Solvent and composition for semiconductor production using same

Abstract

Provided is a solvent or the like having a high boiling point and high solubility.　The solvent contains a compound (B1) represented by general formula (b-1). (In the formula, A represents a C1-10 alkylene group, R1 represents a hydrogen atom, a C-10 alkyl group, a C6-10 aryl group, or a C1-10 acyl group, and R2 represents a C1-10 alkyl group.)

Description

Solvent and composition for semiconductor manufacturing using the same

[0001] The present invention relates to a solvent and a composition for manufacturing a semiconductor using the same.

[0002] In the manufacture of semiconductors, microfabrication is carried out by lithography using photoresist materials. Lithography typically involves forming a resist on a wafer, exposing and developing it, then forming a circuit pattern on the wafer by etching or other methods, and finally removing the resist.

[0003] In recent years, semiconductors have become more sophisticated and smaller in size, and there is a demand for further miniaturization of pattern dimensions.

[0004] In order to cope with such miniaturization of pattern dimensions, short wavelength light sources are 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 laser (wavelength 248 nm) and ArF excimer laser (wavelength 193 nm), and extreme ultraviolet rays (EUV).

[0005] However, when a short-wavelength exposure light source is used, the resolution of the resist may be reduced due to the effects of reflection of the exposure light source from the wafer and standing waves. To address this problem, a technique is known in which a bottom anti-reflective coating (BARC) is formed between the resist and the wafer as a resist auxiliary film (see, for example, Patent Document 1).

[0006] 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 thinner composition is used before the exposure step to remove residues and contaminants from the resist film, anti-reflective coating (BARC), and the like, known as an EBR (edge ​​bead removing) step (see, for example, Patent Document 2).

[0007] 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.

[0008] International Publication No. 2004 / 034148 Japanese Patent Application Laid-Open No. 2015-232708 Japanese Patent Application Laid-Open No. 2019-137612

[0009] Here, the resist film, the resist auxiliary film, etc. are generally formed by applying a solution and heating it. The thinner composition is a solution, and by applying this solution, residues, contaminants, etc. are removed.

[0010] That is, these semiconductor manufacturing compositions are solutions, and in order to respond to further miniaturization of semiconductor pattern dimensions, the selection of solvents used in semiconductor manufacturing compositions is also important. For example, if a solvent with a low boiling point is used, the solvent may volatilize early during coating film formation, which may result in reduced surface flatness and in-plane uniformity of the resulting resist film and resist auxiliary film. Furthermore, if a solvent with low material solubility is used, defects may be more likely to occur in the resulting resist film and resist auxiliary film, and it may take a long time to remove residues and contaminants. Therefore, the present invention provides a solvent or the like having a high boiling point and high solubility.

[0011] The present invention is, for example, as follows.

[0012] [1] A solvent containing a compound (B1) represented by the following general formula (b-1): (wherein, A represents an alkylene group having 1 to 10 carbon atoms; R １ 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; R ２ represents an alkyl group having 1 to 10 carbon atoms.) [2] A represents an alkylene group having 1 to 5 carbon atoms, R １represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms; R ２ represents an alkyl group having 1 to 3 carbon atoms. [3] The solvent according to [1] above, wherein the compound (B1) is 1-methoxypropan-2-yl-2-hydroxy-2-methylpropanoate (PMHIB). [4] The solvent according to any one of [1] to [3] above, wherein the content of the compound (B1) is 5 mass% or more based on the total amount (100 mass%) of the solvent. [5] The solvent according to any one of [1] to [4] above, further comprising, as a solvent (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, R ３ 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; R ４represents an alkyl group having 1 to 10 carbon atoms.) [6] The solvent according to [5] above, wherein the compound represented by general formula (b-2) is one or more selected from the group consisting of methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), isopropyl 2-hydroxyisobutyrate (i-PHIB), butyl 2-hydroxyisobutyrate (n-BHIB), and isobutyl 2-hydroxyisobutyrate (i-BHIB). [7] The solvent according to [5] or [6] above, wherein the content of the compound represented by general formula (b-2) is 10 mass% or more based on the total amount (100 mass%) of the solvent. [8] A composition for manufacturing a semiconductor, comprising the solvent according to any one of [1] to [7] above. [9] The composition for manufacturing a semiconductor according to [8] above, which is a resist composition.

[10] The composition for manufacturing a semiconductor according to [8] above, which is a resist auxiliary film composition.

[11] The composition for manufacturing a semiconductor according to the above

[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 the above [8], which is a thinner composition.

[0013] According to the present invention, a solvent or the like having a high boiling point and high solubility is provided.

[0014] Hereinafter, embodiments of the present invention will be described in detail.

[0015] 1. Solvent The solvent according to the present invention contains a compound (B1) represented by general formula (b-1). The solvent may further contain a solvent (B2) other than the compound (B1). In this specification, when a solvent contains two or more solvents, the solvent may be referred to as a "solvent composition."

