> The composition for manufacturing a semiconductor according to any one of the above <2> to <4>, wherein the solvent (B) contains, as the compound (B2) other than the compound (B1), one or more selected from the group consisting of a compound represented by the following general formula (b-2), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), and γ-butyrolactone (γ-BL): (wherein R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, and R6 represents an alkyl group having 1 to 10 carbon atoms.) <6> The composition for manufacturing a semiconductor according to the above <5>, wherein the compound represented by general formula (b-2) is methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), or isopropyl 2-hydroxyisobutyrate (i-PHIB). <7> The composition for manufacturing a semiconductor according to the above <5> or <6>, containing the compound represented by general formula (b-2) in an amount of 10 mass% or more based on the total amount (100 mass%) of the solvent (B). <8> The semiconductor manufacturing composition according to any one of <2> to <7> above, wherein the compound (B1) is contained in an amount of 0.5% by mass or more based on the total amount (100% by mass) of the solvent (B). <9> The semiconductor manufacturing composition according to any one of <2> to <8> above, wherein the semiconductor manufacturing composition is a resist composition. <10> The semiconductor manufacturing composition according to any one of <2> to <8> above, wherein the semiconductor manufacturing composition is a resist auxiliary film composition. <11> The semiconductor manufacturing composition according to <10> above, wherein the resist auxiliary film is a resist underlayer film or a resist middle layer film. <12> The semiconductor manufacturing composition according to any one of <2> to <8> above, wherein the semiconductor manufacturing composition is a thinner composition.

[0010] According to the present invention, it is possible to provide a composition for manufacturing a semiconductor that is easy to handle and a novel compound that is suitably used in the composition.

[0011] Hereinafter, embodiments of the present invention will be described in detail.

[0012] 1. Novel Compound The novel compound according to the present invention is 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (hereinafter sometimes referred to as "EDDO") represented by the following formula (1):

[0013] The EDDO ​​of the present invention can be synthesized, for example, by the method described in Example 1-1 below. That is, it can be synthesized using 2-hydroxyisobutyric acid, propionaldehyde, paratoluenesulfonic acid monohydrate, and toluene as raw materials. Furthermore, an acid catalyst and a solvent can be used as appropriate during the synthesis.

[0014] 2. Composition for Manufacturing Semiconductor The composition for manufacturing a semiconductor according to the present invention contains a solvent (B) containing a compound (B1) represented by the following general formula (b-1), but also includes a composition containing only the solvent (B):

[0015] In the above formula, R １ , R ２、 R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group.

[0016] The composition for manufacturing a semiconductor according to the present invention is easy to handle.

[0017] For example, the composition for semiconductor manufacturing according to the present invention has at least one of the effects of reducing the amount of resin used, forming a uniform coating film, and suitably dissolving components contained in the resist or resist auxiliary film.

[0018] For example, when the semiconductor manufacturing composition according to the present invention is used as a resist composition for forming a resist film, it is possible to achieve effects such as reducing the amount of resin used and forming a uniform resist film. Furthermore, resist compositions used for forming resist films used in three-dimensional packaging, in particular, contain resins of various structures and photoacid generators, and the formation of insoluble matter or precipitates in the solvent can lead to poor in-plane uniformity. However, the resist composition (semiconductor manufacturing composition) according to the present invention can achieve high in-plane uniformity, and for example, the resist composition (semiconductor manufacturing composition) can suppress defects during film formation.

[0019] Furthermore, when the composition for semiconductor manufacturing according to the present invention is used as a resist auxiliary film composition for forming a resist auxiliary film, it is possible to achieve effects such as reducing the amount of resin used and forming a uniform resist auxiliary film.

[0020] Furthermore, when the composition for manufacturing a semiconductor according to the present invention is used as a thinner composition, it can advantageously dissolve components of a resist film, a resist auxiliary film, etc., such as a resin and a photoacid generator (PAG), etc. As a result, an EBR process or the like can be performed to remove residues and contaminants with high efficiency.

[0021] The effects of the present invention are not limited to those described above, and effects resulting from the excellent handleability described above can also be achieved.

[0022] The configuration of the present invention will be described below.

[0023] [Solvent (B)] The solvent (B) contains a compound (B1) represented by the following general formula (b-1): The solvent (B) may further contain a solvent other than the compound (B1) (hereinafter, also referred to as "another solvent") (compound (B2)).

[0024] (Compound (B1)) The compound (B1) is represented by the following general formula (b-1).

[0025] In the above formula, R １ , R ２、 R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group.

[0026] The alkyl group having 1 to 10 carbon atoms may be linear or branched. Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, and a decyl group.

[0027] In one embodiment, R １ , R ２、 R ３and R ４ are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0028] In one embodiment, R １ and R ２ are each independently preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and particularly preferably a methyl group.

[0029] In one embodiment, R ３ and R ４ are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.

[0030] Specific examples of the compound (B1) include, but are not limited to, 5,5-dimethyl-1,3-dioxolan-4-one (DDO), 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (TDO), 5-methyl-1,3-dioxolan-4-one, 1,3-dioxolan-4-one, 2,5,5-trimethyl-1,3-dioxolan-4-one, 2,5-dimethyl-1,3-dioxola Examples of suitable compounds include 5,5-dimethyl-1,3-dioxolan-4-one, 2-methyl-1,3-dioxolan-4-one, 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO), 2-ethyl-5-methyl-1,3-dioxolan-4-one, 2-ethyl-1,3-dioxolan-4-one, 2,2,5-trimethyl-1,3-dioxolan-4-one, and 2,2-dimethyl-1,3-dioxolan-4-one. Of these, compound (B1) is more preferably 5,5-dimethyl-1,3-dioxolan-4-one (DDO), 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (TDO), or 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO). The above-mentioned compound (B1) may be used alone or in combination of two or more kinds.

