Processing liquid and processing liquid container

Abstract

The present invention addresses the problem of providing a processing solution which makes it possible to prevent the occurrence of defects upon the application of the processing solution on a surface of interest when the processing solution is used as a developing solution or a rinsing solution and also makes it possible to prevent the occurrence of defects on a surface of interest when the processing solution is used after being stored in a container having an inner wall surface composed of a metal. The present invention also addresses the problem of providing a processing solution container. The processing solution according to the present invention comprises an aliphatic hydrocarbon-based solvent, at least one acid component selected from the group consisting of a carboxylic acid having a C1-3 hydrocarbon group and formic acid, and a metal impurity containing at least one metal element selected from the group consisting of Fe, Ni and Cr, in which the mass ratio of the content of the metal element to the content of the acid component is 1.0×10-9 to 3.0×10-5.

Description

[Technical Field]

[0001] This invention relates to a processing liquid and a container for the processing liquid. [Background technology]

[0002] Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) or LSIs (Large Scale Integrated Circuits), microfabrication has been performed using a photolithography process with a photoresist composition. In such photolithography processes, a coating is formed using a photoresist composition (also called a photosensitive or radiation-sensitive resin composition, or a chemically amplified resist composition). The resulting coating is then exposed to light, developed with a developer to obtain a patterned cured film, and finally, the cured film after development is washed with a rinsing solution. For example, Patent Document 1 discloses the use of a chemical solution containing an organic solvent, organic impurities including phosphate esters and adipic acid esters, and metal impurities, wherein the mass ratio of the phosphate ester content to the adipic acid ester content is above a predetermined value, as a developer and a rinse solution. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] International Publication No. 2020 / 071261 [Overview of the project] [Problems that the invention aims to solve]

[0004] In the above Patent Document 1, phosphate ester and adipate ester are included as essential components. However, when using an aliphatic hydrocarbon solvent as an organic solvent and a treatment liquid containing a metal component as a rinse liquid or a developer without using these components, defects may occur on the coated surface, and the inventors have found that there is room for improvement. Such defects are considered to be caused by impurities generated in the treatment liquid during at least one of manufacturing and storage.

[0005] Therefore, an object of the present invention is to provide a treatment liquid that suppresses the occurrence of defects when applied on the coated surface when used as a developer or a rinse liquid, and also suppresses the occurrence of defects on the coated surface when used after being stored in a container whose inner wall surface is made of metal. Another object of the present invention is to provide a treatment liquid container.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the inventors of the present invention have found that the above problems can be solved by the following configuration.

[0007] [1] An aliphatic hydrocarbon solvent, At least one acid component selected from the group consisting of carboxylic acids having a hydrocarbon group with 1 to 3 carbon atoms and formic acid, and A treatment liquid containing a metal impurity containing at least one metal element selected from the group consisting of Fe, Ni, and Cr, wherein The mass ratio of the content of the above metal element to the content of the above acid component is 1.0×10 -9 ~3.0×10 -5 A treatment liquid. [2] The treatment liquid according to [1], wherein the content of the above metal element is 0.03 to 100 mass ppt with respect to the total mass of the above treatment liquid. [3] The treatment liquid according to [1] or [2], wherein the content of the above acid component is 1 to 2000 mass ppm with respect to the total mass of the above treatment liquid. [4] The acid component contains acetic acid, The treatment liquid according to any one of [1] to [3], wherein the content of the acetic acid is 5 to 50 ppm by mass with respect to the total mass of the treatment liquid. [5] The treatment liquid according to any one of [1] to [4], wherein the content of the aliphatic hydrocarbon solvent is 2 to 70% by mass with respect to the total mass of the treatment liquid. [6] The treatment liquid according to any one of [1] to [5], wherein the aliphatic hydrocarbon solvent contains at least one selected from the group consisting of nonane, decane, undecane, dodecane and methyldecane. [7] The treatment liquid according to any one of [1] to [6], further containing an aromatic hydrocarbon. [8] The mass ratio of the content of the acid component to the content of the aromatic hydrocarbon is 1.0×10 -3 ~5, and the treatment liquid according to [7]. [9] The treatment liquid according to [7] or [8], wherein the content of the aromatic hydrocarbon is 1 to 2000 ppm by mass with respect to the total mass of the treatment liquid.

[10] The treatment liquid according to any one of [1] to [9], further containing an ester solvent.

[11] The treatment liquid according to

[10] , wherein the content of the ester solvent is 30 to 99% by mass with respect to the total mass of the treatment liquid.

[12] The treatment liquid according to

[10] or

[11] , wherein the ester solvent contains butyl acetate.

[13] Further containing water, The treatment liquid according to any one of [1] to

[12] , wherein the content of the water is 1 to 1000 ppm by mass with respect to the total mass of the treatment liquid.

[14] Further containing a sulfur-containing compound, The treatment liquid according to any one of [1] to

[13] , wherein the content of the sulfur-containing compound is 0.01 to 10 ppm by mass with respect to the total mass of the treatment liquid.

[15] It also contains alcohol, The treatment solution according to any one of [1] to

[14] , wherein the alcohol content is 1 to 5000 ppm by mass relative to the total mass of the treatment solution.

[16] A processing solution according to any one of [1] to

[15] , used as a developer or rinsing solution.

[17] A processing solution according to any one of [1] to

[16] , used as a developer for a negative-type resist film exposed to extreme ultraviolet light.

[18] A processing liquid container comprising a container and a processing liquid described in any of [1] to

[17] contained within the container.

[19] The liquid treatment container according to

[18] , wherein at least a portion of the liquid-contacting part of the container is made of metal. [Effects of the Invention]

[0008] According to the present invention, when used as a developer or rinsing solution, a processing solution can be provided that suppresses the occurrence of defects when applied to a surface to be coated, and also suppresses the occurrence of defects on the surface to be coated when used after being housed in a container with a metal inner wall. Furthermore, according to the present invention, a processing solution container can also be provided. [Modes for carrying out the invention]

