Resist pattern forming method, semiconductor device manufacturing method, and chemical liquid

Abstract

This invention provides a method for manufacturing a drug solution with excellent defect suppression properties, a drug solution container, a reagent kit, and a semiconductor wafer. The drug solution of this invention contains an organic solvent and contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (V), wherein the total content of the first organic compound relative to the total mass of the drug solution is 0.01 to 100,000 ppt by mass.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a pharmaceutical solution, a pharmaceutical solution container, a reagent kit, and a semiconductor wafer. Prior Technology

[0002] When manufacturing semiconductor devices by means of a wiring formation step including photolithography, solutions containing water and / or organic solvents may be used as pre-wetting solutions, resist solutions (components for resist film formation), developers, rinsing solutions, stripping solutions, chemical mechanical polishing (CMP) slurries and cleaning solutions after CMP, or as diluents for these. In recent years, thanks to advancements in photolithography, the miniaturization of patterns has continued to develop. One method for miniaturizing patterns is to shorten the wavelength of the exposure light source. Experiments have been conducted using EUV (Extreme Ultraviolet) and other ultraviolet light sources with even shorter wavelengths to replace previously used ultraviolet light, KrF excimer lasers, and ArF excimer lasers for pattern formation. As the patterns formed become more refined, the aforementioned chemical solutions used in the process require further defect suppression.

[0003] As a solution used in conventional pattern forming, Patent Document 1 discloses a "method for manufacturing an organic processing solution for pattern forming of a chemically amplified inhibitor film that can reduce particle generation in pattern forming technology (paragraph

[0010] )". [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2015-084122

[0005] The inventors' research on the organic processing solution (chemical solution) for pattern formation manufactured by the above-described manufacturing method revealed potential for improvement in defect suppression. More specifically, when the chemical solution is used as a pre-wetting solution or rinsing solution, there is potential for improvement in the suppression of defects such as metal residue defects, particulate organic residue defects, and spot-like residue defects. Furthermore, when the chemical solution is used as a pattern developing solution, there is potential for improvement in the suppression of defects such as poor development defects, residue defects, and uniformity defects. The objective of this invention is to provide a pharmaceutical solution with excellent defect inhibition properties as described above. Furthermore, the subject of this invention is also to provide a method for manufacturing a liquid medicine container, a reagent kit, and a semiconductor wafer. Summary of the Invention

[0006] In order to solve the above problems, the inventors conducted in-depth research and discovered that the above problems can be solved by the following structure.

[0007] (1) A pharmaceutical solution containing an organic solvent, the pharmaceutical solution containing at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III) described below. The total content of the first organic compound relative to the total mass of the drug solution is 0.01~100000 ppt. (2) The liquid medicine as described in (1) further contains at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VII) described below. (3) The liquid medicine as described in (2) contains at least two of the first organic compound and the second organic compound. (4) The liquid medicine as described in (3), wherein at least one of the two or more compounds has a ClogP value of 5 or more. (5) The liquid medicine as described in 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 liquid medicine as described in (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) The liquid medicine described in any one of (1) to (6) also contains a metallic component. The content of metal components relative to the total mass of the drug solution is 0.1~500 ppt. (8) The liquid medicine as described in (7) wherein the ratio of the total content of the first organic compound to the content of the metal component is 0.01 to 10000. (9) The liquid medicine described in (2) also contains metallic components. (10) The liquid medicine as described in (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 50000. (11) The liquid medicine as described in (9) or (10), wherein the metal component contains metal particles and metal ions. (12) The liquid medicine as described in (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 50000. (13) The liquid medicine as described in (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 30000. (14) The pharmaceutical solution as described in any one of (1) to (13), wherein the organic solvent is selected from the following: 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, diisopentyl ether, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol. The group consisting of ethylene glycol, dipropylene glycol, propylene glycol, ethyl carbonate, propylene carbonate, cyclobutane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isoamyl propionate, ethylcyclohexane, symmetrical trimethylbenzene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate. (15) The liquid medicine as described in any one of (1) to (14), wherein the volume resistivity of the organic solvent is 5,000,000 Ωm or more. (16) A kit containing two or more of the following: a pre-wetting solution containing any one of the solutions described in (1) to (15); a developing solution containing any one of the solutions described in (1) to (15); a rinsing solution containing any one of the solutions described in (1) to (15); a grinding solution containing any one of the solutions described in (1) to (15); and a resist film forming composition containing any one of the solutions described in (1) to (15). (17) A liquid medicine container comprising a container and a liquid medicine as described in any one of (1) to (15) contained within the container. The liquid-contacting part inside the container that comes into contact with the liquid medicine is made of stainless steel or fluorine-based resin that has been electrolytically ground. (18) The liquid container as described in (17) wherein the porosity of the container, as determined by the formula (X) described later, is 5 to 30% of the volume. (19) A method for manufacturing a semiconductor wafer, wherein the semiconductor wafer is manufactured using a solution described in any one of (1) to (15). [Invention Effects]

[0008] According to the present invention, a drug solution with excellent defect inhibition properties can be provided. Furthermore, according to the present invention, a method for manufacturing a liquid medicine container, a reagent kit, and a semiconductor wafer can also be provided. Simple Explanation of the Diagram

[0009] none Implementation

[0010] The present invention will now be described in detail. The following description of the constituent elements is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range represented by “~” refers to the range including the values ​​recorded before and after “~” as the lower and upper limits. Furthermore, in this invention, "ppm" refers to "parts-per-million (10⁻⁶)", "ppb" refers to "parts-per-billion (10⁻⁹)", "ppt" refers to "parts-per-trillion (10⁻¹²)", and "ppq" refers to "parts-per-quadrillion (10⁻¹⁵)". Furthermore, in the designation of groups (atomic clusters) in this invention, the designations without substitution or unsubstituted groups, without impairing the effects of this invention, include not only groups without substituents but also groups containing substituents. For example, the term "hydrocarbon group" includes not only unsubstituted hydrocarbon groups (unsubstituted hydrocarbon groups) but also substituted hydrocarbon groups (substituted hydrocarbon groups). This applies to all compounds as well. Furthermore, in this invention, "radiation" refers to, for example, far-ultraviolet light, extreme ultraviolet light (EUV), X-rays, or electron beams. Also, in this invention, "light" refers to photochemical rays or radiation. The term "exposure" in this invention, unless otherwise stated, includes not only exposure using far-ultraviolet light, X-rays, or EUV, but also depiction using particle beams such as electron beams or ion beams.

[0011] While the mechanism by which the medicinal solution of the present invention solves the above-mentioned problems may not be clear, the inventors speculate on the following mechanism. Furthermore, the following mechanism is speculative and is included within the scope of the present invention even if the effects of the present invention are achieved through different mechanisms. Trace amounts of impurities may be introduced into the solution during storage and transfer through piping, and these impurities can easily cause various defects. Furthermore, these defects include, for example, those that occur when the solution is used in the manufacturing process of semiconductor devices. More specifically, these include defects such as metal residue, particulate organic residue, and spot-like residue when the solution is used as a pre-wetting or rinsing solution; defects such as poor development, residue, and uniformity when the solution is used as a pattern developer; and defects that occur when the solution is used as a piping cleaning solution and then transferred through cleaned piping to the pre-wetting, rinsing, or developing solution. The liquid of the present invention contains a certain amount of the first organic compound described later, thus exhibiting the state of a saturated solution, and impurities (especially impurities that are prone to cause defects) are difficult to mix into the liquid. On the other hand, by setting the content of the first organic compound below a predetermined amount, it is possible to avoid the first organic compound itself becoming a cause of defect. Based on this mechanism, the inventors speculate that in various processes using the pharmaceutical solution of the present invention, the generation of defects in the final product can be suppressed.

[0012] The pharmaceutical 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, wherein the total content of the first organic compound is 0.1 to 100,000 ppt by mass relative to the total mass of the pharmaceutical solution. The ingredients contained in the liquid of the present invention will be described in detail below.

[0013] <Organic solvents> The pharmaceutical solution of the present invention (hereinafter also referred to as "the pharmaceutical solution") contains an organic solvent. In this specification, "organic solvent" refers to a liquid organic compound containing more than 10,000 ppm by mass of each component relative to the total mass of the above-mentioned pharmaceutical solution. That is, in this specification, a liquid organic compound containing more than 10,000 ppm by mass relative to the total mass of the above-mentioned pharmaceutical solution is equivalent to an organic solvent. Furthermore, in this specification, the term "liquid" refers to a liquid state at 25°C and atmospheric pressure.

[0014] There are no particular restrictions on the content of organic solvents in the drug solution, but relative to the total mass of the drug solution, 98.00% by mass or more is preferred, more than 99.00% by mass is even better, more than 99.90% by mass is further preferred, and more than 99.95% by mass is especially preferred. The upper limit is less than 100% by mass. One organic solvent may be used alone, or two or more may be used. When using two or more organic solvents, it is preferable that the total content be within the above-mentioned range.

[0015] There are no particular restrictions on the types of organic solvents used, and known organic solvents can be used. Examples of organic solvents include alkyl glycol monoalkyl ether carboxylic esters, alkyl glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionate esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably with 4 to 10 carbon atoms), alkyl carbonates, alkyl alkoxyacetic acid esters, alkyl pyruvate esters, dialkyl esters, cyclic esters, dialkyl ethers, monohydric alcohols, ethylene glycol, alkyl acetate esters, and N-alkylpyrrolidones.

[0016] Regarding organic solvents, for example, those selected from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene glycol 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, diisopentyl ether, isoamyl acetate, dimethyl sulfoxide, N... One or more of the following groups are preferred: methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethyl carbonate, cyclobutane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, undecane, pentyl propionate, isopentyl propionate, ethylcyclohexane, symmetrical trimethylbenzene, decane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate. Examples of using two or more organic solvents include the combined use of PGMEA and PGME, and the combined use of PGMEA and PC. In addition, the types and contents of organic solvents in the drug solution can be measured using gas chromatography-mass spectrometry.

[0017] There are no particular limitations on the volume resistivity of organic solvents, but those above 500,000,000 Ωm are preferred. There are no particular upper limits, but those below 5,000,000,000 Ωm are preferred. The volume resistivity of organic solvents can be measured, for example, using volume resistivity meters such as the SME-8310 and super-insulator meters such as the SM-8220 manufactured by HIOKI EE CORPORATION.

[0018] Regarding organic solvents, for example, a distance of 3~20 MPa 0.5 (more preferably 5~20 MPa 0.5) relative to the Hansen solubility parameter of eicosene is also preferred. When using two or more organic solvents, it is preferable that at least one of them meets the range of the Hansen solubility parameters mentioned above. When using two or more organic solvents, it is preferable that the weighted average of the molar ratio of the contents of each organic solvent and the Hansen solubility parameter meets the range of the Hansen solubility parameter mentioned above.

[0019] For example, from the perspective of superior defect suppression of the drug solution, it is preferable that the organic solvent is merely an organic solvent that substantially meets the range of the above-mentioned Hansen solubility parameters. An organic solvent that substantially meets the range of the above-mentioned Hansen solubility parameters means that, relative to the total mass of the organic solvent, the content of the organic solvent meeting the range of the above-mentioned Hansen solubility parameters is 99% by mass or more (preferably 99.9% by mass or more).

[0020] Alternatively, for example, a mixed solvent containing organic solvents that satisfy the range of the above-mentioned Hansen solubility parameters and organic solvents that do not satisfy the range of the above-mentioned Hansen solubility parameters is also preferred. In this case, from the viewpoint that the obtained drug solution has better defect suppression properties, it is preferable that the mixed solvent contains 20-80% by mass (preferably 30-70% by mass) of organic solvents that meet the range of the above-mentioned Hansen solubility parameters, relative to the total mass of the mixed solvent, and 20-80% by mass (preferably 30-70% by mass) of organic solvents that do not meet the range of the above-mentioned Hansen solubility parameters, relative to the total mass of the mixed solvent. It is believed that, compared to the case where the amount of organic solvent that does not meet the above-mentioned Hansen solubility parameter range is outside the predetermined range (e.g., 1% or more but less than 20% or more than 80% by mass relative to the total mass of the mixed solvent), when the content of organic solvent that meets the above-mentioned Hansen solubility parameter range and the content of organic solvent that does not meet the above-mentioned Hansen solubility parameter range are both a certain amount or more, the affinity of the drug solution relative to the metal-based raw material and the organic-based raw material can be adjusted within an appropriate range, thereby making the effect of the present invention superior. Furthermore, in this case, it is preferable that the total content of organic solvents satisfying the above-mentioned Hansen solubility parameter range and organic solvents not satisfying the above-mentioned Hansen solubility parameter range, relative to the total mass of the mixed solution, is 99.0% by mass or more. There is no particular upper limit, but it is generally preferable to be 99.99999% by mass or less. In addition, for organic solvents that do not meet the above range of Hansen solubility parameters, the distance of the Hansen solubility parameter relative to eicosene is 0 MPa 0.5 or more and less than 3 MPa 0.5 (preferably more than 0 MPa 0.5 and less than 3 MPa 0.5) or more than 20 MPa 0.5 (preferably more than 20 MPa 0.5 and less than 50 MPa 0.5).

[0021] In this specification, the Hansen solubility parameter refers to the Hansen solubility parameter described in "Hansen Solubility Parameters: A Users Handbook, Second Edition" (pages 1-310, CRC Press, 2007). That is, regarding the Hansen solubility parameter, solubility is represented by a multidimensional vector (dispersion term (δd), interpole 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 distance of the Hansen solubility parameter refers to the distance between two compounds in Hansen space. The distance of the Hansen solubility parameter can be calculated by the following formula. (Ra) 2=4(δd2-δd1) 2+(δp2-δp1) 2+(δh2-δh1) 2 Ra: Distance between the Hansen solubility parameters of compound 1 and compound 2 (unit: MPa 0.5) δd1: Dispersion term of compound 1 (unit: MPa 0.5) δd2: Dispersion term of compound 2 (unit: MPa 0.5) δp1: Interpolar dipole term of compound 1 (unit: MPa 0.5) δp2: Interpolar term of compound 2 (unit: MPa 0.5) δh1: Hydrogen bonding term of compound 1 (unit: MPa 0.5) δh2: Hydrogen bonding term of the second compound (unit: MPa 0.5) In this specification, the Hansen solubility parameter of the compound is specifically calculated using HSPiP (Hansen Solubility Parameter in Practice).

[0022] <Organic Compound 1> The liquid contains at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III).

[0023] [Chemical Formula 1]

[0024] In general formula (I), Y represents a benzene ring group that can be substituted with an alkyl group or a group represented by general formula (A). In general formula (A), * indicates a bond position.

[0025] [Chemical Formula 2]

[0026] In the case where Y represents a benzene ring group, s represents 1, L represents a single bond, and R 1a represents an alkyl group that may contain substituents. Furthermore, the alkyl group may contain heteroatoms (preferably oxygen atoms). When the alkyl group contains oxygen atoms, it is preferable that they are in the form of -O- or -CO-. In other words, the aforementioned alkyl group may contain -O- or -CO-. The alkyl group of R 1a can be straight-chain, branched, or contain a cyclic structure. The alkyl group of R 1a preferably has 1 to 20 carbon atoms, and 1 to 10 is even more preferred. Furthermore, the carbon number of the alkyl group of R 1a does not include the number of carbon atoms contained in any substituents that may be present in the alkyl group of R 1a. The alkyl group of R 1a may contain substituents containing aromatic ring groups (preferably benzene ring groups; other substituents are also preferred). Of the above substituents, aromatic ester groups are more preferred. When an alkyl group replaces a benzene ring group represented by Y, the alkyl group and R1a can bond together to form a ring. Furthermore, when multiple alkyl groups replace a benzene ring group represented by Y, the alkyl groups can bond together to form a ring.

[0027] In the case where Y represents a group represented by general formula (A), s represents 3, L represents methylene, and R 1a independently represents alkyl. In this case, it is preferable for the alkyl group of R 1a to have 1 to 15 carbon atoms, and even more preferable for 1 to 10 carbon atoms. Examples of compounds represented by general formula (I) are given.