[0031] The compound (B1) is preferably contained in an amount of 0.5% by mass or more, more preferably 20% by mass or more, even more preferably 40% by mass or more, and particularly preferably 60% by mass or more, based on the total amount (100% by mass) of the solvent (B). There is no upper limit to the content of the compound (B1), but it may be 95% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. In one embodiment, the compound (B1) is preferably contained in an amount of 0.5 to 100% by mass, more preferably 20 to 95% by mass, even more preferably 40 to 90% by mass, and particularly preferably 60 to 80% by mass, based on the total amount (100% by mass) of the solvent (B).

[0032] (Another Solvent (Compound (B2))) The solvent (B) may further contain a solvent (another solvent) (compound (B2)) other than the compound (B1).

[0033] The other solvent (compound (B2)) is not particularly limited, but preferably includes one or more selected from the group consisting of a compound represented by the following general formula (b-2), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), and γ-butyrolactone (γ-BL).

[0034] In the above formula, R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms.

[0035] The alkyl group having 1 to 10 carbon atoms is R in general formula (b-1). １ ~R ４ The aryl group having 6 to 10 carbon atoms is not particularly limited, but examples thereof include a phenyl group, a naphthyl group, an anthracenyl group, a tolyl group, a xylyl group, a methylphenyl group, and an isopropylphenyl group. The acyl group having 1 to 10 carbon atoms is not particularly limited, but examples thereof include a formyl group, an acetyl group, a propionyl group, a butyryl group, a benzoyl group, and a naphthoyl group.

[0036] Of these, R5 is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, a formyl group, or an acetyl group, and particularly preferably a hydrogen atom.

[0037] R6 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is R in general formula (b-1). １ ~R ４ It is preferably a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, more preferably a methyl group or an i-propyl group, and particularly preferably a methyl group.

[0038] In one embodiment, it is preferred that R5 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms, and R6 is a methyl group, an ethyl group, an n-propyl group, or an i-propyl group; it is more preferred that R5 is a hydrogen atom, a methyl group, an ethyl group, a formyl group, or an acetyl group, and R6 is a methyl group or an i-propyl group; and it is particularly preferred that R5 is a hydrogen atom, a methyl group, or an acetyl group, and R6 is a methyl group.

[0039] Specific examples of the compound represented by general formula (b-2) include, but are not limited to, methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), isopropyl 2-hydroxyisobutyrate (i-PHIB), isobutyl 2-hydroxyisobutyrate (i-BHIB), normal butyl 2-hydroxyisobutyrate (n-BHIB), etc. Of these, the compound represented by general formula (b-2) is preferably methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), or isopropyl 2-hydroxyisobutyrate (i-PHIB), and more preferably methyl 2-hydroxyisobutyrate (HBM).

[0040] In one embodiment, the other solvent (compound (B2)) preferably includes one or more selected from the group consisting of a compound represented by general formula (b-2), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME), more preferably includes a compound represented by general formula (b-2), further preferably includes one or more selected from the group consisting of methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), and isopropyl 2-hydroxyisobutyrate (i-PHIB), and particularly preferably includes methyl 2-hydroxyisobutyrate (HBM).

[0041] The above-mentioned other solvents (compound (B2)) may be used alone or in combination of two or more kinds.

[0042] The other solvent (compound (B2)) is preferably contained in an amount of 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more, based on the total amount (100% by mass) of solvent (B). The upper limit of the content of the other solvent (compound (B2)) is, for example, 90% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, and particularly preferably 50% by mass or less. In one embodiment, the other solvent (compound (B2)) is preferably contained in an amount of 10 to 90% by mass, more preferably 15 to 80% by mass, even more preferably 15 to 70% by mass, particularly preferably 20 to 60% by mass, and most preferably 20 to 50% by mass, based on the total amount (100% by mass) of solvent (B).

[0043] In a preferred embodiment, the compound represented by general formula (b-2) is contained in an amount of preferably 10% by mass or more, more preferably 10 to 90% by mass, even more preferably 15 to 80% by mass, particularly preferably 15 to 70% by mass, very preferably 20 to 60% by mass, and most preferably 20 to 50% by mass, based on the total amount (100% by mass) of the solvent (B).

[0044] (Combination of Compound (B1) and Other Solvent (Compound (B2))) When the solvent (B) contains another solvent (compound (B2)) together with the compound (B1), preferred combinations of the compound (B1) and the other solvent (compound (B2)) include a combination of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM), a combination of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA), a combination of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether (PGME), a combination of 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (TDO) and methyl 2-hydroxyisobutyrate (HBM), a combination of 2,2,5,5-tetramethyl-1, Examples of the combination include a combination of 3-dioxolan-4-one (TDO) and propylene glycol monomethyl ether acetate (PGMEA), a combination of 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (TDO) and propylene glycol monomethyl ether (PGME), a combination of 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO) and methyl 2-hydroxyisobutyrate (HBM), a combination of 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO) and propylene glycol monomethyl ether acetate (PGMEA), and a combination of 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO) and propylene glycol monomethyl ether (PGME).Of these, the combinations of compound (B1) and another solvent (compound (B2)) are preferably, for example, a combination of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM), a combination of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA), and a combination of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether (PGME), from the viewpoint of high solubility and higher in-plane uniformity when applied to the resist composition and resist auxiliary film composition described below. In this case, the content ratio of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) to methyl 2-hydroxyisobutyrate (HBM) (DDO:HBM, mass ratio) is preferably 1:99 to 50:50, more preferably 10:90 to 50:50, even more preferably 20:80 to 50:50, particularly preferably 30:70 to 50:50, very preferably 35:65 to 50:50, and most preferably 40:60 to 50:50.

