Drug solution, kit, pattern forming method, method for producing drug solution, and drug solution container

Abstract

The present invention aims to provide a chemical solution, a reagent kit, a pattern forming method, a method for manufacturing a chemical solution, and a chemical solution container that are excellent in defect suppression performance even after long-term storage. The chemical solution of the present invention is a chemical solution containing an organic solvent, an acid component, and a metal component, wherein the content of the acid component is 1 mass ppt or more and 15 mass ppm or less relative to the total mass of the chemical solution, and the content of the metal component is 0.001 to 100 mass ppt relative to the total mass of the chemical solution.

Description

Technical Field

[0001] The present invention relates to a drug solution, a reagent kit, a pattern forming method, a method for manufacturing a drug solution, and a drug solution container. Background Art

[0002] When manufacturing semiconductor devices through a wiring formation process including photolithography, chemical solutions containing water and / or organic solvents are used as pre-wetting solutions, resist solutions, developers, rinse solutions, stripping solutions, chemical mechanical polishing (CMP) slurries, and post-CMP cleaning solutions.

[0003] Various impurities contained in the chemical solution may cause defects in semiconductor devices. Such defects may cause a decrease in the manufacturing yield of semiconductor devices and electrical abnormalities such as short circuits.

[0004] For example, Patent Document 1 discloses a method for obtaining an ester solvent with reduced acid components and alkali metal contents by devising a distillation method, etc. Also, Patent Document 2 discloses a method for producing butyl acetate by reducing the sulfuric acid content through distillation and treatment with anion exchange resin, etc.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2015-030700

[0008] Patent Document 2: Japanese Patent Application Publication No. 2002-316967 Summary of the invention

[0009] Technical issues to be solved by the invention

[0010] After the drug solution is produced, it is contained in a container, and after being stored for a certain period of time in the form of a drug solution container, the contained drug solution is taken out and used.

[0011] The inventors of the present invention referred to the methods described in Patent Documents 1 and 2 to manufacture a chemical solution, stored the solution for a long time in the form of a chemical solution container contained in a container, took out the chemical solution from the chemical solution container, and applied it to the manufacturing process of a semiconductor device. As a result, it was clearly known that defects may occur on a substrate (e.g., a wafer).

[0012] Therefore, an object of the present invention is to provide a chemical solution, a reagent kit, a pattern forming method, a method for producing a chemical solution, and a chemical solution container that are excellent in defect suppression performance even after long-term storage.

[0013] Means for solving technical problems

[0014] As a result of in-depth research on the above-mentioned topics, the inventors discovered that by using a solution in which the mass ratio of the acid component content to the metal component content is within a specified range, the acid component content to the total mass of the solution is within a specified range, and the metal component content to the total mass of the solution is within a specified range, a solution having excellent defect suppression performance even after long-term storage can be obtained, thereby completing the present invention.

[0015] That is, the present inventors have found that the above-mentioned problems can be solved by the following configuration. [1]

[0017] A liquid medicine containing an organic solvent, an acid component and a metal component.

[0018] The content of the acid component is 1 mass ppt or more and 15 mass ppm or less relative to the total mass of the chemical solution,

[0019] The content of the metal component is 0.001 to 100 ppt by mass relative to the total mass of the chemical solution. [2]

[0021] The liquid medicine as described in [1], wherein

[0022] The mass ratio of the content of the acid component to the content of the metal component is 10 -2 ~10 6 . [3]

[0024] The drug solution as described in [1] or [2], wherein

[0025] The above acid component includes an organic acid,

[0026] The content of the organic acid is 1 ppm by mass or less relative to the total mass of the chemical solution. [4]

[0028] The liquid medicine as described in [3], wherein

[0029] The content of the organic acid having a temperature equal to or higher than the boiling point of the organic solvent in the organic acid is 20% by mass or less relative to the total mass of the organic acid. [5]

[0031] The medicinal solution as described in any one of [1] to [4], wherein

[0032] The above acid component includes an inorganic acid,

[0033] The content of the inorganic acid is 1 ppb by mass or less relative to the total mass of the chemical solution. [6]

[0035] The medicinal solution as described in any one of [1] to [5], wherein

[0036] The metal component includes metal-containing particles containing metal atoms.

[0037] The content of the metal-containing particles is 0.00001 to 10 ppt by mass relative to the total mass of the chemical solution. [7]

[0039] The liquid medicine as described in [6], wherein

[0040] The metal-containing particles contained metal nanoparticles having a particle size of 0.5 to 17 nm in an amount of 1.0×10 -2 ~1.0×10 6 Pieces / cm 3 . [8]

[0042] The medicinal solution as described in any one of [1] to [7], wherein

[0043] The above-mentioned metal components include metal ions,

[0044] The content of the metal ions is 0.01 to 100 ppt by mass relative to the total mass of the chemical solution. [9]

[0046] The medicinal solution as described in any one of [1] to [8], wherein

[0047] The metal component includes metal particles and metal ions.

[0048] The mass ratio of the content of the metal-containing particles to the content of the metal ions is 0.00001 to 1.

[10]

[0050] The medicinal solution as described in any one of [1] to [9], further comprising water,

[0051] The water content is 1 ppm by mass or less relative to the total mass of the chemical solution.

[11]

[0053] The drug solution as described in any one of [1] to

[10] , further comprising at least one organic compound selected from the group consisting of a compound having an amide structure, a compound having a sulfonamide structure, a compound having a phosphoamide structure, a compound having an imide structure, a compound having a urea structure, a compound having a carbamate structure, and an organic acid ester,

[0054] The content of the organic compound is 1 ppm by mass or less relative to the total mass of the chemical solution.

[12]

[0056] The liquid medicine as described in

[11] , wherein

[0057] The above-mentioned organic compound is an organic compound having a boiling point of 300° C. or higher.

[13]

[0059] The drug solution as described in

[11] or

[12] , wherein

[0060] The organic acid ester includes at least one selected from the group consisting of phthalic acid esters and citrate esters.

[14]

[0062] The medicinal solution as described in any one of [1] to

[13] , wherein

[0063] In the organic solvent, the content of the organic solvent having a boiling point of 250° C. or lower is 90% by mass or more relative to the total mass of the organic solvent.

[15]

[0065] The medicinal solution as described in any one of [1] to

[14] , wherein

[0066] The SP value of the organic solvent is 21 or less.

[16]

[0068] The medicinal solution as described in any one of [1] to

[15] , wherein

[0069] The above-mentioned organic solvent has an ester structure.

[17]

[0071] The medicinal solution as described in any one of [1] to

[16] , wherein

[0072] The organic solvent contains butyl acetate, and the acid component contains acetic acid.

[0073] The content of the acetic acid is 0.01 to 15 ppm by mass relative to the total mass of the chemical solution.

[18]

[0075] The medicinal solution as described in any one of [1] to

[17] , wherein

[0076] The organic solvent contains butyl acetate, and the acid component contains n-butyric acid.

[0077] The content of the n-butyric acid is 1 mass ppt or more and 1 mass ppm or less relative to the total mass of the chemical solution.

[19]

[0079] A kit comprising:

[0080] Liquid X, which is the liquid medicine described in

[17] or

[18] ; and

[0081] Liquid medicine Y is a liquid medicine containing an organic solvent, wherein:

[0082] The above-mentioned organic solvent contained in the above-mentioned drug solution Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, undecane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

[20]

[0084] The kit as described in

[20] , wherein

[0085] The chemical solution X is a developer, and the chemical solution Y is a rinser. [twenty one]

[0087] The pattern forming method according to

[19] or

[20] , wherein:

[0088] The organic solvent Y has a Hansen solubility parameter of 3 to 20 MPa relative to eicosene. 0.5 The organic solvent Y1,

[0089] The content of the organic solvent Y1 is 20 to 80% by mass relative to the total mass of the chemical solution Y. [twenty two]

[0091] A pattern forming method, comprising:

[0092] a resist film forming step of forming a resist film using an actinic ray-sensitive or radiation-sensitive resin composition;

[0093] An exposure step of exposing the resist film to light;

[0094] a development step of developing the exposed resist film using the chemical solution X described in

[17] or

[18] ; and

[0095] The rinsing step is performed after the above-mentioned developing step, using a chemical solution Y containing an organic solvent for cleaning.

[0096] The aforementioned organic solvent contained in the above-mentioned drug solution Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, undecane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate. [twenty three]

[0098] The pattern forming method according to

[22] , wherein:

[0099] The organic solvent Y has a Hansen solubility parameter of 3 to 20 MPa relative to eicosene. 0.5 The organic solvent Y1,

[0100] The content of the organic solvent Y1 is 20 to 80% by mass relative to the total mass of the chemical solution Y. [twenty four]

[0102] A method for preparing a liquid medicine, wherein:

[0103] Purifying a substance to be purified containing an organic solvent to obtain the drug solution described in any one of [1] to

[18] ,

[0104] The method includes a filtration step of filtering the substance to be purified, an ion removal step of subjecting the substance to be purified to ion adsorption by an ion exchange method or a chelate group, and a distillation step of distilling the substance to be purified.

[25]

[0106] The method for producing a drug solution as described in

[24] , wherein:

[0107] In the above-mentioned ion exchange method, a cation exchange resin is used.

[26]

[0109] The method for producing a drug solution as described in

[24] , wherein:

[0110] In the above-mentioned ion exchange method, a cation exchange resin and an anion exchange resin are used.

[27]

[0112] A drug solution container comprising a container and the drug solution described in any one of [1] to

[18] contained in the container.

[0113] Effects of the Invention

[0114] As described below, according to the present invention, it is possible to provide a chemical solution, a method for producing a chemical solution, and a chemical solution container that are excellent in defect suppression performance even after long-term storage. DETAILED DESCRIPTION

[0115] Hereinafter, the present invention will be described.

[0116] Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.

[0117] In addition, in this specification, the numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0118] In addition, in the present invention, "ppm" means "parts-per-million (10 -6 ) means parts-per-billion (10 -9 ): parts-per-trillion (10 -12 ), "ppq" means "parts-per-quadrillion (10 -15 ): Gigabit points.

[0119] Furthermore, in the notation of the group (atom group) in the present invention, the notation not indicating substitution and unsubstituted includes groups having no substituent and having substituent within the range that does not impair the effect of the present invention. For example, "hydrocarbon group" includes not only hydrocarbon groups having no substituent (unsubstituted hydrocarbon groups) but also hydrocarbon groups having substituents (substituted hydrocarbon groups). This content is also the same for each compound.

[0120] Furthermore, the "radiation" in the present invention refers to, for example, far ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, or electron beams. Furthermore, the light in the present invention refers to actinic rays or radiation. Unless otherwise specified, the "exposure" in the present invention includes not only exposure using far ultraviolet rays, X-rays, or EUV, but also drawing using particle beams such as electron beams or ion beams.

[0121] In addition, the "boiling point" in the present invention means the normal boiling point.

[0122] [Medicine]

[0123] The chemical solution of the present invention (hereinafter, also referred to as "the present chemical solution") is a chemical solution containing an organic solvent, an acid component, and a metal component.

[0124] Furthermore, in the present chemical solution, the content of the acid component is 1 mass ppt or more and 15 mass ppm or less relative to the total mass of the present chemical solution.

[0125] Furthermore, in the present chemical solution, the content of the above-mentioned metal component is 0.001 to 100 ppt by mass relative to the total mass of the present chemical solution.

[0126] Although the mechanism by which the present drug solution solves the above-mentioned problems is not necessarily clear, the present inventors speculate the mechanism as follows. In addition, the following mechanism is a speculation, and even if the effect of the present invention is obtained by a different mechanism, it is also included in the scope of the present invention.

[0127] The metal components contained in the chemical solution tend to exist as metal ions in the form of ions and metal-containing particles in the form of particles.

[0128] In the case where metal ions form an acid component (especially an organic acid) and a complex in a chemical solution and / or one or more metal ions and one or more acid components form a composite structure through the interaction between the metal ions and the acid component, the interaction between the complex or the composite structure and the surface of the substrate (e.g., a wafer) tends to increase. As a result, the complex or the composite structure is more stabilized than the solvation in the chemical solution, so there is a problem that it is easy to exist as a residue on the surface of the wafer after the chemical solution is used for the treatment of the wafer.

[0129] In addition, there is the following problem: when the above-mentioned complex and composite structure remain on the surface of the chip, when the chip is dry-etched, the above-mentioned complex and composite structure act as an etching mask, and after dry etching, they remain on the surface of the chip as conical defects (conical defects) in an enlarged state.

[0130] Here, as one of the conventional methods for inspecting defects on the surface of a wafer, there is a method of measuring the number of defects remaining on the surface of the wafer after applying a chemical solution on the wafer. However, with the improvement in the accuracy of defect inspection in recent years, defects that were not detected by conventional methods can be detected as cone defects in an enlarged form. In other words, there is a problem that microscopic attachments that were not detected in the past are detected as defects.

[0131] It is believed that the above problem is particularly significant when the drug solution is stored in a container. For example, when the drug solution is stored in a container for a long time, the acid component (especially organic acid) in the drug solution may penetrate into the resin part constituting the liquid contact surface of the container in a trace amount, the acid component (especially organic acid) in the drug solution may enter the small gap of the resin part, or the metal component contained in the resin part interacts with the acid component (especially organic acid) in the drug solution during the manufacturing process of the resin part, or a combination of these, and the metal component is dissolved in the drug solution. That is, it is believed that when the drug solution is stored in a container for a long time, the metal component present on the liquid contact surface of the container is dissolved in the drug solution, and defects are easily detected.

[0132] With regard to this problem, it is speculated that by setting the contents of the acid component and the metal component relative to the drug solution to below the above upper limit, the formation of complexes and composite structures can be suppressed even when the drug solution container is stored for a long time. As a result, it is believed that the defect suppression performance of the drug solution during long-term storage becomes excellent.

[0133] The present inventors have found that if the content of the acid component in the chemical solution is less than the above lower limit, the defect suppression performance of the chemical solution decreases when the chemical solution is stored for a long time. The details of the cause are not clear, but it is presumed to be due to the following reasons.

[0134] The chemical solution may contain a small amount of basic impurities. Examples of basic impurities include amine components transferred from the environment (so-called pollution), decomposed products of plasticizers, and impurities during the synthesis of the resin constituting the container of the chemical solution.

[0135] If the drug solution contains a small amount of alkaline impurities, the resin component constituting the liquid contact surface of the container of the drug solution storage body gradually decomposes along with the small amount of water present in the drug solution. Due to the deterioration of the liquid contact surface caused by the decomposition of the resin component, the decomposed products of the resin component and the metal components contained in the resin component during the manufacturing process of the resin component are dissolved in the drug solution, which accumulates in the drug solution over time, making it easy to detect defects when the drug solution is stored in the container for a long time.

[0136] In view of this problem, it is assumed that if the content of the acid component in the chemical solution is equal to or greater than the lower limit, the decomposition reaction of the material constituting the liquid contact surface of the container caused by the alkaline impurities can be suppressed. This is presumed to suppress the occurrence of defects when the chemical solution is stored in the container for a long time.

[0137] 〔Organic solvent〕

[0138] The present drug solution contains an organic solvent. The content of the organic solvent in the present drug solution is not particularly limited, and is usually preferably 98.0% by mass or more, more preferably 99.0% by mass or more, further preferably 99.9% by mass or more, and particularly preferably 99.99% by mass or more, relative to the total mass of the present drug solution. The upper limit is not particularly limited, and is usually less than 100% by mass.

[0139] The organic solvent may be used alone or in combination of two or more thereof. When two or more organic solvents are used in combination, the total content is within the above range.

[0140] In addition, in this specification, an organic solvent refers to a liquid organic compound containing each component at a content of more than 10,000 mass ppm relative to the total mass of the present chemical solution. That is, in this specification, a liquid organic compound containing an amount of more than 10,000 mass ppm relative to the total mass of the present chemical solution belongs to an organic solvent.

[0141] In this specification, the term "liquid" means a liquid at 25°C and atmospheric pressure.

[0142] There is no particular limitation on the type of organic solvent, and a known organic solvent can be used. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, carboxylates (preferably alkyl acetates and alkyl lactates), alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxy acetates, and alkyl pyruvic acids.

[0143] Furthermore, as the organic solvent, for example, organic solvents described in Japanese Patent Application Laid-Open Nos. 2016-057614, 2014-219664, 2016-138219, and 2015-135379 may be used.

[0144] As the organic solvent, it is preferably selected from propylene glycol monomethyl ether, propylene glycol monoethyl ether (PGME), propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), methyl methoxypropionate, cyclopentanone, cyclohexanone (CHN), γ-butyrolactone, diisoamyl ether, butyl acetate (nBA), isoamyl acetate (iAA), isopropanol, 4-methyl-2-pentanol (MIBC), dimethyl sulfoxide, n-methyl-2-pyrrolidone, diethylene glycol , ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate (PC), cyclohexane sulfone, cycloheptanone, 1-hexanol, decane, 2-heptanone, butyl butyrate, isobutyl isobutyrate, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, undecane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

[0145] The organic solvent may be used alone or in combination of two or more.

[0146] In addition, the type and content of the organic solvent in the chemical solution can be measured using a gas chromatograph-mass spectrometer.

[0147] From the viewpoint of further exerting the effect of the present invention (specifically, the defect suppression performance is excellent even after long-term storage. The same applies below), it is preferred that the organic solvent has an ester structure. As organic solvents having an ester structure, aliphatic carboxylic acid alkyl esters, alicyclic carboxylic acid alkyl esters and substituted aliphatic carboxylic acid alkyl esters (i.e., aliphatic carboxylic acid alkyl esters having a substituent in the aliphatic part) can be listed, and the alkyl group in the alkyl ester part can have a substituent. As substituents, hydroxyl groups, ether bonds, thiol groups, sulfide bonds, amino groups, ester bonds, aromatic groups (e.g., phenyl groups), etc. can be listed. Furthermore, the alkyl group in the alkyl ester part can be linear or branched, and can also form one or more rings.

[0148] Specific examples of the organic solvent having an ester structure include alkylene glycol monoalkyl ether carboxylates, alkyl acetates, alkyl lactates, alkyl alkoxypropionates, and cyclic lactones. From the viewpoint of further exerting the effects of the present invention, it is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), butyl acetate (nBA), and isopentyl acetate (iAA).

[0149] The SP (Solubility Parameter) value of the organic solvent is preferably 21 or less, more preferably 20 or less, and particularly preferably 19 or less.

[0150] In a system (hydrophobic system) in which the SP value of an organic solvent is small, there is the following problem: since the solvation effect in the organic solvent is reduced, the interaction between the acid component (especially the organic acid) and the metal component becomes relatively high, and defects caused by the formation of a complex are easily generated. In view of this problem, if the present chemical solution with a reduced content of the acid component (especially the organic acid) is used, the formation of the complex can be suppressed, so even if an organic solvent with a small SP value is used, the effect of defect suppression performance is fully manifested.

[0151] From the viewpoint of further exerting the effects of the present invention, the lower limit of the SP value of the organic solvent is preferably 14.5 or more, more preferably 15.0 or more.

[0152] The SP value is calculated using the Fedors method described in "Properties of Polymers, 2nd edition, published in 1976". The unit of the SP value is MPa unless otherwise specified. 1 / 2 .

[0153] From the viewpoint of further exerting the effects of the present invention, the content of the organic solvent having a boiling point of 250° C. or lower in the organic solvent is preferably 90% by mass or more based on the total mass of the organic solvent.

[0154] From the viewpoint of further exerting the effects of the present invention, the content of the organic solvent having a boiling point of 250° C. or lower is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 99% by mass or more, and particularly preferably 100% by mass, based on the total mass of the organic solvent.

[0155] The boiling point of the organic solvent is preferably 250°C or lower, more preferably 170°C or lower.

[0156] Here, when the boiling point of the organic solvent is above 170°C, the drying speed of the liquid applied to the substrate is reduced, but before the liquid film is dried by spin coating, particles formed by metal components and acid components, etc., are scattered outside the substrate together with the solvent and are easy to remove. On the other hand, when the boiling point of the organic solvent is below 170°C, there is a problem that particles are easily left on the substrate. In view of this problem, if the present liquid is used, the formation of particles can be suppressed, so even if an organic solvent with a low boiling point is used, the defect suppression performance effect is fully manifested.

[0157] Therefore, even when using an organic solvent having a boiling point of 170° C. or less and an SP value of 21 or less (for example, propylene glycol monomethyl ether acetate, butyl acetate, and isoamyl acetate), the defect suppression performance can be sufficiently exhibited by using this chemical solution.

[0158] The lower limit of the boiling point of the organic solvent is not particularly limited, but is preferably 80° C. or higher, and more preferably 90° C. or higher.

[0159] 〔Acid component〕

[0160] This liquid medicine contains acid.

[0161] The acid component may be intentionally added in the production process of the chemical solution, may be originally contained in the substance to be purified, or may be transferred from the chemical solution production equipment or the like during the production process of the chemical solution (so-called contamination).

[0162] The content of the acid component is 1 mass ppt or more and 15 mass ppm or less, preferably 1 mass ppm or less, more preferably 0.1 mass ppm or less, and preferably 10 mass ppt or more, more preferably 30 mass ppt or more, relative to the total mass of the present chemical solution.

[0163] The content of the acid component is not particularly limited and can be appropriately set so that the pH falls within a desired range.

[0164] The acid component may be used alone or in combination of two or more. When two or more acid components are contained, the total content is within the above range.

[0165] The acid component is not particularly limited, and examples thereof include organic acids and inorganic acids. The acid component can be ionized in the drug solution and exist as ions.

[0166] <Organic Acid>

[0167] Examples of the organic acid include organic carboxylic acids, organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids, and organic carboxylic acids are preferred.