[0028] [Chemical Formula 3]

[0029] In general formula (II), R 2a~R 2h each independently represent an alkyl group that may contain substituents. R2b and R2e can bond to each other to form a ring. The group system formed by the mutual bonding of R2b and R2e is -O-(-Si(R2i)2-O-)a-, which is preferred. 'a' represents an integer greater than or equal to 1. There is no specific upper limit to 'a', but in most cases it is less than or equal to 10. R 2i indicates that it may contain alkyl groups with substituents. There exist multiple R 2i that can be the same or different. The alkyl groups represented by R 2a~R 2i can be straight-chain, branched, or contain cyclic structures. The number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 1 to 5. Furthermore, the number of carbon atoms in the alkyl group does not include the number of carbon atoms contained in any substituents that may be present in the alkyl group. It is preferable that the alkyl groups represented by R 2a~R 2i are each independently unsubstituted alkyl groups, and methyl groups are even more preferred. It is preferable that one of R 2g and R 2h contains a substituent alkyl group. It is also preferable that the substituent contains one or more oxoalkyl groups (preferably with 2-4 carbon atoms in the alkyl moiety, which can be linear, branched, or cyclic). The oxoalkyl groups may contain hydroxyl groups. Examples of compounds represented by general formula (II) are given.

[0030] [Chemical Formula 4]

[0031] [Chemical Formula 5]

[0032] In general formula (III), R 3a represents -N(R 3c)R 3d or -SR 3e. R3c, R3d, and R3e represent hydrogen atoms or substituents. R 3b represents -NH- or -S-. As R 3e, for example, an aromatic thio group can be cited. As an aromatic thio group, a group represented by -S-Ar (Ar: an aromatic cyclic group that may have substituents) is preferred. The aromatic cyclic group in the aforementioned aromatic sulfide group may contain heteroatoms (sulfur atom, nitrogen atom and / or oxygen atom, etc.) or may not contain heteroatoms, with the presence of heteroatoms being preferred. That is, as an aromatic cyclic group, an aromatic heterocyclic group is preferred. The aforementioned aromatic cyclic group may be monocyclic or polycyclic, with polycyclic being preferred. As the aforementioned aromatic cyclic group, the benzothiazole cyclic group is preferred. Examples of compounds represented by general formula (III) are given.

[0033] [Chemical Formula 6]

[0034] There is no particular limitation on the boiling point of the first organic compound, but from the perspective of not being easily volatile and forming an association with the metal component, thereby further suppressing the generation of defects originating from the metal component, a temperature above 250°C is preferred, and above 380°C is even better. There is no particular upper limit, but in most cases it is below 450°C. The boiling point mentioned above refers to the boiling point at 1 atmosphere.

[0035] There is no particular limitation on the molecular weight of the first organic compound, but based on the relationship with the boiling point mentioned above, a molecular weight of 300 or higher is preferred. There is no particular upper limit, but in most cases it is below 1000.

[0036] There are no particular limitations on the ClogP of the first organic compound, but 5.0 or above is preferred, 8.0 to 26.0 is more preferred, and 8.5 to 20.0 is even more preferred. The ClogP value refers to the value obtained by calculating the common logarithm logP of the partition coefficient P of 1-octanol and water. While known methods and software can be used for calculating the ClogP value, unless otherwise specified, the ClogP program incorporated into Cambridge Soft's ChemBioDraw Ultra 12.0 is used in this invention.

[0037] There is no particular limitation on the absolute value of the difference between the ClogP of the first organic compound and the ClogP of the organic solvent. However, from the viewpoint that the first organic compound acts as a hydrophobic compound in the solution and interacts with the metal component, thereby further suppressing the generation of defects originating from the metal component, a value of 3 or higher is preferred, and 5 to 10 is even better.

[0038] The total content of the first organic compound relative to the total mass of the drug solution is 0.01 to 100,000 ppt by mass. From the viewpoint of superior defect inhibition of the drug solution (hereinafter also referred to as "the viewpoint of superior effect of the present invention"), it is preferred to be below 80,000 ppt by mass, more preferably below 10,000 ppt by mass, and further preferably below 2,000 ppt by mass. There is no particular limitation on the lower limit, but it is preferred to be above 0.1 ppt by mass, and more preferably above 1 ppt by mass. The first organic compound can be used alone or in two or more forms. From the viewpoint of further enhancing the effects of the present invention, using two or more forms is preferred.

[0039] In addition, the content of the first organic compound in the drug solution can be measured using GCMS (gas chromatography-mass spectrometry).

[0040] The liquid may contain other components besides the organic solvents and the first organic compound mentioned above. The other components are described in detail below.

[0041] <Second Organic Compound> The solution may contain at least one second organic compound selected from the group consisting of compounds represented by general formulas (IV) to (VIII).

[0042] [Chemical Formula 7]

[0043] In general formula (IV), X represents a benzene cyclogroup that may contain substituents, a cyclohexene cyclogroup that may contain substituents, or a cyclohexane cyclogroup that contains a cycloalkoxy group as a substituent. The aforementioned cyclohexane cyclogroup may also contain other substituents. Examples of other substituents include a hydrocarbon group (e.g., an unsaturated hydrocarbon group) selected from the group consisting of hydroxyl and carboxyl groups. Substituents that can be contained in a benzene ring group include, for example, alkyl, alkoxy, and aryl carbonyl groups. Substituents that can be contained in the cyclohexene cyclogroup include, for example, olefinic groups and cyclohexene cyclogroups.

[0044] As a compound represented by general formula (IV), a compound represented by general formula (IV-1) can be cited. General formula (IV-1) (HO-Ar-L) 4-C In the above formula, Ar represents a benzene ring group that may contain substituents. L represents a divalent linker. Examples of divalent linkers include alkyl groups that may contain ester groups.

[0045] Examples of compounds represented by general formula (IV) are given.

[0046] [Chemical Formula 8]

[0047] [Chemical Formula 9]

[0048] In general formula (V), R 5a indicates that it may have a substituent alkyl group or a hydrogen atom. R 5b and R 5c independently represent a hydrogen atom, -AL-OR 5d, -CO-R 5e, or -CH(OH)-R 5f, respectively. AL indicates that it may contain substituents, specifically alkyl groups (preferably with 1 to 6 carbon atoms). R 5d, R 5e and R 5f each independently represent a substituent (preferably an alkyl group that may also contain a substituent). The alkyl group containing substituents represented by R5a, R5d, R5e and R5f can be either straight-chain or branched, or contain a cyclic structure. The number of carbon atoms in the alkyl group is preferably 1 to 50, and more preferably 1 to 20. Furthermore, the number of carbon atoms in the alkyl group does not include the number of carbon atoms contained in any substituents that may be present in the alkyl group. Substituents that may be contained in the aforementioned alkyl group include, for example, hydroxyl, alkyl ester and alkyl vinyl groups (preferably the alkyl moiety has 3 to 12 carbon atoms). In the case of a plurality of R 5d, each R 5d may be the same or different. Similarly, in the case of a plurality of R 5e, each R 5e may be the same or different. Likewise, in the case of a plurality of R 5f, each R 5f may be the same or different. Selected from the group consisting of substituents that may be contained in an alkyl group represented by R 5a, combinations of two of the group consisting of R 5d, R 5e and R 5f, two R 5ds bonded to each other, two R 5es bonded to each other or two R 5fs bonded to each other to form a ring. The group is selected from substituents that may be contained in an alkyl group represented by R 5a, combinations of two of the group consisting of R 5d, R 5e and R 5f, two R 5ds bonded to each other, two R 5es bonded to each other or two R 5fs bonded to each other, and preferably contains one or more linking groups selected from the group consisting of -O-, -NR 5g- (R 5g is a substituent) and -NHCO-. At least one of R5a, R5b and R5c is a system other than hydrogen atoms.

[0049] As a compound represented by the general formula (V), a compound represented by the general formula (V-1) can be cited.

[0050] [Chemical Formula 10]

[0051] In the above formula, L represents an alkyl group that may contain substituents (preferably an alkyl group with 1 to 10 carbon atoms). q represents 3 to 10 (preferably 4 to 6).

[0052] Examples of compounds represented by the general formula (V) are given.

[0053] [Chemical Formula 11]

[0054] [Chemical Formula 12]

[0055] [Chemical Formula 13]

[0056] In general formula (VI), R 6a and R 6b each independently represent alkyl groups that may contain substituents. The alkyl groups mentioned above can be straight-chain, branched, or contain cyclic structures. The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 2 to 10. Furthermore, the number of carbon atoms in the alkyl group does not include the number of carbon atoms contained in any substituents that may be present in the alkyl group. As the above-mentioned substituents, for example, aromatic cyclic groups (which may also contain substituents; phenyl is preferred) are preferred. Examples of compounds represented by general formula (VI) are given.

[0057] [Chemical Formula 14]

[0058] In general formula (VII), R 7a to R 7c independently represent a hydrogen atom, an alkyl group that may contain substituents, or a benzene ring group that may contain substituents. R 7a to R 7c may contain one or more (preferably two or more) substituents in an alkyl group or may contain a substituted benzene ring group. The alkyl groups mentioned above can be straight-chain, branched, or contain cyclic structures. The number of carbon atoms in the alkyl group is preferably 1 to 20, and more preferably 1 to 5. Furthermore, the number of carbon atoms in the alkyl group does not include the number of carbon atoms contained in any substituents that may be present in the alkyl group. Alkoxy groups (preferably with 2 to 6 carbon atoms) or halogen atoms (fluorine, chlorine, bromine, or iodine atoms, etc.) are preferred as substituents. As a substituent that may be contained in the above-mentioned benzene ring group, an alkyl group (preferably having 2 to 10 carbon atoms) is preferred. Examples of compounds represented by general formula (VII) are given.

[0059] [Chemical Formula 15]

[0060] There is no particular limitation on the boiling point of the second organic compound, but from the perspective that it is not easily volatile and can form an association with the metal component, thereby further suppressing the generation of defects originating from the metal component, a temperature above 250°C is preferred, and above 380°C is even better. There is no particular upper limit, but in most cases it is below 450°C. The boiling point mentioned above refers to the boiling point at 1 atmosphere.

[0061] There is no particular limitation on the molecular weight of the second organic compound, but based on the relationship with the boiling point mentioned above, a molecular weight of 300 or higher is preferred. There is no particular upper limit, but in most cases it is below 2000.

[0062] There are no particular limitations on the ClogP of the second organic compound, but 5.0 or above is preferred, 8.0 to 26.0 is more preferred, and 8.5 to 20.0 is even more preferred.

[0063] There is no particular limitation on the absolute value of the difference between the ClogP of the second organic compound and the ClogP of the organic solvent. However, from the viewpoint that the second organic compound acts as a hydrophobic compound in the solution and interacts with the metal component, thereby further suppressing the generation of defects originating from the metal component, a value of 3 or higher is preferred, and 5 to 10 is even better.

[0064] There is no particular limitation on the total content of the second organic compound, but from the viewpoint of better efficacy of the present invention, it is preferably 0.01 to 100,000 ppt by mass relative to the total mass of the liquid. Specifically, from the viewpoint of better efficacy of the present invention, 80,000 ppt or less by mass is preferred, 20,000 ppt or less by mass is more preferred, 10,000 ppt or less by mass is further preferred, and 2,000 ppt or less by mass is particularly preferred. There is no particular limitation on the lower limit, but 0.1 ppt or more by mass is preferred, and 1 ppt or more by mass is more preferred. The second organic compound can be used alone or in two or more forms. From the viewpoint of achieving better results in this invention, using two or more forms is preferred.

[0065] In cases where the liquid of the present invention contains both a first organic compound and a second organic compound, from the viewpoint of achieving better results, it is preferable that the liquid of the present invention contains at least two of the first organic compound and the second organic compound. For example, forms containing at least one of the first organic compound and at least one of the second organic compound can be cited. It is preferred that at least one of the above two or more compounds has a ClogP ratio of 5 or higher.

[0066] Furthermore, it is preferable that at least one of the two or more compounds is a compound represented by the general formula (VI). In this case, there is no particular limitation on 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), but 0.01 to 1 is preferred.

[0067] <Metal component> The medicine solution may contain metallic components. In this invention, the metal composition can be categorized as metal particles and metal ions. For example, the so-called metal composition content refers to the total content of metal particles and metal ions. The medicinal solution may contain either metal particles or metal ions, or both. A solution containing both metal particles and metal ions is preferred.

[0068] Examples of metallic elements in a metallic composition 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 Zr (zirconium). A metallic composition may contain one or more metallic elements. Metal particles can be monomers, alloys, or combinations of metals and organic matter. Metallic components can be those that are unavoidably included in the various components (raw materials) contained in the solution, those that are unavoidably included during the manufacture, storage and / or transfer of the treatment solution, or those that are intentionally added.

[0069] From the perspective of superior defect inhibition of the solution, when the solution contains metal components, the content relative to the total mass of the solution is preferably 0.01~500 ppt, more preferably 0.01~250 ppt, and even more preferably 0.01~100 ppt. If the metal content is 0.01 ppt or more, it easily forms an association with the aforementioned first organic compound (or second organic compound), thus making it easy to remove from the substrate. As a result, defect suppression can be further improved. Furthermore, if the content of the metal component is below 500 ppt by mass, it is easy to avoid the increase caused by defects originating from the metal component.

[0070] From the perspective of superior defect inhibition of the drug solution, when the drug solution contains metal ions, the content relative to the total mass of the drug solution is preferably 0.01~400 mass ppt, more preferably 0.01~200 mass ppt, and even more preferably 0.01~80 mass ppt. From the perspective of superior defect suppression of the solution, when the solution contains metal particles, the content relative to the total mass of the solution is preferably 0.01~400 mass ppt, more preferably 0.01~150 mass ppt, and even more preferably 0.01~40 mass ppt.

[0071] In addition, the types and contents of specific metal ions and specific metal particles in the drug 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 apparatus as the conventional ICP-MS (Inductively Coupled Plasma Mass Spectrometry) method, with only the data analysis differing. Data analysis for the SP-ICP-MS method can be performed using commercially available software. In ICP-MS, the content of the metal component being measured is determined regardless of its form. Therefore, the total mass of the metal particles and ions being measured is used as the content of the metal component.

[0072] On the other hand, SP-ICP-MS can measure the content of metal particles. Therefore, by subtracting the content of metal particles from the content of metal components in the sample, the content of metal ions in the sample can be calculated. As an apparatus for SP-ICP-MS, an example is the Agilent Technologies 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200), which can perform measurements using the methods described in the examples. Other apparatuses besides the above, such as the PerkinElmer NexION 350S, can also be used, including the Agilent Technologies 8900.

[0073] There is no particular limitation on the ratio of the total content of the first organic compound to the content of the metal component, but from the viewpoint of better performance of the present invention, 0.01 to 10000 is preferred, and 0.1 to 5000 is even more preferred. Furthermore, there is no particular limitation on the ratio of the total content of the first organic compound and the second organic compound to the content of the metal component, but from the viewpoint of achieving better results in this invention, 0.01 to 50,000 is preferred, and 0.1 to 5,000 is even more preferred. There is no particular limitation on the ratio of the total content of the first organic compound and the second organic compound to the content of the metal particles, but from the viewpoint of better performance of the present invention, 0.01 to 50,000 is preferred, and 0.05 to 30,000 is even more preferred. There is no particular limitation on the ratio of the total content of the first organic compound and the second organic compound to the content of metal ions, but from the viewpoint of better performance of the present invention, 0.03 to 30,000 is preferred, and 0.05 to 20,000 is even more preferred.

[0074] <Water> The medicine solution may contain water. As water, there are no special restrictions; for example, distilled water, ion-exchanged water, and pure water can be used. Water can be added to the drug solution, or it can be unintentionally mixed into the drug solution during the manufacturing process. Examples of unintentional mixing during the manufacturing process include situations where the raw materials used in the manufacturing process (e.g., organic solvents) contain water, and situations where water is mixed (e.g., contaminated) during the manufacturing process, but are not limited to the above.

[0075] There are no particular restrictions on the water content in the medicinal solution, but it is preferable to be 0.05 to 2.0% by mass relative to the total mass of the solution. The water content in the medicinal solution refers to the water content measured using an apparatus based on the Karl Fischer moisture measurement method.

[0076] <Resin> The medicine solution may contain resin. As a resin, resin P containing groups that decompose under the action of acid to generate polar groups (repeating units containing acid-decomposing groups) is more preferable. As the aforementioned resin, a resin that reduces the solubility of developer solutions mainly composed of organic solvents under the action of acid, i.e., a resin containing the repeating unit represented by the formula (AI) described later, is more preferable. The resin containing the repeating unit represented by the formula (AI) described later contains groups that decompose under the action of acid to generate alkali-soluble groups. Examples of polar groups include base-soluble groups. Examples of base-soluble groups include carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), phenolic hydroxyl groups, and sulfonyl groups.