[0016] The compound (B1) represented by general formula (b-1) can have a high boiling point and high solubility. Therefore, the solvent according to the present invention can also have a high boiling point and high solubility. Furthermore, by combining a solvent (B2) other than the compound (B1), the boiling point and material solubility can be adjusted. When the solvent according to the present invention is used in, for example, a semiconductor manufacturing composition, the solvent does not volatilize early during coating film formation, which can improve the surface flatness and in-plane uniformity of the coating film (resist film, resist auxiliary film, etc.). Furthermore, due to its high solubility, defects in the coating film (resist film, resist auxiliary film, etc.) are less likely to occur, and residues and contaminants can be removed with a small amount of solvent and / or in a short time.

[0017] <Compound (B1)> The compound (B1) is represented by the following general formula (b-1).

[0018] In the above formula, A represents an alkylene group having 1 to 10 carbon atoms. The alkylene group having 1 to 10 carbon atoms may be linear or branched. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, and groups represented by the following formulas (A-1) to (A-18). In formulas (A-1) to (A-18), "*" represents a bond to an oxygen atom.

[0019] Among these, A is preferably an alkylene group having 1 to 10 carbon atoms, more preferably a methylene group, an ethylene group, a propylene group, a butylene group, or a group represented by any of formulas (A-2) to (A-5), and even more preferably a group represented by any of formulas (A-2) to (A-3).

[0020] R １ 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.

[0021] 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.

[0022] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2-isopropylphenyl group, a 3-isopropylphenyl group, a 2,6-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, a 2-naphthyl group, a 4-biphenyl group, an anthracenyl group, a 1-fluorenyl group, and a 2-fluorenyl group.

[0023] Examples of acyl groups having 1 to 10 carbon atoms include formyl, methylcarbonyl (acetyl), ethylcarbonyl, n-propylcarbonyl, i-propylcarbonyl, n-butylcarbonyl, i-butylcarbonyl, s-butylcarbonyl, t-butylcarbonyl, pentylcarbonyl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, nonylcarbonyl, benzoyl, and naphthoyl groups. The term "acyl group" refers to an alkylcarbonyl group, and in this specification, the carbon atom of the carbonyl group is included in the carbon atoms of the "acyl group." Therefore, for example, a methylcarbonyl group (acetyl group) has 2 carbon atoms.

[0024] Of these, R １is preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acyl group having 1 to 5 carbon atoms, even more preferably a hydrogen atom, 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 formyl group, an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, an n-butylcarbonyl group, an i-butylcarbonyl group, an s-butylcarbonyl group, or a t-butylcarbonyl group, particularly preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms, extremely preferably a hydrogen atom, a methyl group, or an acetyl group, and most preferably a hydrogen atom. １ is preferably a hydrogen atom. １ is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, further preferably 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, or a t-butyl group, particularly preferably an alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. In one embodiment, R １ is preferably an acyl group having 1 to 10 carbon atoms, more preferably an acyl group having 1 to 5 carbon atoms, further preferably a formyl group, an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, an n-butylcarbonyl group, an i-butylcarbonyl group, an s-butylcarbonyl group, or a t-butylcarbonyl group, particularly preferably an acyl group having 1 to 3 carbon atoms, and most preferably an acetyl group.

[0025] R ２represents an alkyl group having 1 to 10 carbon atoms. 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. Of these, R ２ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0026] In one embodiment, A represents an alkylene group having 1 to 5 carbon atoms; R １ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms; R ２ In a preferred embodiment, A represents a group represented by formula (A-2) to (A-3), and R １ represents a hydrogen atom, R ２ In a preferred embodiment, A represents a group represented by formula (A-2) to (A-3), and R １ represents an alkyl group having 1 to 3 carbon atoms, and R ２ preferably represents a methyl group or an ethyl group, A represents a group represented by formula (A-2) to (A-3), and R １ represents a methyl group, R ２ More preferably, A represents a methyl group. In a preferred embodiment, A represents a group represented by formula (A-2) to (A-3), and R １ represents an acyl group having 1 to 3 carbon atoms, and R ２ preferably represents a methyl group or an ethyl group, A represents a group represented by formula (A-2) to (A-3), and R １ represents an acetyl group, and R ２ More preferably, represents a methyl group.

[0027] Examples of compound (B1) include compounds represented by formulas (b-1-1) to (b-1-24). The compound represented by formula (b-1-1) is 1-methoxypropan-2-yl-2-hydroxy-2-methylpropanoate (PMHIB) (boiling point: 202°C).

[0028] Of the above, compound (B1) preferably includes at least one selected from the group consisting of compounds represented by formulas (b-1-1) to (b-1-10), more preferably includes at least one selected from the group consisting of compounds represented by formulas (b-1-1) to (b-1-4), and further preferably includes a compound (PMHIB) represented by formula (b-1-1).