[0009] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits. In numerical ranges described stepwise in this specification, the upper or lower limit stated in one numerical range may be replaced with the upper or lower limit of another numerical range described stepwise. Also, in numerical ranges described in this specification, the upper or lower limit stated in one numerical range may be replaced with the values ​​shown in the examples. Furthermore, in this specification, the amount of each component in the processing solution means the total amount of multiple substances present in the processing solution, unless otherwise specified, if multiple substances corresponding to each component are present in the processing solution. Furthermore, in this invention, "ppm" means "parts-per-million (10 -6 ) means "ppb" is "parts-per-billion (10 -9 ) means "ppt" is "parts-per-trillion (10 -12 ) means "ppq" is "parts-per-quadrillion (10 -15 It means ")". Furthermore, in this invention, 1 Å (angstrom) corresponds to 0.1 nm. Furthermore, in the notation of groups (atomic groups) in this invention, the notation that does not specify substitution or unsubstituted includes both substituted and unsubstituted groups, to the extent that it does not impair the effects of the present invention. For example, "hydrocarbon group" includes not only unsubstituted hydrocarbon groups but also substituted hydrocarbon groups. The same applies to each compound. Furthermore, in this invention, "radiation" means, for example, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, or electron beams. Also, in this invention, "light" means active light or radiation. In this invention, unless otherwise specified, "exposure" includes not only exposure with far ultraviolet light, X-rays, or EUV, but also drawing with particle beams such as electron beams or ion beams. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0010] [Processing liquid] The processing liquid of the present invention (hereinafter also referred to as "this processing liquid") is an aliphatic hydrocarbon solvent, at least one acid component selected from the group consisting of carboxylic acids having a hydrocarbon group with 1 to 3 carbon atoms and formic acid (hereinafter also referred to as "specific acid component"), and a metal impurity containing at least one metal element selected from the group consisting of Fe, Ni, and Cr (hereinafter also referred to as "specific metal impurity"), and the mass ratio of the content of the metal element to the content of the acid component is 1.0×10 -9 ~3.0×10 -5 is. When this processing liquid is used as a developer or a rinse liquid, the occurrence of defects is suppressed when applied on the coated surface, and the occurrence of defects on the coated surface is also suppressed when used after being stored in a container whose inner wall surface is made of metal. Although the details of this reason have not been clarified, it is presumed that in a system containing an aliphatic hydrocarbon solvent, when the content of the specific metal element with respect to the content of the specific acid component is within a predetermined range, the specific acid component and the specific metal component interact well, and the generation of impurities that cause defects in the processing liquid can be suppressed. In addition, when a processing liquid containing an acid component is stored in a container whose inner wall surface is made of metal, the acid component may react with the metal on the inner wall surface of the container to generate impurities. To solve this problem, it is presumed that in a system containing an aliphatic hydrocarbon solvent, when the content of the specific metal element with respect to the content of the specific acid component is within a predetermined range, the specific acid component and the specific metal component interact well in the processing liquid, and the reaction between the acid component in the processing liquid and the metal constituting the inner wall surface is suppressed.

[0011] [Aliphatic hydrocarbon solvent] This processing liquid contains an aliphatic hydrocarbon solvent. The aliphatic hydrocarbon solvent is a component contained in this processing liquid as an organic solvent. In this specification, an organic solvent is defined as an organic solvent present in the treatment solution at a concentration of 8,000 ppm by mass or more relative to the total mass of the treatment solution. Furthermore, any organic solvent present in the treatment solution at a concentration of less than 8,000 ppm by mass relative to the total mass of the treatment solution is considered an organic impurity and not an organic solvent.

[0012] The aliphatic hydrocarbon solvent may be linear, branched, or cyclic (monocyclic or polycyclic), with linear being preferred. Furthermore, the aliphatic hydrocarbon solvent may be either saturated or unsaturated aliphatic hydrocarbons. Aliphatic hydrocarbon solvents often have two or more carbon atoms, preferably five or more, and more preferably nine or more. The upper limit is preferably 30 or less, more preferably 20 or less, even more preferably 15 or less, and particularly preferably 13 or less. Specifically, the aliphatic hydrocarbon solvent has 11 carbon atoms.

[0013] Examples of aliphatic hydrocarbon solvents include pentane, isopentane, hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, heptane, octane, isooctane, nonane, decane, methyldecane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, hepradecane, 2,2,4-trimethylpentane, and 2,2,3-trimethylhexane. Aliphatic hydrocarbon solvents are preferable to contain aliphatic hydrocarbons having 5 or more carbon atoms (preferably 20 or fewer carbon atoms), more preferably contain aliphatic hydrocarbons having 9 or more carbon atoms (preferably 13 or fewer carbon atoms), even more preferably contain at least one selected from the group consisting of nonane, decane, undecane, dodecane, and methyldecane, and particularly preferably contain undecane. Aliphatic hydrocarbon solvents may be used individually or in combination of two or more types.

[0014] The content of the aliphatic hydrocarbon solvent is preferably 1% by mass or more and less than 100% by mass, more preferably 2 to 70% by mass, and even more preferably 5 to 30% by mass, relative to the total mass of the processing solution, in order to provide superior functionality as a developer and rinsing solution. If the aliphatic hydrocarbon solvent content is 2% by mass or more, the resolution of the resist pattern will be further improved. If the aliphatic hydrocarbon solvent content is 70% by mass or less, the occurrence of resist pattern deformation can be further suppressed, and if it is 30% by mass or less, the generation of static electricity can be further suppressed.

[0015] [Specific acid component] This treatment solution contains specific acid components. These specific acid components, as mentioned above, refer to carboxylic acids having hydrocarbon groups with 1 to 3 carbon atoms, and formic acid. These specific acid components may also exist as ions after ionization in this treatment solution. The specific acidic component may be present in the raw materials (e.g., organic solvents) used in the manufacture of this treatment solution, may be intentionally added during the manufacturing process of this treatment solution, or may be transferred (so-called contamination) from the manufacturing equipment of this treatment solution during the manufacturing process of this treatment solution. Specific examples of carboxylic acids having a hydrocarbon group with 1 to 3 carbon atoms include fatty acids having alkyl groups with 1 to 3 carbon atoms, such as acetic acid, propionic acid, n-butanoic acid (butyric acid), and 2-methylpropanoic acid (isobutyric acid), as well as polycarboxylic acids having hydrocarbon groups with 1 to 3 carbon atoms, such as malonic acid, succinic acid, glutaric acid, maleic acid, and fumaric acid. Fatty acids having alkyl groups with 1 to 3 carbon atoms are preferred because they allow the effects of the present invention to be more fully exhibited.

[0016] The content of the specific acid component is preferably 1 to 2000 ppm by mass, more preferably 3 to 700 ppm by mass, and even more preferably 5 to 50 ppm by mass, relative to the total mass of the treatment solution. The effects of the present invention are better when the content of the specific acid component is within the above range. The specific acid component may be used alone or in combination of two or more types.

[0017] Methods for adjusting the content of specific acid components include, for example, selecting raw materials with a low content of specific acid components as raw materials for various components, distilling under conditions that suppress contamination by lining the equipment with Teflon®, and adding specific acid components.

[0018] One preferred embodiment of the treatment solution is one in which the specific acid component contains acetic acid, and the acetic acid content is 5 to 50 ppm by mass relative to the total mass of the treatment solution. Using the treatment solution in this embodiment provides superior effects of the present invention and is more suitable for use as a rinsing solution and a developing solution.

[0019] [Specific Metal Impurities] This processing solution contains specific metallic impurities, including specific metallic elements. As mentioned above, the specific metallic elements are Fe, Ni, and Cr, and the specific metallic impurities contain at least one of these metallic elements. Although the exact reasons are unclear, certain metal elements are particularly closely related to the defect suppression performance of the processing solution compared to other metal elements. Therefore, for example, controlling the content of certain metal elements can easily lead to superior defect suppression performance.

[0020] The specific metal impurities may be present in the treatment solution in the form of particles (metal-containing particles), in the form of ions (metal ions), or in both forms. The specific metal impurities may be present in the raw materials (e.g., organic solvents) used in the manufacture of the treatment solution, may be intentionally added during the manufacturing process of the treatment solution, or may be transferred (so-called contamination) from the manufacturing equipment of the treatment solution during the manufacturing process of the treatment solution.

