Resist pattern forming method and semiconductor device manufacturing method

Abstract

The present invention provides a chemical liquid having excellent defect inhibition properties, a chemical liquid storage body, a kit, and a method for manufacturing a semiconductor chip.SOLUTION: The chemical solution according to the embodiment of the present invention is a chemical solution containing an organic solvent, in which the chemical solution contains at least one kind of first organic compound selected from the group consisting of compounds represented by Formulae (I) to (V), and a total content of the first organic compound is 0.01 to 100000 mass ppt with respect to a total mass of the chemical solution.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a chemical solution, a chemical solution container, a kit, and a method for manufacturing a semiconductor chip. [Background technology]

[0002] During the manufacture of semiconductor devices by a wiring formation process including photolithography, chemical solutions containing water and / or organic solvents are used as pre-wet solutions, resist solutions (resist film-forming compositions), developers, rinse solutions, stripping solutions, chemical mechanical polishing (CMP) slurries, and post-CMP cleaning solutions, or as dilutions thereof. In recent years, advances in photolithography technology have led to advances in pattern miniaturization. One method for achieving this is to shorten the wavelength of the exposure light source, and attempts are being made to form patterns using even shorter wavelength light such as extreme ultraviolet (EUV) as the exposure light source, instead of conventionally used ultraviolet light, KrF excimer lasers, and ArF excimer lasers. As the patterns to be formed become finer, the chemicals used in this process are required to have even greater defect suppression properties.

[0003] As a chemical liquid used in conventional pattern formation, Patent Document 1 discloses "a method for producing an organic processing liquid for patterning chemically amplified resist films, which can reduce particle generation in pattern formation technology (paragraph

[0010] )." [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-84122 Summary of the Invention [Problem to be solved by the invention]

[0005] The inventors have investigated the organic processing liquid (chemical liquid) for patterning manufactured by the above manufacturing method and found that there is room for improvement in defect suppression. More specifically, when the chemical liquid is used as a prewet liquid or a rinse liquid, there is room for improvement in suppressing defects such as metal residue defects, particulate organic residue defects, and stain-like residue defects. Furthermore, when the chemical liquid is used as a pattern developer, there is room for improvement in suppressing defects such as poor development defects, residue defects, and uniformity defects. An object of the present invention is to provide a chemical solution that is excellent in suppressing defects as described above. Another object of the present invention is to provide a drug solution container, a kit, and a method for manufacturing a semiconductor chip. [Means for solving the problem]

[0006] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0007] (1) A chemical solution containing an organic solvent, Contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III) described below, A chemical solution in which the total content of the first organic compounds is 0.01 to 100,000 ppt by mass relative to the total mass of the chemical solution. (2) The chemical solution according to (1), further comprising at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII) described below. (3) The chemical solution according to (2), which contains at least two or more compounds selected from the first organic compound and the second organic compound. (4) The drug solution according to (3), wherein at least one of the two or more compounds has a ClogP value of 5 or more. (5) The drug solution according to any one of (2) to (4), wherein at least one of the two or more compounds contains a compound represented by general formula (VI). (6) The chemical solution according to (5), wherein the ratio of the content of the compound represented by general formula (VI) to the total content of the first organic compound and the second organic compound other than the compound represented by general formula (VI) is 0.01 to 1. (7) Further, it contains a metal component, The chemical solution according to any one of (1) to (6), wherein the content of the metal component is 0.1 to 500 ppt by mass relative to the total mass of the chemical solution. (8) The chemical solution according to (7), wherein the ratio of the total content of the first organic compound to the content of the metal component is 0.01 to 10,000. (9) The chemical solution according to (2), further containing a metal component. (10) The chemical solution according to (9), wherein the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component is 0.01 to 50,000. (11) The chemical solution according to (9) or (10), wherein the metal component contains metal particles and metal ions. (12) The chemical solution according to (11), wherein the ratio of the total content of the first organic compound and the second organic compound to the content of the metal particles is 0.01 to 50,000. (13) The chemical solution according to (11) or (12), wherein the ratio of the total content of the first organic compound and the second organic compound to the content of the metal ions is 0.03 to 30,000. (14) The organic solvent is propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, diisoamyl ether, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol The drug solution according to any one of (1) to (13), wherein the hydroxybenzoate is selected from the group consisting of ethanol, propylene glycol, ethylene carbonate, propylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate. (15) The chemical solution according to any one of (1) to (14), wherein the organic solvent has a volume resistivity of 5,000,000 Ωm or more. (16) A kit containing two or more selected from the group consisting of a pre-wet liquid containing the chemical solution according to any one of (1) to (15), a developer containing the chemical solution according to any one of (1) to (15), a rinse liquid containing the chemical solution according to any one of (1) to (15), a polishing liquid containing the chemical solution according to any one of (1) to (15), and a composition for forming a resist film containing the chemical solution according to any one of (1) to (15). (17) A method for treating a vascular disease comprising: a container; and a medicinal solution according to any one of (1) to (15) contained in the container; A chemical container in which the liquid-contacting portion that comes into contact with the chemical solution in the container is made of electropolished stainless steel or fluorine-based resin. (18) The drug solution container according to (17), wherein the void ratio within the container calculated by the formula (X) described below is 5 to 30% by volume. (19) A method for manufacturing a semiconductor chip, comprising manufacturing a semiconductor chip using the chemical solution according to any one of (1) to (15). [Effects of the Invention]

[0008] According to the present invention, a chemical solution having excellent defect suppression properties can be provided. The present invention also provides a drug solution container, a kit, and a method for manufacturing a semiconductor chip. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. The following description of the components may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In the present invention, "ppm" stands for "parts-per-million (10 -6 ) and "ppb" stands for "parts-per-billion (10 -9 ) and "ppt" stands for "parts-per-trillion (10 -12 ) and "ppq" stands for "parts-per-quadrillion (10 -15 )" Furthermore, in the description of groups (atomic groups) in the present invention, when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups that do not have a substituent and groups that contain a substituent, as long as it does not impair the effects of the present invention. For example, the term "hydrocarbon group" encompasses not only hydrocarbon groups that do not have a substituent (unsubstituted hydrocarbon groups), but also hydrocarbon groups that contain a substituent (substituted hydrocarbon groups). This also applies to each compound. In the present invention, "radiation" refers to, for example, far ultraviolet, extreme ultraviolet (EUV), X-rays, or electron beams. In the present invention, "light" refers to actinic rays or radiation. Unless otherwise specified, "exposure" in the present invention includes not only exposure with far ultraviolet, X-rays, EUV, or the like, but also writing with particle beams such as electron beams or ion beams.

[0010] Although the mechanism by which the drug solution of the present invention solves the above problems is not entirely clear, the inventor speculates that the mechanism is as follows: Note that the following mechanism is speculation, and even if the effects of the present invention are obtained through a different mechanism, it is still within the scope of the present invention. A chemical solution contains trace amounts of impurities that are mixed in during storage, transportation through piping, and the like, and these impurities are likely to cause various defects. The various defects are, for example, defects that occur when the chemical solution is applied to the manufacturing process of a semiconductor device. More specific examples include metal residue defects, particulate organic residue defects, and stain-like residue defects when the chemical solution is used as a pre-wet liquid or rinse liquid; development defects, residue defects, and uniformity defects when the chemical solution is used as a pattern developer; and defects such as those described above that occur when the chemical solution is used as a pipe cleaning liquid and then the pre-wet liquid, rinse liquid, developer, or the like is transported through the cleaned pipe and then used. Since the chemical solution of the present invention contains a predetermined amount or more of the first organic compound described below, it behaves like a saturated solution and is less likely to be contaminated with impurities (especially impurities that are likely to cause defects). On the other hand, by setting the content of the first organic compound to a predetermined amount or less, it is possible to prevent the first organic compound itself from causing defects. The present inventors speculate that, based on this mechanism, various processes using the chemical solution of the present invention were able to suppress the occurrence of defects in the final product.

[0011] The chemical solution of the present invention contains an organic solvent and at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III) described below, and the total content of the first organic compound is 0.1 to 100,000 mass ppt relative to the total mass of the chemical solution. The components contained in the medicinal solution of the present invention will be described in detail below.

[0012] <Organic solvents> The chemical solution of the present invention (hereinafter also simply referred to as "chemical solution") contains an organic solvent. In this specification, the organic solvent refers to a liquid organic compound contained in an amount exceeding 10,000 ppm by mass per component relative to the total mass of the chemical solution. In other words, in this specification, a liquid organic compound contained in an amount exceeding 10,000 ppm by mass relative to the total mass of the chemical solution corresponds to an organic solvent. In addition, in this specification, the term "liquid" means that the substance is liquid at 25°C under atmospheric pressure.

[0013] The content of the organic solvent in the chemical solution is not particularly limited, but is preferably 98.00% by mass or more, more preferably more than 99.00% by mass, even more preferably 99.90% by mass or more, and particularly preferably more than 99.95% by mass, relative to the total mass of the chemical solution. The upper limit is less than 100% by mass. The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used, the total content is preferably within the above range.

[0014] The type of organic solvent is not particularly limited, and known organic solvents can be used. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, dialkyl sulfoxides, cyclic sulfones, dialkyl ethers, monohydric alcohols, glycols, alkyl acetates, and N-alkylpyrrolidones.

[0015] Examples of organic solvents include propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropanol (IPA), 4-methyl-2-pentanol (MIBC), butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, and N-methyl One or more selected from the group consisting of pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, mesitylene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate are preferred. Examples of using two or more organic solvents include a combined use of PGMEA and PGME, and a combined use of PGMEA and PC. The type and content of the organic solvent in the chemical solution can be measured using a gas chromatograph mass spectrometer.

[0016] The volume resistivity of the organic solvent is not particularly limited, but is preferably 500,000,000 Ω·cm or more. The upper limit is not particularly limited, but is preferably 5,000,000,000 Ω·cm or less. The volume resistivity of the organic solvent can be measured using, for example, a volume resistivity meter SME-8310 or a super insulation meter SM-8220 manufactured by Hioki Electric Industry Co., Ltd.

[0017] The organic solvent has a Hansen solubility parameter of 3 to 20 MPa for eicosene. 0.5 (More preferably 5 to 20 MPa 0.5 ) is also preferred. When two or more organic solvents are used, it is preferable that at least one of them satisfies the above range of Hansen solubility parameters. When two or more organic solvents are used, it is preferable that the weighted average value of the Hansen solubility parameters based on the molar ratio of the contents of the respective organic solvents satisfies the above-mentioned range of the Hansen solubility parameters.