[0077] In acid-degradable groups, the polar group is protected by a group that is released under the action of acid (acid-degradable group). Examples of acid-degradable groups include -C(R 36)(R 37)(R 38), -C(R 36)(R 37)(OR 39), and -C(R 01)(R 02)(OR 39).

[0078] In the formula, R36 to R39 independently represent alkyl, cycloalkyl, aryl, aralkyl, or alkenyl groups. R36 and R37 can bond together to form a ring.

[0079] R01 and R02 independently represent hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, or alkenyl, respectively.

[0080] The following section details resin P, which reduces the solubility of developer solutions mainly composed of organic solvents through the action of acid.

[0081] (Formula (AI): a repeating unit containing an acid-decomposing group) Resin P containing repeating units represented by formula (AI) is preferred.

[0082] [Chemical Formula 16]

[0083] In formula (AI), Xa 1 represents a hydrogen atom or an alkyl group that may have substituents. T represents a single bond or a divalent linker. Ra 1 to Ra 3 represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic) compounds, respectively. Two of Ra 1 to Ra 3 can bond together to form a cycloalkyl group (monocyclic or polycyclic).

[0084] The content of repeating units containing acid-degradable groups (preferably repeating units represented by formula (AI)) relative to all repeating units in resin P is preferably 20-90 mol%, more preferably 25-85 mol%, and even more preferably 30-80 mol%.

[0085] Furthermore, besides repeating units containing acid-decomposing groups, resin P may also contain other repeating units. Examples of other repeating units include repeating units containing lactone structures, repeating units containing phenolic hydroxyl groups, repeating units containing polar groups, and repeating units containing silicon atoms on their side chains.

[0086] As a conversion value for polystyrene based on GPC (Gel permeation chromatography), the weight average molecular weight of resin P is preferably 1,000~200,000, more preferably 3,000~20,000, and even more preferably 5,000~15,000. The dispersion (molecular weight distribution) of resin P is usually 1~5, with 1~3 being better, 1.2~3.0 being more better, and 1.2~2.0 being even better.

[0087] In the liquid medicine, the content of resin P in the total solids is preferably 50~99.9% by mass, and even more preferably 60~99.0% by mass. Furthermore, in the medicinal solution, resin P can be one type or multiple types. The aforementioned solid components refer to the components in the drug solution obtained after removing organic solvents and solvents such as water.

[0088] In addition, the solution may also contain known compounds such as acid generators, basic compounds, quenchers, hydrophobic resins, and surfactants. The solution may contain, for example, the components contained in photosensitive or radiosensitive linear resin compositions as described in Japanese Patent Application Publication No. 2013-195844, Japanese Patent Application Publication No. 2016-057645, Japanese Patent Application Publication No. 2015-207006, International Publication No. 2014 / 148241, Japanese Patent Application Publication No. 2016-188385 and Japanese Patent Application Publication No. 2017-219818.

[0089] <Uses of the medicinal solution> The solution of the present invention is preferably used in the manufacture of semiconductor devices. Specifically, it is preferred to use the solution of the present invention to manufacture semiconductor wafers. Specifically, in the manufacturing process of semiconductor devices, which includes lithography, etching, ion implantation and stripping steps, organic matter is processed after each step or before moving to the next step. More specifically, it is preferably used as a pre-wetting solution, developer, rinsing solution and polishing solution. In addition, the solution can also be used as a diluent for the resin contained in the composition for forming an inhibitor film (in other words, as a solvent).

[0090] Furthermore, the above-mentioned solution can also be used for purposes other than the manufacture of semiconductor devices, and can also be used as a developing solution and rinsing solution for polyimide, resists for sensors and lenses. Furthermore, the aforementioned solution can also be used as a solvent for medical or cleaning purposes. For example, it is particularly suitable for cleaning piping, containers, and substrates (e.g., wafers and glass). For the cleaning purposes described above, it is also preferable to use cleaning solutions (pipe cleaning solutions and container cleaning solutions, etc.) for cleaning pipes and containers that come into contact with the pre-wetting solution or other liquids.

[0091] The solution is particularly suitable for use in pre-wetting solutions, developing solutions, rinsing solutions, polishing solutions, and resist film forming components. It exhibits even better results when applied to pre-wetting solutions, developing solutions, and rinsing solutions. Furthermore, it exhibits even better results when applied to piping cleaning solutions used in piping for the transfer of these solutions.

[0092] Additionally, it can be used as a kit containing two or more of the following: a pre-wetting solution containing the pharmaceutical solution of the present invention; a developing solution containing the pharmaceutical solution of the present invention; a rinsing solution containing the pharmaceutical solution of the present invention; a grinding solution containing the pharmaceutical solution of the present invention; and a composition for forming a resist film containing the pharmaceutical solution of the present invention.

[0093] <Method for Manufacturing the Liquid Medicine> There are no particular limitations on the method for manufacturing the aforementioned pharmaceutical solution, and known manufacturing methods can be used. However, from the viewpoint of obtaining better effects of the present invention, it is preferable that the method for manufacturing the pharmaceutical solution includes a filtration step of filtering the purified substance containing organic solvent using a filter to obtain the pharmaceutical solution.

[0094] The purified substance used in the filtration step can be purchased or obtained by reacting raw materials. A lower impurity content is preferable for the purified substance. Commercially available products that are labeled as "high-purity grade products" are an example of such purified substances.

[0095] There are no particular limitations on the method for reacting raw materials to obtain a purified product (typically, a purified product containing an organic solvent), and known methods can be used. For example, a method for obtaining an organic solvent by reacting one or more raw materials in the presence of a catalyst can be cited. More specifically, examples include methods for obtaining butyl acetate by reacting acetic acid and n-butanol in the presence of sulfuric acid; methods for obtaining 1-hexanol by reacting ethylene, oxygen, and water in the presence of Al(C₂H₅)₃; methods for obtaining 4-methyl-2-pentanol by reacting cis-4-methyl-2-pentene in the presence of Ipc₂BH (Diisopinocampheylborane); methods for obtaining PGMEA (propylene glycol 1-monomethyl ether 2-acetic acid) by reacting propylene oxide, methanol, and acetic acid in the presence of sulfuric acid; methods for obtaining IPA (isopropyl alcohol) by reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide; and methods for obtaining ethyl lactate by reacting lactic acid and ethanol; etc.

[0096] (Filtering steps) The method for manufacturing the pharmaceutical solution of the present invention preferably includes a filtration step of filtering the above-mentioned purified substance using a filter to obtain the pharmaceutical solution. There are no particular limitations on the method of filtering the purified substance using a filter, but it is preferable to pass the purified substance through a filter unit having a housing and a filter element housed within the housing, whether under pressure or not.

[0097] • Filter pore diameter There are no particular limitations on the pore diameter of the filter; filters with pore diameters commonly used for filtering the purified substance can be used. However, from the viewpoint of more easily controlling the number of particles (such as metal particles) contained in the drug solution within the desired range, a pore diameter of 200 nm or less is preferred, 20 nm or less is even better, 10 nm or less is further preferred, 5 nm or less is particularly preferred, and 3 nm or less is optimal. There are no particular limitations on the lower limit, but from a production standpoint, 1 nm or more is generally preferred. In addition, in this specification, the pore diameter and pore diameter distribution of the filter refer to the pore diameter and pore diameter distribution determined by the bubble point of isopropanol (IPA) or HFE-7200 (“Novec 7200”, manufactured by 3M Company, hydrofluoroether, C 4F 9OC 2H 5).

[0098] If the pore diameter of the filter is less than 5.0 nm, it is preferable from the viewpoint that it is easier to control the number of particles in the drug solution. Hereinafter, filters with a pore diameter of less than 5 nm will also be referred to as "micropore filters". Furthermore, micropore filters can be used alone or in conjunction with filters having other pore diameters. From a productivity standpoint, it is preferable to use them in conjunction with filters having larger pore diameters. In this case, passing the purified material, which has been pre-filtered through a filter with a larger pore diameter, through the micropore filter can prevent clogging of the micropore filter. In other words, when using a single filter, it is preferable for the pore diameter to be 5.0 nm or less. When using two or more filters, it is preferable for the filter with the smallest pore diameter to have a pore diameter of 5.0 nm or less.

[0099] There are no particular limitations on the configuration of using two or more filters with different pore diameters in sequence, but a method of sequentially arranging the described filter units along the pipeline transporting the purified substance can be cited. In this case, if the flow rate of the purified substance per unit time is to be constant as a whole pipeline, sometimes a greater pressure may be applied to the filter with a smaller pore diameter compared to the filter with a larger pore diameter. In such cases, it is preferable to install pressure regulating valves and dampers between the filters to keep the pressure applied to the filter with the smaller pore diameter constant, or to arrange filter units containing the same type of filter side-by-side along the pipeline to increase the filtration area. This allows for more stable control of the number of particles in the drug solution.

[0100] • Filter material There are no particular restrictions on the materials used for filters, and known materials can be used. Specifically, in the case of resins, examples include polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamide-imide; poly(meth)acrylate; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-trifluorochloroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride, etc., polyfluorocarbons; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc. From the viewpoint of having superior solvent resistance and superior defect suppression properties of the obtained pharmaceutical solution, it is preferable to select at least one polymer from the group comprising nylon (preferably 6,6-nylon), polyolefins (preferably polyethylene), poly(meth)acrylates, and polyfluorocarbons (preferably polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA)). These polymers can be used alone or in combination of two or more. In addition to resin, it can also be made of diatomaceous earth and glass. In addition, polymers obtained by graft copolymerization of polyamide (e.g., nylon-6 or nylon-6, 6, etc.) with polyolefins (such as UPE, described below) (nylon grafted with UPE, etc.) can be used as filter materials.

[0101] Furthermore, the filter can be a surface-treated filter. There are no particular limitations on the surface treatment method, and known methods can be used. Examples of surface treatment methods include chemical modification, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

[0102] Plasma treatment makes the filter surface hydrophilic, which is therefore preferable. There is no particular limitation on the water contact angle on the surface of the filter material that has been hydrophilicized by plasma treatment, but a static contact angle of 60° or less at 25°C, as measured by a contact angle meter, is preferred, 50° or less is even better, and 30° or less is further preferred.

[0103] As a chemical modification treatment, it is preferable to introduce ion exchange groups into the substrate. That is, as a filter, it is preferable to use the materials mentioned above as the substrate and introduce ion exchange groups into the substrate. Typically, a filter comprising a layer of substrate containing ion exchange groups on the surface of the substrate is preferred. There are no particular limitations on the surface-modified substrate, but from the viewpoint of easier manufacturing, a filter incorporating ion exchange groups into the polymer is preferred.

[0104] Regarding ion exchange groups, examples of cation exchange groups include sulfonic acid groups, carboxyl groups, and phosphate groups, while examples of anion exchange groups include quadrivalent ammonium groups. There are no particular limitations on the method of introducing ion exchange groups into polymers; a typical method is grafting, which involves reacting a compound containing ion exchange groups and polymerizable groups with the polymer.

[0105] There are no particular limitations on the method for introducing ion exchange groups. The resin fibers are irradiated with ionizing radiation (alpha rays, beta rays, gamma rays, X-rays, and electron beams, etc.) to generate active components (free radicals) in the resin. The irradiated resin is then impregnated in a solution containing monomers, allowing the monomers to graft polymerize onto the substrate. As a result, a polymer is generated that is bonded to the polyolefin fibers as graft polymer side chains. The resin containing this generated polymer as a side chain is then reacted with a compound containing anion exchange groups or cation exchange groups, introducing ion exchange groups into the graft polymer side chains to obtain the final product.

[0106] Furthermore, the filter can also be composed of a combination of woven or non-woven fabric with ion exchange groups formed by radiation graft polymerization and conventional glass wool, woven or non-woven filter materials.

[0107] Using a filter containing ion exchange groups makes it easier to control the content of metal components (especially particles containing metal atoms) in a pharmaceutical solution within the desired range. There are no particular limitations on the materials used for filters containing ion exchange groups, but materials incorporating ion exchange groups into fluorocarbons and polyolefins are examples, with materials incorporating ion exchange groups into fluorocarbons being preferred. There is no particular limitation on the pore diameter of the filter containing ion exchange groups, but 1-30 nm is preferred, and 5-20 nm is even more preferred. The filter containing ion exchange groups can also be used as the filter with the smallest pore diameter described above, or it can be used separately from the filter with the smallest pore diameter. From the viewpoint of obtaining better effects of the present invention, it is preferable to use both a filter containing ion exchange groups and a filter without ion exchange groups and with the smallest pore diameter in the filtration step. There are no particular limitations on the materials used for filters with the smallest pore diameter as described above. However, from the viewpoint of solvent resistance, etc., it is generally preferred to select at least one from the group containing polyfluorocarbons and polyolefins, with polyolefins being more preferred.

[0108] Therefore, as a filter used in the filtration step, two or more filters of different materials can be used. For example, two or more filters selected from the group consisting of filters containing polyolefins, polyfluorocarbons, polyamides and materials into which ion exchange groups are introduced can be used.

[0109] • The fine pore structure of the filter There are no particular limitations on the pore structure of a filter, and it can be appropriately selected according to the components in the substance being purified. In this specification, the pore structure of a filter refers to the pore diameter distribution, the positional distribution of the pores in the filter, and the shape of the pores, which can typically be controlled by the filter manufacturing method. For example, porous membranes can be obtained by sintering powders such as resins, and fibrous membranes can be obtained by methods such as electrospinning, electroblowing, and meltblowing. The micropore structures of these membranes are different.

[0110] A "porous membrane" refers to a membrane that retains components in a purified substance, such as gels, particles, colloids, cells, and oligomers, but allows components smaller than the pores to pass through. Sometimes, the retention of components in a purified substance using a porous membrane depends on operating conditions, such as surface velocity, the use of surfactants, pH, and combinations thereof, and may also depend on the pore size and structure of the porous membrane, as well as the size and structure of the particles to be removed (hard particles or gels, etc.).

[0111] In cases where the purified material contains negatively charged particles, polyamide filters function as non-sieve membranes to remove these particles. Typical non-sieve membranes include nylon-6 membranes and nylon-6,6 membranes, but are not limited to these. Furthermore, the "non-sieve" based retention mechanism used in this specification refers to retention generated by mechanisms such as obstruction, diffusion, and adsorption that are unrelated to the pressure reduction or pore size of the filter.

[0112] Non-sieve retention includes retention mechanisms that remove target particles from the purified material regardless of filter pressure reduction or filter pore size, such as obstruction, diffusion, and adsorption. Particle adsorption on the filter surface can be mediated, for example, by intermolecular van der Waals forces and electrostatic forces. Particles moving in a non-sieve membrane layer with serpentine pathways may obstruct the flow of particles if they cannot change direction quickly enough to avoid contact with the non-sieve membrane. Diffusion-based particle transport systems are generated primarily by the random or Brownian motion of small particles, resulting in a certain probability of collision between particles and filter material. Non-sieve retention mechanisms can become active when there is no repulsive force between particles and the filter.

[0113] UPE (ultra-high molecular weight polyethylene) filters are typically sieve membranes. Sieve membranes mainly refer to membranes that capture particles through a sieve holding mechanism, or membranes optimized for capturing particles through a sieve holding mechanism. Typical examples of membrane screens include polytetrafluoroethylene (PTFE) membranes and UPE membranes, but are not limited to these. Furthermore, the "sieve holding mechanism" refers to the result of holding the particles to be removed larger than the pore size of the porous membrane. The sieve holding force can be increased by forming a filter cake (an aggregate of the particles to be removed on the membrane surface). The filter cake effectively performs the function of a secondary filter.

[0114] There are no particular restrictions on the material of the fibrous membrane, as long as it is a polymer capable of forming a fibrous membrane. Examples of polymers include polyamide. Examples of polyamides include nylon 6 and nylon 6,6. Poly(ether ether) can be used as the polymer forming the fibrous membrane. When the fibrous membrane is located on the primary side of the porous membrane, it is preferable that the surface energy of the fibrous membrane is higher than that of the polymer material of the porous membrane located on the secondary side. An example of such a combination is a nylon fibrous membrane and a polyethylene (UPE) porous membrane.

[0115] There are no particular limitations on the manufacturing method of the fibrous membrane, and known methods can be used. As mentioned above, examples of manufacturing methods for fibrous membranes include electrospinning, electroblowing, and melt blowing.