[0045] 3. Uses of the Composition for Manufacturing a Semiconductor The composition for manufacturing a semiconductor according to the present invention is easy to handle and can be used in a variety of applications.

[0046] In one embodiment, the composition for semiconductor manufacturing according to the present invention is a resist composition. In another embodiment, the composition for semiconductor manufacturing according to the present invention is a resist auxiliary film composition. In another embodiment, the composition for semiconductor manufacturing according to the present invention is a thinner composition.

[0047] Depending on the intended use of the composition for manufacturing a semiconductor, the composition for manufacturing a semiconductor may further contain components suitable for that intended use. Each intended use will be described below.

[0048] [Resist Composition] The resist composition contains a photosensitive resin (A1) in addition to a solvent (B). If necessary, the resist composition may further contain a photosensitizer, a photoacid generator (PAG), additives, etc. By including the solvent (B), the resist composition may be able to achieve high solubility of the resin and PAG, and form a uniform resist film.

[0049] (Solvent (B)) The solvent (B) includes those described above.

[0050] The content of the solvent (B) is preferably 50% by mass or more, more preferably 60 to 99% by mass, and even more preferably 65 to 99% by mass, based on the total amount (100% by mass) of the resist composition.

[0051] (Photosensitive Resin (A1)) The photosensitive resin (A1) may be a positive-type photosensitive resin or a negative-type photosensitive resin. In addition, a chemical amplification mechanism may be introduced into the resin (A1).

[0052] Specific examples of the photosensitive resin (A1) include novolac resins, phenolic resins, (meth)acrylic resins having an adamantane skeleton, polyimides, polybenzoxazoles, polyvinyl alcohols, polyisoprenes, polyacrylamides, epoxy resins, and ethylenically unsaturated resins. Among these, the photosensitive resin (A1) is preferably a novolac resin, a phenolic resin, a (meth)acrylic resin having an adamantane skeleton, polyimides, polybenzoxazoles, or an ethylenically unsaturated resin, more preferably a novolac resin, a phenolic resin, a (meth)acrylic resin having an adamantane skeleton, or an ethylenically unsaturated resin, and even more preferably an ethylenically unsaturated resin. In this specification, "(meth)acrylic" means methacrylic and / or acrylic.

[0053] The ethylenically unsaturated resin is not particularly limited, but examples thereof include resins obtained by polymerizing at least one selected from the group consisting of aromatic vinyl monomers, phenolic hydroxyl group-containing aromatic vinyl monomers and α-methyl-substituted products thereof, and ethylenically unsaturated monomers.

[0054] In this case, examples of aromatic vinyl monomers include styrene and α-methylstyrene. Furthermore, examples of phenolic hydroxyl group-containing aromatic vinyl monomers and their α-methyl-substituted derivatives include aromatic vinyl monomers having a phenolic hydroxyl group, such as hydroxystyrene, and their α-methyl-substituted derivatives; aromatic vinyl monomers having a phenolic hydroxyl group protected by an acetal group, such as p-(1-methoxyethoxy)styrene, and their α-methyl-substituted derivatives; and aromatic vinyl monomers having a phenolic hydroxyl group protected by an acyl group, such as p-acetoxystyrene, and their α-methyl-substituted derivatives. Furthermore, examples of ethylenically unsaturated monomers include (meth)acrylates protected by an acid-decomposable ester group, such as t-butyl(meth)acrylate.

[0055] In one embodiment, the ethylenically unsaturated resin is preferably a homopolymer of a phenolic hydroxyl group-containing aromatic vinyl monomer and an α-methyl-substituted derivative thereof; a copolymer of an aromatic vinyl monomer and a phenolic hydroxyl group-containing aromatic vinyl monomer and an α-methyl-substituted derivative thereof; or a copolymer of an aromatic vinyl monomer, a phenolic hydroxyl group-containing aromatic vinyl monomer and an α-methyl-substituted derivative thereof, and an ethylenically unsaturated monomer, and more preferably a copolymer of an aromatic vinyl monomer, a phenolic hydroxyl group-containing aromatic vinyl monomer and an α-methyl-substituted derivative thereof, and an ethylenically unsaturated monomer.

[0056] These photosensitive resins (A1) may be used alone or in combination of two or more.

[0057] The content of the photosensitive resin (A1) is preferably 50% by mass or less, more preferably 1 to 40% by mass, and even more preferably 2 to 35% by mass, based on the total amount (100% by mass) of the resist composition.

[0058] (Photosensitizer) The resist composition may contain a photosensitizer. Examples of photosensitizers include those that are generally used as photosensitive components in positive resist compositions.

[0059] Specific examples of the photosensitizer include reaction products of acid chlorides such as naphthoquinone diazide sulfonic acid chloride and benzoquinone diazide sulfonic acid chloride with compounds having a functional group (hydroxyl group, amino group, etc.) that can be condensed with acid chlorides such as hydroquinone, resorcinol, and 2,4-dihydroxybenzophenone.

[0060] Commercially available photosensitizers include "DTEP-350" (diazonaphthoquinone-type photosensitizer, manufactured by Daito ChemiX Co., Ltd.).

[0061] These photosensitizers may be used alone or in combination of two or more.

[0062] The content of the photosensitizer is 0.01 to 80 parts by mass, more preferably 0.05 to 65 parts by mass, even more preferably 0.1 to 50 parts by mass, and still more preferably 0.5 to 30 parts by mass, relative to 100 parts by mass of the photosensitive resin (A1).

