Solvent and semiconductor composition using same

Abstract

The present invention is a solvent containing a compound (A1) represented by general formula (a-1) and having a boiling point of 190°C or higher. (In the formula, R1 represents a hydrogen atom, a C1-10 alkyl group, a C6-10 aryl group, or a C1-10 acyl group, and R2 represents a C1-10 alkyl group.)

Description

Solvent and semiconductor composition using the same

[0001] The present invention relates to a solvent and a semiconductor composition 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, followed by exposure and development, followed by etching or other processes to form a circuit pattern on the wafer, and finally peeling and removing the resist.

[0003] In recent years, semiconductors have become more sophisticated and smaller in size, 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 performance of the resist may be reduced due to the influence of reflection of the exposure light source from the wafer or standing waves. To address this problem, a technique is known in which a bottom anti-reflective coating (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, resist films, resist auxiliary films, etc. can generally be formed by applying a solution in which a resist material is dissolved and heating it at a relatively high temperature. Furthermore, thinner compositions are solutions, and by applying these, residues, contaminants, etc. can be removed. In other words, these semiconductor manufacturing compositions are solutions, and in order to respond to further miniaturization of pattern dimensions in semiconductors, the selection of solvents used in semiconductor manufacturing compositions is also important.

[0010] That is, for solvents that can be used in conventional semiconductor manufacturing compositions, for example, when treating a semiconductor manufacturing composition (solution) at a relatively high temperature to form, for example, a resist film, a resist auxiliary film, etc., there has been a demand for appropriate suppression of solvent evaporation from the solution during high-temperature treatment, from the viewpoint of further improving the quality of the formed film, etc. Furthermore, there has been room for improvement in solubility in order to effectively dissolve a target substance when producing a conventional semiconductor manufacturing composition or when dissolving a substance using a semiconductor manufacturing composition.

[0011] Therefore, an object of the present invention is to provide a solvent having a high boiling point and high solubility, and a composition for manufacturing a semiconductor containing the solvent.

[0012] [1] A solvent containing a compound (A1) represented by the following general formula (a-1) and having a boiling point of 190° C. or higher: (In the formula, 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 ２represents an alkyl group having 1 to 10 carbon atoms.) [2] 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 represents an alkyl group having 5 to 10 carbon atoms. [3] The solvent according to [1] or [2] above, wherein the compound (A1) is isopentyl 2-hydroxy-2-methylpropanoate (iAHIB). [4] The solvent according to any one of [1] to [3] above, containing the compound (A1) in an amount of 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, containing, as the solvent (A2) other than the compound (A1), one or more selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), γ-butyrolactone (GBL), and a compound (A3) represented by the general formula (a-1) and having a boiling point of less than 190°C. [6] The solvent according to [5] above, wherein the compound (A3) is at least one 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] above, wherein the solvent (A2) is contained in an amount of 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

[10] above, 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, it is possible to provide a solvent having a high boiling point and high solubility, and a composition for manufacturing a semiconductor containing the solvent.

[0014] An example of an embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described in detail below, but the present invention is not limited to this embodiment.

[0015] 1. Solvent The solvent of this embodiment contains a compound (A1) represented by the following general formula (a-1) and having a boiling point of 190° C. or higher. In the above formula, 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. Hereinafter, the solvent containing the compound (A1) of this embodiment will also be referred to as solvent (A).

[0016] According to the solvent (A) of this embodiment, the compound (A1) can have a high boiling point and high solubility, and therefore the solvent (A) of this embodiment can also have a high boiling point and high solubility. Therefore, for example, when a composition (solution) obtained by dissolving a desired material is treated at a high temperature (e.g., 200°C or higher), the solvent (A) of this embodiment can appropriately suppress the evaporation of the solvent from the composition (solution) at high temperatures, thereby improving the quality of the product. Furthermore, when used to dissolve a desired material, the solvent (A) can easily dissolve the material. Note that the effects of the solvent (A) of this embodiment are not limited to those described above, and other effects resulting from the high boiling point and high solubility described above can also be exhibited.

