Semiconductor manufacturing composition

Abstract

The present application provides a semiconductor manufacturing composition containing a solvent (B) comprising a compound (B1) represented by the following general formula (b-1). In the formula, R1, R2, R3 and R4 each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a phenyl group or a benzyl group.

Description

Technical Field

[0001] This invention relates to compositions for semiconductor manufacturing. Background Technology

[0002] Photoresist materials are used in semiconductor manufacturing, and photolithography is used for microfabrication. Typically, photolithography is performed by forming a photoresist on a wafer, followed by exposure and development, then etching to form circuit patterns on the wafer, and finally stripping away the photoresist.

[0003] In recent years, with the gradual advancement of high functionality and miniaturization of semiconductors, there is a growing demand for further miniaturization of pattern sizes.

[0004] To address the miniaturization of these patterns, short-wavelength light sources such as g-line (wavelength 436 nm), i-line (wavelength 365 nm) ultraviolet light from high-pressure mercury lamps, far-ultraviolet light such as KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), and extreme ultraviolet (EUV) light are used as exposure light sources.

[0005] However, when using a short-wavelength exposure light source, the resolving power of the resist decreases due to reflection from the wafer and the effect of standing waves. To address this issue, a technique is known to form a bottom anti-reflective coating (BRAC) between the resist and the wafer as a resist auxiliary film (e.g., Patent Document 1).

[0006] Furthermore, when using a short-wavelength exposure light source, it is more sensitive to contaminants. Therefore, it is known that a process is performed before the exposure process to remove residues and contaminants such as resist film and anti-reflective film (BRAC) using a diluent composition, which is called EBR (edge ​​bead removing, photoresist edge repair) process (e.g., Patent Document 2).

[0007] On the other hand, instead of miniaturizing the pattern size mentioned above, it is also known to use microelectrodes (bumps) to three-dimensionally integrate semiconductor elements, thereby achieving a large capacity memory, in relation to three-dimensional mounting techniques (e.g., Patent Document 3). Furthermore, Patent Document 3 describes the use of a resist film of thickness to form microelectrodes (bumps) in three-dimensional mounting, thereby maintaining the distance between semiconductor elements.

[0008] Existing technical documents Patent documents Patent Document 1: International Publication No. 2004 / 034148 Patent Document 2: Japanese Patent Application Publication No. 2015-232708 Patent Document 3: Japanese Patent Application Publication No. 2019-137612 Summary of the Invention

[0009] The technical problem that the invention aims to solve Among them, resist films and resist auxiliary films are usually formed by coating a solution and heating.

[0010] In addition, the diluent composition is a solution, and by applying the diluent composition, residues and contaminants can be removed.

[0011] That is, these semiconductor manufacturing compositions are solutions, and there is room for improvement in the operability of existing liquid semiconductor manufacturing compositions.

[0012] Therefore, the technical problem to be solved by the present invention is to provide a semiconductor manufacturing composition with excellent operability, and a novel compound suitable for the composition.

[0013] Technical means for solving technical problems The present invention provides, for example, compositions for semiconductor manufacturing, and novel compounds suitable for such compositions.

[0014] <1> The compounds shown in formula (1). <2> A composition for semiconductor manufacturing, comprising a solvent (B) comprising a compound (B1) represented by the following general formula (b-1). (In the formula, R1, R2, R3 and R4 independently represent hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, phenyl groups or benzyl groups.) <3> The semiconductor manufacturing composition as described in <2> above, wherein R1, R2, R3 and R4 each independently represent an alkyl group having 1 to 3 hydrogen atoms or carbon atoms.

[0015] <4> The semiconductor manufacturing composition as described in <2> above, wherein the compound (B1) is selected from 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-di ... One or more of the following: -1,3-dioxolane-4-one, 2-methyl-1,3-dioxolane-4-one, 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO), 2-ethyl-5-methyl-1,3-dioxolane-4-one, 2-ethyl-1,3-dioxolane-4-one, 2,2,5-trimethyl-1,3-dioxolane-4-one, and 2,2-dimethyl-1,3-dioxolane-4-one.

[0016] <5> The semiconductor manufacturing composition as described in any one of <2> to <4> above, wherein the solvent (B) above, as a compound (B2) other than the compound (B1) above, includes one or more compounds selected from 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 with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an acyl group with 1 to 10 carbon atoms, and R6 represents an alkyl group with 1 to 10 carbon atoms.) <6> The semiconductor manufacturing composition as described in <5> above, wherein the compound represented by the above general formula (b-2) is methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM) or isopropyl 2-hydroxyisobutyrate (i-PHIB).

[0017] <7> The semiconductor manufacturing composition as described in <5> or <6> above, wherein, based on the total amount (100% by mass) of the solvent (B) above, it contains 10% by mass or more of the compound shown in the general formula (b-2) above.

[0018] <8> The semiconductor manufacturing composition as described in any one of <2> to <7> above, wherein the composition contains 0.5% by mass or more of the above compound (B1) based on the total amount (100% by mass) of the above solvent (B).

[0019] <9> A semiconductor manufacturing composition as described in any one of <2> to <8> above, wherein the semiconductor manufacturing composition is a photoresist composition.

[0020] <10> A semiconductor manufacturing composition as described in any one of <2> to <8> above, wherein the semiconductor manufacturing composition is a resist-assisted film composition.

[0021] <11> The semiconductor manufacturing composition as described in <10> above, wherein the resist auxiliary film is a lower resist film or a middle resist film.

[0022] <12> A semiconductor manufacturing composition as described in any one of <2> to <8> above, wherein the semiconductor manufacturing composition is a diluent composition.

[0023] Invention Effects According to the present invention, a semiconductor manufacturing composition with excellent operability is provided, as well as a novel compound suitable for the composition. Detailed Implementation

[0024] The embodiments of the present invention will now be described in detail.

[0025] 1. Novel compounds The novel compound of the present invention is 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (hereinafter sometimes referred to as "EDDO") as shown in formula (1). The EDDO ​​of the present invention can be synthesized, for example, by the method described in Examples 1-1 below. That is, it can be synthesized using 2-hydroxyisobutyric acid, propionaldehyde, p-toluenesulfonic acid monohydrate, and toluene as raw materials. Furthermore, acid catalysts and solvents can be appropriately used during the synthesis.