[0021] The content of specific metal elements is preferably 0.03 to 100 ppt by mass, more preferably 3 to 60 ppt by mass, and even more preferably 3 to 25 ppt by mass, relative to the total mass of the treatment solution. The effects of the present invention are better when the content of specific metal elements is within the above range. Specific metal elements may be used individually or in combination of two or more. If two or more specific metal elements are included, the total content must be within the above-mentioned range.

[0022] The content of specific metallic elements is measured by ICP-MS (Inductively Coupled Plasma Mass Spectrometry). ICP-MS measures the content of the targeted metallic element regardless of its form of existence. For example, if a specific metal impurity is present in the treatment solution in the form of metal-containing particles, the content of the specific metal element in the metal-containing particles is measured. If the specific metal impurity is present in the treatment solution in the form of metal ions, the content of the specific metal element corresponding to the metal ions is measured. If the specific metal impurity is present in the treatment solution in the form of both metal-containing particles and metal ions, the total amount of the specific metal element content in the metal-containing particles and the content of the specific metal element corresponding to the metal ions is measured. Examples of ICP-MS instruments include the Agilent 8900 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, which can be used for measurement by the method described in the examples. Other instruments that can be used include the PerkinElmer NexION350S and the Agilent 8800 manufactured by Agilent Technologies.

[0023] The mass ratio of the content of a specific metal element to the content of the acid component (content of the specific metal element / content of the acid component) is 1.0 × 10⁻⁶ -9 ~3.0×10 -5 Therefore, the present invention has superior effects, 6.0 × 10 -9 ~2.5×10 -5 Preferably, 5.0 × 10 -8 ~2.5×10 -5 More preferably, 7.5 × 10 -8 ~1.0×10 -6 That is even more preferable.

[0024] Methods for adjusting the content of specific metal elements include, for example, selecting raw materials with a low content of specific metal elements as raw materials constituting various components, distilling under conditions that suppress contamination by lining the inside of the apparatus with Teflon®, and adding specific metal elements or compounds containing specific metal elements.

[0025] [Ester-based solvents] This processing solution preferably further contains an ester-based solvent, which is a type of organic solvent, as it provides superior functionality as both a developer and a rinse solution. Furthermore, the effects of the present invention are even better when the treatment solution contains both an aliphatic hydrocarbon solvent and an ester solvent. Although the details of this reason are not clear, it is presumed that in a system containing both an ester solvent and an aliphatic hydrocarbon solvent, the content of a specific metal element relative to the content of a specific acid component is within a predetermined range, allowing the specific acid component and the specific metal component to interact more effectively, thereby suppressing the generation of impurities that could cause defects. The ester solvent may be linear, branched, or cyclic (monocyclic or polycyclic), with linear being preferred. The carbon number of ester solvents is often 2 or more, preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more. The upper limit is often 20 or less, preferably 10 or less, more preferably 8 or less, and particularly preferably 7 or less. Specifically, the carbon number of ester solvents is preferably 6.

[0026] Specific examples of ester solvents include butyl acetate, isobutyl acetate, tertbutyl acetate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, hexyl acetate, methoxybutyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, amyl formate, isoamyl formate, methyl lactate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, ethyl isobutyrate, propyl isobutyrate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate, and isobutyl propionate. The ester solvent preferably contains at least one selected from the group consisting of butyl acetate, isobutyl acetate, tertbutyl acetate, amyl acetate, isoamyl acetate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, ethyl butyrate, propyl butyrate, isopropyl butyrate, ethyl isobutyrate, propyl isobutyrate, amyl formate, and isoamyl formate, and more preferably contains butyl acetate. Ester solvents may be used individually or in combination of two or more types.

[0027] The content of the ester solvent is preferably 30 to 99% by mass, more preferably 30 to 98% by mass, and even more preferably 70 to 95% by mass, based on the total mass of the treatment solution.

[0028] 〔water〕 This processing solution may further contain water. The type of water is not particularly limited and includes, for example, distilled water, deionized water, and pure water. Water may be added to the treatment solution, or it may be unintentionally mixed into the treatment solution during the manufacturing process. Examples of unintentional mixing during the manufacturing process of the treatment solution include, but are not limited to, cases in which water is contained in the raw materials used in the manufacture of the treatment solution (e.g., organic solvents), or is mixed during the manufacturing process of the treatment solution (e.g., contamination).

[0029] The water content is preferably 1 to 1000 ppm by mass, and more preferably 5 to 100 ppm by mass, relative to the total mass of the treatment solution. The effects of the present invention are better when the water content is within the above range. The water content in this treatment solution refers to the water content measured using an apparatus based on the Karl Fischer moisture content method.

[0030] Methods for adjusting the water content include, for example, selecting raw materials with a low water content as components, distilling under conditions that suppress contamination by lining the equipment with Teflon®, and adding water.

[0031] [Sulfur-containing compounds] This treatment solution may further contain sulfur-containing compounds. Sulfur-containing compounds are not present in organic solvents. Sulfur-containing compounds may be added to the treatment solution, or they may be unintentionally mixed into the treatment solution during the manufacturing process. Examples of unintentional mixing during the manufacturing process include, but are not limited to, cases where sulfur-containing compounds are present in the raw materials used in the manufacture of the treatment solution (e.g., organic solvents), or where they are mixed during the manufacturing process of the treatment solution (e.g., contamination).

[0032] Examples of sulfur-containing compounds include thiol compounds, sulfide compounds, thiophene compounds, and hydrogen sulfide. Examples of thiol compounds include methanethiol, ethanethiol, 3-methyl-2-butene-1-thiol, 2-methyl-3-frantiol, furfurylthiol, 3-mercapto-3-methylbutylformate, phenylmercaptan, methylfurfurylmercaptan, ethyl 3-mercaptobutanoate, 3-mercapto-3-methylbutanol, and 4-mercapto-4-methyl-2-pentanone. Examples of sulfide compounds include dimethyl sulfide, dimethyl trisulfide, diisopropyl trisulfide, and bis(2-methyl-3-furyl) disulfide. Examples of thiophene compounds include alkylthiophene compounds, benzothiophene compounds, dibenzothiophene compounds, phenantrothiophene compounds, benzonaphthothiophene compounds, and thiophenesulfide compounds. As sulfur-containing compounds, sulfide compounds or thiophene compounds are preferred, and dimethyl sulfide or benzothiophene are more preferred. Sulfur-containing compounds may be used individually or in combination of two or more.

[0033] The sulfur-containing compound content is preferably 0.01 to 23 ppm by mass, more preferably 0.01 to 10 ppm by mass, even more preferably 0.01 to 9 ppm by mass, and particularly preferably 0.03 to 0.1 ppm by mass, relative to the total mass of the treatment solution. If the sulfur-containing compound content is within the above range, the occurrence of defects can be further suppressed even when the treatment solution is used after heating. The types and content of sulfur-containing compounds in this treatment solution can be measured using GCMS (gas chromatography-mass spectrometry).

[0034] [Organic impurities] The treatment solution may contain organic impurities. These organic impurities may be added to the treatment solution or may be unintentionally mixed in during the manufacturing process of the treatment solution. Examples of unintentional mixing during the manufacturing process of the treatment solution include, but are not limited to, cases where organic impurities are contained in the raw materials used in the manufacture of the treatment solution (e.g., organic solvents) or are mixed in during the manufacturing process of the treatment solution (e.g., contamination).