[0017] (Compound (A1)) The compound (A1) (hereinafter also simply referred to as compound (A1)) contained in the solvent (A) of the present embodiment and represented by the following general formula (a-1) and having a boiling point of 190°C or higher will be described.

[0018] In the above general formula (a-1), R １represents 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. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. 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, an n-pentyl group, an i-pentyl group, a 2-methylbutyl group, a 1-methylbutyl group, a 1,2-dimethylpropyl group, a neopentyl group, a t-pentyl group, an n-hexyl group, a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,2-dimethylbutyl group, a 2,3-dimethyl Examples thereof include a butyl group, a 3,3-dimethylbutyl group, a 1-ethylbutyl group, a 2-ethylbutyl group, a 1,1,2-trimethylpropyl group, a 1,2,2-trimethylpropyl group, an n-heptyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 2,2-dimethylpentyl group, a 2,3-dimethylpentyl group, a 2,4-dimethylpentyl group, a 3,3-dimethylpentyl group, a 3-ethylpentyl group, a 2,2,3-trimethylbutyl group, an n-octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, and a cyclohexyl group.

[0019] The aryl group having 6 to 10 carbon atoms is not particularly limited, and examples thereof 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.

[0020] The acyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof 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. Note that 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.

[0021] Of these, R １ is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom, a formyl group, or an acetyl group, and most preferably a hydrogen atom.

[0022] In the above general formula (a-1), R ２ represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is R １ The alkyl group having 1 to 10 carbon atoms is preferably an alkyl group having 3 to 10 carbon atoms, more preferably an alkyl group having 5 to 10 carbon atoms, still more preferably an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, an s-butyl group, a t-butyl group, an n-pentyl group, an i-pentyl group, a 2-methylbutyl group, a 1-methylbutyl group, a 1,2-dimethylpropyl group, a neopentyl group, or an n-hexyl group, and particularly preferably an i-pentyl group.

[0023] In one embodiment, R １ is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 3 carbon atoms, and R ２is preferably an alkyl group having 3 to 10 carbon atoms. More preferably, R １ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an acyl group having 1 to 3 carbon atoms, and R ２ is an alkyl group having 5 to 10 carbon atoms. １ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms, and R ２ is an alkyl group having 5 to 10 carbon atoms. １ is a hydrogen atom, a formyl group, or an acetyl group, and R ２ is an n-pentyl group, an i-pentyl group, a 2-methylbutyl group, a 1-methylbutyl group, a 1,2-dimethylpropyl group, a neopentyl group, or an n-hexyl group. １ is a hydrogen atom, and R ２ is an i-pentyl group.

[0024] Furthermore, compound (A1) is a compound represented by the above general formula (a-1) that has a boiling point of 190°C or higher. Because compound (A1) has such a high boiling point, solvent (A) of this embodiment can also have a high boiling point. The boiling point of compound (A1) may be 195°C or higher, or may be 200°C or higher. Furthermore, the upper limit of the boiling point may be 250°C or lower, or may be 230°C or lower.

[0025] Specific examples of the compound (A1) represented by general formula (a-1) and having a boiling point of 190°C or higher include, but are not limited to, compounds represented by formulas (a-1-1) to (a-1-16).

[0026] In this embodiment, among the compounds represented by the above formulas (a-1-1) to (a-1-16), the compound (A1) is preferably a compound represented by formula (a-1-1), (a-1-2), (a-1-3, isopentyl 2-hydroxy-2-methylpropanoate, iAHIB), (a-1-6), (a-1-7), (a-1-13), or (a-1-15), more preferably a compound represented by formula (a-1-3). The above-mentioned compound (A1) may be used alone or in combination of two or more.

[0027] In this embodiment, the viscosity of compound (A1) at room temperature (25°C) is preferably 2.5 mPa·s or more, more preferably 2.6 mPa·s or more. The upper limit of the viscosity is not particularly limited, but may be 6.0 mPa·s or less, or may be 5.0 mPa·s or less. When a solvent (A) containing compound (A1) is used in a semiconductor manufacturing composition, the quality of the resulting 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. The viscosity of the solvent and compound can be measured at 25°C using a viscometer based on an electromagnetic spinning method, a rotational viscometer, or a vibration viscometer.