[0018] For example, in order to obtain a chemical solution with better defect suppression properties, it is also preferable that the organic solvent is substantially only an organic solvent that satisfies the above-mentioned Hansen solubility parameter range. The organic solvent is substantially only an organic solvent that satisfies the above-mentioned Hansen solubility parameter range means that the content of the organic solvent that satisfies the above-mentioned Hansen solubility parameter range is 99% by mass or more (preferably 99.9% by mass or more) based on the total mass of the organic solvent.

[0019] Furthermore, for example, the organic solvent is preferably a mixed solvent containing both an organic solvent that satisfies the above-mentioned range of Hansen solubility parameters and an organic solvent that does not satisfy the above-mentioned range of Hansen solubility parameters. In this case, in order to obtain a chemical solution with better defect suppression properties, it is preferable that the mixed solvent contains 20 to 80 mass % (preferably 30 to 70 mass %) of organic solvents that satisfy the above Hansen solubility parameter range, based on the total mass of the mixed solvent, and 20 to 80 mass % (preferably 30 to 70 mass %) of organic solvents that do not satisfy the above Hansen solubility parameter range, based on the total mass of the mixed solvent. When the content of the organic solvent satisfying the above Hansen solubility parameter range and the content of the organic solvent not satisfying the above Hansen solubility parameter range are each at a certain level or more, the affinity of the chemical solution for the metal-based material and the organic-based material can be adjusted to an appropriate range, compared to when the organic solvent not satisfying the above Hansen solubility parameter range is in an amount outside the specified range (for example, 1% by mass or more but less than 20% by mass or more than 80% by mass based on the total mass of the mixed solvent), and it is believed that the effect of the present invention is more excellent. In this case, the total content of the organic solvent satisfying the above-mentioned Hansen solubility parameter range and the organic solvent not satisfying the above-mentioned Hansen solubility parameter range is preferably 99.0 mass% or more based on the total mass of the mixed solution. Although there is no particular upper limit, it is generally preferably 99.99999 mass% or less. In addition, in organic solvents that do not satisfy the above Hansen solubility parameter range, the distance of the Hansen solubility parameter to eicosene is 0 MPa. 0.5 More than 3MPa 0.5 Less than (preferably 0 MPa 0.5 Super 3MPa 0.5 less than 20 MPa 0.5 More than (preferably 20 MPa 0.5 Super 50MPa 0.5 (See below).

[0020] In this specification, the Hansen solubility parameters refer to the Hansen solubility parameters described in "Hansen Solubility Parameters: A Users Handbook, Second Edition" (pages 1-310, CRC Press, published in 2007), etc. That is, the Hansen solubility parameters express solubility as a multidimensional vector (dispersion term (δd), dipole-dipole term (δp), and hydrogen bond term (δh)), and these three parameters are considered to be the coordinates of a point in a three-dimensional space called Hansen space. The Hansen solubility parameter distance is the distance between two compounds in the Hansen space, and can be calculated using the following formula: (Ra)2 =4(δd2-δd1) 2 +(δp2-δp1) 2 +(δh2-δh1) 2 Ra: The distance between the Hansen solubility parameters of the first compound and the second compound (unit: MPa) 0.5 ) δd1: Dispersion term of the first compound (unit: MPa 0.5 ) δd2: Dispersion term of the second compound (unit: MPa 0.5 ) δp1: dipole-dipole term of the first compound (unit: MPa 0.5 ) δp2: dipole-dipole term of the second compound (unit: MPa 0.5 ) δh1: hydrogen bond term of the first compound (unit: MPa 0.5 ) δh2: Hydrogen bond term of the second compound (unit: MPa 0.5 ) In this specification, the Hansen solubility parameter of a compound is specifically calculated using HSPiP (Hansen Solubility Parameter in Practice).

[0021] <First organic compound> The chemical solution contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III).

[0022] [ka]

[0023] In general formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by general formula (A): In general formula (A), * represents a bonding position.

[0024] [ka]

[0025] When Y represents a benzene ring group, s represents 1, L represents a single bond, and R 1a represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom (preferably an oxygen atom). When the alkyl group contains an oxygen atom, it is preferably contained in the form of -O- or -CO-. In other words, the alkyl group may contain -O- or -CO-. R 1a The alkyl group may be linear or branched, or may contain a cyclic structure. R 1a The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms. 1a The number of carbon atoms in the alkyl group of R 1a This does not include the number of carbon atoms contained in any substituents that the alkyl group may contain. R 1a The substituent that the alkyl group may contain preferably contains an aromatic ring group (preferably a benzene ring group, which may further contain a substituent), and more preferably the substituent is an aromatic ester group. When the benzene ring group represented by Y is substituted with an alkyl group, the alkyl group and R 1a may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group represented by Y, the alkyl groups may be bonded to each other to form a ring.

[0026] When Y represents a group represented by general formula (A), s represents 3, L represents a methylene group, and R 1a each independently represents an alkyl group. In this case, R 1a The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of compounds represented by general formula (I) are as follows:

[0027] [ka]

[0028] In general formula (II), R2a ~R 2h each independently represents an alkyl group which may contain a substituent. R 2b and R 2e may be bonded to each other to form a ring, and R 2b and R 2e The group formed by bonding with each other is -O-(-Si(R 2i )2-O-) a - is preferred. a represents an integer of 1 or more. There is no particular upper limit to a, but it is often 10 or less. R 2i represents an alkyl group which may contain a substituent. Multiple Rs 2i may be the same or different. R 2a ~R 2i The alkyl group represented by the formula (I) may be linear or branched, or may contain a cyclic structure. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in any substituent that the alkyl group may contain. R 2a ~R 2i The alkyl groups represented by the following formula (I) are each independently preferably an unsubstituted alkyl group, more preferably a methyl group. R 2g and R 2h It is also preferable that one of the groups is an alkyl group containing a substituent. The substituent is preferably a group containing one or more oxyalkylene groups (the alkylene group portion preferably has 2 to 4 carbon atoms, and may be linear or branched, or may contain a cyclic structure). The group containing one or more oxyalkylene groups may contain a hydroxyl group. Examples of compounds represented by general formula (II) are shown below.

[0029] [ka]

[0030] [ka]

[0031] In general formula (III), R 3a is -N(R 3c )R 3d or -SR 3e Represents. R 3c , R 3d , and R 3e represents a hydrogen atom or a substituent. R 3b represents -NH- or -S-. R 3e Examples of the aromatic thio group include an aromatic thio group. The aromatic thio group is preferably a group represented by -S-Ar (Ar: an aromatic ring group which may have a substituent). The aromatic ring group in the aromatic thio group may or may not contain a heteroatom (such as a sulfur atom, a nitrogen atom, and / or an oxygen atom), but preferably does. That is, the aromatic ring group is preferably an aromatic heterocyclic group. The aromatic ring group may be monocyclic or polycyclic, but polycyclic is preferred. The aromatic ring group is preferably a benzothiazole ring group. Examples of compounds represented by general formula (III) are shown below.

[0032] [ka]

[0033] The boiling point of the first organic compound is not particularly limited, but is preferably 250° C. or higher, more preferably 380° C. or higher, in that it is less likely to volatilize, forms an association with the metal component, and can further suppress the occurrence of defects due to the metal component. The upper limit is not particularly limited, but is often 450° C. or lower. The boiling point mentioned above means the boiling point under 1 atmospheric pressure.

[0034] The molecular weight of the first organic compound is not particularly limited, but in relation to the boiling point, it is preferably 300 or more. There is no particular upper limit, but it is often 1,000 or less.

[0035] The ClogP of the first organic compound is not particularly limited, but is preferably 5.0 or more, more preferably 8.0 to 26.0, and even more preferably 8.5 to 20.0. The ClogP value is a calculated value of the common logarithm logP of the partition coefficient P between 1-octanol and water. Although known methods and software can be used to calculate the ClogP value, the present invention uses the ClogP program incorporated into Cambridge Soft's ChemBioDraw Ultra 12.0 unless otherwise specified.

[0036] The absolute value of the difference between the ClogP of the first organic compound and the ClogP of the organic solvent is not particularly limited, but is preferably 3 or more, and more preferably 5 to 10, in that the first organic compound acts as a hydrophobic compound in the chemical solution and interacts with the metal components, thereby further suppressing the occurrence of defects due to the metal components.

[0037] The total content of the first organic compounds is 0.01 to 100,000 mass ppt relative to the total mass of the chemical solution, and is preferably 80,000 mass ppt or less, more preferably 10,000 mass ppt or less, and even more preferably 2,000 mass ppt or less, from the viewpoint of more excellent defect suppression properties of the chemical solution (hereinafter simply referred to as "better effects of the present invention"). There is no particular lower limit, but it is preferably 0.1 mass ppt or more, and more preferably 1 mass ppt or more. The first organic compound may be used alone or in combination of two or more, and it is particularly preferred to use two or more in terms of achieving better effects of the present invention.

[0038] The content of the first organic compound in the chemical solution can be measured using a GCMS (gas chromatography mass spectrometry).

[0039] The chemical solution may contain other components in addition to the organic solvent and the first organic compound described above. The other components are described in detail below.

[0040] <Second organic compound> The chemical solution may contain at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VIII).

[0041] [ka]

[0042] In general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent, such as a hydrocarbon group (e.g., an unsaturated hydrocarbon group) that may contain at least one group selected from the group consisting of a hydroxyl group and a carboxyl group. Examples of the substituent that the benzene ring group may contain include an alkyl group, an alkoxy group, and an arylcarbonyl group, each of which may contain a substituent. Examples of the substituent that the cyclohexene ring group may contain include an alkenyloxy group and a cyclohexene ring group that may contain a substituent.

[0043] The compound represented by general formula (IV) includes a compound represented by general formula (IV-1). General formula (IV-1) (HO-Ar-L)4-C In the above formula, Ar represents a benzene ring group which may contain a substituent. L represents a divalent linking group. Examples of the divalent linking group include alkylene groups which may contain an ester group.

[0044] Examples of compounds represented by general formula (IV) are shown below.

