Liquid medicine, kit, pattern forming method, method for producing liquid medicine, and liquid medicine container

Abstract

The present invention addresses the problem of providing a chemical solution having excellent defect suppression performance even after long-term storage, a kit, a pattern forming method, a method for producing a chemical solution, and a chemical solution container. This chemical solution contains an organic solvent, an acid component, and a metal component, the content of the acid component being 1-15 ppm by mass (inclusive) relative to the total mass of the chemical solution, and the content of the metal component being 0.001-100 ppm by mass (inclusive) relative to the total mass of the chemical solution.

Description

[0001] This application is a divisional application of the application with the application number 201980046230.2 and the invention title "Liquid Medicine, Kit, Pattern Forming Method, Method for Manufacturing Liquid Medicine, and Liquid Medicine Container", which was filed by the applicant. The filing date of the parent case of this application is July 10, 2019, and the priority date is July 13, 2018. Technical Field

[0002] The present invention relates to a liquid medicine, a kit, a pattern forming method, a method for manufacturing a liquid medicine, and a liquid medicine container. Background Art

[0003] When manufacturing semiconductor devices through a wiring formation process including lithography, a liquid medicine containing water and / or an organic solvent is used as a pre-wetting liquid, a resist liquid, a developing liquid, a rinsing liquid, a stripping liquid, a chemical mechanical polishing (CMP) slurry, and a cleaning liquid after CMP.

[0004] Various impurities contained in the liquid medicine may cause defects in semiconductor devices. Such defects may cause a reduction in the manufacturing yield of semiconductor devices and electrical abnormalities such as short circuits.

[0005] For example, Patent Document 1 discloses a method for obtaining an ester-based solvent with reduced acid components and alkali metal content by designing a distillation method, etc. And in Patent Document 2, a method for manufacturing butyl acetate with reduced sulfuric acid content by treatment such as distillation and an anion exchange resin is disclosed.

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 2015-030700

[0009] Patent Document 2: Japanese Patent Laid-Open No. 2002-316967 Summary of the Invention

[0010] Technical Problem to be Solved by the Invention

[0011] After the liquid medicine is manufactured and stored in a container, and stored in the form of a liquid medicine container for a certain period, the stored liquid medicine is taken out and used.

[0012] The present inventor manufactured a liquid medicine by referring to the methods described in Patent Documents 1 and 2, and after storing the solution in the form of a liquid medicine container in a container for a long time, taking out the liquid medicine from the liquid medicine container and applying it to the manufacturing process of semiconductor devices, it was clearly found that defects may occur on the substrate (such as a wafer).

[0013] Therefore, an object of the present invention is to provide a liquid chemical, a kit, a pattern forming method, a method for manufacturing a liquid chemical, and a liquid chemical container having excellent defect suppression performance even after long-term storage.

[0014] Means for Solving the Technical Problem

[0015] As a result of intensive studies on the above problems, the present inventors have found that a liquid chemical having excellent defect suppression performance even after long-term storage can be obtained by using a liquid chemical in which the mass ratio of the content of an acid component to the content of a metal component is within a specified range, the content of the acid component is within a specified range with respect to the total mass of the liquid chemical, and the content of the metal component is within a specified range with respect to the total mass of the liquid chemical, thereby completing the present invention.

[0016] That is, the present inventors have found that the above problems can be solved by the following configuration. [1]

[0018] A liquid chemical containing an organic solvent, an acid component, and a metal component,

[0019] With respect to the total mass of the above liquid chemical, the content of the above acid component is 1 mass ppt or more and 15 mass ppm or less,

[0020] With respect to the total mass of the above liquid chemical, the content of the above metal component is 0.001 to 100 mass ppt. [2]

[0022] The liquid chemical according to [1], wherein

[0023] The mass ratio of the content of the above acid component to the content of the above metal component is 10 -2 to 10 6 . [3]

[0025] The liquid chemical according to [1] or [2], wherein

[0026] The above acid component contains an organic acid,

[0027] With respect to the total mass of the above liquid chemical, the content of the above organic acid is 1 mass ppm or less. [4]

[0029] The liquid chemical according to [3], wherein

[0030] In the above organic acid, the content of the organic acid having a boiling point equal to or higher than that of the above organic solvent is 20 mass% or less with respect to the total mass of the above organic acid. [5]

[0032] The liquid chemical according to any one of [1] to [4], wherein

[0033] The above acid component contains inorganic acid,

[0034] With respect to the total mass of the above liquid medicine, the content of the above inorganic acid is 1 mass ppb or less. [6]

[0036] The liquid medicine according to any one of [1] to [5], wherein,

[0037] The above metal component contains metal-containing particles containing metal atoms,

[0038] With respect to the total mass of the above liquid medicine, the content of the above metal-containing particles is 0.00001 to 10 mass ppt. [7]

[0040] The liquid medicine according to [6], wherein,

[0041] Among the above metal-containing particles, the number of particles contained per unit volume of the above liquid medicine of metal nanoparticles with a particle size of 0.5 to 17 nm is 1.0×10 -2 ~1.0×10 6 pieces / cm 3 . [8]

[0043] The liquid medicine according to any one of [1] to [7], wherein,

[0044] The above metal component contains metal ions,

[0045] With respect to the total mass of the above liquid medicine, the content of the above metal ions is 0.01 to 100 mass ppt. [9]

[0047] The liquid medicine according to any one of [1] to [8], wherein,

[0048] The above metal component contains metal-containing particles and metal ions,

[0049] The mass ratio of the content of the above metal-containing particles to the content of the above metal ions is 0.00001 to 1.

[10]

[0051] The liquid medicine according to any one of [1] to [9], which further contains water,

[0052] With respect to the total mass of the above liquid medicine, the content of the above water is 1 mass ppm or less.

[11]

[0054] The liquid medicine according to any one of [1] to

[10] further 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 phosphonamide structure, a compound having an imide structure, a compound having a urea structure, a compound having a carbamate structure, and an organic acid ester.

[0055] The content of the above organic compound is 1 mass ppm or less based on the total mass of the above liquid medicine.

[12]

[0057] The liquid medicine according to

[11] , wherein

[0058] The above organic compound is an organic compound having a boiling point of 300 °C or higher.

[13]

[0060] The liquid medicine according to

[11] or

[12] , wherein

[0061] The above organic acid ester contains at least one selected from the group consisting of phthalate and citrate.

[14]

[0063] The liquid medicine according to any one of [1] to

[13] , wherein

[0064] In the above organic solvent, the content of the organic solvent having a boiling point of 250 °C or lower is 90 mass% or more based on the total mass of the above organic solvent.

[15]

[0066] The liquid medicine according to any one of [1] to

[14] , wherein

[0067] The SP value of the above organic solvent is 21 or less.

[16]

[0069] The liquid medicine according to any one of [1] to

[15] , wherein

[0070] The above organic solvent has an ester structure.

[17]

[0072] The liquid medicine according to any one of [1] to

[16] , wherein

[0073] The above organic solvent contains butyl acetate, and the above acid component contains acetic acid.

[0074] The content of the above acetic acid is 0.01 to 15 mass ppm based on the total mass of the above liquid medicine.

[18]

[0076] The liquid medicine according to any one of [1] to

[17] , wherein

[0077] The above organic solvent contains butyl acetate, and the above acid component contains n-butyric acid.

[0078] The content of the above n-butyric acid is 1 mass ppt or more and 1 mass ppm or less relative to the total mass of the above liquid medicine.

[19]

[0080] A kit, comprising:

[0081] Liquid medicine X, which is the liquid medicine described in

[17] or

[18] ; and

[0082] Liquid medicine Y, which is a liquid medicine containing an organic solvent, wherein

[0083] The above organic solvent contained in the above liquid medicine Y contains at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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]

[0085] The kit according to

[20] , wherein

[0086] The above liquid medicine X is a developer, and the above liquid medicine Y is a rinsing liquid.

[21]

[0088] The pattern forming method according to

[19] or

[20] , wherein

[0089] The above organic solvent Y contains an organic solvent Y1 having a distance of 3 to 20 MPa from the Hansen solubility parameter of icosene 0.5 ;

[0090] The content of the above organic solvent Y1 is 20 to 80 mass% relative to the total mass of the above liquid medicine Y.

[22]

[0092] A pattern forming method, comprising:

[0093] A resist film forming step of forming a resist film using a photosensitive or radiation-sensitive resin composition;

[0094] An exposure step of exposing the above resist film;

[0095] A development step of developing the exposed resist film using the liquid medicine X of the liquid medicine described in

[17] or

[18] ; and

[0096] Rinsing step: After the above-described developing step, cleaning is performed using a liquid medicine Y containing an organic solvent.

[0097] The above-mentioned organic solvent contained in the liquid medicine Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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.

[23]

[0099] The pattern forming method as described in

[22] , wherein

[0100] The above-mentioned organic solvent Y includes an organic solvent Y1 having a distance of 3 to 20 MPa from the Hansen solubility parameter of eicosene. 0.5 of the organic solvent Y1.

[0101] The content of the above-mentioned organic solvent Y1 is 20 to 80% by mass based on the total mass of the above-mentioned liquid medicine Y.

[24]

[0103] A method for manufacturing a liquid medicine, wherein

[0104] The purified product containing an organic solvent is purified to obtain the liquid medicine described in any one of [1] to

[18] .

[0105] This method includes a filtration step of filtering the above-mentioned purified product, an ion removal step of performing ion adsorption on the above-mentioned purified product by an ion exchange method or a chelating group, and a distillation step of distilling the above-mentioned purified product.

[25]

[0107] The method for manufacturing a liquid medicine as described in

[24] , wherein

[0108] A cation exchange resin is used in the above-mentioned ion exchange method.

[26]

[0110] The method for manufacturing a liquid medicine as described in

[24] , wherein

[0111] A cation exchange resin and an anion exchange resin are used in the above-mentioned ion exchange method.

[27]

[0113] A liquid medicine container, which has a container and the liquid medicine described in any one of [1] to

[18] contained in the above-mentioned container.

[0114] Advantages of the invention

[0115] As described below, by the present invention, it is possible to provide a liquid chemical, a method for manufacturing the liquid chemical, and a liquid chemical container, which have excellent defect suppression performance even after long-term storage. Detailed Embodiments

[0116] Hereinafter, the present invention will be described.

[0117] The description of the constituent elements described below is sometimes based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0118] In addition, in this specification, the numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value.

[0119] Moreover, in the present invention, "ppm" means "parts-per-million (10 -6 ) : parts per million", "ppb" means "parts-per-billion (10 -9 ) : parts per billion", "ppt" means "parts-per-trillion (10 -12 ) : parts per trillion", "ppq" means "parts-per-quadrillion (10 -15 ) : parts per quadrillion".

[0120] Moreover, in the notation of a group (atomic group) in the present invention, the notation of unsubstituted and substituted includes groups having no substituent and groups having a substituent within the range not impairing the effects of the present invention. For example, "hydrocarbyl" includes not only a hydrocarbyl having no substituent (unsubstituted hydrocarbyl), but also a hydrocarbyl having a substituent (substituted hydrocarbyl). Regarding this content, the same applies to each compound.

[0121] Moreover, the "radiation" in the present invention means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV; Extreme ultraviolet), X-rays, or electron beams. And the light in the present invention means actinic rays or radiation. The "exposure" in the present invention includes, unless otherwise specified, not only exposure using far ultraviolet rays, X-rays, EUV, etc., but also drawing using particle beams such as electron beams or ion beams.

[0122] Moreover, the "boiling point" in the present invention means the standard boiling point.

[0123] [Liquid Chemical]

[0124] The liquid chemical of the present invention (hereinafter, also referred to as "the present liquid chemical".) is a liquid chemical containing an organic solvent, an acid component, and a metal component.

[0125] Moreover, in this liquid medicine, the content of the above acid component is 1 mass ppt or more and 15 mass ppm or less with respect to the total mass of this liquid medicine.

[0126] Moreover, in this liquid medicine, the content of the above metal component is 0.001 to 100 mass ppt with respect to the total mass of this liquid medicine.

[0127] Although the mechanism for solving the above problems by this liquid medicine is not necessarily clear, the present inventors speculate on the mechanism as follows. In addition, the following mechanism is a speculation and is included in the scope of the present invention even when the effects of the present invention are obtained by a different mechanism.

[0128] The metal components contained in the liquid medicine tend to exist as metal ions in ionic form and metal-containing particles in particle form.

[0129] When metal ions form a complex with the acid component (especially, organic acid) in the liquid medicine and / or when 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 components, the interaction between the complex or the composite structure and the surface of the substrate (e.g., wafer) tends to increase. As a result, in the complex and the composite structure, the one attached to the surface of the substrate is more stabilized compared to solvation in the liquid medicine. Therefore, there is a problem that it is likely to exist as a residue on the surface of the wafer after using the liquid medicine for wafer processing.

[0130] Moreover, there is the following problem: when the above complex and composite structure remain on the surface of the wafer, during dry etching of the wafer, the above complex and composite structure act as an etching mask and remain on the surface of the wafer in an enlarged state as a tapered defect (conical defect) after dry etching.

[0131] 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 coating the liquid medicine on the wafer. However, with the improvement of the accuracy of defect inspection in recent years, defects that were not detected by the conventional methods can be detected in an enlarged form as tapered defects. That is, there is a problem that minute-sized attachments that were not detected previously are detected as defects.

[0132] It is considered that the above problems are particularly significant when storing the liquid medicine in a container. For example, when storing the liquid medicine in a container for a long time, it may be due to the situation where the acid components (especially organic acids) in the liquid medicine slightly penetrate into the resin components that make up the liquid contact surface of the container, the situation where the acid components (especially organic acids) in the liquid medicine enter the minute gaps of the resin components, or the interaction between the metal components contained inside the resin components during the manufacturing process of the resin components and the acid components (especially organic acids) in the liquid medicine, or a combination of these, that the metal components dissolve in the liquid medicine. That is, it is considered that when storing the liquid medicine in a container for a long time, the metal components present on the liquid contact surface of the container dissolve in the liquid medicine, and it is easy to detect defects.

[0133] Regarding such problems, it is speculated that by setting the content of the acid components and metal components relative to the liquid medicine below the above upper limit values, even when storing the liquid medicine container for a long time, the formation of complexes and composite structures can be suppressed. As a result, it is considered that the defect suppression performance of the liquid medicine during long-term storage becomes excellent.

[0134] Furthermore, the present inventors have found that if the content of the acid components in the liquid medicine is less than the above lower limit value, the defect suppression performance of the liquid medicine during long-term storage of the liquid medicine decreases. The detailed content of this reason is not yet clear, but it can be speculated for the following reasons.

[0135] The liquid medicine may contain trace amounts of basic impurities. Examples of basic impurities include amine components transferred from the environment (so-called contamination), decomposition products of plasticizers, and impurities during the synthesis of the resin of the container that constitutes the liquid medicine container.

[0136] If the liquid medicine contains trace amounts of basic impurities, together with the trace amounts of moisture present in the liquid medicine, a decomposition reaction of the resin components that make up the liquid contact surface of the container for the liquid medicine is carried out little by little. Due to the deterioration of the liquid contact surface caused by the decomposition of the resin components, decomposition products of the resin components and metal components contained inside the resin components during the manufacturing process of the resin components, etc., dissolve in the liquid medicine, and this accumulates over time in the liquid medicine, so it is easy to detect defects when storing the liquid medicine in the container for a long time.

[0137] Regarding such problems, it is assumed that if the content of the acid components in the liquid medicine is above the above lower limit value, the decomposition reaction of the materials that make up the liquid contact surface of the container caused by basic impurities can be suppressed. Thereby, it is presumed that the generation of defects when storing the liquid medicine in the container for a long time can be suppressed.

[0138] 〔Organic solvent〕

[0139] This liquid medicine contains an organic solvent. There is no particular limitation on the content of the organic solvent in this liquid medicine. Generally, relative to the total mass of this liquid medicine, 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. There is no particular limitation on the upper limit, and it is generally less than 100% by mass.

[0140] One kind of organic solvent can be used alone, or two or more kinds can be used simultaneously. When two or more kinds of organic solvents are used simultaneously, the total content is within the above range.

[0141] In addition, in this specification, an organic solvent refers to a liquid organic compound containing each component in an amount exceeding 10,000 mass ppm relative to the total mass of this liquid medicine. That is, in this specification, a liquid organic compound containing an amount exceeding 10,000 mass ppm relative to the total mass of this liquid medicine belongs to an organic solvent.

[0142] In addition, in this specification, "liquid" means being a liquid at 25°C and atmospheric pressure.

[0143] There is no particular limitation on the type of organic solvent, and known organic solvents can be used. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, carboxylate (preferably alkyl acetate, alkyl lactate), alkoxypropionic acid alkyl ester, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkoxyacetic acid alkyl ester, and pyruvic acid alkyl ester, etc.

[0144] Moreover, as the organic solvent, for example, the organic solvents described in JP-A-2016-057614, JP-A-2014-219664, JP-A-2016-138219, and JP-A-2015-135379 can also be used.

[0145] As the organic solvent, at least one selected from the group consisting of 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, diisopentyl ether, n-butyl acetate (nBA), isoamyl acetate (iAA), isopropyl alcohol, 4-methyl-2-pentanol (MIBC), dimethyl sulfoxide, N-methyl-2-pyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, propylene carbonate (PC), sulfolane, cycloheptanone, 1-hexanol, decane, 2-heptanone, butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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 is preferred.

[0146] In addition, the organic solvent may be used alone or two or more thereof may be used simultaneously.

[0147] In addition, the type and content of the organic solvent in the liquid medicine can be measured using a gas chromatograph-mass spectrometer.

[0148] From the viewpoint of further exerting the effects of the present invention (specifically, excellent defect suppression performance even after long-term storage. The same applies hereinafter), it is preferred that the organic solvent has an ester structure. As the organic solvent having an ester structure, aliphatic carboxylic acid alkyl esters, alicyclic carboxylic acid alkyl esters, and substituted aliphatic carboxylic acid alkyl esters (that is, aliphatic carboxylic acid alkyl esters having a substituent in the aliphatic part) can be cited, and the alkyl in the alkyl ester part may have a substituent. As the substituent, hydroxyl group, ether bond, thiol group, sulfur bond, amino group, ester bond, aromatic group (for example, phenyl group), etc. can be cited. And the alkyl in the alkyl ester part may be linear, branched, or may form one or more rings.

[0149] As specific examples of the organic solvent having an ester structure, alkylene glycol monoalkyl ether carboxylates, alkyl acetates, alkyl lactates, alkoxypropionic acid alkyl esters, and cyclic lactones can be cited. From the viewpoint of further exerting the effects of the present invention, at least one selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), ethyl lactate (EL), n-butyl acetate (nBA), and isoamyl acetate (iAA) is preferred.

[0150] 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.

[0151] In a system with a low SP value of an organic solvent (hydrophobic system), the following problems exist: Due to the reduced solvation effect in the organic solvent, the interaction between the acid component (especially organic acid) and the metal component becomes relatively high, and defects caused by the formation of complexes are likely to occur. To address this problem, if this liquid medicine with a reduced content of the acid component (especially organic acid) is used, the formation of complexes can be inhibited. Therefore, even when using an organic solvent with a low SP value, the effect of defect inhibition performance can be fully demonstrated.

[0152] From the perspective of further enhancing the effects of the present invention, the lower limit value of the SP value of the organic solvent is preferably 14.5 or more, more preferably 15.0 or more.

[0153] The SP value is obtained by calculation using the Fedors method described in "Properties of Polymers (Properties of Polymers), Second Edition, Published in 1976". In addition, unless otherwise specified, the unit of the SP value is MPa 1 / 2 。

[0154] From the perspective of further enhancing the effects of the present invention, in the organic solvent, the content of the organic solvent with a boiling point of 250 °C or lower is preferably 90% by mass or more based on the total mass of the organic solvent.

[0155] From the perspective of further enhancing the effects of the present invention, the content of the organic solvent with 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% based on the total mass of the organic solvent.

[0156] The boiling point of the organic solvent is preferably 250 °C or lower, more preferably 170 °C or lower.

[0157] Here, when the boiling point of the organic solvent is 170 °C or higher, the drying rate of the liquid medicine coated on the substrate decreases. However, before drying the liquid film by spin coating, the particles formed by the metal component, acid component, etc. fly out of the substrate together with the solvent and are easily removed. On the other hand, when the boiling point of the organic solvent is 170 °C or lower, there is a problem that particles are likely to remain on the substrate. To address this problem, if this liquid medicine is used, the formation of particles can be inhibited. Therefore, even when using an organic solvent with a low boiling point, the effect of defect inhibition performance can be fully demonstrated.

[0158] Therefore, even when using an organic solvent with a boiling point of 170 °C or lower and an SP value of 21 or lower as described above (for example, propylene glycol monomethyl ether acetate, butyl acetate, and isoamyl acetate), if this liquid medicine is used, the effect of defect inhibition performance can be fully exerted.

[0159] In addition, the lower limit of the boiling point of the organic solvent is not particularly limited, preferably 80 °C or higher, more preferably 90 °C or higher.

[0160] 〔Acid component〕

[0161] This liquid medicine contains an acid component.

[0162] The acid component can be intentionally added during the manufacturing process of the liquid medicine, can be originally contained in the purified substance, or can be transferred (so-called contamination) from the manufacturing equipment of the liquid medicine during the manufacturing process.

[0163] 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 this liquid medicine.