[0028] Here, the method for producing the compound (A1) is not particularly limited. For example, the compound (A1) can be produced by adding R １ Side and R ２ The R １ The side part is R １ When the moiety is an alkyl or aryl group, for example, R １ and can be formed by a dehydration etherification reaction between the corresponding alcohol and the acid derivative moiety. １ When is an acyl group, R １ and can be formed by reacting the corresponding acid anhydride with the derivative moiety. ２ The side part is R ２ is an ester structure, so R２ an esterification reaction of an alcohol containing R ２ The derivative can be formed by transesterification with an ester compound containing R １ Side part, R ２ The order in which the side portions are formed is not limited and may be any order. １ is a hydrogen atom, R ２ Form the side parts.

[0029] In this embodiment, the solvent (A) may be a solvent consisting of the compound (A1), but may also contain a solvent other than the compound (A1). Specifically, when a solvent other than the compound (A1) is contained, the solvent (A2) that may be contained preferably includes one or more selected from the group consisting of 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 (GBL) (boiling point: 204°C), diethylene glycol monoethyl ether acetate (DEEA) (boiling point: 216°C), and the compound (A3) represented by the general formula (a-1) and having a boiling point of less than 190°C. More preferably, the solvent (A2) contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), γ-butyrolactone (GBL), and the compound (A3) represented by the general formula (a-1) and having a boiling point of less than 190° C. Even more preferably, the solvent (A2) contains one or more selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), and the compound (A3) represented by the general formula (a-1) and having a boiling point of less than 190° C.

[0030] In this embodiment, the solvent (A) contains the solvent (A2) in addition to the compound (A1), thereby making it possible to adjust the boiling point and solubility. The other solvents (A2) may be used alone or in combination of two or more.

[0031] As the solvent (A2), a compound (A3) represented by general formula (a-1) and having a boiling point of less than 190° C. can be selected. Specifically, the compound (A3) can be as follows: In the compound (A3), 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. Specific examples of the alkyl group having 1 to 10 carbon atoms, the aryl group having 6 to 10 carbon atoms, and the acyl group having 1 to 10 carbon atoms may be the same as those of the compound (A1) described above.

[0032] In the compound (A3), R in the general formula (a-1) １ is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an acyl group having 1 to 3 carbon atoms, and R ２ is preferably a methyl group, an ethyl group, an n-propyl group, or an i-propyl group. １ is a hydrogen atom, a methyl group, an ethyl group, a formyl group, or an acetyl group, and R ２ is more preferably a methyl group or an i-propyl group. １ is a hydrogen atom, a methyl group, or an acetyl group, and R ２ However, it is more preferably a methyl group.

[0033] Furthermore, compound (A3) is a compound represented by the above general formula (a-1) that has a boiling point of less than 190°C. The boiling point of compound (A3) is more preferably 100°C or higher and lower 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.

[0034] Specific examples of compound (A3) include, but are not limited to, 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). Of these, compound (A3) 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). The above-mentioned compound (A3) may be used alone or in combination of two or more kinds.

[0035] In this embodiment, the solvent (A) preferably contains the compound (A1) in an amount of 5% by mass or more, based on the total amount (100% by mass) of the solvent (A). The solvent (A) more preferably contains the compound (A1) in an amount of 7.5% by mass or more, and even more preferably 10% by mass or more, based on the total amount (100% by mass) of the solvent (A). The upper limit of the content of the compound (A1) in the solvent (A) is not particularly limited and can be adjusted, for example, depending on the application. The compound (A1) may be the total amount (100% by mass) of the solvent (A), or may be 95% by mass or less, or 80% by mass or less, based on the total amount (100% by mass) of the solvent (A). The content of the compound (A1) may be 5 to 100% by mass, 5 to 95% by mass, 5 to 80% by mass, 5 to 60% by mass, 5 to 40% by mass, 5 to 35% by mass, 5 to 25% by mass, 5 to 20% by mass, 10 to 100% by mass, 10 to 95% by mass, 10 to 80% by mass, 10 to 60% by mass, 10 to 40% by mass, 10 to 35% by mass, 10 to 25% by mass, 10 to 20% by mass, 20 to 100% by mass, 20 to 95% by mass, 20 to 80% by mass, 20 to 60% by mass, 20 to 40% by mass, or 20 to 35% by mass, based on the total amount (100% by mass) of the solvent (A). By containing 5% by mass or more of the compound (A1) having a high boiling point and high solubility, the solvent (A) can also effectively have a high boiling point and high solubility.