[0026] 2. A composition for semiconductor manufacturing The semiconductor manufacturing composition of the present invention contains a solvent (B) comprising a compound (B1) represented by the following general formula (b-1), but also includes cases containing only the solvent (B). In the above formula, R1, R2, R3 and R4 independently represent hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, phenyl groups or benzyl groups.

[0027] The semiconductor manufacturing composition of the present invention has excellent operability.

[0028] For example, the semiconductor manufacturing composition of the present invention has at least one of the following effects: reducing the amount of resin used, forming a uniform coating film, and being able to effectively dissolve the components contained in the resist and the resist auxiliary film.

[0029] For example, when the semiconductor manufacturing composition of the present invention is used as a resist composition for forming a resist film, effects such as reducing the amount of resin used and forming a uniform resist film can be obtained. Furthermore, especially in resist compositions used for forming resist films for three-dimensional mounting, resins with various structures and photoacid-generating agents are contained, resulting in insoluble substances or precipitates in the solvent, leading to poor in-plane uniformity. However, when using the resist composition (semiconductor manufacturing composition) of the present invention, high in-plane uniformity can be achieved; for example, defects during film formation can be suppressed using the resist composition (semiconductor manufacturing composition).

[0030] Furthermore, when the semiconductor manufacturing composition of the present invention is used as a resist-assisted film composition for forming a resist-assisted film, effects such as reducing the amount of resin used and forming a uniform resist-assisted film can be obtained.

[0031] Furthermore, when the semiconductor manufacturing composition of the present invention is used as a diluent composition, it is possible to obtain effects such as excellent dissolution of components of the resist film, resist auxiliary film, etc., such as resin and photoacid generator (PAG). As a result, EBR processes such as removing residues and contaminants can be performed with high efficiency.

[0032] However, the effects of the present invention are not limited to those described above, and can also exhibit the effects resulting from the excellent operability described above.

[0033] The structure of the present invention will be described below.

[0034] [Solvent (B)] Solvent (B) contains compound (B1) represented by the following general formula (b-1). In addition, it may contain solvents other than compound (B1) (hereinafter sometimes referred to as "other solvents") (compound (B2)), etc.

[0035] (Compound (B1)) Compound (B1) is represented by the following general formula (b-1). In the above formula, R1, R2, R3 and R4 independently represent hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, phenyl groups or benzyl groups.

[0036] Alkyl groups having 1 to 10 carbon atoms can be either straight-chain or branched. Examples of alkyl groups having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl.

[0037] In one embodiment, R1, R2, R3 and R4 are preferably independently hydrogen atoms or alkyl groups having 1 to 3 carbon atoms.

[0038] In one embodiment, R1 and R2 are preferably alkyl groups having 1 to 3 carbon atoms, more preferably methyl, ethyl, n-propyl or isopropyl, and particularly preferably methyl.

[0039] In one embodiment, R3 and R4 are preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, more preferably hydrogen atoms, methyl, ethyl, n-propyl or isopropyl, and particularly preferably hydrogen atoms, methyl or ethyl.

[0040] As specific examples of compound (B1), there are no particular limitations, and examples include 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, and 2,5-dimethyl-1,3-dioxolane-4-one. - Dioxolane-4-one, 2-methyl-1,3-dioxolane-4-one, 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO), 2-ethyl-5-methyl-1,3-dioxolane-4-one, 2-ethyl-1,3-dioxolane-4-one, 2,2,5-trimethyl-1,3-dioxolane-4-one, 2,2-dimethyl-1,3-dioxolane-4-one, etc. Among these, compound (B1) is more preferably 5,5-dimethyl-1,3-dioxolane-4-one (DDO), 2,2,5,5-tetramethyl-1,3-dioxolane-4-one (TDO), or 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO).

[0041] Among them, the above-mentioned compound (B1) can be used alone or in combination of two or more.

[0042] Based on the total amount (100% by mass) of solvent (B), compound (B1) preferably contains 0.5% by mass or more, more preferably 20% by mass or more, further preferably 40% by mass or more, and particularly preferably 60% by mass or more. There is no upper limit to the content of compound (B1), which can be 95% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. In one embodiment, based on the total amount (100% by mass) of solvent (B), compound (B1) preferably contains 0.5 to 100% by mass, more preferably 20 to 95% by mass, further preferably 40 to 90% by mass, and particularly preferably 60 to 80% by mass.

[0043] (Other solvents (compound (B2))) Solvent (B) may also contain solvents other than compound (B1) (other solvents) (compound (B2)).

[0044] Other solvents (compound (B2)) are not particularly limited, but preferably include one or more of the following compounds represented by 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 above formula, R5 represents a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an acyl group with 1 to 10 carbon atoms.

[0045] The alkyl groups having 1 to 10 carbon atoms are the same as those in the general formula (b-1) for R1 to R4.

[0046] There are no particular restrictions on aryl groups with 6 to 10 carbon atoms; examples include phenyl, naphthyl, anthraceneyl, tolyl, xylyl, methylphenyl, isopropylphenyl, etc.

[0047] There are no particular restrictions on the number of carbon atoms in the acyl group (1 to 10), and examples include formyl, acetyl, propionyl, butyryl, benzoyl, and naphthoyl.

[0048] Among 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.

[0049] R6 represents an alkyl group having 1 to 10 carbon atoms. This alkyl group having 1 to 10 carbon atoms is the same as that described in R1 to R4 of general formula (b-1), preferably methyl, ethyl, n-propyl or isopropyl, more preferably methyl or isopropyl, and particularly preferably methyl.

[0050] In one embodiment, 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, and R6 is methyl, ethyl, n-propyl, or isopropyl; more preferably, R5 is a hydrogen atom, methyl, ethyl, formyl, or acetyl, and R6 is methyl or isopropyl; particularly preferably, R5 is a hydrogen atom, methyl, or acetyl, and R6 is methyl.

[0051] Specific examples of compounds represented by general formula (b-2) are not particularly limited, and may include methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), isopropyl 2-hydroxyisobutyrate (i-PHIB), isobutyl 2-hydroxyisobutyrate (i-BHIB), n-butyl 2-hydroxyisobutyrate (n-BHIB), etc. Among 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).