[0168] Examples of the organic carboxylic acid include formic acid, acetic acid, propionic acid, n-butyric acid, valeric acid, lactic acid, adipic acid, maleic acid, fumaric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylvaleric acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, phthalic acid, malic acid, tartaric acid, citric acid, hydroxyethyliminodiacetic acid, and iminodiacetic acid.

[0169] Examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.

[0170] Examples of the organic phosphoric acid include mono- or di-octyl phosphoric acid, mono- or docosyl phosphoric acid, mono- or octacosyl phosphoric acid, and mono- or di-(nonylphenyl) phosphoric acid.

[0171] Examples of the organic phosphonic acid include 1-hydroxyethane-1,1-diphosphonic acid, aminotri(methylenephosphonic acid), and ethylenediaminetetra(methylenephosphonic acid).

[0172] The pKa of the organic acid is preferably 5 or less, more preferably 4 or less, from the viewpoint of being able to further suppress the formation of a complex with a metal component.

[0173] From the viewpoint of further exerting the effects of the present invention, the lower limit of the pKa of the organic acid is preferably -11 or more, more preferably -9 or more.

[0174] Here, pKa (acid dissociation constant) refers to pKa in aqueous solution, such as Chemistry Handbook (II) (Revised 4th Edition, 1993, Japan Chemical Society, Maruzen. Inc.), and the lower the value, the greater the acid strength. The pKa in aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinite dilution aqueous solution, or the following software package 1 can be used to calculate the value of the database based on Hammett substituent constant and known literature values. The pKa values ​​recorded in this specification all represent the values ​​calculated using the software package.

[0175] (Software package 1)Advanced Chemistry Development(ACD / Labs)Software V8.14forSolaris(1994-2007 ACD / Labs)

[0176] From the viewpoint of achieving more excellent defect suppression performance, the boiling point of the organic acid is preferably 300° C. or lower, more preferably 250° C. or lower, and particularly preferably 200° C. or lower.

[0177] The lower limit of the boiling point of the organic acid is not particularly limited, but is preferably 100° C. or higher, and more preferably 110° C. or higher.

[0178] When the acid component contains an organic acid, the content of the organic acid is preferably 1 ppm by mass or less, more preferably 0.5 ppm by mass or less, and particularly preferably 0.1 ppm by mass or less, based on the total mass of the chemical solution, from the viewpoint of achieving better defect suppression performance.

[0179] When the acid component contains an organic acid, the lower limit of the content of the organic acid is preferably 5 ppt or more, more preferably 10 ppt or more, based on the total mass of the present chemical solution, from the viewpoint of further exerting the effects of the present invention.

[0180] The organic acid may be used alone or in combination of two or more. When two or more organic acids are contained, the total content is preferably within the above range.

[0181] From the viewpoint of achieving better defect suppression performance, the content of the organic acid at or above the boiling point of the organic solvent in the organic acid is preferably 20 mass % or less, more preferably 15 mass % or less, and particularly preferably 10 mass % or less, based on the total mass of the organic acid.

[0182] From the viewpoint of further exerting the effects of the present invention, the lower limit of the content of the organic acid at a temperature equal to or higher than the boiling point of the organic solvent is preferably 0% by mass or more, and more preferably 0.01% by mass or more, based on the total mass of the organic acid.

[0183] When the organic solvent contains butyl acetate, the acid component preferably contains acetic acid. In this case, from the viewpoint of better defect suppression performance, the content of acetic acid is preferably 0.001 to 15 mass ppm, more preferably 0.001 to 10 mass ppm, and particularly preferably 0.001 to 5 mass ppm relative to the total mass of the chemical solution.

[0184] Furthermore, when the organic solvent contains butyl acetate, the acid component preferably contains n-butyric acid. In this case, the content of n-butyric acid is preferably 1 mass ppt or more and 1 mass ppm or less, more preferably 1 mass ppt or more and 0.5 mass ppm or less, and particularly preferably 1 mass ppt or more and 0.1 mass ppm or less, relative to the total mass of the present chemical solution.

[0185] When the organic solvent contains butyl acetate, it is preferred that the acid component contains both acetic acid and n-butyric acid from the viewpoint of better defect suppression performance. In this case, the preferred range of the content of each component is as described above.

[0186] <Inorganic Acid>

[0187] Examples of the inorganic acid include boric acid, nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid.

[0188] When the acid component contains an inorganic acid, the content of the inorganic acid is preferably 120 ppb or less, more preferably 1 ppb or less, and particularly preferably 0.6 ppb or less, based on the total mass of the chemical solution, from the viewpoint of achieving better defect suppression performance.

[0189] From the viewpoint of further exerting the effects of the present invention, the lower limit of the content of the inorganic acid is preferably 0 ppb by mass or more, and more preferably 0.001 ppb by mass or more, relative to the total mass of the present chemical solution.

[0190] [Metal component]

[0191] The present chemical solution contains a metal component. Examples of the metal component include metal-containing particles and metal ions. For example, the content of the metal component refers to the total content of the metal-containing particles and the metal ions.

[0192] A preferred method for producing a drug solution will be described later, but the drug solution can generally be produced by purifying a substance to be purified containing the solvent and organic compound described above. The metal component may be intentionally added during the drug solution production process, may be originally contained in the substance to be purified, or may be transferred from a drug solution production device during the drug solution production process (so-called contamination).

[0193] The content of the metal component is 0.001 to 100 mass ppt, preferably 0.001 to 10 mass ppt, and more preferably 0.001 to 5 mass ppt, relative to the total mass of the chemical solution, in order to further exert the effects of the present invention.

[0194] The content of the metal component can be measured by the ICP-MS method described below.

[0195] In the present solution, from the viewpoint of better defect suppression performance, the mass ratio of the content of the acid component to the content of the metal component (acid component / metal component) is preferably 10: -2 ~10 6 , more preferably 1 to 10 6 , more preferably 10 to 10 6 , especially preferably 10 2 ~10 6 , most preferably 10 3 ~10 6 .

[0196] <Containing Metal Particles>

[0197] The present chemical solution may contain metal-containing particles containing metal atoms.

[0198] The metal atom is not particularly limited, and preferably includes a Pb (lead) atom, a Na (sodium) atom, a K (potassium) atom, a Ca (calcium) atom, a Fe (iron) atom, a Cu (copper) atom, a Mg (magnesium) atom, a Mn (manganese) atom, a Li (lithium) atom, an Al (aluminum) atom, a Cr (chromium) atom, a Ni (nickel) atom, a Ti (titanium) atom, a Zn (zinc) atom, and a Zr (zirconium) atom. Among them, Fe atom, Al atom, Cr atom, Ni atom, Pb atom, Zn atom, and Ti atom are preferred.

[0199] In particular, if the content of metal particles containing Fe atoms, Al atoms, Pb atoms, Zn atoms and Ti atoms in the solution is strictly controlled, it is easy to obtain better defect suppression performance. If the content of metal particles containing Pb atoms and Ti atoms in the solution is strictly controlled, it is easy to obtain further better defect suppression performance.

[0200] That is, as the metal atom, at least one selected from the group consisting of Fe atoms, Al atoms, Cr atoms, Ni atoms, Pb atoms, Zn atoms and Ti atoms is preferred, at least one selected from the group consisting of Fe atoms, Al atoms, Pb atoms, Zn atoms and Ti atoms is more preferred, at least one selected from the group consisting of Pb atoms and Ti atoms is further preferred, and it is particularly preferred that the metal-containing particles also contain any one of Pb atoms and Ti atoms.

[0201] The metal-containing particles may contain one type of the above-mentioned metal atoms alone, or may contain two or more types simultaneously.

[0202] The particle size of the metal-containing particles is not particularly limited. For example, in a chemical solution for manufacturing a semiconductor device, the content of particles having a particle size of about 0.1 to 100 nm in the chemical solution is generally controlled.

[0203] Among them, through the research of the inventors, it is known that, in particular, in the liquid medicine used for the resist process of EUV (extreme ultraviolet) exposure, by controlling the content of metal particles (hereinafter also referred to as "metal nanoparticles") with a particle size of 0.5 to 17 nm in the liquid medicine, it is easy to obtain a liquid medicine with excellent defect suppression performance. In the resist process of EUV exposure, fine resist spacing, resist width and resist spacing are usually required. In this case, it is necessary to control finer particles that are not a problem in previous processes in units of their number.

[0204] There is no particular limitation on the particle size distribution based on the number of metal-containing particles. From the perspective of obtaining a drug solution having a more excellent effect of the present invention, it is preferred that at least one of the groups consisting of a particle size range of less than 5 nm and a particle size range of greater than 17 nm has a maximum value.

[0205] In other words, it is preferred that there is no maximum value in the particle size range of 5 to 17 nm. The particle size range of 5 to 17 nm does not have a maximum value, so that the solution has better defect suppression performance, especially better bridge defect suppression performance. Here, bridge defect refers to the defect of cross-linking between wiring patterns.

[0206] Furthermore, from the viewpoint of obtaining a chemical solution having a further excellent effect of the present invention, it is particularly preferred that the particle size distribution based on number has a maximum value in the range of particle size of 0.5 nm or more and less than 5 nm. As described above, the chemical solution has a further excellent bridge defect suppression performance.

[0207] The content of the metal particles is preferably 0.00001 to 10 mass ppt, more preferably 0.0001 to 5 mass ppt, and particularly preferably 0.0001 to 0.5 mass ppt relative to the total mass of the chemical solution. If the content of the metal particles is within the above range, a chemical solution having excellent defect suppression performance (especially defect suppression performance after long-term storage of the chemical solution container) can be obtained.

[0208] The type and content of the metal-containing particles in the chemical solution can be measured by SP-ICP-MS (Single Nanoparticle Inductively Coupled Plasma Mass Spectrometry).

[0209] Here, the so-called SP-ICP-MS method uses the same apparatus as the general ICP-MS method (inductively coupled plasma mass spectrometry), and only the data analysis is different. The data analysis of the SP-ICP-MS method can be performed using commercially available software.

[0210] In the ICP-MS method, the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal-containing particles and metal ions to be measured is determined as the content of the metal component.

[0211] On the other hand, the SP-ICP-MS method can measure the content of metal-containing particles. Therefore, if the content of metal-containing particles is subtracted from the content of metal components in the sample, the content of metal ions in the sample can be calculated.

[0212] As an apparatus for the SP-ICP-MS method, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry: inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, Inc. can be cited, and the measurement can be performed by the method described in the embodiment. As other apparatuses besides the above, in addition to NexION 350S manufactured by PerkinElmer Japan Co., Ltd., Agilent 8900 manufactured by Agilent Technologies, Inc. can also be used.

[0213] (Metal Nanoparticles)

[0214] Metal nanoparticles refer to particles containing metal and having a particle size of 0.5 to 17 nm.

[0215] The number of metal nanoparticles contained per unit volume of the liquid medicine is preferably 1.0×10 -2 ~1.0×10 6 Pieces / cm 3 From the viewpoint of further exerting the effect of the present invention, 1.0×10 -1 Pieces / cm 3 More preferably 5.0×10 -1 Pieces / cm 3 Above, preferably 1.0×10 5 Pieces / cm 3 Below, more preferably 1.0×10 4 Pieces / cm 3 Below, more preferably 1.0×10 3 Pieces / cm 3 the following.

[0216] In particular, if the number of metal nanoparticles contained per unit volume of the chemical solution is 5.0×10 -1 ~1.0×10 3 Pieces / cm 3 , the solution has better defect suppression performance.

[0217] The content of metal nanoparticles in the chemical solution can be measured by the method described in Examples, and the number of metal nanoparticles per unit volume of the chemical solution is determined by rounding off to a double digit.

[0218] There is no particular limitation on the metal atom contained in the metal nanoparticles, and the metal atom contained in the metal-containing particles is the same as the atom described previously. Among them, from the viewpoint of obtaining a drug solution having a more excellent effect of the present invention, as a metal atom, it is preferred to select at least one of the group consisting of Pb atoms and Ti atoms, and more preferably the metal nanoparticles contain both Pb atoms and Ti atoms. The metal nanoparticles contain both Pb atoms and Ti atoms, and typically, the drug solution includes both metal nanoparticles containing Pb atoms and metal nanoparticles containing Ti atoms.

[0219] The ratio of the number of metal nanoparticles containing Pb atoms (hereinafter, also referred to as "Pb nanoparticles") and the number of metal nanoparticles containing Ti atoms (hereinafter, also referred to as "Ti nanoparticles") in the liquid medicine (Pb / Ti) is not particularly limited, but is preferably 1.0×10 -4 ~3.0, more preferably 1.0×10 -3 ~2.0, especially preferably 1.0×10 -2 ~1.5. If Pb / Ti is 1.0×10 -3 ~2.0, the chemical solution has a more excellent effect of the present invention, especially a more excellent bridge defect suppression performance.

[0220] The present inventors have found that Pb nanoparticles and Ti nanoparticles are easily associated when, for example, a chemical solution is applied to a developer sheet, and are likely to cause defects (particularly bridge defects) when developing a resist film.

[0221] If Pb / Ti is 1.0×10 -3 In addition, in this specification, Pb / Ti and A / (B+C) described later are rounded off to obtain two significant figures.

[0222] As long as the metal nanoparticles contain metal atoms, the form thereof is not particularly limited. For example, monomers of metal atoms, compounds containing metal atoms (hereinafter also referred to as "metal compounds"), or complexes thereof, etc. can be cited. Furthermore, the metal nanoparticles may contain multiple metal atoms. In addition, when the metal nanoparticles contain multiple metals, the metal atom with the highest content (atm%) among the multiple metals is taken as the main component. Therefore, when referred to as Pb nanoparticles, when containing multiple metals, it means that among the multiple metals, Pb atoms are the main component.

[0223] The composite is not particularly limited, and examples thereof include so-called core-shell particles having a monomer of a metal atom and a metal compound covering at least a portion of the monomer of the metal atom; solid solution particles containing metal atoms and other atoms; eutectic particles containing metal atoms and other atoms; agglomerate particles of a monomer of a metal atom and a metal compound; agglomerate particles of different types of metal compounds; and metal compounds whose composition changes continuously or intermittently from the surface of the particle toward the center, etc.

[0224] The atoms other than the metal atoms contained in the metal compound are not particularly limited, and examples thereof include carbon atoms, oxygen atoms, nitrogen atoms, hydrogen atoms, sulfur atoms, and phosphorus atoms, among which oxygen atoms are preferred. The metal compound may contain oxygen atoms in any form, and oxides of metal atoms are more preferred.

[0225] From the viewpoint of obtaining a drug solution having a better effect of the present invention, the metal nanoparticles preferably include at least one selected from the group consisting of particles composed of monomers of metal atoms (particle A), particles composed of oxides of metal atoms (particle B), and particles composed of monomers of metal atoms and acids of metal atoms (particle C).

[0226] In addition, the relationship between the number of particles A, the number of particles B, and the number of particles C among the number of particles contained per unit volume of the drug solution is not particularly limited. From the viewpoint of obtaining a drug solution having a more excellent effect of the present invention, the number of particles contained in the particles A relative to the total number of particles contained in the particles B and the number of particles contained in the particles C (hereinafter also referred to as "A / (B+C)") is preferably 1.5 or less, more preferably less than 1.0, and further preferably 2.0×10 -1 Below, especially preferably 1.0×10 -1 Below, preferably 1.0×10 -3 More preferably 1.0×10 -2 above.

[0227] If A / (B+C) is less than 1.0, the chemical solution has better bridge defect suppression performance, better pattern width uniformity and smear defect suppression performance. In addition, smear defect limitation means that defects of metal atoms are not detected.

[0228] Furthermore, when A / (B+C) is 0.1 or less, the chemical solution has a more excellent defect suppression performance.

[0229] <Metal ions>

[0230] The liquid medicine may contain metal ions.

[0231] Examples of metal ions include ions of metal atoms such as Pb (lead), Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), Zn (zinc) and Zr (zirconium).

[0232] The content of metal ions is preferably 0.01 to 100 mass ppt, more preferably 0.01 to 10 mass ppt, and particularly preferably 0.01 to 5 mass ppt relative to the total mass of the chemical solution. If the content of metal ions is within the above range, a chemical solution having excellent defect suppression performance (especially defect suppression performance after long-term storage of the chemical solution container) can be obtained.

[0233] The content of metal ions in the chemical solution is determined by subtracting the content of metal-containing particles measured by the SP-ICP-MS method from the content of metal components in the chemical solution measured by the ICP-MS method as described above.

[0234] From the viewpoint of further exerting the effects of the present invention, the mass ratio of the content of the metal-containing particles to the content of the metal ions (metal-containing particles / metal ions) is preferably 0.00001 to 1, more preferably 0.0001 to 0.2, and particularly preferably 0.001 to 0.05.

[0235] [Other ingredients]

[0236] The chemical solution may contain other components than those mentioned above. Examples of other components include organic compounds other than organic solvents (especially organic compounds having a boiling point of 300° C. or higher), water, and resins.

[0237] <Organic compounds other than organic solvents>

[0238] The drug solution may contain an organic compound other than an organic solvent (hereinafter also referred to as a "specific organic compound"). In this specification, the so-called specific organic compound is a compound different from the organic solvent contained in the drug solution, and refers to an organic compound contained in an amount of 10,000 mass ppm or less relative to the total mass of the drug solution. That is, in this specification, an organic compound contained in an amount of 10,000 mass ppm or less relative to the total mass of the drug solution corresponds to a specific organic compound, and does not correspond to an organic solvent.

[0239] Furthermore, when the chemical solution contains a plurality of specific organic compounds and each specific organic compound is contained in a content of 10000 mass ppm or less, each of the specific organic compounds corresponds to the specific organic compound.

[0240] The specific organic compound may be added to the drug solution or may be accidentally mixed in the process of manufacturing the drug solution. Examples of the case where the specific organic compound is accidentally mixed in the process of manufacturing the drug solution include, but are not limited to, the case where the specific organic compound is contained in a raw material (e.g., an organic solvent) used in the manufacture of the drug solution and is mixed in the process of manufacturing the drug solution (e.g., a contaminant).

[0241] The content of the specific organic compound in the present chemical solution can be measured using GCMS (gas chromatography mass spectrometry).

[0242] The number of carbon atoms in the specific organic compound is not particularly limited, but from the viewpoint that the chemical solution has a more excellent effect of the present invention, it is preferably 8 or more, and more preferably 12 or more. The upper limit of the number of carbon atoms is not particularly limited, but is usually preferably 30 or less.

[0243] Examples of the specific organic compound include by-products and / or unreacted raw materials (hereinafter also referred to as “by-products, etc.”) generated in the synthesis of the organic solvent.

[0244] Examples of the by-products include compounds represented by the following formulae I to V.

[0245] [Chemical formula 1]

[0246]

[0247] In Formula I, R1 and R2 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0248] As the alkyl group or cycloalkyl group represented by R1 and R2, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 6 to 8 carbon atoms is more preferred.

[0249] The ring formed by R1 and R2 bonding to each other is a lactone ring, preferably a 4- to 9-membered lactone ring, more preferably a 4- to 6-membered lactone ring.

[0250] In addition, it is preferred that R1 and R2 satisfy the relationship that the number of carbon atoms in the compound represented by Formula I is 8 or more.

[0251] In Formula II, R3 and R4 are independently hydrogen atoms, alkyl groups, alkenyl groups, cycloalkyl groups or cycloalkenyl groups, or are bonded to each other to form a ring. However, both R3 and R4 are not hydrogen atoms.

[0252] As the alkyl group represented by R3 and R4, for example, an alkyl group having 1 to 12 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.

[0253] As the alkenyl group represented by R3 and R4, for example, an alkenyl group having 2 to 12 carbon atoms is preferred, and an alkenyl group having 2 to 8 carbon atoms is more preferred.

[0254] The cycloalkyl group represented by R3 and R4 is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0255] As the cycloalkenyl group represented by R3 and R4, for example, a cycloalkenyl group having 3 to 12 carbon atoms is preferred, and a cycloalkenyl group having 6 to 8 carbon atoms is more preferred.

[0256] The ring formed by R3 and R4 bonding to each other is a cyclic ketone structure, which may be a saturated cyclic ketone or an unsaturated cyclic ketone. The cyclic ketone is preferably a 6- to 10-membered ring, more preferably a 6- to 8-membered ring.

[0257] In addition, it is preferred that R3 and R4 satisfy the relationship that the number of carbon atoms in the compound represented by Formula II is 8 or more.

[0258] In formula III, R5 represents an alkyl group or a cycloalkyl group.

[0259] The alkyl group represented by R5 is preferably an alkyl group having 6 or more carbon atoms, more preferably an alkyl group having 6 to 12 carbon atoms, and further preferably an alkyl group having 6 to 10 carbon atoms.

[0260] The above-mentioned alkyl group may have an ether bond in the chain, and may have a substituent such as a hydroxyl group.

[0261] The cycloalkyl group represented by R5 is preferably a cycloalkyl group having 6 or more carbon atoms, more preferably a cycloalkyl group having 6 to 12 carbon atoms, and further preferably a cycloalkyl group having 6 to 10 carbon atoms.

[0262] In formula IV, R6 and R7 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0263] As the alkyl group represented by R6 and R7, an alkyl group having 1 to 12 carbon atoms is preferred, and an alkyl group having 1 to 8 carbon atoms is more preferred.

[0264] The cycloalkyl group represented by R6 and R7 is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0265] The ring formed by R6 and R7 bonding to each other is a cyclic ether structure. The cyclic ether structure is preferably a 4- to 8-membered ring, and more preferably a 5- to 7-membered ring.

[0266] In addition, it is preferred that R6 and R7 satisfy the relationship that the number of carbon atoms in the compound represented by Formula IV is 8 or more.