[0036] Furthermore, when solvent (A) contains solvent (A2) as a solvent other than compound (A1), it is preferable that solvent (A2) be contained in an amount of 10% by mass or more based on the total amount (100% by mass) of solvent (A). Furthermore, solvent (A) more preferably contains solvent (A2) in an amount of 30% by mass or more based on the total amount (100% by mass) of solvent (A), even more preferably 45% by mass or more, even more preferably 55% by mass or more, and most preferably 60% by mass or more. The upper limit of the content of solvent (A2) in solvent (A) is not particularly limited and can be adjusted, for example, depending on the application. Solvent (A2) may be 95% by mass or less, 92.5% by mass or less, or 90% by mass or less based on the total amount (100% by mass) of solvent (A). It can also be the total amount of solvent (A) other than compound (A1). In addition, the content of the solvent (A2) is 10 to 95% by mass, 10 to 92.5% by mass, 10 to 85% by mass, 10 to 80% by mass based on the total amount (100% by mass) of the solvent (A). % by mass, 10-75% by mass, 30-95% by mass, 30-92.5% by mass, 30-85% by mass, 30-80% by mass, 30-75% by mass, 45-95% by mass, 4 5-92.5% by mass, 45-85% by mass, 45-80% by mass, 45-75% by mass, 55-95% by mass, 55-92.5% by mass, 55-85% by mass, 55- It may be 80% by mass, 55-75% by mass, 60-95% by mass, 60-92.5% by mass, 60-85% by mass, 60-80% by mass, or 60-75% by mass. When the solvent (A) contains the solvent (A2) in an amount of 10 mass % or more based on the total amount (100 mass %) of the solvent (A), the boiling point and solubility can be adjusted.

[0037] In the present embodiment, when the solvent (A) contains a solvent other than the compound (A1), the boiling point of the solvent other than the compound (A1) is preferably 130°C or higher and lower than 190°C, and may also be 130 to 180°C or 135 to 170°C.

[0038] In this embodiment, the solvent contained in solvent (A) having a boiling point of 190°C or higher preferably has a viscosity of 2.5 mPa·s or higher at room temperature (25°C), more preferably 2.6 mPa·s or higher. The upper limit of the viscosity is not particularly limited, but may be 6.0 mPa·s or lower, or may be 5.0 mPa·s or lower. When solvent (A) has a viscosity of 2.5 mPa·s or higher, when the solvent is used in a semiconductor manufacturing composition, the quality of the resulting 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. The viscosity of the solvent and compound can be measured at 25°C using a viscometer based on an electromagnetic spinning method, a rotational viscometer, or a vibration viscometer.

[0039] In this embodiment, when solvent (A) contains solvent (A2) as a solvent other than compound (A1), preferred combinations of compound (A1) and solvent (A2) in solvent (A) include a combination of isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and propylene glycol monomethyl ether acetate (PGMEA), a combination of isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and methyl 2-hydroxyisobutyrate (HBM), and a combination of isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and propylene glycol monomethyl ether (PGME). When solvent (A) contains a combination of isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and propylene glycol monomethyl ether acetate (PGMEA), the ratio of iAHIB to PGMEA is preferably 5:95 to 35:65. When the solvent (A) contains a combination of isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and methyl 2-hydroxyisobutyrate (HBM), the ratio of iAHIB to HBM is preferably 5:95 to 35:65.