[0045] [ka]

[0046] [ka]

[0047] In general formula (V), R 5a represents an alkyl group which may have a substituent or a hydrogen atom. R 5b and R 5c are each independently a hydrogen atom, -AL-OR 5d , -CO-R 5e , or -CH(OH)-R 5f Represents. AL represents an alkylene group (preferably having 1 to 6 carbon atoms) which may contain a substituent. R 5d , R 5e , and R 5f each independently represents a substituent (preferably an alkyl group which may further contain a substituent). R 5a , R 5d , R 5e , and R 5f The alkyl groups which may contain a substituent represented by the following formula (I) may each independently be linear or branched, or may contain a cyclic structure. The number of carbon atoms in the alkyl group is preferably 1 to 50, more preferably 1 to 20. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in any substituent that the alkyl group may contain. Examples of the substituent that the alkyl group may contain include a hydroxyl group, an alkyl ester group, and an alkyl vinyl group (preferably an alkyl group moiety having 3 to 12 carbon atoms). R 5d If there are multiple R 5d Each may be the same or different. 5e If there are multiple R 5e Each may be the same or different. 5f If there are multiple R 5fEach may be the same or different. R 5a The substituent that may be contained in the alkyl group represented by R 5d , R 5e , and R 5f a combination of two selected from the group consisting of two R 5d Comrades, two R 5e Two or two R 5f They may be bonded to each other to form a ring. R 5a The substituent that may be contained in the alkyl group represented by R 5d , R 5e , and R 5f a combination of two selected from the group consisting of two R 5d Comrades, two R 5e Two or two R 5f The groups formed by bonding together are -O- and -NR 5g -(R 5g is a substituent), and —NHCO—. R 5a , R 5b , and R 5c At least one of these is not a hydrogen atom.

[0048] The compound represented by general formula (V) includes a compound represented by general formula (V-1).

[0049] [ka]

[0050] In the above formula, L represents an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms) which may contain a substituent, and q represents 3 to 10 (preferably 4 to 6).

[0051] Examples of compounds represented by general formula (V) are shown below.

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] In general formula (VI), R 6a and R 6b each independently represents an alkyl group which may contain a substituent. The alkyl group may be linear or branched, or may contain a cyclic structure. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 10. The number of carbon atoms in the alkyl group does not include the number of carbon atoms in any substituent that the alkyl group may contain. The substituent is preferably, for example, an aromatic ring group (which may further contain a substituent, and is preferably a phenyl group). Examples of compounds represented by general formula (VI) are shown below.

[0056] [ka]

[0057] In general formula (VII), R 7a ~R 7c each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent. R 7a ~R 7c Among these, it is preferable that one or more (preferably two or more) are alkyl groups which may contain a substituent, or benzene ring groups which may contain a substituent. The alkyl group may be linear or branched, or may contain a cyclic structure. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 5. The number of carbon atoms in the alkyl group does not include the number of carbon atoms contained in any substituent that the alkyl group may have. The substituent is preferably an alkoxy group (preferably having 2 to 6 carbon atoms) or a halogen atom (such as a fluorine atom, chlorine atom, bromine atom, or iodine atom). The substituent that the benzene ring group may contain is preferably an alkyl group (preferably having 2 to 10 carbon atoms). Examples of the compound represented by general formula (VII) are shown below.

[0058] [ka]

[0059] The boiling point of the second organic compound is not particularly limited, but is preferably 250°C or higher, more preferably 380°C or higher, in that it is less likely to volatilize, forms an association with the metal component, and can further suppress the occurrence of defects due to the metal component. The upper limit is not particularly limited, but is often 450°C or lower. The boiling point mentioned above means the boiling point under 1 atmospheric pressure.

[0060] The molecular weight of the second organic compound is not particularly limited, but in relation to the boiling point, it is preferably 300 or more. There is no particular upper limit, but it is often 2000 or less.

[0061] The ClogP of the second organic compound is not particularly limited, but is preferably 5.0 or more, more preferably 8.0 to 26.0, and even more preferably 8.5 to 20.0.

[0062] The absolute value of the difference between the ClogP of the second organic compound and the ClogP of the organic solvent is not particularly limited, but is preferably 3 or more, and more preferably 5 to 10, in that the second organic compound acts as a hydrophobic compound in the chemical solution and interacts with the metal components, thereby further suppressing the occurrence of defects due to the metal components.

[0063] The total content of the second organic compounds is not particularly limited, but is preferably 0.01 to 100,000 mass ppt relative to the total mass of the chemical solution, in order to obtain better effects of the present invention. Of these, in order to obtain better effects of the present invention, the content is preferably 80,000 mass ppt or less, more preferably 20,000 mass ppt or less, even more preferably 10,000 mass ppt or less, and particularly preferably 2,000 mass ppt or less. The lower limit is not particularly limited, but is preferably 0.1 mass ppt or more, and more preferably 1 mass ppt or more. The second organic compound may be used alone or in combination of two or more, and it is particularly preferred to use two or more in terms of achieving better effects of the present invention.

[0064] When the chemical solution of the present invention contains the first organic compound and the second organic compound, the chemical solution of the present invention preferably contains at least two or more compounds selected from the first organic compound and the second organic compound, in order to obtain a more excellent effect of the present invention. For example, the chemical solution of the present invention may contain at least one or more of the first organic compounds and at least one or more of the second organic compounds. Of the two or more compounds, it is preferred that at least one compound has a ClogP of 5 or more.

[0065] Furthermore, it is preferable that at least one of the two or more compounds is a compound represented by the above general formula (VI). In this case, the ratio of the total content of the first organic compound and the second organic compound other than the compound represented by general formula (VI) to the content of the compound represented by general formula (VII) is not particularly limited, but is preferably 0.01 to 1.

[0066] <Metal components> The chemical solution may contain a metal component. In the present invention, the metal component includes metal particles and metal ions, and for example, the content of the metal component refers to the total content of the metal particles and metal ions. The chemical solution may contain either metal particles or metal ions, or may contain both, and preferably contains both metal particles and metal ions.

[0067] Examples of the metal element in the metal component include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zn (zirconium). The metal component may contain one or more metal elements. The metal particles may be a simple substance or an alloy, or the metal may exist in a state associated with an organic substance. The metal components may be metal components that are inevitably contained in each component (raw material) contained in the chemical solution, or metal components that are inevitably contained during the production, storage, and / or transportation of the treatment solution, or may be intentionally added.

[0068] When the chemical solution contains a metal component, the content thereof is preferably 0.01 to 500 mass ppt, more preferably 0.01 to 250 mass ppt, and even more preferably 0.01 to 100 mass ppt, relative to the total mass of the chemical solution, in order to obtain better defect suppression properties of the chemical solution. When the content of the metal component is 0.01 ppt by mass or more, the metal component is likely to form an association with the first organic compound (or the second organic compound) and is therefore likely to be removed from the substrate, thereby further improving the defect suppression property. Furthermore, if the content of the metal component is 500 mass ppt or less, it is easy to avoid an increase in the occurrence of defects resulting from the metal component.

[0069] When the chemical solution contains metal ions, the content thereof is preferably 0.01 to 400 mass ppt, more preferably 0.01 to 200 mass ppt, and even more preferably 0.01 to 80 mass ppt, relative to the total mass of the chemical solution, in order to obtain better defect suppression properties of the chemical solution. When the chemical solution contains metal particles, the content thereof is preferably 0.01 to 400 mass ppt, more preferably 0.01 to 150 mass ppt, and even more preferably 0.01 to 40 mass ppt, relative to the total mass of the chemical solution, in order to obtain better defect suppression properties of the chemical solution.

[0070] The types and contents of specific metal ions and specific metal particles in the chemical solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). Here, the SP-ICP-MS method uses the same equipment as the regular ICP-MS method (inductively coupled plasma mass spectrometry), but differs only in the data analysis, which can be performed using commercially available software. In ICP-MS, the content of the target metal component is measured regardless of the form of its existence. Therefore, the total mass of the target metal particles and metal ions is quantified as the content of the metal component.

[0071] On the other hand, the SP-ICP-MS method can measure the content of metal particles, so the content of metal ions in a sample can be calculated by subtracting the content of metal particles from the content of metal components in the sample. An example of an apparatus for the SP-ICP-MS method is the Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, and measurements can be performed using the method described in the Examples. Other apparatuses that can be used include the NexION350S manufactured by PerkinElmer and the Agilent 8900 manufactured by Agilent Technologies.

[0072] The ratio of the total content of the first organic compound to the content of the metal component is not particularly limited, but is preferably 0.01 to 10,000, more preferably 0.1 to 5,000, in terms of achieving better effects of the present invention. Furthermore, the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component is not particularly limited, but is preferably 0.01 to 50,000, more preferably 0.1 to 5,000, in terms of achieving better effects of the present invention. The ratio of the total content of the first organic compound and the second organic compound to the content of the metal particles is not particularly limited, but is preferably 0.01 to 50,000, more preferably 0.05 to 30,000, in terms of achieving better effects of the present invention. The ratio of the total content of the first organic compound and the second organic compound to the content of the metal ions is not particularly limited, but is preferably 0.03 to 30,000, more preferably 0.05 to 20,000, in terms of achieving better effects of the present invention.

[0073] <Water> The chemical solution may contain water. The water is not particularly limited, and for example, distilled water, ion-exchanged water, pure water, etc. can be used. Water may be added to the chemical solution, or may be unintentionally mixed into the chemical solution during the production process of the chemical solution. Examples of unintentional mixing during the production process of the chemical solution include, but are not limited to, when water is contained in a raw material (e.g., an organic solvent) used in the production of the chemical solution, or when water is mixed during the production process of the chemical solution (e.g., contamination).

[0074] The water content in the chemical solution is not particularly limited, but is preferably 0.05 to 2.0 mass % relative to the total mass of the chemical solution. The water content in the chemical solution refers to the water content measured using an apparatus that employs the Karl Fischer water content determination method as its measurement principle.

[0075] <Resin> The chemical solution may contain a resin. The resin is more preferably a resin P containing a group that decomposes under the action of an acid to generate a polar group (a repeating unit containing an acid-decomposable group).The resin is more preferably a resin containing a repeating unit represented by formula (AI) described below, which is a resin whose solubility in a developer mainly composed of an organic solvent decreases under the action of an acid.The resin containing a repeating unit represented by formula (AI) described below contains a group that decomposes under the action of an acid to generate an alkali-soluble group. Examples of the polar group include an alkali-soluble group, such as a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group, and a sulfo group.

[0076] In the acid-decomposable group, the polar group is protected by a group that is detached by an acid (acid-detachable group). Examples of the acid-detachable group include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), and -C(R 01 )(R 02 )(OR 39 ) etc.

[0077] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring.

[0078] R 01 and R 02 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0079] The resin P whose solubility in a developer containing an organic solvent as its main component decreases due to the action of an acid will be described in detail below.

[0080] (Formula (AI): Repeating unit containing an acid-decomposable group) Resin P preferably contains a repeating unit represented by formula (AI).