[0164] The content of the acid component is not particularly limited and can be appropriately set so that the pH is within the desired range.

[0165] The acid component can be used alone or two or more kinds can be used simultaneously. When two or more kinds of acid components are contained, the total content is within the above range.

[0166] The acid component is not particularly limited and examples include organic acids and inorganic acids. The acid component can ionize in the liquid medicine and exist as ions.

[0167] <Organic acid>

[0168] Examples of the organic acid include organic carboxylic acids, organic sulfonic acids, organic phosphoric acids, and organic phosphonic acids, etc., and organic carboxylic acids are preferred.

[0169] 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-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, iminodiacetic acid, etc.

[0170] Examples of the organic sulfonic acid include methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid, etc.

[0171] Examples of the organic phosphoric acid include mono- or dioctyl phosphoric acid, mono- or didocosyl phosphoric acid, mono- or dioctacosyl phosphoric acid, and mono- or bis(nonylphenyl) phosphoric acid, etc.

[0172] Examples of the organic phosphonic acid include 1-hydroxyethane-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and the like.

[0173] From the viewpoint of further suppressing the formation of a complex with a metal component, the pKa of the organic acid is preferably 5 or less, more preferably 4 or less.

[0174] From the viewpoint of further exerting the effects of the present invention, the lower limit value of the pKa of the organic acid is preferably -11 or more, more preferably -9 or more.

[0175] Here, pKa (acid dissociation constant) refers to the pKa in an aqueous solution. As described in, for example, "Kagaku Binran (II)" (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen.Inc.), the lower this value is, the stronger the acid strength. Specifically, the pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution, or can be calculated using the following Package 1 to obtain a value based on the Hammett substituent constant and a database of known literature values. All the pKa values described in this specification represent the values calculated using this package.

[0176] (Package 1) Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994 - 2007 ACD / Labs)

[0177] From the viewpoint of more excellent defect suppression performance, the boiling point of the organic acid is preferably 300°C or less, more preferably 250°C or less, and particularly preferably 200°C or less.

[0178] The lower limit value of the boiling point of the organic acid is not particularly limited, and is preferably 100°C or more, more preferably 110°C or more.

[0179] When the acid component contains an organic acid, from the viewpoint of more excellent defect suppression performance, the content of the organic acid is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less, and particularly preferably 0.1 mass ppm or less with respect to the total mass of this liquid medicine.

[0180] When the acid component contains an organic acid, from the viewpoint of further exerting the effects of the present invention, the lower limit value of the content of the organic acid is preferably 5 mass ppt or more, more preferably 10 mass ppt or more with respect to the total mass of this liquid medicine.

[0181] The organic acid can be used alone or two or more kinds can be used simultaneously. When two or more kinds of organic acids are contained, the total content is preferably within the above range.

[0182] From the viewpoint of more excellent defect suppression performance, the content of the organic acid above the boiling point of the organic solvent in the organic acid is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less, relative to the total mass of the organic acid.

[0183] From the viewpoint of further exerting the effects of the present invention, the lower limit of the content of the organic acid above the boiling point of the organic solvent is preferably 0% by mass or more, more preferably 0.01% by mass or more, relative to the total mass of the organic acid.

[0184] When the organic solvent contains butyl acetate, it is preferable that the acid component contains acetic acid. In this case, from the viewpoint of more excellent 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 this liquid medicine.

[0185] Moreover, when the organic solvent contains butyl acetate, it is preferable that the acid component 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 this liquid medicine.

[0186] When the organic solvent contains butyl acetate, from the viewpoint of more excellent defect suppression performance, it is preferable that the acid component contains both acetic acid and n-butyric acid. In this case, the preferable ranges of the contents of the respective components are as described above.

[0187] <Inorganic acid>

[0188] Examples of the inorganic acid include boric acid, nitric acid, hydrochloric acid, sulfuric acid, and phosphoric acid.

[0189] When the acid component contains an inorganic acid, from the viewpoint of more excellent defect suppression performance, the content of the inorganic acid is preferably 120 mass ppb or less, more preferably 1 mass ppb or less, and particularly preferably 0.6 mass ppb or less, relative to the total mass of this liquid medicine.

[0190] From the viewpoint of further exerting the effects of the present invention, the lower limit value of the content of the inorganic acid is preferably 0 mass ppb or more, more preferably 0.001 mass ppb or more, relative to the total mass of this liquid medicine.

[0191] 〔Metal component〕

[0192] This liquid medicine contains a metal component. Examples of the metal component include metal-containing particles and metal ions. For example, the so-called content of the metal component refers to the total content of the metal-containing particles and the metal ions.

[0193] Preferred embodiments of the method for manufacturing the liquid medicine will be described later. Generally, the liquid medicine can be manufactured by purifying a purified product containing the solvent and organic compound described above. A metal component can be intentionally added during the manufacturing process of the liquid medicine, can be originally contained in the purified product, or can be transferred (so-called contamination) from the manufacturing apparatus of the liquid medicine during the manufacturing process of the liquid medicine.

[0194] The content of the metal component is 0.001 to 100 mass ppt relative to the total mass of the liquid medicine. From the viewpoint of further exerting the effects of the present invention, 0.001 to 10 mass ppt is preferred, and 0.001 to 5 mass ppt is more preferred.

[0195] The content of the metal component can be measured by the ICP-MS method described later.

[0196] In the present liquid medicine, from the viewpoint of more excellent defect suppression performance, the mass ratio (acid component / metal component) of the content of the acid component to the content of the metal component is preferably 10 -2 ~10 6 ,more preferably 1 to 10 6 ,even more preferably 10 to 10 6 ,particularly preferably 10 2 ~10 6 ,most preferably 10 3 ~10 6 。

[0197] <Metal-containing particles>

[0198] The present liquid medicine may contain metal-containing particles containing metal atoms.

[0199] There is no particular limitation on the metal atom, and preferred examples include Pb (lead) atom, Na (sodium) atom, K (potassium) atom, Ca (calcium) atom, Fe (iron) atom, Cu (copper) atom, Mg (magnesium) atom, Mn (manganese) atom, Li (lithium) atom, Al (aluminum) atom, Cr (chromium) atom, Ni (nickel) atom, Ti (titanium) atom, Zn (zinc) atom, and Zr (zirconium) atom. Among them, Fe atom, Al atom, Cr atom, Ni atom, Pb atom, Zn atom, and Ti atom, etc.

[0200] In particular, if the content of metal-containing particles containing Fe atom, Al atom, Pb atom, Zn atom, and Ti atom in the liquid medicine is strictly controlled, it is easy to obtain more excellent defect suppression performance. If the content of metal-containing particles containing Pb atom and Ti atom in the liquid medicine is strictly controlled, it is easy to obtain further excellent defect suppression performance.

[0201] That is, as the metal atom, it is preferably at least one selected from the group consisting of Fe atom, Al atom, Cr atom, Ni atom, Pb atom, Zn atom, Ti atom, etc., more preferably at least one selected from the group consisting of Fe atom, Al atom, Pb atom, Zn atom, and Ti atom, further preferably at least one selected from the group consisting of Pb atom and Ti atom, and particularly preferably the metal-containing particles also contain any one of Pb atom and Ti atom.

[0202] In addition, the metal-containing particles may contain one of the above metal atoms alone, or may contain two or more at the same time.

[0203] There is no particular limitation on the particle diameter of the metal-containing particles. For example, in a liquid medicine for manufacturing semiconductor devices, the content of particles having a particle diameter of about 0.1 to 100 nm in the liquid medicine is usually the object to be controlled.

[0204] Among them, through the research of the present inventors, it is known that especially in a liquid medicine for a resist process applied to EUV (extreme ultraviolet) exposure, by controlling the content of metal-containing particles (hereinafter, also referred to as "metal nanoparticles") having a particle diameter of 0.5 to 17 nm in the liquid medicine, it is easy to obtain a liquid medicine having excellent defect suppression performance. In the resist process of EUV exposure, fine resist spacings, resist widths, and resist pitches are usually required. In this case, it is necessary to control finer particles that have not been a problem in the previous processes in terms of their number units.

[0205] There is no particular limitation on the particle size distribution of the metal-containing particles as a number basis. From the viewpoint of obtaining a liquid medicine with more excellent effects of the present invention, it is preferably to have a maximum value in at least one of the ranges consisting of a range with a particle size less than 5 nm and a range with a particle size greater than 17 nm.

[0206] In other words, it is preferably not to have a maximum value in the range of 5 to 17 nm in particle size. Since there is no maximum value in the range of 5 to 17 nm in particle size, the liquid medicine has more excellent defect suppression performance, especially more excellent bridge defect suppression performance. Here, a bridge defect refers to a cross-linked defect between wiring patterns.

[0207] And, from the viewpoint of obtaining a liquid medicine with further excellent effects of the present invention, in the particle size distribution based on the number, it is particularly preferably to have a maximum value in the range of 0.5 nm or more and less than 5 nm in particle size. Through the above, the liquid medicine has further excellent bridge defect suppression performance.

[0208] The content of the metal-containing 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 liquid medicine. If the content of the metal-containing particles is within the above range, a liquid medicine with excellent defect suppression performance (especially the defect suppression performance after long-term storage of the liquid medicine container) can be obtained.

[0209] The type and content of the metal-containing particles in the liquid medicine can be measured by the SP-ICP-MS method (Single NanoParticle Induetively Coupled Plasma Mass Spectrometry).

[0210] Here, the SP-ICP-MS method uses the same device as the ordinary ICP-MS method (Inductively Coupled Plasma Mass Spectrometry), except for the data analysis. The data analysis of the SP-ICP-MS method can be implemented by commercially available software.

[0211] 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.

[0212] On the other hand, in the SP-ICP-MS method, the content of the metal-containing particles can be measured. Therefore, if the content of the metal-containing particles is subtracted from the content of the metal component in the sample, the content of the metal ions in the sample can be calculated.

[0213] As the device for the SP-ICP-MS method, for example, Agilent8800 triple quadrupole ICP-MS (Inductively Coupled Plasma Mass Spectrometry for semiconductor analysis, option #200) manufactured by Agilent Technologies, Inc. can be cited, and the measurement can be carried out by the method described in the examples. As other devices other than the above, in addition to NexION350S manufactured by PerkinElmer Japan Co., Ltd., Agilent 8900 manufactured by Agilent Technologies, Inc. can also be used.

[0214] (Metal nanoparticles)

[0215] Metal nanoparticles refer to particles among the metal-containing particles with a particle size of 0.5 to 17 nm.

[0216] The number of metal nanoparticles per unit volume of the liquid medicine is preferably 1.0×10 -2 ~1.0×10 6 particles / cm 3 From the viewpoint of further exerting the effects of the present invention, it is preferably 1.0×10 -1 particles / cm 3 or more, more preferably 5.0×10 -1 particles / cm 3 or more, preferably 1.0×10 5 particles / cm 3 or less, more preferably 1.0×10 4 particles / cm 3 or less, and further preferably 1.0×10 3 particles / cm 3 or less.

[0217] In particular, if the number of metal nanoparticles per unit volume of the liquid medicine is 5.0×10 -1 ~1.0×10 3 particles / cm 3 , the liquid medicine has more excellent defect suppression performance.

[0218] In addition, the content of metal nanoparticles in the liquid medicine can be measured by the method described in the examples, and the number of particles (pieces) per unit volume of the liquid medicine of metal nanoparticles is obtained by rounding off so that the significant figures become two digits.

[0219] There is no particular limitation on the metal atoms contained in the metal nanoparticles. As the metal atoms contained in the metal-containing particles, they are the same as the atoms described above. Among them, from the viewpoint of obtaining a liquid medicine with more excellent effects of the present invention, as the metal atoms, at least one selected from the group consisting of Pb atoms and Ti atoms is preferred, and more preferably the metal nanoparticles contain both Pb atoms and Ti atoms. When the metal nanoparticles contain both Pb atoms and Ti atoms, typically, a mode in which the liquid medicine contains both metal nanoparticles containing Pb atoms and metal nanoparticles containing Ti atoms can be cited.

[0220] In addition, there is no particular limitation on the particle number ratio (Pb / Ti) of the metal nanoparticles containing Pb atoms (hereinafter, also referred to as "Pb nanoparticles") and the metal nanoparticles containing Ti atoms (hereinafter, also referred to as "Ti nanoparticles") in the liquid medicine. Generally, it is preferably 1.0×10 -4 ~3.0, more preferably 1.0×10 -3 ~2.0, and particularly preferably 1.0×10 -2 ~1.5. If Pb / Ti is 1.0×10 -3~2.0, the liquid chemical has more excellent effects of the present invention, especially more excellent performance in suppressing bridge defects.

[0221] The present inventors have found that Pb nanoparticles and Ti nanoparticles are liable to associate with each other, for example, when the liquid chemical is coated on a wafer, and are liable to cause defects (especially the cause of bridge defects) during the development of the resist film.

[0222] If Pb / Ti is 1.0×10 -3 ~2.0, surprisingly, the generation of defects can be more easily suppressed. In addition, in this specification, Pb / Ti and A / (B + C) described later are obtained by rounding off so that the significant figures become two digits.

[0223] The metal nanoparticles only need to contain metal atoms, and the form is not particularly limited. For example, monomers of metal atoms, compounds containing metal atoms (hereinafter also referred to as "metal compounds"), and complexes thereof can be mentioned. In addition, the metal nanoparticles can contain multiple kinds of metal atoms. When the metal nanoparticles contain multiple kinds of metals, the metal atom with the highest content (atm%) among the above-mentioned multiple kinds of metals is used as the main component. Therefore, when referring to Pb nanoparticles, in the case of containing multiple kinds of metals, it means that among the multiple kinds of metals, the Pb atom is the main component.

[0224] The complex is not particularly limited, and examples thereof include so-called core-shell type particles having a monomer of a metal atom and at least a part of the monomer covering the metal atom; solid solution particles containing a metal atom and other atoms; eutectic particles containing a metal atom and other atoms; aggregate particles of a monomer of a metal atom and a metal compound; aggregate particles of metal compounds of different types; and metal compounds whose composition continuously or discontinuously changes from the particle surface toward the center.

[0225] The atoms other than the metal atoms contained in the metal compound are not particularly limited. For example, carbon atoms, oxygen atoms, nitrogen atoms, hydrogen atoms, sulfur atoms, and phosphorus atoms can be mentioned. Among them, an oxygen atom is preferred. The manner in which the metal compound contains an oxygen atom is not particularly limited, and an oxide of a metal atom is more preferred.

[0226] From the viewpoint of obtaining a liquid chemical having more excellent effects of the present invention, as the metal nanoparticles, it is preferable to 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 oxides of metal atoms (particle C).

[0227] In addition, the relationship among the number of particles of particle A, the number of particles of particle B, and the number of particles of particle C in the number of particles of metal nanoparticles per unit volume of the liquid medicine is not particularly limited. From the viewpoint of obtaining a liquid medicine with more excellent effects of the present invention, the ratio of the number of particles of particle A to the total number of particles of particle B and particle 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 Hereinafter, particularly preferably 1.0×10 -1 Hereinafter, preferably 1.0×10 -3 Above, more preferably 1.0×10 -2 Above.

[0228] If A / (B+C) is less than 1.0, the liquid medicine has more excellent bridge defect suppression performance, more excellent pattern width uniformity, and stain-like defect suppression performance. In addition, the stain-like defect limitation refers to a defect in which metal atoms are not detected.

[0229] Moreover, if A / (B+C) is 0.1 or less, the liquid medicine has more excellent defect suppression performance.

[0230] <Metal ion>

[0231] This liquid medicine may contain metal ions.

[0232] Examples of the 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).

[0233] The content of the 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 with respect to the total mass of this liquid medicine. If the content of the metal ions is within the above range, a liquid medicine with excellent defect suppression performance (especially the defect suppression performance after long-term storage of the liquid medicine container) can be obtained.

[0234] The content of the metal ions in the liquid medicine is obtained by subtracting the content of the metal particles measured by the SP-ICP-MS method from the content of the metal components in the liquid medicine measured by the ICP-MS method as described above.

[0235] 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 from 0.00001 to 1, more preferably from 0.0001 to 0.2, and particularly preferably from 0.001 to 0.05.

[0236] [Other components]

[0237] The liquid medicine may contain other components other than those described above. Examples of other components include organic compounds other than organic solvents (in particular, organic compounds having a boiling point of 300°C or higher), water, resins, and the like.

[0238] <Organic compounds other than organic solvents>

[0239] The liquid medicine may contain organic compounds other than organic solvents (hereinafter, also referred to as "specific organic compounds"). In the present specification, the specific organic compound is a compound different from the organic solvent contained in the liquid medicine, and is an organic compound contained in an amount of 10,000 mass ppm or less relative to the total mass of the present liquid medicine. That is, in the present specification, an organic compound contained in an amount of 10,000 mass ppm or less relative to the total mass of the present liquid medicine is equivalent to the specific organic compound and is not equivalent to the organic solvent.

[0240] In addition, when the liquid medicine contains a plurality of specific organic compounds and each specific organic compound is contained in an amount of 10,000 mass ppm or less, each is equivalent to the specific organic compound.

[0241] The specific organic compound may be added to the liquid medicine or may be inadvertently mixed in the manufacturing process of the liquid medicine. As a case of being inadvertently mixed in the manufacturing process of the liquid medicine, for example, a case where the specific organic compound is contained in a raw material (for example, an organic solvent) used in the manufacture of the liquid medicine and a case of being mixed in the manufacturing process of the liquid medicine (for example, a contaminant), etc. are exemplified, but are not limited to the above.

[0242] In addition, the content of the specific organic compound in the present liquid medicine can be measured using GCMS (gas chromatography mass spectrometry).

[0243] There is no particular limitation on the number of carbon atoms of the specific organic compound. From the viewpoint of the liquid medicine having more excellent effects of the present invention, it is preferably 8 or more, more preferably 12 or more. In addition, there is no particular limitation on the upper limit of the number of carbon atoms, and it is usually preferably 30 or less.

[0244] As a specific organic compound, for example, it may be a by-product generated during the synthesis of an organic solvent and / or an unreacted raw material (hereinafter, also referred to as "by-products, etc.").

[0245] Examples of the above by-products, etc. include compounds represented by the following formulas I to V, etc.

[0246] [Chemical formula 1]

[0247]

[0248] In formula I, R 1 and R 2 each independently represents an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0249] As the alkyl group or cycloalkyl group represented by R 1 and R 2 it is preferably an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 6 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms or a cycloalkyl group having 6 to 8 carbon atoms.

[0250] The ring formed by the bonding of R 1 and R 2 is a lactone ring, preferably a lactone ring having 4 to 9 members, more preferably a lactone ring having 4 to 6 members.

[0251] In addition, it is preferable that R 1 and R 2 satisfy the relationship that the number of carbon atoms of the compound represented by formula I is 8 or more.

[0252] In formula II, R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group, or are bonded to each other to form a ring. Among them, R 3 and R 4 are not both hydrogen atoms.

[0253] As the alkyl group represented by R 3 and R 4 for example, it is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

[0254] As the alkenyl group represented by R 3 and R 4 for example, it is preferably an alkenyl group having 2 to 12 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms.

[0255] As the cycloalkyl group represented by R 3 and R 4 it is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0256] As the cycloalkenyl group represented by R 3 and R 4 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.

[0257] R 3 and R 4 The ring formed by 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.

[0258] In addition, it is preferred that R 3 and R 4 satisfy the relationship that the number of carbon atoms of the compound represented by Formula II is 8 or more.

[0259] In Formula III, R 5 represents an alkyl group or a cycloalkyl group.

[0260] The alkyl group represented by R 5 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.

[0261] The above alkyl group may have an ether bond in the chain or a substituent such as a hydroxyl group.

[0262] The cycloalkyl group represented by R 5 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.

[0263] In Formula IV, R 6 and R 7 each independently represents an alkyl group or a cycloalkyl group, or are bonded to each other to form a ring.

[0264] As the alkyl group represented by R 6 and R 7 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

[0265] As the cycloalkyl group represented by R 6 and R 7 is preferably a cycloalkyl group having 6 to 12 carbon atoms, more preferably a cycloalkyl group having 6 to 8 carbon atoms.

[0266] R 6 and R 7 are bonded to each other to form a cyclic ether structure. The cyclic ether structure is preferably a 4- to 8-membered ring, more preferably a 5- to 7-membered ring.

[0267] In addition, it is preferred that R 6 and R 7The number of carbon atoms of the compound represented by Formula IV satisfies the relationship of being 8 or more.

[0268] In Formula V, R 8 and R 9 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.

[0269] As the alkyl group represented by R 8 and R 9 , 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.

[0270] As the cycloalkyl group represented by R 8 and R 9 , a cycloalkyl group having 6 to 12 carbon atoms is preferred, and a cycloalkyl group having 6 to 10 carbon atoms is more preferred.

[0271] The ring formed by bonding R 8 and R 9 to each other has a cyclic diketone structure. The cyclic diketone structure is preferably a 6- to 12-membered ring, more preferably a 6- to 10-membered ring.

[0272] 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.

[0273] In addition, R 8 , R 9 and L satisfy the relationship that the number of carbon atoms of the compound represented by Formula V is 8 or more.

[0274] Although there is no particular limitation, when the organic solvent is an amide compound, an imide compound, or a sulfoxide compound, in one aspect, an amide compound, an imide compound, and a sulfoxide compound having 6 or more carbon atoms can be exemplified. And, as specific organic compounds, the following compounds can also be exemplified, for example.