[0040] 2. Composition for Manufacturing Semiconductors Next, the composition for manufacturing semiconductors according to this embodiment will be described. The composition for manufacturing semiconductors according to this embodiment contains the solvent (A) of this embodiment described above. As described above, the solvent (A) has a high boiling point and high solubility. By including the solvent (A) in the composition for manufacturing semiconductors, volatilization of the solvent in the composition for manufacturing semiconductors can be suppressed when the composition for manufacturing semiconductors is treated at a relatively high temperature to form, for example, a resist film, a resist auxiliary film, or the like. As a result, the quality of the obtained product, for example, uniformity and surface flatness, can be further improved.

[0041] Furthermore, by including the solvent (A) in the semiconductor manufacturing composition, when preparing the semiconductor manufacturing composition or when dissolving a substance using the semiconductor manufacturing composition, the target substance can be quickly and appropriately dissolved. Specifically, various resins, additives, etc. are dissolved to prepare the semiconductor manufacturing composition, and their good and rapid dissolution can affect the quality and productivity of the product from the semiconductor manufacturing composition. Therefore, when the solvent (A) has high solubility, various resins, additives, etc. can be quickly or appropriately dissolved, resulting in, for example, improved product quality. Alternatively, when using the semiconductor manufacturing composition to remove residues or contaminants generated during the semiconductor manufacturing process, the substance to be removed can be quickly and appropriately dissolved.

[0042] Here, the semiconductor manufacturing composition of this embodiment may be a resist composition, a resist auxiliary film composition, or a thinner composition.For example, when the semiconductor manufacturing composition of this embodiment is a resist composition, specifically, for example, when the semiconductor manufacturing composition 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, since the semiconductor manufacturing composition contains a solvent (A) with a high boiling point, the solvent may not volatilize early during coating film formation.As a result, the surface flatness and in-plane uniformity of the coating film (resist film, resist auxiliary film) may be improved.

[0043] Furthermore, when the composition for manufacturing a semiconductor of this embodiment is a resist composition or a resist auxiliary film composition, since the composition for manufacturing a semiconductor contains the solvent (A) exhibiting high solubility, defects, etc., may be less likely to occur in the resulting resist film, resist auxiliary film, etc. Furthermore, particularly when used as a resist composition, the ability to dissolve a high concentration of resin allows the resist film to be made thick, and a resist film used for three-dimensional mounting can be formed.

[0044] Furthermore, when the composition for manufacturing a semiconductor of this embodiment is a thinner composition, the composition for manufacturing a semiconductor contains the solvent (A) exhibiting high solubility, and therefore can suitably dissolve components of the resist film, resist auxiliary film, etc., such as resins and photoacid generators (PAGs), thereby enabling an EBR process or the like to be performed, which removes residues and contaminants with high efficiency.

[0045] 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.

[0046] Depending on the intended use of the composition for manufacturing a semiconductor, the composition for manufacturing a semiconductor may further contain components suitable for that intended use. Each intended use will be described below.

[0047] [Resist Composition] The resist composition contains a photosensitive resin (B1) in addition to the solvent (A) of this embodiment described above. It may further contain a photosensitizer, a photoacid generator (PAG), additives, etc., as necessary. By including the solvent (A), 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.

[0048] (Solvent (A)) The solvent (A) includes those described above.

[0049] The content of the solvent (A) 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.

[0050] (Photosensitive Resin (B1)) The photosensitive resin (B1) 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 (B1).

[0051] Specific examples of the photosensitive resin (B1) 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 (B1) 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.

[0052] 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.

[0053] 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.

[0054] 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.

[0055] These photosensitive resins (B1) may be used alone or in combination of two or more.

[0056] The content of the photosensitive resin (B1) 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.

[0057] (Photosensitizer) The resist composition may contain a photosensitizer. Examples of photosensitizers include those that are generally used as photosensitive components in positive resist compositions.

[0058] 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.

[0059] Commercially available photosensitizers include "DTEP-350" (diazonaphthoquinone-type photosensitizer, manufactured by Daito ChemiX Co., Ltd.).

[0060] These photosensitizers may be used alone or in combination of two or more.

[0061] The content of the photosensitizer is 0.01 to 80 parts by mass, more preferably 0.05 to 65 parts by mass, even more preferably 0.1 to 50 parts by mass, and still more preferably 0.5 to 30 parts by mass, relative to 100 parts by mass of the resin (B1).