[0081] [ka]

[0082] In formula (AI), Xa1 represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Ra1 to Ra3 each independently represent an alkyl group (straight-chain or branched) or a cycloalkyl group (monocyclic or polycyclic). Two of Ra1 to Ra3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0083] The content of the repeating unit containing an acid-decomposable group (preferably a repeating unit represented by formula (AI)) is preferably 20 to 90 mol %, more preferably 25 to 85 mol %, and even more preferably 30 to 80 mol %, based on all repeating units in the resin P.

[0084] Resin P may contain other repeating units in addition to the repeating unit containing an acid-decomposable group, such as a repeating unit containing a lactone structure, a repeating unit containing a phenolic hydroxyl group, a repeating unit containing a polar group, and a repeating unit containing a silicon atom in the side chain.

[0085] The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000, as determined by GPC (gel permeation chromatography) in terms of polystyrene. The dispersity (molecular weight distribution) of the resin P is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0.

[0086] In the chemical solution, the content of the resin P is preferably 50 to 99.9 mass % of the total solid content, and more preferably 60 to 99.0 mass %. In addition, in the chemical solution, one type of resin P may be used, or a plurality of types may be used. The solid content means the components in the chemical solution excluding the organic solvent and solvents such as water.

[0087] The chemical solution may also contain known compounds such as an acid generator, a basic compound, a quencher, a hydrophobic resin, and a surfactant. The chemical solution may contain components contained in actinic ray-sensitive or radiation-sensitive resin compositions described in, for example, JP 2013-195844 A, JP 2016-057645 A, JP 2015-207006 A, WO 2014 / 148241 A, JP 2016-188385 A, and JP 2017-219818 A.

[0088] <Chemical use> The chemical solution of the present invention is preferably used in the manufacture of semiconductor devices, and particularly, it is preferable to manufacture semiconductor chips using the chemical solution of the present invention. Specifically, in the manufacturing process of semiconductor devices, which includes a lithography process, an etching process, an ion implantation process, a peeling process, and the like, the liquid is used to treat organic substances after the completion of each process or before moving on to the next process, and is suitably used as a pre-wet liquid, a developer, a rinse liquid, a polishing liquid, and the like. In addition, the chemical liquid may also be used as a dilution liquid (in other words, a solvent) for the resin contained in the composition for forming a resist film.

[0089] Furthermore, the chemical solution can be used for purposes other than the manufacture of semiconductor devices, and can also be used as a developer and rinse for polyimide, resist for sensors, resist for lenses, and the like. The chemical solution can also be used as a solvent for medical or cleaning purposes, for example, for cleaning pipes, containers, and substrates (such as wafers and glass). As for the cleaning application, it is also preferable to use it as a cleaning liquid (pipe cleaning liquid, container cleaning liquid, etc.) for cleaning pipes, containers, etc. that come into contact with the above-mentioned pre-wet liquid or other liquid.

[0090] Among these, the chemical liquid is preferably used for a prewet liquid, a developer, a rinse liquid, a polishing liquid, and a composition for forming a resist film. In particular, when applied to a prewet liquid, a developer, and a rinse liquid, the chemical liquid exerts a more excellent effect. Furthermore, when applied to a pipe cleaning liquid used for the pipes used to transport these liquids, the chemical liquid exerts a more excellent effect.

[0091] The chemical solution of the present invention may also be used as a kit containing two or more selected from the group consisting of a pre-wet liquid containing the chemical solution of the present invention, a developer containing the chemical solution of the present invention, a rinse liquid containing the chemical solution of the present invention, a polishing liquid containing the chemical solution of the present invention, and a composition for forming a resist film containing the chemical solution of the present invention.

[0092] <Method of manufacturing chemical solution> The method for producing the chemical solution is not particularly limited, and any known production method can be used. Among them, in terms of obtaining a more excellent effect of the present invention, the method for producing the chemical solution preferably includes a filtration step of filtering a material to be purified containing an organic solvent using a filter to obtain the chemical solution.

[0093] The material to be purified used in the filtration step may be procured by purchase or may be obtained by reacting raw materials. The material to be purified preferably has a low impurity content. Examples of commercially available products of such materials include those known as "high purity grade products."

[0094] The method for obtaining a product to be purified (typically, a product to be purified containing an organic solvent) by reacting raw materials is not particularly limited, and known methods can be used. For example, there is a method for obtaining an organic solvent by reacting one or more raw materials in the presence of a catalyst. More specifically, examples of such methods include a method of reacting acetic acid with n-butanol in the presence of sulfuric acid to obtain butyl acetate; a method of reacting ethylene, oxygen, and water in the presence of Al(C2H5)3 to obtain 1-hexanol; a method of reacting cis-4-methyl-2-pentene in the presence of Ipc2BH (Diisopinocampheylborane) to obtain 4-methyl-2-pentanol; a method of reacting propylene oxide, methanol, and acetic acid in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); a method of reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide to obtain IPA (isopropyl alcohol); and a method of reacting lactic acid and ethanol to obtain ethyl lactate.

[0095] (filtration process) The method for producing a chemical solution of the present invention preferably includes a filtration step of filtering the material to be purified using a filter to obtain a chemical solution. The method for filtering the material to be purified using a filter is not particularly limited, but it is preferable to pass the material to be purified (liquid) through a filter unit having a housing and a filter cartridge housed in the housing, with or without pressure.

[0096] Filter pore size The pore size of the filter is not particularly limited, and filters having pore sizes commonly used for filtering materials to be purified can be used. In particular, the pore size of the filter is preferably 200 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, particularly preferably 5 nm or less, and most preferably 3 nm or less, because this makes it easier to control the number of particles (metal particles, etc.) contained in the chemical solution within a desired range. The lower limit is not particularly limited, but a pore size of 1 nm or more is generally preferred from the viewpoint of productivity. In this specification, the pore size and pore size distribution of a filter refer to the pore size and pore size distribution determined by the bubble point of isopropanol (IPA) or HFE-7200 ("Novec 7200", manufactured by 3M, hydrofluoroether, C4F9OC2H5).

[0097] A filter having a pore size of 5.0 nm or less is preferable because it is easier to control the number of particles contained in the drug solution. Hereinafter, a filter having a pore size of 5 nm or less will also be referred to as a "micropore filter." The micropore filter may be used alone or in combination with a filter having a different pore size. From the viewpoint of superior productivity, it is preferable to use the micropore filter in combination with a filter having a larger pore size. In this case, clogging of the micropore filter can be prevented by passing the purified product, which has been previously filtered through a filter having a larger pore size, through the micropore filter. That is, when one filter is used, the pore size of the filter is preferably 5.0 nm or less, and when two or more filters are used, the pore size of the filter having the smallest pore size is preferably 5.0 nm or less.

[0098] The sequential use of two or more filters with different pore sizes is not particularly limited, but may include a method in which the filter units described above are arranged in sequence along a pipeline through which the purified product is transported. In this case, if an attempt is made to maintain a constant flow rate per unit time of the purified product throughout the entire pipeline, filters with smaller pore sizes may be subjected to greater pressure than filters with larger pore sizes. In this case, it is preferable to arrange a pressure control valve, a damper, or the like between the filters to maintain a constant pressure on the filters with smaller pore sizes, or to arrange filter units containing the same filters in parallel along the pipeline to increase the filtration area. This allows for more stable control of the number of particles in the chemical solution.

[0099] Filter material The filter material is not particularly limited, and known filter materials can be used. Specifically, resins include polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; poly(meth)acrylate; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, and the like. Among these, at least one selected from the group consisting of nylon (e.g., 6,6-nylon is preferred), polyolefins (e.g., polyethylene is preferred), poly(meth)acrylate, and polyfluorocarbons (e.g., polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) are preferred) is preferred because of their superior solvent resistance and the resulting chemical solution's superior defect suppression performance. These polymers may be used alone or in combination of two or more. In addition to resin, materials such as diatomaceous earth and glass may also be used. Alternatively, a polymer (such as nylon-grafted UPE) obtained by graft copolymerizing polyamide (for example, nylon such as nylon-6 or nylon-6,6) with polyolefin (such as UPE described below) may be used as the material for the filter.

[0100] The filter may also be a surface-treated filter. The surface treatment method is not particularly limited, and known methods can be used. Examples of surface treatment methods include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

[0101] Plasma treatment is preferred because it hydrophilizes the filter surface. The water contact angle on the surface of the filter material hydrophilized by plasma treatment is not particularly limited, but the static contact angle at 25°C measured with a contact angle meter is preferably 60° or less, more preferably 50° or less, and even more preferably 30° or less.

[0102] As the chemical modification treatment, a method of introducing ion exchange groups into the substrate is preferred. That is, the filter is preferably a filter in which the above-mentioned materials are used as a substrate and ion exchange groups are introduced into the substrate. Typically, a filter is preferred that includes a layer containing a substrate containing ion exchange groups on the surface of the substrate. The surface-modified substrate is not particularly limited, and a filter in which ion exchange groups are introduced into the above-mentioned polymer is preferred in terms of ease of production.

[0103] Examples of the ion exchange group include a sulfonic acid group, a carboxyl group, and a phosphate group as a cation exchange group, and a quaternary ammonium group as an anion exchange group. The method for introducing the ion exchange group into the polymer is not particularly limited, but includes a method in which a compound containing an ion exchange group and a polymerizable group is reacted with the polymer to typically perform grafting.

[0104] The method for introducing ion exchange groups is not particularly limited, but may involve irradiating fibers of the above resins with ionizing radiation (such as α-rays, β-rays, γ-rays, X-rays, and electron beams) to generate active moieties (radicals) in the resin. The irradiated resin is then immersed in a monomer-containing solution to graft polymerize the monomer onto the substrate. As a result, a polymer is generated that is bonded to the polyolefin fibers as a graft-polymerized side chain. The resin containing this generated polymer as a side chain is then contacted with a compound containing anion exchange groups or cation exchange groups to introduce ion exchange groups into the graft-polymerized side chain polymer, yielding the final product.

[0105] The filter may also be constructed by combining a woven or nonwoven fabric on which ion exchange groups have been formed by radiation graft polymerization with a conventional glass wool, woven or nonwoven fabric filtering material.