[0063] (Photoacid Generator (PAG)) The resist composition may contain a photoacid generator. A photoacid generator is a compound that can generate an acid directly or indirectly when irradiated with radiation such as visible light, ultraviolet light, an excimer laser, an electron beam, extreme ultraviolet light (EUV), X-rays, or an ion beam.

[0064] The photoacid generator is not particularly limited, but examples thereof include ionic photoacid generators such as triarylsulfonium salts and diaryliodonium salts; and nonionic photoacid generators such as imidosulfonates, diazodisulfones, and oximesulfonates.

[0065] The triarylsulfonium salt is not particularly limited, but examples thereof include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, diphenyl-4-methoxyphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluoro-n-butanesulfonate.

[0066] The aryl iodonium salt is not particularly limited, but examples thereof include bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate, and the like.

[0067] The imide sulfonate is not particularly limited, but examples thereof include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, and N-(trifluoromethylsulfonyloxy)diphenylmaleimide.

[0068] The diazodisulfone is not particularly limited, but examples thereof include bis(cyclohexylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, and the like.

[0069] The oxime sulfonate is not particularly limited, but examples thereof include α-(methylsulfonyloxyimino)-phenylacetonitrile, α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile-phenylacetonitrile, α-(methylsulfonyloxyimino)-4-methoxyphenylacetonitrile, and the like.

[0070] From the viewpoint of high solubility in the solvent (B), the photoacid generator preferably contains at least one of a triarylsulfonium salt and a diazodisulfone, and more preferably contains at least one selected from the group consisting of diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, and bis(cyclohexylsulfonyl)diazomethane.

[0071] Commercially available photoacid generators include "WPAG-145", "WPAG-149", "WPAG-170", "WPAG-199", "WPAG-336", "WPAG-367", "WPAG-370", "WPAG-469", and "WPAG-638" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), "NDS-169" (manufactured by Midori Chemical Industry Co., Ltd.), and "TPS-CS" (manufactured by Toyo Gosei Co., Ltd.).

[0072] These photoacid generators may be used alone or in combination of two or more.

[0073] The content of the photoacid generator is preferably 0.01 to 80 parts by mass, more preferably 0.05 to 65 parts by mass, even more preferably 0.1 to 50 parts by mass, and particularly preferably 0.5 to 30 parts by mass, relative to 100 parts by mass of the photosensitive resin (A1).

[0074] (Additives) The resist composition may contain additives.

[0075] The additives are not particularly limited, and examples thereof include acid crosslinkers, acid diffusion controllers, dissolution promoters, dissolution control agents, sensitizers, surfactants, organic carboxylic acids or phosphorus oxoacids or derivatives thereof, dyes, pigments, adhesion aids, antihalation agents, storage stabilizers, antioxidants, antifoaming agents, shape improvers, etc. These additives may be used alone or in combination of two or more.

[0076] The content of the additive is not particularly limited, but is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 70 parts by mass, still more preferably 0.1 to 50 parts by mass, and particularly preferably 0.3 to 30 parts by mass, relative to 100 parts by mass of the photosensitive resin (A1).

[0077] (Coating Method) The coating method for the resist composition according to the present invention is not particularly limited, and examples include spin coating and slit coating. Of these, the coating method for the resist composition according to the present invention is preferably spin coating. That is, in one embodiment, the resist composition according to the present invention is a resist composition that is coated by spin coating. Applying the resist composition by spin coating has the effect of, for example, providing a resist film with excellent in-plane uniformity.

[0078] [Resist auxiliary film composition] The resist auxiliary film is a film that can be used together with the above-mentioned resist film, and examples thereof include a resist underlayer film used in a two-layer resist method, a resist underlayer film used in a three-layer resist method, a resist middle layer film, etc. Note that the resist auxiliary film does not include the resist film, i.e., the outermost film of the resist.

[0079] In one embodiment, the resist assist film is a resist underlayer film or a resist interlayer film. In other words, the resist assist film composition is a resist underlayer film composition or a resist interlayer film composition.

[0080] In one embodiment, the resist back-up coating is a BRAC coating.

[0081] The resist auxiliary film composition varies depending on the desired function, but contains a resin (A2) in addition to a solvent (B). If necessary, the resist auxiliary film composition may further contain a photosensitizer, a photoacid generator, a crosslinking agent, an additive, etc. By including the solvent (B), the resist auxiliary film composition may be able to form a uniform resist auxiliary film, etc.

[0082] (Solvent (B)) The solvent (B) includes those described above.

[0083] The content of the solvent (B) is preferably 50% by mass or more, more preferably 60 to 99% by mass, and even more preferably 65 to 99% by mass, based on the total amount (100% by mass) of the resist auxiliary film composition.

[0084] (Resin (A2)) Examples of the resin (A2) include photosensitive resin (A1), silicon-containing resin, and naphthalene formaldehyde resin.

[0085] The photosensitive resin (A1) is the same as that described above.

[0086] The silicon-containing resin is a resin containing silicon element. Specific examples of the silicon-containing resin include known resins described in JP-A-2007-226170 and JP-A-2007-226204.

[0087] Naphthalene formaldehyde resins include reaction products of naphthalene and / or alkylnaphthalene with formaldehyde.

[0088] These resins (A2) may be used alone or in combination of two or more.

[0089] The content of the resin (A2) is preferably 50% by mass or less, more preferably 1 to 40% by mass, and even more preferably 1 to 35% by mass, based on the total amount (100% by mass) of the resist auxiliary film composition.

[0090] (Photosensitizer and Photoacid Generator) The photosensitizer and photoacid generator are the same as those described above.

[0091] The content of the photosensitizer is preferably 0.01 to 80 parts by mass, more preferably 0.05 to 65 parts by mass, even more preferably 0.1 to 50 parts by mass, and particularly preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (A2).