[0029] The above-mentioned compound (B1) may be used alone or in combination of two or more kinds.

[0030] The boiling point of the compound (B1) is preferably 190°C or higher, more preferably 190 to 260°C, more preferably 200 to 260°C, even more preferably 190 to 240°C, even more preferably 200 to 240°C, and particularly preferably 200 to 220°C.

[0031] The viscosity of compound (B1) is preferably 2.5 mPa·s or more, more preferably 2.6 mPa·s or more, even more preferably 3.0 mPa·s or more, and particularly preferably 3.5 mPa·s or more. The upper limit of the viscosity is not particularly limited, but may be 10.0 mPa·s or less, 8.0 mPa·s or less, 6.0 mPa·s or less, or even 5.0 mPa·s or less. When the viscosity of compound (B1) is 2.5 mPa·s or more, when a solvent containing compound (B1) is used in a semiconductor manufacturing composition, the quality of the obtained product can be more effectively improved when the semiconductor manufacturing composition is treated at a relatively high temperature to form, for example, a resist film, a resist auxiliary film, etc. In this specification, the viscosity of compound (B1) and solvent (B2) can be measured at 25°C using a viscometer based on an electromagnetic spinning method, a rotational viscometer, or a vibration viscometer.

[0032] The content of compound (B1) is preferably 3% by mass or more, more preferably 5% by mass or more, based on the total amount (100% by mass) of the solvent, and is preferably 5 to 100% by mass, 15 to 100% by mass, 40 to 100% by mass, 5 to 90% by mass, 15 to 90% by mass, 40 to 90% by mass, 5 to 70% by mass, 15 to 70% by mass, 40 to 70% by mass, 5 to 50% by mass, 15 to 50% by mass, 40 to 50% by mass, It is more preferably 0 mass%, 5 to 25 mass%, 15 to 25 mass%, or 5 to 15 mass%, particularly preferably 5 to 90 mass%, 15 to 90 mass%, 5 to 70 mass%, 15 to 70 mass%, 5 to 50 mass%, 15 to 50 mass%, 5 to 25 mass%, 15 to 25 mass%, or 5 to 15 mass%, and most preferably 5 to 25 mass%, 15 to 25 mass%, or 5 to 15 mass%.

[0033] <Solvent (B2) Other Than Compound (B1)> The solvent according to the present invention preferably further contains a solvent (B2) other than compound (B1). By combining compound (B1) with solvent (B2), the volatility and solubility of the solvent can be adjusted.

[0034] The solvent (B2) is not particularly limited as long as it is a solvent other than the compound (B1). Examples of the solvent (B2) include, but are not particularly limited to, a compound represented by the following general formula (b-2), propylene glycol monomethyl ether acetate (PGMEA) (boiling point: 146°C), propylene glycol monomethyl ether (PGME) (boiling point: 120°C), cyclohexanone (CHN) (boiling point: 155.6°C), ethyl lactate (EL) (boiling point: 154°C), γ-butyrolactone (γ-BL) (boiling point: 204°C), dipropylene glycol methyl ether acetate (DPMA) (boiling point: 213°C), and diethylene glycol monoethyl ether acetate (DEEA) (boiling point: 216°C).

[0035]

[0036] In general formula (b-2), R ３ 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.

[0037] 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.

[0038] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2-isopropylphenyl group, a 3-isopropylphenyl group, a 2,6-dimethylphenyl group, a 3,5-dimethylphenyl group, a 2,4,6-trimethylphenyl group, a naphthyl group, a 2-naphthyl group, a 4-biphenyl group, an anthracenyl group, a 1-fluorenyl group, and a 2-fluorenyl group.

[0039] Examples of the acyl group having 1 to 10 carbon atoms include a formyl group, a methylcarbonyl group (acetyl group), an ethylcarbonyl group, an n-propylcarbonyl group, an i-propylcarbonyl group, an n-butylcarbonyl group, an i-butylcarbonyl group, an s-butylcarbonyl group, a t-butylcarbonyl group, a pentylcarbonyl group, a hexylcarbonyl group, a heptylcarbonyl group, an octylcarbonyl group, a 2-ethylhexylcarbonyl group, a nonylcarbonyl group, a benzoyl group, and a naphthoyl group.

[0040] Of these, R ３ 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 even more preferably a hydrogen atom. ３ is a hydrogen atom. ３ is preferably an alkyl group having 1 to 3 carbon atoms or an acyl group having 1 to 3 carbon atoms, more preferably a methyl group, an ethyl group, a formyl group or an acetyl group, and even more preferably a methyl group.