[0116] There are no particular limitations on the pore structure of porous membranes (e.g., porous membranes containing UPE and PTFE). Examples of pore shapes include lace-like, string-like, and nodular shapes. There are no particular restrictions on the size distribution and positional distribution of pores in a porous membrane. The pores can have a smaller size distribution and be symmetrically positioned within the membrane. Alternatively, the pores can have a larger size distribution and be asymmetrically positioned within the membrane (these membranes are also referred to as "asymmetric porous membranes"). In asymmetric porous membranes, the pore size varies within the membrane; typically, the pore diameter increases from one surface to the other. In this case, the surface with more large pores is called the "open side," and the surface with more small pores is called the "tite side." Furthermore, as an asymmetric porous membrane, one can cite, for example, a membrane in which the size of the pores is smallest at a certain point within the membrane's thickness (also known as an "hourglass shape").

[0117] If an asymmetric porous membrane is used and the primary side is made into a larger pore size, in other words, if the primary side is made into an open side, it will produce a pre-filtration effect.

[0118] Porous membranes can contain thermoplastic polymers such as PESU (polyethersulfone), PFA (a copolymer of perfluoroalkoxyalkane, ethylene tetrafluoride and perfluoroalkoxyalkane), polyamide and polyolefin, and can also contain polytetrafluoroethylene. Among them, ultra-high molecular weight polyethylene (UHMWPE) is preferred as a material for porous membranes. UHMWPE refers to thermoplastic polyethylene with extremely long chains, and a molecular weight of over one million, typically 2 to 6 million, is preferred.

[0119] As a filter used in the filtration step, two or more filters with different pore structures can be used, or filters using both porous membranes and fiber membranes can be used. As a specific example, a method using a nylon fiber membrane filter and a UPE porous membrane filter can be given.

[0120] As mentioned above, filters are available on the market. When such filters are distributed, they are usually packaged in bags and sealed to prevent contamination. However, when the part of the packaging material that comes into contact with the filter is made of polyolefin (such as polyethylene, including high-density polyethylene), it is easier for impurities to adhere to the filter and cause contamination compared to when the contact part is made of fluoropolymers or stainless steel. Therefore, it is preferable to package the filter with packaging material in which at least a portion of the contact parts with the filter are made of fluorinated resin or stainless steel.

[0121] Examples of fluorinated resins used in the contact portion include PTFE and PFA. Stainless steel used in contact parts can be exemplified by stainless steel as a corrosion-resistant material, which will be described later. Among these, stainless steel that has undergone electrolytic polishing (EP-SUS) is preferred for contact parts. The contact area of ​​fluorinated resins and / or stainless steel is preferably 50-100% relative to the total contact area, more preferably 90-100%, and even more preferably 99-100%. There are no particular restrictions on the form of packaging materials; they can be in the form of bags or capsules. Regarding packaging materials, at least a portion of the contact parts can be made of fluoropolymer resin and / or stainless steel. The entire packaging material can be fluoropolymer resin and / or stainless steel, or it can be a composite material with other materials. For example, it can be a composite material with a layered structure where the contact parts are formed of fluoropolymer resin and / or stainless steel, and the parts other than the contact parts are formed of fluoropolymer resin and / or stainless steel.

[0122] Also, regarding the filter, it is best to clean it thoroughly before use. When using an uncleaned filter (or a filter that has not been thoroughly cleaned), impurities contained in the filter can easily enter the drug solution.

[0123] As described above, the filtration step of an embodiment of the present invention can be a multi-stage filtration step in which the purified substance is passed through at least one of two or more different filters selected from the group consisting of filter materials, pore diameters and pore structures. Furthermore, the purified substance can be passed through the same filter multiple times, or it can be passed through the same type of filter multiple times.

[0124] There are no particular limitations on the material used for the receiving portion (the inner wall surface, etc., that may come into contact with the purified substance and the pharmaceutical solution) of the purification apparatus used in the filtration step. However, it is preferable that it be formed from at least one material selected from the group consisting of non-metallic materials (such as fluorinated resins) and electrolytically polished metallic materials (such as stainless steel) (hereinafter, these will also be collectively referred to as "corrosion-resistant materials"). For example, the case where the receiving portion of the manufacturing tank is formed from a corrosion-resistant material can be exemplified by the manufacturing tank itself being formed from a corrosion-resistant material, or the inner wall surface of the manufacturing tank being covered with a corrosion-resistant material.

[0125] There are no particular restrictions on the non-metallic materials mentioned above, and known materials can be used. As a non-metallic material, examples include at least one selected from the group comprising polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorinated resins (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 fluorinated vinyl resin, etc.), but are not limited thereto.

[0126] There are no particular restrictions on the aforementioned metallic materials; known materials can be used. As for metallic materials, examples include those where the combined chromium and nickel content exceeds 25% by mass relative to the total mass of the metallic material, with 30% by mass or more being preferred. There is no particular upper limit to the combined chromium and nickel content in metallic materials, but it is generally preferred to be below 90% by mass. Examples of metallic materials include stainless steel and nickel-chromium alloys.

[0127] There are no particular restrictions on the type of stainless steel used; any known stainless steel can be used. However, alloys containing 8% by mass or more nickel are preferred, and austenitic stainless steels containing 8% by mass or more nickel are even better. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (8% Ni, 18% Cr), SUS304L (9% Ni, 18% Cr), SUS316 (10% Ni, 16% Cr), and SUS316L (12% Ni, 16% Cr).

[0128] There are no particular restrictions on the nickel-chromium alloy used; any known nickel-chromium alloy can be used. Among them, nickel-chromium alloys with a nickel content of 40-75% by mass and a chromium content of 1-30% by mass are preferred. Examples of nickel-chromium alloys include, for example, Hoechst alloys (trade name, hereinafter the same), Monel alloys (trade name, hereinafter the same), and Ingonane alloys (trade name, hereinafter the same). More specifically, examples include Hoechst alloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hoechst alloy-C (Ni content 60% by mass, Cr content 17% by mass), and Hoechst alloy C-22 (Ni content 61% by mass, Cr content 22% by mass). In addition to the alloys mentioned above, nickel-chromium alloys may also contain boron, silicon, tungsten, molybdenum, copper, and cobalt, depending on the requirements.

[0129] There are no particular restrictions on the method for electrolytic polishing of metallic materials, and known methods can be used. For example, the methods described in paragraphs

[0011] to

[0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Application Publication No. 2008-264929 can be used.

[0130] Regarding metallic materials, it is speculated that the chromium content in the passivation layer on the surface, achieved through electrolytic polishing, becomes higher than that in the parent phase. Therefore, it is speculated that if a purification device with a contact portion formed from electrolytically polished metallic material is used, it would be difficult for metallic components to flow into the purified solution. In addition, metallic materials can also be polished. There are no particular restrictions on the polishing method; well-known methods can be used. There are no particular restrictions on the size of the abrasive grains used in fine polishing, but from the viewpoint that the surface roughness of metallic materials is more easily reduced, a size of #400 or lower is preferable. Furthermore, polishing is best performed before electrolytic polishing.

[0131] (Other steps) The method for manufacturing the pharmaceutical solution may also include steps other than filtration. Examples of steps other than filtration include distillation, reaction, and electrolysis.

[0132] (Distillation step) The distillation step is the process of distilling a purified substance containing an organic solvent to obtain a distilled purified substance. There are no particular limitations on the method used to distill the purified substance, and known methods can be used. Typically, a method can be described where a distillation column is arranged on the primary side of a purification apparatus used for a filtration step, and the distilled purified substance is introduced into a manufacturing tank. At this point, there are no particular restrictions on the liquid receiving part of the distillation column, but it is preferable to form it from the corrosion-resistant material already described.

[0133] (Reaction steps) A reaction step is a step in which the raw materials are reacted to produce a purified substance containing an organic solvent as a reactant. There are no particular limitations on the method for producing the purified substance, and known methods can be used. Typically, a method is described where a reaction vessel is placed on the primary side of a purification apparatus (or distillation column) used in a filtration step, and the reactants are introduced into the purification vessel (or distillation column). At this point, there are no particular restrictions on the liquid receiving part of the manufacturing tank, but it is preferable to form it from the corrosion-resistant material already described.

[0134] (Electrostatic removal step) The de-electrolysis step is a step that removes the charge potential of the purified substance by de-electrolysis. There are no particular limitations on the method of removing static electricity, and known methods can be used. For example, a method of contacting the substance to be purified with a conductive material can be cited as a static electricity removal method. The contact time between the purified substance and 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 seconds. Examples of conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon. As a method for bringing the purified substance into contact with a conductive material, one example is to arrange a grounded mesh formed of a conductive material inside a pipeline and allow the purified substance to pass through it.

[0135] Regarding the purification of the substance being purified, it is preferable that all processes, including opening the accompanying containers, cleaning the containers and apparatus, containing the solution, and analysis, are carried out in a cleanroom. A cleanroom with a cleanliness level of 4 or higher as specified in the International Organization for Standardization (ISO) standard ISO 14644-1:2015, is preferred. Specifically, meeting any one of ISO Class 1, ISO Class 2, ISO Class 3, or ISO Class 4 is preferred; meeting ISO Class 1 or ISO Class 2 is more preferred; and meeting ISO Class 1 is even more preferred.

[0136] There is no particular limitation on the storage temperature of the liquid medicine. However, from the viewpoint that a storage temperature of 4°C or higher is preferred, as it is easier to obtain the effect of the present invention when a small amount of impurities contained in the liquid medicine are difficult to dissolve.

[0137] <Drug Liquid Containment Container> The pharmaceutical solution produced using the above purification method can be contained in a container and stored until it is used. Such containers and the medicinal liquid contained within them are collectively referred to as medicinal liquid containers. The medicinal liquid is then removed from the stored medicinal liquid container for use.

[0138] For storage of the aforementioned liquid medicine, a high level of cleanliness and minimal leaching of impurities are preferable for use in semiconductor device manufacturing. Specifically, examples of usable containers include the "Clean Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "Pure Bottle" manufactured by KODAMA PLASTICS CO., LTD., but are not limited to these.

[0139] As a container, it is preferable to use a multi-layer bottle with an inner wall structure based on a 6-layer structure of 6 types of resin or a multi-layer bottle with a 7-layer structure of 6 types of resin for the purpose of preventing impurities from entering (contaminating) the liquid medicine. For example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited as such a container.

[0140] The liquid-receiving portion of the container can be made of the corrosion-resistant material described (preferably electrolytically polished stainless steel or fluorinated resin) or glass. From the viewpoint of obtaining better effects of the present invention, it is preferable that more than 90% of the area of ​​the liquid-receiving portion is formed of the above-mentioned material, and it is even more preferable that the entire liquid-receiving portion is formed of the above-mentioned material.

[0141] The porosity of the drug solution containment body or container is preferably 2-80% by volume, more preferably 2-50% by volume, and even more preferably 5-30% by volume. In addition, the porosity mentioned above is calculated according to equation (1). Equation (1): Porosity = {1 - (volume of liquid in container / volume of container)} × 100 The aforementioned container volume has the same meaning as the container's internal volume (capacity). By setting the porosity within this range, storage stability can be ensured by limiting contamination from impurities and other contaminants. [Example]

[0142] The present invention will now be described in further detail based on embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0143] Furthermore, in the preparation of the drug solutions in the examples and comparative examples, the handling of containers, preparation, filling, storage and analysis of the drug solutions were all carried out in a cleanroom that meets ISO Class 2 or 1 standards.

[0144] (Filter) The following filters were used as filters. • Filter A: NIHON FILTER CO.,LTD.'s activated carbon filter "FCC-S" (fiber) • "Purasol 200nm": UPE membrane (material) manufactured by Entegris, with a pore size of 200nm. • "PTFE 7nm": A polytetrafluoroethylene filter manufactured by Entegris, with a pore size of 7nm. • "UPE 1nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, with a pore size of 1nm. • "UPE 3nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, with a pore size of 3nm. • "UPE 5nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall, with a pore size of 5nm. • "Nylon 5nm": Nylon filter, manufactured by Pall, with a pore size of 5nm.

[0145] <Purified substance> In order to prepare the pharmaceutical solutions of the examples and comparative examples, the following organic solvents were used as the purified substances. PGMM: Propylene Glycol Monomethyl Ether ·PGME: Propylene Glycol Monoethyl Ether ·PGMP: Propylene Glycol Monopropyl Ether ·PGMEA: Propylene glycol monomethyl ether acetate (In addition, “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 (In addition, “CyHe” and “CyHe(A)” to “CyHe(D)” in the table represent five types of CyHe obtained from different companies.) γBL: Butyrolactone ·DIAE: Diisopentyl ether MIBC: 4-Methyl-2-pentanol (In addition, “MIBC” and “MIBC(A)” to “MIBC(D)” in the table represent five types of MIBC obtained from different companies.) IPA: Isopropyl alcohol ·DMSO: Dimethyl sulfoxide NMP: N-methylpyrrolidone DEG: Diethylene glycol ·EG: Ethylene glycol • DPG: Dipropylene glycol PG: Propylene Glycol PC: Propylene carbonate Sulfolane: A type of cyclone ·2-Heptanone:2-Heptanone nBA: Butyl acetate (In addition, “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) Additionally, the values ​​in parentheses are the distances (MPa 0.5) between isopentyl ether and dimethyl malonate and eicosene, according to the Hansen solubility parameter.

[0146] <container> The following container was used as a container for holding the liquid medicine. EP-SUS: Containers with wetted parts made of electrolytically polished stainless steel. • PFA: A container whose wetted parts are coated with perfluoroalkoxyalkane.

[0147] <Purification Steps> One of the above-mentioned substances was selected and subjected to the distillation purification process described in Table 1. Additionally, in the "Distillation and Purification" column of the table, "-1" indicates that atmospheric distillation using a distillation column (theoretical plate number: 15 stages) was performed; "-2" indicates that vacuum distillation using a distillation column (theoretical plate number: 25 stages) was performed; "-3" indicates that vacuum distillation using a distillation column (theoretical plate number: 30 stages) was performed twice; "-4" indicates that atmospheric distillation using a distillation column (theoretical plate number: 20 stages) was performed; "-5" indicates that atmospheric distillation using a distillation column (theoretical plate number: 10 stages) was performed; and "-6" indicates that atmospheric distillation using a distillation column (theoretical plate number: 8 stages) was performed. However, "None" in the "Distillation and Purification" column of the table indicates that no distillation process was performed. In the example where "None" is displayed in the "Distillation and Purification" column, no distillation and purification was performed.

[0148] Next, the following cyclic filtration process was performed: the purified substance after distillation was stored in a storage tank, and the purified substance stored in the storage tank was filtered using filters 1 and 2 as described in Table 1. The purified substance after being filtered by filter 2 was circulated upstream of filter 1 and filtered again using filters 1 and 2. Next, the purified material, which has undergone cyclic filtration using filters 1 and 2, is passed sequentially through filters 3 and 4 as described in Table 1 and stored in a storage tank. Next, the following cyclic filtration process was performed: the purified substance stored in the storage tank was filtered using the filter 5 described in Table 1, and the purified substance after being filtered by the filter 5 was circulated upstream of the filter 5 and filtered again using the filter 5. After the circulating filtration process, the contents are contained in the containers listed in Table 1 with a predetermined porosity.

[0149] In addition, in the above series of purification processes, the liquid contact parts of various devices (e.g., distillation columns, piping, storage tanks, etc.) that come into contact with the purified substance are made of electrolytically polished stainless steel.

[0150] The contents of organic and metallic components in the drug solution were measured using the method described below.

[0151] <Content of organic components> The content of organic components (first organic compound, second organic compound, etc.) in various drug solutions was analyzed using a gas chromatography-mass spectrometry (GC / MS) instrument (manufactured by Agilent Technologies, GC: 7890B, MS: 5977B EI / CI MSD).