[0267] In Formula V, R8 and R9 each independently represent an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring. L represents a single bond or an alkylene group.

[0268] As the alkyl group represented by R8 and R9, for example, an alkyl group having 6 to 12 carbon atoms is preferred, and an alkyl group having 6 to 10 carbon atoms is more preferred.

[0269] The cycloalkyl group represented by R8 and R9 is preferably a cycloalkyl group having 6 to 12 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms.

[0270] The ring formed by R8 and R9 bonding to each other is a cyclic dione structure. The cyclic dione structure is preferably a 6- to 12-membered ring, and more preferably a 6- to 10-membered ring.

[0271] As the alkylene group represented by L, for example, an alkylene group having 1 to 12 carbon atoms is preferred, and an alkylene group having 1 to 10 carbon atoms is more preferred.

[0272] In addition, R8, R9 and L satisfy the relationship that the number of carbon atoms in the compound represented by Formula V is 8 or more.

[0273] Although not particularly limited, when the organic solvent is an amide compound, an imide compound, or a sulfoxide compound, in one embodiment, examples thereof include amide compounds, imide compounds, and sulfoxide compounds having 6 or more carbon atoms. In addition, examples of the specific organic compound include the following compounds.

[0274] [Chemical formula 2]

[0275]

[0276] [Chemical formula 3]

[0277]

[0278] In addition, as specific organic compounds, antioxidants such as butylated hydroxytoluene (BHT), distearyl thiodipropionate (DSTP), 4,4'-butylenebis-(6-tert-butyl-3-methylphenol), 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol) and antioxidants described in Japanese Patent Gazette No. 2015-200775 can also be listed; unreacted raw materials; structural isomers and by-products produced when manufacturing organic solvents; eluted materials from parts of the manufacturing device that constitutes the organic solvent (for example, plasticizers eluted from rubber parts such as O-rings); etc.

[0279] In addition, examples of the specific organic compound include dioctyl phthalate (DOP), di(2-ethylhexyl) phthalate (DEHP), di(2-propylheptyl) phthalate (DPHP), dibutyl phthalate (DBP), benzyl butyl phthalate (BBzP), diisodecyl phthalate (DIDP), diisooctyl phthalate (DIOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), dihexyl phthalate, diisononyl phthalate (DINP), tri(2-ethylhexyl) phthalate (DINP), and tri(2-propylheptyl) phthalate (DINP). esters, such as terephthalate (TEHTM), tri(n-octyl-n-decyl) trimellitate (ATM), di(2-ethylhexyl) adipate (DEHA), monomethyl adipate (MMAD), dioctyl adipate (DOA), dibutyl sebacate (DBS), dibutyl maleate (DBM), diisobutyl maleate (DIBM), azelaic acid esters, benzoic acid esters, terephthalic acid esters (e.g. dioctyl terephthalate (DEHT)), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), epoxidized vegetable oils, sulfonamides (e.g. N-(2-hydroxypropyl)benzenesulfonamide (HP BSA), N-(n-butyl)benzenesulfonamide (BBSA-NBBS)), organic phosphates (e.g., tricresyl phosphate (TCP), tributyl phosphate (TBP)), acetylated monoglycerides, triethyl citrate (TEC), acetyl triethyl citrate (ATEC), tributyl citrate (TBC), acetyl tributyl citrate (ATBC), trioctyl citrate (TOC), acetyl trioctyl citrate (ATOC), trihexyl citrate (THC), acetyl trihexyl citrate (ATHC), epoxidized soybean oil, ethylene propylene rubber, polybutene, addition polymers of 5-ethylidene-2-norbornene, and the polymer plasticizers exemplified below.

[0280] These specific organic compounds are presumed to be mixed into the purified product or the chemical solution from filters, pipes, tanks, O-rings, containers, etc., which come into contact during the purification process. In particular, compounds other than alkyl olefins are associated with the generation of bridge defects.

[0281] [Chemical formula 4]

[0282]

[0283] (Organic compounds with specific polar structures)

[0284] The present drug solution may contain an organic compound having the following specific polar structure among specific organic compounds. The organic compound having a specific polar structure preferably contains at least one organic compound selected from the group consisting of a compound having an amide structure, a compound having a sulfonamide structure, a compound having a phosphinamide structure, a compound having an imide structure, a compound having a urea structure, a compound having a carbamate structure, and an organic acid ester.

[0285] Examples of the compound having an amide structure include oleic acid amide, stearic acid amide, erucic acid amide, methylene bis-stearic acid amide, methylene bis-octadecanoic acid amide (707° C.), and ethylene bis-octadecanoic acid amide.

[0286] Examples of the compound having a sulfonamide structure include N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-(2-hydroxypropyl)benzenesulfonamide, and N-butylbenzenesulfonamide.

[0287] Examples of the compound having an imide structure include phthalimide (366° C.), hexahydrophthalimide, N-2-ethylhexylphthalimide, N-butylphthalimide, and N-isopropylphthalimide.

[0288] Examples of the compound having a urea structure include aliphatic diureas, alicyclic diureas, and aromatic diureas.

[0289] From the viewpoint of further exerting the effect of the present invention, the organic acid ester preferably contains at least one selected from the group consisting of phthalic acid esters such as dioctyl phthalate (boiling point 385°C), diisononyl phthalate (boiling point 403°C) and dibutyl phthalate (boiling point 340°C), and di(2-ethylhexyl) terephthalate (boiling point 416°C / 101.3 kPa).

[0290] The content of the organic compound having a specific polar structure is preferably 5 mass ppm or less relative to the total mass of the present chemical solution, more preferably 1 mass ppm or less from the viewpoint of better defect suppression performance, further preferably 0.1 mass ppm or less, and particularly preferably 0.01 mass ppm or less.

[0291] From the viewpoint of further exerting the effects of the present invention, the lower limit of the content of the organic compound having a specific polar structure is preferably 0.0001 ppm by mass or more, and more preferably 0.001 ppm by mass or more, based on the total mass of the present chemical solution.

[0292] (Organic compounds with a boiling point of 300°C or above)

[0293] The present chemical solution may also contain an organic compound having a boiling point of 300°C or higher (hereinafter also referred to as a "high-boiling-point organic compound") among the organic compounds having the above-mentioned specific polar structure. When the present chemical solution contains a high-boiling-point organic compound, the boiling point is high and it is not easy to volatilize in the photolithography process. Therefore, in order to obtain a chemical solution with excellent defect suppression performance, it is preferable to strictly control the content and presence of the high-boiling-point organic compound in the chemical solution.

[0294] The content of the high boiling point organic compound is preferably 5 mass ppm or less, more preferably 1 mass ppm or less, further preferably 0.1 mass ppm or less, and particularly preferably 0.01 mass ppm or less, based on the total mass of the chemical solution, from the viewpoint of better defect suppression performance.

[0295] From the viewpoint of further exerting the effects of the present invention, the lower limit of the content of the high-boiling-point organic compound is preferably 0.0001 ppm by mass or more, and more preferably 0.001 ppm by mass or more, based on the total mass of the present chemical solution.

[0296] The inventors have found that there are various forms when the organic compound or high-boiling-point organic compound having the above-mentioned polar structure is contained in a liquid medicine. Examples of the forms in which the organic compound or high-boiling-point organic compound having a polar structure exists in a liquid medicine include particles formed by agglomeration of particles composed of metal atoms or metal compounds and particles of the organic compound or high-boiling-point organic compound having a polar structure; particles having particles composed of metal atoms or metal compounds and particles of the organic compound or high-boiling-point organic compound having a polar structure arranged in a manner to cover at least a portion of the particles; particles formed by coordination bonding between metal atoms and the organic compound or high-boiling-point organic compound having a polar structure; and the like.

[0297] Among them, as a method that has a great influence on the defect suppression performance of the drug solution, metal nanoparticles (particles U) containing organic compounds with polar structures or high-boiling point organic compounds can be listed. The present inventors have found that the defect suppression performance of the drug solution can be dramatically improved by controlling the number of particles contained per unit volume of the drug solution of the above-mentioned particles U.

[0298] Although this reason is not necessarily clear, particle U is compared with the metal nanoparticle (particle V) that does not contain the organic compound with polar structure or the high boiling point organic compound, and surface free energy easily becomes relatively reduced. This particle U is not easy to remain on the substrate processed by the liquid medicine, and, even if remaining, when contacting with the liquid medicine again, also easily removes. For example, when the liquid medicine is used as developer and rinse solution, during development, particle U is more difficult to remain on the substrate, and further, is easily removed by rinse etc. That is, the result contains the particle both sides of the high boiling point organic compound and the metal atom more easily removed.

[0299] Furthermore, since the resist film is generally hydrophobic, it is estimated that the particles U having a lower surface energy are less likely to remain on the substrate.

[0300] The ratio of the number of particles U to the number of particles V per unit volume of the liquid medicine is preferably 10 or more, preferably 1.0×10 2 It is preferably 50 or less, more preferably 35 or less, and particularly preferably 25 or less.

[0301] <Water>

[0302] The present drug solution may contain water. The water is not particularly limited, and examples thereof include distilled water, ion-exchanged water, and pure water.

[0303] Water may be added to the drug solution or may be accidentally mixed into the drug solution during the drug solution manufacturing process. Examples of unintentional mixing during the drug solution manufacturing process include, but are not limited to, the case where water is contained in a raw material (e.g., an organic solvent) used in the drug solution manufacturing process and mixed during the drug solution manufacturing process (e.g., a contaminant).

[0304] The water content is preferably 30 mass ppm or less, more preferably 1 mass ppm or less, further preferably 0 to 0.6 mass ppm, and particularly preferably 0 to 0.3 mass ppm relative to the total mass of the chemical solution. If the water content is 1 mass ppm or less, the formation of a complex between the metal component and the acid component can be suppressed, thereby obtaining a chemical solution having excellent defect suppression performance (especially, defect suppression performance after long-term storage of the chemical solution container).

[0305] The water content in the present chemical solution refers to the water content measured using an apparatus using the Karl Fischer water measurement method as the measurement principle.

[0306] <Resin>

[0307] The present liquid medicine may contain a resin. As the resin, a resin P having a group that is decomposed by the action of an acid to generate a polar group is more preferred. As the above-mentioned resin, a resin whose solubility in a developer mainly composed of an organic solvent is reduced by the action of an acid, that is, a resin having a repeating unit represented by the formula (AI) described later is more preferred. The resin having a repeating unit represented by the formula (AI) described later has a group that is decomposed by the action of an acid to generate an alkali-soluble group (hereinafter also referred to as an "acid-decomposable group").

[0308] Examples of the polar group include alkali-soluble groups, such as carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), phenolic hydroxyl groups, and sulfonic groups.

[0309] In the acid-decomposable group, the polar group is protected by a group that is detached by the action of an acid (acid-detachable group). Examples of the acid-detachable group include -C(R 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 ) and -C(R 01 )(R 02 )(OR 39 )wait.

[0310] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0311] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0312] Hereinafter, the resin P whose solubility in a developer mainly composed of an organic solvent is reduced by the action of an acid will be described in detail.

[0313] (Formula (AI): repeating unit having an acid-decomposable group)

[0314] It is preferred that the resin P contains a repeating unit represented by the formula (AI).

[0315] [Chemical formula 5]

[0316]

[0317] In formula (AI),

[0318] Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.

[0319] T represents a single bond or a divalent linking group.

[0320] Ra1 to Ra3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

[0321] Two of Ra1 to Ra3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0322] Examples of the alkyl group which may have a substituent represented by Xa1 include a methyl group and -CH2-R 11 The group represented by R 11It represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent organic group.

[0323] Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0324] Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0325] T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group or a -(CH2)3- group.

[0326] As the alkyl group of Ra1 to Ra3, an alkyl group having 1 to 4 carbon atoms is preferred.

[0327] The cycloalkyl group for Ra1 to Ra3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecyl or adamantyl.

[0328] The cycloalkyl group formed by bonding two of Ra1 to Ra3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0329] Regarding the cycloalkyl group formed by bonding two of Ra1 to Ra3, for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

[0330] The repeating unit represented by the formula (AI) is preferably in an embodiment in which Ra1 is a methyl group or an ethyl group, and Ra2 and Ra3 are bonded to form the above-mentioned cycloalkyl group.

[0331] Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably has 8 or less carbon atoms.

[0332] The content of the repeating unit represented by the formula (AI) is preferably 20 to 90 mol %, more preferably 25 to 85 mol %, and further preferably 30 to 80 mol % based on all the repeating units in the resin P.

[0333] (Repeating unit having a lactone structure)

[0334] Furthermore, it is preferred that the resin P contains a repeating unit Q having a lactone structure.

[0335] The repeating unit Q having a lactone structure preferably has a lactone structure in a side chain, and is more preferably a repeating unit derived from a (meth)acrylic acid derivative monomer.

[0336] The repeating unit Q having a lactone structure may be used alone or in combination of two or more. However, it is preferred that one be used alone.

[0337] The content of the repeating unit Q having a lactone structure is preferably 3 to 80 mol % based on all the repeating units in the resin P, and more preferably 3 to 60 mol %.

[0338] The lactone structure is preferably a 5- to 7-membered ring lactone structure, and more preferably a structure in which another ring structure is condensed with a 5- to 7-membered ring lactone structure to form a bicyclic structure or a spirocyclic structure.

[0339] As the lactone structure, it is preferred to contain a repeating unit having a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-17). As the lactone structure, it is preferred to contain a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5) or formula (LC1-8), and more preferably a lactone structure represented by formula (LC1-4).

[0340] [Chemical formula 6]

[0341]

[0342] The lactone structure part may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) may be the same or different, and the multiple substituents (Rb2) may be bonded to each other to form a ring.

[0343] (Repeating unit having phenolic hydroxyl group)

[0344] Furthermore, the resin P may contain a repeating unit having a phenolic hydroxyl group.

[0345] Examples of the repeating unit having a phenolic hydroxyl group include repeating units represented by the following general formula (I).

[0346] [Chemical formula 7]

[0347]

[0348] In the formula,

[0349] R 41 , R42 and R 43 Each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can bond with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0350] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0351] L4 represents a single bond or an alkylene group.

[0352] Ar4 represents an (n+1) valent aromatic ring group, when combined with R 42 When they are bonded to form a ring, they represent an aromatic ring group with a valence of (n+2).

[0353] n represents an integer of 1-5.

[0354] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and further preferably an alkyl group having 3 or less carbon atoms.

[0355] As R in the general formula (I) 41 , R 42 and R 43 The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.

[0356] As R in the general formula (I) 41 , R 42 and R 43 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0357] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably the same as the above R 41 , R 42 and R 43 The same group as the alkyl group in .

[0358] Examples of substituents in the above groups include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, carbamate groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups, and the number of carbon atoms in the substituents is preferably 8 or less.

[0359] Ar4 represents an (n+1)-valent aromatic ring group. The divalent aromatic ring group when n is 1 may have a substituent, for example, arylene groups having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene and anthracene, and aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole.

[0360] Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or more include groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group.

[0361] The (n+1)-valent aromatic ring group may further have a substituent.

[0362] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R in the general formula (I): 41 , R 42 and R 43 The alkyl groups mentioned in the above; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl.

[0363] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom or an alkyl group) 64 Examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl groups which may have a substituent, and more preferably alkyl groups having 8 or less carbon atoms.

[0364] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0365] The alkylene group in L4 is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may have a substituent.

[0366] Ar4 is preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and more preferably a benzene ring group, a naphthyl ring group or a biphenylene ring group.

[0367] It is preferred that the repeating unit represented by the general formula (I) has a hydroxystyrene structure. That is, Ar4 is preferably a benzene ring group.

[0368] The content of the repeating units having a phenolic hydroxyl group is preferably 0 to 50 mol %, more preferably 0 to 45 mol %, and further preferably 0 to 40 mol % based on all the repeating units in the resin P.

[0369] (Repeating unit containing an organic group having a polar group)

[0370] The resin P may further contain a repeating unit containing an organic group having a polar group, in particular, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, the substrate adhesion and the developer affinity are improved.

[0371] As the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group, a diamondyl group or a norbornyl group is preferred. As the polar group, a hydroxyl group or a cyano group is preferred.

[0372] When the resin P contains repeating units containing an organic group having a polar group, the content thereof is preferably 1 to 50 mol %, more preferably 1 to 30 mol %, further preferably 5 to 25 mol %, and particularly preferably 5 to 20 mol % relative to all repeating units in the resin P.

[0373] (Repeating unit represented by general formula (VI))

[0374] The resin P may contain a repeating unit represented by the following general formula (VI).

[0375] [Chemical formula 8]

[0376]

[0377] In the general formula (VI),

[0378] R 61 , R 62 and R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 62 It can bond with Ar6 to form a ring. In this case, R 62 represents a single bond or an alkylene group.

[0379] X6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0380] L6 represents a single bond or an alkylene group.

[0381] Ar6 represents an (n+1) valent aromatic ring group. 62When they are bonded to form a ring, they represent an aromatic ring group with a valence of (n+2).

[0382] Regarding Y2, when n≥2, each independently represents a hydrogen atom or a group that is dissociated by the action of an acid. Among them, at least one of Y2 represents a group that is dissociated by the action of an acid.

[0383] n represents an integer of 1 to 4.

[0384] As the group Y2 that is dissociated by the action of an acid, a structure represented by the following general formula (VI-A) is preferred.

[0385] [Chemical formula 9]

[0386]

[0387] L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group consisting of an alkylene group and an aryl group.

[0388] M represents a single bond or a divalent linking group.

[0389] Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.

[0390] At least two of Q, M, and L1 may be bonded to form a ring (preferably a 5-membered or 6-membered ring).

[0391] The repeating unit represented by the general formula (VI) is preferably a repeating unit represented by the following general formula (3).

[0392] [Chemical formula 10]

[0393]

[0394] In the general formula (3),

[0395] Ar3 represents an aromatic ring group.

[0396] R3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.

[0397] M3 represents a single bond or a divalent linking group.

[0398] Q3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

[0399] At least two of Q3, M3 and R3 may be bonded to form a ring.

[0400] The aromatic ring group represented by Ar3 is the same as Ar6 in the above general formula (VI) when n in the above general formula (VI) is 1, and is preferably a phenylene group or a naphthylene group, and more preferably a phenylene group.

[0401] (Repeating unit having silicon atoms in the side chain)

[0402] Resin P may further contain repeating units having silicon atoms on the side chains. Examples of repeating units having silicon atoms on the side chains include (meth)acrylate repeating units having silicon atoms and vinyl repeating units having silicon atoms. Repeating units having silicon atoms on the side chains are typically repeating units having groups having silicon atoms on the side chains. Examples of groups having silicon atoms include trimethylsilyl, triethylsilyl, triphenylsilyl, tricyclohexylsilyl, tris(trimethylsiloxysilyl), tris(trimethylsilylsilyl), methylbistrimethylsilylsilyl, methylbistrimethylsiloxysilyl, dimethyltrimethylsilylsilyl, dimethyltrimethylsiloxysilyl, and cyclic or linear polysiloxanes as described below, or cage-type, ladder-type, or random silsesquioxane structures. In the formula, R and R 1 Each independently represents a monovalent substituent. * represents a bonding bond.

[0403] [Chemical formula 11]

[0404]

[0405] As the repeating unit having the above group, for example, a repeating unit derived from an acrylate compound or methacrylate compound having the above group, or a repeating unit derived from a compound having the above group and a vinyl group is preferable.

[0406] When the resin P has the above-mentioned repeating unit having a silicon atom in the side chain, the content thereof is preferably 1 to 30 mol %, more preferably 5 to 25 mol %, and further preferably 5 to 20 mol % relative to all the repeating units in the resin P.

[0407] The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and further preferably 5,000 to 15,000, as a polystyrene conversion value based on the GPC (Gel permeation chromatography) method. By setting the weight average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and it is possible to prevent deterioration of developability or deterioration of film forming properties due to increased viscosity.

[0408] The dispersion degree (molecular weight distribution) is usually preferably 1 to 5, 1 to 3, more preferably 1.2 to 3.0, and further preferably 1.2 to 2.0.

[0409] In the present chemical solution, the content of the resin P is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.

[0410] Furthermore, in the present chemical solution, the resin P may be used alone or in combination of two or more.

[0411] Regarding other components (such as acid generators, alkaline compounds, quenchers, hydrophobic resins, surfactants, and solvents) contained in this liquid, known components can be used. As liquids, for example, components contained in photosensitive or radiation-sensitive resin compositions described in Japanese Patent Publication No. 2013-195844, Japanese Patent Publication No. 2016-057645, Japanese Patent Publication No. 2015-207006, International Publication No. 2014 / 148241, Japanese Patent Publication No. 2016-188385, and Japanese Patent Publication No. 2017-219818 can be cited.

[0412] 〔Use of the liquid medicine〕

[0413] The present chemical solution is preferably used in the manufacture of semiconductor devices, and is more preferably used in the formation of fine patterns with a node size of 10 nm or less (for example, including a pattern formation process using EUV).

[0414] This chemical solution is particularly preferably used as a chemical solution (pre-wetting solution, developer, rinse solution, solvent for resist solution and stripping solution, etc.) used in a resist process in which the pattern width and / or pattern spacing is less than 17nm (preferably less than 15nm, more preferably less than 12nm) and / or the obtained wiring width and / or wiring spacing is less than 17nm. In other words, it is used for the manufacture of semiconductor devices manufactured using resist films with a pattern width and / or pattern spacing of less than 17nm.

[0415] Specifically, in the manufacturing process of semiconductor devices including photolithography process, etching process, ion implantation process and stripping process, it is used to treat organic matter after each process is completed or before transferring to the next process. Specifically, it is preferably used as a pre-wetting liquid, developer, rinse liquid and stripping liquid. For example, it can also be used for rinsing the edge line of the semiconductor substrate before and after the resist coating.