[0041] R ４represents an alkyl group having 1 to 10 carbon atoms. 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. Of these, R ４ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0042] In one embodiment, R ３ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms; R ４ preferably represents a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. ３ represents a hydrogen atom, R ４ preferably represents a methyl group or an ethyl group, and R ３ represents a hydrogen atom, R ４ More preferably, R represents a methyl group. ３ represents an alkyl group having 1 to 3 carbon atoms, and R ４ preferably represents a methyl group or an ethyl group, and R ３ represents a methyl group, R ４ More preferably, R represents a methyl group. ３ represents an acyl group having 1 to 3 carbon atoms, and R ４ preferably represents a methyl group or an ethyl group, and R ３ represents an acetyl group, and R ４ More preferably, represents a methyl group.

[0043] Specific examples of the compound represented by general formula (b-2) are not particularly limited, and include methyl 2-hydroxyisobutyrate (HBM) (boiling point: 137°C), methyl α-formyloxyisobutyrate (FBM) (boiling point: 160°C), methyl α-acetoxyisobutyrate (ABM) (boiling point: 162°C), isopropyl 2-hydroxyisobutyrate (i-PHIB) (boiling point: 155°C), isobutyl 2-hydroxyisobutyrate (i-BHIB) (boiling point: 181°C), and normal butyl 2-hydroxyisobutyrate (n-BHIB) (boiling point: 187°C). Among these, the compound represented by general formula (b-2) preferably contains 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 more preferably contains methyl 2-hydroxyisobutyrate (HBM).

[0044] In one embodiment, the solvent (B2) preferably contains one or more selected from the group consisting of the compound 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). It is more preferable that the compound contains one or more selected from the group consisting of methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), isopropyl 2-hydroxyisobutyrate (i-PHIB), butyl 2-hydroxyisobutyrate (n-BHIB), and isobutyl 2-hydroxyisobutyrate (i-BHIB), and it is more preferable that the compound contains a compound represented by general formula (b-2), and it is even more preferable that the compound contains one or more selected from the group consisting of methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), isopropyl 2-hydroxyisobutyrate (i-PHIB), butyl 2-hydroxyisobutyrate (n-BHIB), and isobutyl 2-hydroxyisobutyrate (i-BHIB).

[0045] The other solvents (B2) may be used alone or in combination of two or more.

[0046] The boiling point of the solvent (B2) is preferably less than 190°C, more preferably 100°C or more and less than 190°C, and even more preferably 100 to 180°C, 120 to 180°C, 140 to 180°C, 160 to 180°C, 100 to 160°C, 120 to 160°C, 140 to 160°C, 100 to 140°C, 120 to 140°C, or 100 to 120°C.

[0047] The content of the solvent (B2) is preferably 10% by mass or more, more preferably 10 to 95% by mass, 20 to 95% by mass, 40 to 95% by mass, 60 to 95% by mass, 80 to 95% by mass, 10 to 80% by mass, 20 to 80% by mass, 40 to 80% by mass, 60 to 80% by mass, 10 to 60% by mass, 20 to 60% by mass, 40 to 60% by mass, 10 to 40% by mass, 20 to 40% by mass, or 10 to 20% by mass, still more preferably 60 to 95% by mass, 80 to 95% by mass, or 60 to 80% by mass, and particularly preferably 80 to 95% by mass. In one embodiment, the content of the compound represented by general formula (b-2) is preferably 10% by mass or more, more preferably 10 to 95% by mass, 20 to 95% by mass, 40 to 95% by mass, 60 to 95% by mass, 80 to 95% by mass, 10 to 80% by mass, 20 to 80% by mass, 40 to 80% by mass, 60 to 80% by mass, 10 to 60% by mass, 20 to 60% by mass, 40 to 60% by mass, 10 to 40% by mass, 20 to 40% by mass, or 10 to 20% by mass, still more preferably 60 to 95% by mass, 80 to 95% by mass, or 60 to 80% by mass, and particularly preferably 80 to 95% by mass.

[0048] 2. Composition for Manufacturing Semiconductors According to one aspect of the present invention, a composition for manufacturing semiconductors is provided. The composition for manufacturing semiconductors includes the solvent according to the present invention. The solvent according to the present invention has a high boiling point and high solubility, and is therefore preferably used in semiconductor manufacturing applications. For example, the composition for manufacturing semiconductors according to the present invention has at least one of the following effects: a uniform coating film is formed; components contained in a resist film or a resist auxiliary film are suitably dissolved; and the like.

[0049] According to one embodiment, the semiconductor manufacturing composition is a resist composition. According to another embodiment, the semiconductor manufacturing composition is a resist auxiliary film composition. According to another embodiment, the semiconductor manufacturing composition is a thinner composition.

[0050] For example, since the composition for semiconductor manufacturing according to the present invention contains a solvent with a high boiling point, when it is used as a resist composition used to form a resist film or a resist auxiliary film composition used to form a resist auxiliary film, the solvent does not volatilize early during the formation of the coating film, which can improve the surface flatness and in-plane uniformity of the coating film (resist film, resist auxiliary film).