[0092] The content of the photoacid generator is preferably 0.01 to 80 parts by mass, more preferably 0.05 to 65 parts by mass, even more preferably 0.1 to 50 parts by mass, and particularly preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (A2).

[0093] (Crosslinking Agent) The crosslinking agent has the function of crosslinking the resin (A2) to prevent intermixing.

[0094] The crosslinking agent is not particularly limited, but examples thereof include epoxy compounds such as tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, and trimethylolpropane triglycidyl ether; melamine compounds such as hexamethylolmelamine, hexamethoxymethylmelamine, and hexamethylolmelamine; guanamine compounds such as tetramethylolguanamine, tetramethoxyethylguanamine, and tetraacyloxytetramethylolguanamine; glycoluril compounds such as tetramethylolglycoluril and tetramethoxyglycoluril; urea compounds such as tetramethylolurea and tetramethoxymethylurea; and alkenyl ether compounds such as ethylene glycol divinyl ether and triethylene glycol divinyl ether.

[0095] These crosslinking agents may be used alone or in combination of two or more.

[0096] The content of the crosslinking agent is preferably 5 to 50 parts by mass, more preferably 20 to 40 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the resin (A2).

[0097] (Additives) The additives are the same as those described above.

[0098] The content of the additive is not particularly limited, but is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 70 parts by mass, even more preferably 0.1 to 50 parts by mass, and particularly preferably 0.3 to 30 parts by mass, relative to 100 parts by mass of the resin (A2).

[0099] (Coating method) The coating method of the resist auxiliary film composition of the present invention is not particularly limited, and examples thereof include spin coating and slit coating. Among these, the coating method of the resist auxiliary film composition of the present invention is preferably spin coating. That is, in one embodiment, the resist auxiliary film composition of the present invention is a resist auxiliary film composition coated by spin coating. By applying the resist auxiliary film composition by spin coating, for example, the obtained resist auxiliary film has the effect of having excellent in-plane uniformity.

[0100] [Thinner Composition] The thinner composition contains a solvent (B). It may further contain additives, etc., as needed. By including the solvent (B), the thinner composition can favorably dissolve components of the resist film, resist auxiliary film, etc., such as resins and photoacid generators (PAGs). As a result, an EBR process or the like can be performed to remove residues and contaminants with high efficiency.

[0101] (Solvent (B)) The content of the solvent (B) is preferably 50% by mass or more, more preferably 60 to 100% by mass, and even more preferably 80 to 100% by mass, based on the total amount (100% by mass) of the thinner composition.

[0102] (Additives) Examples of additives include surfactants, dyes, pigments, storage stabilizers, adhesion aids, storage stabilizers, antioxidants, antifoaming agents, etc. These additives may be used alone or in combination of two or more.

[0103] The content of the additive is preferably 0.000000001 to 1 part by mass, more preferably 0.000001 to 0.1 part by mass, and even more preferably 0.00001 to 0.001 part by mass, relative to 1 part by mass of the solvent (B).

[0104] [Method for Manufacturing a Semiconductor] According to one aspect of the present invention, a method for manufacturing a semiconductor is provided.

[0105] In one embodiment, the method for manufacturing a semiconductor device includes a resist film forming step of applying (preferably by spin coating) a resist composition onto a wafer to form a resist film, a resist pattern forming step, and an etching step. If necessary, the method may further include a pretreatment step of applying a thinner composition to the wafer before the resist film forming step, and a resist film cleaning step of contacting the wafer with a thinner composition after the resist film forming step to remove at least a portion of residues and contaminants from the resist film.

[0106] In a preferred embodiment, the method includes a pretreatment step, a resist film-forming step, a resist film cleaning step, a resist pattern-forming step, and an etching step, in this order, wherein at least one of the thinner composition used in the pretreatment step, the resist composition used in the resist film-forming step, and the thinner composition used in the resist film cleaning step is the composition for semiconductor manufacturing according to the present invention (resist composition or thinner composition).

[0107] By performing the pretreatment step, it is possible to coat the substrate with a small amount of photoresist. Furthermore, a resist film can be formed in the resist film formation step. Residues and contaminants on the edge and / or back surface of the substrate can be removed in the resist film cleaning step. As a result, resolution performance can be improved in the resist pattern formation step. In the resist pattern formation step, a pattern can be formed by exposing and developing the resist. In this case, a short-wavelength exposure light source is preferably used for the exposure. This allows for miniaturization of the pattern dimensions.

[0108] In another embodiment, the method for manufacturing a semiconductor device includes a resist auxiliary film forming step of applying (preferably spin coating) a resist auxiliary film composition onto a wafer to form a resist auxiliary film, a resist film forming step of applying (preferably spin coating) a resist composition onto the resist auxiliary film to form a resist film, a resist pattern forming step, and an etching step. If necessary, the method may further include a pretreatment step of applying a thinner composition to the wafer before the resist auxiliary film forming step, a resist auxiliary film cleaning step of contacting the wafer with a thinner composition after the resist film forming step to remove at least a portion of the residues and contaminants of the resist auxiliary film, and a resist auxiliary film and / or resist film cleaning step of contacting the wafer with a thinner composition after the resist film forming step to remove at least a portion of the residues and contaminants of the resist auxiliary film and / or resist film.