[0416] Furthermore, the present chemical solution can also be used as a diluent for the resin contained in the resist solution or as a solvent contained in the resist solution. Furthermore, the chemical solution can be diluted with other organic solvents and / or water.

[0417] Furthermore, the present chemical solution can be used for purposes other than the production of semiconductor devices, and can be used as a developer and rinser for polyimide, sensor resist, lens resist, and the like.

[0418] Furthermore, the present liquid medicine can also be used as a solvent for medical purposes or cleaning purposes. In particular, it can be preferably used for cleaning containers, piping, and substrates (for example, wafers and glass, etc.).

[0419] Among them, if this chemical solution is used as a raw material for at least one liquid selected from the group consisting of a developer, a rinse liquid, a chip cleaning liquid, a line cleaning liquid, a pre-wetting liquid, an anti-etching agent liquid, a lower film forming liquid, an upper film forming liquid and a hard coating forming liquid, the effect can be further exerted.

[0420] [Method for producing liquid medicine]

[0421] The method for producing the present drug solution is not particularly limited, and a known method can be used. In particular, from the viewpoint of further exerting the effect of the present invention, the present drug solution is preferably obtained by purifying a substance to be purified containing an organic solvent. Specifically, as a preferred embodiment of the method for producing the present drug solution, there can be cited a method including a filtration step of filtering the substance to be purified, an ion removal step of subjecting the substance to be purified to ion exchange or ion adsorption, and a distillation step of distilling the substance to be purified.

[0422] The purified product is obtained by supplying and reacting raw materials based on purchase or the like. The purified product preferably has a low content of impurities. Commercially available products of such purified products include, for example, those called "high purity grade products".

[0423] The method for obtaining a purified product (typically a purified product containing an organic solvent) by reacting the raw materials is not particularly limited, and a known method can be used. For example, a method of obtaining an organic solvent by reacting one or more raw materials in the presence of a catalyst can be mentioned.

[0424] More specifically, for example, there can be listed: a method for obtaining butyl acetate by reacting acetic acid and n-butanol in the presence of sulfuric acid; a method for obtaining 1-hexanol by reacting ethylene, oxygen and water in the presence of Al(C2H5)3; a method for obtaining 4-methyl-2-pentanol by reacting cis-4-methyl-2-pentene in the presence of Ipc2BH (Diisopinocampheylborane); a method for obtaining PGMEA (propylene glycol 1-monomethyl ether 2-acetate) by reacting propylene oxide, methanol and acetic acid in the presence of sulfuric acid; a method for obtaining IPA (isopropyl alcohol) by reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide; and a method for obtaining ethyl lactate by reacting lactic acid and ethanol, etc.

[0425] <Filtration process>

[0426] The filtration step is a step of filtering the purified product using a filter. The components removed by the filtration step are not limited thereto, and examples thereof include metal-containing particles that may be included in the metal component.

[0427] The method of filtering the substance to be purified using a filter is not particularly limited, but it is preferable to allow the substance to be purified to pass (flow) through a filtration unit having a housing and a filter element accommodated in the housing under pressure or without pressure.

[0428] (pore size of filter)

[0429] There is no particular restriction on the pore size of the filter, and a filter with a pore size that is usually used for filtering the purified product can be used. Among them, from the viewpoint of making it easier to control the number of particles (including metal particles, etc.) contained in the liquid to the desired range, the pore size of the filter is preferably less than 200nm, more preferably less than 20nm, further preferably less than 10nm, particularly preferably less than 5nm, and most preferably less than 3nm. It is not particularly limited as a lower limit, but from the viewpoint of productivity, it is usually preferably more than 1nm.

[0430] 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 isopropyl alcohol (IPA) or HFE-7200 ("Novec 7200", manufactured by 3M Company, hydrofluoroether, C4F9OC2H5).

[0431] If the pore size of the filter is 5.0 nm or less, it is preferred from the viewpoint of being easier to control the number of particles contained in the drug solution. Hereinafter, a filter having a pore size of 5 nm or less is also referred to as a "micropore filter".

[0432] In addition, the micropore filter can be used alone or in combination with a filter having other pore diameters. Among them, from the viewpoint of better productivity, it is preferably used in combination with a filter having a larger pore diameter. In this case, if the purified product previously filtered through a filter having a large pore diameter is passed through the micropore filter, clogging of the micropore filter can be prevented.

[0433] That is, when one filter is used, the pore diameter of the filter is preferably 5.0 nm or less, and when two or more filters are used, the pore diameter of the filter having the smallest pore diameter is preferably 5.0 nm or less.

[0434] There is no particular limitation on the method of sequentially using two or more filters with different pore sizes, and a method of sequentially arranging the previously described filter units along the pipeline that transports the purified substance can be cited. At this time, if the flow rate per unit time of the purified substance in the entire pipeline is to be kept constant, sometimes a greater pressure is applied to the filter unit with a smaller pore size than to the filter unit with a larger pore size. In this case, it is preferred to arrange a pressure regulating valve and a damper between the filter units, and increase the filtration area by setting the pressure applied to the filter unit with a small pore size to be constant, or arranging filter units containing the same filter in parallel along the pipeline. This makes it possible to more stably control the number of particles in the liquid medicine.

[0435] (Filter material)

[0436] There is no particular limitation on the material of the filter, and known materials can be used as the material of the filter. Specifically, in the case of resin, polyamides such as nylon (for example, 6-nylon and 6,6-nylon) can be listed; polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamide-imide; poly(meth)acrylate; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polytrifluorochloroethylene, polyvinylidene fluoride and polyvinyl fluoride and other polyfluorocarbons; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc. Among them, from the viewpoint of having better solvent resistance and the obtained liquid having better defect suppression performance, it is preferably selected from at least one of the group consisting of nylon (preferably 6,6-nylon), polyolefin (preferably polyethylene), poly(meth)acrylate and polyfluorocarbon (preferably polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA).) These polymers can be used alone or in combination of two or more.

[0437] Furthermore, other than the resin, diatomaceous earth, glass, etc. may also be used.

[0438] Alternatively, a polymer obtained by graft-copolymerizing a polyamide (for example, nylon 6 or nylon 6,6) with a polyolefin (UPE described below) (nylon graft UPE, etc.) may be used as the filter material.

[0439] Furthermore, the filter may be a surface treated filter. The surface treatment method is not particularly limited, and known methods can be used. Examples of surface treatment methods include chemical modification, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

[0440] Plasma treatment is preferred because it makes the surface of the filter hydrophilic. The water contact angle on the surface of the filter material hydrophilized by plasma treatment is not particularly limited, but the static contact angle at 25°C measured by a contact angle meter is preferably 60° or less, more preferably 50° or less, and particularly preferably 30° or less.

[0441] As the chemical modification treatment, a method of introducing an ion exchange group into the substrate is preferred.

[0442] That is, as a filter, it is preferred that each of the materials listed above is used as a substrate, and an ion exchange group is introduced into the above-mentioned substrate. Typically, it is preferred to include a filter having a layer of a substrate containing ion exchange groups on the surface of the above-mentioned substrate. There is no particular limitation on the surface-modified substrate, but from the viewpoint of easier manufacture, a filter in which an ion exchange group is introduced into the above-mentioned polymer is preferred.

[0443] Regarding the ion exchange group, sulfonic acid group, carboxyl group and phosphoric acid group etc. can be cited as the cation exchange group, and quaternary ammonium group etc. can be cited as the anion exchange group. The method of introducing the ion exchange group into the polymer is not particularly limited, and a method of typically grafting by reacting a compound containing an ion exchange group and a polymerizable group with the polymer can be cited.

[0444] The method for introducing ion exchange groups is not particularly limited. Ionizing radiation (α-rays, β-rays, γ-rays, X-rays, electron beams, etc.) is irradiated onto the fibers of the above-mentioned resin to generate active parts (free radicals) in the resin. The irradiated resin is immersed in a solution containing a monomer to graft polymerize the monomer onto the substrate. As a result, a polymer in which the monomer is bonded to the polyolefin fiber as a grafted polymerized side chain is generated. The resin containing the generated polymer as a side chain is contacted and reacted with a compound containing an anion exchange group or a cation exchange group, and an ion exchange group is introduced into the polymer of the grafted polymerized side chain to obtain the final product.

[0445] Furthermore, the filter may be a combination of a woven or nonwoven fabric having ion exchange groups formed thereon by radiation graft polymerization and a conventional filter material of glass wool, woven or nonwoven fabric.

[0446] If a filter containing an ion exchange group is used, it is easy to control the content of the particles containing metal atoms in the drug solution within a desired range. There is no particular limitation on the material of the filter containing an ion exchange group, and materials such as the ion exchange group introduced into polyfluorocarbons and polyolefins can be cited, and materials such as the ion exchange group introduced into polyfluorocarbons are more preferred.

[0447] The pore size of the filter containing ion exchange groups is not particularly limited, and is preferably 1 to 30 nm, and more preferably 5 to 20 nm. The filter containing ion exchange groups can also serve as a filter having the above-mentioned minimum pore size, or can be used separately from a filter having the minimum pore size. Among them, from the perspective of obtaining a drug solution showing a more excellent effect of the present invention, it is preferred that the filtration process uses a filter containing ion exchange groups and a filter having the minimum pore size without ion exchange groups.

[0448] The material of the filter having the smallest pore size is not particularly limited, but is preferably at least one selected from the group consisting of polyfluorocarbons and polyolefins, and more preferably polyolefins, from the viewpoint of solvent resistance and the like.

[0449] Therefore, as the filter used in the filtration step, two or more filters made of different materials may be used. For example, two or more filters selected from the group consisting of filters made of polyolefins, polyfluorocarbons, polyamides, and materials into which ion exchange groups are introduced may be used.

[0450] (Filter pore structure)

[0451] The pore structure of the filter is not particularly limited and can be appropriately selected according to the components in the purified product. In this specification, the pore structure of the filter refers to the pore size distribution, the position distribution of the pores in the filter, and the shape of the pores, which can typically be controlled by the filter manufacturing method.

[0452] For example, a porous membrane is obtained by sintering a powder of a resin or the like, and a fiber membrane is obtained by electrospinning, electroblowing, meltblowing, etc. These have different pore structures.

[0453] "Porous membrane" refers to a membrane that retains components in the purified material such as gels, particles, colloids, cells and oligomers, but allows components substantially smaller than the pores to pass through the pores. The retention of components in the purified material based on a porous membrane sometimes depends on the operating conditions, such as the surface velocity, the use of surfactants, pH and a combination of these, and may depend on the pore size and structure of the porous membrane and the size and structure of the particles to be removed (hard particles or gels, etc.).

[0454] When the purified material contains negatively charged particles, the polyamide filter functions as a non-sieving membrane to remove such particles. Typical non-sieving membranes include nylon membranes such as nylon-6 membrane and nylon-6,6 membrane, but are not limited to these.

[0455] In addition, the retention mechanism based on "non-sieve" as used in this specification refers to retention by a mechanism such as hindrance, diffusion, and adsorption that is not related to the pressure drop or pore size of the filter.

[0456] Non-sieve retention includes retention mechanisms such as obstruction, diffusion and adsorption that remove the particles to be removed from the purified material regardless of the pressure drop of the filter or the pore size of the filter. The adsorption of particles on the filter surface can be mediated by, for example, van der Waals and electrostatic forces between molecules. The obstruction effect occurs when particles moving in a non-sieve membrane layer having a serpentine passage cannot change direction quickly enough to avoid contact with the non-sieve membrane. Diffusion-based particle transport is caused by the random motion or Brownian motion of small particles, which forms a certain probability of collision between particles and filter materials. The non-sieve retention mechanism can become active when there is no repulsive force between the particles and the filter.

[0457] 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 that are optimized for capturing particles through a sieve holding mechanism.

[0458] Typical examples of the sieve membrane include polytetrafluoroethylene (PTFE) membrane and UPE membrane, but are not limited to these.

[0459] In addition, 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 improved by forming a filter cake (agglomeration of particles to be removed on the surface of the membrane). The filter cake effectively functions as a secondary filter.

[0460] The material of the fiber membrane is not particularly limited as long as it is a polymer that can form a fiber membrane. As a polymer, for example, polyamides can be cited. As polyamides, for example, nylon 6 and nylon 6,6 can be cited. As a polymer that forms a fiber membrane, it can be poly(ether sulfone). When the fiber membrane is located on the primary side of the porous membrane, it is preferred that the surface energy of the fiber membrane is higher than the polymer of the material of the porous membrane located on the secondary side. As such a combination, for example, the material of the fiber membrane is nylon and the porous membrane is polyethylene (UPE).

[0461] The method for producing the fiber membrane is not particularly limited, and a known method can be used. Examples of the method for producing the fiber membrane include electrospinning, electroblowing, and meltblowing.

[0462] The pore structure of the porous membrane (for example, a porous membrane made of UPE, PTFE, etc.) is not particularly limited, and examples of the shape of the pores include lace-like, string-like, and node-like shapes.

[0463] The size distribution of the pores in the porous film and the position distribution in the film are not particularly limited. The size distribution can be smaller and the distribution position in the film can be symmetrical. In addition, the size distribution is larger, and the distribution position in the film can be asymmetric (the above-mentioned film is also referred to as "asymmetric porous film".). In an asymmetric porous film, the size of the hole changes in the film, and typically, the pore size increases from the surface of one side of the film toward the other surface of the film. At this time, the surface of the side with more pores with a large pore size is called "open (open) side", and the surface of the side with more pores with a small pore size is called "dense (tite) side".

[0464] Furthermore, examples of asymmetric porous membranes include membranes in which the size of pores is the smallest at a certain position within the thickness of the membrane (this is also referred to as an "hourglass shape").

[0465] When an asymmetric porous membrane is used and the pores on the primary side are made larger, in other words, when the primary side is made an open side, a pre-filtration effect is produced.

[0466] The porous membrane may include thermoplastic polymers such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, copolymer of tetrafluoroethylene and perfluoroalkoxyalkane), polyamide, and polyolefin, and may also include polytetrafluoroethylene.

[0467] Among them, ultra-high molecular weight polyethylene is preferred as a material for the porous membrane. Ultra-high molecular weight polyethylene refers to thermoplastic polyethylene having an extremely long chain, and has a molecular weight of one million or more, typically preferably 2 to 6 million.

[0468] As the filter used in the filtration step, two or more filters with different pore structures can be used, and a porous membrane filter and a fiber membrane filter can also be used simultaneously. As a specific example, a method using a nylon fiber membrane filter and a UPE porous membrane filter can be cited.

[0469] Furthermore, it is preferred that the filter be thoroughly cleaned before use.

[0470] When an uncleaned filter (or a filter that has not been sufficiently cleaned) is used, impurities contained in the filter are easily brought into the drug solution.

[0471] Impurities contained in the filter include, for example, the above-mentioned organic compounds. If the filtration step is performed using an unwashed filter (or an insufficiently washed filter), the content of the organic compounds in the drug solution may exceed the allowable range for the drug solution of the present invention.

[0472] For example, when polyolefins such as UPE and polyfluorocarbons such as PTFE are used for the filter, the filter is likely to contain alkanes having 12 to 50 carbon atoms as impurities.

[0473] Furthermore, when a polymer obtained by graft-copolymerizing polyamide (nylon, etc.) with polyamide such as nylon, polyimide, and polyolefin (UPE, etc.) is used in a filter, the filter is likely to contain olefins having 12 to 50 carbon atoms as impurities.

[0474] The filter can be cleaned by, for example, immersing the filter in an organic solvent with a low impurity content (for example, a distilled purified organic solvent (PGMEA, etc.)) for one week or more. In this case, the liquid temperature of the organic solvent is preferably 30 to 90°C.

[0475] The purified product is filtered using the filter whose degree of cleaning has been adjusted, and the obtained drug solution can be adjusted so as to contain a desired amount of the organic compound derived from the filter.

[0476] The filtration step may be a multi-stage filtration step in which the substance to be purified is passed through two or more filters selected from the group consisting of filters having at least one different filter material, pore diameter, and pore structure.

[0477] Furthermore, the object to be purified may be passed through the same filter multiple times, or may be passed through multiple filters of the same type.

[0478] The material of the liquid contact part (referring to the inner wall surface that the purified substance and the drug solution may contact) of the purification device used in the filtration process is not particularly limited, but is preferably formed of at least one selected from the group consisting of non-metallic materials (fluorine-based resins, etc.) and electrolytically polished metal materials (stainless steel, etc.) (hereinafter, these are also collectively referred to as "corrosion-resistant materials."). For example, the liquid contact part of the manufacturing tank is formed of a corrosion-resistant material, and examples include the case where the manufacturing tank itself is composed of a corrosion-resistant material or the inner wall surface of the manufacturing tank is coated with a corrosion-resistant material.

[0479] The non-metal material is not particularly limited, and a known material can be used.

[0480] As non-metallic materials, for example, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluorine-based resins (for example, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin and vinyl fluoride resin, etc.) can be listed, but it is not limited to this.

[0481] The metal material is not particularly limited, and a known material can be used.

[0482] As the metal material, for example, the total content of chromium and nickel relative to the total mass of the metal material can be listed as a metal material exceeding 25 mass%, wherein more preferably 30 mass% or more. There is no particular upper limit to the total content of chromium and nickel in the metal material, but it is usually preferably 90 mass% or less.

[0483] Examples of the metal material include stainless steel and nickel-chromium alloys.

[0484] Stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing more than 8% by mass of nickel is preferred, and austenitic stainless steel containing more than 8% by mass of nickel is more preferred. As austenitic stainless steel, for example, SUS (Steel Use Stainless: stainless steel) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), SUS316 (Ni content 10% by mass, Cr content 16% by mass), and SUS316L (Ni content 12% by mass, Cr content 16% by mass) can be listed.

[0485] The nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferred.

[0486] Examples of nickel-chromium alloys include Hastelloy (product name, the same below), Monel (product name, the same below), and Inconel (product name, the same below). More specifically, Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), and Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%) may be cited.

[0487] Furthermore, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like in addition to the above alloys as required.

[0488] The method for electrolytically polishing the metal material is not particularly limited, and a known method can be used, for example, the method described in paragraphs

[0011] to

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

[0036] to

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

[0489] It is speculated that the electrolytic polishing of the metal material causes the chromium content in the surface passivation layer to be higher than the chromium content in the parent phase. Therefore, it is speculated that when a purification device having a liquid contact portion formed of the electrolytically polished metal material is used, it is difficult for the metal-containing particles to flow out into the purified product.

[0490] In addition, the metal material may also be polished. The polishing method is not particularly limited, and a known method can be used. The size of the abrasive grains used in fine polishing is not particularly limited, but from the viewpoint that the surface irregularities of the metal material are easily reduced, preferably #400 or less. In addition, polishing is preferably performed before electrolytic polishing.

[0491] <Ion Removal Process>

[0492] The ion removal step is a step of subjecting the purified product containing an organic solvent to ion exchange or ion adsorption by a chelate group. Components removed by the ion removal step are not limited thereto, and examples thereof include metal ions contained in acid components and metal components.

[0493] The method for carrying out the ion exchange method is not particularly limited, and a known method can be used. Typically, there is a method in which a substance to be purified is passed through a packing portion filled with an ion exchange resin.

[0494] In the ion removal step, the purified material may be passed through the same ion exchange resin multiple times, or may be passed through different ion exchange resins.

[0495] Examples of the ion exchange resin include cation exchange resins and anion exchange resins. From the viewpoint of easily setting the mass ratio of the content of the acid component to the content of the metal component within the above range by adjusting the content of the metal component, it is preferred to use at least a cation exchange resin. From the viewpoint of being able to adjust the content of the acid component, it is more preferred to use an anion exchange resin together with the cation exchange resin.

[0496] When both a cation exchange resin and an anion exchange resin are used, the resin may be passed through a filling section filled with a mixed resin containing both resins, or may be passed through a plurality of filling sections filled with each resin.

[0497] As the cation exchange resin, a known cation exchange resin can be used, and among them, a gel type cation exchange resin is preferred.

[0498] Specific examples of the cation exchange resin include sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins.

[0499] As the cation exchange resin, commercially available products can be used, for example, AMBERLITE IR-124, AMBERLITE IR-120B, AMBERLITE IR-200CT, ORLITE DS-1, ORLITEDS-4 (all manufactured by ORGANO CORPORATION), DUOLITE C20J, DUOLITE C20LF, DUOLITE C255LFH, DUOLITE C-433LF (all manufactured by Sumika Chemtex Co., Ltd.), DIAION SK-110, DIAION SK1B and DIAION SK1BH (all manufactured by Mitsubishi Chemical Corporation), PUROLITE S957 and PUROLITE S985 (all manufactured by Purolite Corporation), etc.

[0500] As the anion exchange resin, a known anion exchange resin can be used, and among them, a gel-type anion exchange resin is preferably used.

[0501] Here, as the acid component present in the form of ions in the purified material, inorganic acids from the catalyst when producing the purified material and organic acids (e.g., reaction raw materials, isomers, and by-products) produced after the reaction when producing the purified material can be cited. From the perspective of the HSAB (Hard and Soft Acids and Bases: hard and soft acids and bases) rule, such acid components are classified as hard acids to acids of medium hardness. Therefore, in order to improve the removal efficiency when removing these acid components through interaction with the anion exchange resin, it is preferred to use an anion exchange resin containing a base of hard base to medium hardness.

[0502] The anion exchange resin containing a hard base to a medium hardness base is preferably at least one anion exchange resin selected from the group consisting of a strong base type I anion exchange resin having a trimethylammonium group, a slightly weaker strong base type II anion exchange resin having a dimethylethanolammonium group, and a weak base type anion exchange resin such as dimethylamine and diethylenetriamine.