[0051] Furthermore, since the semiconductor manufacturing composition according to the present invention contains a solvent exhibiting high solubility, when used as a resist composition or resist auxiliary film composition, defects in the resulting resist film, resist auxiliary film, etc. can be reduced. Furthermore, particularly when used as a resist composition, the ability to dissolve high concentrations of resins allows for thicker resist films to be formed, making it possible to form resist films used in three-dimensional packaging. When the semiconductor manufacturing composition according to the present invention is used as a thinner composition, it can favorably dissolve components of the resist film, resist auxiliary film, etc., such as resins and photoacid generators (PAGs). As a result, EBR processes, etc., that remove residues and contaminants can be performed with high efficiency.

[0052] The composition for manufacturing a semiconductor may further contain components suitable for the intended use, depending on the intended use of the composition for manufacturing a semiconductor. Each intended use will be described below.

[0053] [Resist Composition] The resist composition contains a photosensitive resin (A1) in addition to the solvent of the present invention. It may further contain a photosensitizer, a photoacid generator (PAG), additives, etc., as necessary. By including the solvent of the present invention, the resist composition may be able to achieve low viscosity and form a uniform resist film. In particular, the resist composition is suitable for use in the production of thick resist films for applications such as three-dimensional packaging. In this specification, the term "thick film" refers to a film thickness of 1 μm or more, preferably 1 to 100 μm, more preferably 1 to 20 μm, and even more preferably 1 to 15 μm.

[0054] (Solvent) The solvent includes the solvent according to the present invention described above.

[0055] The content of the solvent is preferably 50% by mass or more, more preferably 60 to 99.5% by mass, and even more preferably 65 to 99% by mass, based on the total amount (100% by mass) of the resist composition.

[0056] (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).

[0057] Specific examples of the photosensitive resin (A1) include novolac resins, cresol 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] These photosensitive resins (A1) may be used alone or in combination of two or more.

[0062] The content of the photosensitive resin (A1) is preferably 50% by mass or less, more preferably 0.5 to 40% by mass, and even more preferably 1 to 35% by mass, based on the total amount (100% by mass) of the resist composition.

[0063] (Photosensitizer) The resist composition may contain a photosensitizer. Examples of photosensitizers include those that are generally used as photosensitive components in positive resist compositions.

[0064] 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.

[0065] Commercially available photosensitizers include "DTEP-350" (diazonaphthoquinone-type photosensitizer, manufactured by Daito ChemiX Co., Ltd.).

[0066] These photosensitizers may be used alone or in combination of two or more.

[0067] 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 particularly preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (A1).

[0068] (Photoacid Generator (PAG)) The resist composition may contain a photoacid generator (PAG). 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.

[0069] The photoacid generator is not particularly limited, but examples thereof include ionic photoacid generators such as sulfonium salts and iodonium salts; and nonionic photoacid generators such as imidosulfonates, diazodisulfones, and oximesulfonates.

[0070] The sulfonium 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, triphenylsulfonium nonafluoro-n-butanesulfonate, and (4,7-dihydroxy-1-naphthyl)dimethylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0071] The iodonium salt is not particularly limited, but examples thereof include bis(4-t-butylphenyl)iodonium trifluoromethanesulfonate and bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate.

[0072] The imide sulfonate is not particularly limited, but examples thereof include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, and N-(trifluoromethylsulfonyloxy)diphenylmaleimide.

[0073] The diazodisulfone is not particularly limited, but examples thereof include bis(cyclohexylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, and the like.

[0074] 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.

[0075] From the viewpoint of high solubility in solvents, the above-mentioned photoacid generator preferably contains at least one of a sulfonium 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, (4,7-dihydroxynaphthyl)dimethylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate, and bis(cyclohexylsulfonyl)diazomethane.

[0076] 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.), and NDS-169 (manufactured by Midori Chemical Industry Co., Ltd.).

[0077] These photoacid generators may be used alone or in combination of two or more.

[0078] The content of the photoacid generator 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 particularly preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (A1).

[0079] (Additives) The resist composition may contain additives.

[0080] 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.

[0081] 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 (A1).

[0082] (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 advantages of, for example, providing a resist film with excellent in-plane uniformity and easily thickening the resist film.

[0083] [Resist auxiliary film composition] The resist auxiliary film is a film that can be used together with a 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.

[0084] 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.

[0085] In one embodiment, the resist sub-coat is a bottom anti-reflective coating (BARC).

[0086] The resist auxiliary film composition varies depending on the desired function, but contains a resin (A2) in addition to the solvent of the present invention. If necessary, the resist auxiliary film composition may further contain a photosensitizer, a photoacid generator (PAG), a crosslinking agent, an additive, etc. By including the solvent of the present invention, the resist auxiliary film composition may be able to form a uniform resist auxiliary film, etc.