[0109] In a preferred embodiment, the method includes a pretreatment step, a resist auxiliary film forming step, a resist auxiliary film cleaning step, a resist film forming step, a resist auxiliary film and / or resist film cleaning step, a resist pattern forming step, and an etching step, in this order. In this case, one of the resist auxiliary film cleaning step and the resist auxiliary film and / or resist film cleaning step may be omitted. Furthermore, at least one of the thinner composition used in the pretreatment step, the resist auxiliary film composition used in the resist auxiliary film forming step, the thinner composition used in the resist auxiliary film cleaning step, the resist film composition used in the resist film forming step, and the thinner composition used in the resist auxiliary film and / or resist film cleaning step is a semiconductor manufacturing composition (resist composition, resist auxiliary film composition, or thinner composition) according to the present invention.

[0110] The resist auxiliary film formed may have a single-layer structure of a resist underlayer film, or a two-layer structure of a resist underlayer film and a resist intermediate film. When the resist auxiliary film has a two-layer structure, the layer structures of the resist underlayer film and the resist intermediate film can be appropriately set depending on the desired physical properties, application, pattern formation method, etc.

[0111] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, the "%" in the examples is based on mass.

[0112] The analytical methods for the physical properties in the examples are as follows. (1) Purity of the product The purity of the product was quantified by gas chromatography (GC). The column used was DB-WAX (length 30 m, diameter 0.25 mm) manufactured by Agilent. (2) Nuclear Magnetic Resonance (NMR) NMR was used to determine the structure of the compounds. The nuclear magnetic resonance apparatus used was a JNM-ECA500 manufactured by JEOL Ltd. The deuterated solvent and measurement frequency used are listed in the identification of each compound. (3) Film Thickness The film thickness of the coating film formed from the resist composition was measured in a constant temperature and humidity chamber at a temperature of 23°C and a humidity of 50% (relative humidity) using a film thickness measurement system (apparatus name "F50", manufactured by Filmetrics). (4) Content of structural units of the resin The content of structural units of the resin was measured using １３ C-NMR (model "JNM-ECA500", manufactured by JEOL Ltd., 125 MHz) was used, using deuterated chloroform as a solvent. １３ Measurements were made by integrating 1,024 times in the quantitative mode of the HPLC-C. (5) Resin Weight-Average Molecular Weight (Mw), Number-Average Molecular Weight (Mn), and Molecular Weight Distribution (Mw / Mn) The resin's Mw and Mn were measured by gel permeation chromatography (GPC) under the following conditions using polystyrene as a standard substance. Apparatus: Hitachi LaChrom series Detector: RI detector L-2490 Column: Tosoh TSKgel GMHHR-M (2 columns) + guard column HHR-H Solvent: THF (containing stabilizer) Flow rate: 1 mL / min Column temperature: 40°C The ratio of the calculated resin's Mw to Mn [Mw / Mn] was then calculated as the value of the resin's molecular weight distribution.

[0113] 1. Production of Semiconductor Solvents Example 1-1 Synthesis of 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO) 100.0 g of 2-hydroxyisobutyric acid (Mitsubishi Gas Chemical Company, Inc.), 67.0 g of propionaldehyde (Fujifilm Wako Pure Chemical Industries, Ltd.), 5.5 g of paratoluenesulfonic acid monohydrate (Fujifilm Wako Pure Chemical Industries, Ltd.), and 125.0 g of toluene (Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a 500 mL glass round-bottom flask equipped with a condenser, a stirrer, and a Dean-Stark apparatus. The mixture was allowed to react under reflux at atmospheric pressure, and the resulting water was azeotroped with toluene and separated using a Dean-Stark apparatus for 5 hours. After washing twice with 200 g of a 10% aqueous sodium hydrogen carbonate solution and once with 200 g of a saturated aqueous sodium chloride solution, the mixture was distilled under reduced pressure to obtain 64.1 g of 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (GC purity 99.2%) represented by the following structural formula as a fraction at 107 hPa and 103°C.

[0114] Since the structure of EDDO ​​obtained in Example 1-1 is a novel substance, １ H NMR, １３ Identification was made from various spectra, including C NMR, DEPT (Distortionless Enhancement by Polarization Transfer), H-H COSY (Correlation Spectroscopy), and HMQC (Heteronuclear Multiple Quantum Correlation). １ H NMR (500MHz, CDCl ３ ) δ0.93 (3H, t, J = 7.5Hz), δ1.35 (3H, s), δ1.41 (3H, s), δ1.75 (2H, m), δ5.47 (H, t, J = 4.5Hz) １３ C NMR (125 MHz, CDCl ３ ) δ6.7, 21.5, 24.6, 27.4, 77.2, 102.9, 176.0

[0115] Example 1-2 Synthesis of 5,5-dimethyl-1,3-dioxolan-4-one (DDO) Using the same reaction apparatus as in Example 1-1, a reaction was carried out using 100 g of hydroxyisobutyric acid, 28.9 g of trioxane (Tokyo Chemical Industry Co., Ltd.), 5.51 g of paratoluenesulfonic acid monohydrate, and 125 g of toluene. Operated in the same manner as in Example 1-1, 67.3 g of 5,5-dimethyl-1,3-dioxolan-4-one (GC purity 99.6%) represented by the following structural formula was obtained as a fraction at 126 hPa and 91°C by reduced pressure distillation.

[0116] Example 1-3 Synthesis of 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (TDO) Using the same reaction apparatus as in Example 1-1, a reaction was carried out using 75 g of hydroxyisobutyric acid, 83.7 g of acetone (Fujifilm Wako Pure Chemical Industries, Ltd.), 4.14 g of paratoluenesulfonic acid monohydrate, and 93.8 g of toluene. Operated in the same manner as in Example 1-1, 40.1 g of 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (GC purity 99.8%) represented by the following structural formula was obtained as a fraction at 116 hPa and 95°C by reduced pressure distillation.

[0117] The solvent obtained by the above method was subjected to various evaluations.