[0106] The use of a filter containing ion exchange groups makes it easy to control the content of metal components (particularly particles containing metal atoms) in a chemical solution within a desired range. The material for the filter containing ion exchange groups is not particularly limited, but examples include polyfluorocarbons and materials in which ion exchange groups have been introduced into polyolefins, and materials in which ion exchange groups have been introduced into polyfluorocarbons are more preferred. The pore size of the filter containing ion exchange groups is not particularly limited, but is preferably 1 to 30 nm, more preferably 5 to 20 nm. The filter containing ion exchange groups may also serve as the filter having the smallest pore size described above, or may be used separately from the filter having the smallest pore size. Among these, in terms of obtaining better effects of the present invention, a form in which a filter containing ion exchange groups and a filter not having ion exchange groups and having the smallest pore size are used in the filtration step is preferred. The material for the filter having the minimum pore size already described is not particularly limited, but from the viewpoint of solvent resistance and the like, generally, at least one selected from the group consisting of polyfluorocarbons and polyolefins is preferred, and polyolefins are more preferred.

[0107] Therefore, the filters used in the filtration step may be two or more filters made of different materials, for example, two or more filters selected from the group consisting of filters made of polyolefins, polyfluorocarbons, polyamides, and materials into which ion exchange groups have been introduced.

[0108] ·Porous structure of the filter The pore structure of the filter is not particularly limited and may be appropriately selected depending on the components in the product to be purified. In this specification, the pore structure of the filter refers to the pore size distribution, the positional distribution of the pores in the filter, the shape of the pores, etc., and can typically be controlled by the filter manufacturing method. For example, porous membranes can be obtained by sintering powders of resins or the like, and fibrous membranes can be obtained by methods such as electrospinning, electroblowing, and meltblowing, each of which has a different pore structure.

[0109] By "porous membrane" is meant a membrane that retains components of a product to be purified, such as gels, particles, colloids, cells, and poly-oligomers, while allowing components substantially smaller than the pores to pass through the pores. The retention of components of a product by a porous membrane may depend on operating conditions, such as face velocity, the use of surfactants, pH, and combinations thereof, and may depend on the pore size and structure of the porous membrane and the size and structure of the particles to be removed (e.g., hard particles or gels).

[0110] When the product to be purified contains negatively charged particles, polyamide filters can function as non-sieving membranes to remove such particles. Typical non-sieving membranes include, but are not limited to, nylon membranes such as nylon-6 membranes and nylon-6,6 membranes. As used herein, "non-sieving" retention mechanisms refer to retention that occurs through mechanisms such as obstruction, diffusion, and adsorption that are not related to the pressure drop or pore size of the filter.

[0111] Non-sieving retention includes retention mechanisms such as obstruction, diffusion, and adsorption that remove target particles in a purified product, regardless of the filter's pressure drop or pore size. Particle adsorption to the filter surface can be mediated, for example, by intermolecular van der Waals and electrostatic forces. Obstruction occurs when particles moving through a non-sieving membrane layer with a tortuous path cannot be redirected quickly enough to avoid contact with the non-sieving membrane. Diffusion-based particle transport results primarily from the random or Brownian motion of small particles, which creates a certain probability of particle collision with the filter media. Non-sieving retention mechanisms can be active when there are no repulsive forces between the particles and the filter.

[0112] UPE (ultra-high molecular weight polyethylene) filters are typically sieving membranes, meaning membranes that capture particles primarily through sieving retention mechanisms or membranes optimized for capturing particles through sieving retention mechanisms. Typical examples of sieving membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes. The "sieve retention mechanism" refers to the retention of particles that are larger than the pore size of the porous membrane. Sieve retention is improved by forming a filter cake (an agglomeration of particles to be removed on the membrane surface). The filter cake effectively performs the function of a secondary filter.

[0113] The material of the fiber membrane is not particularly limited as long as it is a polymer capable of forming a fiber membrane. Examples of polymers include polyamides. Examples of polyamides include nylon 6 and nylon 6,6. The polymer forming the fiber membrane may be poly(ether sulfone). When the fiber membrane is on the primary side of the porous membrane, it is preferable that the surface energy of the fiber membrane is higher than that of the polymer that is the material of the porous membrane on the secondary side. An example of such a combination is when the fiber membrane is made of nylon and the porous membrane is made of polyethylene (UPE).

[0114] The method for producing the fiber membrane is not particularly limited, and known methods can be used, including, as described above, electrospinning, electroblowing, meltblowing, and the like.

[0115] The pore structure of the porous membrane (e.g., a porous membrane containing UPE, PTFE, etc.) is not particularly limited, but examples of the pore shape include lace-like, string-like, and node-like. The pore size distribution in the porous membrane and the distribution of its positions within the membrane are not particularly limited. The size distribution may be narrower and the distribution positions within the membrane may be symmetrical. Alternatively, the size distribution may be wider and the distribution positions within the membrane may be asymmetrical (the above membrane is also referred to as an "asymmetric porous membrane"). In an asymmetric porous membrane, the pore size varies within the membrane, and typically, the pore size increases from one surface of the membrane to the other. In this case, the surface with more pores with larger pore sizes is referred to as the "open side," and the surface with more pores with smaller pore sizes is also referred to as the "tight side." Furthermore, examples of asymmetric porous membranes include membranes in which the size of the pores is smallest at a certain position within the thickness of the membrane (also called "hourglass-shaped" membranes).

[0116] With asymmetric porous membranes, the primary side has larger pore size, in other words the primary side is open, creating a pre-filtration effect.

[0117] The porous membrane may include a thermoplastic polymer such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, a copolymer of tetrafluoroethylene and perfluoroalkoxyalkane), polyamide, and polyolefin, or may include polytetrafluoroethylene, etc. Among these, ultra-high molecular weight polyethylene is preferred as a material for the porous membrane. Ultra-high molecular weight polyethylene refers to thermoplastic polyethylene with an extremely long chain, and preferably has a molecular weight of one million or more, typically 2 to 6 million.

[0118] The filters used in the filtration step may be two or more types of filters with different pore structures, or a porous membrane filter and a fiber membrane filter may be used in combination. A specific example is a method using a nylon fiber membrane filter and a UPE porous membrane filter.

[0119] As described above, filters may be commercially available. When such filters are distributed, they are often packaged in packaging material, such as by being placed in a packaging bag and sealed to prevent contamination. In this case, if the portion of the packaging material that may come into contact with the filter (contact portion) is made of polyolefin (e.g., polyethylene including high-density polyethylene), impurities are more likely to adhere to the filter, causing contamination, compared to when the contact portion is made of fluororesin or stainless steel. Therefore, it is preferable that the filter is packed in a packing material in which at least a part of the contact area with the filter is made of fluororesin or stainless steel.

[0120] Examples of the fluorine-based resin in the contact portion include PTFE and PFA. The stainless steel in the contact portion may be a corrosion-resistant material such as stainless steel described below, and among these, it is preferable that the contact portion is made of electrolytically polished stainless steel (EP-SUS). The area of ​​the contact portion that is fluororesin and / or stainless steel is preferably 50 to 100% of the total area of ​​the contact portion, more preferably 90 to 100%, and even more preferably 99 to 100%. There is no particular limitation on the form of the packaging material, and it may be in the form of a bag or a capsule. The packaging material only needs to have at least a portion of the contact area made of fluororesin and / or stainless steel, and the entire packaging material may be made of fluororesin and / or stainless steel, or may be a composite material with other materials. For example, it may be a composite material with a layer structure in which the contact area is made of fluororesin and / or stainless steel and the area other than the contact area is made of fluororesin and / or stainless steel.

[0121] It is also preferable to thoroughly wash the filter before use. When an unwashed filter (or a filter that has not been washed sufficiently) is used, impurities contained in the filter are likely to be carried into the chemical solution.

[0122] As described above, the filtration step according to an embodiment of the present invention may be a multistage filtration step in which the material to be purified is passed through two or more types of filters that differ in at least one property selected from the group consisting of filter material, pore size, and pore structure. The material to be purified may be passed through the same filter multiple times, or may be passed through multiple filters of the same type.

[0123] The material of the liquid-contacting parts of the purification equipment used in the filtration process (meaning the inner wall surfaces that may come into contact with the product to be purified and the chemical solution) is not particularly limited, but is preferably made of at least one material selected from the group consisting of non-metallic materials (such as fluororesins) and electropolished metallic materials (such as stainless steel) (hereinafter, these are collectively referred to as "corrosion-resistant materials"). For example, "the liquid-contacting parts of a production tank are made of a corrosion-resistant material" means that the production tank itself is made of a corrosion-resistant material, or the inner wall surfaces of the production tank are coated with a corrosion-resistant material.

[0124] The non-metallic material is not particularly limited, and known materials can be used. Examples of non-metallic materials include, but are not limited to, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorine-based resin (e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin, and vinyl fluoride resin).

[0125] The metal material is not particularly limited, and known materials can be used. The metal material may be, for example, a metal material having a total chromium and nickel content of more than 25 mass% relative to the total mass of the metal material, and more preferably 30 mass% or more. There is no particular upper limit to the total chromium and nickel content in the metal material, but it is generally preferably 90 mass% or less. Examples of metallic materials include stainless steel and nickel-chromium alloys.

[0126] The stainless steel is not particularly limited, and known stainless steels can be used. Among them, an alloy containing 8% or more by mass of nickel is preferred, and an austenitic stainless steel containing 8% or more by mass of nickel is more preferred. Examples of austenitic stainless steel include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), SUS316 (Ni content 10% by mass, Cr content 16% by mass), and SUS316L (Ni content 12% by mass, Cr content 16% by mass).

[0127] The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used, among which a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferred. Examples of nickel-chromium alloys include Hastelloy (trade name, the same applies hereinafter), Monel (trade name, the same applies hereinafter), and Inconel (trade name, the same applies hereinafter), etc. More specific examples include Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), and Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%), etc. Furthermore, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like in addition to the above alloy, as required.

[0128] The method for electrolytically polishing a metal material is not particularly limited, and known methods can be used, such as those described in paragraphs

[0011] to

[0014] of JP 2015-227501 A and paragraphs

[0036] to

[0042] of JP 2008-264929 A.

[0129] It is believed that electrolytic polishing of metal materials results in a higher chromium content in the surface passive layer than in the parent phase, and therefore, it is believed that using a refining device with wetted parts made of electrolytically polished metal materials makes it less likely for metal components to leak into the product being refined. The metal material may be buffed. The buffing method is not particularly limited, and known methods can be used. The size of the abrasive grains used for the buffing finish is not particularly limited, but #400 or smaller is preferred, as this tends to reduce the surface irregularities of the metal material. Buffing is preferably performed before electrolytic polishing.

[0130] (Other processes) The method for producing a chemical solution may further include steps other than the filtration step, such as a distillation step, a reaction step, and a static elimination step.