[0503] Among the acid components, for example, organic acids are hard acids, and among inorganic acids, sulfate ions are acids of medium hardness. Therefore, if the above-mentioned strong base type or slightly weak strong base type anion exchange resin and the weak base type anion exchange resin of medium hardness are used at the same time, the content of the acid component can be easily reduced to the preferred range.

[0504] As the anion exchange resin, commercially available products can be used, for example, AMBERLITE IRA-400J, AMBERLITE IRA-410J, AMBERLITE IRA-900J, AMBERLITE IRA67, ORLITE DS-2, ORLITE DS-5, ORLITE DS-6 (manufactured by ORGANO CORPORATION), DUOLITE A113LF, DUOLITE A116, DUOLITE A-375LF (manufactured by Sumika Chemtex Co., Ltd.) and DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, DIAION WA10 (manufactured by Mitsubishi Chemical Corporation), etc.

[0505] Among them, examples of the anion exchange resin containing a base having a hard base to a medium hardness include ORLITE DS-6, ORLITE DS-4 (all manufactured by ORGANO CORPORATION), DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, DIAION WA10 (all manufactured by Mitsubishi Chemical Corporation), PUROLITE A400, PUROLITE A500, PUROLITE A850 (all manufactured by Purolite Corporation), and the like.

[0506] Ion absorption by chelate group can for example be used to carry out with the chelate resin of chelate group. Chelate resin does not discharge and replace ion when capturing ion, and, by not using the chemical high activity functional group of strong acidity and strong basicity, thereby can suppress the secondary reaction with respect to the organic solvent that becomes the purification object of hydrolysis and condensation reaction.Therefore, can carry out more efficient purification.

[0507] Examples of the chelating resin include resins having an amide oxime group, a thiourea group, a thiourea-onium group, iminodiacetic acid, amidophosphoric acid, phosphonic acid, aminophosphoric acid, aminocarboxylic acid, N-methylglucamine, an alkylamino group, a pyridine ring, a cyclic cyanine, a phthalocyanine ring, a cyclic ether, and the like, a chelating group or a chelating ability.

[0508] As the chelating resin, commercially available products can be used, for example, DUOLITE ES371N, DUOLITE C467, DUOLITE C747UPS, SUMICHELATE MC760, SUMICHELATE MC230, SUMICHELATE MC300, SUMICHELATE MC850, SUMICHELATE MC640 and SUMICHELATE MC900 (all manufactured by Sumika Chemtex Co., Ltd.), PUROLITE S106, PUROLITE S910, PUROLITE S914, PUROLITE S920, PUROLITE S930, PUROLITE S950, PUROLITE S957 and PUROLITE S985 (all manufactured by Purolite Corporation), etc. can be mentioned.

[0509] The method for performing ion adsorption is not particularly limited, and a known method can be used. Typically, there is a method in which the substance to be purified is passed through a filling portion filled with a chelate resin.

[0510] In the ion removal step, the purified material may be passed through the same chelating resin for multiple times, or may be passed through different chelating resins.

[0511] The filling unit generally includes a container and the ion exchange resin filled in the container.

[0512] Examples of the container include a column, a cartridge, and a packed tower. Any container other than the above-mentioned containers may be used as long as the container can allow the substance to be purified to pass therethrough after being filled with the ion exchange resin.

[0513] <Distillation process>

[0514] The distillation step is a step of distilling the product to be purified containing the organic solvent to obtain a distilled product to be purified. Components removed by the distillation step are not limited thereto, and examples thereof include acid components, other organic compounds, and water.

[0515] The method for distilling the product to be purified is not particularly limited, and a known method can be used. Typically, there is a method in which a distillation column is arranged on the primary side of a purification device used in the filtration step, and the distilled product to be purified is introduced into a production tank.

[0516] In this case, the liquid contact portion of the distillation column is not particularly limited, but is preferably formed of the corrosion-resistant material described above.

[0517] In the distillation step, the product to be purified may be passed through the same distillation column a plurality of times, or may be passed through different distillation columns.

[0518] When the product to be purified is passed through different distillation towers, for example, a method can be exemplified in which, after a crude distillation treatment of removing low-boiling acid components and the like by passing the product to be purified through a distillation tower, a rectification treatment of removing acid components and other organic compounds and the like by passing through a distillation tower different from the crude distillation treatment is performed. In this case, the distillation tower for the crude distillation treatment may be a plate type distillation tower, and the distillation tower for the rectification treatment may be a distillation tower including at least one of a plate type distillation tower and a vacuum plate type distillation tower.

[0519] Furthermore, in order to achieve both thermal stability during distillation and precision of purification, reduced pressure distillation can be selected.

[0520] <Other Processes>

[0521] The method for producing a chemical solution may further include steps other than the above. Examples of steps other than the filtration step include a reaction step and a static elimination step.

[0522] (Reaction process)

[0523] The reaction step is a step of reacting the raw materials to generate a purified product containing an organic solvent as a reactant. There is no particular limitation on the method for generating the purified product, and a known method can be used. Typically, a method of disposing a reaction tank on the primary side of a production tank (or a distillation tower) of a purification device used in a filtration step and introducing the reactants into the production tank (or distillation tower) can be cited.

[0524] In this case, the liquid contact portion of the manufacturing tank is not particularly limited, but is preferably formed of the corrosion-resistant material described above.

[0525] (Electrical removal process)

[0526] The static removal step is a step of removing static electricity from the object to be purified to reduce the charge potential of the object to be purified.

[0527] The static elimination method is not particularly limited, and a known static elimination method can be used. For example, the static elimination method includes a method of bringing the object to be purified into contact with a conductive material.

[0528] The contact time between the object to be purified and the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and particularly preferably 0.01 to 0.1 second. Examples of the conductive material include stainless steel, gold, platinum, diamond, and glassy carbon.

[0529] As a method of bringing the object to be purified into contact with the conductive material, for example, there is a method in which a grounded mesh made of a conductive material is arranged inside a pipe and the object to be purified is passed through the mesh.

[0530] Regarding the purification of the purified substance, it is preferred that the opening of the container attached thereto, the cleaning of the container and the device, the storage of the solution, and the analysis are all performed in a clean room. The clean room is preferably a clean room that satisfies the cleanliness level of Class 4 or higher defined in the international standard ISO14644-1:2015 defined by the International Organization for Standardization. Specifically, it is preferred that any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4 be satisfied, and ISO Class 1 or ISO Class 2 is more preferred, and ISO Class 1 is particularly preferred.

[0531] The storage temperature of the drug solution is not particularly limited, but is preferably 4° C. or higher from the viewpoint that impurities contained in the drug solution in trace amounts are less likely to be eluted, thereby achieving more excellent effects of the present invention.

[0532] [Medicine liquid container]

[0533] The drug solution is stored in a container until it is used. Such a container and the drug solution stored in the container are collectively referred to as a drug solution container. The drug solution is taken out from the stored drug solution container and then used.

[0534] As a container for storing the present chemical solution, for use in semiconductor device manufacturing, a container having high cleanliness inside the container and little elution of impurities is preferred.

[0535] Specific examples of the container that can be used include "Clean Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and "Pure Bottle" manufactured by KODAMA PLASTICS CO., LTD., but the container is not limited to these.

[0536] As the container, it is also preferred to use a multilayer bottle with a six-layer structure based on six kinds of resins or a multilayer bottle with a seven-layer structure based on six kinds of resins for the purpose of preventing impurities from mixing into the drug solution (contamination). Examples of such containers include the containers described in Japanese Patent Application Publication No. 2015-123351.

[0537] At least a portion of the liquid contact portion of the container may be made of the corrosion-resistant material described above (preferably electrolytically polished stainless steel or fluorine resin) or glass. From the perspective of obtaining a more excellent effect of the present invention, preferably 90% or more of the area of ​​the liquid contact portion is composed of the above material, and more preferably the entire liquid contact portion is composed of the above material.

[0538] [Reagent test kit]

[0539] The kit of the present invention comprises the following chemical solution X and the following chemical solution Y. When the kit of the present invention is used in the pattern forming method described below (particularly, when the chemical solution X is used as a developer and the chemical solution Y is used as a rinser), a pattern in which the generation of defects is suppressed by the action of the chemical solution X can be obtained, and due to the synergistic effect of the chemical solutions X and Y, the resolution of the obtained pattern is also excellent.

[0540] The form of the kit is not particularly limited, and examples thereof include a form having a drug solution container X and a drug solution container Y, wherein the drug solution container X has a container X and a drug solution X contained in the container X, and the drug solution container Y has a container Y and a drug solution Y contained in the container Y. As the container X and the container Y, the containers described above as containers of the drug solution containers are preferably used.

[0541] The chemical solution X is the chemical solution X1 or the chemical solution X2 shown below. The chemical solution X1 is a chemical solution in which the organic solvent contains butyl acetate and the acid component contains acetic acid, and the content of acetic acid is 0.01 to 15 mass ppm relative to the total mass of the chemical solution X1. Furthermore, the chemical solution X2 is a chemical solution in which the organic solvent contains butyl acetate and the acid component contains n-butyric acid, and the content of n-butyric acid is 1 mass ppt or more and 1 mass ppm or less relative to the total mass of the chemical solution X2.

[0542] The chemical solution Y contains an organic solvent. The organic solvent contained in the chemical solution Y contains at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, undecane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate. When the chemical solution Y is used as a rinse liquid in the pattern forming method described below, the resolution of the obtained pattern can be improved by the action of the organic solvent Y.

[0543] The drug solution Y may be the above-mentioned present drug solution (i.e., a drug solution containing an organic solvent, an acid component and a metal component, wherein the content of the acid component is greater than 1 mass ppt and less than 15 mass ppm relative to the total mass of the drug solution, and the content of the metal component is 0.001 to 100 mass ppt relative to the total mass of the drug solution), or it may be a drug solution other than the above-mentioned present drug solution.

[0544] A chemical solution other than the above-mentioned chemical solution refers to a chemical solution that satisfies at least one of the following conditions: the content of the acid component is less than 1 mass ppt or greater than 15 mass ppm relative to the total mass of the chemical solution; and the content of the metal component is less than 0.001 mass ppt or greater than 100 mass ppt relative to the total mass of the chemical solution.

[0545] The content of the organic solvent Y in the drug solution Y is preferably 20% by mass or more, more preferably 30% by mass or more, further preferably 40% by mass or more, and particularly preferably 50% by mass, relative to the total mass of the drug solution Y. As a further preferred embodiment, it is preferably 98.0% by mass or more, more preferably 99.0% by mass or more, further preferably 99.9% by mass or more, and particularly preferably 99.99% by mass or more. The upper limit is not particularly limited, and is 100% by mass or less.

[0546] The preferred range of the content of the organic solvent Y relative to the total mass of the organic solvent contained in the chemical solution Y is the same as the content of the organic solvent Y in the chemical solution Y described above.

[0547] The organic solvent Y may be used alone or in combination of two or more thereof. When two or more organic solvents Y are used in combination, the total content is within the above range.

[0548] The chemical solution Y may contain an organic solvent other than the organic solvent Y. Examples of the organic solvent other than the organic solvent Y include organic solvents other than the organic solvent Y exemplified as the organic solvent of the chemical solution described above, and ethanol.

[0549] When the chemical solution Y contains an organic solvent other than the organic solvent Y, the content of the organic solvent other than the organic solvent Y is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 10% by mass or less, relative to the total mass of the chemical solution Y. When the chemical solution Y contains an organic solvent other than the organic solvent Y, the lower limit of the content of the organic solvent other than the organic solvent Y is greater than 0% by mass, preferably 0.1% by mass or more, and more preferably 1% by mass or more.

[0550] When the chemical solution Y contains an organic solvent other than organic solvent Y, the preferred range of the content of the organic solvent other than organic solvent Y relative to the total mass of the organic solvent contained in the chemical solution Y is the same as the content of the organic solvent other than organic solvent Y in the above-mentioned chemical solution Y.

[0551] The content of the organic solvent in the liquid medicine Y (i.e., the total content of the organic solvent Y and the organic solvent other than the organic solvent Y) is preferably 98.0% by mass or more, more preferably 99.0% by mass or more, further preferably 99.9% by mass or more, and particularly preferably 99.99% by mass or more, relative to the total mass of the liquid medicine Y. The upper limit is not particularly limited, but is 100% by mass or less.

[0552] Preferably, the organic solvent Y has a Hansen solubility parameter of 3 to 20 MPa relative to eicosene. 0.5 (More preferably 5 to 20 MPa 0.5 ) of an organic solvent Y1.

[0553] When the chemical solution Y contains two or more organic solvents Y, it is preferred that at least one of them is the organic solvent Y1.

[0554] When two or more organic solvents Y are contained in the chemical solution Y, it is preferred that the weighted average value of the Hansen solubility parameter based on the molar ratio of the content of each organic solvent satisfies the above-mentioned range of the Hansen solubility parameter.

[0555] In organic solvent Y, the distance as the Hansen solubility parameter to eicosene is 3 to 20 MPa 0.5 Examples of organic solvents (ie, organic solvent Y1) include butyl butyrate (4.6), isobutyl isobutyrate (3.6), and dimethyl malonate (10.3). In addition, the values ​​in parentheses in the compounds represent the distance from the Hansen solubility parameter of eicosene.

[0556] As one of the preferred embodiments of the drug solution Y, there is a mode in which the organic solvent Y is substantially only the organic solvent Y1. The case in which the organic solvent Y is substantially only the organic solvent Y1 means that the content of the organic solvent Y1 relative to the total mass of the organic solvent Y in the drug solution Y is 99 mass % or more (preferably 99.9 mass % or more).

[0557] One preferred embodiment of the chemical solution Y includes a mixed solvent containing both the organic solvent Y and an organic solvent other than the organic solvent Y (for example, methanol), and the organic solvent Y is substantially only the organic solvent Y1.

[0558] In this case, the content of the organic solvent Y1 is preferably 20 to 90 mass % based on the total mass of the chemical solution Y, more preferably 20 to 80 mass %, and further preferably 30 to 70 mass % from the viewpoint of better pattern resolution.

[0559] The content of the organic solvent other than the organic solvent Y is preferably 10 to 80% by mass relative to the total mass of the chemical solution Y, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass from the viewpoint of achieving better pattern resolution.

[0560] Furthermore, as one of the preferred embodiments of the medicinal solution Y, there can be listed a embodiment in which the organic solvent in the medicinal solution is composed of an organic solvent Y, and the organic solvent Y is a mixed solvent comprising an organic solvent Y1 and an organic solvent that does not satisfy the above-mentioned range of Hansen solubility parameters (hereinafter also referred to as "organic solvent Y2").

[0561] In this case, the content of the organic solvent Y1 is preferably 20 to 90 mass % based on the total mass of the chemical solution Y, more preferably 20 to 80 mass %, and further preferably 30 to 70 mass % from the viewpoint of better pattern resolution.

[0562] The content of the organic solvent Y2 is preferably 10 to 80% by mass relative to the total mass of the chemical solution Y, more preferably 20 to 80% by mass, and further preferably 30 to 70% by mass from the viewpoint of achieving better pattern resolution.

[0563] When the content of organic solvent Y1 and the content of organic solvent Y2 are respectively within a certain range, it can be inferred that the affinity of liquid Y with respect to organic raw materials can be adjusted to an appropriate range and the resolution of the pattern can be better compared to the case where the content of organic solvent Y2 is excessive or insufficient.

[0564] In addition, the distance between the Hansen solubility parameter of organic solvent Y2 and eicosene is 0 MPa. 0.5 Above and less than 3MPa 0.5 (Preferably greater than 0 MPa 0.5 And less than 3MPa 0.5 ) or greater than 20MPa 0.5 (Preferably greater than 20MPa 0.5 And 50MPa 0.5 the following).

[0565] In this specification, the Hansen solubility parameters refer to the Hansen solubility parameters described in "Hansen Solubility Parameters: A Users Handbook, Second Edition" (pages 1-310, CRC Press, published in 2007), etc. That is, the Hansen solubility parameters represent solubility as a multidimensional vector (dispersion term (δd), inter-dipole term (δp) and hydrogen bonding term (δh)), and these three parameters can be regarded as the coordinates of a point in a three-dimensional space called Hansen space.

[0566] The distance of the Hansen solubility parameters is the distance between two compounds in the Hansen space, and the distance of the Hansen solubility parameters is calculated by the following formula.

[0567] (Ra) 2 =4(δd2-δd1) 2 +(δp2-δp1) 2 +(δh2-δh1) 2

[0568] Ra: The distance between the Hansen solubility parameters of the first compound and the second compound (unit: MPa 0.5 )

[0569] δd1: Dispersion term of the first compound (unit: MPa 0.5 )

[0570] δd2: Dispersion term of the second compound (unit: MPa 0.5 )

[0571] δp1: dipole term of the first compound (unit: MPa 0.5 )

[0572] δp2: dipole term of the second compound (unit: MPa 0.5 )

[0573] δh1: Hydrogen bond term of the first compound (unit: MPa 0.5 )

[0574] δh2: Hydrogen bond term of the second compound (unit: MPa 0.5 )

[0575] In the present specification, the Hansen solubility parameter of a compound is specifically calculated using HSPiP (Hansen Solubility Parameter in Practice).

[0576] [Pattern Formation Method]

[0577] The present chemical solution is preferably used to form a resist pattern (hereinafter, simply referred to as a "pattern") used in semiconductor manufacturing applications. The pattern forming method using the present chemical solution is not particularly limited, and a known pattern forming method can be mentioned.

[0578] As one of the preferred embodiments of the pattern forming method of the present invention, preferably, the chemical solution X described in the above-mentioned kit is used as a developer and the chemical solution Y described in the above-mentioned kit is used as a rinser. Specifically, the method includes the following steps.

[0579] (A) Resist film forming step of forming a resist film using an actinic ray-sensitive or radiation-sensitive resin composition

[0580] (B) Exposure step of exposing the resist film

[0581] (C) A developing step of developing the resist film after exposure using chemical solution X

[0582] (D) After the development step, a rinsing step using chemical solution Y is performed

[0583] Hereinafter, the method of each of the above steps will be described. In addition, since the chemical solution X and the chemical solution Y are as described above, their description will be omitted.

[0584] [Resist film forming step]

[0585] The resist film forming step is a step of forming a resist film using an actinic ray or a radiation-sensitive resin composition.

[0586] Hereinafter, first, the aspect of the actinic ray or the radiation-sensitive resin composition will be described.

[0587] <Acticular Ray or Radiation-Sensitive Resin Composition>

[0588] The actinic ray-sensitive or radiation-sensitive resin composition that can be used in the resist film forming step is not particularly limited, and a known actinic ray-sensitive or radiation-sensitive resin composition can be used.

[0589] The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "resist composition") preferably contains a repeating unit resin having a group that generates a polar group (carboxyl group, phenolic hydroxyl group, etc.) by decomposition by the action of an acid (hereinafter also referred to as "acid-decomposable resin" in this specification) and a compound that generates an acid by irradiation with actinic rays or radiation (hereinafter also referred to as "photoacid generator" in this specification).

[0590] Among them, from the viewpoint of obtaining more excellent effects of the present invention, the following resist compositions are preferred.

[0591] A resist composition containing a resin represented by formula (I) described below

[0592] A resist composition containing an acid-decomposable resin having a phenolic hydroxyl group described below

[0593] · A resist composition containing a hydrophobic resin and an acid-decomposable resin described below

[0594] Hereinafter, each component of the resist composition will be described.

[0595] (Acid decomposable resin)

[0596] In the acid-decomposable group, the polar group is protected by a group that is detached by the action of an acid (acid-detachable group). Examples of the acid-detachable group include -C(R 36 )( R3 7)(R 38 )、-C(R 36 )(R 37 )(OR 39 ) and -C(R 01 )(R 02 )(OR 39 )wait.

[0597] In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. 36 With R 37 They may be bonded to each other to form a ring.

[0598] R 01 and R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0599] Examples of the acid-decomposable resin include resins P having an acid-decomposable group represented by the formula (AI).

[0600] [Chemical formula 12]

[0601]

[0602] In formula (AI),

[0603] Xa1 represents a hydrogen atom or an alkyl group which may have a substituent.

[0604] T represents a single bond or a divalent linking group.

[0605] Ra1 to Ra3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

[0606] Two of Ra1 to Ra3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0607] Examples of the alkyl group which may have a substituent represented by Xa1 include a methyl group and -CH2-R 11 The group represented by R 11 It represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent organic group.

[0608] Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0609] Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0610] T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group or a -(CH2)3- group.

[0611] As the alkyl group of Ra1 to Ra3, an alkyl group having 1 to 4 carbon atoms is preferred.

[0612] The cycloalkyl group for Ra1 to Ra3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecanyl, tetracyclododecyl or adamantyl.

[0613] The cycloalkyl group formed by bonding two of Ra1 to Ra3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0614] Regarding the cycloalkyl group formed by bonding two of Ra1 to Ra3, for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

[0615] The repeating unit represented by the formula (AI) is preferably in an embodiment in which Ra1 is a methyl group or an ethyl group, and Ra2 and Ra3 are bonded to form the above-mentioned cycloalkyl group.

[0616] Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably has 8 or less carbon atoms.

[0617] The total content of the repeating units represented by the formula (AI) is preferably 20 to 90 mol %, more preferably 25 to 85 mol %, and further preferably 30 to 80 mol % based on all the repeating units in the resin P.

[0618] Specific examples of the repeating unit represented by the general formula (AI) are shown below, but the present invention is not limited thereto.