[0062] (Photoacid Generator (PAG)) The resist composition may contain a photoacid generator. A photoacid generator is a compound that can generate an acid directly or indirectly when irradiated with radiation such as visible light, ultraviolet light, an excimer laser, an electron beam, extreme ultraviolet light (EUV), X-rays, or an ion beam.

[0063] 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.

[0064] 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-dihydroxynaphthyl)dimethylsulfonium 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate.

[0065] 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.

[0066] The imide sulfonate is not particularly limited, but examples thereof include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, and N-(trifluoromethylsulfonyloxy)diphenylmaleimide.

[0067] The diazodisulfone is not particularly limited, but examples thereof include bis(cyclohexylsulfonyl)diazomethane, bis(4-methylphenylsulfonyl)diazomethane, and the like.

[0068] 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.

[0069] 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.

[0070] 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.).

[0071] These photoacid generators may be used alone or in combination of two or more.

[0072] 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 still more preferably 0.5 to 30 parts by mass, relative to 100 parts by mass of the resin (B1).

[0073] (Additives) The resist composition may contain additives.

[0074] 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.

[0075] 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 still more preferably 0.3 to 30 parts by mass, relative to 100 parts by mass of the resin (B1).

[0076] (Coating Method) The coating method for the resist composition of this embodiment is not particularly limited, and examples include spin coating and slit coating. Of these, the coating method for the resist composition of this embodiment is preferably spin coating. That is, the resist composition of this embodiment may be 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.

[0077] [Resist auxiliary film composition] The resist auxiliary film is a film that can be used together with the above-mentioned resist film, and examples thereof include a resist underlayer film used in a two-layer resist method, a resist underlayer film used in a three-layer resist method, a resist middle layer film, etc. Note that the resist auxiliary film does not include the resist film, i.e., the outermost film of the resist.

[0078] 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.

[0079] In one embodiment, the resist sub-coat is a bottom anti-reflective coating (BARC).

[0080] The resist auxiliary film composition varies depending on the desired function, but contains a resin (B2) in addition to the solvent (A) of this embodiment. 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 (A), the resist auxiliary film composition may be able to form a uniform resist auxiliary film, etc.

[0081] (Solvent (A)) The solvent includes the above-mentioned solvent (A).

[0082] The content of the solvent (A) in the resist auxiliary film composition is preferably 50 mass % or more, more preferably 60 to 98 mass %, and even more preferably 65 to 95 mass %, based on the total amount (100 mass %) of the resist auxiliary film composition.

[0083] (Resin (B2)) Examples of the resin (B2) include photosensitive resin (B1), silicon-containing resin, and naphthalene formaldehyde resin.

[0084] The photosensitive resin (B1) is the same as that described above.

[0085] 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.

[0086] Naphthalene formaldehyde resins include reaction products of naphthalene and / or alkylnaphthalene with formaldehyde.

[0087] These resins (B2) may be used alone or in combination of two or more.

[0088] The content of the resin (B2) 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.

[0089] (Photosensitizer and Photoacid Generator (PAG)) The photosensitizer and photoacid generator (PAG) are the same as those described above.

[0090] The content of the photosensitizer is 0.01 to 80 parts by mass, more preferably 0.05 to 65 parts by mass, even more preferably 0.1 to 50 parts by mass, and still more preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (B2).

[0091] 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 still more preferably 0.5 to 30 parts by mass, per 100 parts by mass of the resin (B2).

[0092] (Crosslinking Agent) The crosslinking agent has the function of crosslinking the resin (B2) to prevent intermixing.

[0093] 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); and alkenyl ether compounds such as ethylene glycol divinyl ether and triethylene glycol divinyl ether.

[0094] These crosslinking agents may be used alone or in combination of two or more.

[0095] 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 (B2).

[0096] 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.

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

[0098] The content of the additive is not particularly limited, but is preferably 0.001 to 100 parts by mass, more preferably 0.01 to 70 parts by mass, even more preferably 0.1 to 50 parts by mass, and still more preferably 0.3 to 30 parts by mass, relative to 100 parts by mass of resin (B2).