[0052] In one embodiment, the other solvent (compound (B2)) preferably comprises one or more selected from the compounds shown in general formula (b-2), propylene glycol monomethyl ether acetate (PGMEA), and propylene glycol monomethyl ether (PGME), more preferably the compounds shown in general formula (b-2), and even more preferably one or more selected from methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), and isopropyl 2-hydroxyisobutyrate (i-PHIB), particularly preferably methyl 2-hydroxyisobutyrate (HBM).

[0053] Furthermore, the other solvents mentioned above (compound (B2)) can be used alone or in combination of two or more.

[0054] Based on the total amount (100% by mass) of solvent (B), other solvents (compound (B2)) preferably contain 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit of the content of other solvents (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, based on the total amount (100% by mass) of solvent (B), other solvents (compound (B2)) preferably contain 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.

[0055] In a preferred embodiment, based on the total amount (100% by mass) of the solvent (B) described above, the compound represented by general formula (b-2) preferably contains more than 10% by mass, more preferably 10 to 90% by mass, even more preferably 15 to 80% by mass, particularly preferably 15 to 70% by mass, especially preferably 20 to 60% by mass, and most preferably 20 to 50% by mass.

[0056] (A combination of compound (B1) and other solvents (compound (B2)) When solvent (B) contains compound (B1) and other solvents (compound (B2)), preferred combinations of compound (B1) and other solvents (compound (B2)) include combinations of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM), combinations of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA), combinations of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether (PGME), and combinations of 2,2,5,5-tetramethyl-1,3-dioxolane-4-one (TDO) and methyl 2-hydroxyisobutyrate (HBM). Combinations of 2,2,5,5-tetramethyl-1,3-dioxolane-4-one (TDO) and propylene glycol monomethyl ether acetate (PGMEA), combinations of 2,2,5,5-tetramethyl-1,3-dioxolane-4-one (TDO) and propylene glycol monomethyl ether (PGME), combinations of 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO) and methyl 2-hydroxyisobutyrate (HBM), combinations of 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO) and propylene glycol monomethyl ether acetate (PGMEA), and combinations of 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO) and propylene glycol monomethyl ether (PGME), etc. Among these, when the combination of compound (B1) and other solvents (compound (B2)) is applied to, for example, the resist composition and resist auxiliary film composition described later, from the viewpoint of high solubility and higher in-plane uniformity, the combination of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM), the combination of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA), and the combination of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether (PGME) are preferred.

[0057] At this point, the content ratio (DDO:HBM, mass ratio) of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) to methyl 2-hydroxyisobutyrate (HBM) 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, especially preferably 35:65 to 50:50, and most preferably 40:60 to 50:50.

[0058] 3. Applications of compositions for semiconductor manufacturing The semiconductor manufacturing composition of the present invention has excellent operability and can therefore be used in a variety of applications.

[0059] In one embodiment, the semiconductor manufacturing composition of the present invention is a photoresist composition.

[0060] In another embodiment, the semiconductor manufacturing composition of the present invention is a resist-assisted film composition.

[0061] In another embodiment, the semiconductor manufacturing composition of the present invention is a diluent composition.

[0062] Furthermore, depending on the intended use of the semiconductor manufacturing composition, the composition may also contain components suitable for that use. Various uses are described below.

[0063] [Resist Composition] In addition to a solvent (B), the photoresist composition also contains a photosensitive resin (A1). Furthermore, it may contain a photosensitizer, a photoacid generator (PAG), additives, etc., as needed. Moreover, by including solvent (B) in the photoresist composition, high solubility of the resin and PAG can be achieved, resulting in the formation of a uniform photoresist film.

[0064] (Solvent (B)) Solvent (B) contains the above-mentioned components.

[0065] Based on the total amount (100% by mass) of the resist composition, the content of 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.

[0066] (Photosensitive resin (A1)) The photosensitive resin (A1) can be either a positive or negative photosensitive resin. Furthermore, the resin (A1) can incorporate a chemical amplification mechanism.

[0067] Specific examples of photosensitive resins (A1) include linear phenolic resins, phenolic resins, (meth)acrylic resins having an adamantane backbone, polyimide, polybenzoxazole, polyvinyl alcohol, polyisoprene, polyacrylamide, epoxy resins, and olefinically unsaturated resins. Among these, the photosensitive resin (A1) is preferably a linear phenolic resin, phenolic resin, (meth)acrylic resin having an adamantane backbone, polyimide, polybenzoxazole, or an olefinically unsaturated resin; more preferably, a linear phenolic resin, phenolic resin, (meth)acrylic resin having an adamantane backbone, or an olefinically unsaturated resin; and even more preferably, an olefinically unsaturated resin. In this specification, "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0068] Among them, there are no particular limitations on the above-mentioned olefin unsaturated resins, and resins polymerized from at least one of the following can be listed: aromatic vinyl monomers, aromatic vinyl monomers containing phenolic hydroxyl groups and their α-methyl substitutes, and olefin unsaturated monomers.

[0069] At this point, aromatic vinyl monomers, such as styrene or α-methylstyrene, can be listed.

[0070] In addition, examples of aromatic vinyl monomers containing phenolic hydroxyl groups and their α-methyl substitutes include: aromatic vinyl monomers with phenolic hydroxyl groups such as hydroxystyrene and their α-methyl substitutes; aromatic vinyl monomers with phenolic hydroxyl groups protected by acetal groups such as p-(1-methoxyethoxy)styrene and their α-methyl substitutes; and aromatic vinyl monomers with phenolic hydroxyl groups protected by acyl groups such as p-acetoxystyrene and their α-methyl substitutes.

[0071] Furthermore, as olefinic unsaturated monomers, examples include tert-butyl methacrylate and other methacrylates protected by acid-degradable ester groups.