[0275] [Chemical formula 2]

[0276]

[0277] [Chemical formula 3]

[0278]

[0279] Also, as specific organic compounds, antioxidants such as dibutylhydroxytoluene (BHT), distearyl thiodipropionate (DSTP), 4,4'-butylidenebis-(6-tert-butyl-3-methylphenol), 2,2'-methylenebis-(4-ethyl-6-tert-butylphenol), and antioxidants described in JP-A-2015-200775; unreacted raw materials; structural isomers and by-products generated during the production of organic solvents; eluates from components of the production apparatus constituting the organic solvent (for example, plasticizers eluted from rubber components such as O-rings); etc. can be cited.

[0280] Also, as specific organic compounds, dioctyl phthalate (DOP), bis(2-ethylhexyl) phthalate (DEHP), bis(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), tris(2-ethylhexyl) trimellitate (TEHTM), tris(n-octyl n-decyl) trimellitate (ATM), bis(2-ethylhexyl) adipate (DEHA), monomethyl adipate (MMAD), dioctyl adipate (DOA), dibutyl sebacate (DBS), dibutyl maleate (DBM), diisobutyl maleate (DIBM), azelaate, benzoate, terephthalate (e.g., dioctyl terephthalate (DEHT)), diisononyl 1,2-cyclohexanedicarboxylate (DINCH), epoxidized vegetable oil, sulfonamide (e.g., N-(2-hydroxypropyl)benzenesulfonamide (HP BSA), N-(n-butyl)benzenesulfonamide (BBSA-NBBS)), organophosphate (e.g., tricresyl phosphate (TCP), tributyl phosphate (TBP)), acetylated monoglyceride, triethyl citrate (TEC), acetyltriethyl citrate (ATEC), tributyl citrate (TBC), acetyltributyl citrate (ATBC), trioctyl citrate (TOC), acetyltrioctyl citrate (ATOC), trihexyl citrate (THC), acetyltrihexyl citrate (ATHC), epoxidized soybean oil, ethylene propylene rubber, polybutene, addition polymer of 5-ethylidene-2-norbornene, and the following exemplified high molecular weight plasticizers can be cited.

[0281] It is presumed that these specific organic compounds are mixed into the purified product or the liquid medicine from filters, pipes, tanks, O-rings, and containers, etc. that are in contact during the purification process. In particular, compounds other than alkyl olefins are related to the generation of bridge defects.

[0282] [Chemical formula 4]

[0283]

[0284] (Organic compounds with specific polar structures)

[0285] This liquid medicine may contain organic compounds having the following specific polar structures among specific organic compounds. The organic compounds having specific polar structures preferably contain at least one organic compound selected from the group consisting of compounds having an amide structure, compounds having a sulfonamide structure, compounds having a phosphonamide structure, compounds having an imide structure, compounds having a urea structure, compounds having a carbamate structure, and organic acid esters.

[0286] Examples of the compounds having an amide structure include oleic acid amide, stearic acid amide, erucic acid amide, methylene bisstearic acid amide, methylene bisoctadecanoic acid amide (707 °C), ethylene bisoctadecanoic acid amide, etc.

[0287] Examples of the compounds having a sulfonamide structure include N-ethyl-o-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-(2-hydroxypropyl)benzenesulfonamide, N-butylbenzenesulfonamide, etc.

[0288] Examples of the compounds having an imide structure include phthalimide (366 °C), hexahydrophthalimide, N-2-ethylhexylphthalimide, N-butylphthalimide, N-isopropylphthalimide, etc.

[0289] Examples of the compounds having a urea structure include aliphatic diureas, alicyclic diureas, and aromatic diureas.

[0290] From the viewpoint of further exerting the effects of the present invention, the organic acid esters preferably contain 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 bis(2-ethylhexyl) terephthalate (boiling point 416 °C / 101.3 kPa).

[0291] The content of the organic compounds having specific polar structures 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 with respect to the total mass of this liquid medicine.

[0292] From the viewpoint of further exerting the effects of the present invention, the lower limit value of the content of the organic compounds having specific polar structures is preferably 0.0001 mass ppm or more, more preferably 0.001 mass ppm or more with respect to the total mass of this liquid medicine.

[0293] (Organic compounds with a boiling point of 300 °C or higher)

[0294] This liquid medicine may also contain an organic compound having the above-specified polar structure and having a boiling point of 300 °C or higher (hereinafter, also referred to as "high-boiling organic compound"). When this liquid medicine contains a high-boiling organic compound, since the boiling point is high, it is not easily volatilized in the lithography process. Therefore, in order to obtain a liquid medicine having excellent defect suppression performance, it is preferable to strictly control the content and the existing form, etc. of the high-boiling organic compound in the liquid medicine.

[0295] The content of the high-boiling organic compound is preferably 5 mass ppm or less, more preferably 1 mass ppm or less, still more preferably 0.1 mass ppm or less, and particularly preferably 0.01 mass ppm or less, based on the total mass of this liquid medicine.

[0296] From the viewpoint of further exerting the effects of the present invention, the lower limit value of the content of the high-boiling organic compound is preferably 0.0001 mass ppm or more, and more preferably 0.001 mass ppm or more, based on the total mass of this liquid medicine.

[0297] The present inventors have found that when an organic compound having the above-specified polar structure or a high-boiling organic compound is contained in a liquid medicine, there are various forms. As the existing form of the organic compound having a polar structure or the high-boiling organic compound in the liquid medicine, there can be mentioned particles formed by aggregation of particles composed of a metal atom or a metal compound and particles of the organic compound having a polar structure or the high-boiling organic compound; particles having particles composed of a metal atom or a metal compound and an organic compound having a polar structure or a high-boiling organic compound arranged so as to coat at least a part of the above particles; particles formed by coordination bonding of a metal atom and an organic compound having a polar structure or a high-boiling organic compound; etc.

[0298] Among them, as a form that has a great influence on the defect suppression performance of the liquid medicine, there can be mentioned metal nanoparticles (particle U) containing an organic compound having a polar structure or a high-boiling organic compound. The present inventors have found that the defect suppression performance of the liquid medicine can be dramatically improved by controlling the number of particles contained per unit volume of the above particle U in the liquid medicine.

[0299] Although the reason may not be clear, compared with metal nanoparticles (particle V) that do not contain an organic compound or a high-boiling organic compound having a polar structure, the surface free energy of particle U tends to become relatively reduced. Such particle U is not likely to remain on the substrate treated with the liquid chemical, and even if it remains, it is easily removed when it comes into contact with the liquid chemical again. For example, when the liquid chemical is used as a developer and a rinse liquid, etc., during development, particle U is more difficult to remain on the substrate, and furthermore, it is easily removed by rinsing or the like. That is, as a result, both particles containing a high-boiling organic compound and metal atoms are more easily removed.

[0300] Moreover, since the resist film is usually hydrophobic, it is presumed that particle U with a lower surface energy is difficult to remain on the substrate.

[0301] From the viewpoint of obtaining a liquid chemical with more excellent effects of the present invention, the particle number ratio of particle U to particle V per unit volume of the liquid chemical is preferably 10 or more, preferably 1.0×10 2 Hereinafter, more preferably 50 or less, further preferably 35 or less, and particularly preferably 25 or less.

[0302] <Water>

[0303] This liquid chemical may contain water. There is no particular limitation on the water, and examples thereof include distilled water, ion-exchanged water, and pure water.

[0304] Water can be added to the liquid chemical, or can be inadvertently mixed into the liquid chemical during the manufacturing process of the liquid chemical. As a case where it is not intentionally mixed during the manufacturing process of the liquid chemical, for example, cases where water is contained in the raw materials (e.g., organic solvents) used in the manufacturing of the liquid chemical and cases where it is mixed (e.g., contaminants) during the manufacturing process of the liquid chemical, etc. are included, but are not limited to the above.

[0305] The content of water relative to the total mass of this liquid chemical 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. If the content of water is 1 mass ppm or less, the formation of a complex of a metal component and an acid component can be suppressed, and thus a liquid chemical with excellent defect suppression performance (particularly, defect suppression performance after long-term storage of the liquid chemical container) can be obtained.

[0306] The content of water in this liquid chemical refers to the water content measured using a device based on the Karl Fischer moisture measurement method as the measurement principle.

[0307] <Resin>

[0308] The liquid medicine may contain a resin. As the resin, resin P having a group that decomposes by the action of an acid to generate a polar group is more preferable. As the above resin, a resin whose solubility in a developer mainly composed of an organic solvent decreases by the action of an acid, that is, a resin having a repeating unit represented by the following formula (AI), is more preferable. The resin having a repeating unit represented by the following formula (AI) has a group that decomposes by the action of an acid to generate an alkali-soluble group (hereinafter, also referred to as "acid-decomposable group").

[0309] Examples of the polar group include an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a phenolic hydroxyl group, and a sulfo group.

[0310] In the acid-decomposable group, the polar group is protected by a group that detaches under 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 ) and the like.

[0311] In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R 36 and R 37 may bond to each other to form a ring.

[0312] R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0313] Hereinafter, resin P whose solubility in a developer mainly composed of an organic solvent decreases by the action of an acid will be described in detail.

[0314] (Formula (AI): Repeating unit having an acid-decomposable group)

[0315] Preferably, resin P contains a repeating unit represented by formula (AI).

[0316] [Chemical formula 5]

[0317]

[0318] In formula (AI),

[0319] Xa 1represents a hydrogen atom or an alkyl group which may have substituents.

[0320] T represents a single bond or a divalent linking group.

[0321] Ra 1 ~Ra 3 each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

[0322] Ra 1 ~Ra 3 Two of Ra

[0323] ~Ra 1 may bond to form a cycloalkyl group (monocyclic or polycyclic).

[0324] As the alkyl group represented by Xa 2 which may have substituents, examples include a methyl group and a group represented by -CH 11 -R 11 1 . R 2 represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group.

[0325] As the divalent linking group of T, examples include an alkylene group, a -C00-Rt- group and a -0-Rt- group, etc. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0326] T is preferably a single bond or a -C00-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH 2 - group, a -(CH) 2 - group or a -(CH 2 ) 3 - group.

[0327] As the alkyl group of Ra 1 ~Ra 3 it is preferably an alkyl group having 1 to 4 carbon atoms.

[0328] As the cycloalkyl group of Ra 1 ~Ra 3 it is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group.

[0329] As the cycloalkyl group formed by the bonding of two of Ra 1 ~Ra 3 ~Ra

[0330] Regarding Ra 1 ~Ra 3 For the above cycloalkyl group formed by bonding two of them, for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

[0331] The repeating unit represented by formula (AI) is preferably Ra 1 being methyl or ethyl, and Ra 2 bonded to Ra 3 in the manner of forming the above cycloalkyl group.

[0332] The above groups may have substituents. Examples of the substituents include alkyl groups (having 1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (having 1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (having 2 to 6 carbon atoms), etc., and preferably those having 8 or fewer carbon atoms.

[0333] The content of the repeating unit represented by formula (AI) relative to all the repeating units in resin P is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and still more preferably 30 to 80 mol%.

[0334] (Repeating unit having a lactone structure)

[0335] Moreover, it is preferred that resin P contains a repeating unit Q having a lactone structure.

[0336] It is preferred that the repeating unit Q having a lactone structure has a lactone structure in the side chain, and more preferably a repeating unit derived from a (meth)acrylic acid derivative monomer.

[0337] The repeating unit Q having a lactone structure may be used alone or two or more thereof may be used simultaneously, but it is preferred to use one alone.

[0338] The content of the repeating unit Q having a lactone structure relative to all the repeating units in resin P is preferably 3 to 80 mol%, more preferably 3 to 60 mol%.

[0339] As the lactone structure, a lactone structure of 5 to 7 membered rings is preferred, and more preferably a structure in which another ring structure is condensed in the lactone structure of 5 to 7 membered rings to form a bicyclic structure or a spiro ring structure.

[0340] 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, a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5), or formula (LC1-8) is preferred, and a lactone structure represented by formula (LC1-4) is more preferred.

[0341] [Chemical formula 6]

[0342]

[0343] The lactone structural moiety may have a substituent (Rb 2 ). As preferred substituents (Rb 2 ), there may be mentioned an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group, etc. n 2 represents an integer of 0 to 4. When n 2 is 2 or more, a plurality of substituents (Rb 2 ) may be the same or different, and a plurality of substituents (Rb 2 ) may bond to each other to form a ring.

[0344] (Repeating unit having a phenolic hydroxyl group)

[0345] Moreover, the resin P may contain a repeating unit having a phenolic hydroxyl group.

[0346] As the repeating unit having a phenolic hydroxyl group, for example, there may be mentioned a repeating unit represented by the following general formula (I).

[0347] [Chemical formula 7]

[0348]

[0349] In the formula,

[0350] R 41 , R 42 and R 43 each independently represent a hydrogen atom, an alkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Among them, R 42 may bond to Ar 4 to form a ring, and in this case, R 42 represents a single bond or an alkylene group.

[0351] X 4 represents a single bond, -COO- or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group.

[0352] L 4 represents a single bond or an alkylene group.

[0353] Ar 4 represents an (n + 1)-valent aromatic ring group, and represents an (n + 2)-valent aromatic ring group when bonding to R 42 to form a ring.

[0354] n represents an integer of 1 to 5.

[0355] As R in the general formula (I) 41 , R 42 and R 43 is an alkyl group, preferably an alkyl group having 20 or fewer carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, which may have substituents, more preferably an alkyl group having 8 or fewer carbon atoms, and still more preferably an alkyl group having 3 or fewer carbon atoms.

[0356] As R in the general formula (I) 41 , R 42 and R 43 is a cycloalkyl group, which may be monocyclic or polycyclic. As the cycloalkyl group, preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl, which may have substituents.

[0357] As R in the general formula (I) 41 , R 42 and R 43 is a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

[0358] As R in the general formula (I) 41 , R 42 and R 43 is an alkyl group contained in an alkoxycarbonyl group, and preferably the same group as the alkyl group in the above R 41 , R 42 and R 43 .

[0359] As substituents in the above groups, examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a urea group, a carbamate group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group, and the number of carbon atoms of the substituents is preferably 8 or less.

[0360] Ar 4 represents an (n + 1)-valent aromatic ring group. When n is 1, the divalent aromatic ring group may have substituents, and examples thereof include arylene groups having 6 to 18 carbon atoms such as phenylene, methylene phenylene, naphthylene, and anthrylene, and aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0361] As a specific example of the (n + 1)-valent aromatic ring group when n is an integer of 2 or more, a group formed by removing (n - 1) arbitrary hydrogen atoms from the above specific examples of the divalent aromatic ring group can be cited.

[0362] The (n + 1)-valent aromatic ring group may further have substituents.

[0363] Examples of the substituents that the above alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1)-valent aromatic ring group can have include R in the general formula (I). 41 , R 42 and R 43 The alkyl groups exemplified above; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl.

[0364] As the -CONR 4 - (wherein R 64 represents a hydrogen atom or an alkyl group) represented by X 64 , examples of the alkyl group of R 64 include alkyl groups having 20 or fewer carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, which may have substituents, and more preferably alkyl groups having 8 or fewer carbon atoms.

[0365] As X 4 , a single bond, -COO-, or -CONH- is preferred, and a single bond or -COO- is more preferred.

[0366] As the alkylene group in L 4 , alkylene groups having 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, and octylene, which may have substituents, are preferred.

[0367] As Ar 4 , an aromatic ring group having 6 to 18 carbon atoms, which may have substituents, is preferred, and a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferred.

[0368] Preferably, the repeating unit represented by the general formula (I) has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.

[0369] The content of the repeating unit 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.

[0370] (Repeating unit containing an organic group having a polar group)

[0371] The resin P may further contain a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Thereby, the substrate adhesion and the developer affinity are improved.

[0372] As the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group, a diamond alkyl group or a norbornyl group is preferred. As the polar group, a hydroxyl group or a cyano group is preferred.

[0373] When the resin P contains a repeating unit containing an organic group having a polar group, its content is preferably 1 to 50 mol%, more preferably 1 to 30 mol%, still more preferably 5 to 25 mol%, and particularly preferably 5 to 20 mol% with respect to all the repeating units in the resin P.

[0374] (Repeating unit represented by the general formula (VI))

[0375] The resin P may contain a repeating unit represented by the following general formula (VI).

[0376] [Chemical formula 8]

[0377]

[0378] In the general formula (VI),

[0379] R 61 , R 62 and R 63 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Among them, R 62 may be bonded to Ar 6 to form a ring, and in this case, R 62 represents a single bond or an alkylene group.

[0380] X 6 represents a single bond, -COO- or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0381] L 6 represents a single bond or an alkylene group.

[0382] Ar 6 represents an (n + 1)-valent aromatic ring group, and represents an (n + 2)-valent aromatic ring group when bonded to R 62 to form a ring.

[0383] Regarding Y 2 , when n ≥ 2, each independently represents a hydrogen atom or a group that is cleaved by the action of an acid. Among them, at least one of Y 2 represents a group that is cleaved by the action of an acid.

[0384] n represents an integer of 1 to 4.

[0385] As the group Y 2 that is cleaved by the action of an acid, a structure represented by the following general formula (VI-A) is preferred.

[0386] [Chemical Formula 9]

[0387]

[0388] L 1 and L 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group.

[0389] M represents a single bond or a divalent linking group.

[0390] Q represents an alkyl group, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group.

[0391] Q, M, L 1 at least two of which may bond to form a ring (preferably a 5- or 6-membered ring).

[0392] The repeating unit represented by the above general formula (VI) is preferably the repeating unit represented by the following general formula (3).

[0393] [Chemical Formula 10]

[0394]

[0395] In general formula (3),

[0396] Ar 3 represents an aromatic ring group.

[0397] R 3 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.

[0398] M 3 represents a single bond or a divalent linking group.

[0399] Q 3 represents an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group.

[0400] Q 3 , M 3 and R 3 at least two of which may bond to form a ring.

[0401] Ar 3 The aromatic ring group represented by is the same as Ar in the above general formula (VI) when n = 1 in the above general formula (VI), preferably a phenylene group or a naphthylene group, more preferably a phenylene group. 6 Same as above, preferably a phenylene group or a naphthylene group, more preferably a phenylene group.

[0402] (Repeating unit having a silicon atom in the side chain)

[0403] Resin P may further contain repeating units having a silicon atom in the side chain. Examples of the repeating units having a silicon atom in the side chain include (meth)acrylate-based repeating units having a silicon atom and vinyl-based repeating units having a silicon atom. The repeating units having a silicon atom in the side chain are typically repeating units having a group having a silicon atom in the side chain. Examples of the group having a silicon atom include trimethylsilyl, triethylsilyl, triphenylsilyl, tricyclohexylsilyl, tris(trimethylsiloxysilyl), tris(trimethylsilylsilyl), methylbis(trimethylsilylsilyl), methylbis(trimethylsiloxysilyl), dimethyl(trimethylsilylsilyl), dimethyl(trimethylsiloxysilyl), and the following cyclic or linear polysiloxanes, or cage-type or ladder-type or random-type silsesquioxane structures, etc. In the formula, R and R 1 each independently represent a monovalent substituent. * represents a bonding bond.

[0404] [Chemical formula 11]

[0405]

[0406] As the repeating units having the above groups, preferably, for example, repeating units derived from acrylate compounds or methacrylate compounds having the above groups or repeating units derived from compounds having the above groups and vinyl groups.

[0407] When resin P has the repeating units having a silicon atom in the side chain, its content is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, and still more preferably 5 to 20 mol% relative to all the repeating units in resin P.

[0408] As the polystyrene conversion value based on the GPC (Gel permeation chromatography) method, the weight average molecular weight of resin P is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and still more preferably 5,000 to 15,000. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability or film-forming property due to increased viscosity can be prevented.

[0409] The dispersity (molecular weight distribution) is generally preferably 1 to 5, 1 to 3, more preferably 1.2 to 3.0, and still more preferably 1.2 to 2.0.

[0410] In this liquid medicine, the content of resin P in the total solid content is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass.

[0411] Moreover, in this liquid medicine, one kind of resin P can be used, or multiple kinds can be used simultaneously.

[0412] Regarding other components contained in the liquid medicine (such as acid generators, basic compounds, quenchers, hydrophobic resins, surfactants, solvents, etc.), known components can be used. As the liquid medicine, for example, those described in Japanese Patent Application Laid-Open No. 2013-195844, Japanese Patent Application Laid-Open No. 2016-057645, Japanese Patent Application Laid-Open No. 2015-207006, International Publication No. 2014 / 148241, Japanese Patent Application Laid-Open No. 2016-188385, Japanese Patent Application Laid-Open No. 2017-219818, etc., such as components contained in photosensitive or radiation-sensitive resin compositions can be used.

[0413] 〔Use of the liquid medicine〕

[0414] Preferably, this liquid medicine is used in the manufacture of semiconductor devices. In particular, it is more preferably used for forming fine patterns with a node of 10 nm or less (for example, including the process of pattern formation using EUV).

[0415] This liquid medicine is particularly preferably used as a liquid medicine (pre-wetting liquid, developing liquid, rinsing liquid, solvent for resist liquid, stripping liquid, etc.) used in a resist process where the pattern width and / or pattern pitch is 17 nm or less (preferably 15 nm or less, more preferably 12 nm or less) and / or the obtained wiring width and / or wiring pitch is 17 nm or less. In other words, it is used for the manufacture of semiconductor devices manufactured using a resist film with a pattern width and / or pattern pitch of 17 nm or less.