[0099] (Coating method) The coating method of the resist auxiliary film composition of this embodiment 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 this embodiment is preferably spin coating. That is, the resist auxiliary film composition of this embodiment may be a resist auxiliary film composition that is coated by spin coating. By applying the resist auxiliary film composition by spin coating, for example, the obtained resist auxiliary film has the effect of having excellent in-plane uniformity.

[0100] [Thinner Composition] The thinner composition contains the solvent (A) of the present embodiment described above. It may further contain additives, etc., as necessary. Since the solvent (A) has high solubility, the thinner composition containing the solvent (A) can suitably dissolve components of the resist film, resist auxiliary film, etc. (resin (B1), resin (B2), photoacid generator (PAG), crosslinker, etc.). As a result, an EBR process or the like can be performed to remove residues and contaminants with high efficiency.

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

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

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

[0104] [Semiconductor Manufacturing Method] Next, a semiconductor manufacturing method of this embodiment will be described. The semiconductor manufacturing method of this embodiment includes a resist film forming step of applying (preferably spin coating) a resist composition onto a wafer to form a resist film, a resist pattern forming step, and an etching step. In this case, 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.

[0105] 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, in which 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 of this embodiment (resist composition or thinner composition) described above.

[0106] By performing the pretreatment step, it is possible to coat the substrate with a small amount of photoresist. Furthermore, a resist film can be formed in the resist film formation step. Residues and contaminants on the edge and / or back surface of the substrate can be removed in the resist film cleaning step. As a result, resolution performance can be improved in the resist pattern formation step. In the resist pattern formation step, a pattern can be formed by exposing and developing the resist. In this case, a short-wavelength exposure light source is preferably used for the exposure. This allows for miniaturization of the pattern dimensions.

[0107] 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.

[0108] In a preferred embodiment, the method includes a pretreatment step, a resist auxiliary film forming step, a resist auxiliary film cleaning step, a resist film forming step, a resist auxiliary film and / or resist film cleaning step, a resist pattern forming step, and an etching step, in this order. In this case, one of the resist auxiliary film cleaning step and the resist auxiliary film and / or resist film cleaning step may be omitted. Furthermore, at least one of the thinner composition used in the pretreatment step, the resist auxiliary film composition used in the resist auxiliary film forming step, the thinner composition used in the resist auxiliary film cleaning step, the resist film composition used in the resist film forming step, and the thinner composition used in the resist auxiliary film and / or resist film cleaning step is the semiconductor manufacturing composition of this embodiment (resist composition, resist auxiliary film composition, or thinner composition).

[0109] 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.

[0110] Although the embodiments of the present invention have been described above, the present invention is not limited to the above examples and can be modified as appropriate.

[0111] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples in any way.

[0112] A resist auxiliary film composition was formed using the solvent of each Example and Comparative Example, and a resist underlayer film was further formed using the composition, and the solvent was evaluated.

[0113] 1. Preparation of Solvents The solvents used in each Example and Comparative Example were prepared as follows. [Example 1-1] The solvent used in Example 1-1 was a mixture of isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of 10:90. Isopentyl 2-hydroxy-2-methylpropanoate was prepared by the following method. 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.), 176.3 g of 3-methyl-1-butanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.42 g of tetraisopropyl orthotitanate. The mixture was reacted under reflux at atmospheric pressure for 9 hours, with the resulting methanol being withdrawn from the top of the column. The reaction temperature fluctuated from 113.6° C. to 152.4° C. Distillation under reduced pressure gave 107.2 g of isopentyl 2-hydroxy-2-methylpropanoate (GC purity 99.6%) as a fraction at 81 hPa and 118.6° C.

[0114] Example 1-2 As the solvent in Example 1-2, a solvent prepared by mixing isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of 30:70 was used.

[0115] Example 1-3 As the solvent in Example 1-3, a solvent prepared by mixing isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and methyl 2-hydroxyisobutyrate (HBM) in a mass ratio of 10:90 was used.