[0072] In one embodiment, the olefinically unsaturated resin is preferably a homopolymer of aromatic vinyl monomers containing phenolic hydroxyl groups and their α-methyl substitutes; a copolymer of aromatic vinyl monomers and aromatic vinyl monomers containing phenolic hydroxyl groups and their α-methyl substitutes; or a copolymer of aromatic vinyl monomers, aromatic vinyl monomers containing phenolic hydroxyl groups and their α-methyl substitutes, and olefinically unsaturated monomers. More preferably, it is a copolymer of aromatic vinyl monomers, aromatic vinyl monomers containing phenolic hydroxyl groups and their α-methyl substitutes, and olefinically unsaturated monomers.

[0073] These photosensitive resins (A1) can be used alone or in combination of two or more.

[0074] Based on the total amount (100% by mass) of the resist composition, the content of 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.

[0075] (Photosensitive agent) The resist composition may contain a photosensitizer.

[0076] Examples of photosensitizers include substances that are commonly used as photosensitizing components in positive resist compositions.

[0077] Specific examples of photosensitizers include acyl chlorides such as naphthoquinone diazidesulfonyl chloride and benzoquinone diazidesulfonyl chloride, and reaction products of compounds with functional groups (hydroxyl, amino, etc.) that can condense with acyl chlorides, such as hydroquinone, resorcinol, and 2,4-dihydroxybenzophenone.

[0078] Commercially available photosensitizers include "DTEP-350" (a diazonaphthoquinone type photosensitizer manufactured by Daito Chemix Corporation).

[0079] These photosensitizers can be used alone or in combination of two or more.

[0080] The content of photosensitizer is 0.01 to 80 parts by weight relative to 100 parts by weight of photosensitive resin (A1), more preferably 0.05 to 65 parts by weight, even more preferably 0.1 to 50 parts by weight, and even more preferably 0.5 to 30 parts by weight.

[0081] (Photoacid-producing agent (PAG)) The resist composition may contain a photoacid-generating agent.

[0082] Photoacid generators are compounds that can produce acids directly or indirectly through irradiation by radiation such as visible light, ultraviolet light, excimer lasers, electron beams, extreme ultraviolet light (EUV), X-rays, and ion beams.

[0083] There are no particular limitations on photoacid-producing agents. Examples include ionic photoacid-producing agents such as triarylsulfonium salts and diaryliodonium salts, and nonionic photoacid-producing agents such as imide sulfonates, diazodisulfones, and oxime sulfonates.

[0084] There are no particular limitations on the above-mentioned triarylsulfonium salts, and examples include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium p-toluenesulfonate, diphenyl-4-methoxyphenylsulfonium trifluoromethanesulfonate, and triphenylsulfonium nonafluorobutanesulfonate, etc.

[0085] There are no particular limitations on the aryl iodonium salts mentioned above; examples include bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate and bis(4-tert-butylphenyl)iodonium nonafluoron-butanesulfonate.

[0086] There are no particular limitations on the above-mentioned imide sulfonates, and examples include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, and N-(trifluoromethylsulfonyloxy)diphenylmaleimide.

[0087] There are no particular limitations on the diazonium disulfone mentioned above; examples include bis(cyclohexylsulfonyl)diazomethane and bis(4-methylphenylsulfonyl)diazomethane.

[0088] There are no particular limitations on the oxime sulfonates mentioned above, and examples include α-(methanesulfonyloxyimino)-phenylacetonitrile, α-(methanesulfonyloxyimino)-4-methoxyphenylacetonitrile-phenylacetonitrile, and α-(methanesulfonyloxyimino)-4-methoxyphenylacetonitrile.

[0089] From the viewpoint of high solubility in solvent (B), the above-mentioned photoacid-generating agent preferably contains at least one of triarylsulfonate and diazonium disulfone, more preferably contains at least one selected from diphenyl-4-methylphenylsulfonate trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonate p-toluenesulfonate and bis(cyclohexylsulfonyl)diazomethane.

[0090] Commercially available photoacid-generating agents include "WPAG-145", "WPAG-149", "WPAG-170", "WPAG-199", "WPAG-336", "WPAG-367", "WPAG-370", "WPAG-469", "WPAG-638" (manufactured by Fujifilm and Koh Geny Co., Ltd.), "NDS-169" (manufactured by Midori Kagaku Co., Ltd.), and "TPS-CS" (manufactured by Toyosei Kogyo Co., Ltd.).

[0091] These photoacid-producing agents can be used alone or in combination of two or more.

[0092] The content of photoacid generator relative to 100 parts by weight of photosensitive resin (A1) is preferably 0.01 to 80 parts by weight, more preferably 0.05 to 65 parts by weight, even more preferably 0.1 to 50 parts by weight, and particularly preferably 0.5 to 30 parts by weight.

[0093] (additive) The resist composition may also contain additives.

[0094] As additives, there are no particular limitations, and examples include acid crosslinking agents, acid diffusion control agents, solubility promoters, solubility control agents, sensitizers, surfactants, oxyacids of organic carboxylic acids or phosphorus or their derivatives, dyes, pigments, adhesive aids, anti-halo agents, preservation stabilizers, antioxidants, defoamers, shape modifiers, etc. These additives can be used alone or in combination of two or more.

[0095] There is no particular limitation on the content of the additive, but it is preferably 0.001 to 100 parts by weight relative to 100 parts by weight of the photosensitive resin (A1), more preferably 0.01 to 70 parts by weight, even more preferably 0.1 to 50 parts by weight, and particularly preferably 0.3 to 30 parts by weight.

[0096] (Coating method) The coating method for the resist composition of the present invention is not particularly limited, and methods such as spin coating and slot coating can be included. However, spin coating is preferred for the coating method of the resist composition of the present invention. That is, in one embodiment, the resist composition of the present invention is a resist composition coated using a spin coating method. By using a spin coating method to coat the resist composition, effects such as excellent in-plane uniformity of the resulting resist film can be obtained.

[0097] [Resist-assisted film composition] A resist auxiliary film is a film that can be used with the resist films described above. Examples include the lower resist film used in a two-layer resist method, the lower resist film used in a three-layer resist method, and the intermediate resist film. However, the resist auxiliary film does not include the resist film itself, that is, it does not include the outermost layer of the resist.

[0098] In one embodiment, the resist auxiliary film is a resist lower layer film or a resist intermediate layer film. In other words, the resist auxiliary film composition is a resist lower layer film composition or a resist intermediate layer film composition.