[0035] The content and type of organic impurities in this treatment solution can be measured using GCMS (gas chromatography-mass spectrometry).

[0036] <Aromatic hydrocarbons> This treatment solution may further contain aromatic hydrocarbons, which are a type of organic impurity. Aromatic hydrocarbons are not included in the organic solvents mentioned above and are considered organic impurities. In other words, the aromatic hydrocarbon content is less than 8000 ppm by mass relative to the total mass of this treatment solution.

[0037] The number of carbon atoms in the aromatic hydrocarbon is preferably 6 to 30, more preferably 6 to 20, and even more preferably 10 to 12. The aromatic rings in aromatic hydrocarbons may be monocyclic or polycyclic. The number of members in the aromatic ring of an aromatic hydrocarbon is preferably 6 to 12, more preferably 6 to 8, and even more preferably 6. The aromatic ring of the aromatic hydrocarbon may have further substituents. Examples of substituents include alkyl groups, alkenyl groups, and groups combining them. The alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group and alkenyl group is preferably 1 to 10, and more preferably 1 to 5. Examples of aromatic rings in aromatic hydrocarbons include optionally substituted benzene rings, optionally substituted naphthalene rings, and optionally substituted anthracene rings, with optionally substituted benzene rings being preferred. In other words, benzene, which may have substituents, is preferred as the aromatic hydrocarbon.

[0038] Aromatic hydrocarbons are C 10 H 14 , C 11 H 16 and C 10 H 12 Preferably, it includes at least one selected from the group consisting of the following: Furthermore, as aromatic hydrocarbons, compounds represented by formula (c) are also preferred.

[0039] [ka]

[0040] In formula (c), R c represents a substituent. c represents an integer from 0 to 6.

[0041] R c represents a substituent. Rc The substituents represented are preferably alkyl groups or alkenyl groups. The alkyl group and alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group and alkenyl group is preferably 1 to 10, and more preferably 1 to 5. R c If there are multiple instances, R c They may be the same or different, R c These elements may join together to form a ring. Also, R c (R c If multiple R c A part or all of () and the benzene ring in formula (c) may condense to form a fused ring.

[0042] c represents an integer between 0 and 6. c is preferably an integer between 1 and 5, and more preferably an integer between 1 and 4.

[0043] The molecular weight of the aromatic hydrocarbon is preferably 50 or more, more preferably 100 or more, and even more preferably 120 or more. The upper limit is preferably 1000 or less, more preferably 300 or less, and even more preferably 150 or less.

[0044] Examples of aromatic hydrocarbons include C1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene, and 1-ethyl-2,4-dimethyl-benzene. 10 H 14 ;C such as 1-methyl-4-(1-methylpropyl)-benzene and (1-methybutyl)-benzene 11 H 16 ;C such as 1-methyl-2-(2-propenyl)-benzene and 1,2,3,4-tetrahydro-naphthalene 10 H 12 These are some examples. Aromatic hydrocarbons include 1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-methyl-4-(1-methylpropyl)-benzene, and C 10 H 12 Preferably, 1-ethyl-3,5-dimethylbenzene or 1,2,3,5-tetramethylbenzene is more preferred. Aromatic hydrocarbons may be used individually or in combination of two or more.

[0045] The aromatic hydrocarbon content is preferably 1 to 3500 ppm by mass, more preferably 1 to 2000 ppm by mass, even more preferably 10 to 1200 ppm by mass, and particularly preferably 60 to 360 ppm by mass, relative to the total mass of the treatment solution. The effects of the present invention are better when the aromatic hydrocarbon content is within the above range.

[0046] The mass ratio of the acidic component content to the aromatic hydrocarbon content (acidic component content / aromatic hydrocarbon content) is 1.0 × 10⁻⁶ -3 ~5 is preferred, 2.5 × 10 -3 ~1.3 is more preferable, 9.7 × 10 -2 ~8.3×10 -1 This is even more preferable. The effects of the present invention are better if the mass ratio is within the above range.

[0047] Methods for adjusting the aromatic hydrocarbon content include, for example, selecting raw materials with a low aromatic hydrocarbon content as constituent materials for various components, distilling under conditions that suppress contamination by lining the equipment with Teflon®, and adding aromatic hydrocarbons.

[0048] 〔alcohol〕 This treatment solution may further contain alcohol, which is a type of organic impurity. Alcohol is not included in the organic solvents mentioned above and is considered an organic impurity. In other words, the alcohol content is less than 8000 ppm by mass relative to the total mass of the treatment solution. The number of carbon atoms in the alcohol is preferably 1 to 20, more preferably 1 to 5, and even more preferably 2 to 5. The alcohol preferably contains at least one selected from the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, and 2-methyl-1-butanol, more preferably containing 1-butanol, 2-butanol, and tert-butanol, and even more preferably containing 1-butanol. Alcohol may be used alone or in combination of two or more types.

[0049] The alcohol content is preferably 1 to 5000 ppm by mass, more preferably 10 to 400 ppm by mass, and even more preferably 20 to 60 ppm by mass, relative to the total mass of the treatment solution. The effects of the present invention are better when the alcohol content is within the above range.

[0050] Methods for adjusting the alcohol content include, for example, selecting raw materials with a low alcohol content as components, distilling under conditions that suppress contamination by lining the equipment with Teflon®, and adding alcohol.

[0051] [Other ingredients] This processing solution may contain other components besides those listed above. Other components include organic solvents such as ketone solvents, amide solvents, and ether solvents, as well as surfactants.

[0052] [Application] This processing solution is preferably used as a developer or rinse solution in the manufacturing process of semiconductor devices, and more preferably as a developer for negative-type resist films exposed to extreme ultraviolet (EUV) light, as this allows the effects of the present invention to be more fully realized. Furthermore, this processing solution can also be used as a pre-wetting solution in the manufacturing process of semiconductor devices. Furthermore, this processing solution is also suitable for processing resist films exposed by light sources other than EUV. Specifically, it is preferable to use it for processing (especially developing) resist compositions (particularly negative-type resist films) exposed by KrF, ArF, ArF immersion, or electron beam (EB). Furthermore, this processing solution can also be used as a cleaning solution for the edge and surrounding bevels of the wafer, and as a cleaning solution for the back surface (the side of the wafer opposite to the side where the semiconductor substrate is formed). Furthermore, this treatment solution can also be used as a cleaning solution for various manufacturing equipment, coating equipment, and transfer containers.

[0053] [Method for producing the treatment solution] The method for producing the treatment solution is not particularly limited, and known production methods can be used. In particular, in order to obtain a treatment solution that exhibits the effects of the present invention, it is preferable that the method for producing the treatment solution includes a filtration step in which the material to be purified containing an organic solvent is filtered using a filter to obtain the treatment solution.

[0054] The material to be purified used in the filtration process may be procured by purchase or obtained by reacting raw materials. Preferably, the material to be purified has a low impurity content. Examples of commercially available products of this type include those called "high-purity grade products."