[0152] <Metal content> The content of metal components (metal ions, metal particles) in the drug solution was measured using ICP-MS and SP-ICP-MS methods. Regarding the apparatus, the following apparatus was used. Manufacturer: PerkinElmer Model: NexION350S The following parsing software was used in the parsing process. • Syngistix Nano Application Module Dedicated to "SP-ICP-MS" Syngistix for ICP-MS software

[0153] The “ClogP” in the table represents the ClogP value of the organic solvent. The "purity" in the table refers to the content (mass%) of organic solvent in the obtained drug solution relative to the total mass of the drug solution. In the table, "Total content 1 (mass ppt)" represents the total content (mass ppt) of the first organic compound, and "Total content 2 (mass ppt)" represents the total content (mass ppt) 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 and second organic compounds to the content of metal particles; "Ratio 3" represents the ratio of the total content of the first and second organic compounds to the content of metal ions; "Ratio 4" represents the ratio of the total content of the first and second organic compounds to the content of the metal component; and "Ratio 5" represents the ratio of the total content of the first and second organic compounds (excluding compound (VI)) to the content of compound (VI). The "Porosity" column in the table contains values ​​obtained using formula (X). Formula (X): Porosity = {1 - (volume of liquid in container / volume of container)} × 100

[0154] The liquid obtained by means of the above contains the compounds shown in the columns “Compound (I)” to “Compound (VII)”. The compounds listed in the "Type" column of the "Compound (I)" to "Compound (VII)" columns in the table represent the following contents. In addition, the ClogP values ​​of the compounds described later are 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

[0155] [Chemical Formula 17]

[0156] The asterisk (*) in L1 of compounds 8 and 9 indicates the bond position.

[0157] [Chemical Formula 18]

[0158] [Chemical Formula 19]

[0159] [Chemical Formula 20]

[0160] [Chemical Formula 21]

[0161] [Chemical Formula 22]

[0162] [Chemical Formula 23]

[0163] [Chemical Formula 24]

[0164] [Chemical Formula 25]

[0165] [Chemical Formula 26]

[0166] <Experiment> [Pre-wetting solution, rinsing solution] The defect suppression properties of the manufactured liquid, when used as a pre-wetting solution and rinsing solution, were evaluated using the method shown below. First, the chemical solution was rotary sprayed onto a 300mm diameter silicon substrate while the substrate was rotated. 0.5cc of each chemical solution was sprayed onto the substrate surface. Then, the substrate was rotary dried. Next, the number of defects present on the substrate after the chemical coating was applied was measured using a KLA-Tencor SP-5 wafer inspection system (this value was set as the measured value). Next, using EDAX (energy-dispersive X-ray spectroscopy), the particulate foreign matter in the wafer's defects was classified into "metallic residue defects" with metal as the main component and "particulate organic residue defects" with organic matter as the main component, and measurements were performed separately. Furthermore, non-particulate spot-like defects were counted as "spot-like defects". In addition, if any of the evaluations for metal residue defects, particulate organic residue defects, and spot-like residue defects is C or above, then it contains the defect inhibition properties required for the drug solution.

[0167] <Individual Evaluation (Metallic Residue Defects, Particulate Organic Residue Defects, Spotted Residue Defects)> A: The corresponding defect count is less than 20 per wafer. B: The corresponding number of defects exceeds 20 per wafer, but is less than 50 per wafer. C: The corresponding number of defects exceeds 50 per wafer but is less than 100 per wafer. D: The corresponding number of defects exceeds 100 per wafer.

[0168] [Developing solution] The defect suppression properties of the manufactured solution when used as a developer were evaluated using the method shown below. First, a resist pattern is formed through the operation shown below. An antireflective film with a thickness of 78 nm was formed by coating an organic antireflective film forming composition ARC29SR (manufactured by NISSAN CHEMICAL CORPORATION) onto a silicon substrate with a diameter of 300 mm and baking it at 205 °C for 60 seconds. To improve coatability, a pre-wetting liquid (using CyHe from Example 30) was dropped onto the surface of the silicon wafer with the antireflective film formed thereon, and spin coating was performed. Next, the (photosensitive or radiosensitive linear resin composition 1) or (photosensitive or radiosensitive linear resin composition 2) described later is coated onto the antireflective film after the pre-wetting step, and pre-baked (PB) at 100°C for 60 seconds to form a resist film with a thickness of 150 nm. In addition, (photosensitive radioactive or radioactive linear resin composition 1) was used in Examples 49 to 59 and Comparative Examples 3 to 4, and (photosensitive radioactive or radioactive linear resin composition 2) was used in Examples 60 to 70.

[0169] (Photosensitive or radiosensitive linear resin composition 1) Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the values ​​recorded in each repeating unit are expressed in moles): 100 parts by mass)

[0170] [Chemical Formula 27]

[0171] The photoacid generating agent shown below: 8 parts by weight

[0172] [Chemical Formula 28]

[0173] The quencher described below: 5 parts by mass (mass ratio from left to right: 0.1:0.3:0.3:0.2). Furthermore, in the quenchers described below, the polymer-type quenchers have a weight-average molecular weight (Mw) of 5000. Also, the values ​​listed in each repeating unit represent molar ratios.

[0174] [Chemical Formula 29]

[0175] The hydrophobic resins shown below are in quantities of 4 parts by weight (the mass ratio from left to right is 0.5:0.5). Furthermore, the weight-average molecular weight (Mw) of the hydrophobic resin on the left is 7000, and the weight-average molecular weight (Mw) of the hydrophobic resin on the right is 8000. Additionally, the values ​​listed in each repeating unit for each hydrophobic resin represent molar ratios.

[0176] [Chemical Formula 30]

[0177] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate): 3 parts by weight Cyclohexanone: 600 parts by weight γ-BL (γ-butyrolactone): 100 parts by weight

[0178] (Photosensitive or radiosensitive linear resin composition 2) Acid-degradable resin (resin represented by the following formula (weight average molecular weight (Mw): 8000): 100 parts by mass)

[0179] [Chemical Formula 31]

[0180] In addition, relative to all repeating units, the contents of each repeating unit in the above formula are, from left to right, 30 mol%, 15 mol%, 15 mol%, 20 mol%, and 20 mol.

[0181] The photoacid generating agent shown below: 15 parts by weight

[0182] [Chemical Formula 32]

[0183] The quencher shown below: 7 parts by weight (mass ratio from left to right is 1:1).

[0184] [Chemical Formula 33]

[0185] The hydrophobic resin shown below: 20 parts by weight (mass ratio from top to bottom is 3:7). Furthermore, the weight average molecular weight (Mw) of the hydrophobic resin in the upper section is 10,000, and the weight average molecular weight (Mw) of the hydrophobic resin in the lower section is 7,000. Additionally, in the hydrophobic resins shown in the lower section, the values ​​recorded in each repeating unit represent molar ratios.

[0186] [Chemical Formula 34]

[0187] Solvent: PGMEA (Propylene Glycol Monomethyl Ether Acetate): 50 parts by weight PGME (Propylene Glycol Monomethyl Ether): 100 parts by weight 2-Hepagonal: 100 parts by weight γ-BL (γ-butyrolactone): 500 parts by weight

[0188] For wafers with resist films, patterning was performed using an ArF excimer laser scanner (Numerical Aperture: 0.75) at 25 mJ / cm². Then, the wafer was heated at 120°C for 60 seconds. Next, it was developed with each developer solution for 30 seconds. Then, the wafer was 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 these steps, an L / S pattern with a line / space ratio of 1:1 (average pattern width: 45 nm) was obtained. The developability and defect suppression of each pattern were evaluated.

[0189] <Defect Suppression> The pattern on the formed wafer was observed using a pattern defect apparatus (Hitachi High-Technologies Corporation, multi-purpose SEM (Scanning Electron Microscope) "Inspago" RS6000 series), and the number of defects was measured. • Poor development defect: A defect in which space is not formed to the bottom of the pattern. • Defective residue: A defect in which foreign objects are present in the pattern. • Uniformity defects: Defects where the pattern width is greater than ±1 nm relative to the specified value. In addition, if any of the evaluations for poor development defects, residue defects, and uniformity defects is C or above, then it contains the defect suppression properties required by the solution.

[0190] <Individual Evaluation (Development Defects, Residue Defects, Uniformity Defects)> AA: The corresponding number of defects is less than 3 per wafer. A: The corresponding number of defects exceeds 3 per wafer, but is less than 5 per wafer. B: The corresponding number of defects exceeds 5 per wafer, but is less than 10 per wafer. C: The corresponding number of defects exceeds 10 per wafer, but is less than 30 per wafer. D: The corresponding number of defects exceeds 30 per wafer.

[0191] In Table 1, "Use 1" refers to using the solutions described in the examples and comparative examples as pre-wetting solutions and rinsing solutions to carry out the above tests. "Use 2" refers to using the solutions described in the examples and comparative examples as developing solutions to carry out the above tests. In addition, in Example 75, dimethyl malonate and isopentyl ether were mixed in a 5:5 (mass ratio).

[0192] [Table 1] Table 1 [Part 1] <1> medicine organic solvents ClogP Purification device purity(%) Distillation purification Filter 1 Filter 2 Filter 3 Filter 4 Filter 5 Example 1 PGMM -0.45 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 2 PGME 0.08 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 3 PGMP 0.61 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 4 PGMEA(A) 0.26 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 5 EL -0.19 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 6 MPM 0.19 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 7 CyPn 0.2 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 8 CyHe 0.76 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 9 γBL -0.76 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 10 DIAE 3.8 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 11 MIBC 1.57 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 12 IPA 0.16 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 13 DMSO -1.35 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 14 NMP -0.4 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 15 DEG -1.51 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 16 EG -1.69 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 17 DPG 0.71 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 18 PG -1.34 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 19 PC -0.41 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 20 Sulfolane -0.77 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 21 2-Heptanone 1.97 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 22 CyHe(A) 0.76 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.0% Example 23 CyHe(A) 0.76 -1 Filter A Purasol 200nm PTFE 7nm Nylon 5nm UPE1nm >99.95% Example 24 CyHe(A) 0.76 -2 Filter A Purasol 200nm >99.95% Example 25 CyHe(A) 0.76 -3 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 26 CyHe(A) 0.76 none Filter A Purasol 200nm PTFE 7nm >99.0% Example 27 CyHe(B) 0.76 -4 Filter A Purasol 200nm PTFE 7nm Nylon 5nm Nylon 5nm >99.95% Example 28 CyHe(C) 0.76 -5 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 29 CyHe(D) 0.76 There is -6 Filter A Purasol 200nm UPE5nm >99.95% Example 30 CyHe(A) 0.76 -1 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 31 PGMEA(A) 0.26 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.0% Example 32 PGMEA(A) 0.26 -1 Filter A Purasol 200nm PTFE 7nm Nylon 5nm UPE1nm >99.95% Example 33 PGMEA(A) 0.26 -2 Filter A Purasol 200nm >99.95% Example 34 PGMEA(A) 0.26 -3 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 35 PGMEA(A) 0.26 none Filter A Purasol 200nm PTFE 7nm >99.0% Example 36 PGMEA(B) 0.26 -4 Filter A Purasol 200nm PTFE 7nm Nylon 5nm Nylon 5nm >99.95% Example 37 PGMEA(C) 0.26 -5 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 38 PGMEA(D) 0.26 There is -6 Filter A Purasol 200nm UPE5nm >99.95% Example 39 PGMEA(A) 0.26 -1 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 40 MIBC(A) 1.57 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.0% Example 41 MIBC(A) 1.57 -1 Filter A Purasol 200nm PTFE 7nm Nylon 5nm UPE1nm >99.95% Example 42 MIBC(A) 1.57 -2 Filter A Purasol 200nm >99.95% Example 43 MIBC(A) 1.57 -3 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 44 MIBC(A) 1.57 none Filter A Purasol 200nm PTFE 7nm >99.0% Example 45 MIBC(B) 1.57 -4 Filter A Purasol 200nm PTFE 7nm Nylon 5nm Nylon 5nm >99.95% Example 46 MIBC(C) 1.57 -5 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 47 MIBC(D) 1.57 There is -6 Filter A Purasol 200nm UPE5nm >99.95% Example 48 MIBC(A) 1.57 -1 Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 71 Butyl butyrate 2.83 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 72 Isobutyl isobutyrate 2.47 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 73 Isopentyl ether 3.88 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 74 Undecane 6.6 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 75 Dimethyl malonate-isoamyl ether = 5.5 1.93 -1 Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Comparative Example 1 CyHe(D) 0.76 -3 Filter A Purasol 200nm PTFE 7nm UPE5nm UPE1nm >99.95% Comparative Example 2 CyHe(A) 0.76 none >99.95%

[0193] [Table 2] Table 1 [Part 1] <2> medicine Metal composition metal ions Total (Quality PPT) Al ions (Quality PPT) Ca ions (Quality PPT) Cr ions (Quality PPT) Cu ions (Quality PPT) Fe ions (Quality PPT) K ions (Quality PPT) Mg ions (Quality PPT) Na ions (Quality PPT) Ni ions (Quality PPT) Zn ions (Quality PPT) Pb ions (Quality PPT) Example 1 35.0 2.8 3.9 0.4 1.8 5.3 1.1 1.4 3.5 1.1 0.7 2.1 Example 2 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 3 42.0 3.4 4.6 0.4 2.1 6.3 1.3 1.7 4.2 1.3 0.8 2.5 Example 4 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 5 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 6 35.0 2.8 3.9 0.4 1.8 5.3 1.1 1.4 3.5 1.1 0.7 2.1 Example 7 28.0 2.2 3.1 0.3 1.4 4.2 0.8 1.1 2.8 0.8 0.6 1.7 Example 8 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 9 56.0 4.5 6.2 0.6 2.8 8.4 1.7 2.2 5.6 1.7 1.1 3.4 Example 10 73.5 5.9 8.1 0.7 3.7 11.0 2.2 2.9 7.4 2.2 1.5 4.4 Example 11 87.5 7.0 9.6 0.9 4.4 13.1 2.6 3.5 8.8 2.6 1.8 5.3 Example 12 80.5 6.4 8.9 0.8 4.0 12.1 2.4 3.2 8.1 2.4 1.6 4.8 Example 13 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 14 56.0 4.5 6.2 0.6 2.8 8.4 1.7 2.2 5.6 1.7 1.1 3.4 Example 15 49.0 3.9 5.4 0.5 2.5 7.4 1.5 2.0 4.9 1.5 1.0 2.9 Example 16 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 17 35.0 2.8 3.9 0.4 1.8 5.3 1.1 1.4 3.5 1.1 0.7 2.1 Example 18 59.5 4.8 6.5 0.6 3.0 8.9 1.8 2.4 6.0 1.8 1.2 3.6 Example 19 56.0 4.5 6.2 0.6 2.8 8.4 1.7 2.2 5.6 1.7 1.1 3.4 Example 20 63.0 5.0 6.9 0.6 3.2 9.5 1.9 2.5 6.3 1.9 1.3 3.8 Example 21 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 22 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 23 0.008 0.001 0.001 0.0001 0.0004 0.001 0.0002 0.0003 0.001 0.0002 0.0002 0.0005 Example 24 502.0 40.2 55.2 5.0 25.1 75.3 15.1 20.1 50.2 15.1 10.0 30.1 Example 25 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 26 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 27 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 28 73.5 5.9 8.1 0.7 3.7 11.0 2.2 2.9 7.4 2.2 1.5 4.4 Example 29 80.5 6.4 8.9 0.8 4.0 12.1 2.4 3.2 8.1 2.4 1.6 4.8 Example 30 87.5 7.0 9.6 0.9 4.4 13.1 2.6 3.5 8.8 2.6 1.8 5.3 Example 31 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 32 0.008 0.001 0.001 0.0001 0.0004 0.001 0.0002 0.0003 0.001 0.0002 0.0002 0.0005 Example 33 502.0 40.2 55.2 5.0 25.1 75.3 15.1 20.1 50.2 15.1 10.0 30.1 Example 34 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 35 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 36 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 37 73.5 5.9 8.1 0.7 3.7 11.0 2.2 2.9 7.4 2.2 1.5 4.4 Example 38 80.5 6.4 8.9 0.8 4.0 12.1 2.4 3.2 8.1 2.4 1.6 4.8 Example 39 87.5 7.0 9.6 0.9 4.4 13.1 2.6 3.5 8.8 2.6 1.8 5.3 Example 40 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 41 0.008 0.001 0.001 0.0001 0.0004 0.001 0.0002 0.0003 0.001 0.0002 0.0002 0.0005 Example 42 502.0 40.2 55.2 5.0 25.1 75.3 15.1 20.1 50.2 15.1 10.0 30.1 Example 43 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 44 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 45 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 46 73.5 5.9 8.1 0.7 3.7 11.0 2.2 2.9 7.4 2.2 1.5 4.4 Example 47 80.5 6.4 8.9 0.8 4.0 12.1 2.4 3.2 8.1 2.4 1.6 4.8 Example 48 87.5 7.0 9.6 0.9 4.4 13.1 2.6 3.5 8.8 2.6 1.8 5.3 Example 71 35.0 2.8 2.0 0.4 1.8 5.3 1.1 3.0 3.5 1.1 0.7 2.1 Example 72 59.5 4.8 5.0 0.6 3.0 8.9 1.8 2.0 6.0 1.8 1.2 3.6 Example 73 56.0 4.5 3.0 0.6 2.8 8.4 1.7 1.0 5.6 1.7 1.1 3.4 Example 74 63.0 5.0 4.0 0.6 3.2 9.5 1.9 5.0 6.3 1.9 1.3 3.8 Example 75 63.0 5.0 4.0 0.6 3.2 9.5 1.9 5.0 6.3 1.9 1.3 3.8 Comparative Example 1 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Comparative Example 2 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7