[0099] In another embodiment, the resist auxiliary film is an anti-reflective film (BRAC).

[0100] Regarding the resist-assisted film composition, although it varies depending on the desired function, it contains a solvent (B) and a resin (A2). Furthermore, it may further contain photosensitizers, photoacid-generating agents, crosslinking agents, additives, etc., as needed. Moreover, by including solvent (B) in the resist-assisted film composition, it is possible to achieve the formation of a uniform resist-assisted film.

[0101] (Solvent (B)) Solvent (B) contains the above-mentioned substances.

[0102] Based on the total amount (100% by mass) of the resist-assisted film composition, the content of 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.

[0103] (Resin (A2)) Examples of resins (A2) include photosensitive resins (A1), silicone-containing resins, and naphthaldehyde resins.

[0104] The photosensitive resin (A1) is the same as the substances mentioned above.

[0105] Silicon-containing resins are resins that contain silicon. Specific examples of silicon-containing resins include those known in Japanese Patent Application Publication Nos. 2007-226170 and 2007-226204.

[0106] Examples of naphthalene-formaldehyde resins include reaction products of naphthalene and / or alkylnaphthalene with formaldehyde.

[0107] These resins (A2) can be used alone or in combination of two or more.

[0108] Based on the total amount (100% by mass) of the resist-assisted film composition, the content of 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.

[0109] (Photosensitive agents and photoacid-producing agents) The photosensitizers and photoacid-producing agents are the same as the substances mentioned above.

[0110] The content of photosensitizer relative to 100 parts by weight of resin (A2) is preferably 0.01 to 80 parts by weight, more preferably 0.05 to 65 parts by weight, even more preferably 0.1 to 50 parts by weight, and particularly preferably 0.5 to 30 parts by weight.

[0111] The content of photoacid generator relative to 100 parts by weight of resin (A2) is preferably 0.01 to 80 parts by weight, more preferably 0.05 to 65 parts by weight, even more preferably 0.1 to 50 parts by weight, and particularly preferably 0.5 to 30 parts by weight.

[0112] (Cross-linking agent) Crosslinking agents have the function of crosslinking resin (A2) to prevent miscibility.

[0113] As a crosslinking agent, there are no particular limitations, and examples include: epoxy compounds such as tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triglycidyl ether, and trimethylolpropane triglycidyl ether; melamine compounds such as hexamethylolmelamine, hexamethoxymethylmelamine, and hexamethylolmelamine; guanidine compounds such as tetramethylolguanidine, tetramethoxyethylguanidine, and tetraacyloxytetramethylolguanidine; glycourea compounds such as tetramethylolglycourea and tetramethoxyglycourea; urea compounds such as tetramethylolurea and tetramethoxymethylurea; and alkenyl ether compounds such as ethylene glycol divinyl ether and triethylene glycol divinyl ether.

[0114] These crosslinking agents can be used alone or in combination of two or more.

[0115] The content of crosslinking agent relative to 100 parts by weight of resin (A2) is preferably 5 to 50 parts by weight, more preferably 20 to 40 parts by weight, and even more preferably 10 to 40 parts by weight.

[0116] (additive) The additives are the same as the substances mentioned above.

[0117] There is no particular limitation on the content of the additive, but it is preferably 0.001 to 100 parts by weight relative to 100 parts by weight of resin (A2), more preferably 0.01 to 70 parts by weight, even more preferably 0.1 to 50 parts by weight, and particularly preferably 0.3 to 30 parts by weight.

[0118] (Coating method) The coating method for the resist auxiliary film composition of the present invention is not particularly limited, and methods such as spin coating and slot coating can be included. However, spin coating is preferred for the coating method of the resist auxiliary film composition of the present invention. That is, in one embodiment, the resist auxiliary film composition of the present invention is a resist auxiliary film composition coated using a spin coating method. By using a spin coating method to coat the resist auxiliary film composition, effects such as excellent in-plane uniformity of the obtained resist auxiliary film can be obtained.

[0119] [Diluent Composition] The diluent composition contains solvent (B). Furthermore, additives may be added as needed. By containing solvent (B) in the diluent composition, components such as resins or photoacid generators (PAGs) of the resist film and resist auxiliary film can be effectively dissolved. As a result, EBR processes for removing residues and contaminants can be performed with high efficiency.

[0120] (Solvent (B)) Based on the total amount (100% by mass) of the diluent composition, the content of 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.

[0121] (additive) Examples of additives include surfactants, dyes, pigments, preservation stabilizers, adhesives, antioxidants, and defoamers. These additives can be used alone or in combination of two or more.

[0122] The content of additives is preferably 0.000000001 to 1 part by mass relative to 1 part by mass of solvent (B), more preferably 0.000001 to 0.1 parts by mass, and even more preferably 0.00001 to 0.001 parts by mass.

[0123] Semiconductor manufacturing methods According to one aspect of the present invention, a method for manufacturing a semiconductor is provided.

[0124] In one embodiment, a semiconductor manufacturing method includes: a resist film formation step of coating (preferably spin-coating) a resist composition onto a wafer to form a resist film; a resist pattern formation step; and an etching step. Where necessary, this method may further include: a pretreatment step of coating a diluent composition onto the wafer before the resist film formation step; and a resist film cleaning step after the resist film formation step, involving contact with the diluent composition to remove at least a portion of residues or contaminants from the resist film.

[0125] In a preferred embodiment, the process sequentially includes a pretreatment step, a resist film formation step, a resist film cleaning step, a resist pattern formation step, and an etching step. In this case, at least one of the diluent composition used in the pretreatment step, the resist composition used in the resist film formation step, and the diluent composition used in the resist film cleaning step is a semiconductor manufacturing composition (resist composition or diluent composition) of the present invention.

[0126] By performing a pretreatment process, a small amount of photoresist can be used to coat the substrate.

[0127] In addition, a resist film can be formed through the resist film formation process.

[0128] The resist film cleaning process removes residues and contaminants from the edges and / or back of the substrate. As a result, resolution is improved during the resist patterning process.

[0129] In the resist patterning process, a pattern can be formed by exposing and developing the resist. Preferably, a low-wavelength exposure light source is used for this exposure. This allows for miniaturization of the pattern size.