[0131] (Distillation process) The distillation step is a step of distilling a purified product containing an organic solvent to obtain a distilled purified product. The method for distilling the purified product is not particularly limited, and known methods can be used. A typical method is to place a distillation column on the upstream side of a purification device subjected to the filtration step, and introduce the distilled purified product into a production tank. In this case, the liquid-contacting parts of the distillation column are not particularly limited, but are preferably made of the corrosion-resistant materials already described.

[0132] (Reaction step) The reaction step is a step in which raw materials are reacted to produce a product to be purified that contains an organic solvent as a reaction product. The method for producing the product to be purified is not particularly limited, and known methods can be used. A typical example is a method in which a reaction tank is placed on the upstream side of a production tank (or distillation column) of a purification device that is subjected to the filtration step, and the reaction product is introduced into the production tank (or distillation column). In this case, the liquid-contacting parts of the production tank are not particularly limited, but are preferably made of the corrosion-resistant materials already described.

[0133] (static elimination process) The charge removal step is a step of removing static electricity from the material to be purified to reduce the charged potential of the material to be purified. The method for removing static electricity is not particularly limited, and any known method can be used, such as contacting the product to be purified with a conductive material. The contact time for contacting the material to be purified with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and even more preferably 0.01 to 0.1 second. Examples of conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon. As a method for bringing the material to be purified into contact with the conductive material, for example, a grounded mesh made of a conductive material is placed inside the pipeline and the material to be purified is passed through the mesh.

[0134] It is preferable that the purification of the target substance, including the opening of containers, cleaning of containers and equipment, storage of solutions, and analysis, be all performed in a clean room. The clean room is preferably a clean room with a cleanliness level of Class 4 or higher as defined by the international standard ISO14644-1:2015 established by the International Organization for Standardization. Specifically, it is preferable that the clean room meets any of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0135] The storage temperature of the drug solution is not particularly limited, but a storage temperature of 4°C or higher is preferred because this makes it more difficult for impurities contained in trace amounts in the drug solution to be eluted, resulting in more excellent effects of the present invention.

[0136] <Medicine container> The drug solution produced by the above purification method may be stored in a container until use. Such a container and the liquid medicine contained therein are collectively referred to as a liquid medicine container. The liquid medicine is taken out of the stored liquid medicine container and used.

[0137] The container for storing the chemical solution is preferably one that is highly clean and allows little elution of impurities, for use in semiconductor device manufacturing. Specific examples of containers that can be used include the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these.

[0138] As the container, it is also preferable to use a multi-layer bottle whose inner wall has a six-layer structure made of six types of resin, or a multi-layer bottle whose inner wall has a seven-layer structure made of six types of resin, in order to prevent impurities from being mixed in (contaminated) with the drug solution. Examples of such containers include the container described in JP 2015-123351 A.

[0139] The liquid-contacting portion of this container may be made of the corrosion-resistant material already described (preferably electrolytically polished stainless steel or fluororesin) or glass. In order to obtain a more excellent effect of the present invention, it is preferable that 90% or more of the area of ​​the liquid-contacting portion is made of the above material, and it is more preferable that the entire liquid-contacting portion is made of the above material.

[0140] The porosity within the container of the drug solution container is preferably 2 to 80% by volume, more preferably 2 to 50% by volume, and even more preferably 5 to 30% by volume. The porosity is calculated according to formula (1). Formula (1): Porosity = {1 - (Volume of the drug solution in the container / Volume of the container)} x 100 The container volume is synonymous with the internal volume (capacity) of the container. By setting the porosity within this range, contamination such as impurities can be limited, thereby ensuring storage stability. [Example]

[0141] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0142] In addition, in preparing the chemical solutions in the Examples and Comparative Examples, handling of containers, preparation of chemical solutions, filling, storage, and analytical measurements were all carried out in a clean room meeting ISO class 2 or 1 standards.

[0143] (Filter) The following filters were used: Filter A: Nippon Filter Co., Ltd. activated carbon filter "FCC-S" (fiber) "Purasol 200nm": UPE membrane (material) manufactured by Entegris, pore size 200nm "PTFE 7nm": Polytetrafluoroethylene filter, manufactured by Entegris, pore size 7nm "UPE 1nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 1nm "UPE 3nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 3nm "UPE 5nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 5nm "Nylon 5nm": Nylon filter, manufactured by Pall, pore size 5nm

[0144] <Product to be purified> The following organic solvents were used as materials to be purified in the production of the chemical solutions of the Examples and Comparative Examples. PGMM: Propylene glycol monomethyl ether PGME: Propylene glycol monoethyl ether PGMP: Propylene glycol monopropyl ether PGMEA: Propylene glycol monomethyl ether acetate (Note that "PGMEA(A)" to "PGMEA(D)" in the table represent four types of PGMEA obtained from different companies.) EL: Ethyl lactate MPM: Methyl methoxypropionate CyPn: Cyclopentanone CyHe: Cyclohexanone (Note that "CyHe," "CyHe(A)," "CyHe(D)," and "CyHe(D)" in the table represent five types of CyHe obtained from different companies.) γBL: Butyrolactone DIAE: Diisoamyl ether ·MIBC: 4-methyl-2-pentanol (Note that "MIBC," "MIBC(A)," and "MIBC(D)" in the table represent five types of MIBC obtained from different companies.) IPA: Isopropanol DMSO: Dimethyl sulfoxide NMP: N-methylpyrrolidone DEG: Diethylene glycol EG: Ethylene glycol DPG: Dipropylene glycol PG: Propylene glycol PC: Propylene carbonate Sulfolane 2-Heptanone nBA: Butyl acetate (Note that "nBA(A)" to "nBA(D)" in the table represent four types of nBA obtained from different companies.) ·iAA: Isoamyl acetate Butyl butyrate Isobutyl isobutyrate Isoamyl ether (2.1) Undecane Dimethyl malonate (10.3) The values ​​in parentheses are the distances (MPa) between the Hansen solubility parameters of isoamyl ether and dimethyl malonate relative to eicosene. 0.5 )

[0145] <Container> The following containers were used to store the drug solutions. EP-SUS: A vessel with electropolished stainless steel parts in contact with the liquid PFA: Container with liquid-contacting parts coated with perfluoroalkoxyalkane

[0146] <Purification procedure> One of the above-mentioned products to be purified was selected and subjected to the distillation purification treatment shown in Table 1. In the "Distillation purification" column in the table, "Yes-1" indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 15), "Yes-2" indicates that vacuum distillation was performed using a distillation tower (theoretical number of plates: 25), "Yes-3" indicates that vacuum distillation was performed twice using a distillation tower (theoretical number of plates: 30), "Yes-4" indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 20), "Yes-5" indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 10), and "Yes-6" indicates that atmospheric distillation was performed using a distillation tower (theoretical number of plates: 8). However, "No" in the "Distillation purification" column in the table indicates that distillation treatment was not carried out, and in the examples where the "Distillation purification" column has "No", distillation purification was not carried out.

[0147] Next, the distilled and purified product was stored in a storage tank, and the product stored in the storage tank was filtered through filters 1 and 2 shown in Table 1. After filtering through filter 2, the product was circulated upstream of filter 1 and filtered again through filters 1 and 2, thereby carrying out a circulating filtration process. Next, the purified product that had been subjected to circulating filtration using filters 1 and 2 was passed through filters 3 and 4 shown in Table 1 in this order, and stored in a storage tank. Next, the purified product stored in the storage tank was filtered using filter 5 shown in Table 1, and the purified product after filtration using filter 5 was circulated upstream of filter 5 and filtered again using filter 5, thereby carrying out a circulating filtration process. After the circulating filtration treatment, the mixture was placed in a container shown in Table 1 with a predetermined void ratio.

[0148] In the above-mentioned series of purification processes, the liquid-contacting parts of various devices (for example, distillation columns, piping, storage tanks, etc.) that come into contact with the product to be purified were made of electrolytically polished stainless steel.

[0149] The contents of organic components and metal components in the chemical solution were measured by the following method.

[0150] <Organic ingredient content> The contents of organic components (first organic compound, second organic compound, etc.) in various chemical solutions were analyzed using a gas chromatograph mass spectrometer (GC / MS) (Agilent, GC: 7890B, MS: 5977B EI / CI MSD).

[0151] <Metal component content> The content of metal components (metal ions, metal particles) in the chemical solution was measured by a method using ICP-MS and SP-ICP-MS. The following equipment was used: Manufacturer: PerkinElmer Model: NexION350S The following analysis software was used for the analysis. ·Syngistix Nano Application Module for "SP-ICP-MS" Syngistix for ICP-MS software

[0152] "ClogP" in the table represents the ClogP value of the organic solvent. "Purity" in the table indicates the content (mass %) of the organic solvent in the obtained chemical solution relative to the total mass of the chemical solution. In the table, "Total content 1 (ppt by mass)" represents the total content (ppt by mass) of the first organic compound, and "Total content 2 (ppt by mass)" represents the total content (ppt by mass) of the second organic compound. In the table, "Ratio 1" represents the ratio of the total content of the first organic compound to the content of the metal component, "Ratio 2" represents the ratio of the total content of the first organic compound and the second organic compound to the content of metal particles, "Ratio 3" represents the ratio of the total content of the first organic compound and the second organic compound to the content of metal ions, "Ratio 4" represents the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component, and "Ratio 5" represents the ratio of the total content of the first organic compound and the second organic compound other than compound (VI) to the content of compound (VI). The "porosity" column in the table is the value calculated using formula (X). Formula (X): Porosity = {1 - (Volume of the drug solution in the container / Volume of the container)} x 100

[0153] The drug solution obtained as described above contained the compounds shown in the columns "Compound (I)" to "Compound (VII)". In the "Compound (I)" to "Compound (VII)" columns in the table, the "Type" column indicates each compound as follows. The ClogP values ​​of each compound described below were as follows: Compound 5: ClogP 6.20 Compound 6: ClogP 8.87 Compound 7: ClogP -2.0~5.0 Compound 8: ClogP -3.0~1.0 Compound 9: ClogP -3.0~1.0 Compound 10: ClogP 0~4.0 Compound 11: ClogP 0~8.0 Compound 12: ClogP -0.15 Compound 13: ClogP 2.25 Compound 14: ClogP 4.0~6.0 Compound 15: ClogP 18.89 Compound 16: ClogP 4.0~8.0 Compound 17: ClogP 4.0~8.0 Compound 18:ClogP 7.36 Compound 19: ClogP 8.71 Compound 20: ClogP 4.82 Compound 21: ClogP 8.01 Compound 22: ClogP 5.00 Compound 24: ClogP 5.0~8.5 Compound 25: ClogP 5.0~8.5 Compound 26: ClogP 3.0~4.5 Compound 27: ClogP 0.78 Compound 28: ClogP 8.23 Compound 29:ClogP 14.23 Compound 30:ClogP 4.1 Compound 31: ClogP 2.7 Compound 32: ClogP 0.48 Compound 33: ClogP 4.26 Compound 35: ClogP 6.92 Compound 36: ClogP 4.34 Compound 37: ClogP 3.64

[0154] [ka]

[0155] The * in L1 in Compounds 8 and 9 indicates the bonding position.