[0619] In the specific example, Rx and Xa1 each independently represent a hydrogen atom, CH3, CF3 or CH2OH. Rxa and Rxb each represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when there are multiple substituents, they are independent of each other. p represents 0 or a positive integer. As a substituent containing a polar group represented by Z, for example, a hydroxyl group, a cyano group, an amino group, an alkylamide group, a sulfonamide group, and a linear or branched alkyl or cycloalkyl group having these groups can be listed.

[0620] [Chemical formula 13]

[0621]

[0622] (Repeating unit having a lactone structure)

[0623] Furthermore, it is preferred that the resin P contains a repeating unit Q having a lactone structure.

[0624] The repeating unit Q having a lactone structure preferably has a lactone structure in a side chain, and for example, a repeating unit derived from a (meth)acrylic acid derivative monomer is more preferred.

[0625] The repeating unit Q having a lactone structure may be used alone or in combination of two or more. However, it is preferred that one be used alone.

[0626] The content of the repeating unit Q having a lactone structure relative to all the repeating units of the resin P is, for example, 3 to 80 mol %, and preferably 3 to 60 mol %.

[0627] The lactone structure is preferably a 5- to 7-membered ring lactone structure, and more preferably a structure in which another ring structure is condensed with a 5- to 7-membered ring lactone structure to form a bicyclic structure or a spirocyclic structure.

[0628] As the lactone structure, it is preferred to contain a repeating unit having a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-17). As the lactone structure, it is preferred to contain a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5) or formula (LC1-8), and more preferably a lactone structure represented by formula (LC1-4).

[0629] [Chemical formula 14]

[0630]

[0631] The lactone structure part may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) may be the same or different, and the multiple substituents (Rb2) may be bonded to each other to form a ring.

[0632] The resin P preferably includes a resin having the following repeating units (hereinafter, the resin is also referred to as "resin represented by formula (I)"), wherein the repeating units are selected from the group consisting of a repeating unit represented by formula (a), a repeating unit represented by formula (b), a repeating unit represented by formula (c), a repeating unit represented by formula (d) and a repeating unit represented by formula (e).

[0633] The resin represented by the following formula (I) is a resin whose solubility in a developer (a chemical solution described later) containing an organic solvent as the main component is reduced by the action of an acid, and contains an acid-decomposable group. The above chemical solution has excellent solubility in the resin represented by formula (I), so it is easy to obtain a uniform resist film using a smaller amount of resist composition. The resin represented by formula (I) is described below.

[0634] The resin represented by formula (I)

[0635] [Chemical formula 15]

[0636]

[0637] The above formula (I) is composed of a repeating unit (a) (a repeating unit represented by formula (a)), a repeating unit (b) (b repeating unit represented by formula (b)), a repeating unit (c) (c repeating unit represented by formula (c)), a repeating unit (d) (d repeating unit represented by formula (d)) and a repeating unit (e) (e repeating unit represented by formula (e)).

[0638] R x1 ~R x5 Each independently represents a hydrogen atom or an alkyl group which may have a substituent.

[0639] R1 to R4 each independently represent a monovalent substituent, and p1 to p4 each independently represent 0 or a positive integer.

[0640] R a It represents a linear or branched alkyl group.

[0641] T1 to T5 each independently represent a single bond or a divalent linking group.

[0642] R5 represents a monovalent organic group.

[0643] a to e represent mol %, and each independently represents a number within the range of 0≤a≤100, 0≤b≤100, 0≤c<100, 0≤d<100, and 0≤e<100. However, a+b+c+d+e=100, and a+b≠0.

[0644] In formula (I), the repeating unit (e) has a structure different from any of the repeating units (a) to (d).

[0645] As R x1 ~R x5 The alkyl group which may contain a substituent is represented by methyl and -CH2-R 11 The group represented by R 11 It represents a halogen atom (fluorine atom or the like), a hydroxyl group or a monovalent organic group.

[0646] Preferred R x1 ~R x5 are each independently a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0647] In the formula (I), examples of the divalent linking groups represented by T1 to T5 include an alkylene group, a -COO-Rt- group, and a -O-Rt- group, etc. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0648] Preferably, T1 to T5 are each independently a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group or a -(CH2)3- group.

[0649] In formula (I), R a represents a linear or branched alkyl group. Examples thereof include methyl, ethyl, and tert-butyl groups. Among them, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred.

[0650] In formula (I), R1 to R4 each independently represent a monovalent substituent. R1 to R4 are not particularly limited, and examples thereof include hydroxyl group, cyano group, and linear or branched alkyl or cycloalkyl group having a hydroxyl group or cyano group.

[0651] In formula (I), p1 to p4 each independently represent 0 or a positive integer. The upper limit of p1 to p4 corresponds to the number of substitutable hydrogen atoms in each repeating unit.

[0652] In formula (I), R5 represents a monovalent organic group. R5 is not particularly limited, and examples thereof include a monovalent organic group having a sultone structure, a monovalent organic group having a cyclic ether such as tetrahydrofuran, dioxane, 1,4-thioxane, dioxolane, and 2,4,6-trioxabicyclo[3.3.0]octane, or an acid-decomposable group (for example, an adamantyl group quaternized by replacing the carbon at the position bonding to the -COO group with an alkyl group).

[0653] Furthermore, in the formula (I), the repeating unit (b) is preferably a repeating unit formed from the monomers described in paragraphs 0014 to 0018 of JP-A-2016-138219.

[0654] In formula (I), a to e represent mol %, and each independently represents a number included in the range of 0≤a≤100, 0≤b≤100, 0≤c<100, 0≤d<100, 0≤e<100. However, a+b+c+d+e=100, and a+b≠0.

[0655] In formula (I), a+b (the content of repeating units having an acid-decomposable group relative to all repeating units) is preferably 20 to 90 mol %, more preferably 25 to 85 mol %, further preferably 30 to 80 mol %.

[0656] Furthermore, in the formula (I), c+d (the content of the repeating unit having a lactone structure relative to all repeating units) is preferably 3 to 80 mol %, more preferably 3 to 60 mol %.

[0657] In addition, each of the repeating units (a) to (e) may be used alone or in combination of two or more. When two or more repeating units are used in combination, the total content is preferably within the above range.

[0658] The weight average molecular weight (Mw) of the resin represented by formula (I) is usually preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and further preferably 3,000 to 15,000. The weight average molecular weight is a polystyrene conversion value determined by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a developing solvent.

[0659] In the actinic ray or radiation sensitive resin composition, the content of the resin represented by the formula (I) is usually preferably 30 to 99% by mass, more preferably 50 to 95% by mass, based on the total solid content of the actinic ray or radiation sensitive resin composition.

[0660] (Repeating unit having phenolic hydroxyl group)

[0661] Furthermore, the resin P may contain a repeating unit having a phenolic hydroxyl group.

[0662] Examples of the repeating unit having a phenolic hydroxyl group include repeating units represented by the following general formula (I).

[0663] [Chemical formula 16]

[0664]

[0665] In the formula,

[0666] R 41 , R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can bond with Ar4 to form a ring. In this case, R 42 represents a single bond or an alkylene group.

[0667] X4 represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group.

[0668] L4 represents a single bond or an alkylene group.

[0669] Ar4 represents an (n+1) valent aromatic ring group, when combined with R 42 When they are bonded to form a ring, they represent an aromatic ring group with a valence of (n+2).

[0670] n represents an integer of 1-5.

[0671] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group is preferably an alkyl group having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and further preferably an alkyl group having 3 or less carbon atoms.

[0672] As R in the general formula (I) 41 , R 42 and R 43 The cycloalkyl group may be monocyclic or polycyclic. The cycloalkyl group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent.

[0673] As R in the general formula (I) 41 , R 42 and R 43 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferred.

[0674] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably the same as the above R 41 , R 42 and R 43 The same group as the alkyl group in .

[0675] Examples of substituents in the above groups include alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, carbamate groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, and nitro groups, and the number of carbon atoms in the substituents is preferably 8 or less.

[0676] Ar4 represents an (n+1)-valent aromatic ring group. The divalent aromatic ring group when n is 1 may have a substituent, for example, arylene groups having 6 to 18 carbon atoms such as phenylene, tolylene, naphthylene and anthracene, and aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole and thiazole.

[0677] Specific examples of the (n+1)-valent aromatic ring group when n is an integer of 2 or more include groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group.

[0678] The (n+1)-valent aromatic ring group may further have a substituent.

[0679] Examples of the substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n+1)-valent aromatic ring group may have include R in the general formula (I): 41 , R 42 and R 43 The alkyl groups mentioned in the above; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; aryl groups such as phenyl.

[0680] As -CONR represented by X4 64 -(R 64 represents a hydrogen atom, an alkyl group) 64 Examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl groups which may have a substituent, and more preferably alkyl groups having 8 or less carbon atoms.

[0681] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0682] The alkylene group in L4 is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may have a substituent.

[0683] Ar4 is preferably an aromatic ring group having 6 to 18 carbon atoms which may have a substituent, and more preferably a benzene ring group, a naphthyl ring group or a biphenylene ring group.

[0684] It is preferred that the repeating unit represented by the general formula (I) has a hydroxystyrene structure. That is, Ar4 is preferably a benzene ring group.

[0685] As the repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (p1) is preferred.

[0686] [Chemical formula 17]

[0687]

[0688] R in the general formula (p1) represents a hydrogen atom, a halogen atom, or a linear or branched alkyl group having 1 to 4 carbon atoms. A plurality of Rs may be the same or different. R in the general formula (p1) is preferably a hydrogen atom.

[0689] Ar in the general formula (p1) represents an aromatic ring, for example, an aromatic hydrocarbon ring having 6 to 18 carbon atoms which may have a substituent, such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring, and an aromatic heterocyclic ring including a heterocyclic ring, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. Among them, a benzene ring is more preferred.

[0690] In the general formula (p1), m represents an integer of 1 to 5, and 1 is preferred.

[0691] Specific examples of the repeating unit having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto.

[0692] [Chemical formula 18]

[0693]

[0694] [Chemical formula 19]

[0695]

[0696] [Chemical formula 20]

[0697]

[0698] The content of the repeating units having a phenolic hydroxyl group is preferably 0 to 50 mol % based on all the repeating units in the resin P, more preferably 0 to 45 mol %, and even more preferably 0 to 40 mol %.

[0699] (Repeating unit containing an organic group having a polar group)

[0700] The resin P may further include a repeating unit containing an organic group having a polar group, in particular, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.

[0701] Thereby, the substrate adhesion and developer affinity are improved. As the alicyclic hydrocarbon structure substituted with a polar group, adamantyl, diamond alkyl or norbornyl is preferred. As the polar group, a hydroxyl group or a cyano group is preferred.

[0702] Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited to these.

[0703] [Chemical formula 21]

[0704]

[0705] When the resin P contains repeating units containing an organic group having a polar group, the content thereof is preferably 1 to 50 mol %, more preferably 1 to 30 mol %, further preferably 5 to 25 mol %, and particularly preferably 5 to 20 mol % relative to all repeating units in the resin P.

[0706] (Repeating unit having a group that generates an acid by irradiation with actinic rays or radiation (photoacid generating group))

[0707] The resin P may contain a repeating unit having a group that generates an acid (photoacid generating group) upon irradiation with actinic rays or radiation.

[0708] Examples of the repeating unit of a group that generates an acid upon irradiation with actinic rays or radiation (photoacid generating group) include repeating units represented by the following formula (4).

[0709] [Chemical formula 22]

[0710]

[0711] R 41 represents a hydrogen atom or a methyl group. 41 represents a single bond or a divalent linking group. 42 W represents a structural site which is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain.

[0712] Specific examples of the repeating unit represented by formula (4) are shown below, but the present invention is not limited thereto.

[0713] [Chemical formula 23]

[0714]

[0715] Examples of the repeating unit represented by the formula (4) include the repeating units described in paragraphs

[00094] to

[0105] of JP-A-2014-041327.

[0716] When the resin P contains a repeating unit having a photoacid generating group, the content of the repeating unit having the photoacid generating group relative to all repeating units in the resin P is preferably 1 to 40 mol %, more preferably 5 to 35 mol %, and further preferably 5 to 30 mol %.

[0717] The resin P may contain a repeating unit represented by the following formula (VI).

[0718] [Chemical formula 24]

[0719]

[0720] In formula (VI),

[0721] R 61 , R 62 and R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 62 It can bond with Ar6 to form a ring. In this case, R 62 represents a single bond or an alkylene group.

[0722] X6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0723] L6 represents a single bond or an alkylene group.

[0724] Ar6 represents an (n+1) valent aromatic ring group. 62 When they are bonded to form a ring, they represent an aromatic ring group with a valence of (n+2).

[0725] Regarding Y2, when n≥2, each independently represents a hydrogen atom or a group that is dissociated by the action of an acid. Among them, at least one of Y2 represents a group that is dissociated by the action of an acid.

[0726] n represents an integer of 1 to 4.

[0727] As the group Y2 that is dissociated by the action of an acid, a structure represented by the following formula (VI-A) is preferred.

[0728] [Chemical formula 25]

[0729]

[0730] L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group consisting of an alkylene group and an aryl group.

[0731] M represents a single bond or a divalent linking group.

[0732] Q represents an alkyl group, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group or an aldehyde group.

[0733] At least two of Q, M, and L1 may be bonded to form a ring (preferably a 5-membered or 6-membered ring).

[0734] The repeating unit represented by the above formula (VI) is preferably a repeating unit represented by the following formula (3).

[0735] [Chemical formula 26]

[0736]

[0737] In formula (3),

[0738] Ar3 represents an aromatic ring group.

[0739] R3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.

[0740] M3 represents a single bond or a divalent linking group.

[0741] Q3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

[0742] At least two of Q3, M3 and R3 may be bonded to form a ring.

[0743] The aromatic ring group represented by Ar3 is the same as Ar6 in the above formula (VI) when n in the above formula (VI) is 1, and is more preferably a phenylene group or a naphthylene group, and further preferably a phenylene group.

[0744] Specific examples of the repeating unit represented by formula (VI) are shown below, but the present invention is not limited thereto.

[0745] [Chemical formula 27]

[0746]

[0747] [Chemical formula 28]

[0748]

[0749] The resin P may contain a repeating unit represented by the following formula (4).

[0750] [Chemical formula 29]

[0751]

[0752] In formula (4),

[0753] R 41 , R 42 and R 43 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. 42 It can bond with L4 to form a ring. In this case, R 42 represents an alkylene group.

[0754] L4 represents a single bond or a divalent linking group. 42 When a ring is formed, it represents a trivalent linking group.

[0755] R 44 and R 45 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkoxy group, an acyl group or a heterocyclic group.

[0756] M4 represents a single bond or a divalent linking group.

[0757] Q4 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

[0758] Q4, M4 and R 44 At least two of the may be bonded to form a ring.

[0759] R 41 , R 42 and R 43 has the same meaning as R in the above formula (IA) 41 , R 42 and R 43 The preferred ranges are the same.

[0760] L4 has the same meaning as T in the aforementioned formula (AI), and the preferred range is also the same.

[0761] R 44 and R 45 The meaning is the same as that of R3 in the aforementioned formula (3), and the preferred range is also the same.

[0762] M4 has the same meaning as M3 in the aforementioned formula (3), and the preferred range is also the same.

[0763] Q4 has the same meaning as Q3 in the above formula (3), and the preferred range is also the same.

[0764] As Q4, M4 and R 44 The ring formed by bonding at least two of Q3, M3 and R3 can be mentioned, and the preferred range is also the same.

[0765] Specific examples of the repeating unit represented by formula (4) are shown below, but the present invention is not limited thereto.

[0766] [Chemical formula 30]

[0767]

[0768] Furthermore, the resin P may contain a repeating unit represented by the following formula (BZ).

[0769] [Chemical formula 31]

[0770]

[0771] In formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and AR may be bonded to each other to form a non-aromatic ring.

[0772] R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

[0773] Specific examples of the repeating unit represented by the formula (BZ) are shown below, but the present invention is not limited to these.

[0774] [Chemical formula 32]

[0775]

[0776] [Chemical formula 33]

[0777]

[0778] The content of the repeating unit having an acid-decomposable group in the resin P (the total when multiple types are contained) is preferably 5 to 80 mol %, more preferably 5 to 75 mol %, and further preferably 10 to 65 mol % based on all the repeating units in the resin P.

[0779] The resin P may contain a repeating unit represented by the following formula (V) or the following formula (VI).

[0780] [Chemical formula 34]

[0781]

[0782] In the formula,

[0783] R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an alkoxy group or an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms) or a carboxyl group.

[0784] n3 represents an integer from 0 to 6.

[0785] n4 represents an integer from 0 to 4.

[0786] X 4 It is a methylene group, an oxygen atom or a sulfur atom.

[0787] Specific examples of the repeating unit represented by formula (V) or formula (VI) are shown below, but the present invention is not limited to these.

[0788] [Chemical formula 35]

[0789]

[0790] Resin P may further contain repeating units having silicon atoms on the side chains. Examples of repeating units having silicon atoms on the side chains include (meth)acrylate repeating units having silicon atoms, vinyl repeating units having silicon atoms, and the like. Repeating units having silicon atoms on the side chains are typically repeating units having groups having silicon atoms on the side chains, and examples of groups having silicon atoms include trimethylsilyl, triethylsilyl, triphenylsilyl, tricyclohexylsilyl, tris(trimethylsiloxysilyl), tris(trimethylsilylsilyl), methylbistrimethylsilylsilyl, methylbistrimethylsiloxysilyl, dimethyltrimethylsilylsilyl, dimethyltrimethylsiloxysilyl, and cyclic or linear polysiloxanes as described below, or cage-type, ladder-type, or random silsesquioxane structures, and the like. In the formula, R and R 1 Each independently represents a monovalent substituent. * represents a bonding bond.

[0791] [Chemical formula 36]

[0792]

[0793] As the repeating unit having the above group, for example, a repeating unit derived from an acrylate or methacrylate compound having the above group or a repeating unit derived from a compound having the above group and a vinyl group is preferable.

[0794] The repeating unit having a silicon atom is preferably a repeating unit having a silsesquioxane structure, thereby being able to exhibit very excellent collapse performance when forming an ultra-fine pattern (for example, a line width of less than 50 nm) and a cross-sectional shape with a high aspect ratio (for example, film thickness / line width of 3 or more).

[0795] Examples of the silsesquioxane structure include a cage silsesquioxane structure, a ladder silsesquioxane structure (ladder silsesquioxane structure), and a random silsesquioxane structure. Among them, a cage silsesquioxane structure is preferred.

[0796] Here, the cage silsesquioxane structure is a silsesquioxane structure having a cage-like skeleton. The cage silsesquioxane structure may be a complete cage silsesquioxane structure or an incomplete cage silsesquioxane structure, and is preferably a complete cage silsesquioxane structure.

[0797] Also, the ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.

[0798] Furthermore, the random silsesquioxane structure is a silsesquioxane structure having a random skeleton.

[0799] The cage silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

[0800] [Chemical formula 37]

[0801]

[0802] In the above formula (S), R represents a monovalent organic group. A plurality of Rs may be the same or different.

[0803] The above-mentioned organic group is not particularly limited. Specific examples include hydroxyl, nitro, carboxyl, alkoxy, amino, mercapto, blocked mercapto (for example, mercapto blocked (protected) by acyl), acyl, imide, phosphino, phosphinyl, silyl, vinyl, hydrocarbon group which may have heteroatoms, group containing (meth)acryloyl group and group containing epoxy group.

[0804] Examples of the hetero atom of the hydrocarbon group which may have a hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.

[0805] Examples of the hydrocarbon group of the hydrocarbon group which may have a hetero atom include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are combined.

[0806] The aliphatic hydrocarbon group may be any of a linear, branched, and cyclic group. Specific examples of the aliphatic hydrocarbon group include a linear or branched alkyl group (especially, having 1 to 30 carbon atoms), a linear or branched alkenyl group (especially, having 2 to 30 carbon atoms), and a linear or branched alkynyl group (especially, having 2 to 30 carbon atoms).

[0807] Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.

[0808] When the resin P has the above-mentioned repeating unit having a silicon atom in the side chain, the content thereof is preferably 1 to 30 mol %, more preferably 5 to 25 mol %, and further preferably 5 to 20 mol % relative to all the repeating units in the resin P.

[0809] The weight average molecular weight of the resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and further preferably 5,000 to 15,000, as a polystyrene conversion value based on the GPC (Gel permeation chromatography) method. By setting the weight average molecular weight to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and it is possible to prevent deterioration of developability or deterioration of film forming properties due to increased viscosity.

[0810] The dispersion degree (molecular weight distribution) is usually preferably 1 to 5, 1 to 3, more preferably 1.2 to 3.0, and further preferably 1.2 to 2.0.

[0811] In the actinic ray-sensitive or radiation-sensitive composition, the content of the resin P is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content.

[0812] Furthermore, in the actinic ray-sensitive or radiation-sensitive composition, the resin P may be used alone or in combination of two or more.

[0813] (Photoacid generator)

[0814] The above-mentioned actinic ray-sensitive or radiation-sensitive resin composition preferably contains a photoacid generator. The photoacid generator is not particularly limited, and a known photoacid generator can be used.

[0815] The content of the photoacid generator in the photosensitive ray or radiation-sensitive resin composition is not particularly limited, and is generally preferably 0.1 to 20% by mass, more preferably 0.5 to 20% by mass, relative to the total solid content of the photosensitive ray or radiation-sensitive resin composition. The photoacid generator may be used alone or in combination of two or more. When two or more photoacid generators are used in combination, the total content is preferably within the above range.

[0816] Examples of the photoacid generator include those described in JP-A Nos. 2016-057614, 2014-219664, 2016-138219, and 2015-135379.

[0817] (Quencher)

[0818] The actinic ray-sensitive or radiation-sensitive resin composition may contain a quencher. The quencher is not particularly limited, and a known quencher can be used.