[0416] Specifically, in the manufacturing process of semiconductor devices including photolithography process, etching process, ion implantation process, stripping process, etc., after each process is completed or before transferring to the next process, it is used to treat organic substances. Specifically, it is preferably used as a pre-wetting liquid, developing liquid, rinsing liquid, stripping liquid, etc. For example, it can also be used for rinsing the edge lines of semiconductor substrates before and after resist coating.

[0417] Moreover, this liquid medicine can also be used as a diluent for the resin contained in the resist liquid and a solvent for the resist liquid. And it can also be diluted with other organic solvents and / or water, etc.

[0418] Furthermore, this liquid medicine can also be used for other purposes other than the manufacture of semiconductor devices, and can also be used as a developing liquid and a rinsing liquid for polyimide, resist for sensors, resist for lenses, etc.

[0419] Moreover, this liquid medicine can also be used as a solvent for medical use or cleaning use. In particular, it can be preferably used for cleaning containers, pipes, substrates (such as wafers and glass, etc.).

[0420] Among them, when this liquid medicine is used as a raw material for at least one liquid selected from the group consisting of a developer, a rinsing liquid, a wafer cleaning liquid, a wire cleaning liquid, a pre-wetting liquid, a resist liquid, a lower layer film forming liquid, an upper layer film forming liquid, and a hard coat forming liquid, the effects can be further exerted.

[0421] 〔Manufacturing method of the liquid medicine〕

[0422] The manufacturing method of this liquid medicine is not particularly limited, and known manufacturing methods can be used. Among them, from the viewpoint of further exerting the effects of the present invention, it is preferable that this liquid medicine is obtained by purifying a purified product containing an organic solvent. Specifically, as a preferable mode of the manufacturing method of this liquid medicine, a mode including a filtration step of filtering the purified product, an ion removal step of subjecting the purified product to an ion exchange method or ion adsorption, and a distillation step of distilling the purified product can be cited.

[0423] The purified product is obtained by supply based on purchase or the like and by reacting raw materials. As the purified product, it is preferable that the content of impurities is small. As commercially available products of such purified products, for example, commercially available products called "high-purity grade products" can be cited.

[0424] As a method of reacting raw materials to obtain a purified product (typically a purified product containing an organic solvent), there is no particular limitation, and known methods can be used. For example, a method of reacting one or more raw materials in the presence of a catalyst to obtain an organic solvent can be cited.

[0425] More specifically, for example, a method of reacting acetic acid with n-butanol in the presence of sulfuric acid to obtain butyl acetate; a method of reacting ethylene, oxygen, and water in the presence of Al(C 2 H 5 ) 3 to obtain 1-hexanol; a method of reacting cis-4-methyl-2-pentene in the presence of Ipc2BH (Diisopinocampheylborane: diisopinocampheylborane) to obtain 4-methyl-2-pentanol; a method of reacting propylene oxide, methanol, and acetic acid in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); a method of reacting acetone and hydrogen in the presence of copper oxide-zinc oxide-aluminum oxide to obtain IPA (isopropyl alcohol: isopropyl alcohol); and a method of reacting lactic acid and ethanol to obtain ethyl lactate, etc.

[0426] <Filtration step>

[0427] The filtration step is a step of filtering the above-mentioned purified product using a filter. The components removed by the filtration step are not limited thereto. For example, metal-containing particles that may be included in metal components can be cited.

[0428] There is no particular limitation on the method of using a filter to filter the purified substance. Preferably, the purified substance is passed (liquid passing) through a filtration unit having a housing and a filter element accommodated in the housing under pressure or non-pressure.

[0429] (Fine pore diameter of the filter)

[0430] There is no particular limitation on the fine pore diameter of the filter, and a filter having a fine pore diameter commonly used for filtering the purified substance can be used. Among them, from the viewpoint of more easily controlling the number of particles (including metal particles, etc.) contained in the liquid medicine within the desired range, the fine pore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, further preferably 10 nm or less, particularly preferably 5 nm or less, and most preferably 3 nm or less. The lower limit value is not particularly limited, but from the viewpoint of productivity, it is generally preferably 1 nm or more.

[0431] In addition, in this specification, the fine pore diameter and the fine pore diameter distribution of the filter refer to the fine pore diameter and the fine pore diameter distribution determined by the bubble point of isopropyl alcohol (IPA) or HFE-7200 (“Novec7200”, manufactured by 3M Company, hydrofluoroether, C 4 F 9 OC 2 H 5 ).

[0432] If the fine pore diameter of the filter is 5.0 nm or less, it is preferably from the viewpoint of more easily controlling the number of contained particles in the liquid medicine. Hereinafter, a filter having a fine pore diameter of 5 nm or less is also referred to as a “micro-fine pore filter”.

[0433] In addition, the micro-fine pore filter can be used alone or in combination with a filter having other fine pore diameters. Among them, from the viewpoint of more excellent productivity, it is preferably used in combination with a filter having a larger fine pore diameter. In this case, if the purified substance preliminarily filtered through a filter having a large fine pore diameter is passed through the micro-fine pore filter, clogging of the micro-fine pore filter can be prevented.

[0434] That is, as the fine pore diameter of the filter, when using one filter, the fine pore diameter is preferably 5.0 nm or less, and when using two or more filters, the fine pore diameter of the filter having the smallest fine pore diameter is preferably 5.0 nm or less.

[0435] There is no particular limitation on the method of successively using two or more filters with different fine pore diameters. Examples include a method of successively arranging them along the pipeline for conveying the purified material in the filtering unit described above. At this time, if it is desired to keep the flow rate per unit time of the purified material in the entire pipeline constant, sometimes a greater pressure is applied to the filtering unit with a smaller fine pore diameter than to the filtering unit with a larger fine pore diameter. In this case, it is preferable to arrange a pressure regulating valve, a damper, etc. between the filtering units, and by keeping the pressure applied to the filtering unit with a small fine pore diameter constant, or alternatively arranging filtering units containing the same filters in parallel along the pipeline to increase the filtering area. In this way, the number of particles in the liquid medicine can be controlled more stably.

[0436] (Material of the filter)

[0437] 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, examples include polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; poly(meth)acrylate; polyfluorocarbons such as polytetrafluoroethylene, perfluoroalkoxy alkane, perfluoroethylene propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc. Among them, from the viewpoint of having more excellent solvent resistance and the obtained liquid medicine having more excellent defect suppression performance, at least one selected from the group consisting of nylon (preferably 6,6-nylon), polyolefins (preferably polyethylene), poly(meth)acrylate, and polyfluorocarbons (preferably polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA)) is preferred. These polymers can be used alone or in combination of two or more.

[0438] In addition to resin, it can also be diatomaceous earth, glass, etc.

[0439] In addition, a polymer obtained by graft copolymerizing polyamide (e.g., nylon such as nylon-6 or nylon-6,6) with polyolefin (UPE, etc. described later) (nylon graft UPE, etc.) can also be used as the material of the filter.

[0440] Moreover, the filter can also be a surface-treated filter. The method of surface treatment is not particularly limited, and known methods can be used. As the method of surface treatment, for example, chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, sintering, etc. can be cited.

[0441] Plasma treatment hydrophilizes the surface of the filter, so it is preferred. The water contact angle on the surface of the filter material hydrophilized by plasma treatment is not particularly limited, but the static contact angle at 25 °C measured with a contact angle meter is preferably 60° or less, more preferably 50° or less, and particularly preferably 30° or less.

[0442] As the chemical modification treatment, a method of introducing an ion exchange group into the substrate is preferred.

[0443] That is, as the filter, it is preferred to use each of the above-listed materials as the substrate and introduce an ion exchange group into the filter of the above substrate. Typically, a filter including a layer of a substrate containing an ion exchange group on the surface of the above substrate is preferred. The substrate subjected to surface modification is not particularly limited, and from the viewpoint of easier manufacture, a filter in which an ion exchange group is introduced into the above polymer is preferred.

[0444] Regarding the ion exchange group, examples of the cation exchange group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group, etc., and examples of the anion exchange group include a quaternary ammonium group, etc. The method of introducing an ion exchange group into a 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 a polymer can be cited.

[0445] The method of introducing an ion exchange group 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 resin to generate active sites (free radicals) in the resin. The irradiated resin is immersed in a solution containing a monomer, and the monomer is graft-polymerized onto the substrate. As a result, a polymer in which the monomer is bonded as a graft polymer side chain to the polyolefin fiber is formed. The resin containing the generated polymer as a side chain is brought into contact with a compound containing an anion exchange group or a cation exchange group to react, and an ion exchange group is introduced into the polymer of the graft-polymerized side chain to obtain the final product.

[0446] Moreover, the filter may also have a structure in which a woven or non-woven fabric having an ion exchange group formed by radiation graft polymerization is combined with a conventional filter material such as glass wool, a woven or non-woven fabric.

[0447] When a filter containing an ion exchange group is used, it is easy to control the content in the liquid medicine containing metal atom particles within a desired range. The material of the filter containing an ion exchange group is not particularly limited, and examples include materials in which an ion exchange group is introduced into a polyfluorohydrocarbon and a polyolefin, etc., and a material in which an ion exchange group is introduced into a polyfluorohydrocarbon is more preferred.

[0448] The pore diameter of the filter containing ion exchange groups is not particularly limited, preferably 1 to 30 nm, more preferably 5 to 20 nm. The filter containing ion exchange groups can also serve as the filter having the above-mentioned minimum pore diameter, or can be used separately from the filter having the minimum pore diameter. Among them, from the viewpoint of obtaining a liquid medicine showing more excellent effects of the present invention, a method using a filter containing ion exchange groups and a filter having the minimum pore diameter without ion exchange groups in the filtration step is preferred.

[0449] The material of the filter having the above-mentioned minimum pore diameter is not particularly limited. From the viewpoint of solvent resistance and the like, at least one selected from the group consisting of polyfluorohydrocarbons and polyolefins is preferably used, and polyolefins are more preferably used.

[0450] Therefore, as the filter used in the filtration step, two or more filters having different materials can be used. For example, two or more selected from the group consisting of polyolefins, polyfluorohydrocarbons, polyamides, and materials obtained by introducing ion exchange groups into these can be used.

[0451] (Pore structure of the filter)

[0452] The pore structure of the filter is not particularly limited and can be appropriately selected according to the components in the purified product. In the present specification, the pore structure of the filter refers to the pore diameter distribution, the position distribution of pores in the filter, the shape of pores, etc. Typically, it can be controlled by the manufacturing method of the filter.

[0453] For example, if sintering is performed on powders such as resins to form, a porous membrane is obtained, and if formed by methods such as electrospinning, electroblowing, and meltblowing, a fibrous membrane is obtained. The pore structures of these are different from each other.

[0454] The "porous membrane" refers to a membrane that retains components in the purified product such as gels, particles, colloids, cells, and polyoligomers, but components substantially smaller than the pores pass through the pores. Sometimes, the retention of components in the purified product by the porous membrane depends on operating conditions such as face velocity, use of surfactants, pH, and combinations thereof, and may depend on the pore diameter and structure of the porous membrane and the size and structure of the particles (hard particles or gels, etc.) to be removed.

[0455] When the purified product contains negatively charged particles, in order to remove such particles, a filter made of polyamide functions as a non-sieving membrane. Typical non-sieving membranes include nylon membranes such as nylon-6 membranes and nylon-6,6 membranes, but are not limited to these.

[0456] In addition, the "non-sieving" retention mechanism used in this specification refers to retention generated by mechanisms such as obstruction, diffusion, and adsorption that are independent of the pressure drop or pore size of the filter.

[0457] Non-sieving retention includes retention mechanisms such as obstruction, diffusion, and adsorption that remove target particles in the purified material independently of the pressure drop of the filter or the fine pore size of the filter. Adsorption of particles on the filter surface can be mediated, for example, by intermolecular van der Waals and electrostatic forces. An obstruction effect occurs when particles moving in a non-sieving membrane layer with a meandering path cannot change direction quickly enough to avoid contact with the non-sieving membrane. Particle transport based on diffusion is generated mainly by the random motion or Brownian motion of small particles, which forms a certain probability of particle collisions with the filter material. When there is no repulsive force between the particles and the filter, the non-sieving retention mechanism can become active.

[0458] UPE (ultra-high molecular weight polyethylene) filters are typically sieve membranes. A sieve membrane mainly refers to a membrane that captures particles through a sieve retention mechanism or a membrane optimized to capture particles through a sieve retention mechanism.

[0459] Typical examples of sieve membranes include polytetrafluoroethylene (PTFE) membranes and UPE membranes, but are not limited to these.

[0460] In addition, the "sieve retention mechanism" refers to the result of retaining target particles larger than the fine pore size of the porous membrane. The sieve retention force can be increased by forming a filter cake (aggregation of particles to be removed on the surface of the membrane). The filter cake effectively functions as a secondary filter.

[0461] The material of the fiber membrane is not particularly limited as long as it is a polymer capable of forming a fiber membrane. Examples of polymers include polyamides. Examples of polyamides include nylon 6 and nylon 6,6, etc. The polymer forming the fiber membrane 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 that of the polymer of the material of the porous membrane located on the secondary side. As such a combination, for example, there is a case where the material of the fiber membrane is nylon and the porous membrane is polyethylene (UPE).

[0462] The manufacturing method of the fiber membrane is not particularly limited, and known methods can be used. Examples of manufacturing methods of the fiber membrane include electrospinning, electrospraying, and meltblowing.

[0463] The pore structure of the porous membrane (for example, a porous membrane containing UPE, PTFE, etc.) is not particularly limited. Examples of the shape of the pores include lace-like, string-like, and node-like.

[0464] The size distribution and positional distribution in the membrane of the pores in the porous membrane are not particularly limited. The size distribution can be smaller and the distribution position in the membrane can be symmetric. Also, the size distribution can be larger, and the distribution position in the membrane can be asymmetric (such a membrane is also referred to as an "asymmetric porous membrane"). In an asymmetric porous membrane, the pore size varies in the membrane. Typically, the pore diameter increases from one surface of the membrane towards the other surface of the membrane. At this time, the surface with more large pores is called the "open side", and the surface with more small pores is called the "tight side".

[0465] Also, as an asymmetric porous membrane, for example, a membrane in which the pore size is minimized at a certain position within the thickness of the membrane (this is also referred to as an "hourglass shape") can be cited.

[0466] If an asymmetric porous membrane is used and the primary side is set to have larger-sized pores, in other words, if the primary side is set to the open side, a pre-filtering effect is produced.

[0467] The porous membrane can contain thermoplastic polymers such as PESU (polyethersulfone), PFA (perfluoroalkoxy alkane, copolymer of tetrafluoroethylene and perfluoroalkoxy alkane), polyamide, and polyolefin, and can also contain polytetrafluoroethylene, etc.

[0468] Among them, as the material of the porous membrane, ultra-high molecular weight polyethylene is preferred. Ultra-high molecular weight polyethylene is a thermoplastic polyethylene with extremely long chains, having a molecular weight of over one million, typically preferably 2 to 6 million.

[0469] As the filter used in the filtration process, two or more filters with different pore structures can be used, or filters of porous membrane and fiber membrane can be used simultaneously. As a specific example, a method of using a filter of nylon fiber membrane and a filter of UPE porous membrane can be cited.

[0470] Also, it is preferred that the filter be used after being thoroughly cleaned before use.

[0471] When an uncleaned filter (or a filter that has not been thoroughly cleaned) is used, impurities contained in the filter are easily introduced into the liquid medicine.

[0472] As impurities contained in the filter, for example, the above-mentioned organic compounds can be cited. If the filtration process is carried out using an uncleaned filter (or a filter that has not been thoroughly cleaned), the content of organic compounds in the liquid medicine sometimes exceeds the allowable range for the liquid medicine of the present invention.

[0473] For example, when polyolefins such as UPE and polyfluorocarbons such as PTFE are used for the filter, the filter is likely to contain alkanes with 12 to 50 carbon atoms as impurities.

[0474] Also, when a polymer obtained by graft copolymerizing polyamide (such as nylon) with polyamides such as nylon, polyimide, and polyolefin (such as UPE) is used for a filter, the filter is likely to contain olefins having 12 to 50 carbon atoms as impurities.

[0475] Examples of the filter cleaning method include a method of immersing the filter in an organic solvent with a low impurity content (for example, an organic solvent after distillation purification (such as PGMEA)) for 1 week or more. In this case, the liquid temperature of the above-mentioned organic solvent is preferably 30 to 90 °C.

[0476] Filter the purified material using a filter whose cleaning degree has been adjusted, and the obtained medicinal liquid can be adjusted to contain a desired amount of organic compounds from the filter.

[0477] The filtration step can be a multi-stage filtration step in which the purified material is passed through two or more filters at least one of which is different selected from the group consisting of the filter material, pore diameter, and pore structure.

[0478] Also, the purified material can be passed through the same filter multiple times, or the purified material can be passed through multiple filters of the same type.

[0479] There is no particular limitation on the material of the liquid receiving part (referring to the inner wall surface etc. where the purified material and the medicinal liquid may come into contact) of the purification device used in the filtration step, and it is preferably formed of at least one selected from the group consisting of non-metallic materials (such as fluorine-based resins) and electrolytically polished metallic materials (such as stainless steel) (hereinafter, these are also collectively referred to as "corrosion-resistant materials"). For example, as for the liquid receiving part of the tank being formed of a corrosion-resistant material, examples include the case where the tank itself is composed of a corrosion-resistant material or the inner wall surface etc. of the tank is coated with a corrosion-resistant material.

[0480] There is no particular limitation on the above-mentioned non-metallic material, and known materials can be used.

[0481] As the non-metallic material, for example, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene - polypropylene resin, and fluorine-based resins (such as tetrafluoroethylene resin, tetrafluoroethylene - perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene - hexafluoropropylene copolymer resin, tetrafluoroethylene - ethylene copolymer resin, vinylidene fluoride - ethylene copolymer resin, vinylidene fluoride copolymer resin, and vinyl fluoride resin, etc.) can be cited, but it is not limited thereto.

[0482] There is no particular limitation on the above-mentioned metallic material, and known materials can be used.

[0483] As the metal material, for example, a metal material in which the total content of chromium and nickel exceeds 25% by mass relative to the total mass of the metal material can be cited, and more preferably 30% by mass or more. There is no particular limitation on the upper limit value of the total content of chromium and nickel in the metal material, and usually 90% by mass or less is preferred.

[0484] As the metal material, for example, stainless steel and nickel-chromium alloy can be cited.

[0485] The stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferred, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferred. As the austenitic stainless steel, for example, SUS (Steel Use Stainl ess) 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 cited.

[0486] The nickel-chromium alloy is not particularly limited, and known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy with a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferred.

[0487] As the nickel-chromium alloy, for example, Hastelloy (product name, the same below), Monel alloy (product name, the same below), and Inconel alloy (product name, the same below) can be cited. More specifically, Hastelloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hastelloy-C (Ni content 60% by mass, Cr content 17% by mass), Hastelloy C-22 (Ni content 61% by mass, Cr content 22% by mass) can be cited.

[0488] And, if necessary, in addition to the above alloys, the nickel-chromium alloy can further contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc.

[0489] The method for electrolytic polishing the metal material is not particularly limited, and known methods can be used. For example, the methods 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.

[0490] It is speculated that the content of chromium in the passive layer on the surface of the metal material is more than that in the matrix phase by electrolytic polishing. Therefore, it is speculated that if a purification device with a liquid contact part formed of an electrolytically polished metal material is used, the metal-containing particles are difficult to flow out into the material to be purified.

[0491] In addition, the metal material can also be polished. The polishing method is not particularly limited, and known methods can be used. The size of the abrasive grains used in fine polishing is not particularly limited, but from the viewpoint that the unevenness on the surface of the metal material is likely to become smaller, it is preferably #400 or less. In addition, it is preferable to perform polishing before electrolytic polishing.

[0492] <Ion removal process>

[0493] The ion removal process is a process of subjecting the purified product containing an organic solvent to an ion exchange method or ion adsorption based on a chelating group. The components removed by the ion removal process are not limited thereto, and for example, acid components and metal ions contained in metal components can be cited.

[0494] The method for implementing the ion exchange method is not particularly limited, and known methods can be used. Typically, a method of passing the purified product through a filling portion filled with an ion exchange resin can be cited.

[0495] In the ion removal process, the purified product can pass through the same ion exchange resin multiple times, or the purified product can pass through different ion exchange resins.

[0496] As the ion exchange resin, cation exchange resins and anion exchange resins can be cited. 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 preferable 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 preferable to use an anion exchange resin together with the cation exchange resin.

[0497] When using both a cation exchange resin and an anion exchange resin, it can be passed through a filling portion filled with a mixed resin containing the two resins, or it can be passed through a plurality of filling portions filled with each resin.

[0498] As the cation exchange resin, known cation exchange resins can be used, and among them, gel-type cation exchange resins are preferred.

[0499] Specifically, as the cation exchange resin, sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins can be cited.

[0500] 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, ORLITE DS-4 (the above are manufactured by ORGANOCORPORATION), DUOLITE C20J, DUOLITE C20LF, DUOLITE C255LFH, DUOLITE C-433LF (the above are manufactured by Sumika Chemtex Co., Ltd.), DIAION SK-110, DIAION SK1B and DIAION SK1BH (the above are manufactured by Mitsubishi Chemical Corporation), PUROLITE S957 and PUROLITE S985 (the above are manufactured by Purolite Corporation), etc. can be cited.