[0156] [ka]

[0157] [ka]

[0158] [ka]

[0159] [ka]

[0160] [ka]

[0161] [ka]

[0162] [ka]

[0163] [ka]

[0164] [ka]

[0165] <Test> [Pre-wet liquid, rinse liquid] The defect suppression ability of the prepared chemical solutions when used as pre-wet solutions and rinse solutions was evaluated by the method described below. First, the chemical solutions were spin-discharged onto a 300 mm diameter silicon substrate, and while the substrate was rotating, 0.5 cc of each chemical solution was dispensed onto the surface of the substrate. The substrate was then spin-dried. Next, using a KLA-Tencor wafer inspection system "SP-5," the number of defects present on the substrate after the chemical solution was applied was counted (this was taken as the measurement value). Next, using EDAX (energy-dispersive X-ray spectroscopy), the particulate foreign matter on the wafer was classified into "metal residue defects" primarily composed of metal and "particulate organic residue defects" primarily composed of organic matter, and measured. Furthermore, non-particulate stain-like defects were counted as "stain-like defects." If the evaluation of metal residue defects, particulate organic residue defects, and stain-like residue defects is C or higher, the chemical solution has the defect suppression properties required for the chemical solution.

[0166] <Individual evaluation (metal residue defects, particulate organic residue defects, stain-like residue defects)> A: The corresponding number of defects was 20 or less per wafer. B: The corresponding defect count was greater than 20 / wafer and less than or equal to 50 / wafer. C: The corresponding defect count was greater than 50 / wafer and less than or equal to 100 / wafer. D: The number of corresponding defects exceeded 100 / wafer.

[0167] [Developer] The defect suppression ability of the prepared chemical solution when used as a developer was evaluated by the method described below. First, a resist pattern was formed by the following procedure. An organic anti-reflective coating composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied to a silicon substrate having a diameter of 300 mm and baked at 205° C. for 60 seconds to form an anti-reflective coating having a thickness of 78 nm. To improve the coating properties, a pre-wet liquid (CyHe in Example 30 was used) was dropped onto the surface of the silicon wafer on which the anti-reflection film had been formed, on the side of the anti-reflection film, and spin coating was carried out. Next, the actinic ray-sensitive or radiation-sensitive resin composition 1 or actinic ray-sensitive or radiation-sensitive resin composition 2 described below was applied onto the anti-reflective film after the prewetting process, and prebaked (PB) at 100°C for 60 seconds to form a resist film with a thickness of 150 nm. In Examples 49 to 59 and Comparative Examples 3 and 4, (actinic ray-sensitive or radiation-sensitive resin composition 1) was used, and in Examples 60 to 70, (actinic ray-sensitive or radiation-sensitive resin composition 2) was used.

[0168] (Actinic ray-sensitive or radiation-sensitive resin composition 1) Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value shown for each repeating unit means mol %): 100 parts by mass

[0169] [ka]

[0170] Photoacid generator shown below: 8 parts by mass

[0171] [ka]

[0172] The quencher shown below: 5 parts by mass (the mass ratio, from left to right, was 0.1:0.3:0.3:0.2). Of the quenchers listed below, the polymer-type quencher has a weight-average molecular weight (Mw) of 5,000. The numerical values ​​listed for each repeating unit indicate the molar ratio.

[0173] [ka]

[0174] Hydrophobic resin shown below: 4 parts by mass (the mass ratio, from left to right, was 0.5:0.5). Of the hydrophobic resins shown below, the hydrophobic resin on the left has a weight average molecular weight (Mw) of 7000, and the hydrophobic resin on the right has a weight average molecular weight (Mw) of 8000. In each hydrophobic resin, the numerical value written for each repeating unit means the molar ratio.

[0175] [ka]

[0176] solvent: PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass Cyclohexanone: 600 parts by mass γ-BL (γ-butyrolactone): 100 parts by mass

[0177] (Actinic ray-sensitive or radiation-sensitive resin composition 2) Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 8000)): 100 parts by mass

[0178] [ka]

[0179] The contents of the repeating units in the above formula were, from left to right, 30 mol %, 15 mol %, 15 mol %, 20 mol %, and 20 mol % relative to all repeating units.

[0180] Photoacid generator shown below: 15 parts by mass

[0181] [ka]

[0182] 7 parts by mass of the quencher shown below (mass ratio, from left to right, was 1:1)

[0183] [ka] JPEG2026034518000034.jpg2134

[0184] 20 parts by mass of the hydrophobic resin shown below (the mass ratio, from top to bottom, was 3:7) Of the hydrophobic resins shown below, the hydrophobic resin in the upper row has a weight average molecular weight (Mw) of 10,000, and the hydrophobic resin in the lower row has a weight average molecular weight (Mw) of 7,000. In the hydrophobic resins shown in the lower row, the numerical values ​​written for each repeating unit indicate the molar ratio.

[0185] [ka] JPEG2026034518000036.jpg3563

[0186] solvent: PGMEA (propylene glycol monomethyl ether acetate): 50 parts by mass PGME (propylene glycol monomethyl ether): 100 parts by mass 2-heptanone: 100 parts by mass γ-BL (γ-butyrolactone): 500 parts by mass

[0187] The wafer on which the resist film was formed was scanned with an ArF excimer laser scanner (Numerical Aperture: 0.75) at 25 mJ / cm 2 The wafer was subjected to pattern exposure at 120°C for 60 seconds. The wafer was then developed by puddling with each developer (chemical) for 30 seconds. The wafer was then rotated at 4000 rpm for 30 seconds to form a negative resist pattern. The resulting negative pattern was then heated at 200°C for 300 seconds. Through the above process, an L / S pattern with a line / space ratio of 1:1 (average pattern width: 45 nm) was obtained. Each pattern was evaluated for developability and defect suppression.

[0188] <Defect suppression> The formed wafer patterns were observed using a pattern defect measurement device (Hitachi High-Technologies Corporation's Multipurpose SEM (Scanning Electron Microscope) "Inspago" RS6000 series) and the number of defects listed below was counted. Poor development defect: A defect in which the space is not formed all the way to the bottom of the pattern Residue defect: A defect where foreign matter exists on the pattern Uniformity defect: A defect where the pattern width is more than ±1 nm from the specified value If the evaluation of any of the development defects, residue defects, and uniformity defects is C or higher, the chemical solution has the defect suppression properties required of the chemical solution.

[0189] <Individual evaluation (development defects, residue defects, uniformity defects)> AA: The corresponding number of defects was 3 or less per wafer. A: The corresponding number of defects was greater than 3 / wafer and less than 5 / wafer. B: The corresponding number of defects was greater than 5 / wafer and less than or equal to 10 / wafer. C: The corresponding defect count was greater than 10 / wafer and less than or equal to 30 / wafer. D: The number of corresponding defects exceeded 30 / wafer.

[0190] In Table 1, "Application 1" means that the above test was conducted using the chemical solution described in each Example and Comparative Example as a pre-wet solution and a rinse solution. "Application 2" means that the above test was conducted using the chemical solution described in each Example and Comparative Example as a developer. In Example 75, dimethyl malonate and isoamyl ether were mixed in a 5:5 (mass ratio).

[0191] [Table 1]

[0192] [Table 2]

[0193] [Table 3]

[0194] Table 4

[0195] Table 5

[0196] Table 6

[0197] Table 7

[0198] Table 8

[0199] Table 9

[0200] Table 10

[0201] Table 11

[0202] Table 12

[0203] Table 13

[0204] Table 14

[0205] In Table 1, the data for each Example and Comparative Example are shown in Table 1 [Part 1]. <1> ~ <7> , and Table 1 [Part 2] <1> ~ <7> For example, in Example 1, Table 1 [Part 1] <1> As shown in Table 1 [Part 1], PGMM was used as the organic solvent. <2> As shown in Table 1, the total amount of metal ions in the chemical solution is 35 mass ppt. <3> As shown in Table 1, the total amount of metal particles in the solution is 12.3 mass ppt. <4> As shown in Table 1, the total amount of Compound (I) is 89 mass ppt. <5> As shown in Table 1, the total amount of compound (V) is 45 mass ppt. <6> As shown in Table 1, the ratio is 2.12. <7> As shown in Figure 1, the metal residue is "A." The same applies to the other examples and comparative examples.

[0206] From the results shown in the table, it was confirmed that the chemical solution of the present invention is excellent in suppressing defects when applied to the production of semiconductor devices. In particular, when Examples 23, 24, 32, 33, 41, 42, and other Examples were compared, the effect was more excellent when the content of the metal component was 0.1 to 500 ppt by mass relative to the total mass of the chemical solution. Furthermore, a comparison of Examples 26, 35, 44, and other Examples showed that the effect was better when the total content 1 (total content of the first organic compounds) was 10,000 mass ppt or less (preferably 2,000 mass ppt or less). Furthermore, a comparison of Examples 23, 25, and other Examples showed that when Ratio 1 (the ratio of the total content of the first organic compound to the content of the metal component) was 0.01 to 10,000, the effect was more excellent.

[0207] <EUV exposure> (Actinic ray-sensitive or radiation-sensitive resin composition (resist composition 1)) First, resist composition 1 was obtained by mixing the components in the following ratio. ·Resin (A-1): 0.77g Photoacid generator (B-1): 0.03g Basic compound (E-3): 0.03g PGMEA (commercially available, high-purity grade): 67.5g Ethyl lactate (commercially available, high-purity grade): 75g

[0208] Resin (A-1) As the resin (A-1), the following resin was used.

[0209] [ka]

[0210] Photoacid generator (B-1) The following compound was used as the photoacid generator (B-1).

[0211] [ka]

[0212] Basic compounds (E-3) As the basic compound (E-3), the following compound was used.

[0213] [ka]

[0214] (Pattern formation and evaluation) First, AL412 (manufactured by Brewer Science) was applied to a 300 mm diameter silicon wafer and baked at 200°C for 60 seconds to form a 20 nm thick resist underlayer film. A pre-wet liquid (cyclohexanone / manufactured by FFUS) was applied on top of that, and then the resist composition was applied on top of that and baked at 100°C for 60 seconds (PB: Prebake) to form a 30 nm thick resist film.