[0194] [Table 3] Table 1 [Part 1] <3> medicine Metal composition Total amount of metal particles (Quality PPT) Al particles (Quality PPT) Ca particles (Quality PPT) Cr particles (Quality PPT) Cu particles (Quality PPT) Fe particles (Quality PPT) K particles (Quality PPT) Mg particles (Quality PPT) Na particles (Quality PPT) Ni particles (Quality PPT) Zn particles (Quality PPT) Pb particles (Quality PPT) Total amount of metal components (Quality PPT) Example 1 12.3 1.2 1.6 0.1 0.4 1.5 0.2 0.2 1.1 0.1 0.1 0.1 47.3 Example 2 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 3 14.7 1.5 1.9 0.1 0.4 1.8 0.3 0.3 1.3 0.1 0.1 0.1 56.7 Example 4 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 5 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 6 12.3 1.2 1.6 0.1 0.4 1.5 0.2 0.2 1.1 0.1 0.1 0.1 47.3 Example 7 9.8 1.0 1.3 0.0 0.3 1.2 0.2 0.2 0.9 0.1 0.1 0.0 37.8 Example 8 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 9 19.6 2.0 2.5 0.1 0.6 2.4 0.4 0.4 1.8 0.2 0.2 0.1 75.6 Example 10 25.7 2.6 3.3 0.1 0.8 3.1 0.5 0.5 2.3 0.3 0.3 0.1 99.2 Example 11 30.6 3.1 4.0 0.2 0.9 3.7 0.6 0.6 2.8 0.3 0.3 0.2 118.1 Example 12 28.2 2.8 3.7 0.1 0.8 3.4 0.6 0.6 2.5 0.3 0.3 0.1 108.7 Example 13 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 14 19.6 2.0 2.5 0.1 0.6 2.4 0.4 0.4 1.8 0.2 0.2 0.1 75.6 Example 15 17.2 1.7 2.2 0.1 0.5 2.1 0.3 0.3 1.5 0.2 0.2 0.1 66.2 Example 16 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 17 12.3 1.2 1.6 0.1 0.4 1.5 0.2 0.2 1.1 0.1 0.1 0.1 47.3 Example 18 20.8 2.1 2.7 0.1 0.6 2.5 0.4 0.4 1.9 0.2 0.2 0.1 80.3 Example 19 19.6 2.0 2.5 0.1 0.6 2.4 0.4 0.4 1.8 0.2 0.2 0.1 75.6 Example 20 22.1 2.2 2.9 0.1 0.7 2.6 0.4 0.4 2.0 0.2 0.2 0.1 85.1 Example 21 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 22 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 23 0.003 0.0003 0.0004 0.00001 0.0001 0.0003 0.0001 0.0001 0.0003 0.00003 0.00003 0.00001 0.01 Example 24 175.7 17.6 22.8 0.9 5.3 21.1 3.5 3.5 15.8 1.8 1.8 0.9 677.7 Example 25 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 26 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 27 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 28 25.7 2.6 3.3 0.1 0.8 3.1 0.5 0.5 2.3 0.3 0.3 0.1 99.2 Example 29 28.2 2.8 3.7 0.1 0.8 3.4 0.6 0.6 2.5 0.3 0.3 0.1 108.7 Example 30 30.6 3.1 4.0 0.2 0.9 3.7 0.6 0.6 2.8 0.3 0.3 0.2 118.1 Example 31 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 32 0.003 0.0003 0.0004 0.00001 0.0001 0.0003 0.0001 0.0001 0.0003 0.00003 0.00003 0.00001 0.01 Example 33 175.7 17.6 22.8 0.9 5.3 21.1 3.5 3.5 15.8 1.8 1.8 0.9 677.7 Example 34 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 35 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 36 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 37 25.7 2.6 3.3 0.1 0.8 3.1 0.5 0.5 2.3 0.3 0.3 0.1 99.2 Example 38 28.2 2.8 3.7 0.1 0.8 3.4 0.6 0.6 2.5 0.3 0.3 0.1 108.7 Example 39 30.6 3.1 4.0 0.2 0.9 3.7 0.6 0.6 2.8 0.3 0.3 0.2 118.1 Example 40 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 41 0.003 0.0003 0.0004 0.00001 0.0001 0.0003 0.0001 0.0001 0.0003 0.00003 0.00003 0.00001 0.01 Example 42 175.7 17.6 22.8 0.9 5.3 21.1 3.5 3.5 15.8 1.8 1.8 0.9 677.7 Example 43 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 44 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 45 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 46 25.7 2.6 3.3 0.1 0.8 3.1 0.5 0.5 2.3 0.3 0.3 0.1 99.2 Example 47 28.2 2.8 3.7 0.1 0.8 3.4 0.6 0.6 2.5 0.3 0.3 0.1 108.7 Example 48 30.6 3.1 4.0 0.2 0.9 3.7 0.6 0.6 2.8 0.3 0.3 0.2 118.1 Example 71 12.3 1.2 1.6 0.1 0.4 1.5 0.2 0.2 1.1 0.1 0.1 0.1 47.3 Example 72 20.8 2.1 2.7 0.1 0.6 2.5 0.4 0.4 1.9 0.2 0.2 0.1 80.3 Example 73 19.6 2.0 2.5 0.1 0.6 2.4 0.4 0.4 1.8 0.2 0.2 0.1 75.6 Example 74 22.1 2.2 2.9 0.1 0.7 2.6 0.4 0.4 2.0 0.2 0.2 0.1 85.1 Example 75 22.1 2.2 2.9 0.1 0.7 2.6 0.4 0.4 2.0 0.2 0.2 0.1 85.1 Comparative Example 1 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Comparative Example 2 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4

[0195] [Table 4] Table 1 [Part 1] <4> medicine Compound (I) Compound (II) Compound (III) Compound (IV) Total (Quality PPT) type Total (Quality PPT) type Total (Quality PPT) type Total (Quality PPT) type Example 1 89 Compounds 35-37 11 Compound 23 30 Compounds 15-18 Example 2 92 Compounds 35-37 18 Compound 23 twenty four Compounds 15-18 Example 3 105 Compounds 35-37 15 Compound 23 30 Compounds 15-18 Example 4 20 Compound 23 20 Compounds 15-18 Example 5 67 Compounds 35-37 26 Compound 23 108 Compounds 26-27 36 Compounds 15-18 Example 6 84 Compounds 35-37 twenty one Compound 23 84 Compounds 26-27 28 Compounds 15-18 Example 7 96 Compounds 35-37 twenty three Compounds 23-25 96 Compounds 26-27 Example 8 150 Compounds 35-37 38 Compounds 23-25 150 Compounds 26-27 Example 9 72 Compounds 35-37 18 Compound 23 72 Compounds 26-27 twenty four Compounds 15-18 Example 10 89 Compounds 35-37 10 Compound 23 50 Compounds 15-18 Example 11 150 Compounds 35-37 25 Compound 23 Example 12 114 Compounds 35-37 twenty four Compound 23 114 Compounds 26-27 38 Compounds 15-18 Example 13 90 Compounds 35-37 30 Compound 23 90 Compounds 26-27 30 Compounds 15-18 Example 14 60 Compounds 35-37 14 Compound 23 85 Compounds 26-27 20 Compounds 15-18 Example 15 64 Compounds 35-37 13 Compound 23 64 Compounds 26-27 twenty one Compounds 15-18 Example 16 92 Compounds 35-37 29 Compound 23 92 Compounds 26-27 60 Compounds 15-18 Example 17 102 Compounds 35-37 58 Compound 23 180 Compounds 26-27 Example 18 138 Compounds 35-37 62 Compound 23 138 Compounds 26-27 46 Compounds 15-18 Example 19 72 Compounds 35-37 63 Compound 23 72 Compounds 26-27 twenty four Compounds 15-18 Example 20 65 Compounds 35-37 55 Compound 23 90 Compounds 26-27 30 Compounds 15-18 Example 21 66 Compounds 35-37 32 Compound 23 66 Compounds 26-27 twenty two Compounds 15-18 Example 22 150 Compounds 35-37 33 Compounds 23-25 150 Compounds 26-27 Example 23 72 Compounds 35-37 9 Compounds 23-25 72 Compounds 26-27 Example 24 4 Compounds 35-37 15 Compounds 23-25 5 Compounds 26-27 Example 25 0.15 Compounds 35-37 0.04 Compounds 23-25 0.15 Compounds 26-27 Example 26 6500 Compounds 35-37 1625 Compounds 23-25 6500 Compounds 26-27 Example 27 127.8 Compounds 35-37 0.5 Compounds 23-25 127.8 Compounds 26-27 Example 28 90 Compounds 35-37 38 Compounds 23-25 90 Compounds 26-27 Example 29 60 Compounds 35-37 48 Compounds 23-25 85 Compounds 26-27 Example 30 64 Compounds 35-37 13 Compounds 23-25 64 Compounds 26-27 Example 31 43 Compound 23 36 Compounds 15-18 Example 32 12 Compound 23 32 Compounds 15-18 Example 33 20 Compound 23 45 Compounds 15-18 Example 34 0.05 Compound 23 0.01 Compounds 15-18 Example 35 2113 Compound 23 6532 Compounds 15-18 Example 36 0.7 Compound 23 2.0 Compounds 15-18 Example 37 49 Compound 23 38 Compounds 15-18 Example 38 62 Compound 23 54 Compounds 15-18 Example 39 17 Compound 23 58 Compounds 15-18 Example 40 195 Compounds 35-37 56 Compound 23 47 Compounds 15-18 Example 41 94 Compounds 35-37 15 Compound 23 42 Compounds 15-18 Example 42 5 Compounds 35-37 25 Compound 23 58.5 Compounds 15-18 Example 43 0.20 Compounds 35-37 0.06 Compound 23 0.01 Compounds 15-18 Example 44 8450 Compounds 35-37 2746 Compound 23 8492 Compounds 15-18 Example 45 166 Compounds 35-37 1 Compound 23 3 Compounds 15-18 Example 46 117 Compounds 35-37 64 Compound 23 50 Compounds 15-18 Example 47 78 Compounds 35-37 81 Compound 23 70 Compounds 15-18 Example 48 83 Compounds 35-37 twenty two Compound 23 75 Compounds 15-18 Example 71 102 Compounds 35-37 58 Compound 23 180 Compounds 26-27 Example 72 138 Compounds 35-37 62 Compound 23 138 Compounds 26-27 46 Compounds 15-18 Example 73 72 Compounds 35-37 63 Compound 23 72 Compounds 26-27 twenty four Compounds 15-18 Example 74 65 Compounds 35-37 55 Compound 23 90 Compounds 26-27 30 Compounds 15-18 Example 75 65 Compounds 35-37 55 Compound 23 90 Compounds 26-27 30 Compounds 15-18 Comparative Example 1 0.001 Compounds 35-37 0.002 Compounds 23-25 0.001 Compounds 26-27 Comparative Example 2 75000 Compounds 35-37 16500 Compounds 23-25 45000 Compounds 26-27

[0196] [Table 5] Table 1 [Part 1] <5> medicine Compound (V) Compound (VI) Compound (VII) Total content 1 (Quality PPT) Total content 2 (Quality PPT) Total (Quality PPT) type Total (Quality PPT) type Total (Quality PPT) type Example 1 45 Compound 6 60 Compounds 19-22 100 235 Example 2 36 Compound 6 48 Compounds 19-22 110 218 Example 3 45 Compound 6 60 Compounds 19-22 120 255 Example 4 30 Compound 6 40 Compounds 19-22 20 110 Example 5 54 Compound 6 72 Compounds 19-22 45 Compounds 28-33 201 408 Example 6 42 Compound 6 56 Compounds 19-22 35 Compounds 28-33 189 350 Example 7 48 Compounds 5-14 10 Compounds 19-22 40 Compounds 28-33 215 313 Example 8 75 Compounds 8-14 53 Compounds 19-22 63 Compounds 28-33 338 528 Example 9 36 Compounds 5-14 48 Compounds 19-22 15 Compounds 28-33 162 285 Example 10 45 Compounds 5-14 60 Compounds 19-22 99 254 Example 11 75 Compound 6 32 Compounds 19-22 63 Compounds 28-33 175 345 Example 12 57 Compound 6 76 Compounds 19-22 48 Compounds 28-33 252 471 Example 13 45 Compound 6 60 Compounds 19-22 38 Compounds 28-33 210 383 Example 14 30 Compound 6 40 Compounds 19-22 25 Compounds 28-33 159 274 Example 15 32 Compound 6 43 Compounds 19-22 27 Compounds 28-33 141 263 Example 16 46 Compound 6 61 Compounds 19-22 38 Compounds 28-33 213 419 Example 17 90 Compound 6 78 Compounds 19-22 340 508 Example 18 69 Compound 6 92 Compounds 19-22 58 Compounds 28-33 338 603 Example 19 36 Compound 6 48 Compounds 19-22 30 Compounds 28-33 207 345 Example 20 45 Compound 6 60 Compounds 19-22 210 345 Example 21 33 Compound 6 65 Compounds 19-22 28 Compounds 28-33 164 312 Example 22 75 Compounds 5-14 5 Compounds 19-22 63 Compounds 28-33 333 475 Example 23 36 Compounds 5-14 29 Compounds 19-22 15 Compounds 28-33 153 233 Example 24 45 Compounds 5-14 36 Compounds 19-22 12 Compounds 28-33 twenty four 117 Example 25 0.08 Compounds 5-14 0.06 Compounds 19-22 0.03 Compounds 28-33 0.34 0.50 Example 26 3250 Compounds 5-14 2600 Compounds 19-22 2708 Compounds 28-33 14625 23183 Example 27 64 Compounds 5-14 51 Compounds 19-22 53 Compounds 28-33 256.1 424 Example 28 45 Compounds 5-14 36 Compounds 19-22 38 Compounds 28-33 218 337 Example 29 30 Compounds 5-14 twenty four Compounds 19-22 25 Compounds 28-33 193 272 Example 30 32 Compounds 5-14 26 Compounds 19-22 27 Compounds 28-33 141 225 Example 31 98 Compound 6 2 Compounds 19-22 43 178 Example 32 47 Compound 6 62 Compounds 19-22 12 153 Example 33 59 Compound 6 78 Compounds 19-22 20 201 Example 34 0.10 Compound 6 0.36 Compounds 19-22 0.05 0.52 Example 35 4225 Compound 6 5633 Compounds 19-22 2113 18503 Example 36 83.1 Compound 6 110.8 Compounds 19-22 0.7 196.5 Example 37 59 Compound 6 78 Compounds 19-22 49 224 Example 38 39 Compound 6 52 Compounds 19-22 62 207 Example 39 42 Compound 6 55 Compounds 19-22 17 172 Example 40 65 Compound 6 3 Compounds 19-22 4 Compounds 28-33 251 369 Example 41 63 Compound 6 56 Compounds 19-22 73 Compounds 28-33 109 343 Example 42 62 Compound 6 70 Compounds 19-22 91.3 Compounds 28-33 31 313 Example 43 0.05 Compound 6 0.12 Compounds 19-22 0.10 Compounds 28-33 0.26 0.54 Example 44 6520 Compound 6 5070 Compounds 19-22 6591 Compounds 28-33 11196 37869 Example 45 85 Compound 6 100 Compounds 19-22 130 Compounds 28-33 167 484 Example 46 68 Compound 6 70 Compounds 19-22 91 Compounds 28-33 181 461 Example 47 70 Compound 6 47 Compounds 19-22 61 Compounds 28-33 159 407 Example 48 70 Compound 6 50 Compounds 19-22 65 Compounds 28-33 105 365 Example 71 90 Compound 6 78 340 508 Example 72 69 Compound 6 92 Compounds 19-22 58 Compounds 28-33 338 603 Example 73 36 Compound 6 48 Compounds 19-22 30 Compounds 28-33 207 345 Example 74 45 Compound 6 60 Compounds 19-22 210 345 Example 75 45 Compound 6 60 Compounds 19-22 210 345 Comparative Example 1 0.005 Compounds 8-14 310251 Compounds 19-22 0.003 Compounds 28-33 0.0040 310251 Comparative Example 2 125800 Compounds 8-14 100640 Compounds 19-22 31250 Compounds 28-33 136500.0 394190