[0501] As the anion exchange resin, known anion exchange resins can be used. Among them, gel-type anion exchange resins are preferably used.

[0502] Here, as the acid components present in the purified product in ionic form, inorganic acids derived from catalysts during the production of the purified product and organic acids generated after the reaction during the production of the purified product (for example, reaction raw materials, isomers, and by-products) can be cited. From the perspective of the HSAB (Hard and Soft Acids and Bases) rule, such acid components are classified as acids from hard acids to moderately hard acids. Therefore, for the purpose of improving the removal efficiency when removing these acid components through interaction with the anion exchange resin, an anion exchange resin containing a base from hard base to moderately hard base is preferably used.

[0503] Such an anion exchange resin containing a base from hard base to moderately hard base is preferably at least one anion exchange resin selected from the group consisting of strongly basic type I anion exchange resins having a trimethylammonium group, slightly less strongly basic type II anion exchange resins having a dimethylethanolammonium group, and weakly basic anion exchange resins such as dimethylamine and diethylenetriamine.

[0504] Among the acid components, for example, organic acids are hard acids, and sulfate ions in inorganic acids are moderately hard acids. Therefore, if the above-mentioned strongly basic or slightly less strongly basic anion exchange resin and the weakly basic anion exchange resin of moderately hard base are used simultaneously, it is easy to reduce the content of the acid components to a preferred range.

[0505] 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. can be mentioned.

[0506] Among them, as the anion exchange resin containing an alkali from a hard base to a medium-hardness base, for example, ORLITE DS-6, ORLITE DS-4 (both 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) etc. can be mentioned.

[0507] Ion adsorption by a chelating group can be carried out, for example, using a chelating resin having a chelating group. When the chelating resin captures an ion, it does not release a substitution ion, and by not using strongly acidic and strongly basic chemically highly reactive functional groups, secondary reactions with the organic solvent to be purified, which are hydrolysis and condensation reactions, can be suppressed. Therefore, more efficient purification can be carried out.

[0508] As the chelating resin, resins having a chelating group or chelating ability such as an amidoxime group, a thiourea group, a thiouronium group, iminodiacetic acid, amide phosphoric acid, phosphonic acid, aminophosphoric acid, aminocarboxylic acid, N-methylglucamine, alkylamino, pyridine ring, cyclic cyanine, phthalocyanine ring, and cyclic ether etc. can be mentioned.

[0509] 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 (the above are manufactured by Sumika Chemtex Co., Ltd.), PUROLITE S106, PUROLITE S910, PUROLITE S914, PUROLITE S920, PUROLITE S930, PUROLITE S950, PUROLITE S957, and PUROLITE S985 (the above are manufactured by Purolite Corporation), etc. can be cited.

[0510] The method for carrying out ion adsorption is not particularly limited, and known methods can be used. Typically, a method of passing the purified product through a packed portion filled with a chelating resin can be cited.

[0511] In the ion removal step, the purified product can be passed through the same chelating resin multiple times, or the purified product can be passed through different chelating resins.

[0512] The packed portion generally includes a container and the above-mentioned ion exchange resin packed in the container.

[0513] As the container, a column, a cylinder, a packed tower, etc. can be cited. As long as the purified product can pass through after packing the above-mentioned ion exchange resin, it can be a container other than the above examples.

[0514] <Distillation step>

[0515] The distillation step is a step of distilling the purified product containing an organic solvent to obtain a distilled purified product. The components removed by the distillation step are not limited thereto. For example, an acid component, other organic compounds, and moisture can be cited.

[0516] The method for distilling the purified product is not particularly limited, and known methods can be used. Typically, a method of arranging a distillation column on the primary side of the purification device used for the filtration step and introducing the distilled purified product into the production tank can be cited.

[0517] At this time, there is no particular limitation on the liquid receiving portion of the distillation column, and it is preferably formed of the corrosion-resistant material described above.

[0518] In the distillation step, the purified product can be passed through the same distillation column multiple times, or the purified product can be passed through different distillation columns.

[0519] When passing the purified material through different distillation columns, the following methods can be cited, for example: after performing a rough distillation process of passing the purified material through a distillation column to remove low-boiling acid components and the like, a rectification process of passing the purified material through a distillation column different from the rough distillation process to remove acid components and other organic compounds and the like is performed. At this time, as the distillation column for the rough distillation process, a tray distillation column can be cited, and as the distillation column for the rectification process, a distillation column including at least one of a tray distillation column and a vacuum tray can be cited.

[0520] Furthermore, for the purpose of balancing the thermal stability during distillation and the purification accuracy, vacuum distillation can also be selected.

[0521] <Other processes>

[0522] The method for manufacturing the liquid medicine may also have processes other than the above. As processes other than the filtration process, reaction processes and deelectrification processes can be cited, for example.

[0523] (Reaction process)

[0524] The reaction process is a process of reacting raw materials to generate a purified material containing an organic solvent as a reactant. There is no particular limitation on the method for generating the purified material, and known methods can be used. Typically, a method of arranging a reaction tank on the primary side of a manufacturing tank (or distillation column) for the purification device used in the filtration process and introducing the reactants into the manufacturing tank (or distillation column) can be cited.

[0525] At this time, there is no particular limitation on the liquid receiving part of the manufacturing tank, and it is preferably formed of the corrosion-resistant material described above.

[0526] (Deelectrification process)

[0527] The deelectrification process is a process of reducing the charged potential of the purified material by deelectrifying the purified material.

[0528] There is no particular limitation on the deelectrification method, and known deelectrification methods can be used. As the deelectrification method, for example, a method of bringing the purified material into contact with a conductive material can be cited.

[0529] The contact time for bringing the purified material into contact with 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. As the conductive material, stainless steel, gold, platinum, diamond, glassy carbon, etc. can be cited.

[0530] As the method for bringing the purified material into contact with the conductive material, for example, the following methods can be cited: arranging a grounded mesh formed of a conductive material inside a pipeline and passing the purified material through it.

[0531] Regarding the purification of the purified substance, preferably, the opening of the container attached thereto, the cleaning of the container and the device, the accommodation of the solution, the analysis, etc. are all carried out in a clean room. The clean room preferably meets the international standard ISO14644-1 defined by the International Organization for Standardization: a clean room with a cleanliness level of Class 4 or higher defined in 2015. Specifically, it is preferably to meet any one of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably to meet ISO Class 1 or ISO Class 2, and particularly preferably to meet ISO Class 1.

[0532] There is no particular limitation on the storage temperature of the liquid medicine. From the perspective that impurities in the liquid medicine are more difficult to dissolve in trace amounts and as a result, more excellent effects of the present invention can be obtained, the storage temperature is preferably 4°C or higher.

[0533] [Liquid medicine container]

[0534] This liquid medicine is accommodated in a container and stored until use. This container and the liquid medicine accommodated in the container are collectively referred to as a liquid medicine container. After taking out this liquid medicine from the stored liquid medicine container, it is used.

[0535] As the container for storing this liquid medicine, for semiconductor device manufacturing applications, a container with high cleanliness inside the container and less elution of impurities is preferred.

[0536] As containers that can be used, specifically, the "Clean Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "Pure Bottle" manufactured by KODAMA PLASTICS C0., LTD. can be cited, but it is not limited to these.

[0537] As the container, it is also preferred to use a multi-layer bottle with a six-layer structure of the inner wall of the container based on six resins or a multi-layer bottle with a seven-layer structure of the inner wall of the container based on six resins for the purpose of preventing the mixing (contamination) of impurities into the liquid medicine. As these containers, for example, the containers described in Japanese Patent Laid-Open No. 2015-123351 can be cited.

[0538] At least a part of the liquid contact part of the container can be the corrosion-resistant materials described above (preferably electrolytically polished stainless steel or fluorine-based resin) or glass. From the perspective of obtaining more excellent effects of the present invention, it is preferred that more than 90% of the area of the liquid contact part is composed of the above materials, and more preferably the entire liquid contact part is composed of the above materials.

[0539] [Kit]

[0540] The kit of the present invention includes a liquid X shown below and a liquid Y shown below. When the kit of the present invention is used in the pattern forming method described later (in particular, when the liquid X is used as a developer and the liquid Y is used as a rinsing liquid), a pattern with defect generation inhibited by the action of the liquid X can be obtained, and due to the synergistic effect of the liquid X and the liquid Y, the resolution of the obtained pattern is also excellent.

[0541] The form of the kit is not particularly limited, and examples thereof include a form having a liquid container X and a liquid container Y. The liquid container X has a container X and a liquid X accommodated in the container X, and the liquid container Y has a container Y and a liquid Y accommodated in the container Y. As the container X and the container Y, it is preferable to use the container described above as the container of the liquid container.

[0542] The liquid X is the following liquid X1 or liquid X2. The liquid X1 is a liquid in the above-mentioned liquid 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 with respect to the total mass of the liquid X1. And the liquid X2 is a liquid in the above-mentioned liquid 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 with respect to the total mass of the liquid X2.

[0543] The liquid Y contains an organic solvent. The organic solvent contained in the liquid Y contains at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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 liquid Y is used as a rinsing liquid in the pattern forming method described later, the resolution of the obtained pattern can be improved by the action of the organic solvent Y.

[0544] The liquid Y may be the above-mentioned liquid (that is, a liquid containing an organic solvent, an acid component, and a metal component, the content of the acid component is 1 mass ppt or more and 15 mass ppm or less with respect to the total mass of the liquid, and the content of the metal component is 0.001 to 100 mass ppt with respect to the total mass of the liquid.), or may be a liquid other than the above-mentioned liquid.

[0545] The liquid other than the above-mentioned liquid means a case where the content of the acid component is less than 1 mass ppt or more than 15 mass ppm with respect to the total mass of the liquid and a case where the content of the metal component is less than 0.001 mass ppt or more than 100 mass ppt with respect to the total mass of the liquid, at least one of which is satisfied.

[0546] The content of organic solvent Y in liquid medicine 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, based on the total mass of liquid medicine 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. There is no particular limitation on the upper limit, which is 100% by mass or less.

[0547] The preferred range of the content of organic solvent Y relative to the total mass of the organic solvents contained in liquid medicine Y is the same as the content of organic solvent Y in liquid medicine Y described above.

[0548] Organic solvent Y can be used alone or two or more kinds can be used simultaneously. When two or more kinds of organic solvent Y are used simultaneously, the total content is within the above range.

[0549] Liquid medicine Y can contain organic solvents other than organic solvent Y. As organic solvents other than organic solvent Y, organic solvents other than organic solvent Y among the organic solvents exemplified as the organic solvents of the present liquid medicine and ethanol, etc. can be cited.

[0550] When liquid medicine Y contains organic solvents other than organic solvent Y, the content of the organic solvents other than 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, based on the total mass of liquid medicine Y. When liquid medicine Y contains organic solvents other than organic solvent Y, the lower limit value of the content of the organic solvents other than organic solvent Y is greater than 0% by mass, preferably 0.1% by mass or more, and more preferably 1% by mass or more.

[0551] When liquid medicine Y contains organic solvents other than organic solvent Y, the preferred range of the content of the organic solvents other than organic solvent Y relative to the total mass of the organic solvents contained in liquid medicine Y is the same as the content of the organic solvents other than organic solvent Y in liquid medicine Y described above.

[0552] The content of the organic solvents in liquid medicine Y (i.e., the total of the content of organic solvent Y and the organic solvents other than 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, based on the total mass of liquid medicine Y. There is no particular limitation on the upper limit, which is 100% by mass or less.

[0553] Preferably, organic solvent Y includes organic solvent Y1 having a distance of 3 to 20 MPa 0.5 (more preferably 5 to 20 MPa 0.5 ) from the Hansen solubility parameter of eicosene.

[0554] When two or more organic solvents Y are included in the liquid medicine Y, it is preferable that at least one of them is the organic solvent Y1.

[0555] When two or more organic solvents Y are included in the liquid medicine Y, it is preferable that the weighted average of the Hansen solubility parameters based on the molar ratio of the contents of the respective organic solvents satisfies the above range of the Hansen solubility parameters.

[0556] Among the organic solvents Y, the organic solvents (i.e., the organic solvent Y1) having a distance of 3 to 20 MPa from the Hansen solubility parameter with respect to eicosene 0.5 include butyl butyrate (4.6), isobutyl isobutyrate (3.6), and dimethyl malonate (10.3). In addition, the numerical value in parentheses in the compound indicates the distance from the Hansen solubility parameter with respect to eicosene.

[0557] As one of the preferred modes of the liquid medicine Y, a mode in which the organic solvent Y is substantially only the organic solvent Y1 can be cited. The case where the organic solvent Y is substantially only the organic solvent Y1 means that the content of the organic solvent Y1 is 99% by mass or more (preferably 99.9% by mass or more) with respect to the total mass of the organic solvents Y in the liquid medicine Y.

[0558] Moreover, as one of the preferred modes of the liquid medicine Y, a mode can be cited in which a mixed solvent containing both the organic solvent Y and an organic solvent other than the organic solvent Y (for example, methanol, etc.) is included, and the organic solvent Y is substantially only the organic solvent Y1.

[0559] In this case, the content of the organic solvent Y1 is preferably 20 to 90% by mass with respect to the total mass of the liquid medicine Y, more preferably 20 to 80% by mass from the viewpoint of more excellent pattern resolution, and further preferably 30 to 70% by mass.

[0560] Moreover, the content of the organic solvent other than the organic solvent Y is preferably 10 to 80% by mass with respect to the total mass of the liquid medicine Y, more preferably 20 to 80% by mass from the viewpoint of more excellent pattern resolution, and further preferably 30 to 70% by mass.

[0561] Moreover, as one of the preferred modes of the liquid medicine Y, a mode can be cited in which the organic solvent in the liquid medicine is composed of the organic solvent Y, and the organic solvent Y is a mixed solvent containing both the organic solvent Y1 and an organic solvent that does not satisfy the above range of the Hansen solubility parameter (hereinafter, also referred to as "organic solvent Y2").

[0562] In this case, the content of the organic solvent Y1 is preferably 20 to 90% by mass with respect to the total mass of the liquid medicine Y, more preferably 20 to 80% by mass from the viewpoint of more excellent pattern resolution, and further preferably 30 to 70% by mass.

[0563] Moreover, the content of organic solvent Y2 is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass, based on the total mass of liquid medicine Y, in view of more excellent pattern resolution.

[0564] When the contents of organic solvent Y1 and upper organic solvent Y2 are within certain ranges respectively, it is speculated that, compared with the cases where the content of organic solvent Y2 is excessive or too small, the affinity of liquid medicine Y for the organic raw material can be adjusted to an appropriate range, and the pattern resolution is more excellent.

[0565] In addition, the distance between the Hansen solubility parameter of organic solvent Y2 and that of icosene is 0 MPa 0.5 or more and less than 3 MPa 0.5 (preferably greater than 0 MPa 0.5 and less than 3 MPa 0.5 ) or greater than 20 MPa 0.5 (preferably greater than 20 MPa 0.5 and 50 MPa 0.5 or less).

[0566] In this specification, the Hansen solubility parameter refers to the Hansen solubility parameter described in "Hansen Solubility Parameters: A Users Handbook, Second Edition" (pages 1-310, CRC Press, published in 2007), etc. That is, the Hansen solubility parameter represents solubility by a multi-dimensional vector (dispersion term (δd), dipole-dipole term (δp), and hydrogen bond term (δh)), and these three parameters can be regarded as the coordinates of points in a three-dimensional space called Hansen space.

[0567] The distance of the Hansen solubility parameter is the distance between two compounds in Hansen space, and the distance of the Hansen solubility parameter is calculated by the following formula.

[0568] (Ra) 2 = 4(δd2 - δd1) 2 +(δp2 - δp1) 2 +(δh2 - δh1) 2

[0569] Ra: The distance between the Hansen solubility parameters of the first compound and the second compound (unit: MPa 0.5 )

[0570] δd1: The dispersion term of the first compound (unit: MPa 0.5 )

[0571] δd2: The dispersion term of the second compound (unit: MPa 0.5 )

[0572] δp1: Dipole-dipole term of the first compound (unit: MPa 0.5 )

[0573] δp2: Dipole-dipole term of the second compound (unit: MPa 0.5 )

[0574] δh1: Hydrogen bond term of the first compound (unit: MPa 0.5 )

[0575] δh2: Hydrogen bond term of the second compound (unit: MPa 0.5 )

[0576] In this specification, the Hansen solubility parameter of a compound is specifically calculated using HSPiP (Hansen Solubility Parameter in Practice).

[0577] [Pattern formation method]

[0578] Preferably, this liquid medicine is used to form a resist pattern (hereinafter simply referred to as "pattern") used in semiconductor manufacturing applications. As a pattern formation method using this liquid medicine, there is no particular limitation, and known pattern formation methods can be cited.

[0579] As one of the preferred embodiments of the pattern formation method of the present invention, preferably, a method can be cited in which the liquid medicine X described in the above kit item is used as a developer, and the liquid medicine Y described in the above kit item is used as a rinse liquid, and specifically includes the following respective steps.

[0580] (A) Resist film formation step of forming a resist film using a photosensitive or radiation-sensitive resin composition

[0581] (B) Exposure step of exposing the resist film

[0582] (C) Development step of developing the resist film before exposure using the liquid medicine X

[0583] (D) Rinse step of rinsing with the liquid medicine Y after the development step

[0584] Hereinafter, the method of each of the above steps will be described. In addition, for the liquid medicine X and the liquid medicine Y, since they are as described above, their descriptions are omitted.

[0585] [Resist film formation step]

[0586] The resist film formation step is a step of forming a resist film using a photosensitive or radiation-sensitive resin composition.

[0587] Hereinafter, the method of the photosensitive radiation or radiation-sensitive resin composition will be described first.

[0588] <Photosensitive radiation or radiation-sensitive resin composition>

[0589] The photosensitive radiation or radiation-sensitive resin composition that can be used in the resist film forming step described above is not particularly limited, and known photosensitive radiation or radiation-sensitive resin compositions can be used.

[0590] As the photosensitive radiation or radiation-sensitive resin composition (hereinafter, also referred to as "resist composition"), it preferably contains the following: a repeating unit resin containing a group that decomposes by the action of an acid to generate a polar group (such as a carboxyl group and a phenolic hydroxyl group) (hereinafter, also referred to as "acid-decomposable resin" in this specification) and a compound that generates an acid upon irradiation with actinic radiation or radiation (hereinafter, also referred to as "photoacid generator" in this specification).

[0591] Among them, from the viewpoint of obtaining more excellent effects of the present invention, the following resist compositions are preferred.

[0592] · A resist composition containing the resin represented by the following formula (I)

[0593] · A resist composition containing an acid-decomposable resin having a phenolic hydroxyl group described later

[0594] · A resist composition containing a hydrophobic resin and an acid-decomposable resin described later

[0595] Hereinafter, each component of the resist composition will be described.

[0596] (Acid-decomposable resin)

[0597] In the acid-decomposable group, the polar group is protected by a group that dissociates under the action of an acid (acid-dissociable group). Examples of the acid-dissociable group include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ) and -C(R 01 )(R 02 )(OR 39 ) and the like.

[0598] In the formula, R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 and R 37 may be bonded to each other to form a ring.

[0599] R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

[0600] As the acid-decomposable resin, a resin P having an acid-decomposable group represented by the formula (AI) can be mentioned.

[0601] [Chemical formula 12]

[0602]

[0603] In the formula (AI),

[0604] Xa 1 represents a hydrogen atom or an alkyl group which may have a substituent.

[0605] T represents a single bond or a divalent linking group.

[0606] Ra 1 ~Ra 3 each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic).

[0607] Ra 1 ~Ra 3 Two of them may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0608] As the alkyl group which may have a substituent represented by Xa 1 , for example, a methyl group and a group represented by -CH 2 -R 11 can be mentioned. R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group.

[0609] Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

[0610] As the divalent linking group of T, an alkylene group, a -COO-Rt- group, an -O-Rt- group, etc. can be mentioned. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0611] T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH 2 - group, a -(CH 2 ) 2 - group or a -(CH 2 ) 3 - group.

[0612] As the alkyl group of Ra 1 ~Ra 3 , an alkyl group having 1 to 4 carbon atoms is preferred.

[0613] As Ra 1 ~Ra 3 The cycloalkyl group of ~ Ra is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl.

[0614] As Ra 1 ~Ra 3 The cycloalkyl group formed by bonding two of ~ Ra is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclodecyl, tetracyclododecyl or adamantyl. More preferably, it is a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

[0615] Regarding Ra 1 ~Ra 3 In the above cycloalkyl group formed by bonding two of ~ Ra, for example, one of the methylene groups constituting the ring may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

[0616] The repeating unit represented by formula (AI) is preferably, for example, Ra 1 is methyl or ethyl, Ra 2 and Ra 3 The manner of bonding to form the above cycloalkyl group.

[0617] The above groups may have substituents. Examples of the substituents include alkyl groups (having 1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (having 1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (having 2 to 6 carbon atoms), etc., and preferably have 8 or fewer carbon atoms.

[0618] The total content of the repeating unit represented by formula (AI) relative to all the repeating units in resin P is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and still more preferably 30 to 80 mol%.

[0619] Specific examples of the repeating unit represented by the general formula (AI) are shown below, but are not limited thereto.