[0055] The method for reacting raw materials to obtain a product to be purified (typically a product containing an organic solvent) is not particularly limited, and known methods can be used. For example, one method is to react one or more raw materials in the presence of a catalyst to obtain an organic solvent.

[0056] <Filtration process> The method for producing the processing liquid according to the embodiment of the present invention includes a filtration step of filtering the substance to be purified using a filter to obtain the processing liquid. There are no particular limitations on the method of filtering the substance to be purified using a filter, but it is preferable to pass the substance to be purified through a filter unit having a housing and a filter cartridge housed in the housing, under or without pressure.

[0057] (Pore diameter of the filter) There are no particular restrictions on the pore size of the filter, and filters with pore sizes commonly used for filtering materials to be purified can be used. In particular, the pore size of the filter is preferably 200 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, especially preferably 5 nm or less, and most preferably 3 nm or less, as it allows for easy control of the number of particles (metal-containing particles, etc.) that may be contained in the processing solution within a desired range. There are no particular restrictions on the lower limit, but generally, 1 nm or more is preferred from the viewpoint of productivity. In this specification, the pore size and pore size distribution of a filter refer to the pore size and pore size distribution determined by the bubble points of isopropanol (IPA) or HFE-7200 ("Novec 7200", manufactured by 3M, hydrofluoric acid ether, C4F9OC2H5).

[0058] A filter with a pore size of 5.0 nm or less is preferable because it allows for easier control of the number of particles contained in the processing solution. Hereinafter, filters with a pore size of 5 nm or less will also be referred to as "micropore filters." Micropore filters may be used alone or in combination with filters of other pore sizes. In particular, from the viewpoint of superior productivity, it is preferable to use them with filters that have larger pore sizes. In this case, if the material to be purified is filtered beforehand using a filter with a larger pore size and then passed through the micropore filter, clogging of the micropore filter can be prevented. In other words, when using one filter, the pore size is preferably 5.0 nm or less, and when using two or more filters, the pore size of the filter with the smallest pore size is preferably 5.0 nm or less.

[0059] There are no particular limitations on the configuration in which two or more filters with different pore sizes are used sequentially, but one method is to arrange the filter units described above in order along the pipeline through which the material to be purified is transported. In this case, if the flow rate of the material to be purified per unit time is to be kept constant throughout the pipeline, the filter units with smaller pore sizes may experience greater pressure compared to the filter units with larger pore sizes. In this case, it is preferable to place pressure regulating valves and dampers between the filter units to keep the pressure on the filter units with smaller pore sizes constant, or to arrange filter units containing the same filters in parallel along the pipeline to increase the filtration area. In this way, the number of particles in the processing liquid can be controlled more stably.

[0060] (Filter materials) The material of the filter is not particularly limited, and known materials can be used as filter materials. Specifically, if it is a resin, examples include polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamide-imide; poly(meth)acrylate; polyfluorocarbons such as polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylenepropene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc. Among these, at least one selected from the group consisting of nylon (6,6-nylon is preferred), polyolefins (polyethylene is preferred), poly(meth)acrylate, and polyfluorocarbons (polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) are preferred) is preferred because it has better solvent resistance and the resulting treated solution has better defect suppression performance. These polymers can be used individually or in combination of two or more. In addition to resin, diatomaceous earth and glass may also be used. Alternatively, a polymer (such as nylon-grafted UPE) obtained by graft copolymerizing polyolefin (such as UPE described later) with polyamide (for example, nylon-6 or nylon-6,6) may be used as the filter material.

[0061] Furthermore, the filter may be a surface-treated filter. The surface treatment method is not particularly limited, and known methods can be used. Examples of surface treatment methods include chemical modification, plasma treatment, hydrophilic / hydrophobic treatment, coating, gas treatment, and sintering.

[0062] Plasma treatment is preferred because it makes the filter surface hydrophilic. There are no particular limitations on the water contact angle on the surface of the plasma-treated and hydrophilic filter material, 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.

[0063] As for the chemical modification treatment, a method of introducing ion exchange groups into the substrate is preferred. In other words, as a filter, a filter is preferred in which each of the materials listed above is used as a base material and ion exchange groups are introduced into the base material. Typically, a filter is preferred in which a layer containing a base material containing ion exchange groups is included on the surface of the base material. The surface-modified base material is not particularly limited, but a filter in which ion exchange groups are introduced into the polymer is preferred because it is easier to manufacture.

[0064] Examples of ion exchange groups include sulfonic acid groups, carboxyl groups, and phosphate groups as cation exchange groups, and quaternary ammonium groups as anion exchange groups. There are no particular limitations on the method of introducing ion exchange groups into a polymer, but a typical method involves grafting by reacting a compound containing ion exchange groups and polymerizable groups with the polymer.

[0065] There are no particular restrictions on the method of introducing ion exchange groups, but the resin fibers described above are irradiated with ionizing radiation (alpha rays, beta rays, gamma rays, X-rays, and electron beams, etc.) to generate active parts (radicals) in the resin. The irradiated resin is then immersed in a monomer-containing solution to graft polymerize the monomer onto the substrate. As a result, a polymer is produced in which this monomer is bonded to the polyolefin fibers as graft polymerization side chains. The resin containing this generated polymer as side chains is then brought into contact with a compound containing anion exchange groups or cation exchange groups to introduce ion exchange groups into the graft polymerized side chain polymer, yielding the final product.

[0066] Furthermore, the filter may also be constructed by combining a woven or nonwoven fabric in which ion exchange groups have been formed by radiation graft polymerization with a conventional glass wool, woven fabric, or nonwoven fabric filter material.

[0067] Using a filter containing ion exchange groups makes it easier to control the content of metal atom-containing particles in the treatment solution within a desired range. The material of the filter containing ion exchange groups is not particularly limited, but examples include polyfluorocarbons and materials in which ion exchange groups have been introduced into polyolefins, with materials in which ion exchange groups have been introduced into polyfluorocarbons being more preferred. The pore size of the filter containing the ion exchange group is not particularly limited, but is preferably 1 to 200 nm, more preferably 1 to 30 nm, and even more preferably 3 to 20 nm. The filter containing the ion exchange group may also serve as the filter having the minimum pore size described above, or it may be used separately from the filter having the minimum pore size. In particular, in order to obtain the processed liquid that exhibits the effects of the present invention more effectively, the filtration step is preferably configured to use a filter containing the ion exchange group and a filter that does not have the ion exchange group but has the minimum pore size. While there are no particular limitations on the material of the filter having the minimum pore size as described above, from the viewpoint of solvent resistance and other factors, at least one selected from the group consisting of polyfluorocarbons and polyolefins is generally preferred, and polyolefins are more preferred.

[0068] Therefore, two or more filters made of different materials may be used as filters in the filtration process. For example, two or more filters selected from the group consisting of polyolefins, polyfluorocarbons, polyamides, and materials to which ion exchange groups have been introduced may be used.

[0069] (Pore structure of the filter) The pore structure of the filter is not particularly limited and can be appropriately selected depending on the components in the product to be purified. In this specification, the pore structure of the filter refers to the pore size distribution, the positional distribution of pores in the filter, and the shape of the pores, etc., and is typically controllable by the filter manufacturing method. For example, porous films can be obtained by sintering powders such as resin, and fibrous films can be obtained by methods such as electrospinning, electroblowing, and meltblowing. These films each have different pore structures.