[0130] In another embodiment, the semiconductor manufacturing method includes: a resist-assisted film forming step of coating (preferably spin-coating) a resist-assisted film composition on a wafer to form a resist-assisted film; a resist film forming step of coating (preferably spin-coating) a resist composition on the resist-assisted film to form a resist film; a resist patterning step; and an etching step. In this case, if necessary, it may further include: a pretreatment step of coating a diluent composition on the wafer before the resist-assisted film forming step; a resist-assisted film cleaning step of contacting the resist composition with the resist composition after the resist film forming step to remove at least a portion of residues or contaminants from the resist-assisted film; and a resist-assisted film and / or resist film cleaning step of contacting the resist composition with the resist composition after the resist film forming step to remove at least a portion of residues or contaminants from the resist-assisted film and / or the resist film.

[0131] In a preferred embodiment, the process sequentially includes: a pretreatment step; a resist-assisted film formation step; a resist-assisted film cleaning step; a resist film formation step; a resist-assisted film and / or resist film cleaning step; a resist patterning step; and an etching step. In this case, one of the resist-assisted film cleaning step or the resist-assisted film and / or resist film cleaning step may be omitted. Furthermore, at least one of the diluent composition used in the pretreatment step, the resist-assisted film composition used in the resist-assisted film formation step, the diluent composition used in the resist-assisted film cleaning step, the resist film composition used in the resist film formation step, and the diluent composition used in the resist-assisted film and / or resist film cleaning step is a semiconductor manufacturing composition (resist composition, resist-assisted film composition, or diluent composition) of the present invention.

[0132] Furthermore, the formed resist auxiliary film can be a single-layer structure consisting of a lower resist film or a two-layer structure consisting of a lower resist film and an intermediate resist film. When the resist auxiliary film is a two-layer structure, the layer composition of the lower resist film and the intermediate resist film can be appropriately set according to the required physical properties, applications, and pattern formation methods of each layer.

[0133] Example The following examples illustrate the invention in more detail. The materials, quantities, proportions, processing contents, and processing steps shown in the following examples can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the invention is not limited to the specific examples shown below.

[0134] Unless otherwise specified, the "%" in the embodiments refers to the quality standard.

[0135] The analysis methods for physical properties, etc., in the embodiments are as follows.

[0136] (1) Purity of the product The purity of the product was determined by gas chromatography (GC). The chromatographic column used was an Agilent DB-WAX (30 m in length, 0.25 mm in diameter).

[0137] (2) Nuclear Magnetic Resonance (NMR) The structure of a compound is determined using NMR.

[0138] The nuclear magnetic resonance (NMR) apparatus used is a JNM-ECA500 manufactured by NEC Corporation. The deuterated solvent used and the measurement frequency are recorded in the classification of each compound.

[0139] (3) Coating thickness The film thickness of the coating formed by the resist composition was measured using a film thickness measurement system (device name "F50", manufactured by Filmetrics Inc.) in a constant temperature and humidity chamber at 23°C and 50% (relative humidity).

[0140] (4) The proportion of structural units in the resin The proportion of structural units in the resin, used 13 C-NMR (model "JNM-ECA500", manufactured by Nippon Electronics Co., Ltd., 125 MHz), using deuterated chloroform as a solvent to... 13 The C quantitative mode was used to perform 1024 cumulative measurements.

[0141] (5) Weight-average molecular weight (Mw), number-average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the resin The Mw and Mn of the resin were determined using gel permeation chromatography (GPC) with polystyrene as a standard under the following conditions.

[0142] Device Name: Hitachi LaChrom Series • Detector: RI detector L-2490 • Chromatographic column: 2 TSKgel GMHHR-M columns + HHR-H guard column manufactured by Tosoh Corporation Solvent: THF (containing stabilizer) • Flow rate: 1 mL / min Column temperature: 40℃ Then, the calculated ratio of Mw to Mn of the resin [Mw / Mn] is used as the value of the molecular weight distribution of the resin.

[0143] 1. Manufacturing of solvents for semiconductors Example 1-1 Synthesis of 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO) In a 500 mL round-bottom glass flask equipped with a condenser, stirrer, and Dean-Stark apparatus, 100.0 g of 2-hydroxyisobutyric acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.), 67.0 g of propionaldehyde (manufactured by Fujifilm and Kogyo Pure Chemical Co., Ltd.), 5.5 g of p-toluenesulfonic acid monohydrate (manufactured by Fujifilm and Kogyo Pure Chemical Co., Ltd.), and 125.0 g of toluene (manufactured by Fujifilm and Kogyo Pure Chemical Co., Ltd.) were added. The reaction was carried out under reflux at atmospheric pressure, allowing the generated water and toluene to azeotropically react, while the reaction was separated using a Dean-Stark apparatus for 5 hours. The sample was washed twice with 200 g of 10% sodium bicarbonate aqueous solution and once with 200 g of saturated sodium chloride aqueous solution. Then, it was subjected to vacuum distillation, and the fraction obtained at 107 hPa and 103 °C yielded 64.1 g of 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (GC purity 99.2%), as shown in the following structural formula. Since the structure of EDDO ​​obtained in Example 1-1 is a new substance, according to... 1 H NMR, 13 The identification was performed using various spectra, including C NMR, DEPT (Distortionless Enhancement by Polarization Transfer), H-HCOSY (Correlation Spectroscopy), and HMQC (Heteronuclear Multiple Quantum Correlation).