[0197] [Table 6] Table 1 [Part 1] <6> 1 to 1 2 3 4 5 Fill container Porosity (volume%) Example 1 2.12 4.97 19.18 6.71 0.34 EP-SUS 5 Example 2 1.79 3.55 13.69 4.79 0.28 EP-SUS 5 Example 3 2.12 4.50 17.35 6.07 0.31 PFA 5 Example 4 0.28 1.55 5.99 2.10 0.57 EP-SUS 10 Example 5 2.13 4.32 16.65 5.83 0.21 EP-SUS 20 Example 6 4.00 7.41 28.57 10.00 0.19 EP-SUS 5 Example 7 5.69 8.28 31.94 11.18 0.03 EP-SUS 5 Example 8 4.76 7.45 28.73 10.06 0.11 EP-SUS 5 Example 9 2.14 3.77 14.54 5.09 0.20 EP-SUS 30 Example 10 1.00 2.56 9.87 3.46 0.31 EP-SUS 5 Example 11 1.48 2.92 11.25 3.94 0.10 EP-SUS 15 Example 12 2.32 4.33 16.70 5.84 0.19 EP-SUS 10 Example 13 2.22 4.05 15.61 5.46 0.19 EP-SUS 5 Example 14 2.10 3.62 13.98 4.89 0.17 EP-SUS 15 Example 15 2.13 3.98 15.35 5.37 0.19 EP-SUS 5 Example 16 3.47 6.83 26.34 9.22 0.17 EP-SUS 20 Example 17 7.20 10.75 41.47 14.51 0.18 EP-SUS 5 Example 18 4.21 7.50 28.93 10.13 0.18 EP-SUS 5 Example 19 2.74 4.56 17.60 6.16 0.16 PFA 5 Example 20 2.47 4.06 15.65 5.48 0.21 EP-SUS 5 Example 21 1.74 3.30 12.71 4.45 0.26 EP-SUS 5 Example 22 4.70 6.70 25.85 9.05 0.01 EP-SUS 5 Example 23 14167 21556 83143 29100 0.14 EP-SUS 5 Example 24 0.04 0.17 0.67 0.23 0.44 EP-SUS 5 Example 25 0.005 0.007 0.03 0.010 0.14 EP-SUS 5 Example 26 238.10 377.43 1455.78 509.52 0.13 EP-SUS 5 Example 27 2.71 4.49 17.32 6.06 0.14 EP-SUS 5 Example 28 2.20 3.39 13.08 4.58 0.12 EP-SUS 5 Example 29 1.78 2.50 9.65 3.38 0.10 EP-SUS 5 Example 30 1.19 1.90 7.34 2.57 0.13 PFA 5 Example 31 0.61 2.51 9.68 3.39 0.01 EP-SUS 5 Example 32 1083 14157 54607 19113 0.69 EP-SUS 5 Example 33 0.03 0.30 1.14 0.40 0.63 EP-SUS 5 Example 34 0.001 0.007 0.03 0.010 2.30 EP-SUS 5 Example 35 34.39 301.23 1161.87 406.66 0.44 EP-SUS 5 Example 36 0.01 2.08 8.02 2.81 1.29 EP-SUS 5 Example 37 0.50 2.26 8.72 3.05 0.53 EP-SUS 5 Example 38 0.57 1.91 7.36 2.58 0.33 EP-SUS 5 Example 39 0.14 1.45 5.61 1.96 0.48 PFA 5 Example 40 3.54 5.21 20.08 7.03 0.01 EP-SUS 5 Example 41 10075 31720 122349 42822 0.20 EP-SUS 5 Example 42 0.05 0.46 1.78 0.62 0.29 EP-SUS 5 Example 43 0.004 0.008 0.03 0.010 0.28 EP-SUS 5 Example 44 182 617 2378 832 0.15 EP-SUS 5 Example 45 1.77 5.12 19.75 6.91 0.26 EP-SUS 5 Example 46 1.83 4.64 17.90 6.27 0.18 EP-SUS 5 Example 47 1.46 3.74 14.44 5.06 0.13 EP-SUS 5 Example 48 0.89 3.09 11.92 4.17 0.16 PFA 5 Example 71 7.20 10.75 41.47 14.51 0.18 EP-SUS 5 Example 72 4.21 7.50 28.93 10.13 0.18 EP-SUS 5 Example 73 2.74 4.56 17.60 6.16 0.16 PFA 5 Example 74 2.47 4.06 15.65 5.48 0.21 EP-SUS 5 Example 75 2.47 4.06 15.65 5.48 0.21 EP-SUS 5 Comparative Example 1 0.0001 5050.89 19482.01 6818.70 25854250.03 EP-SUS 5 Comparative Example 2 2222.22 6417.42 24752.90 8663.52 0.34 EP-SUS 5

[0198] [Table 7] Table 1 [Part 1] <7> use evaluate Metal residue Particulate organic residue speckled residue Example 1 Application 1 A A A Example 2 Application 1 A A A Example 3 Application 1 A A A Example 4 Application 1 A A A Example 5 Application 1 A A A Example 6 Application 1 A A A Example 7 Application 1 A A A Example 8 Application 1 A A A Example 9 Application 1 A A A Example 10 Application 1 A A A Example 11 Application 1 A A A Example 12 Application 1 A A A Example 13 Application 1 A A A Example 14 Application 1 A A A Example 15 Application 1 A A A Example 16 Application 1 A A A Example 17 Application 1 A A A Example 18 Application 1 A A A Example 19 Application 1 A A A Example 20 Application 1 A A A Example 21 Application 1 A A A Example 22 Application 1 A A A Example 23 Application 1 B B A Example 24 Application 1 C B A Example 25 Application 1 B B A Example 26 Application 1 A A C Example 27 Application 1 A A A Example 28 Application 1 A A A Example 29 Application 1 A A A Example 30 Application 1 A A A Example 31 Application 1 A A A Example 32 Application 1 B A A Example 33 Application 1 C B A Example 34 Application 1 C C A Example 35 Application 1 A A C Example 36 Application 1 A A A Example 37 Application 1 A A A Example 38 Application 1 A A A Example 39 Application 1 A A A Example 40 Application 1 A A A Example 41 Application 1 B B A Example 42 Application 1 C B A Example 43 Application 1 B A A Example 44 Application 1 A A C Example 45 Application 1 A A A Example 46 Application 1 A A A Example 47 Application 1 A A A Example 48 Application 1 A A A Example 71 Application 1 A A A Example 72 Application 1 A A A Example 73 Application 1 A A A Example 74 Application 1 A A A Example 75 Application 1 A A A Comparative Example 1 Application 1 C D D Comparative Example 2 Application 1 C D D

[0199] [Table 8] Table 1 [Part 2] <1> medicine organic solvents ClogP Purification device purity(%) Distillation purification Filter 1 Filter 2 Filter 3 Filter 4 Filter 5 Example 49 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 50 iAA 2.12 -1 Special Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 51 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.0% Example 52 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm Nylon 5nm UPE1nm >99.95% Example 53 nBA(A) 1.77 -2 Special Filter A Purasol 200nm >99.95% Example 54 nBA(A) 1.77 -3 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 55 nBA(A) 1.77 none Special Filter A Purasol 200nm PTFE 7nm >99.0% Example 56 nBA(B) 1.77 -4 Special Filter A Purasol 200nm PTFE 7nm Nylon 5nm Nylon 5nm >99.95% Example 57 nBA(C) 1.77 -5 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 58 nBA(D) 1.77 There is -6 Special Filter A Purasol 200nm UPE5nm >99.95% Example 59 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Comparative Example 3 nBA(D) 0.76 -3 Special Filter A Purasol 200nm PTFE 7nm UPE5nm UPE1nm >99.95% Comparative Example 4 nBA(A) 0.76 none >99.95% Example 60 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 61 iAA 2.12 -1 Special Filter A Purasol 200nm PTFE 7nm UPE3nm UPE1nm >99.95% Example 62 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.0% Example 63 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm Nylon 5nm UPE1nm >99.95% Example 64 nBA(A) 1.77 -2 Special Filter A Purasol 200nm >99.95% Example 65 nBA(A) 1.77 -3 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 66 nBA(A) 1.77 none Special Filter A Purasol 200nm PTFE 7nm >99.0% Example 67 nBA(B) 1.77 -4 Special Filter A Purasol 200nm PTFE 7nm Nylon 5nm Nylon 5nm >99.95% Example 68 nBA(C) 1.77 -5 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95% Example 69 nBA(D) 1.77 There is -6 Special Filter A Purasol 200nm UPE5nm >99.95% Example 70 nBA(A) 1.77 -1 Special Filter A Purasol 200nm PTFE 7nm UPE5nm >99.95%

[0200] [Table 9] Table 1 [Part 2] <2> medicine Metal composition metal ions Total (Quality PPT) Al ions (Quality PPT) Ca ions (Quality PPT) Cr ions (Quality PPT) Cu ions (Quality PPT) Fe ions (Quality PPT) K ions (Quality PPT) Mg ions (Quality PPT) Na ions (Quality PPT) Ni ions (Quality PPT) Zn ions (Quality PPT) Pb ions (Quality PPT) Example 49 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 50 84.0 6.7 9.2 0.8 4.2 12.6 2.5 3.4 8.4 2.5 1.7 5.0 Example 51 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 52 0.008 0.01 0.001 0.0001 0.0004 0.001 0.0002 0.0003 0.001 0.0002 0.0002 0.0005 Example 53 502.0 40.2 55.2 5.0 25.1 75.3 15.1 20.1 50.2 15.1 10.0 30.1 Example 54 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 55 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 56 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 57 73.5 5.9 8.1 0.7 3.7 11.0 2.2 2.9 7.4 2.2 1.5 4.4 Example 58 80.5 6.4 8.9 0.8 4.0 12.1 2.4 3.2 8.1 2.4 1.6 4.8 Example 59 87.5 7.0 9.6 0.9 4.4 13.1 2.6 3.5 8.8 2.6 1.8 5.3 Comparative Example 3 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Comparative Example 4 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 60 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 61 84.0 6.7 9.2 0.8 4.2 12.6 2.5 3.4 8.4 2.5 1.7 5.0 Example 62 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 63 0.008 0.001 0.001 0.0001 0.0004 0.001 0.0002 0.0003 0.001 0.0002 0.0002 0.0005 Example 64 502.0 40.2 55.2 5.0 25.1 75.3 15.1 20.1 50.2 15.1 10.0 30.1 Example 65 52.5 4.2 5.8 0.5 2.6 7.9 1.6 2.1 5.3 1.6 1.1 3.2 Example 66 45.5 3.6 5.0 0.5 2.3 6.8 1.4 1.8 4.6 1.4 0.9 2.7 Example 67 70.0 5.6 7.7 0.7 3.5 10.5 2.1 2.8 7.0 2.1 1.4 4.2 Example 68 73.5 5.9 8.1 0.7 3.7 11.0 2.2 2.9 7.4 2.2 1.5 4.4 Example 69 80.5 6.4 8.9 0.8 4.0 12.1 2.4 3.2 8.1 2.4 1.6 4.8 Example 70 87.5 7.0 9.6 0.9 4.4 13.1 2.6 3.5 8.8 2.6 1.8 5.3

[0201] [Table 10] Table 1 [Part 2] <3> medicine Metal composition metal particles Total (Quality PPT) Al particles (Quality PPT) Ca particles (Quality PPT) Cr particles (Quality PPT) Cu particles (Quality PPT) Fe particles (Quality PPT) K particles (Quality PPT) Mg particles (Quality PPT) Na particles (Quality PPT) Ni particles (Quality PPT) Zn particles (Quality PPT) Pb particles (Quality PPT) Metal composition Total (Quality PPT) Example 49 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 50 29.4 2.9 3.8 0.1 0.9 3.5 0.6 0.6 2.6 0.3 0.3 0.1 113.4 Example 51 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 52 0.003 0.0003 0.0004 0.00001 0.0001 0.0003 0.0001 0.0001 0.0003 0.00003 0.00003 0.00001 0.011 Example 53 175.7 17.6 22.8 0.9 5.3 21.1 3.5 3.5 15.8 1.8 1.8 0.9 677.7 Example 54 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 55 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 56 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 57 25.7 2.6 3.3 0.1 0.8 3.1 0.5 0.5 2.3 0.3 0.3 0.1 99.2 Example 58 28.2 2.8 3.7 0.1 0.8 3.4 0.6 0.6 2.5 0.3 0.3 0.1 108.7 Example 59 30.6 3.1 4.0 0.2 0.9 3.7 0.6 0.6 2.8 0.3 0.3 0.2 118.1 Comparative Example 3 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Comparative Example 4 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 60 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 61 29.4 2.9 3.8 0.1 0.9 3.5 0.6 0.6 2.6 0.3 0.3 0.1 113.4 Example 62 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 63 0.003 0.0003 0.0004 0.00001 0.0001 0.0003 0.0001 0.0001 0.0003 0.00003 0.00003 0.00001 0.011 Example 64 175.7 17.6 22.8 0.9 5.3 21.1 3.5 3.5 15.8 1.8 1.8 0.9 677.7 Example 65 18.4 1.8 2.4 0.1 0.6 2.2 0.4 0.4 1.7 0.2 0.2 0.1 70.9 Example 66 15.9 1.6 2.1 0.1 0.5 1.9 0.3 0.3 1.4 0.2 0.2 0.1 61.4 Example 67 24.5 2.5 3.2 0.1 0.7 2.9 0.5 0.5 2.2 0.2 0.2 0.1 94.5 Example 68 25.7 2.6 3.3 0.1 0.8 3.1 0.5 0.5 2.3 0.3 0.3 0.1 99.2 Example 69 28.2 2.8 3.7 0.1 0.8 3.4 0.6 0.6 2.5 0.3 0.3 0.1 108.7 Example 70 30.6 3.1 4.0 0.2 0.9 3.7 0.6 0.6 2.8 0.3 0.3 0.2 118.1

[0202] [Table 11] Table 1 [Part 2] <4> medicine Compound (I) Compound (II) Compound (III) Compound (IV) Total (Quality PPT) type Total (Quality PPT) type Total (Quality PPT) type Total (Quality PPT) type Example 49 54 Compounds 35-37 18 Compound 23 54 Compounds 26-27 18 Compounds 15-18 Example 50 144 Compounds 35-37 twenty one Compound 23 144 Compounds 26-27 48 Compounds 15-18 Example 51 143 Compounds 35-37 41 Compound 23 143 Compounds 26-27 34 Compounds 15-18 Example 52 68 Compounds 35-37 11 Compound 23 68 Compounds 26-27 30 Compounds 15-18 Example 53 4 Compounds 35-37 19 Compound 23 5 Compounds 26-27 43 Compounds 15-18 Example 54 5.66 Compounds 35-37 0.05 Compound 23 1.95 Compounds 26-27 0.13 Compounds 15-18 Example 55 6175 Compounds 35-37 2007 Compound 23 6175 Compounds 26-27 6205 Compounds 15-18 Example 56 121 Compounds 35-37 1 Compound 23 121 Compounds 26-27 2 Compounds 15-18 Example 57 86 Compounds 35-37 47 Compound 23 86 Compounds 26-27 36 Compounds 15-18 Example 58 57 Compounds 35-37 59 Compound 23 81 Compounds 26-27 51 Compounds 15-18 Example 59 61 Compounds 35-37 16 Compound 23 61 Compounds 26-27 55 Compounds 15-18 Comparative Example 3 0.001 Compounds 35-37 0.006 Compounds 23-25 0.001 Compounds 26-27 0.0008 Compounds 15-18 Comparative Example 4 82500 Compounds 35-37 18150 Compounds 23-25 49500 Compounds 26-27 26532 Compounds 15-18 Example 60 54 Compounds 35-37 18 Compound 23 54 Compounds 26-27 18 Compounds 15-18 Example 61 144 Compounds 35-37 twenty one Compound 23 144 Compounds 26-27 48 Compounds 15-18 Example 62 143 Compounds 35-37 41 Compound 23 143 Compounds 26-27 34 Compounds 15-18 Example 63 68 Compounds 35-37 11 Compound 23 68 Compounds 26-27 30 Compounds 15-18 Example 64 4 Compounds 35-37 19 Compound 23 5 Compounds 26-27 43 Compounds 15-18 Example 65 5.66 Compounds 35-37 0.05 Compound 23 1.95 Compounds 26-27 0.13 Compounds 15-18 Example 66 6175 Compounds 35-37 2007 Compound 23 6175 Compounds 26-27 6205 Compounds 15-18 Example 67 121 Compounds 35-37 1 Compound 23 121 Compounds 26-27 2 Compounds 15-18 Example 68 86 Compounds 35-37 47 Compound 23 86 Compounds 26-27 36 Compounds 15-18 Example 69 57 Compounds 35-37 59 Compound 23 81 Compounds 26-27 51 Compounds 15-18 Example 70 61 Compounds 35-37 16 Compound 23 61 Compounds 26-27 55 Compounds 15-18