[0070] A "porous membrane" refers to a membrane that retains components in a material being purified, such as gels, particles, colloids, cells, and polyoligomers, but allows components substantially smaller than the pores to pass through. The retention of components in the material being purified by a porous membrane may depend on operating conditions, such as face velocity, use of surfactants, pH, and combinations thereof, and may also depend on the pore size and structure of the porous membrane, as well as the size and structure (hard particles or gel, etc.) of the particles to be removed.

[0071] When the material to be purified contains negatively charged particles, a polyamide filter acts as a non-sieving membrane to remove such particles. Typical non-sieving membranes include, but are not limited to, nylon membranes such as nylon-6 and nylon-6,6 membranes. Furthermore, the term "non-sieve" retention mechanism used herein refers to retention resulting from the pressure drop of the filter or from mechanisms such as interference, diffusion, and adsorption, which are not related to the pore size.

[0072] Non-sieve retention includes retention mechanisms such as interference, diffusion, and adsorption that remove target particles from the purified material, regardless of the filter's pressure drop or pore size. Adsorption of particles to the filter surface can be mediated, for example, by intermolecular van der Waals forces and electrostatic forces. Interference occurs when particles moving through a non-sieve film layer with a meandering path cannot change direction quickly enough to avoid contact with the non-sieve film. Particle transport by diffusion arises mainly from the random motion or Brownian motion of small particles, creating a certain probability of collision between particles and the filter material. Non-sieve retention mechanisms can be active when there is no repulsive force between the particles and the filter.

[0073] UPE (ultra-high molecular weight polyethylene) filters are typically sieve membranes. A sieve membrane is a membrane that primarily captures particles via a sieve-holding mechanism, or a membrane optimized for capturing particles via a sieve-holding mechanism. Typical examples of sieving membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes. The "sieve retention mechanism" refers to the retention of particles that are to be removed because their size exceeds the pore diameter of the porous membrane. Sieve retention can be improved by forming a filter cake (an aggregation of particles to be removed on the membrane surface). The filter cake effectively functions as a secondary filter.

[0074] The material of the fiber film is not particularly limited as long as it is a polymer capable of forming a fiber film. Examples of polymers include polyamides. Examples of polyamides include nylon 6 and nylon 6,6. The polymer forming the fiber film may also be poly(ethersulfone). When the fiber film is on the primary side of the porous film, it is preferable that the surface energy of the fiber film is higher than that of the polymer material of the porous film on the secondary side. An example of such a combination is when the material of the fiber film is nylon and the porous film is polyethylene (UPE).

[0075] The method for manufacturing the fiber film is not particularly limited, and known methods can be used. Examples of methods for manufacturing the fiber film include electrospinning, electroblowing, and meltblowing.

[0076] The pore structure of the porous membrane (for example, porous membranes containing UPE and PTFE, etc.) is not particularly limited, but examples of pore shapes include lace-like, string-like, and node-like structures. The distribution of pore size and its position within a porous membrane is not particularly limited. The size distribution may be smaller and the distribution within the membrane may be symmetrical. Alternatively, the size distribution may be larger and the distribution within the membrane may be asymmetrical (the above membrane is also called an "asymmetric porous membrane"). In an asymmetric porous membrane, the pore size changes within the membrane, and typically, the pore diameter increases from one surface of the membrane to the other. In this case, the surface with more pores of larger diameter is called the "open side," and the surface with more pores of smaller diameter is called the "tight side." Furthermore, an example of an asymmetric porous membrane is a membrane in which the size of the pores is smallest at a certain point within the membrane's thickness (this is also called an "hourglass shape").

[0077] By using an asymmetric porous membrane and making the primary side a larger pore size, or in other words, making the primary side an open side, a pre-filtration effect can be produced.

[0078] The porous membrane may contain thermoplastic polymers such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, a copolymer of tetrafluoroethylene and perfluoroalkoxyalkane), polyamide, and polyolefin, or it may contain polytetrafluoroethylene, etc. Among these, ultra-high molecular weight polyethylene is preferred as a material for porous membranes. Ultra-high molecular weight polyethylene refers to thermoplastic polyethylene with extremely long chains, and its molecular weight is over one million, typically preferably between 2 and 6 million.

[0079] The filters used in the filtration process may consist of two or more filters with different pore structures, and porous membrane filters and fiber membrane filters may be used in combination. A specific example is the use of a nylon fiber membrane filter and a UPE porous membrane filter.

[0080] Furthermore, it is preferable to thoroughly wash the filter before use. If an unwashed filter (or a filter that has not been thoroughly washed) is used, impurities contained in the filter are easily introduced into the treatment solution. Examples of impurities contained in filters include the organic impurities mentioned above. If the filtration process is carried out using an unwashed filter (or a filter that has not been sufficiently washed), the amount of organic impurities in the treated solution may exceed the acceptable range for this solution. For example, when using polyolefins such as UPE and polyfluorocarbons such as PTFE as filters, the filters tend to contain alkanes with 12 to 50 carbon atoms as impurities. Furthermore, when using polymers such as nylon, polyimides, and polyolefins (such as UPE) graft copolymerized with polyamides (such as nylon) as filters, the filters tend to contain alkenes with 12 to 50 carbon atoms as impurities. One method for cleaning the filter is to immerse it in an organic solvent with a low impurity content (for example, a distilled and purified organic solvent (such as PGMEA)) for more than one week. In this case, the liquid temperature of the organic solvent is preferably 30 to 90°C. The material to be purified may be filtered using a filter with an adjusted degree of washing, and the resulting processed liquid may be adjusted to contain a desired amount of organic impurities derived from the filter.

[0081] The filtration process may be a multi-stage filtration process in which the material to be purified is passed through two or more filters, each having at least one different characteristic selected from the group consisting of filter material, pore size, and pore structure. Furthermore, the substance to be purified may be passed through the same filter multiple times, or through multiple filters of the same type. There are no particular restrictions on the filtration path; a single-pass filtration system is acceptable, or a recirculating filtration system can be implemented.

[0082] The material of the wetted parts (meaning the inner wall surface, etc., that may come into contact with the product to be purified and the processing liquid) of the purification apparatus used in the filtration process is not particularly limited, but it is preferable that they be made of at least one selected from the group consisting of non-metallic materials (such as fluororesin) and electropolished metallic materials (such as stainless steel) (hereinafter, these are collectively referred to as "corrosion-resistant materials"). For example, when the wetted parts of a manufacturing tank are made of a corrosion-resistant material, this means that the manufacturing tank itself is made of a corrosion-resistant material, or that the inner wall surface, etc., of the manufacturing tank is covered with a corrosion-resistant material.

[0083] The above non-metallic material is not particularly limited, and known materials can be used. Examples of nonmetallic materials include, but are not limited to, at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluororesins (e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluoroethylene chloride-ethylene copolymer resin, vinylidene fluoride resin, trifluoroethylene chloride copolymer resin, and vinyl fluoride resin).