[0116] Example 1-4 As the solvent in Example 1-4, a solvent prepared by mixing isopentyl 2-hydroxy-2-methylpropanoate (iAHIB) and methyl 2-hydroxyisobutyrate (HBM) in a mass ratio of 30:70 was used.

[0117] Comparative Example 1-1 As the solvent for Comparative Example 1-1, a solvent prepared by mixing isopropyl 2-hydroxyisobutyrate (iPHIB) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of 10:90 was used.

[0118] Comparative Example 1-2 As the solvent for Comparative Example 1-2, a solvent obtained by mixing propylene glycol monomethyl ether (PGME) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of 30:70 was used.

[0119] Comparative Example 1-3 As the solvent for Comparative Example 1-3, a solvent obtained by mixing diethylene glycol monoethyl ether acetate (DEEA) and propylene glycol monomethyl ether acetate (PGMEA) in a mass ratio of 10:90 was used.

[0120] The solvents produced in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3 are shown in Table 1 below.

[0121]

[0122] The structures of the compound (A1) and the solvent (A2) are shown below.

[0123] The viscosities of the compounds (A1) and (A2) used are as follows: iAHIB: 3.54 mPa·s PGMEA: 1.1 mPa·s HBM: 2.82 mPa·s iPHIB: 2.21 mPa·s PGME: 1.7 mPa·s DEEA: 2.49 mPa·s The viscosities of the solvents and compounds 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.

[0124] 2. Preparation of Resist Auxiliary Coating Composition (Semiconductor Manufacturing Composition) Resist auxiliary coating compositions were prepared as follows using the solvents prepared in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-3. [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 1-1 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 7.61% 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 coating composition. In this case, FTX-218 was used in an amount of 0.1% by mass relative to the mass of the novolak resin.

[0125] Examples 2-2 to 2-4, Comparative Examples 2-1 to 2-3 Resist auxiliary film compositions were prepared in the same manner as in Example 2-1, except that the solvents prepared in Examples 1-2 to 1-4 or Comparative Examples 1-1 to 1-3 were used instead of the solvent prepared in Example 1-1. 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.

[0126] [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 to 2-3, and the in-plane uniformity and EBR properties were evaluated.

[0127] (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.

[0128] (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 2 below. 3σ (%) = 3 × 115 film thickness standard deviation (nm) / 115-point average film thickness (nm) × 100 A: 3σ < 0.8% C: 3σ ≥ 0.8%

[0129] (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 2 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.

[0130]

[0131] The results in Table 2 show that the semiconductor manufacturing compositions of Examples 2-1 to 2-4 were able to form uniform resist underlayer films by containing iAHIB, which has a high boiling point and excellent solubility. On the other hand, the semiconductor manufacturing compositions of Comparative Examples 2-1 and 2-2 are thought to have had poor in-plane uniformity due to the early evaporation of the solvent during curing and baking. Furthermore, the semiconductor manufacturing composition of Comparative Example 2-3 contained DEEA, which has a high boiling point, and was therefore able to suppress the early evaporation of the solvent during curing and baking, thereby demonstrating excellent 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 after EBR, resulting in poor EBR properties.

[0132] According to the present invention, it is possible to provide a solvent having a high boiling point and high solubility, and a composition for manufacturing a semiconductor containing the solvent.

Claims

1. A solvent containing a compound (A1) represented by the following general formula (a-1) and having a boiling point of 190°C or higher: (In the formula, 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. 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 5 to 10 carbon atoms.

3. The solvent according to claim 1, wherein the compound (A1) is isopentyl 2-hydroxy-2-methylpropanoate (iAHIB).

4. The solvent according to claim 1, containing the compound (A1) in an amount of 5 mass % or more based on the total amount (100 mass %) of the solvent.

5. The solvent according to claim 1, wherein the solvent (A2) other than the compound (A1) comprises one or more selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), γ-butyrolactone (GBL), and a compound (A3) represented by the general formula (a-1) and having a boiling point of less than 190°C.

6. The solvent according to claim 5, wherein the compound (A3) 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 solvent (A2) is contained in an amount of 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.

Images