[0819] The quencher is a basic compound and has a function of suppressing the acid-decomposable resin from being unintentionally decomposed in the unexposed region due to the acid diffused from the exposed region.

[0820] The content of the quencher in the actinic ray or radiation-sensitive resin composition is not particularly limited, but is generally preferably 0.1 to 15% by mass, more preferably 0.5 to 8% by mass, relative to the total solid content of the actinic ray or radiation-sensitive resin composition. The quencher may be used alone or in combination of two or more. When two or more quenchers are used in combination, the total content is preferably within the above range.

[0821] Examples of the quencher include quenchers described in JP-A Nos. 2016-057614, 2014-219664, 2016-138219, and 2015-135379.

[0822] (Hydrophobic resin)

[0823] The above-mentioned actinic ray-sensitive or radiation-sensitive resin composition may contain a hydrophobic resin.

[0824] The hydrophobic resin is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule and may not contribute to uniform mixing of polar substances and non-polar substances.

[0825] Examples of the effects of adding a hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water and suppression of degassing.

[0826] From the viewpoint of partial localization to the film surface, the hydrophobic resin preferably has any one or more of "fluorine atom", "silicon atom" and "CH3 partial structure contained in the side chain part of the resin", and more preferably has two or more. In addition, it is preferred that the hydrophobic resin has a hydrocarbon group with a carbon number of 5 or more. These groups may be present in the main chain of the resin or substituted in the side chain.

[0827] When the hydrophobic resin contains fluorine atoms and / or silicon atoms, the fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[0828] When the hydrophobic resin contains a fluorine atom, as the partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is preferred.

[0829] The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

[0830] The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

[0831] Examples of the aryl group having a fluorine atom include an aryl group such as a phenyl group and a naphthyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the aryl group may further have a substituent other than a fluorine atom.

[0832] Examples of the repeating unit having a fluorine atom or a silicon atom include the repeating units exemplified in paragraph

[0519] of US 2012 / 0251948 A1.

[0833] Furthermore, as described above, it is also preferred that the hydrophobic resin contains a CH3 partial structure in the side chain portion.

[0834] Here, the CH3 partial structure of the side chain part in the hydrophobic resin includes the CH3 partial structure of an ethyl group, a propyl group, or the like.

[0835] On the other hand, since the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl group of the repeating unit having a methacrylic acid structure) contributes little to the surface localization of the hydrophobic resin due to the influence of the main chain, it is considered not to be included in the CH3 partial structure in the present invention.

[0836] Regarding the hydrophobic resin, reference can be made to the description in paragraphs

[0348] to

[0415] of Japanese Patent Application Laid-Open No. 2014-010245, and these contents are incorporated into the specification of the present application.

[0837] Moreover, as a hydrophobic resin, resins described in Unexamined-Japanese-Patent No. 2011-248019, Unexamined-Japanese-Patent No. 2010-175859, and Unexamined-Japanese-Patent No. 2012-032544 can also be preferably used.

[0838] As the hydrophobic resin, for example, resins represented by the following formula (1b) to formula (5b) are preferred.

[0839] [Chemical formula 38]

[0840]

[0841] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the composition.

[0842] (Solvent)

[0843] The above-mentioned actinic ray-sensitive or radiation-sensitive resin composition may contain a solvent. There is no particular limitation on the solvent, and a known solvent can be used.

[0844] The solvent contained in the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition may be the same as or different from the organic solvent contained in the mixture in the above-described chemical solution.

[0845] The content of the solvent in the photosensitive radiation-curable or radiation-sensitive resin composition is not particularly limited, and it is preferably contained in an amount of usually 0.1 to 20% by mass based on the total solid content of the photosensitive radiation-curable or radiation-sensitive resin composition. The solvent may be used alone or two or more solvents may be used simultaneously. When two or more solvents are used simultaneously, the total content is preferably within the above range.

[0846] Examples of the solvent include those described in JP-A-2016-057614, JP-A-2014-219664, JP-A-2016-138219, and JP-A-2015-135379.

[0847] (Other additives)

[0848] Furthermore, the above-mentioned photosensitive radiation-curable or radiation-sensitive resin composition may further contain a surfactant, an acid proliferator, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin other than the above, and / or a dissolution inhibitor, etc. as needed.

[0849] 〔Exposure process〕

[0850] The exposure process is a process of exposing the resist film. The method of exposing the resist film is not particularly limited, and a known method can be used.

[0851] Examples of the method of exposing the resist film include a method of irradiating actinic rays or radiation through a prescribed mask on the resist film. And, in the case of a method of irradiating an electron beam on the resist film, it can be irradiated without passing through a mask (this is also called "direct writing").

[0852] The actinic rays or radiation used in the exposure are not particularly limited, and examples include KrF excimer laser, ArF excimer laser, extreme ultraviolet rays (EUV, Extreme Ultra Violet), and electron beam (EB, Eleetron Beam), etc., and extreme ultraviolet rays or electron beam are preferred. The exposure can also be immersion exposure.

[0853] <PEB (Post Exposure Bake: Post-exposure baking) process>

[0854] The above-mentioned pattern forming method preferably further includes an exposure process and a PEB process of baking the exposed resist film (PEB: Post Exposure Bake) before the development process. By baking, the reaction in the exposed part is promoted, and the sensitivity and / or the pattern shape are better.

[0855] The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and further preferably 80 to 130°C.

[0856] The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0857] Heating can be performed by a mechanism included in a general exposure / developing machine, or can be performed using a heating plate or the like.

[0858] 〔Development process〕

[0859] The development step is a step of developing the exposed resist film (hereinafter also referred to as “exposed resist film”) with a developer. In the present embodiment, a chemical solution X is used as the developer.

[0860] The developing method is not particularly limited, and a known developing method can be used. Examples of the developing method include an immersion method, a liquid coating method, a spray method, and a dynamic dispensing method.

[0861] Furthermore, the pattern forming method may further include a step of replacing the developing solution with another solvent and stopping the development after the developing step.

[0862] The development time is not particularly limited, but is usually preferably 10 to 300 seconds, more preferably 10 to 120 seconds. The temperature of the developer is preferably 0 to 50° C., more preferably 15 to 35° C. The pattern forming method may include at least one development step or may include multiple development steps.

[0863] In the development step, both development using the chemical solution X and development using an alkali developer may be performed (so-called double development may also be performed).

[0864] 〔Rinsing process〕

[0865] The rinsing step is a step of washing the wafer having the developed resist film with a rinsing liquid. In this embodiment, a chemical solution Y is used as a developer.

[0866] The cleaning method is not particularly limited, and a known cleaning method can be used. Examples of the cleaning method include a rotary discharge method, an immersion method, and a spray method.

[0867] Among them, it is preferable to perform cleaning by a spin discharge method, and after cleaning, the wafer is rotated at a rotation speed of 2000 to 4000 rpm to remove the rinse liquid from the substrate.

[0868] The rinsing time is usually preferably 10 to 300 seconds, more preferably 10 to 180 seconds, and still more preferably 20 to 120 seconds. The temperature of the rinsing liquid is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0869] 〔Other processes〕

[0870] The pattern forming method may include other steps in addition to the steps described above. Examples of other steps include a pre-wetting step, a cleaning step using a supercritical fluid, and a heating step.

[0871] <Prewetting process>

[0872] The pre-wetting process is a process of applying a chemical solution on a substrate for forming a resist film before the resist film forming process. The pre-wetting process can adopt a known method. In addition, as the chemical solution used in the pre-wetting process, this chemical solution can be used, and a chemical solution other than this chemical solution can also be used.

[0873] The substrate is not particularly limited, and any known substrate used for semiconductor manufacturing can be used. Examples of the substrate include inorganic substrates such as silicon, SiO2, or SiN, or coated inorganic substrates such as SOG (Spin On Glass), but are not limited thereto.

[0874] Furthermore, the substrate may be a substrate provided with an antireflection film. The antireflection film is not particularly limited, and a known organic or inorganic antireflection film may be used.

[0875] There is no particular limitation on the method for coating the chemical solution on the substrate, and a known coating method can be used. In particular, in the resist film forming step described later, spin coating is preferred from the viewpoint of being able to form a uniform resist film with less actinic ray or radiation-sensitive resin composition.

[0876] There is no particular limitation on the method for coating the chemical solution on the substrate, and a known coating method can be used. In particular, in the resist film forming step described later, spin coating is preferred from the viewpoint of being able to form a uniform resist film with less actinic ray or radiation-sensitive resin composition.

[0877] The thickness of the chemical solution layer formed on the substrate using the chemical solution is not particularly limited, but is usually preferably 0.001 to 10 μm, more preferably 0.005 to 5 μm.

[0878] Here, the resist liquid to be coated is assumed to be a resist for ArF immersion exposure. The surface tension of the resist liquid is set to 28.8 mN / m. In this case, the surface tension of the mixture as the chemical solution is not particularly limited, but it is preferably made higher than the surface tension of the resist liquid and supplied to the wafer as a pre-wetting liquid.

[0879] As a method for supplying the chemical solution to the wafer, a pre-wetting nozzle is usually moved to above the center of the wafer, and then the chemical solution is supplied to the wafer by opening and closing a valve.

[0880] When the wafer is stopped, a predetermined amount of the above-mentioned chemical solution is supplied from the pre-wetting nozzle to the center of the wafer. Then, the wafer is rotated at a first speed V1 of about 500 rpm (rotation per minute), for example, and the chemical solution on the wafer spreads to the entire surface of the wafer, so that the entire surface of the wafer becomes wetted with the chemical solution.

[0881] In addition, the upper limit of the first speed V1 is not particularly limited, but is preferably 3000 rpm or less.

[0882] Then, by opening the valve of the line connected to the resist liquid, the resist liquid starts to be ejected from the resist nozzle, thereby starting to supply the resist liquid to the center portion of the wafer.

[0883] In this way, the resist film forming process is started. In the resist film forming process, the rotation speed of the developer is increased from the first speed V1 to a high-speed second speed V2 of, for example, about 2000 to 4000 rpm. The rotation of the wafer, which was at the first speed V1 before the start of the resist film forming process, is gradually accelerated so that the speed changes continuously and smoothly thereafter. At this time, the rotation acceleration of the wafer gradually increases from zero, for example. Then, at the end of the resist film forming process, the rotation acceleration of the wafer gradually decreases, and the rotation speed of the wafer W smoothly converges to the second speed V2. In this way, in the resist film forming process, the rotation speed of the wafer changes from the first speed V1 to the second speed V2 in an S-shape. In the resist film forming process, the resist liquid supplied to the center of the wafer is diffused to the entire surface of the wafer by centrifugal force, so that the resist liquid is applied to the surface of the wafer.

[0884] In addition, the resist saving technology due to the change in the rotation speed of the wafer when applying such a resist is described in detail in Japanese Patent Application No. 2008-131495 and Japanese Patent Application Laid-Open No. 2009-279476.

[0885] The interval from the end of the pre-wetting step to the start of the application of the resist solution in the resist film forming step is not particularly limited, but is usually preferably 7 seconds or less.

[0886] The chemical solution can be reused. That is, the chemical solution used in the pre-wetting process can be recovered and further used in the pre-wetting process of other wafers.

[0887] When the chemical solution is reused, it is preferable to adjust the contents of metal impurities, organic impurities, water, etc. contained in the recovered chemical solution.

[0888] <Removal process using supercritical fluid>

[0889] The removal process using a supercritical fluid is a process of removing a developing solution and / or a rinsing solution attached to a pattern using a supercritical fluid after the developing process and / or the rinsing process.

[0890] <Heating process>

[0891] The heating step is a step of heating the resist film in order to remove the solvent remaining in the pattern after the development step, the rinsing step, or the removal step using a supercritical fluid.

[0892] The heating temperature is not particularly limited, but is usually preferably 40 to 160°C, more preferably 50 to 150°C, and further preferably 50 to 110°C.

[0893] The heating time is not particularly limited, but is usually preferably 15 to 300 seconds, more preferably 15 to 180 seconds.

[0894] Example

[0895] Below, the present invention is further described in detail based on examples. The materials, usage amounts, ratios, processing contents and processing steps shown in the following examples, as long as they do not depart from the gist of the present invention, can be appropriately changed. Thus, the scope of the present invention should not be interpreted in a limited manner by the examples shown below.

[0896] Furthermore, when preparing the chemical solutions of the examples and comparative examples, the handling of containers, preparation, filling, storage, and analytical measurements of the chemical solutions were all performed in a clean room that meets ISO Class 2 or 1. In order to improve the measurement accuracy, in the measurement of the content of organic compounds and the measurement of the content of metal components, when measuring components below the detection limit by normal measurement, the chemical solution was concentrated and measured, and the content was calculated by converting it into the concentration of the solution before concentration.

[0897] [Purification of Drug Solution A1]

[0898] A purified product (commercially available product) containing propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent was prepared.

[0899] Next, a purification apparatus was prepared in which a first distillation section having a first plate-type distillation column without a pressure reducing mechanism (distillation step for crude distillation), a first packed section having three packed columns filled with a cation exchange resin connected in series (ion removal step), a second packed section having two packed columns filled with anion exchange resin connected in series (ion removal step), a second distillation section having a second plate-type distillation column without a pressure reducing mechanism and a third plate-type distillation column with a pressure reducing mechanism connected in series in sequence (distillation step for fractionation treatment), and a filtration section having a first filter and a second filter connected in series in sequence (filtration step) were sequentially connected from the upstream side.

[0900] Then, the purified product was purified using the purification device to produce a drug solution. In addition, the purification of the purified product was performed twice in total, with one pass through the purification device being counted as one pass (in the table, the number of cycles is shown as 2 times).

[0901] Hereinafter, the details of each component in the purification device will be described in order from the upstream side (primary side).

[0902] ·1st plate distillation tower (theoretical plate number: 10 plates)

[0903] Cation exchange resin (ORLITE DS-4, manufactured by ORGANO CORPORATION)

[0904] Anion exchange resin (ORLITE DS-6, manufactured by ORGANO CORPORATION)

[0905] ·The second plate distillation tower (theoretical plate number: 23 plates)

[0906] · 3rd plate distillation tower (theoretical plate number: 23 plates, vacuum distillation)

[0907] ・First filter (Purasol SP / SN solvent purifier, manufactured by Nihon Entegris GK, UPE (ultra-high molecular weight polyethylene) filter)

[0908] ・Second filter (product name: "trent", manufactured by Nihon Entegris GK, polytetrafluoroethylene (PTFE) filter)

[0909] [Purification of other drug solutions]

[0910] The purified product containing the organic solvent described in Table 1 was purified under the conditions described in Table 1. Each chemical solution was obtained by passing the purified product through each component described in Table 1 in sequence from the upstream side (in addition, the chemical solution with a blank column means that the component was not used.), and repeating this for the number of times described in "Number of cycles".

[0911] However, in Comparative Example NA2, the ion removal step was performed using a third filling section filled with an adsorption resin (product name "DUOLITE 874", styrene-based resin) instead of the first filling section and the second filling section used in the ion removal step.

[0912] In addition, for the first plate type distillation column, the second plate type distillation column, and the third plate type distillation column, distillation columns having the theoretical plate numbers shown in Table 1 were used. The number of plates of cation exchange resin refers to the number of columns filled with cation exchange resin connected in series, the number of plates of anion exchange resin refers to the number of columns filled with anion exchange resin connected in series, and the number of plates of adsorption resin refers to the number of columns filled with adsorption resin connected in series.

[0913] Furthermore, the purified products listed in Table 1 are purchased from different lots. Therefore, components other than the organic solvent initially contained in each purified product may be different.

[0914] In addition, the abbreviations in Table 1 represent the following respectively.

[0915] ·PGMEA: Propylene glycol monomethyl ether acetate (boiling point: 146°C, SP value: 17.86)

[0916] nBA: Butyl acetate (boiling point: 126°C, SP value: 17.80)

[0917] iAA: isoamyl acetate (boiling point: 142°C, SP value: 17.42)

[0918] ·CHN: Cyclohexanone (boiling point: 155.6°C, SP value: 20.05)

[0919] PGME: Propylene glycol monoethyl ether (boiling point: 132.8°C, SP value: 23.05)

[0920] MIBC: 4-methyl-2-pentanol (boiling point: 131.6°C, SP value: 21.15)

[0921] EL: Ethyl lactate (boiling point: 154°C, SP value: 24.41)

[0922] PC: Propylene carbonate (boiling point: 242°C, SP value: 20.26)

[0923] [Table 1]

[0924]

[0925] [Table 2]

[0926]

[0927] [Measurement of the content of each component in the drug solution, etc.]

[0928] The following method was used to measure the content of each component in the liquid medicine. In addition, the following measurements were all performed in a clean room that meets the standard of ISO (International Organization for Standardization) level 2 or below. In order to improve the measurement accuracy, in the measurement of each component, when it is below the detection limit in the usual measurement, the volume conversion is concentrated to 1 / 100 and the content is calculated by converting it to the content of the organic solvent before concentration. The results are summarized in Table 2.

[0929] In addition, the content of each component in the drug solution was measured immediately after the drug solution was prepared.

[0930] 〔Acid components and organic compounds〕

[0931] The contents of the acid component and the organic compound in each chemical solution were measured using a gas chromatograph-mass spectrometer (product name: "GCMS-2020", manufactured by Shimadzu Corporation, measurement conditions are as follows).

[0932] <Measurement conditions>

[0933] Capillary column: InertCap 5MS / NP 0.25mm I.D.×30m df=0.25μm

[0934] Sample introduction method: split flow 75kPa constant pressure

[0935] Vaporization chamber temperature: 230℃

[0936] Column oven temperature: 80℃(2min)-500℃(13min) Heating rate: 15℃ / min

[0937] Carrier gas: Helium

[0938] Septum purge flow rate: 5mL / min

[0939] Split ratio: 25:1

[0940] Interface temperature: 250℃

[0941] Ion source temperature: 200°C

[0942] Measurement mode: Scan m / z = 85 ~ 500

[0943] Sample introduction volume: 1μL

[0944] [Metal component]

[0945] The content of metal components (metal ions and metal-containing particles) in the chemical solution was measured by using ICP-MS and SP-ICP-MS.

[0946] The following apparatus was used. The results are shown in Table 2.

[0947] Manufacturer: PerkinElmer

[0948] Model: NexION350S

[0949] The following analysis software was used for the analysis.

[0950] Syngistix Nano Application Module for "SP-ICP-MS"

[0951] Syngistix for ICP-MS software

[0952] 〔Metal Nanoparticles〕

[0953] The number of metal nanoparticles (metal-containing particles having a particle size of 0.5 to 17 nm) contained in the chemical solution was measured by the following method.

[0954] First, a constant amount of liquid medicine is applied to a silane-based substrate to form a substrate with a liquid medicine layer. The surface of the substrate with the liquid medicine layer is scanned by a laser beam, and the scattered light is detected. In this way, the position and particle size of the defects on the surface of the substrate with the liquid medicine layer are determined. Next, elemental analysis is performed using the EDX (energy dispersive X-ray) analysis method based on the position of the defect, and the composition of the defect is checked. This method is used to determine the number of particles on the substrate of metal nanoparticles, and this is converted into the number of particles per unit volume of the liquid medicine (particles / cm 3 ).

[0955] The analysis used a combination of a wafer inspection device "SP-5" manufactured by KLA-Tencor Corporation and a fully automatic defect inspection and classification device "SEMVision G6" manufactured by Applied Materials, Inc.

[0956] In addition, for samples in which particles of the desired particle size could not be detected due to the resolution of the measuring device, the method described in paragraphs 0015 to 0067 of Japanese Patent Publication No. 2009-188333 was used for detection. That is, SiO was formed on a substrate by CVD (chemical vapor deposition) method. x Then, a chemical solution layer was formed on the SiO2 layer. xThe composite layer of the layer and the drug solution layer coated thereon is dry-etched, the obtained protrusions are irradiated with light, the scattered light is detected, and the volume of the protrusions is calculated from the scattered light, and the particle size of the particles is calculated from the volume of the protrusions.

[0957] [Evaluation of defect suppression performance]

[0958] The obtained chemical solution was used as a pre-wetting solution to evaluate the defect suppression performance.

[0959] Here, the defect suppression performance is implemented for both the case of using a drug solution just after manufacturing (indicated as "just to after" in the table) and the case of using a drug solution after the drug solution is contained in a drug solution container (material of the liquid contact part: high-density polyethylene (HDPE) resin) is stored at 40°C for 45 days (indicated as "over time" in the table).

[0960] In addition, the resist composition used was as follows.

[0961] [Resist composition 1]

[0962] The resist composition 1 is obtained by mixing the components in the following composition.

[0963] Resin (A-1): 0.77 g

[0964] Acid generator (B-1): 0.03 g

[0965] Basic compound (E-3): 0.03 g

[0966] PGMEA: 67.5g

[0967] EL: 75g

[0968] <Resin (A), etc.>

[0969] (Synthesis Example 1) Synthesis of Resin (A-1)

[0970] 600 g of cyclohexanone was placed in a 2L flask, and nitrogen was replaced for one hour at a flow rate of 100 mL / min. Then, 4.60 g (0.02 mol) of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the temperature was raised to 80°C. Next, the following monomers and 4.60 g (0.02 mol) of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 200 g of cyclohexanone to prepare a monomer solution. The monomer solution was added dropwise to the flask heated to 80°C for 6 hours. After the addition was completed, the reaction was further carried out at 80°C for 2 hours.