[0087] (Solvent) The solvent includes the solvent according to the present invention described above.

[0088] The content of the solvent is preferably 50% by mass or more, more preferably 60 to 98% by mass, and even more preferably 65 to 95% by mass, based on the total amount (100% by mass) of the resist auxiliary film composition.

[0089] (Resin (A2)) Examples of the resin (A2) include photosensitive resin (A1), silicon-containing resin, and naphthalene formaldehyde resin.

[0090] The photosensitive resin (A1) is the same as that described above.

[0091] 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.

[0092] Naphthalene formaldehyde resins include reaction products of naphthalene and / or alkylnaphthalene with formaldehyde.

[0093] These resins (A2) may be used alone or in combination of two or more.

[0094] The content of the resin (A2) 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 auxiliary film composition.

[0095] (Photosensitizer and Photoacid Generator (PAG)) The photosensitizer and photoacid generator (PAG) are the same as those described above.

[0096] 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 particularly preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (A2).

[0097] The content of the photoacid generator 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 particularly preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (A2).

[0098] (Crosslinking Agent) The crosslinking agent has the function of crosslinking the resin (A2) to prevent intermixing.

[0099] 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, tetramethoxymethylurea, and 1,3,4,6-tetrakis(methoxymethyl)tetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione (MX-270 manufactured by Nippon Carbide Industries Co., Ltd.); and alkenyl ether compounds such as ethylene glycol divinyl ether and triethylene glycol divinyl ether.

[0100] These crosslinking agents may be used alone or in combination of two or more.

[0101] 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).

[0102] In addition, a crosslinking catalyst such as p-toluenesulfonic acid (PPTS), dinonylnaphthalenedisulfonic acid, dinonylnaphthalene(mono)sulfonic acid, phosphoric acid, or the like can be used in combination with the crosslinking agent.

[0103] (Additives) The additives are the same as those described above.

[0104] 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).

[0105] (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.

[0106] [Thinner Composition] The thinner composition contains the solvent according to the present invention. It may further contain additives, etc., as necessary. By containing the solvent according to the present invention, the thinner composition can suitably dissolve components of the resist film, resist auxiliary film, etc. (resin (A1), resin (A2), photoacid generator (PAG), crosslinking agent, etc.). As a result, an EBR process or the like can be performed to remove residues and contaminants with high efficiency.

[0107] (Solvent) The content of the solvent 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.

[0108] (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.

[0109] 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.

[0110] [Method for Manufacturing a Semiconductor] According to one aspect of the present invention, a method for manufacturing a semiconductor is provided.

[0111] 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.

[0112] 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).

[0113] 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. The resist film cleaning step can remove residues and contaminants from the edge and / or back surface of the substrate. As a result, the 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.

[0114] 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.

[0115] In a preferred embodiment, the method includes, in this order, 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 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.

[0116] 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.

[0117] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0118] 1. Preparation of Solvent [Example 1-1] 1-Methoxypropan-2-yl-2-hydroxy-2-methylpropanoate (PMHIB) (boiling point: 202°C) was used alone as the solvent.

[0119] PMHIB was produced by the following method. That is, a 500 mL glass round-bottom flask equipped with a condenser, a distillation column (height: 500 mm, inner diameter: 30φ), and a stirrer was charged with 118.1 g of methyl 2-hydroxyisobutyrate (manufactured by Mitsubishi Gas Chemical Company, Inc.), 180.2 g of propylene glycol monomethyl ether (PGME, boiling point: 120 ° C, manufactured by Sigma-Aldrich), and 2.84 g of tetraisopropyl orthotitanate (TTIP). The mixture was heated to reflux under normal pressure (1 atm) and reacted for 5 hours while withdrawing the resulting methanol from the top of the column. The reaction temperature ranged from 124.7 ° C to 135.2 ° C. 61.2 g of PMHIB (GC purity 99.4%) was produced as a fraction at 40 hPa and 95 ° C by vacuum distillation.

[0120] Example 1-2 A mixture of PMHIB and propylene glycol monomethyl ether acetate (PGMEA) (boiling point: 146° C.) was used as a solvent, with a mass ratio of PHMIB to PGMEA (PHMIB:PGMEA) of 10:90.

[0121] Example 1-3 A solvent was prepared in the same manner as in Example 1-2, except that the mass ratio of PHMIB to PGMEA (PHMIB:PGMEA) was changed to 30:70.

[0122] [Examples 1-4] A mixture of PMHIB and methyl 2-hydroxyisobutyrate (HBM) (boiling point: 137°C) was used as a solvent, with a mass ratio of PHMIB to HBM (PHMIB:HBM) of 10:90.

[0123] Example 1-5 A solvent was prepared in the same manner as in Example 1-4, except that the mass ratio of PHMIB to HBM (PHMIB:HBM) was changed to 30:70.