[0620] In the specific examples, Rx and Xa 1 each independently represent a hydrogen atom, CH 3 , CF 3 or CH 2 OH. 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, they are independent of each other. p represents 0 or a positive integer. Examples of the substituent containing the polar group represented by Z include 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.

[0621] [Chemical Formula 13]

[0622]

[0623] (Repeating unit having a lactone structure)

[0624] Furthermore, it is preferable that the resin P contains a repeating unit Q having a lactone structure.

[0625] Preferably, the repeating unit Q having a lactone structure has a lactone structure in the side chain. For example, a repeating unit derived from a (meth)acrylic acid derivative monomer is more preferable.

[0626] The repeating unit Q having a lactone structure may be used alone or two or more thereof may be used simultaneously, but it is preferable to use one alone.

[0627] The content of the repeating unit Q having a lactone structure is, for example, 3 to 80 mol%, preferably 3 to 60 mol%, relative to all the repeating units of the resin P.

[0628] As the lactone structure, a 5- to 7-membered lactone structure is preferable, and a structure in which another ring structure is condensed in the 5- to 7-membered lactone structure to form a bicyclic structure or a spiro ring structure is more preferable.

[0629] As the lactone structure, it is preferable 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, a lactone structure represented by formula (LC1-1), formula (LC1-4), formula (LC1-5), or formula (LC1-8) is preferable, and a lactone structure represented by formula (LC1-4) is more preferable.

[0630] [Chemical Formula 14]

[0631]

[0632] The lactone structure moiety may have a substituent (Rb 2 ). As preferable substituents (Rb 2 ), an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group can be mentioned. n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the plurality of substituents (Rb 2 ) may be the same or different, and the plurality of substituents (Rb 2 ) may bond to each other to form a ring.

[0633] The resin P preferably includes a resin having the following repeating units (hereinafter, this resin is also referred to as "the resin represented by formula (I)"), and the aforementioned repeating units are selected from the group consisting of the repeating unit represented by formula (a), the repeating unit represented by formula (b), the repeating unit represented by formula (c), the repeating unit represented by formula (d), and the repeating unit represented by formula (e).

[0634] The resin represented by the following formula (I) is a resin whose solubility in a developer (the liquid medicine described later) mainly composed of an organic solvent is reduced by the action of an acid and contains an acid-decomposable group. The above-mentioned liquid medicine has excellent solubility in the resin represented by formula (I), so it is easy to obtain a uniform resist film with less resist composition. Hereinafter, the resin represented by formula (I) will be described.

[0635] · The resin represented by formula (I)

[0636] [Chemical formula 15]

[0637]

[0638] The above formula (I) is composed of a repeating unit (a) (the repeating unit represented by formula (a)), a repeating unit (b) (the repeating unit represented by formula (b)), a repeating unit (c) (the repeating unit represented by formula (c)), a repeating unit (d) (the repeating unit represented by formula (d)), and a repeating unit (e) (the repeating unit represented by formula (e)).

[0639] R x1 ~R x5 Each independently represents a hydrogen atom or an alkyl group which may contain a substituent.

[0640] R 1 ~R 4 Each independently represents a monovalent substituent, and p 1 ~p 4 Each independently represents 0 or a positive integer.

[0641] R a represents a linear or branched alkyl group.

[0642] T 1 ~T 5 Each independently represents a single bond or a divalent linking group.

[0643] R 5 represents a monovalent organic group.

[0644] a to e represent mol%, and independently represent numbers in the ranges of 0 ≤ a ≤ 100, 0 ≤ b ≤ 100, 0 ≤ c < 100, 0 ≤ d < 100, and 0 ≤ e < 100. Among them, a + b + c + d + e = 100, and a + b ≠ 0.

[0645] Among them, in formula (I), the above-mentioned repeating unit (e) has a structure different from any of the above-mentioned repeating units (a) to (d).

[0646] As the alkyl group represented by R x1 ~R x5 which may contain substituents, for example, methyl and -CH 2 -R 11 group represented. R 11 represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group.

[0647] Preferably, R x1 ~R x5 are each independently a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0648] In formula (I), as the divalent linking group represented by T 1 ~T 5 for example, an alkylene group, a -COO-Rt- group, an -O-Rt- group, etc. can be cited. In the formula, Rt represents an alkylene group or a cycloalkylene group.

[0649] Preferably, T 1 ~T 5 are each independently a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably a -CH 2 - group, a -(CH 2 ) 2 - group, or a -(CH 2 ) 3 - group.

[0650] In formula (I), R a represents a linear or branched alkyl group. For example, methyl, ethyl, tert-butyl, etc. can be cited. Among them, a linear or branched alkyl group having 1 to 4 carbon atoms is preferred.

[0651] In formula (I), R 1 ~R 4 each independently represents a monovalent substituent. As R 1 ~R 4 , there is no particular limitation. For example, a hydroxyl group, a cyano group, and a linear or branched alkyl group or cycloalkyl group having a hydroxyl group or a cyano group, etc. can be cited.

[0652] In formula (I), p 1 ~p 4Each independently represents 0 or a positive integer. Further, p 1 ~p 4 The upper limit value corresponds to the number of hydrogen atoms that can be substituted in each repeating unit.

[0653] In formula (I), R 5 represents a monovalent organic group. As R 5 , there is no particular limitation, 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 in which the carbon at the position bonded to the -C00 group is substituted with an alkyl group and quaternized).

[0654] Further, in formula (I), the repeating unit (b) is also preferably a repeating unit formed from the monomers described in paragraphs 0014 to 0018 of Japanese Patent Application Laid-Open No. 2016-138219.

[0655] 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, and 0 ≤ e < 100. Among them, a + b + c + d + e = 100, and a + b ≠ 0.

[0656] In formula (I), a + b (the content of the repeating unit having an acid-decomposable group relative to all repeating units) is preferably 20 to 90 mol%, more preferably 25 to 85 mol%, and still more preferably 30 to 80 mol%.

[0657] Further, in 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%.

[0658] In addition, each of the repeating units (a) to (e) can be used alone, or two or more of each repeating unit can be used simultaneously. When two or more of each repeating unit are used simultaneously, the total content is preferably within the above ranges respectively.

[0659] The weight average molecular weight (Mw) of the resin represented by formula (I) is generally preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3,000 to 15,000. Further, the above weight average molecular weight is a polystyrene conversion value obtained by using tetrahydrofuran (THF) as an eluent and by gel permeation chromatography (GPC).

[0660] In the above photosensitive radiation-curable or radiation-curable resin composition, based on the total solid content of the photosensitive radiation-curable or radiation-curable resin composition, the content of the resin represented by the above formula (I) is usually preferably 30 to 99% by mass, more preferably 50 to 95% by mass.

[0661] (Repeating unit having a phenolic hydroxyl group)

[0662] Moreover, the resin P may contain a repeating unit having a phenolic hydroxyl group.

[0663] As the repeating unit having a phenolic hydroxyl group, for example, a repeating unit represented by the following general formula (I) can be cited.

[0664] [Chemical formula 16]

[0665]

[0666] In the formula,

[0667] 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. Among them, R 42 may bond with Ar 4 to form a ring, and in this case, R 42 represents a single bond or an alkylene group.

[0668] X 4 represents a single bond, -COO- or -CONR 64 -, and R 64 represents a hydrogen atom or an alkyl group.

[0669] L 4 represents a single bond or an alkylene group.

[0670] Ar 4 represents an (n + 1)-valent aromatic ring group, and represents an (n + 2)-valent aromatic ring group when bonding with R 42 to form a ring.

[0671] n represents an integer of 1 to 5.

[0672] As the alkyl groups of R 41 , R 42 and R 43 in the general formula (I), alkyl groups having 20 or less carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl which may preferably have substituents are more preferably alkyl groups having 8 or less carbon atoms, and still more preferably alkyl groups having 3 or less carbon atoms.

[0673] As R 41, R 42 and R 43 The cycloalkyl group of and may be monocyclic or polycyclic. As the cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms and being monocyclic such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent is preferable.

[0674] As R in the general formula (I) 41 , R 42 and R 43 The halogen atom of may be exemplified by a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

[0675] As R in the general formula (I) 41 , R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group of is preferably the same group as the alkyl group in the above R 41 , R 42 and R 43 .

[0676] As the substituent in each of the above groups, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a urea group, a carbamate group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group can be exemplified, and the number of carbon atoms of the substituent is preferably 8 or less.

[0677] Ar 4 represents an (n + 1)-valent aromatic ring group. The divalent aromatic ring group when n is 1 may have a substituent, and examples thereof include arylene groups having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthrylene group, and aromatic ring groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0678] As a specific example of the (n + 1)-valent aromatic ring group when n is an integer of 2 or more, a group obtained by removing (n - 1) arbitrary hydrogen atoms from the above specific examples of the divalent aromatic ring group can be exemplified.

[0679] The (n + 1)-valent aromatic ring group may further have a substituent.

[0680] As the substituent that the above alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n + 1)-valent aromatic ring group can have, for example, the alkyl group exemplified in R 41 , R 42 and R 43 in the general formula (I); alkoxy groups such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; and aryl groups such as a phenyl group.

[0681] As formed by X 4-CONR- 64 -(R 64 which represents a hydrogen atom, an alkyl group) where R 64 is an alkyl group, examples of which include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups having 20 or fewer carbon atoms and which may have substituents, and more preferably an alkyl group having 8 or fewer carbon atoms.

[0682] As X 4 , a single bond, -COO-, or -CONH- is preferred, and a single bond or -COO- is more preferred.

[0683] As the alkylene group in L 4 , an alkylene group having 1 to 8 carbon atoms such as methylene, ethylene, propylene, butylene, hexylene, and octylene groups which may have substituents is preferred.

[0684] As Ar 4 , an aromatic ring group having 6 to 18 carbon atoms which may have substituents is preferred, and a benzene ring group, a naphthalene ring group, or a biphenylene ring group is more preferred.

[0685] Preferably, the repeating unit represented by the general formula (I) has a hydroxystyrene structure. That is, Ar 4 is preferably a benzene ring group.

[0686] As the repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (p1) is preferred.

[0687] [Chemical formula 17]

[0688]

[0689] In the general formula (p1), R 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. As R in the general formula (p1), a hydrogen atom is preferred.

[0690] In the general formula (p1), Ar represents an aromatic ring, examples of which include aromatic hydrocarbon rings having 6 to 18 carbon atoms such as benzene ring, naphthalene ring, anthracene ring, fluorene ring, and phenanthrene ring which may have substituents, and aromatic heterocyclic rings containing heteroatoms such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring. Among them, a benzene ring is more preferred.

[0691] In the general formula (p1), m represents an integer of 1 to 5, and 1 is preferred.

[0692] Hereinafter, specific examples of the repeating unit having a phenolic hydroxyl group are shown, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[0693] [Chemical Formula 18]

[0694]

[0695] [Chemical Formula 19]

[0696]

[0697] [Chemical Formula 20]

[0698]

[0699] The content of the repeating unit having a phenolic hydroxyl group is preferably 0 to 50 mol%, more preferably 0 to 45 mol%, and further preferably 0 to 40 mol% relative to all the repeating units in Resin P.

[0700] (Repeating unit containing an organic group having a polar group)

[0701] Resin P may further contain a repeating unit containing an organic group having a polar group, particularly a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group.

[0702] Thereby, the substrate adhesion and the developer affinity are improved. As the alicyclic hydrocarbon structure of the alicyclic hydrocarbon structure substituted with a polar group, adamantyl group, diamond alkyl group or norbornyl group is preferred. As the polar group, hydroxyl group or cyano group is preferred.

[0703] Specific examples of the repeating unit having a polar group are listed below, but the present invention is not limited to these.

[0704] [Chemical Formula 21]

[0705]

[0706] When Resin P contains a repeating unit containing an organic group having a polar group, its content 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 the repeating units in Resin P.

[0707] (Repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (photoacid generator))

[0708] Resin P may also contain a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (photoacid generator).

[0709] As the repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (photoacid generator), for example, the repeating unit represented by the following formula (4) can be cited.

[0710] [Chemical Formula 22]

[0711]

[0712] R 41 represents a hydrogen atom or a methyl group. L 41 represents a single bond or a divalent linking group. L 42 represents a divalent linking group. W represents a structural moiety that generates an acid in the side chain upon decomposition by irradiation with actinic rays or radiation.

[0713] Specific examples of the repeating unit represented by the formula (4) are shown below, but the present invention is not limited thereto.

[0714] [Chemical Formula 23]

[0715]

[0716] In addition, as the repeating unit represented by the formula (4), for example, the repeating units described in paragraphs

[0094] to

[0105] of Japanese Patent Application Laid-Open No. 2014-041327 can be cited.

[0717] When the resin P contains a repeating unit having a photoacid generator group, the content of the repeating unit having a photoacid generator group is preferably 1 to 40 mol%, more preferably 5 to 35 mol%, and still more preferably 5 to 30 mol% with respect to all the repeating units in the resin P.

[0718] The resin P may contain a repeating unit represented by the following formula (VI).

[0719] [Chemical Formula 24]

[0720]

[0721] In the formula (VI),

[0722] 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. Among them, R 62 may be bonded to Ar 6 to form a ring, and in this case, R 62 represents a single bond or an alkylene group.

[0723] X 6 represents a single bond, -COO-, or -CONR 64 -. R 64 represents a hydrogen atom or an alkyl group.

[0724] L 6 represents a single bond or an alkylene group.

[0725] Ar 6 represents an aromatic ring group with a valence of (n + 1), and represents an aromatic ring group with a valence of (n + 2) when bonded to R 62 to form a ring.

[0726] Regarding Y 2 , when n ≥ 2, they each independently represent a hydrogen atom or a group that detaches by the action of an acid. Among them, at least one of Y 2 represents a group that detaches by the action of an acid.

[0727] n represents an integer from 1 to 4.

[0728] As the group Y that detaches by the action of an acid 2 , it is preferably a structure represented by the following formula (VI-A).

[0729] [Chemical formula 25]

[0730]

[0731] L 1 and L 2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group.

[0732] M represents a single bond or a divalent linking group.

[0733] Q represents an alkyl group, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group.

[0734] Q, M, L 1 Among them, at least two can bond to form a ring (preferably a 5-membered or 6-membered ring).

[0735] The repeating unit represented by the above formula (VI) is preferably a repeating unit represented by the following formula (3).

[0736] [Chemical formula 26]

[0737]

[0738] In formula (3),

[0739] Ar 3 represents an aromatic ring group.

[0740] R 3 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.

[0741] M 3 represents a single bond or a divalent linking group.

[0742] Q3 represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

[0743] Q 3 , M 3 and R 3 at least two of which may be bonded to form a ring.

[0744] Ar 3 The aromatic ring group represented by is the same as Ar in the above formula (VI) when n = 1 in the above formula (VI), 6 more preferably a phenylene group or a naphthylene group, and still more preferably a phenylene group.

[0745] Specific examples of the repeating unit represented by the formula (VI) are shown below, but the present invention is not limited thereto.

[0746] [Chemical formula 27]

[0747]

[0748] [Chemical formula 28]

[0749]

[0750] Resin P may contain a repeating unit represented by the following formula (4).

[0751] [Chemical formula 29]

[0752]

[0753] In the formula (4),

[0754] R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R 42 may be bonded to L 4 to form a ring, and in this case, R 42 represents an alkylene group.

[0755] L 4 represents a single bond or a divalent linking group, and represents a trivalent linking group when forming a ring with R 42 .

[0756] R 44 and R 45 represent 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.

[0757] M 4 represents a single bond or a divalent linking group.

[0758] Q 4Represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group.

[0759] Q 4 , M 4 and R 44 at least two of which may bond to form a ring.

[0760] R 41 , R 42 and R 43 have the same meanings as R 41 , R 42 and R 43 in the aforementioned formula (IA), and preferably have the same ranges.

[0761] L 4 has the same meaning as T in the aforementioned formula (AI), and preferably has the same range.

[0762] R 44 and R 45 have the same meanings as R 3 in the aforementioned formula (3), and preferably have the same ranges.

[0763] M 4 has the same meaning as M 3 in the aforementioned formula (3), and preferably has the same range.

[0764] Q 4 has the same meaning as Q 3 in the aforementioned formula (3), and preferably has the same range.

[0765] As a ring formed by bonding at least two of Q 4 , M 4 and R 44 , rings formed by bonding at least two of Q 3 , M 3 and R 3 can be enumerated, and preferably have the same ranges.

[0766] Specific examples of the repeating unit represented by formula (4) are shown below, but the present invention is not limited thereto.

[0767] [Chemical formula 30]

[0768]

[0769] And the resin P may contain a repeating unit represented by the following formula (BZ).

[0770] [Chemical formula 31]

[0771]

[0772] In formula (BZ), AR represents an aryl group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and AR may bond to each other to form a non-aromatic ring.

[0773] R 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

[0774] Specific examples of the repeating unit represented by formula (BZ) are shown below, but are not limited to these.

[0775] [Chemical formula 32]

[0776]

[0777] [Chemical formula 33]

[0778]

[0779] The content of the repeating unit having an acid-decomposable group in resin P (the total when there are multiple types) is preferably 5 to 80 mol%, more preferably 5 to 75 mol%, and still more preferably 10 to 65 mol% with respect to all the repeating units in the above resin P.

[0780] Resin P may contain a repeating unit represented by the following formula (V) or the following formula (VI).

[0781] [Chemical formula 34]

[0782]

[0783] In the formula,

[0784] R 6 and R 7 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, 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.

[0785] n 3 represents an integer from 0 to 6.

[0786] n 4 represents an integer from 0 to 4.

[0787] X 4 is a methylene group, an oxygen atom, or a sulfur atom.

[0788] Specific examples of the repeating unit represented by formula (V) or formula (VI) are shown below, but are not limited to these.

[0789] [Chemical formula 35]

[0790]

[0791] Resin P may further contain a repeating unit having a silicon atom in the side chain. Examples of the repeating unit having a silicon atom in the side chain include (meth)acrylate-based repeating units having a silicon atom and vinyl-based repeating units having a silicon atom. The repeating unit having a silicon atom in the side chain is typically a repeating unit having a group having a silicon atom in the side chain. Examples of the group having a silicon atom include trimethylsilyl, triethylsilyl, triphenylsilyl, tricyclohexylsilyl, tris(trimethylsiloxysilyl), tris(trimethylsilylsilyl), methylditrimethylsilylsilyl, methylditrimethylsiloxysilyl, dimethylditrimethylsilylsilyl, dimethylditrimethylsiloxysilyl, and the following cyclic or linear polysiloxanes, or cage-type or ladder-type or random-type silsesquioxane structures, etc. In the formula, R and R 1 each independently represent a monovalent substituent. * represents a bonding bond.

[0792] [Chemical formula 36]

[0793]

[0794] 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 preferred.

[0795] The repeating unit having a silicon atom preferably has a silsesquioxane structure. Thereby, when forming an ultra-fine pattern (for example, a line width of 50 nm or less) with a high aspect ratio of the cross-sectional shape (for example, a film thickness / line width of 3 or more), very excellent collapse performance can be exhibited.

[0796] Examples of the silsesquioxane structure include a cage-type silsesquioxane structure, a ladder-type silsesquioxane structure (ladder silsesquioxane structure), and a random-type silsesquioxane structure. Among them, a cage-type silsesquioxane structure is preferred.

[0797] Here, the cage-type silsesquioxane structure is a silsesquioxane structure having a cage-like skeleton. The cage-type silsesquioxane structure may be a complete cage-type silsesquioxane structure or an incomplete cage-type silsesquioxane structure, and a complete cage-type silsesquioxane structure is preferred.

[0798] And, the ladder-type silsesquioxane structure is a silsesquioxane structure having a ladder-like skeleton.

[0799] And, the random-type silsesquioxane structure is a silsesquioxane structure with a random skeleton.

[0800] The above-mentioned cage-type silsesquioxane structure is preferably a siloxane structure represented by the following formula (S).

[0801] [Chemical formula 37]

[0802]

[0803] In the above formula (S), R represents a monovalent organic group. Multiple Rs may be the same or different.

[0804] There is no particular limitation on the above-mentioned organic group. As specific examples, hydroxyl group, nitro group, carboxyl group, alkoxy group, amino group, mercapto group, blocked mercapto group (for example, a mercapto group blocked (protected) by an acyl group), acyl group, imide group, phosphino group, phosphinyl group, silyl group, vinyl group, a hydrocarbon group which may have a heteroatom, a group containing (meth)acryloyl group, a group containing an epoxy group, etc. can be cited.

[0805] As the heteroatom of the hydrocarbon group which may have the above-mentioned heteroatom, for example, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, etc. can be cited.

[0806] As the hydrocarbon group of the hydrocarbon group which may have the above-mentioned heteroatom, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by combining these can be cited.

[0807] The above-mentioned aliphatic hydrocarbon group may be any of linear, branched, and cyclic. As specific examples of the above-mentioned aliphatic hydrocarbon group, linear or branched alkyl groups (especially, having 1 to 30 carbon atoms), linear or branched alkenyl groups (especially, having 2 to 30 carbon atoms), linear or branched alkynyl groups (especially, having 2 to 30 carbon atoms), etc. can be cited.

[0808] As the above-mentioned aromatic hydrocarbon group, for example, aromatic hydrocarbon groups having 6 to 18 carbon atoms such as phenyl group, tolyl group, xylyl group, naphthyl group, etc. can be cited.

[0809] When the resin P has the above-mentioned repeating unit having a silicon atom in the side chain, its content 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.