[0118] 2. Production of a composition for manufacturing a semiconductor Example 2-1 5,5-dimethyl-1,3-dioxolan-4-one (DDO) was used as a composition for manufacturing a semiconductor.

[0119] Example 2-2 2-Ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO) was used as a composition for manufacturing semiconductors.

[0120] Example 2-3 2,2,5,5-tetramethyl-1,3-dioxolan-4-one (TDO) was used as a composition for manufacturing semiconductors.

[0121] Example 2-4 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM) in a mass ratio of DDO:HBM of 1:99.

[0122] Example 2-5 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of DDO:PGMEA of 1:99.

[0123] Example 2-6 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether (PGME) in a mass ratio of DDO:PGME of 1:99.

[0124] Example 2-7 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM) in a mass ratio of DDO:HBM of 25:75.

[0125] Example 2-8 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of DDO:PGMEA of 25:75.

[0126] Example 2-9 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether (PGME) in a mass ratio of DDO:PGME of 25:75.

[0127] Example 2-10 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM) in a mass ratio of DDO:HBM of 50:50.

[0128] Example 2-11 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of DDO:PGMEA = 50:50.

[0129] Example 2-12 A composition for manufacturing a semiconductor was produced by mixing 5,5-dimethyl-1,3-dioxolan-4-one (DDO) and propylene glycol monomethyl ether (PGME) in a mass ratio of DDO:PGME = 50:50.

[0130] Comparative Example 2-1 Propylene glycol monomethyl ether acetate (PGMEA) was used as the composition for manufacturing semiconductors.

[0131] Comparative Example 2-2 Propylene glycol monomethyl ether (PGME) was used as the composition for manufacturing semiconductors.

[0132] Comparative Example 2-3 Gamma-butyrolactone (GBL) was used as the composition for manufacturing semiconductors.

[0133] The compositions for manufacturing semiconductors produced in Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3 are shown in Table 1 below.

[0134] 3. Solubility of Acid Generator, Resist Resin, and Underlayer Film Resin The resins and underlayer films used in the following examples and comparative examples are as follows: Resin (i) Cresol novolak resin EP4080G (manufactured by Asahi Organic Chemicals Co., Ltd.) Resin (ii) Copolymer having structural units of hydroxystyrene / t-butyl acrylate / styrene=3 / 1 / 1 (molar ratio) (manufactured by Maruzen Petrochemical Co., Ltd., Mw=12,000) Resin (iii) Copolymer having structural units of MADM (2-methyl-2-adamantyl methacrylate) / GBLM (α-methacryloyloxy-γ-butyrolactone)=25 / 75 (molar ratio) (Mn=3770) Resin (iv) XBisN-1:13-(biphenyl-4-yl)-13H-dibenzoxanthene-3,10-diol (synthesized with reference to WO 2013 / 024778 ).

[0135] The acid generators used in the following examples and comparative examples are as follows: Acid generator (i): WPAG336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Acid generator (ii): WPAG145 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Acid generator (iii): triphenylsulfonium nonafluorobutanesulfonate (manufactured by Sigma-Aldrich) Acid generator (iv): NDS-169 (manufactured by Midori Chemical Industry Co., Ltd.) Acid generator (v): TPS-CS (manufactured by Toyo Gosei Co., Ltd.)

[0136] [Solubility Evaluation] The solvents (thinner compositions) produced in Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3 were used to evaluate the solubility of resins (i) to (iv) and acid generators (i) to (v) shown in Tables 2 and 3. Resins were added to the solvents (thinner compositions) so that the resin (i) concentration was 30 wt %, the resin (ii) concentration was 35 wt %, the resin (iii) concentration was 15 wt %, and the resin (iv) concentration was 25 wt %, respectively. After stirring at room temperature for 24 hours, the state was visually evaluated according to the following criteria: Evaluation A: Dissolved (clear solution confirmed visually). Evaluation C: Insoluble (cloudy solution confirmed visually). Acid generators (i) to (v) were added to the solvents (thinner compositions) so that the acid generator concentrations were 1 wt % and 10 wt %, respectively. After stirring at room temperature for 1 hour, the state was visually evaluated according to the following criteria: Evaluation A: 10% dissolved (visually confirmed clear solution) Evaluation B: 1% dissolved (visually confirmed clear solution) Evaluation C: Insoluble (visually confirmed cloudy solution) The results are shown in Tables 2 and 3.

[0137]

[0138]

[0139] When the thinner composition of the present invention was used, the solubility of the resins (i) to (iv) and the acid generators (i) to (v) was excellent, and it was confirmed that the thinner composition is particularly useful as a thinner composition for EBR and rework applications. On the other hand, when the thinner composition of the comparative example was used, some of the resins (i) to (iv) and the acid generators (i) to (v) were insoluble, and it was confirmed that the thinner composition is not useful as a thinner composition.

[0140] In this way, when a thinner composition satisfying the requirements of this embodiment is used, better solubility can be imparted compared to thinner compositions of comparative examples that do not satisfy these requirements. As long as the requirements of this embodiment are satisfied, thinner compositions other than those described in the examples also exhibit the same effect.

[0141] [Solubility Evaluation] Thinner compositions of Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3 were prepared using the solvents shown in Table 1. Using these thinner compositions, the solubility of resins (i) to (iv) and acid generators (ii) and (v) shown in Tables 4 and 5 was evaluated.