[0084] The above-mentioned metal material is not particularly limited, and known materials can be used. Examples of metallic materials include those in which the combined content of chromium and nickel exceeds 25% by mass of the total mass of the metallic material, with 30% by mass or more being more preferable. There is no particular upper limit on the combined content of chromium and nickel in the metallic material, but generally 90% by mass or less is preferred. Examples of metallic materials include stainless steel and nickel-chromium alloys.

[0085] There are no particular restrictions on the stainless steel used, and any known stainless steel can be used. Among these, alloys containing 8% by mass or more nickel are preferred, and austenitic stainless steel containing 8% by mass or more nickel is more preferred. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (8% by mass Ni content, 18% by mass Cr content), SUS304L (9% by mass Ni content, 18% by mass Cr content), SUS316 (10% by mass Ni content, 16% by mass Cr content), and SUS316L (12% by mass Ni content, 16% by mass Cr content).

[0086] The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Among these, a nickel-chromium alloy with a nickel content of 40-75% by mass and a chromium content of 1-30% by mass is preferred. Examples of nickel-chromium alloys include Hastelloy (product name, same hereinafter), Monel (product name, same hereinafter), and Inconel (product name, same hereinafter). More specifically, examples include 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), and Hastelloy C-22 (Ni content 61% by mass, Cr content 22% by mass). Furthermore, the nickel-chromium alloy may, if necessary, contain boron, silicon, tungsten, molybdenum, copper, and cobalt in addition to the alloys mentioned above.

[0087] The method for electropolishing 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 Publication No. 2015-227501 and paragraphs

[0036] to

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

[0088] It is presumed that, due to electropolishing, the chromium content in the passive layer of the metal material surface is higher than that in the matrix phase. Therefore, it is presumed that using a refining apparatus in which the wetted parts are made from electropolished metal material will reduce the likelihood of metal-containing particles leaking into the refined material. The metal material may be buffed. The buffing method is not particularly limited, and known methods can be used. The size of the abrasive grains used for finishing the buffing is not particularly limited, but #400 or smaller is preferred as it tends to reduce surface irregularities of the metal material. It is preferable that buffing be performed before electrolytic polishing.

[0089] <Other processes> The method for producing this processed liquid may further include steps other than the filtration step. Examples of steps other than the filtration step include a distillation step, a reaction step, and an electrostatic removal step.

[0090] (Distillation process) The distillation process involves distilling a material containing an organic solvent to obtain a distilled material. The method of distilling the material is not particularly limited, and known methods can be used. Typically, a distillation column is placed on the primary side of a purification apparatus used in the filtration process, and the distilled material is introduced into a production tank. In this case, there are no particular restrictions on the wetted parts of the distillation column, but it is preferable that they be made of the corrosion-resistant material described above.

[0091] (Reaction process) The reaction step is a process of reacting raw materials to produce a product to be purified, which contains an organic solvent as a reactant. There are no particular limitations on the method of producing the product to be purified, and known methods can be used. Typically, a reaction vessel is placed on the primary side of the production tank (or distillation column) of the purification apparatus used in the filtration step, and the reactant is introduced into the production tank (or distillation column). In this case, there are no particular restrictions on the wetted parts of the manufacturing tank, but it is preferable that they be formed from the corrosion-resistant materials described above.

[0092] (static elimination process) The static elimination process is a process that removes static electricity from the material to be refined, thereby reducing its charge potential. There are no particular restrictions on the method of static elimination, and known static elimination methods can be used. One example of a static elimination method is to bring the object to be purified into contact with a conductive material. The contact time for bringing the material to be purified 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 seconds. Examples of conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon. One method for bringing the material to be purified into contact with a conductive material is to place a grounded mesh made of a conductive material inside a conduit and pass the material to be purified through it.

[0093] The purification of the product to be purified, including all associated steps such as opening containers, cleaning containers and equipment, filling solutions, and analysis, is preferably carried out in a cleanroom. The cleanroom should preferably be a cleanroom with a cleanliness level of Class 4 or higher as defined by the international standard ISO 14644-1:2015 established by the International Organization for Standardization. Specifically, it is preferable that the cleanroom meets any of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and particularly preferably ISO Class 1.

[0094] While there are no particular restrictions on the storage temperature of the treatment solution, a storage temperature of 4°C or higher is preferable, as this makes it less likely for trace amounts of impurities contained in the treatment solution to leach out, resulting in superior effects of the present invention.

[0095] In addition, a dehydration process may be carried out as a step other than those mentioned above. The dehydration process can be carried out, for example, by distillation and molecular sieves.

[0096] [Container for processing liquid] This processing solution may be used immediately after production, or it may be stored in a container until use. The container and the processing solution contained within it are collectively referred to as a processing solution container. The processing solution is then taken from the stored processing solution container and used.

[0097] For storing this processing solution, a container with a high degree of cleanliness and minimal leaching of impurities is preferable, especially for semiconductor device manufacturing applications. Examples of usable containers include, but are not limited to, the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd.

[0098] As for the container, it is also preferable to use a multilayer bottle with a six-layer structure of six types of resins on the inner wall, or a multilayer bottle with a seven-layer structure of six types of resins, for the purpose of preventing contamination of the processing liquid with impurities. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0099] At least a portion of the liquid-contacting parts of the container may be made of metal (preferably stainless steel, more preferably electropolished stainless steel), fluororesin, or glass, and it is preferable that the parts be made of metal in that the effects of the present invention are better exhibited. [Examples]

[0100] The present invention will be described in more detail below based on the following examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.

[0101] [Production of treatment solutions for the examples and comparative examples] The components shown in the table below were mixed to obtain the treatment solutions for the examples and comparative examples. First, the organic solvents (aliphatic hydrocarbon solvents and ester solvents) were purified by low-temperature distillation in a sealed container made of Teflon® and by filter filtration, and the purification process was repeated until the content of specific metal elements (measured by the ICP-MS method described later) was less than 1 ppt by mass. Next, the purified aliphatic carbonized aqueous solvent and ester solvent were mixed to the content shown in the table below, and then components other than the organic solvent were added to the content shown in Table 1. In this way, the treatment solutions for the examples and comparative examples were obtained. In preparing the processing solution, to prevent contamination, all preparation work for each component was carried out in an ISO Class 3 clean booth. Furthermore, the containers and equipment used for preparing each component and measuring their content were selected to have wetted parts made of Teflon®, glass, or electropolished stainless steel, and these wetted parts were thoroughly cleaned beforehand using Fujifilm Electronic Materials' FN-DP001. Furthermore, the filters used for filtration included 7nm PTFE filters, 10nm PE (polyethylene) filters, and 5nm nylon filters manufactured by Nippon Entegris Co., Ltd., either individually or in appropriate combinations. Furthermore, the organic solvent used in Example 12 underwent a concentration pretreatment by low-temperature heating, and the content of specific metals contained in the original solvent was measured so that it could be detected to the order of 0.01 mass ppt. The wetted parts of the concentration pretreatment apparatus were made of Teflon® or glass, and were thoroughly washed with the treatment solution from Example 12 before use in the concentration pretreatment.