[0810] As the polystyrene conversion value based on the GPC (Gel permeation chromatography) method, 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. By setting the weight average molecular weight to 1,000 to 200,000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability or film-forming property due to high viscosity can be prevented.

[0811] The dispersity (molecular weight distribution) is usually preferably from 1 to 5, more preferably from 1 to 3, still more preferably from 1.2 to 3.0, and even more preferably from 1.2 to 2.0.

[0812] In the photosensitive radiation-curable or radiation-sensitive composition, the content of resin P is preferably from 50 to 99.9% by mass, more preferably from 60 to 99.0% by mass, in the total solid content.

[0813] Moreover, in the photosensitive radiation-curable or radiation-sensitive composition, one kind of resin P may be used, or a plurality of kinds may be used simultaneously.

[0814] (Photoacid generator)

[0815] The above-mentioned photosensitive radiation-curable or radiation-sensitive resin composition preferably contains a photoacid generator. As the photoacid generator, there is no particular limitation, and known photoacid generators can be used.

[0816] The content of the photoacid generator in the photosensitive radiation-curable or radiation-sensitive resin composition is not particularly limited, and is usually preferably from 0.1 to 20% by mass, more preferably from 0.5 to 20% by mass, relative to the total solid content of the photosensitive radiation-curable or radiation-sensitive resin composition. The photoacid generator may be used alone or two or more kinds may be used simultaneously. When two or more kinds of photoacid generators are used simultaneously, the total content is preferably within the above range.

[0817] Examples of the photoacid generator include those described in JP-A-2016-057614, JP-A-2014-219664, JP-A-2016-138219, and JP-A-2015-135379.

[0818] (Quencher)

[0819] The above-mentioned photosensitive radiation-curable or radiation-sensitive resin composition may contain a quencher. As the quencher, there is no particular limitation, and known quenchers can be used.

[0820] The quencher is a basic compound and has a function of suppressing the unintentional decomposition of the acid-decomposable resin in the unexposed area due to the acid diffused from the exposed area.

[0821] The content of the quencher in the photosensitive radiation-curable or radiation-sensitive resin composition is not particularly limited, and is usually preferably from 0.1 to 15% by mass, more preferably from 0.5 to 8% by mass, relative to the total solid content of the photosensitive radiation-curable or radiation-sensitive resin composition. The quencher may be used alone or two or more kinds may be used simultaneously. When two or more kinds of quenchers are used simultaneously, the total content is preferably within the above range.

[0822] Examples of the quencher include the quenchers described in JP-A No. 2016-057614, JP-A No. 2014-219664, JP-A No. 2016-138219, and JP-A No. 2015-135379.

[0823] (Hydrophobic resin)

[0824] The above photosensitive or radiation-sensitive resin composition may contain a hydrophobic resin.

[0825] Preferably, the hydrophobic resin is designed to be biased toward the surface of the resist film. However, unlike a surfactant, it does not necessarily have a hydrophilic group in the molecule and may not contribute to the uniform mixing of polar and non-polar substances.

[0826] Examples of the effects of adding the hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of degassing.

[0827] From the viewpoint of bias toward the film surface layer, the hydrophobic resin preferably has any one or more of "fluorine atoms", "silicon atoms", and "CH contained in the side chain portion of the resin" 3 partial structure", and more preferably has two or more. Further, it is preferred that the above hydrophobic resin has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

[0828] When the hydrophobic resin contains fluorine atoms and / or silicon atoms, the above fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or may be contained in the side chain.

[0829] When the hydrophobic resin contains fluorine atoms, as the partial structure having fluorine atoms, an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms is preferred.

[0830] The alkyl group having fluorine atoms (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.

[0831] The cycloalkyl group having fluorine atoms 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.

[0832] Examples of the aryl group having fluorine atoms include aryl groups such as phenyl and naphthyl in which at least one hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

[0833] As an example of a repeating unit having a fluorine atom or a silicon atom, the repeating unit exemplified in paragraph

[0519] of US2012 / 0251948A1 can be cited.

[0834] Further, as described above, it is also preferable that the hydrophobic resin contains a CH 3 partial structure in the side chain portion.

[0835] Here, the CH 3 partial structure possessed by the side chain portion in the hydrophobic resin includes the CH 3 partial structure possessed by ethyl, propyl, etc.

[0836] On the other hand, since the methyl group directly bonded to the main chain of the hydrophobic resin (for example, the α-methyl of the repeating unit having a methacrylic acid structure) is less helpful for the surface segregation of the hydrophobic resin due to the influence of the main chain, it is regarded as not being included in the CH 3 partial structure in the present invention.

[0837] Regarding the hydrophobic resin, reference can be made to the descriptions in paragraphs

[0348] to

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

[0838] In addition, as the hydrophobic resin, resins described in Japanese Patent Application Laid-Open No. 2011-248019, Japanese Patent Application Laid-Open No. 2010-175859, and Japanese Patent Application Laid-Open No. 2012-032544 can also be preferably used.

[0839] As the hydrophobic resin, for example, resins represented by the following formulas (1b) to (5b) are preferred.

[0840] [Chemical formula 38]

[0841]

[0842] 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.

[0843] (Solvent)

[0844] The above-described photosensitive or radiation-sensitive resin composition may contain a solvent. There is no particular limitation on the solvent, and known solvents can be used.

[0845] The solvent contained in the above-described photosensitive or radiation-sensitive resin composition may be the same as or different from the organic solvents contained in the mixture in the liquid medicine described above.

[0846] 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 adjusted to 0.1 to 20% by mass of the total solid content of the photosensitive radiation-curable or radiation-sensitive resin composition. One type of solvent can be used alone, or two or more types can be used simultaneously. When two or more types of solvents are used simultaneously, the total content is preferably within the above range.

[0847] 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.

[0848] (Other additives)

[0849] 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.

[0850] 〔Exposure process〕

[0851] 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.

[0852] 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 the method of irradiating an electron beam on the resist film, it can be irradiated without passing through a mask (this is also referred to as "direct writing").

[0853] 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, Electron Beam), etc. Extreme ultraviolet rays or electron beam are preferred. The exposure can also be immersion exposure.

[0854] <PEB (Post Exposure Bake: Post-exposure baking) process>

[0855] 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.

[0856] The heating temperature is preferably 80 to 150 °C, more preferably 80 to 140 °C, and still more preferably 80 to 130 °C.

[0857] The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and still more preferably 60 to 600 seconds.

[0858] Heating can be performed by the mechanism provided in a usual exposure / development machine, or can also be performed using a hot plate or the like.

[0859] 〔Development process〕

[0860] The development process is a process of developing the exposed resist film (hereinafter, also referred to as "the exposed resist film") with a developer. In addition, in the present embodiment, liquid X is used as the developer.

[0861] There is no particular limitation on the development method, and a known development method can be used. As the development method, for example, dipping method, liquid covering method, spraying method, dynamic dispensing method, etc. can be cited.

[0862] Furthermore, the above-mentioned pattern forming method may further include a process of replacing the developer with another solvent and stopping the development after the development process.

[0863] There is no particular limitation on the development time, and it is usually preferably 10 to 300 seconds, more preferably 10 to 120 seconds. As the temperature of the developer, it is preferably 0 to 50 °C, more preferably 15 to 35 °C. The pattern forming method may include at least one development process, or may include multiple times.

[0864] In addition, in the development process, both development using liquid X and development based on an alkaline developer can be performed (so-called double development can also be performed).

[0865] 〔Rinsing process〕

[0866] The rinsing process is a process of cleaning the wafer having the developed resist film with a rinsing liquid. In addition, liquid Y is used as the rinsing liquid in the present embodiment.

[0867] There is no particular limitation on the cleaning method, and a known cleaning method can be used. As the cleaning method, for example, spin ejection method, dipping method, spraying method, etc. can be cited.

[0868] Among them, it is preferably cleaned by the spin ejection method. After cleaning, the wafer is rotated at a rotational speed of 2000 to 4000 rpm, and the rinsing liquid is removed from the substrate.

[0869] As the rinsing time, it is generally preferably 10 to 300 seconds, more preferably 10 to 180 seconds, and still more preferably 20 to 120 seconds. As the temperature of the rinsing liquid, it is preferably 0 to 50 °C, more preferably 15 to 35 °C.

[0870] 〔Other processes〕

[0871] In addition to the processes already described, the above-described pattern forming method may include other processes. As other processes, for example, a pre-wetting process, a cleaning process using a supercritical fluid, a heating process, etc. can be cited.

[0872] <Pre-wetting process>

[0873] The pre-wetting process is a process of coating 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. And, as the chemical solution for the pre-wetting process, this chemical solution can be used, or a chemical solution other than this chemical solution can also be used.

[0874] As the substrate, there is no particular limitation, and a known substrate used for semiconductor manufacturing can be used. As the substrate, for example, inorganic substrates such as silicon, SiO 2 or SiN, or coated inorganic substrates such as SOG (Spin On Glass), etc. are exemplified, but not limited thereto.

[0875] And, the substrate can also be a substrate having an antireflection film and with the antireflection film. As the antireflection film, there is no particular limitation, and a known organic or inorganic antireflection film can be used.

[0876] As the method of coating the chemical solution on the substrate, there is no particular limitation, and a known coating method can be used. Among them, from the viewpoint of being able to form a uniform resist film with less photosensitized radiation or radiation-sensitive resin composition in the resist film forming process described later, as the coating method, spin coating is preferred.

[0877] As the method of coating the chemical solution on the substrate, there is no particular limitation, and a known coating method can be used. Among them, from the viewpoint of being able to form a uniform resist film with less photosensitized radiation or radiation-sensitive resin composition in the resist film forming process described later, as the coating method, spin coating is preferred.

[0878] As the thickness of the chemical solution layer formed on the substrate using the chemical solution, there is no particular limitation, and it is generally preferably 0.001 to 10 μm, more preferably 0.005 to 5 μm.

[0879] Here, assume that the resist liquid to be coated is an ArF immersion exposure resist. The surface tension of this resist liquid is set to 28.8 mN / m. In this case, there is no particular limitation on the surface tension of the mixture of the liquid medicine, but it is preferably higher than the surface tension of the resist liquid and supplied to the wafer as a pre-wetting liquid.

[0880] As a method for supplying the liquid medicine to the wafer, usually the pre-wetting nozzle is moved above the center of the wafer. Then, the liquid medicine is supplied to the wafer by opening and closing the valve.

[0881] In a state where the wafer is stopped, a predetermined amount of the above liquid medicine is supplied from the pre-wetting nozzle to the center of the wafer. Then, the wafer rotates at a first speed V1 of about 500 rpm (rotation per minute), and the liquid medicine on the wafer diffuses over the entire surface of the wafer, and the entire surface of the wafer becomes a state wetted by the liquid medicine.

[0882] In addition, there is no particular limitation on the upper limit value of the first speed V1, and it is preferably 3000 rpm or less.

[0883] Then, by opening the valve connected to the line of the resist liquid, the resist liquid starts to be ejected from the resist nozzle, and thus the supply of the resist liquid to the center of the wafer starts.

[0884] In this way, the resist film formation process starts. In this resist film formation process, the rotation speed of the wafer is increased from the first speed V1 to a high speed, for example, a second speed V2 of about 2000 to 4000 rpm. The rotation of the wafer at the first speed V1 before the start of the resist film formation process is gradually accelerated so that the subsequent speed changes continuously and smoothly. At this time, the rotational acceleration of the wafer gradually increases from zero, for example. Then, at the end of the resist film formation process, the rotational 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 formation 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 formation process, the resist liquid supplied to the center of the wafer diffuses over the entire surface of the wafer by centrifugal force, and thus the resist liquid is coated on the surface of the wafer.

[0885] In addition, the resist saving technology due to the change in the rotation speed of the wafer when coating such a resist is described in detail in Japanese Patent Application No. 2008-131495 and Japanese Patent Laid-Open No. 2009-279476.

[0886] In addition, there is no particular limitation on the interval from the end of the pre-wetting process until the start of the coating of the resist liquid in the resist film formation process, and it is usually preferably 7 seconds or less.

[0887] The above-mentioned liquid medicine can be reused. That is, the liquid medicine used in the above-mentioned pre-wetting process can be recovered and further used in the pre-wetting process of other wafers.

[0888] When reusing the liquid medicine, it is preferable to adjust the contents of impurity metals, organic impurities, water, etc. contained in the recovered liquid medicine.

[0889] <Removal process based on supercritical fluid>

[0890] The removal process based on supercritical fluid is a process of using supercritical fluid to remove the developing solution and / or rinsing solution attached to the pattern after the developing process and / or rinsing process.

[0891] <Heating process>

[0892] The heating process is a process of heating the resist film to remove the solvent remaining in the pattern after the developing process, rinsing process, or removal process based on supercritical fluid.

[0893] The heating temperature is not particularly limited, and usually preferably 40 to 160 °C, more preferably 50 to 150 °C, and further preferably 50 to 110 °C.

[0894] The heating time is not particularly limited, and usually preferably 15 to 300 seconds, more preferably 15 to 180 seconds.

[0895] Examples

[0896] Hereinafter, the present invention will be described in further detail based on examples. The materials, amounts used, ratios, treatment contents, treatment steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0897] Moreover, when preparing the liquid medicines of the preparation examples and comparative examples, the treatment of the containers, the preparation, filling, storage, and analysis and measurement of the liquid medicines are all carried out in a clean room satisfying ISO class 2 or 1. In order to improve the measurement accuracy, when measuring the components below the detection limit in the measurement of the content of organic compounds and the content of metal components, the liquid medicine is concentrated for measurement, and the content is calculated by converting to the concentration of the solution before concentration.

[0898] [Purification of Liquid Medicine A1]

[0899] A purified product (commercial product) containing propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent was prepared.

[0900] Next, a purification apparatus was prepared by connecting, from the upstream side in sequence, a first distillation section (distillation step for rough distillation) having a first tray-type distillation column without a decompression mechanism, a first packed section (ion removal step) in which three packed columns filled with cation exchange resin were connected in series, a second packed section (ion removal step) in which two packed columns filled with anion exchange resin were connected in series, a second distillation section (distillation step for rectification treatment) in which a second tray-type distillation column without a decompression mechanism and a third tray-type distillation column with a decompression mechanism were connected in series in sequence, and a filtration section (filtration step) in which a first filter and a second filter were connected in series in sequence.

[0901] Then, the above-mentioned purified material was purified using the above purification apparatus to produce a pharmaceutical solution. In addition, one pass through the purification apparatus was counted as one time, and the purification of the purified material was performed a total of two times (in the table, shown as the number of cycles being 2 times).

[0902] Hereinafter, the details of each component in the purification apparatus are presented in sequence from the upstream side (primary side).

[0903] · First tray-type distillation column (theoretical plate number: 10 plates)

[0904] · Cation exchange resin (ORLITE DS-4, manufactured by ORGANO CORPORATION)

[0905] · Anion exchange resin (ORLITE DS-6, manufactured by ORGANO CORPORATION)

[0906] · Second tray-type distillation column (theoretical plate number: 23 plates)

[0907] · Third tray-type distillation column (theoretical plate number: 23 plates, vacuum distillation)

[0908] · First filter (Purasol SP / SN solvent purifier, manufactured by Nihon Entegris G.K., UPE (ultra-high molecular weight polyethylene) filter)

[0909] · Second filter (product name “trent”, manufactured by Nihon Entegris G.K., polytetrafluoroethylene (PTFE) filter)

[0910] [Purification of other pharmaceutical solutions]

[0911] Under the conditions described in Table 1, a purified material containing the organic solvent described in Table 1 was purified to obtain it. In addition, each pharmaceutical solution was obtained by passing the purified material through each component described in Table 1 in sequence from the upstream side (moreover, the pharmaceutical solution in the blank column indicates that its component was not used), and repeating this for the number of times described in “number of cycles”.

[0912] Among them, regarding Comparative Example NA2, in place of the first filling part and the second filling part used in the ion removal process, a third filling part filled with an adsorption resin (product name "DUOLITE 874", styrene resin) was used for the ion removal process.

[0913] In addition, regarding the first plate-type distillation column, the second plate-type distillation column, and the third plate-type distillation column, distillation columns with the number of theoretical plates recorded in Table 1 were used. And the number of plates of the cation exchange resin refers to the number of packed towers filled with cation exchange resin connected in series. Regarding the number of plates of the anion exchange resin, it also refers to the number of packed towers filled with anion exchange resin connected in series. Regarding the number of plates of the adsorption resin, it also refers to the number of packed towers filled with adsorption resin connected in series.

[0914] Moreover, the purified substances recorded in Table 1 are purified substances with different procurement batches. Therefore, the components other than the organic solvents initially contained in each purified substance may be different.

[0915] In addition, the abbreviations in Table 1 represent the following contents respectively.

[0916] · PGMEA: Propylene glycol monomethyl ether acetate (boiling point: 146 °C, SP value: 17.86)

[0917] · nBA: Butyl acetate (boiling point: 126 °C, SP value: 17.80)

[0918] · iAA: Isoamyl acetate (boiling point: 142 °C, SP value: 17.42)

[0919] · CHN: Cyclohexanone (boiling point: 155.6 °C, SP value: 20.05)

[0920] · PGME: Propylene glycol monoethyl ether (boiling point: 132.8 °C, SP value: 23.05)

[0921] · MIBC: 4-Methyl-2-pentanol (boiling point: 131.6 °C, SP value: 21.15)

[0922] · EL: Ethyl lactate (boiling point: 154 °C, SP value: 24.41)

[0923] · PC: Propylene carbonate (boiling point: 242 °C, SP value: 20.26)

[0924] [Table 1]

[0925]

[0926] [Table 2]

[0927]

[0928] [Measurement of the content, etc. of each component in the liquid medicine]

[0929] The following method was used to measure the content, etc. of each component in the liquid medicine. In addition, all the following measurements were carried out in a clean room that meets the level of ISO (International Organization for Standardization) class 2 or lower. To improve the measurement accuracy, in the measurement of each component, when it is below the detection limit in the normal measurement, it is concentrated to 1 / 100 in terms of volume and then measured, and the content is calculated by converting it to the content of the organic solvent before concentration. The results are summarized in Table 2.

[0930] In addition, the measurement of the content of each component in the liquid medicine was carried out immediately after the preparation of the liquid medicine.

[0931] 〔Acid components and organic compounds〕

[0932] The content of acid components and organic compounds in each liquid medicine was measured using a gas chromatography - mass spectrometer (product name "GCMS - 2020", manufactured by Shimadzu Corporation, and the measurement conditions are as follows).

[0933] <Measurement conditions>

[0934] Capillary column: InertCap 5MS / NP 0.25mm I.D.×30m df = 0.25μm

[0935] Sample introduction method: Split flow, 75kPa pressure constant

[0936] Vaporization chamber temperature: 230°C

[0937] Column oven temperature: 80°C (2min) - 500°C (13min), heating rate 15°C / min

[0938] Carrier gas: Helium

[0939] Septum purge flow rate: 5mL / min

[0940] Split ratio: 25∶1

[0941] Interface temperature: 250°C

[0942] Ion source temperature: 200°C

[0943] Measurement mode: Scan m / z = 85 - 500

[0944] Sample introduction volume: 1μL

[0945] 〔Metal components〕

[0946] The content of metal components (metal ions and metal-containing particles) in the liquid medicine was measured by using ICP-MS and SP-ICP-MS methods.

[0947] The following equipment was used. The results are shown in Table 2.

[0948] · Manufacturer: PerkinElmer

[0949] · Model: NexION350S

[0950] The following analysis software was used for the analysis.

[0951] · Syngistix Nano Application Module dedicated to "SP-ICP-MS"

[0952] · Syngistix for ICP-MS software

[0953] 〔Metal nanoparticles〕

[0954] The number of metal nanoparticles (metal-containing particles with a particle size of 0.5 to 17 nm) in the liquid medicine was measured by the following method.

[0955] First, a constant amount of the liquid medicine was coated on a silane substrate to form a substrate with a liquid medicine layer. The surface of the substrate with the liquid medicine layer was scanned by a laser beam, and the scattered light was detected. Thereby, the positions and particle sizes of the defects present on the surface of the substrate with the liquid medicine layer were determined. Then, elemental analysis was performed by EDX (energy dispersive X-ray) analysis based on the positions of the defects, and the composition of the defects was examined. By this method, the number of particles of metal nanoparticles on the substrate was obtained, and this was converted into the number of particles contained per unit volume of the liquid medicine (pieces / cm 3 ).

[0956] In addition, a wafer inspection device "SP-5" manufactured by KLA-Tencor Corporation and a full-automatic defect inspection and classification device "SEMVision G6" of Applied Materials, Inc. were used in combination for the analysis.

[0957] Furthermore, for samples of particles with a particle size that could not be detected due to the resolution of the measuring device, etc., the method described in paragraphs 0015 to 0067 of Japanese Patent Laid-Open No. 2009-188333 was used for detection. That is, an SiO X layer was formed on the substrate by CVD (chemical vapor deposition) method, and then a liquid medicine layer was formed so as to cover the above layer. Then, the following method was used: for the SiO XA dry etching is performed on the composite layer of the layer and the liquid medicine layer coated thereon, light is irradiated on the obtained protrusions, scattered light is detected, 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.

[0958] [Evaluation of defect suppression performance]

[0959] The obtained liquid medicine was used as a pre-wetting liquid, and the defect suppression performance was evaluated.