[0142] Resins were added to the thinner compositions shown in Tables 4 and 5 so that the resin (i) concentration was 30 wt %, the resin (ii) concentration was 35 wt %, the resin (iii) concentration was 15 wt %, and the resin (iv) concentration was 25 wt %, and acid generators were added so that the acid generator concentrations shown in Tables 4 and 5 were 1 wt %. After stirring at room temperature for 24 hours, the state was visually evaluated according to the following criteria. Evaluation A: Dissolved (clear solution confirmed by visual observation) Evaluation B: Almost dissolved (almost clear solution confirmed by visual observation) Evaluation C: Insoluble (cloudy solution confirmed by visual observation) The results are shown in Tables 4 and 5.

[0143]

[0144]

[0145] Tables 4 and 5 show that the thinner compositions prepared in Examples 2-1 to 2-12 have superior solubility for resins and acid generators compared to the thinner compositions of Comparative Examples 2-1 to 2-3.

[0146] The thinner composition of the present invention has excellent solubility in a variety of photoresist films, photoresist underlayer films (films coated on the underlayer of a photoresist, such as bottom antireflective coating (BARC) or spin-on carbon film), and photoresist overlayer films (top antireflective coating (TARC)). This not only improves the EBR characteristics, rework characteristics, and coating performance of photoresist films, photoresist underlayer films, and photoresist overlayer films, but also provides excellent RRC characteristics. In particular, in the case of photoresists for g-line, i-line, KrF, ArF, EUV, or EB, the basic structures of the constituent photoresists are different, so that it is necessary to adjust the organic solvent content in the composition to improve the solubility and coating properties of all of these. The thinner composition of the present invention satisfies this requirement. As long as the requirements of this embodiment are met, the same effects can be achieved with thinner compositions other than those described in the examples.

[0147] 4. In-Plane Uniformity The aforementioned resins (i) to (iv) were mixed with the solvents listed in Table 1 to prepare compositions with a resin (i) concentration of 30 wt%, a resin (ii) concentration of 35 wt%, a resin (iii) concentration of 15 wt%, and a resin (iv) concentration of 25 wt%, respectively. The concentrations of acid generators (ii) and (v) were also adjusted to 1 wt%. Furthermore, 500 ppm of the nonionic surfactant FTX-218 (polyoxyethylene alkyl ether, manufactured by Neos Corporation) was added to the resins to prepare a semiconductor manufacturing composition for measuring in-plane uniformity. The prepared semiconductor manufacturing composition was then spin-coated onto a silicon wafer at 1500 rpm to form a coating film, which was then pre-baked at 110°C or 240°C for 90 seconds to form a resist film. The thickness of the resist film was measured at 49 points in the diameter direction of the silicon wafer to evaluate in-plane uniformity. The in-plane uniformity was evaluated as follows. The results are shown in Tables 6 and 7. 3σ (%) = 3 × standard deviation of film thickness at 49 points (nm) / average film thickness at 49 points (nm) × 100 Rating A: 3σ < 2% Rating B: 2% ≦ 3σ < 5% Rating C: 3σ ≧ 5%

[0148]

[0149]

[0150] From Tables 6 and 7, it can be seen that the compositions for manufacturing semiconductors prepared in Examples 7-1 to 7-6 and 8-1 to 8-6 have superior in-plane uniformity when forming resin films compared to Comparative Examples 7-1 to 7-3 and 8-1 to 8-3.

Claims

1. A compound represented by the following formula (1):

2. A composition for manufacturing a semiconductor, comprising a solvent (B) containing a compound (B1) represented by the following general formula (b-1): (In the formula, R １ , R ２、 R ３ and R ４ each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group.

3. R １ , R ２、 R ３ and R ４ wherein each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

4. The compound (B1) is 5,5-dimethyl-1,3-dioxolane-4-one (DDO), 2,2,5,5-tetramethyl-1,3-dioxolane-4-one (TDO), 5-methyl-1,3-dioxolane-4-one, 1,3-dioxolane-4-one, 2,5,5-trimethyl-1,3-dioxolane-4-one, 2,5-dimethyl-1,3-dioxolane-4-one, 2-methyl-1,3-dioxolane 3. The composition for manufacturing a semiconductor according to claim 2, which is one or more selected from the group consisting of 2-ethyl-5,5-dimethyl-1,3-dioxolan-4-one (EDDO), 2-ethyl-5-methyl-1,3-dioxolan-4-one, 2-ethyl-1,3-dioxolan-4-one, 2,2,5-trimethyl-1,3-dioxolan-4-one, and 2,2-dimethyl-1,3-dioxolan-4-one.

5. The composition for manufacturing a semiconductor according to any one of claims 2 to 4, wherein the solvent (B) contains, as a compound (B2) other than the compound (B1), one or more selected from the group consisting of a compound represented by the following general formula (b-2), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), and γ-butyrolactone (γ-BL): (In the formula, R5 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, and R6 represents an alkyl group having 1 to 10 carbon atoms.) 6. The composition for manufacturing a semiconductor according to claim 5, wherein the compound represented by general formula (b-2) is methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), or isopropyl 2-hydroxyisobutyrate (i-PHIB).

7. The composition for manufacturing a semiconductor according to claim 5 or 6, comprising the compound represented by general formula (b-2) in an amount of 10 mass% or more based on the total amount (100 mass%) of the solvent (B).

8. The composition for manufacturing a semiconductor according to any one of claims 2 to 7, comprising the compound (B1) in an amount of 0.5 mass% or more based on the total amount (100 mass%) of the solvent (B).

9. The composition for manufacturing a semiconductor according to any one of claims 2 to 8, which is a resist composition.

10. The composition for manufacturing a semiconductor according to any one of claims 2 to 8, which is a resist auxiliary film composition.

11. The composition for manufacturing a semiconductor according to claim 10, wherein the resist auxiliary film is a resist underlayer film or a resist intermediate layer film.

12. The composition for manufacturing a semiconductor according to any one of claims 2 to 8, which is a thinner composition.

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