[0124] Comparative Example 1-1 PGMEA was used alone as the solvent.

[0125] Comparative Example 1-2 Dipropylene glycol monomethyl ether acetate (DPMA) (boiling point: 213° C.) (mixture of isomers) was used alone as the solvent.

[0126] Comparative Example 1-3 A mixture of diethylene glycol monoethyl ether acetate (DEEA) (boiling point: 216° C.) and PGMEA was used as a solvent, with a mass ratio of DEEA to PGMEA (DEEA:PGMEA) of 10:90.

[0127] Comparative Example 1-4 A mixture of PGME and PGMEA was used as a solvent, with a mass ratio of PGME to PGMEA (PGME:PGMEA) of 30:70.

[0128] The solvents produced in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-4 are shown in Table 1 below.

[0129]

[0130] The structures of the compound (B1) and the solvent (B2) are shown below.

[0131] The viscosities of the compound (B1) and the solvent (B2) were measured at 25°C using an EMS viscometer (manufactured by Kyoto Electronics Manufacturing Co., Ltd.), which is a viscometer based on the electromagnetic spinning method. The results are as follows: PMHIB: 4.8 mPa·s, PGMEA: 1.1 mPa·s, HBM: 2.82 mPa·s, DPMA: 2.31 mPa·s, DEEA: 2.49 mPa·s, PGME: 1.7 mPa·s

[0132] [Solubility Evaluation] Solubility evaluation was carried out for the solvents of Examples 1-1 to 1-5 and Comparative Example 1-2.

[0133] Specifically, MX-270, a crosslinking agent represented by the following formula, was added to the solvent at a concentration of 5% by mass, or p-toluenesulfonic acid pyridinium salt (PPTS), a crosslinking catalyst, was added to the solvent at a concentration of 0.1% by mass. After stirring at room temperature (25°C) for 24 hours, the solubility was evaluated according to the following criteria. The results are shown in Table 2 below. A: The added crosslinking agent or crosslinking catalyst was dissolved (a clear solution was confirmed by visual inspection). C: The added crosslinking agent or crosslinking catalyst was insoluble (a cloudy solution was confirmed by visual inspection).

[0134]

[0135] The results in Table 2 show that the solvents of Examples 1-1 to 1-5 can suitably dissolve the crosslinking agent and the crosslinking catalyst. Therefore, it is believed that the solvents of Examples 1-1 to 1-5 can be suitably used in semiconductor compositions, such as resist compositions and resist auxiliary film compositions.

[0136] 2. Preparation of Resist Auxiliary Film Composition (Semiconductor Manufacturing Composition) [Example 2-1] EP4050G (weight average molecular weight: 4000-6000, manufactured by Asahi Organic Chemicals Co., Ltd.), a novolak resin represented by the following formula, crosslinker A represented by the following formula, and PPTS, a crosslinking catalyst, were added to the solvent of Example 1-2 and mixed. Crosslinker A was used in an amount of 30% by mass relative to the mass of EP4050G, and PPTS was used in an amount of 2.5% by mass relative to the mass of EP4050G. The total solids content (total content of components excluding the solvent) was 7.37% by mass. Next, FTX-218 (polyoxyethylene alkyl ether, manufactured by Neos Corporation), a nonionic surfactant, was further added, and the mixture was filtered through a membrane filter with a pore size of 0.2 μm to prepare a resist auxiliary film composition. FTX-218 was used in an amount of 0.1% by mass relative to the mass of the novolak resin.

[0137] Examples 2-2 to 2-4, Comparative Examples 2-1 to 2-2 Resist auxiliary film compositions were prepared in the same manner as in Example 2-1, except that the solvents prepared in Examples 1-3 to 1-5 or Comparative Examples 1-3 and 1-4 were used instead of the solvent prepared in Example 1-2. However, in the evaluation of the resist compositions described below, the solid content was appropriately adjusted so that the formed resist underlayer film had a thickness of 190 nm.

[0138] [Evaluation of Resist Compositions] Resist underlayer films were formed using the resist auxiliary film compositions produced in Examples 2-1 to 2-4 and Comparative Examples 2-1 and 2-2, and the in-plane uniformity and EBR properties were evaluated.

[0139] (Formation of resist underlayer film) The resist auxiliary film composition thus prepared was applied to an 8-inch silicon wafer by spin coating at 1500 rpm, and then a mixed solution of PGMEA and PGME (mass ratio: PGMEA:PGME=70:30) was used to perform EBR (Edge Bead Removal) treatment and back-rinse treatment to form a coating film. The obtained coating film was cured and baked at 240°C for 60 seconds to form a resist underlayer film with a thickness of 190 nm.