[0960] Here, the defect suppression performance was implemented for both the case of using the liquid medicine just after manufacturing (indicated as "just after ~" in the table) and the case of the liquid medicine after storing the liquid medicine in a liquid medicine container (material of the liquid receiving part: high-density polyethylene (HDPE) resin) at 40 °C for 45 days (shown as "over time" in the table).

[0961] In addition, the resist composition used was as follows.

[0962] [Resist composition 1]

[0963] Resist composition 1 was obtained by mixing the following components.

[0964] · Resin (A-1): 0.77 g

[0965] · Acid generator (B-1): 0.03 g

[0966] · Basic compound (E-3): 0.03 g

[0967] · PGMEA: 67.5 g

[0968] · EL: 75 g

[0969] [Resin (A), etc.]

[0970] (Synthesis example 1) Synthesis of resin (A-1)

[0971] 600 g of cyclohexanone was placed in a 2 L flask, and nitrogen replacement was performed at a flow rate of 100 mL / min for one hour. 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 an internal temperature of 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 above flask heated to 80 °C over 6 hours. After the addition was completed, the reaction was further carried out at 80 °C for 2 hours.

[0972] 4-Acetoxystyrene 48.66 g (0.3 mol)

[0973] 1-Ethylcyclopentyl methacrylate 109.4 g (0.6 mol)

[0974] Monomer 1 22.2 g (0.1 mol)

[0975] [Chemical formula 39]

[0976]

[0977] The reaction solution was cooled to room temperature and dropped into 3 L of hexane to precipitate the polymer. The solid obtained by filtration was dissolved in 500 mL of acetone and dropped again into 3 L of hexane, and 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).

[0978] 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 were added to a reaction vessel, heated to 80 °C and stirred for 5 hours. The reaction solution was cooled to room temperature and dropped into 3 L of distilled water. The solid obtained by filtration was dissolved in 200 mL of acetone and dropped again into 3 L of distilled water, and the solid obtained by filtration was dried under reduced pressure to obtain resin (A-1) (8.5 g). The weight-average molecular weight (Mw) in terms of standard polystyrene obtained by gel permeation chromatography (GPC) (solvent: THF (tetrahydrofuran)) was 11,200, and the molecular weight dispersity (Mw / Mn) was 1.45. The structure of resin A-1 and the like are shown below.

[0979] [Chemical formula 40]

[0980]

[0981] <Photoacid generator (B)>

[0982] As the photoacid generator, the following photoacid generator was used.

[0983] [Chemical formula 41]

[0984]

[0985] <Basic compound (E)>

[0986] As the basic compound, the following basic compound was used.

[0987] [Chemical formula 42]

[0988]

[0989] (Defect suppression performance)

[0990] The defect suppression performance of the liquid medicine was evaluated by the following method. In addition, a coater developer "RF" manufactured by SOKUDO Co., Ltd. was used for the test. 3S ".

[0991] First, AL412 (manufactured by Brewer Science, Inc.) was coated on a silicon wafer and baked at 200 °C for 60 seconds to form an underlayer resist film with a film thickness of 20 nm. A pre-wetting solution (liquid medicine 1) was coated thereon, and a resist composition 1 was coated thereon, followed by baking at 100 °C for 60 seconds (PB: Prebake) to form a resist film with a film thickness of 30 nm.

[0992] An EUV exposure machine (manufactured by ASML Corporation; NXE3350, NA0.33, Dipole 90°, Outer Sigma 0.87, Inner Sigma 0.35) was used to expose the resist film through a reflective mask with a pitch of 20 nm and a pattern width of 15 nm. Then, it was heated (PEB: Post Exposure Bake) at 85 °C for 60 seconds. Next, it was developed with an organic solvent-based developer for 30 seconds and rinsed for 20 seconds. Then, the wafer was rotated at a speed of 2000 rpm for 40 seconds to form a line-and-space pattern with a pitch of 20 nm and a pattern line width of 15 nm.

[0993] An image of the above pattern was obtained, and the pattern defect inspection device "UVsion 7" of Applied Materials, Inc. and the fully automatic defect inspection and classification device "SEMVision G6" of Applied Materials, Inc. were combined and used to analyze the obtained image, and the number of residues in the unexposed part per unit area was measured.

[0994] In addition, for a sample in which particles with a desired particle size could not be detected due to the resolution of the measuring device, etc., the method described in paragraphs 0015 to 0067 of Japanese Patent Laid-Open No. 2009-188333 was used for detection. That is, an SiO X layer was formed on a substrate by CVD (Chemical Vapor Deposition) method, and then a liquid medicine layer was formed so as to cover the above layer. Then, the following method was used: The composite layer having the above SiO X layer and the liquid medicine layer coated thereon was dry-etched, light was irradiated on the obtained protrusions, scattered light was detected, the volume of the protrusions was calculated from the above scattered light, and the particle size of the particles was calculated from the volume of the above protrusions.

[0995] Evaluation is carried out based on the following criteria, and the results are shown in Table 2.

[0996] A: The number of defects is less than 50.

[0997] B: The number of defects is 50 or more and less than 70.

[0998] C: The number of defects is 70 or more and less than 90.

[0999] D: The number of defects is 90 or more and less than 110.

[1000] E: The number of defects is 110 or more and less than 130.

[1001] F: The number of defects is 130 or more.

[1002]

[1003]

[1004] In Table 2 above, the values recorded in the columns of "acid component" and "acid component / metal component (mass ratio)" are sometimes abbreviated and shown as exponents. For example, "1.1E+05" represents "1.1×10 5 ", and "6.3E-03" represents "6.3×10 -3 ".

[1005] As shown in Table 2, it shows that if a liquid medicine with the content of the acid component being 1 mass ppt or more and 15 mass ppm or less relative to the total mass of the liquid medicine, and the content of the metal component being 0.001 to 100 mass ppt relative to the total mass of the liquid medicine is used, a liquid medicine with excellent defect suppression performance even after long-term storage can be obtained (Examples).

[1006] For example, through the comparison between Example A1 and A2, it shows that if the content of the organic acid is 1 mass ppm or less relative to the total mass of the liquid medicine (Example A2), the defect suppression performance of the liquid medicine is excellent both immediately after manufacturing and after long-term storage.

[1007] For example, through the comparison between Example A2 and A3, it shows that if 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 liquid medicine after long-term storage is more excellent.

[1008] For example, through the comparison between Example A1 and A4, it shows that if the content of the inorganic acid is 1 mass ppb or less relative to the total mass of the liquid medicine (Example A1), the defect suppression performance of the liquid medicine is excellent both immediately after manufacturing and after long-term storage.

[1009] For example, by comparing Example A15 and A16, it shows that if the water content is 1 mass ppm or less relative to the total mass of the liquid medicine (Example A15), the defect suppression performance of the liquid medicine after long-term storage is also excellent.

[1010] For example, by comparing Example A8 and A17, it shows that if the content of metal particles is in the range of 0.00001 to 10 mass ppt relative to the total mass of the liquid medicine (Example A8), the defect suppression performance of the liquid medicine after long-term storage is also excellent.

[1011] For example, by comparing Example A8 and A18, it shows that if the number of particles contained per unit volume of the liquid medicine of metal nanoparticles is in the range of 1.0×10 -2 ~1.0×10 6 pieces / cm 3 (Example A8), the defect suppression performance of the liquid medicine after long-term storage is more excellent.

[1012] For example, by comparing Example A8 and A19, it shows that if the content of metal ions is in the range of 0.01 to 100 mass ppt relative to the total mass of the liquid medicine (Example A8), the defect suppression performance of the liquid medicine after long-term storage is also excellent.

[1013] As shown in Table 2, if a liquid medicine outside the above range is used for at least one of the content of the acid component relative to the total mass of the liquid medicine and the content of the metal component relative to the total mass of the liquid medicine, it indicates that the defect suppression performance of the liquid medicine after long-term storage is poor (comparative example).

[1014] In addition, as an evaluation method for defect performance other than the above, as a result of evaluating the defect performance by the methods described in the following Literature (1) and Literature (2), it can be seen that the evaluation results of the defect performance of the examples and comparative examples all show the same tendency as the above defect performance.

[1015] Literature (1) Journal of photopolymer science and technology, Vol28, No.1 (2015) 17 - 24 (Renesus)

[1016] Literature (2) “Development of Novel Purifiers with Approproate FunctionalGroups Based on Solvent Polarities at Bulk Filtration” Enteglis News letter (May 2017)

[1017] [Example X1]

[1018] As the liquid medicine X for the developing solution, the above-mentioned liquid medicine B1 was prepared.

[1019] And, as the liquid medicine Y for the rinsing solution, butyl butyrate was prepared. Here, the butyl butyrate used as the liquid medicine Y was directly used as a purchased item without performing the above-mentioned filtration treatment or the like.

[1020] In addition, for the organic solvents used as the liquid medicine Y in the following examples and comparative examples, the above-mentioned filtration treatment or the like was not performed, and they were directly used as purchased items.

[1021] [Examples X2 to X16]

[1022] As the liquid medicine Y (rinsing solution), the organic solvents shown in the column of the liquid medicine Y in Table 3 were used. Except for this, in the same manner as in Example X1, the liquid medicine X and the liquid medicine Y were prepared in a combination shown in Table 3.

[1023] [Example X17]

[1024] As the liquid medicine Y (rinsing solution), a mixed solvent A1 of butyl butyrate and undecane (butyl butyrate: undecane = 1:1 (mass basis)) was prepared.

[1025] Except for this, in the same manner as in Example X1, the liquid medicine X and the liquid medicine Y were prepared in a combination shown in Table 3.

[1026] [Example X18]

[1027] As the liquid medicine X for the developing solution, the above-mentioned liquid medicine B2 was prepared.

[1028] As the liquid medicine Y (rinsing solution), a mixed solvent B1 of butyl butyrate and methanol (butyl butyrate: methanol = 1:1 (mass basis)) was prepared.

[1029] [Example X19]

[1030] As the liquid medicine Y (rinsing solution), a mixed solvent A2 of butyl butyrate and undecane (butyl butyrate: undecane = 9:1 (mass basis)) was prepared.

[1031] Except for this, in the same manner as in Example X1, the liquid medicine X and the liquid medicine Y were prepared in a combination shown in Table 3.

[1032] [Example X20]

[1033] As the liquid medicine Y (rinsing solution), a mixed solvent B2 of butyl butyrate and methanol (butyl butyrate: methanol = 9:1 (mass basis)) was prepared.

[1034] In addition, in the same manner as in Example X1, liquid medicine X and liquid medicine Y were prepared in the combinations shown in Table 3.

[1035] [Examples X21 to X26]

[1036] As liquid medicine Y (rinsing liquid), the organic solvents shown in Table 3 were used. In addition, in the same manner as in Example X1, liquid medicine X and liquid medicine Y were prepared in the combinations shown in Table 3.

[1037] Among them, in Example X26, liquid medicine Y (rinsing liquid) was not used.

[1038] [Comparative Examples NX1 to NX16]

[1039] As liquid medicine X (developer), the above-mentioned liquid medicine NB1 was used, and as liquid medicine Y (rinsing liquid), the organic solvents shown in Table 3 were used. Liquid medicine X and liquid medicine Y were prepared in the combinations shown in Table 3.

[1040] [Comparative Examples NX17 to NX20]

[1041] As liquid medicine Y (rinsing liquid), the above-mentioned mixed solvents A1, A2, B1 or B2 were used. In addition, in the same manner as in Comparative Example NX1, liquid medicine X and liquid medicine Y were prepared in the combinations shown in Table 3.

[1042] [Comparative Examples NX21 to NX26]

[1043] As liquid medicine Y (rinsing liquid), the organic solvents shown in Table 3 were used. In addition, in the same manner as in Comparative Example NX1, liquid medicine X and liquid medicine Y were prepared in the combinations shown in Table 3.

[1044] Among them, in Comparative Example NX26, liquid medicine Y (rinsing liquid) was not used.

[1045] [Evaluation of Defect Inhibition Performance]

[1046] PGMEA was used as the pre-wetting liquid, and the developer and rinsing liquid in the combinations of Table 3 were used. The exposure conditions of the resist film and the cleaning conditions based on the rinsing liquid were changed as follows. In addition, in the same manner as in the above evaluation of defect inhibition performance, the defect inhibition performance of Examples X1 to X26 and Comparative Examples NX1 to NX26 was evaluated respectively. Regarding the evaluation criteria, they were also set to be the same as those in the above evaluation of defect inhibition performance.

[1047] In addition, the PEGMEA used as the pre-wetting liquid was directly used as a purchased item without performing the above-mentioned filtration treatment, etc.

[1048] Moreover, the defect suppression performance was evaluated for the case of liquid chemical X (developer) stored in a liquid chemical container (material of the liquid receiving part: high-density polyethylene (HDPE) resin) at 40 °C for 45 days (denoted as "aging" in the table). For the pre-wetting liquid and liquid chemical Y (rinsing liquid), no storage was performed, and they were used immediately after preparation or immediately after opening a commercially available product.

[1049] (Exposure conditions for the resist film)

[1050] The fabricated wafer with a resist film was subjected to EUV exposure at NA (lens numerical aperture, Numerical Aperture: 0.25) and dipole illumination (Dipole60x, outer sigma 0.81, inner sigma 0.43). Specifically, EUV exposure was performed through a mask containing a pattern for forming lines and spaces with a pitch of 40 nm and a width of 20 nm on the wafer, and the exposure dose was changed. After irradiation, the wafer was taken out from the EUV exposure apparatus and immediately baked at 90 °C for 60 seconds (PEB).

[1051] (Cleaning conditions)

[1052] While rotating the wafer at 50 revolutions per minute (rpm), liquid chemical Y (at 23 °C) was sprayed at a flow rate of 200 mL / min for 15 seconds to perform a rinsing process. Finally, the wafer was dried by rotating it at 2000 rpm for T R seconds.

[1053] [Analytical property (pattern collapse performance)]

[1054] Using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.), the resolution of the lines and spaces patterns exposed with different exposure doses was observed at a magnification of 200k, and the minimum line width at which no pattern collapse occurred within the observed field of view was determined as an index of pattern collapse. The smaller this value, the better the pattern collapse performance. The obtained minimum line width was evaluated according to the following evaluation criteria. In addition, the pattern collapse performance was evaluated for the patterns formed using a mask for forming dense patterns.

[1055] (Evaluation criteria)

[1056] "A": The minimum line width is 16 nm or less

[1057] "B": The minimum line width exceeds 16 nm and is 18 nm or less

[1058] "C": The minimum line width exceeds 18 nm and is 20 nm or less

[1059] "D": The minimum line width exceeds 20 nm and is less than 22 nm

[1060] "E": The minimum line width exceeds 22 nm

[1061] [Comprehensive evaluation]

[1062] For Examples X1 to X26 and Comparative Examples NX1 to NX26, regarding the evaluation results of the defect suppression performance, the evaluation criteria A to F were converted to 5 points to 0 points in this order. And regarding the evaluation results of the resolvability, the evaluation criteria A to E were converted to 4 points to 0 points in this order.

[1063] Then, based on the total points of the points for the defect suppression performance and the points for the resolvability, a comprehensive evaluation was carried out according to the following criteria.

[1064] S: The total points are 9 points

[1065] A: The total points are 8 points

[1066] B: The total points are 6 to 7 points

[1067] C: The total points are 5 points or less

[1068] In addition, in terms of practical use, an evaluation of "B" or above is preferred.

[1069] The evaluation results are shown in Table 3. In addition, in Liquid Y, the values in parentheses in the organic solvents contained in the mixed solution represent the distance of the organic solvents from the Hansen solubility parameter of icosene [unit: MPa 0.5 .

[1070] [Table 5]

[1071]

[1072] [Table 6]

[1073]

[1074] As shown in Table 3 (Part 1), in any of the liquid medicine and the rinsing liquid, when the liquid medicine of the present invention is used, it indicates excellent defect suppression (Examples X1 to X26).

[1075] In particular, when the liquid medicine of the present invention is used as Liquid X (developer), and when Organic Solvent Y1 is used as Liquid Y (rinsing liquid) (Examples X1 to X16) compared with the case where an organic solvent other than Organic Solvent Y1 is used as Liquid Y (rinsing liquid) (Examples X21 to X26), it can be seen that the comprehensive evaluation is high, and the defect suppression performance and the resolution performance can be compatible at a high level.

[1076] Further, from the comparison between Examples X17 and X18 and Examples X19 and X20, if the content of the above organic solvent Y1 (organic solvent with a distance of 3 to 20 MPa from the Hansen solubility parameter of eicosene) is 20 to 80% by mass relative to the total mass of the liquid medicine Y (Examples X17 and X18), it indicates that the comprehensive evaluation is more excellent. 0.5 On the other hand, as shown in Table 3 (part 2), when neither the liquid medicine nor the rinsing liquid uses the liquid medicine of the present invention, it indicates that at least the defect suppression performance is insufficient and the comprehensive evaluation is also poor (Comparative Examples NX1 to NX26).

[1077] ​

Claims

1. A method for manufacturing a semiconductor device, comprising: a resist film forming step of forming a resist film using a photosensitive or radiation-sensitive resin composition; an exposure step of exposing the resist film; a developing step of developing the exposed resist film using a liquid X; and a rinsing step of cleaning with a liquid Y containing an organic solvent after the developing step, wherein the liquid X is a liquid containing an organic solvent, an acid component, and a metal component, the content of the acid component is 1 mass ppt or more and 15 mass ppm or less with respect to the total mass of the liquid X, the content of the metal component is 0.001 mass ppt to 100 mass ppt with respect to the total mass of the liquid X, the organic solvent contains butyl acetate, and the acid component contains acetic acid, and the content of acetic acid is 0.01 mass ppm to 15 mass ppm with respect to the total mass of the liquid X, the organic solvent contained in the liquid Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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.

2. A method for manufacturing a semiconductor device, comprising: a resist film forming step of forming a resist film using a photosensitive or radiation-sensitive resin composition; an exposure step of exposing the resist film; a developing step of developing the exposed resist film using a liquid X; and a rinsing step of cleaning with a liquid Y containing an organic solvent after the developing step, wherein the liquid X is a liquid containing an organic solvent, an acid component, and a metal component, the content of the acid component is 1 mass ppt or more and 15 mass ppm or less with respect to the total mass of the liquid X, the content of the metal component is 0.001 mass ppt to 100 mass ppt with respect to the total mass of the liquid X, 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 with respect to the total mass of the liquid X, the organic solvent contained in the liquid Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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.

3. A method for manufacturing a semiconductor device, comprising: a resist film forming step of forming a resist film using a photosensitive or radiation-sensitive resin composition; an exposure step of performing extreme ultraviolet exposure on the resist film; a developing step of developing the exposed resist film using a liquid X; and A rinsing step, after the developing step, is to perform cleaning using a liquid medicine Y containing an organic solvent. The liquid medicine X is a liquid medicine containing an organic solvent, an acid component, and a metal component. With respect to the total mass of the liquid medicine X, the content of the acid component is 1 mass ppt or more and 15 mass ppm or less. With respect to the total mass of the liquid medicine X, the content of the metal component is 0.001 mass ppt to 100 mass ppt. The organic solvent contains butyl acetate, and the acid component contains acetic acid. With respect to the total mass of the liquid medicine X, the content of acetic acid is 0.01 mass ppm to 15 mass ppm. The organic solvent contained in the liquid medicine Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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.

4. A method for manufacturing a semiconductor device, comprising: A resist film forming step of forming a resist film using a photosensitive or radiation-sensitive resin composition; An exposure step of performing extreme ultraviolet exposure on the resist film; A developing step of developing the exposed resist film using the liquid medicine X; and A rinsing step, after the developing step, is to perform cleaning using a liquid medicine Y containing an organic solvent. The liquid medicine X is a liquid medicine containing an organic solvent, an acid component, and a metal component. With respect to the total mass of the liquid medicine X, the content of the acid component is 1 mass ppt or more and 15 mass ppm or less. With respect to the total mass of the liquid medicine X, the content of the metal component is 0.001 mass ppt to 100 mass ppt. The organic solvent contains butyl acetate, and the acid component contains n-butyric acid. With respect to the total mass of the liquid medicine X, the content of n-butyric acid is 1 mass ppt or more and 1 mass ppm or less. The organic solvent contained in the liquid medicine Y includes at least one organic solvent Y selected from the group consisting of butyl butyrate, isobutyl isobutyrate, amyl propionate, isopentyl 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.

5. The method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein, the metal component includes metal-containing particles containing metal atoms, and with respect to the total mass of the liquid medicine X, the content of the metal-containing particles is 0.00001 mass ppt to 10 mass ppt.

6. The method for manufacturing a semiconductor device according to claim 5, wherein, Among the metal-containing particles, the number of particles of metal nanoparticles with a particle size of 0.5 nm to 17 nm contained per unit volume of the liquid medicine is 1.0×10 -2 particles / cm 3 to 1.0×10 6 particles / cm 3 .

7. The method for manufacturing a semiconductor device according to any one of claims 1 to 4, wherein, the metal component includes metal ions, and with respect to the total mass of the liquid medicine X, the content of the metal ions is 0.01 mass ppt to 100 mass ppt.

8. The manufacturing method of the semiconductor device according to any one of claims 1 to 4, wherein, the metal component includes metal-containing 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.

9. The manufacturing method of the semiconductor device according to any one of claims 1 to 4, wherein, the liquid medicine X further contains water, the content of the water is 1 mass ppm or less relative to the total mass of the liquid medicine X.

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