[0215] This resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 90°, outer sigma 0.87, inner sigma 0.35). It was then baked at 85°C for 60 seconds (PEB: Post Exposure Bake). Next, a developer (butyl acetate / manufactured by FETW) was sprayed onto the silicon wafer for 30 seconds for development, and a rinse solution was sprayed onto the silicon wafer for 20 seconds for rinsing. The silicon wafer was then rotated at 2000 rpm for 40 seconds to form a line-and-space pattern with a space width of 20 nm and a pattern line width of 15 nm. The rinse solutions used were the same as those used in Examples 1 to 48 and 71 to 75. Evaluations of defects such as metal residue defects, particulate organic residue defects, and stain-like residue defects were carried out, and the results are shown in Table 1 [Part 1]. <7> The desired effect was obtained in the same manner as above.

Claims

1. pattern-exposing the resist film; and developing the resist film to form a negative resist pattern, the developer used for the development is a chemical solution containing an organic solvent, the chemical solution contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III), the total content of the first organic compounds is 0.01 to 100,000 mass ppt relative to the total mass of the chemical solution; Furthermore, the chemical solution contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII), a total content of the second organic compounds in the chemical solution of 0.01 ppt by mass or more and 100,000 ppt by mass or less, based on the total mass of the chemical solution; 【Chemistry 1】 In general formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by general formula (A). 【Chemistry 2】 When Y represents a benzene ring group, s represents 1, L represents a single bond, and R １ａ represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom. When the benzene ring group is substituted with an alkyl group, the alkyl group and R １ａ may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group, the alkyl groups may be bonded to each other to form a ring. When Y represents a group represented by general formula (A), s represents 3, L represents a methylene group, and R １ａ each independently represents an alkyl group. In general formula (II), R ２ａ ~R ２ｈ each independently represents an alkyl group which may contain a substituent. R ２ｂ and R ２ｅ may be bonded to each other to form a ring. R ２ｂ and R ２ｅ The group formed by bonding with each other is —O—(—Si(R ２ｉ ) ２ -O-) ａ - is. a represents an integer of 1 or more. R ２ｉ represents an alkyl group which may contain a substituent. Multiple Rs ２ｉ may be the same or different. In general formula (III), R ３ａ is -N(R ３ｃ ) R ３ｄ or -SR ３ｅ Represents. R ３ｃ , R ３ｄ , and R ３ｅ represents a hydrogen atom or a substituent. R ３ｂ represents —NH— or —S—. 【Transformation 3】 In general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent. In general formula (V), R ５ａ represents an alkyl group which may contain a substituent or a hydrogen atom. R ５ｂ and R ５ｃ are each independently a hydrogen atom, -AL-O-R ５ｄ , -CO-R ５ｅ , or —CH(OH)—R ５ｆ Represents. AL represents an alkylene group which may contain a substituent. R ５ｄ , R ５ｅ , and R ５ｆ each independently represents a substituent. R ５ｄ If there are multiple R ５ｄ may be the same or different. ６ｅ If there are multiple R ５ｅ may be the same or different. ５ｆ If there are multiple R ５ｆ may be the same or different. R ５ａ a substituent that may be contained in the alkyl group represented by R ５ｄ , R ５ｅ , and R ５ｆ a combination of two selected from the group consisting of two R ５ｄ Comrades, two R ５ｅ Two or two R ５ｆ They may be bonded to each other to form a ring. R ５ａ , R ５ｂ , and R ５ｃ At least one of these is other than a hydrogen atom. In general formula (VI), R ６ａ and R ６ｂ each independently represents an alkyl group which may contain a substituent. In general formula (VII), R ７ａ ~R ７ｃ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent.

2. applying a pre-wet liquid; forming a resist film; pattern-exposing the resist film; and developing the resist film to form a negative resist pattern, the pre-wet liquid is a chemical liquid containing an organic solvent, the chemical solution contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III), the total content of the first organic compounds is 0.01 to 100,000 mass ppt relative to the total mass of the chemical solution; Furthermore, the chemical solution contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII), The method for forming a resist pattern, wherein the total content of the second organic compounds is 0.01 mass ppt or more and 100,000 mass ppt or less with respect to the total mass of the chemical solution. 【Chemistry 4】 In general formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by general formula (A). 【Transformation 5】 When Y represents a benzene ring group, s represents 1, L represents a single bond, and R １ａ represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom. When the benzene ring group is substituted with an alkyl group, the alkyl group and R １ａ may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group, the alkyl groups may be bonded to each other to form a ring. When Y represents a group represented by general formula (A), s represents 3, L represents a methylene group, and R １ａ each independently represents an alkyl group. In general formula (II), R ２ａ ~R ２ｈ each independently represents an alkyl group which may contain a substituent. R ２ｂ and R ２ｅ may be bonded to each other to form a ring. R ２ｂ and R ２ｅ The group formed by bonding with each other is —O—(—Si(R ２ｉ ) ２ -O-) ａ - is. a represents an integer of 1 or more. R ２ｉ represents an alkyl group which may contain a substituent. Multiple Rs ２ｉ may be the same or different. In general formula (III), R ３ａ is -N(R ３ｃ ) R ３ｄ or -SR ３ｅ Represents. R ３ｃ , R ３ｄ , and R ３ｅ represents a hydrogen atom or a substituent. R ３ｂ represents —NH— or —S—. 【Transformation 6】 In general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent. In general formula (V), R ５ａ represents an alkyl group which may contain a substituent or a hydrogen atom. R ５ｂ and R ５ｃ are each independently a hydrogen atom, -AL-O-R ５ｄ , -CO-R ５ｅ , or —CH(OH)—R ５ｆ Represents. AL represents an alkylene group which may contain a substituent. R ５ｄ , R ５ｅ , and R ５ｆ each independently represents a substituent. R ５ｄ If there are multiple R ５ｄ may be the same or different. ６ｅ If there are multiple R ５ｅ may be the same or different. ５ｆ If there are multiple R ５ｆ may be the same or different. R ５ａ a substituent that may be contained in the alkyl group represented by R ５ｄ , R ５ｅ , and R ５ｆ a combination of two selected from the group consisting of two R ５ｄ Comrades, two R ５ｅ Two or two R ５ｆ They may be bonded to each other to form a ring. R ５ａ , R ５ｂ , and R ５ｃ At least one of these is other than a hydrogen atom. In general formula (VI), R ６ａ and R ６ｂ each independently represents an alkyl group which may contain a substituent. In general formula (VII), R ７ａ ~R ７ｃ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent.

3. pattern-exposing the resist film; developing the resist film to form a negative resist pattern; and rinsing the negative resist pattern, the rinse liquid is a chemical liquid containing an organic solvent, the chemical solution contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III), the total content of the first organic compounds is 0.01 to 100,000 mass ppt relative to the total mass of the chemical solution; Furthermore, the chemical solution contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII), a total content of the second organic compounds in the chemical solution of 0.01 ppt by mass or more and 100,000 ppt by mass or less, based on the total mass of the chemical solution; 【Transformation 7】 In general formula (I), Y represents a benzene ring group which may be substituted with an alkyl group, or a group represented by general formula (A). 【Transformation 8】 When Y represents a benzene ring group, s represents 1, L represents a single bond, and R １ａ represents an alkyl group which may contain a substituent. The alkyl group may contain a heteroatom. When the benzene ring group is substituted with an alkyl group, the alkyl group and R １ａ may be bonded to each other to form a ring. When a plurality of alkyl groups are substituted on the benzene ring group, the alkyl groups may be bonded to each other to form a ring. When Y represents a group represented by general formula (A), s represents 3, L represents a methylene group, and R １ａ each independently represents an alkyl group. In general formula (II), R ２ａ ~R ２ｈ each independently represents an alkyl group which may contain a substituent. R ２ｂ and R ２ｅ may be bonded to each other to form a ring. R ２ｂ and R ２ｅ The group formed by bonding with each other is —O—(—Si(R ２ｉ ) ２ -O-) ａ - is. a represents an integer of 1 or more. R ２ｉ represents an alkyl group which may contain a substituent. Multiple Rs ２ｉ may be the same or different. In general formula (III), R ３ａ is -N(R ３ｃ ) R ３ｄ or -SR ３ｅ Represents. R ３ｃ , R ３ｄ , and R ３ｅ represents a hydrogen atom or a substituent. R ３ｂ represents —NH— or —S—. 【Chemistry 9】 In general formula (IV), X represents a benzene ring group which may contain a substituent, a cyclohexene ring group which may contain a substituent, or a cyclohexane ring group which contains a cycloalkyloxy group as a substituent. The cyclohexane ring group may further contain another substituent. In general formula (V), R ５ａ represents an alkyl group which may contain a substituent or a hydrogen atom. R ５ｂ and R ５ｃ are each independently a hydrogen atom, -AL-O-R ５ｄ , -CO-R ５ｅ , or —CH(OH)—R ５ｆ Represents. AL represents an alkylene group which may contain a substituent. R ５ｄ , R ５ｅ , and R ５ｆ each independently represents a substituent. R ５ｄ If there are multiple R ５ｄ may be the same or different. ６ｅ If there are multiple R ５ｅ may be the same or different. ５ｆ If there are multiple R ５ｆ may be the same or different. R ５ａ a substituent that may be contained in the alkyl group represented by R ５ｄ , R ５ｅ , and R ５ｆ a combination of two selected from the group consisting of two R ５ｄ Comrades, two R ５ｅ Two or two R ５ｆ They may be bonded to each other to form a ring. R ５ａ , R ５ｂ , and R ５ｃ At least one of these is other than a hydrogen atom. In general formula (VI), R ６ａ and R ６ｂ each independently represents an alkyl group which may contain a substituent. In general formula (VII), R ７ａ ~R ７ｃ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a benzene ring group which may have a substituent.

4. 4. The method for forming a resist pattern according to claim 1, wherein ArF exposure is used in the step of patternwise exposing the resist film.

5. the resist film contains a resin, 5. The method for forming a resist pattern according to claim 4, wherein the resin contains a repeating unit having a lactone structure.

6. 4. The method for forming a resist pattern according to claim 1, wherein EUV exposure is used in the step of patternwise exposing the resist film.

7. the resist film contains a resin, 7. The method for forming a resist pattern according to claim 6, wherein the resin contains a repeating unit containing a phenolic hydroxyl group.

8. A method for manufacturing a semiconductor device, comprising the method for forming a resist pattern according to any one of claims 1 to 3.

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