[0140] (Evaluation of In-Plane Uniformity) The thickness of the resist underlayer film was measured at 115 points across the entire surface of the silicon wafer. The film thickness unevenness 3σ was calculated using the following formula, and the in-plane uniformity was evaluated according to the following criteria. The results are shown in Table 3 below. 3σ (%) = 3 × standard deviation of film thickness at 115 points (nm) / average film thickness at 115 points (nm) × 100 A: 3σ < 0.8% C: 3σ ≥ 0.8%

[0141] (Evaluation of EBR properties) The edge shape of the resist underlayer film was observed using a digital microscope. The width (μm) of the interference fringes at the edge of the resist underlayer film was measured, and the EBR properties were evaluated according to the following criteria. The results are shown in Table 3 below. A: The width of the interference fringes is less than 20 μm. B: The width of the interference fringes is 20 μm or more and less than 60 μm. C: The width of the interference fringes is 60 μm or more.

[0142]

[0143] The results in Table 3 demonstrate that the semiconductor manufacturing compositions of Examples 2-1 to 2-4, containing PMHIB, which has a high boiling point and excellent solubility, are capable of forming uniform resist underlayer films. On the other hand, the semiconductor manufacturing composition of Comparative Example 2-1, containing DEEA, which has a high boiling point, was able to suppress early volatilization of the solvent during curing and baking, thereby demonstrating excellent effects in in-plane uniformity. However, DEEA has a low viscosity and a large amount of residual solvent in the coating film, which is thought to have caused sagging at the edge portions after EBR and resulted in poor EBR performance. Furthermore, the semiconductor manufacturing composition of Comparative Example 2-2, containing PGME, which has a low boiling point, was able to reduce the amount of residual solvent in the coating film and reduced sagging at the edge portions after EBR, thereby demonstrating excellent effects in EBR performance. However, it is thought that the early volatilization of the solvent during curing and baking resulted in poor in-plane uniformity.

[0144] 3. Production of thinner compositions (compositions for manufacturing semiconductors) [Examples 3-1 to 3-5] The solvents produced in Examples 1-1 to 1-5 were used as thinner compositions.

[0145] Comparative Example 3-1 The solvent prepared in Comparative Example 1-1 was used as a thinner composition.

[0146] [Evaluation of Thinner Compositions] The thinner compositions produced in Examples 3-1 to 3-5 and Comparative Example 3-1 were evaluated for solubility of a photoacid generator (PAG).

[0147] WPAG-336 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) or NDS-169 (manufactured by Midori Chemical Co., Ltd.), a photoacid generator (PAG) represented by the following formula, was added to the thinner composition so that the concentration was 5 wt %, and the mixture was stirred at room temperature (25°C). After 24 hours, the presence or absence of dissolution of the photoacid generator was confirmed visually and evaluated according to the following criteria. The results are shown in Table 4 below. A: The added photoacid generator was dissolved (a clear solution was confirmed visually). C: The added photoacid generator was insoluble (a cloudy solution was confirmed visually).

[0148]

[0149] The results in Table 4 show that the thinner compositions of the examples were able to dissolve the photoacid generators effectively. Therefore, by using the thinner compositions of Examples 3-1 to 3-5, residues and contaminants can be removed with high efficiency.

Claims

1. A solvent containing a compound (B1) represented by the following general formula (b-1): (wherein, A represents an alkylene group having 1 to 10 carbon atoms; R １ 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; R ２ represents an alkyl group having 1 to 10 carbon atoms.

2. A represents an alkylene group having 1 to 5 carbon atoms, and R １ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms; R ２ The solvent according to claim 1, wherein represents an alkyl group having 1 to 3 carbon atoms.

3. The solvent according to claim 1, wherein the compound (B1) is 1-methoxypropan-2-yl-2-hydroxy-2-methylpropanoate (PMHIB).

4. The solvent according to claim 1, wherein the content of the compound (B1) is 5% by mass or more based on the total amount (100% by mass) of the solvent.

5. The solvent according to claim 1, further comprising, as a solvent (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, R ３ 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; R ４ represents an alkyl group having 1 to 10 carbon atoms.

6. The solvent according to claim 5, wherein the compound represented by general formula (b-2) is one or more selected from the group consisting of methyl 2-hydroxyisobutyrate (HBM), methyl α-formyloxyisobutyrate (FBM), methyl α-acetoxyisobutyrate (ABM), isopropyl 2-hydroxyisobutyrate (i-PHIB), butyl 2-hydroxyisobutyrate (n-BHIB), and isobutyl 2-hydroxyisobutyrate (i-BHIB).

7. The solvent according to claim 5, wherein the content of the compound represented by general formula (b-2) is 10 mass % or more based on the total amount (100 mass %) of the solvent.

8. A composition for semiconductor manufacturing, comprising the solvent according to any one of claims 1 to 7.

9. The composition for semiconductor manufacturing according to claim 8, which is a resist composition.

10. The composition for semiconductor manufacturing according to claim 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 semiconductor manufacturing according to claim 8, which is a thinner composition.

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