[0144] 1 H NMR (500MHz, CDCl3) 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 (125MHz, CDCl3) δ6.7, 21.5, 24.6, 27.4, 77.2, 102.9, 176.0 Examples 1-2 Synthesis of 5,5-dimethyl-1,3-dioxolane-4-one (DDO) Using the same reaction apparatus as in Example 1-1, 100 g of hydroxyisobutyric acid, 28.9 g of trioxymethylene (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.51 g of p-toluenesulfonic acid monohydrate, and 125 g of toluene were reacted. Following the same procedure as in Example 1-1, 67.3 g of 5,5-dimethyl-1,3-dioxolane-4-one (GC purity 99.6%) was obtained as the fraction distilled under reduced pressure at 126 hPa and 91°C, as shown in Example 1-1. Examples 1-3 Synthesis of 2,2,5,5-Tetramethyl-1,3-dioxolane-4-one (TDO) Using the same reaction apparatus as in Examples 1-1, 75 g of hydroxyisobutyric acid, 83.7 g of acetone (manufactured by Fujifilm and Kohden Chemical Co., Ltd.), 4.14 g of p-toluenesulfonic acid monohydrate, and 93.8 g of toluene were reacted. Following the same procedure as in Examples 1-1, by vacuum distillation, 40.1 g of 2,2,5,5-tetramethyl-1,3-dioxolane-4-one (GC purity 99.8%), as the fraction obtained at 116 hPa and 95°C, was obtained. Various evaluations were performed on the solvents obtained by the above methods.

[0145] 2. Manufacturing of compositions for semiconductor manufacturing Example 2-1 5,5-Dimethyl-1,3-dioxolane-4-one (DDO) is used as a composition for semiconductor manufacturing.

[0146] Example 2-2 2-Ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO) is used as a composition for semiconductor manufacturing.

[0147] Examples 2-3 2,2,5,5-Tetramethyl-1,3-dioxolane-4-one (TDO) is used as a composition for semiconductor manufacturing.

[0148] Examples 2-4 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM). In this case, the mass ratio of DDO to HBM is 1:99.

[0149] Examples 2-5 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA). In this case, the mass ratio of DDO to PGMEA is 1:99.

[0150] Examples 2-6 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether (PGME). In this case, the mass ratio of DDO to PGME is 1:99.

[0151] Examples 2-7 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM). In this case, the mass ratio of DDO to HBM is 25:75.

[0152] Examples 2-8 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA). In this case, the mass ratio of DDO to PGMEA is 25:75.

[0153] Examples 2-9 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether (PGME). In this case, the mass ratio of DDO to PGME is 25:75.

[0154] Example 2-10 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and methyl 2-hydroxyisobutyrate (HBM). In this case, the mass ratio of DDO to HBM is 50:50.

[0155] Example 2-11 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether acetate (PGMEA). In this case, the mass ratio of DDO to PGMEA is 50:50.

[0156] Example 2-12 A semiconductor manufacturing composition is prepared by mixing 5,5-dimethyl-1,3-dioxolane-4-one (DDO) and propylene glycol monomethyl ether (PGME). In this case, the mass ratio of DDO to PGME is 50:50.

[0157] Comparative Example 2-1 Propylene glycol monomethyl ether acetate (PGMEA) is used as a composition for semiconductor manufacturing.

[0158] Comparative Example 2-2 Propylene glycol monomethyl ether (PGME) is used as a composition for semiconductor manufacturing.

[0159] Comparative Examples 2-3 γ-Butyrolactone (GBL) is used as a composition for semiconductor manufacturing.

[0160] Table 1 below shows the semiconductor manufacturing compositions manufactured from Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3.

[0161] [Table 1] 3. Solubility of acid-producing agents, corrosion-resistant resins, and lower film resins. The resins and underlying films used in the following examples and comparative examples are as follows.

[0162] Resin (i) Cresol linear phenolic resin EP4080G (manufactured by Asahi Organic Materials Co., Ltd.) Resin (ii) is a copolymer of structural units of hydroxystyrene / tert-butyl acrylate / styrene in a molar ratio of 3 / 1 / 1 (manufactured by Maruzen Petrochemical Co., Ltd., Mw=12000). Resin (iii) is a copolymer of structural units having a MADM (2-methyl-2-adamantyl methacrylate) / GBLM (α-methacryloyloxy-γ-butyrolactone) ratio of 25 / 75 (molar ratio) (Mn = 3770). Resin (iv) XBisN-1: 13-(biphenyl-4-yl)-13H-dibenzoxanth-3,10-diol (Synthesized according to "WO2013 / 024778"). The acid-producing agents used in the following examples and comparative examples are as follows.

[0163] • Acid-generating agent (i): WPAG336 (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) • Acid-generating agent (ii): WPAG145 (manufactured by Fujifilm and Wako Pure Chemical Industries, Ltd.) • Acid-generating agent (iii): Triphenylthionium nonafluorobutane sulfonate (manufactured by Sigma-Aldrich) • Acid-generating agent (iv): NDS-169 (manufactured by Midori Kagaku Co., Ltd.) • Acid-generating agent (v): TPS-CS (manufactured by Toyo Sangyo Kogyo Co., Ltd.) [Solubility Evaluation] The solubility of the resins (i) to (iv) and acid-producing agents (i) to (v) shown in Tables 2 to 3 was evaluated using the solvents (diluent compositions) prepared in Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3.

[0164] Resins were added to the solvent (diluent composition) to achieve resin concentrations of 30 wt%, 35 wt%, 15 wt%, and 25 wt%, respectively. The state of the resin was then visually evaluated at room temperature after stirring for 24 hours according to the following criteria.

[0165] Evaluation A: Dissolved (visually confirmed as a clear solution) Rating C: Insoluble (visually confirmed as a turbid solution) For acid-producing agents (i) to (v), the acid-producing agents were added to the solvent (diluent composition) to achieve an acid-producing agent concentration of 1 wt% and 10 wt%, respectively, and the state was visually evaluated at room temperature after stirring for 1 hour according to the following criteria.

[0166] Evaluation A: 10% dissolved (visually confirmed as a clear solution) Evaluation B: Dissolves at 1% (visually confirmed as a clear solution). Rating C: Insoluble (visually confirmed as a turbid solution) The results are shown in Tables 2 and 3.

[0167] [Table 2] [Table 3] It has been confirmed that the diluent composition of the present invention exhibits excellent solubility for both resins (i) to (iv) and acid-producing agents (i) to (v), making it particularly useful as a diluent composition for EBR applications and repair applications. On the other hand, it has been confirmed that the diluent composition of the comparative examples exhibits partial insolubility for both resins (i) to (iv) and acid-producing agents (i) to (v), making it unsuitable as a diluent composition.

[0168] As described above, when using a diluent composition that satisfies the requirements of this embodiment, it can impart good solubility compared to a comparative example diluent composition that does not satisfy these requirements. Compositions other than the diluent compositions described in the examples also exhibit the same effect, provided that the requirements of this embodiment are met.