[0971] 4-Acetoxystyrene 48.66 g (0.3 mol)

[0972] 1-Ethylcyclopentyl methacrylate 109.4 g (0.6 mol)

[0973] Monomer 1 22.2 g (0.1 mol)

[0974] [Chemical formula 39]

[0975]

[0976] The reaction solution was cooled to room temperature and added dropwise to 3 L of hexane to precipitate a polymer. The solid obtained by filtration was dissolved in 500 mL of acetone and added dropwise to 3 L of hexane again. The solid obtained by filtration was dried under reduced pressure to obtain 160 g of a 4-acetoxystyrene / 1-ethylcyclopentyl methacrylate / monomer 1 copolymer (A-1).

[0977] Add 10 g of the polymer obtained above, 40 mL of methanol, 200 mL of 1-methoxy-2-propanol and 1.5 mL of concentrated hydrochloric acid to the reaction container, heat to 80°C and stir for 5 hours. Cool the reaction solution to room temperature and add it dropwise to 3 L of distilled water. Dissolve the solid obtained by filtration in 200 mL of acetone and add it dropwise to 3 L of distilled water again. Dry the solid obtained by filtration under reduced pressure to obtain resin (A-1) (8.5 g). The weight average molecular weight (Mw) converted to standard polystyrene obtained by gel permeation chromatography (GPC) (solvent: THF (tetrahydrofuran)) is 11200, and the molecular weight dispersion (Mw / Mn) is 1.45. The structure of resin A-1 is shown below.

[0978] [Chemical formula 40]

[0979]

[0980] <Photoacid generator (B)>

[0981] As the photoacid generator, the following photoacid generators were used.

[0982] [Chemical formula 41]

[0983]

[0984] <Basic compound (E)>

[0985] As the basic compound, the following basic compounds were used.

[0986] [Chemical formula 42]

[0987]

[0988] (Defect suppression performance)

[0989] The defect suppression performance of the chemical solution was evaluated by the following method. In addition, the test used coater developer "RF 3S ”.

[0990] First, AL412 (manufactured by Brewer Science, Inc.) was applied to a silicon wafer and baked at 200°C for 60 seconds to form a resist underlayer film with a thickness of 20 nm. A pre-wetting liquid (chemical solution 1) was applied thereon, and a resist composition 1 was applied thereon, and baked at 100°C for 60 seconds (PB: Prebake) to form a resist film with a thickness of 30 nm.

[0991] The resist film was exposed using an EUV exposure machine (manufactured by ASML; NXE3350, NA0.33, Dipole 90°, outer sigma 0.87, inner sigma 0.35) through a reflective mask with a pitch of 20nm and a pattern width of 15nm. Then, it was heated at 85°C (PEB: Post Exposure Bake) for 60 seconds. Next, it was developed for 30 seconds using an organic solvent-based developer and rinsed for 20 seconds. Then, the wafer was rotated at a speed of 2000rpm for 40 seconds to form a line and space pattern with a pitch of 20nm and a pattern line width of 15nm.

[0992] The image of the pattern was acquired and analyzed using a combination of a pattern defect inspection device "UVsion 7" from Applied Materials, Inc. and a fully automatic defect inspection and classification device "SEMVision G6" from Applied Materials, Inc., to measure the number of residues in the unexposed portion per unit area.

[0993] In addition, for samples where particles of the desired particle size could not be detected due to the resolution of the measuring device, the method described in paragraphs 0015 to 0067 of Japanese Patent Application Publication No. 2009-188333 was used for detection. That is, SiO was formed on a substrate by CVD (chemical vapor deposition). X Then, a chemical solution layer was formed on the SiO2 layer. X The composite layer of the layer and the drug solution layer coated thereon is dry-etched, the obtained protrusions are irradiated with light, the scattered light is detected, and the volume of the protrusions is calculated from the scattered light, and the particle size of the particles is calculated from the volume of the protrusions.

[0994] Evaluation was performed based on the following criteria, and the results are shown in Table 2.

[0995] A: The number of defects is less than 50.

[0996] B: The number of defects is 50 or more and less than 70.

[0997] C: The number of defects is 70 or more and less than 90.

[0998] D: The number of defects is 90 or more and less than 110.

[0999] E: The number of defects is 110 or more and less than 130.

[1000] F: The number of defects is 130 or more.

[1001]

[1002]

[1003] In Table 2 above, the numerical values ​​recorded in the columns of "acid component" and "acid component / metal component (mass ratio)" are sometimes abbreviated as exponents. For example, "1.1E+05" means "1.1×10 5 ”, “6.3E-03” means “6.3×10 -3 ”.

[1004] As shown in Table 2, it is shown that if a solution is used in which the content of the acid component is greater than 1 mass ppt and less than 15 mass ppm relative to the total mass of the solution, and the content of the metal component is 0.001 to 100 mass ppt relative to the total mass of the solution, a solution having excellent defect suppression performance even after long-term storage can be obtained (Example).

[1005] For example, a comparison between Examples A1 and A2 shows that when the content of the organic acid is 1 ppm by mass or less relative to the total mass of the chemical solution (Example A2), the chemical solution has excellent defect suppression performance immediately after production and after long-term storage.

[1006] For example, a comparison between Examples A2 and A3 shows that when the content of the organic acid above the boiling point of the organic solvent is 20 mass % or less relative to the total mass of the organic acid (Example A2), the defect suppression performance of the chemical solution after long-term storage is more excellent.

[1007] For example, a comparison between Examples A1 and A4 shows that when the content of the inorganic acid is 1 ppb or less relative to the total mass of the chemical solution (Example A1), the defect suppression performance of the chemical solution is excellent even immediately after production and after long-term storage.

[1008] For example, a comparison between Examples A15 and A16 shows that when the water content is 1 ppm by mass or less relative to the total mass of the chemical solution (Example A15), the defect suppression performance of the chemical solution after long-term storage is excellent.

[1009] For example, comparison between Examples A8 and A17 shows that when the content of metal-containing particles is within the range of 0.00001 to 10 ppt by mass relative to the total mass of the chemical solution (Example A8), the defect suppression performance of the chemical solution after long-term storage is excellent.

[1010] For example, by comparing Examples A8 and A18, it is shown that if the number of particles contained per unit volume of the metal nanoparticle solution is 1.0×10 -2 ~1.0×10 6 Pieces / cm 3 range (Example A8), the defect suppression performance of the drug solution after long-term storage is more excellent.

[1011] For example, a comparison between Examples A8 and A19 shows that when the content of metal ions is within the range of 0.01 to 100 ppt by mass relative to the total mass of the chemical solution (Example A8), the defect suppression performance of the chemical solution after long-term storage is also excellent.

[1012] As shown in Table 2, when at least one of the acid content relative to the total mass of the chemical solution and the metal content relative to the total mass of the chemical solution is outside the above range, the defect suppression performance of the chemical solution after long-term storage is poor (comparative example).

[1013] In addition, as an evaluation method for defect performance other than the above, the defect performance was evaluated by the methods described in the following documents (1) and (2). It can be seen that the evaluation results of the defect performance of the embodiments and comparative examples all show the same tendency as the above-mentioned defect performance.

[1014] Literature (1) Journal of photopolymer science and technology, Vol28, No.1 (2015) 17-24 (Renesus)

[1015] Document (2) "Development of Novel Purifiers with Approproate FunctionalGroups Based on Solvent Polarities at Bulk Filtration" Enteglis News letter (May 2017)

[1016] [Example X1]

[1017] As the chemical solution X of the developer, the chemical solution B1 described above was prepared.

[1018] In addition, butyl butyrate was prepared as the rinse liquid chemical solution Y. Here, butyl butyrate used as the chemical solution Y was not subjected to the above-mentioned filtration process, etc., but was used as purchased.

[1019] In addition, the organic solvent used as the chemical solution Y used in the following examples and comparative examples was not subjected to the above-mentioned filtration treatment and the like, but was used as purchased.

[1020] [Examples X2 to X16]

[1021] Chemical solution X and chemical solution Y were prepared in the same manner as in Example X1 so as to have the combination shown in Table 3, except that an organic solvent shown in the column of Chemical solution Y in Table 3 was used as Chemical solution Y (rinsing solution).

[1022] [Example X17]

[1023] As the chemical solution Y (rinsing solution), a mixed solvent A1 of butyl butyrate and undecane (butyl butyrate:undecane=1:1 (based on mass)) was prepared.

[1024] In the same manner as in Example X1, chemical solution X and chemical solution Y were prepared in the combination shown in Table 3.

[1025] [Example X18]

[1026] As the chemical solution X of the developer, the chemical solution B2 described above was prepared.

[1027] As the chemical solution Y (rinsing solution), a mixed solvent B1 of butyl butyrate and methanol (butyl butyrate:methanol=1:1 (mass basis)) was prepared.

[1028] [Example X19]

[1029] As the chemical solution Y (rinsing solution), a mixed solvent A2 of butyl butyrate and undecane (butyl butyrate:undecane=9:1 (mass basis)) was prepared.

[1030] In the same manner as in Example X1, chemical solution X and chemical solution Y were prepared in the combination shown in Table 3.

[1031] [Example X20]

[1032] As the chemical solution Y (rinsing solution), a mixed solvent B2 of butyl butyrate and methanol (butyl butyrate:methanol=9:1 (mass basis)) was prepared.

[1033] In the same manner as in Example X1, chemical solution X and chemical solution Y were prepared in the combination shown in Table 3.

[1034] [Examples X21 to X26]

[1035] Chemical solution X and chemical solution Y were prepared in the same manner as in Example X1 to have the combination shown in Table 3, except that an organic solvent shown in Table 3 was used as chemical solution Y (rinsing solution).

[1036] However, in Example X26, the chemical solution Y (rinsing solution) was not used.

[1037] [Comparative Examples NX1 to NX16]

[1038] The chemical solution NB1 described above was used as the chemical solution X (developer), and the organic solvents shown in Table 3 were used as the chemical solution Y (rinsing solution). The chemical solutions X and Y were prepared so as to have the combination shown in Table 3.

[1039] [Comparative Examples NX17 to NX20]

[1040] Chemical solution X and chemical solution Y were prepared in the same manner as in Comparative Example NX1 so as to have the combination shown in Table 3, except that the above-mentioned mixed solvent A1, A2, B1, or B2 was used as chemical solution Y (rinsing solution).

[1041] [Comparative Examples NX21 to NX26]

[1042] Chemical solution X and chemical solution Y were prepared in the same manner as in Example NX1 so as to have the combination shown in Table 3, except that an organic solvent shown in Table 3 was used as chemical solution Y (rinsing solution).

[1043] However, in Comparative Example NX26, the chemical solution Y (rinsing solution) was not used.

[1044] [Evaluation of defect suppression performance]

[1045] The defect suppression performance of Examples X1 to X26 and Comparative Examples NX1 to NX26 was evaluated in the same manner as the above-mentioned defect suppression performance evaluation except that PGMEA was used as the pre-wetting liquid, and the developer and rinse liquid in the combination of Table 3 were used, and the exposure conditions of the resist film and the cleaning conditions by the rinse liquid were changed as follows. The evaluation criteria were also the same as those for the above-mentioned defect suppression performance evaluation.

[1046] In addition, PEGMEA used as a pre-wetting liquid was used as purchased without being subjected to the above-mentioned filtration treatment and the like.

[1047] The defect suppression performance was evaluated for the case where a chemical solution X (developer) was stored in a chemical solution container (material of the liquid contact portion: high-density polyethylene (HDPE) resin) at 40°C for 45 days (indicated as "time" in the table). In addition, the pre-wetting solution and chemical solution Y (rinsing solution) were not stored but used immediately after preparation or immediately after opening a commercial product.

[1048] (Exposure Conditions of Resist Film)

[1049] The wafer with the resist film was exposed to EUV at NA (Numerical Aperture) 0.25 and dipole illumination (Dipole 60x, outer sigma 0.81, inner sigma 0.43). Specifically, EUV exposure was performed through a mask containing a pattern for forming a line and space pattern with a pitch of 40nm and a width of 20nm on the wafer, and the exposure amount was changed. After irradiation, it was taken out from the EUV exposure device and immediately baked (PEB) at 90°C for 60 seconds.

[1050] (Cleaning conditions)

[1051] The developer was rinsed by spraying a solution Y (23° C.) at a flow rate of 200 mL / min for 15 seconds while rotating the developer at 50 rpm. R seconds to dry the wafer.

[1052] [Analysis (pattern collapse performance)]

[1053] A scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) was used to observe the analysis of line and space patterns exposed at different exposure amounts at a magnification of 200k, and the minimum line width without pattern collapse in an observed field of view was obtained, which was set as an indicator of pattern collapse. The smaller the value, the better the pattern collapse performance. The minimum line width obtained was evaluated by the following evaluation criteria. In addition, the pattern collapse performance was evaluated for the pattern formed using a mask for dense pattern formation.

[1054] (Evaluation Criteria)

[1055] "A": minimum line width is less than 16nm

[1056] "B": minimum line width is more than 16nm and less than 18nm

[1057] "C": minimum line width is more than 18nm and less than 20nm

[1058] "D": minimum line width is more than 20nm and less than 22nm

[1059] "E": minimum line width exceeds 22nm

[1060] [Comprehensive evaluation]

[1061] For Examples X1 to X26 and Comparative Examples NX1 to NX26, the evaluation results of defect suppression performance were converted from 5 points to 0 points in this order of evaluation criteria A to F. Also, the evaluation results of analytic performance were converted from 4 points to 0 points in this order of evaluation criteria A to E.

[1062] Then, comprehensive evaluation was performed based on the total points of defect suppression performance and analytical performance according to the following criteria.

[1063] S: Total points is 9 points

[1064] A: The total points are 8 points

[1065] B: Total points: 6 to 7 points

[1066] C: Total points are less than 5 points

[1067] In addition, from a practical point of view, a rating of "B" or higher is preferred.

[1068] The evaluation results are shown in Table 3. In the chemical solution Y, the numerical values ​​in parentheses in the organic solvent contained in the mixed solution represent the distance between the organic solvent and the Hansen solubility parameter of eicosene [unit: MPa 0.5 ].

[1069] [Table 5]

[1070]

[1071] [Table 6]

[1072]

[1073] As shown in Table 3 (Part 1), when the chemical solution of the present invention was used in either the chemical solution or the rinse solution, excellent defect suppression performance was demonstrated (Examples X1 to X26).

[1074] In particular, the case where the chemical solution of the present invention is used as the chemical solution X (developer) and the above-mentioned organic solvent Y1 is used as the chemical solution Y (rinsing solution) (Examples X1 to X16) is compared with the case where an organic solvent other than the organic solvent Y1 is used as the chemical solution Y (rinsing solution) (Examples X21 to X26). It can be seen that the overall evaluation is high and the defect suppression performance and the analysis performance can be compatible at a high level.

[1075] Furthermore, from the comparison between Examples X17 and X18 and Examples X19 and X20, if the organic solvent Y1 (with respect to the distance of the Hansen solubility parameter of eicosene from 3 to 20 MPa) 0.5 The content of the organic solvent) relative to the total mass of the drug solution Y is 20 to 80 mass % (Examples X17 and X18), which indicates that the comprehensive evaluation is more excellent.

[1076] On the other hand, as shown in Table 3 (Part 2), when the chemical solution of the present invention was not used for both the chemical solution and the rinse solution, at least the defect suppression performance was insufficient and the overall evaluation was poor (Comparative Examples NX1 to NX26).

Claims

1. A liquid medicine comprising an organic solvent, an acid component and a metal component, The organic solvent is selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, methyl methoxypropionate, cyclopentanone, cyclohexanone, γ-butyrolactone, diisoamyl ether, butyl acetate, isoamyl acetate, isopropanol, 4-methyl-2-pentanol, dimethyl sulfoxide, n-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate, cyclopentanone, 1-hexanol, 2-heptanone, butyl butyrate, isobutyl isobutyrate, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, undecane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate, and dimethyl oxalate. The content of the acid component is 1 mass ppt or more and 15 mass ppm or less relative to the total mass of the chemical solution, The content of the metal component is 0.001 mass ppt to 100 mass ppt relative to the total mass of the liquid medicine. The mass ratio of the acid component content to the metal component content is 10 -2 ~10 6 , The acid component comprises an organic acid and / or an inorganic acid, The organic acid is selected from the group consisting of formic acid, acetic acid, propionic acid, n-butyric acid, valeric acid, lactic acid, adipic acid, maleic acid, fumaric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, phthalic acid, malic acid, tartaric acid, citric acid, hydroxyethyliminodiacetic acid, and iminodiacetic acid. The inorganic acid is selected from boric acid, nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid. The metal component comprises metal-containing particles containing metal atoms, The content of the metal-containing particles is 0.00001 mass ppt to 10 mass ppt relative to the total mass of the liquid medicine. The metal-containing particles contain metal nanoparticles with a particle size of 0.5 nm to 17 nm, and the number of particles contained per unit volume of the drug solution is 1.0×10 -2 Pieces / cm 3 ~1.0×10 6 Pieces / cm 3 .

2. The liquid medicine according to claim 1, wherein The acid component comprises an organic acid, The content of the organic acid is 1 ppm by mass or less relative to the total mass of the chemical solution.

3. The liquid medicine according to claim 2, wherein: In the organic acid, a content of the organic acid having a temperature equal to or higher than the boiling point of the organic solvent is 20% by mass or less relative to the total mass of the organic acid.

4. The liquid medicine according to claim 1 or 2, wherein: The acid component comprises an inorganic acid, The content of the inorganic acid is 1 ppb by mass or less relative to the total mass of the chemical solution.

5. The liquid medicine according to claim 1 or 2, wherein: The metal component comprises metal ions, The content of the metal ions is 0.01 to 100 ppt by mass relative to the total mass of the drug solution.

6. The liquid medicine according to claim 1 or 2, wherein: The metal component comprises metal particles and metal ions. The mass ratio of the content of the metal-containing particles to the content of the metal ions is 0.00001 to 1.

7. The liquid medicine according to claim 1 or 2, further comprising water, The water content is 1 ppm by mass or less relative to the total mass of the chemical solution.

8. The drug solution according to claim 1, further comprising at least one organic compound selected from the group consisting of a compound having an amide structure, a compound having a sulfonamide structure, a compound having a phosphoamide structure, a compound having an imide structure, a compound having a urea structure, a compound having a carbamate structure, and an organic acid ester, The content of the organic compound is 1 ppm by mass or less relative to the total mass of the chemical solution.

9. The liquid medicine according to claim 8, wherein The organic compound is an organic compound having a boiling point of 300° C. or higher.

10. The liquid medicine according to claim 8, wherein The organic acid ester includes at least one selected from the group consisting of phthalic acid esters and citrate esters.

11. The liquid medicine according to claim 1 or 2, wherein: In the organic solvent, a content of an organic solvent having a boiling point of 250° C. or lower is 90% by mass or more relative to the total mass of the organic solvent.

12. The liquid medicine according to claim 1 or 2, wherein: The organic solvent has an SP value of 21 or less.

13. The liquid medicine according to claim 1 or 2, wherein: The organic solvent has an ester structure.

14. The liquid medicine according to claim 1, wherein The organic solvent contains butyl acetate, and the acid component contains acetic acid, The content of the acetic acid is 0.01 ppm by mass to 15 ppm by mass relative to the total mass of the chemical solution.

15. The liquid medicine according to claim 1 or 2, wherein: The organic solvent contains butyl acetate, and the acid component contains n-butyric acid, The content of the n-butyric acid is 1 mass ppt or more and 1 mass ppm or less relative to the total mass of the chemical solution.

16. A kit comprising: Liquid medicine X, which is the liquid medicine according to claim 14 or 15; and Liquid Y, which is a liquid containing an organic solvent, The organic solvent contained in the drug solution Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, undecane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

17. The kit according to claim 16, wherein The chemical solution X is a developer, and the chemical solution Y is a rinser.

18. The kit according to claim 16, wherein The organic solvent Y comprises a distance of 3 MPa relative to the Hansen solubility parameter of eicosene. 0.5 ~20MPa 0.5 The organic solvent Y1, The content of the organic solvent Y1 relative to the total mass of the chemical solution Y is 20 mass % to 80 mass %.

19. A pattern forming method, comprising: a resist film forming step of forming a resist film using an actinic ray-sensitive or radiation-sensitive resin composition; An exposure step of exposing the resist film to light; A developing step of developing the exposed resist film using a chemical solution X; and A rinsing step, after the development step, is performed using a chemical solution Y containing an organic solvent. The drug solution X is the drug solution according to claim 14 or 15, The organic solvent contained in the drug solution Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isoamyl propionate, ethylcyclohexane, mesitylene, decane, undecane, 3,7-dimethyl-3-octanol, 2-ethyl-1-hexanol, 1-octanol, 2-octanol, ethyl acetoacetate, dimethyl malonate, methyl pyruvate and dimethyl oxalate.

20. The pattern forming method according to claim 19, wherein: The organic solvent Y comprises a distance of 3 MPa relative to the Hansen solubility parameter of eicosene. 0.5 ~20MPa 0.5 The organic solvent Y1, The content of the organic solvent Y1 relative to the total mass of the chemical solution Y is 20 mass % to 80 mass %.

21. A method for producing a liquid medicine, wherein: Purifying a substance to be purified containing an organic solvent to obtain the drug solution according to any one of claims 1 to 15, The method includes a filtration step of filtering the object to be purified, an ion removal step of adsorbing ions on the object to be purified by an ion exchange method or a chelating group, and a distillation step of distilling the object to be purified.

22. The method for producing a drug solution according to claim 21, wherein: In the ion exchange method, a cation exchange resin is used.

23. The method for producing a drug solution according to claim 21, wherein: In the ion exchange method, a cation exchange resin and an anion exchange resin are used.

24. A drug solution container, comprising a container and the drug solution according to any one of claims 1 to 15 contained in the container, At least a portion of the liquid contact portion of the container is made of a corrosion-resistant material or glass, and the corrosion-resistant material is at least one selected from the group consisting of a non-metallic material and an electrolytically ground metal material.

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