[0203] [Table 12] Table 1 [Part 2] <5> medicine Compound (V) Compound (VI) Compound (VII) Total content 1 (Quality PPT) Total content 2 (Quality PPT) Total (Quality PPT) type Total (Quality PPT) type Total (Quality PPT) type Example 49 27 Compound 6 36 Compounds 19-22 twenty three Compounds 28-33 126 230 Example 50 72 Compound 6 96 Compounds 19-22 60 Compounds 28-33 309 585 Example 51 71 Compound 6 4 Compounds 19-22 59 Compounds 28-33 326 495 Example 52 34 Compound 6 27 Compounds 19-22 14 Compounds 28-33 148 254 Example 53 43 Compound 6 34 Compounds 19-22 11 Compounds 28-33 27 158 Example 54 0.67 Compound 6 0.23 Compounds 19-22 0.08 Compounds 28-33 7.66 8.77 Example 55 3088 Compound 6 2470 Compounds 19-22 2573 Compounds 28-33 14357 28693 Example 56 61 Compound 6 49 Compounds 19-22 51 Compounds 28-33 243 405 Example 57 43 Compound 6 34 Compounds 19-22 36 Compounds 28-33 218 367 Example 58 29 Compound 6 twenty three Compounds 19-22 twenty four Compounds 28-33 197 323 Example 59 30 Compound 6 twenty four Compounds 19-22 25 Compounds 28-33 137 272 Comparative Example 3 0.001 Compound 6 294738 Compounds 19-22 0.003 Compounds 28-33 0.0080 294738 Comparative Example 4 138380 Compound 6 10064 Compounds 19-22 34375 Compounds 28-33 150150 359501 Example 60 27 Compound 6 36 Compounds 19-22 twenty three Compounds 28-33 126 230 Example 61 72 Compound 6 96 Compounds 19-22 60 Compounds 28-33 309 585 Example 62 71 Compound 6 4 Compounds 19-22 59 Compounds 28-33 326 495 Example 63 34 Compound 6 27 Compounds 19-22 14 Compounds 28-33 148 254 Example 64 43 Compound 6 34 Compounds 19-22 11 Compounds 28-33 27 158 Example 65 0.67 Compound 6 0.23 Compounds 19-22 0.08 Compounds 28-33 7.66 8.77 Example 66 3088 Compound 6 2470 Compounds 19-22 2573 Compounds 28-33 14357 28693 Example 67 61 Compound 6 49 Compounds 19-22 51 Compounds 28-33 243 405 Example 68 43 Compound 6 34 Compounds 19-22 36 Compounds 28-33 218 367 Example 69 29 Compound 6 twenty three Compounds 19-22 twenty four Compounds 28-33 197 324 Example 70 30 Compound 6 twenty four Compounds 19-22 25 Compounds 28-33 137 272

[0204] [Table 13] Table 1 [Part 2] <6> 1 to 1 2 3 4 5 Fill container Porosity (volume%) Example 49 1.33 2.43 9.37 3.28 0.19 EP-SUS 5 Example 50 2.72 5.16 19.90 6.96 0.20 PFA 5 Example 51 4.60 6.98 26.93 9.43 0.01 EP-SUS 5 Example 52 13696 23530 90759 31766 0.12 EP-SUS 5 Example 53 0.04 0.23 0.90 0.32 0.28 EP-SUS 5 Example 54 0.11 0.12 0.48 0.17 0.03 EP-SUS 5 Example 55 234 467 1802 631 0.09 EP-SUS 5 Example 56 2.58 4.29 16.54 5.79 0.14 EP-SUS 5 Example 57 2.20 3.70 14.27 4.99 0.10 EP-SUS 5 Example 58 1.81 2.98 11.48 4.02 0.08 EP-SUS 5 Example 59 1.16 2.31 8.90 3.11 0.10 PFA 5 Comparative Example 3 0.0001 4798 18508 6478 23026441 EP-SUS 5 Comparative Example 4 2444 5853 22575 7901 0.03 EP-SUS 5 Example 60 1.33 2.43 9.37 3.28 0.19 EP-SUS 5 Example 61 2.72 5.16 19.90 6.96 0.20 PFA 5 Example 62 4.60 6.98 26.93 9.43 0.01 EP-SUS 5 Example 63 13696 23530 90759 31766 0.12 EP-SUS 5 Example 64 0.04 0.23 0.90 0.32 0.28 EP-SUS 5 Example 65 0.11 0.12 0.48 0.17 0.03 EP-SUS 5 Example 66 234 467 1802 631 0.09 EP-SUS 5 Example 67 2.58 4.29 16.54 5.79 0.14 EP-SUS 5 Example 68 2.20 3.70 14.27 4.99 0.10 EP-SUS 5 Example 69 1.82 2.98 11.49 4.02 0.08 EP-SUS 5 Example 70 1.16 2.31 8.90 3.11 0.10 PFA 5

[0205] [Table 14] Table 1 [Part 2] <7> use evaluate Poor development residue Uniformity Example 49 Application 2 A A A Example 50 Application 2 A A A Example 51 Application 2 A A A Example 52 Application 2 B A A Example 53 Application 2 C B A Example 54 Application 2 A A A Example 55 Application 2 A C A Example 56 Application 2 A A A Example 57 Application 2 A A A Example 58 Application 2 A A A Example 59 Application 2 A A A Comparative Example 3 Application 2 D D D Comparative Example 4 Application 2 D D D Example 60 Application 2 AA AA AA Example 61 Application 2 AA AA AA Example 62 Application 2 AA AA AA Example 63 Application 2 C C C Example 64 Application 2 C B A Example 65 Application 2 AA AA AA Example 66 Application 2 B B B Example 67 Application 2 AA AA AA Example 68 Application 2 AA AA AA Example 69 Application 2 AA AA AA Example 70 Application 2 AA AA AA

[0206] Table 1 presents the data for each embodiment and comparative example [Table 1, Part 1]. <1> ~ <7> and Table 1 [Part 2] <1> ~ <7> In each row. For example, in Example 1, as shown in Table 1 [1] <1> As shown in Table 1 [1], PGMM was used as the organic solvent. <2> As shown, the total amount of metal ions in the drug solution is 35 ppt by mass, as shown in Table 1 [1]. <3> As shown, the total amount of metal particles in the drug solution is 12.3 ppt, as shown in Table 1 [1]. <4> As shown, the total amount of compound (I) is 89 ppt, as shown in Table 1 [1]. <5> As shown, the total amount of compound (V) is 45 ppt by mass, as shown in Table 1 [1]. <6> As shown, the ratio to 1 is 2.12, as shown in Table 1 [Part 1]. <7> As shown, the metal residue is designated "A". The same applies to other embodiments and comparative examples.

[0207] Based on the results shown in the table, it is confirmed that when the solution of the present invention is applied to the manufacture of semiconductor devices, the defect suppression performance is excellent. Among them, based on the comparison of Examples 23, 24, 32, 33, 41, 42 and other examples, the effect is better when the content of metal components relative to the total mass of the drug solution is 0.1~500 ppt by mass. Furthermore, based on comparisons with Examples 26, 35, 44, and other examples, the effect is even better when the total content 1 (the total content of the first organic compound) is 10,000 ppt by mass or less (preferably 2,000 ppt by mass or less). Furthermore, based on comparisons with Examples 23, 25, and other examples, the effect is even better when the ratio 1 (the ratio of the total content of the first organic compound to the content of the metal component) is 0.01 to 10000.

[0208] EUV Exposure (Photosensitive or radiosensitive linear resin composition (resistor composition 1)) First, the components were mixed in the following manner to obtain inhibitor composition 1. • Resin (A-1): 0.77g • Photoacid generator (B-1): 0.03g • Alkaline compound (E-3): 0.03g • PGMEA (commercially available, high purity): 67.5g Ethyl lactate (commercially available, high purity): 75g

[0209] • Resin (A-1) The following resin was used as resin (A-1).

[0210] [Chemical Formula 35]

[0211] • Photoacid generator (B-1) The following compound was used as a photoacid generator (B-1).

[0212] [Chemical Formula 36]

[0213] • Basic compounds (E-3) The following compound was used as a basic compound (E-3).

[0214] [Chemical Formula 37]

[0215] (The formation and evaluation of patterns) First, AL412 (manufactured by Brewer Science) was coated onto a 300mm diameter silicon wafer and baked at 200°C for 60 seconds to form a 20nm thick lower resist layer. A pre-wetting solution (manufactured by cyclohexanone / FFUS) was then coated onto this layer, followed by the resist composition, and baked at 100°C for 60 seconds to form a 30nm thick resist film.

[0216] For this resist film, exposure was performed using an EUV exposure machine (ASML NXE3350, NA 0.33, Dipole 90°, outer sigma 0.87, inner sigma 0.35) through a reflective mask. Then, it was heated at 85°C (PEB: Post Exposure Bake) for 60 seconds. Next, development was performed by spraying developer (butyl acetate / FETW) for 30 seconds, followed by rinsing by spin coating for 20 seconds. Finally, the silicon wafer was rotated at 2000 rpm for 40 seconds, forming a line and space pattern with a spatial width of 20 nm and a line width of 15 nm. The rinsing solutions described above were the solutions used in Examples 1 to 48 and Examples 71 to 75, respectively. Furthermore, the evaluation results of the defects described above, including metal residue defects, particulate organic residue defects, and spot-like residue defects, were consistent with those in Table 1 [1]. <7> The desired effect of the same tendency.

[0217] none

Claims

1. A method for forming a resist pattern, comprising: a step of patterning a resist film; and a step of developing the resist film to form a negative resist pattern, the method using a solution containing an organic solvent as a developing solution, the solution containing 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 compound being 0.01 ppt to 100,000 ppt relative to the total mass of the solution, wherein in general formula (I), Y represents a benzene ring group that can be substituted with an alkyl group or a group represented by general formula (A). When Y represents a benzene ring group, s represents 1, L represents a single bond, and R1a represents an alkyl group that may contain substituents. This alkyl group may also contain heteroatoms. When an alkyl group replaces the benzene ring group, the alkyl group and R1a can bond together to form a ring. Furthermore, when multiple alkyl groups replace the benzene ring group, the alkyl groups can bond together to form a ring. When Y represents a group represented by general formula (A), s represents 3, L represents methylene, and R1a independently represents an alkyl group. In general formula (II), R2a to R2h independently represent alkyl groups that may contain substituents. R2b and R2e can bond together to form a ring. The group formed by the bonding of R2b and R2e is -O-(-Si(R2i)2-O-)a-, where a represents an integer greater than or equal to 1. R2i represents an alkyl group that may contain substituents. Multiple R2i groups may be the same or different. In general formula (III), R3a represents -N(R3c)R3d or -SR3e, R3c, R3d and R3e represent hydrogen atoms or substituents, and R3b represents -NH- or -S-.

2. A method for forming a resist pattern, comprising: a step of coating a pre-wetting liquid; a step of forming a resist film; a step of patterning the resist film; and a step of developing the resist film to form a negative resist pattern, the method for forming the resist pattern using a solution containing an organic solvent as the pre-wetting liquid, the solution containing at least one first organic compound selected from the group comprising compounds represented by general formulas (I) to (III), the total content of the first organic compound being 0.01 ppt to 100,000 ppt relative to the total mass of the solution, wherein in general formula (I), Y represents a benzene ring group that can be substituted with an alkyl group or a group represented by general formula (A). When Y represents a benzene ring group, s represents 1, L represents a single bond, and R1a represents an alkyl group that may contain substituents. This alkyl group may also contain heteroatoms. When an alkyl group replaces the benzene ring group, the alkyl group and R1a can bond together to form a ring. Furthermore, when multiple alkyl groups replace the benzene ring group, the alkyl groups can bond together to form a ring. When Y represents a group represented by general formula (A), s represents 3, L represents methylene, and R1a independently represents an alkyl group. In general formula (II), R2a to R2h independently represent alkyl groups that may contain substituents. R2b and R2e can bond together to form a ring. The group formed by the bonding of R2b and R2e is -O-(-Si(R2i)2-O-)a-, where a represents an integer greater than or equal to 1. R2i represents an alkyl group that may contain substituents. Multiple R2i groups may be the same or different. In general formula (III), R3a represents -N(R3c)R3d or -SR3e, R3c, R3d and R3e represent hydrogen atoms or substituents, and R3b represents -NH- or -S-.

3. A method for forming a resist pattern, comprising: a step of pattern exposure of a resist film; a step of developing the resist film to form a negative resist pattern; and a step of washing the negative resist pattern, wherein the method for forming the resist pattern uses a solution containing an organic solvent as the washing solution, the solution containing at least one first organic compound selected from the group comprising compounds represented by general formulas (I) to (III), the total content of the first organic compound being 0.01 ppt to 100,000 ppt relative to the total mass of the solution, wherein in general formula (I), Y represents a benzene ring group that can be substituted with an alkyl group or a group represented by general formula (A). When Y represents a benzene ring group, s represents 1, L represents a single bond, and R1a represents an alkyl group that may contain substituents. This alkyl group may also contain heteroatoms. When an alkyl group replaces the benzene ring group, the alkyl group and R1a can bond together to form a ring. Furthermore, when multiple alkyl groups replace the benzene ring group, the alkyl groups can bond together to form a ring. When Y represents a group represented by general formula (A), s represents 3, L represents methylene, and R1a independently represents an alkyl group. In general formula (II), R2a to R2h independently represent alkyl groups that may contain substituents. R2b and R2e can bond together to form a ring. The group formed by the bonding of R2b and R2e is -O-(-Si(R2i)2-O-)a-, where a represents an integer greater than or equal to 1. R2i represents an alkyl group that may contain substituents. Multiple R2i groups may be the same or different. In general formula (III), R3a represents -N(R3c)R3d or -SR3e, R3c, R3d and R3e represent hydrogen atoms or substituents, and R3b represents -NH- or -S-.

4. The method for forming a resist pattern as described in any one of claims 1 to 3, wherein the step of patterning the resist film is performed using ArF exposure.

5. The method for forming a resist pattern as described in claim 4, wherein the resist film comprises a resin, the resin comprising repeating units containing a lactone structure.

6. The method for forming a resist pattern as described in any one of claims 1 to 3, wherein the step of patterning the resist film uses EUV exposure.

7. The method for forming a resist pattern as described in claim 6, wherein the resist film comprises a resin containing repeating units having phenolic hydroxyl groups.

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

9. A solution containing an organic solvent, the solution containing at least one first organic compound selected from the group consisting of compounds represented by general formulas (I) to (III), wherein the total content of the first organic compound is 0.01 ppt to 100,000 ppt relative to the total mass of the solution, and is used as a developer, rinsing solution, or pre-wetting solution, wherein in general formula (I), Y represents a benzene ring group that can be substituted with an alkyl group or a group represented by general formula (A), where s represents 1, L represents a single bond, and R1a represents an alkyl group that may contain a substituent, and the alkyl group may contain a heteroatom; where the alkyl group replaces the benzene ring group, the alkyl group and R1a may bond to each other to form a ring; and where a plurality of alkyl groups replace the benzene ring group, the alkyl groups may bond to each other to form a ring. In the case where Y represents a group represented by general formula (A), s represents 3, L represents methylene, and R1a represents alkyl groups independently. In general formula (II), R2a to R2h represent alkyl groups that may contain substituents independently. R2b and R2e can bond to each other to form a ring. The group formed by the bonding of R2b and R2e is -O-(-Si(R2i)2-O-)a-, where a represents an integer greater than 1. R2i represents alkyl groups that may contain substituents. Multiple R2i groups may be the same or different. In general formula (III), R3a represents -N(R3c)R3d or -SR3e. R3c, R3d, and R3e represent hydrogen atoms or substituents. R3b represents -NH- or -S-.

Images