[0169] [Solubility Evaluation] Using the solvents listed in Table 1, diluent compositions for Examples 2-1 to 2-12 and Comparative Examples 2-1 to 2-3 were prepared, respectively. The solubility of these diluent compositions in the resins (i) to (iv) and acid-producing agents (ii) and (v) shown in Tables 4 and 5 was evaluated.

[0170] Resins were added to the diluent compositions shown in Tables 4 and 5 respectively, such that resin (i) concentration reached 30 wt%, resin (ii) concentration reached 35 wt%, resin (iii) concentration reached 15 wt%, and resin (iv) concentration reached 25 wt%. An acid-generating agent was added to achieve an acid-generating agent concentration of 1 wt%, as shown in Tables 4 and 5. The condition was visually evaluated at room temperature after stirring for 24 hours according to the following criteria.

[0171] Evaluation A: Dissolved (visually confirmed as a clear solution) Rating B: Mostly dissolved (visually confirmed as a mostly clear solution) Rating C: Insoluble (visually confirmed as a turbid solution) The results are shown in Tables 4 and 5.

[0172] [Table 4] [Table 5] As shown in Tables 4 and 5, the diluent compositions prepared in Examples 2-1 to 2-12 have superior solubility for resins and acid-producing agents compared to the diluent compositions in Comparative Examples 2-1 to 2-3.

[0173] The diluent composition of the present invention exhibits excellent solubility in various photoresist films, photoresist underlayer films (films coated on the underside of photoresist, such as lower antireflective film (BARC) or spin-coated carbon film), or photoresist toplayer films (upper antireflective film (TARC)). It not only improves EBR characteristics, repair characteristics, and coating performance of the photoresist film, photoresist underlayer film, or photoresist toplayer film, but also provides excellent RRC characteristics. Particularly in the case of g-line, i-line, KrF, ArF, EUV, or EB photoresists, since the basic structures of the constituent photoresists differ, the composition content of the organic solvent must be adjusted to improve the solubility and coating properties of all compositions; however, the diluent composition of the present invention meets this requirement. As long as the requirements of this embodiment described above are met, compositions other than the diluent composition described in the examples also exhibit the same effects.

[0174] 4. In-plane uniformity The resins (i) to (iv) described above were mixed with the solvents listed in Table 1, and the concentrations of resin (i) were adjusted to 30 wt%, resin (ii) to 35 wt%, resin (iii) to 15 wt%, and resin (iv) to 25 wt%, respectively. The concentrations of the acid-producing agents (ii) and (v) were also adjusted to 1 wt%. Then, a nonionic surfactant FTX-218 (polyoxyethylene alkyl ether, manufactured by Neos Corporation) at a weight relative to the resin was added at 500 ppm to prepare a semiconductor manufacturing composition for in-plane uniformity measurement.

[0175] Then, using the prepared semiconductor manufacturing composition, a coating was spin-coated onto a silicon wafer at 1500 rpm to form a film. This coating 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 along the diameter of the silicon wafer to evaluate in-plane uniformity. The evaluation method for in-plane uniformity is as follows. The results are shown in Tables 6 and 7.

[0176] 3σ (%) = 3 × 49 points standard deviation of film thickness (nm) / 49 points average film thickness (nm) × 100 Evaluation A: 3σ < 2% Evaluation B: 2% ≤ 3σ < 5% Evaluation C: 3σ ≥ 5% [Table 6] [Table 7] As shown in Tables 6 and 7, the semiconductor manufacturing compositions prepared in Examples 7-1 to 7-6 and 8-1 to 8-6 exhibit 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. The compound represented by formula (1), 。 2. A composition for semiconductor manufacturing, characterized in that, It contains a solvent (B), which comprises a compound (B1) represented by the following general formula (b-1). In the formula, R1, R2, R3 and R4 independently represent hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, phenyl groups or benzyl groups.

3. The semiconductor manufacturing composition according to claim 2, characterized in that, R1, R2, R3, and R4 each independently represent an alkyl group having 1 to 3 hydrogen atoms or carbon atoms.

4. The semiconductor manufacturing composition according to claim 2, characterized in that, The compound (B1) is selected from 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, and 2,5-dimethyl-1,3-dioxolane-4-one. One or more of the following: 2-methyl-1,3-dioxolane-4-one, 2-ethyl-5,5-dimethyl-1,3-dioxolane-4-one (EDDO), 2-ethyl-5-methyl-1,3-dioxolane-4-one, 2-ethyl-1,3-dioxolane-4-one, 2,2,5-trimethyl-1,3-dioxolane-4-one, and 2,2-dimethyl-1,3-dioxolane-4-one.

5. The composition for semiconductor manufacturing as claimed in any one of claims 2 to 4, characterized in that, The solvent (B) contains, as compound (B2) other than compound (B1), one or more compounds selected from those shown in 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 with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, or an acyl group with 1 to 10 carbon atoms, and R6 represents an alkyl group with 1 to 10 carbon atoms.

6. The semiconductor manufacturing composition as claimed in claim 5, characterized in that, 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 semiconductor manufacturing composition as described in claim 5 or 6, characterized in that, Based on a total amount of solvent (B) of 100% by mass, it contains more than 10% by mass of the compound represented by the general formula (b-2).

8. The composition for semiconductor manufacturing as claimed in any one of claims 2 to 7, characterized in that, Based on a total amount of solvent (B) of 100% by mass, the compound (B1) contains more than 0.5% by mass.

9. The composition for semiconductor manufacturing as claimed in any one of claims 2 to 8, characterized in that, The composition for semiconductor manufacturing is a photoresist composition.

10. The composition for semiconductor manufacturing as claimed in any one of claims 2 to 8, characterized in that, The composition for semiconductor manufacturing is a resist-assisted film composition.

11. The semiconductor manufacturing composition as claimed in claim 10, characterized in that, The resist auxiliary film is either a lower resist film or an intermediate resist film.

12. The composition for semiconductor manufacturing as claimed in any one of claims 2 to 8, characterized in that, The composition for semiconductor manufacturing is a diluent composition.

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