[0102] [Aliphatic hydrocarbon solvents] • Undecane: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Decane: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Dodecane: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Wako Special Grade) Methyldecane: Reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Nonan: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0103] [Specific acid component] • Acetic acid: Kanto Chemical Co., Ltd., ultra-high purity chemicals • Propionic acid: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Butyric acid: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Formic acid: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Isobutyric acid: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0104] [Ester-based solvents] • Butyl acetate: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Isobutyl acetate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Tert-butyl acetate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Amyl acetate: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Isoamyl acetate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Propyl propionate: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Isopropyl propionate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Butyl propionate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Isobutyl propionate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Ethyl butyrate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Ethyl isobutyrate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Amyl formate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Isoamyl formate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Wako Special Grade. • Propyl butyrate: Reagent from Tokyo Chemical Industry Co., Ltd. Isopropyl butyrate: Reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. • Propyl isobutyrate: Reagent from Tokyo Chemical Industry Co., Ltd.

[0105] 〔water〕 • Ultrapure water: Water collected from an ultrapure water system manufactured by Nomura Microscience Co., Ltd.

[0106] [Sulfur-containing compounds] • Thiofen: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0107] [Aromatic hydrocarbons] • 1,2,3,5-Tetramethylbenzene: Reagent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0108] 〔alcohol〕 • 1-Butanol: Wako Special Grade, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0109] [Specific metal elements] • Fe: ICPMS standard solution manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Fe concentration: 100 ppm by mass) • Ni: ICPMS standard solution manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Ni concentration: 100 ppm by mass) • Cr: ICPMS standard solution manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (Cr concentration: 100 ppm by mass) In each example and comparative example, a mixture was used, prepared by mixing equal volumes of the above-mentioned ICPMS standard solution containing Fe, the above-mentioned ICPMS standard solution containing Ni, and the above-mentioned ICPMS standard solution containing Cr. The mixture was added by serially diluting it using the mother liquor of each example and comparative example so that the total content of each element, Fe, Ni, and Cr, matched the values ​​in Table 1.

[0110] [Measurement of the content of each component] The content of hydrocarbon solvents and ester solvents in the treatment solution was calculated from the amount of material used. Furthermore, regarding the content of components other than hydrocarbon solvents and ester solvents, after the production of the treatment solution, the content of each component was confirmed to be as shown in the table below using the following measurement method.

[0111] <Content of specific acid components, sulfur-containing components, aromatic hydrocarbons, and alcohols> The content of specific acid components, sulfur-containing components, aromatic hydrocarbons, and alcohols in the treatment solution was measured using a gas chromatograph-mass spectrometer (product name "GCMS-2020", manufactured by Shimadzu Corporation). (Measurement conditions) Capillary column: InertCap 5MS / NP 0.25mmI.D. ×30m df=0.25μm Sample introduction method: Split 75kPa constant pressure Evaporation chamber temperature: 230℃ Column oven temperature: 80℃ (2 min) - 500℃ (13 min), heating rate 15℃ / min Carrier gas: Helium Septum purge flow rate: 5 mL / min Split ratio: 25:1 Interface temperature: 250℃ Ion source temperature: 200℃ Measurement mode: Scan m / z=85~500 Sample introduction volume: 1 μL

[0112] <Content of specific metal elements> The content of specific metal elements (Fe, Ni, and Cr) in the processing solution (total content of each element) was measured using an Agilent 8900 triple quadrupole ICP-MS (for semiconductor analysis, option #200) according to the following measurement conditions. (Measurement conditions) The sample introduction system used a quartz torch, a coaxial PFA (perfluoroalkoxyalkane) nebulizer (for self-priming), and a platinum interface cone. The measurement parameters for the cool plasma conditions are as follows: • RF (Radio Frequency) output (W): 600 Carrier gas flow rate (L / min): 0.7 Makeup gas flow rate (L / min): 1 • Sampling depth (mm): 18 For treatment solutions containing trace amounts of specific metal elements, the solution was first subjected to low-temperature evaporation and concentration using a synthetic quartz container, and then measured. The content of the specific metal element was determined by dividing the measured value by the concentration ratio.

[0113] [Water content] The water content in the treated liquid was measured using a device that employs the Karl Fischer moisture meter method (Karl Fischer moisture meter MKA-610, manufactured by Kyoto Electronics Manufacturing Co., Ltd.).

[0114] [Evaluation Test] The following evaluations were performed using the processing solutions from the examples and comparative examples.

[0115] 〔defect〕 (Preparation of the resist composition) The following components were mixed to prepare a mixture. • Polymer 1 54 parts by mass • Photoacid generator 31 parts by mass • Acid diffusion control agent 15 parts by mass • Propylene glycol monomethyl ether acetate 3430 parts by mass • Propylene glycol monomethyl ether 1470 parts by mass

[0116] Polymer 1 is a polymer having the following two repeating units, with a weight-average molecular weight of 8700 and a dispersion degree (Mw / Mn) of 1.23. Furthermore, the molar ratio between the repeating unit represented by U-01 and the repeating unit represented by U-19 was 1:1.

[0117] [ka]

[0118] Photoacid generator (see structural formula below)

[0119] [ka]

[0120] Acid diffusion control agent (see structural formula below)

[0121] [ka]

[0122] Next, the mixture obtained above was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare resist composition R-1.

[0123] (Method for evaluating defects) First, the underlayer film formation composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied to a 12-inch silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. On top of that, the resist composition R-1 prepared above was applied and baked (PB) at 90°C for 60 seconds to form a resist film with a thickness of 35 nm. This resulted in the fabrication of a silicon wafer with a resist film. A silicon wafer having the obtained resist film was patterned using an EUV exposure system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A photomask with a line size of 22 nm and a line-to-space ratio of 1:1 was used as the rectil. After baking (PEB) at 100°C for 60 seconds, the wafer was developed by paddleding with the processing solution (developer) of the examples and comparative examples for 30 seconds, and the wafer was rotated at a speed of 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 28 to 50 nm. The obtained patterns were evaluated by detecting defects on the substrate using Uvision8+ (manufactured by AMAT), and the number of defects was used for evaluation. The evaluation criteria are as follows: • Evaluation criteria A: Less than 50 pieces B: More than 50 pieces, less than 200 pieces C: More than 200 pieces, less than 1,000 pieces D: More than 1,000 pieces, less than 10,000 pieces E: Over 10,000 pieces

[0124] [Defects due to heating over time] The evaluation was carried out in the same manner as the defect evaluation method described above, except that the treatment solution was stored at 70°C for 6 months in a SUS304 electropolishing container. The evaluation criteria are as follows. • Evaluation criteria A: Less than 50 pieces B: More than 50 pieces, less than 200 pieces C: More than 200 pieces, less than 1,000 pieces D: More than 1,000 pieces, less than 10,000 pieces E: Over 10,000 pieces

[0125] [Metal-containing defects] Using an Applied Materials G-6 review SEM system, the number of defects on the substrate containing at least one of Fe, Ni, or Cr was counted in the defect evaluation described above. The evaluation criteria are shown below. • Evaluation criteria A: 1 or less B: More than 1, less than 5 C: More than 5 pieces, less than 10 pieces D: More than 10 pieces, less than 20 pieces E: More than 20 pieces

[0126] [Defects due to heating over time in metal-containing materials] Using the APPLIED MATERIALS G-6 review SEM system, the number of defects on the substrate containing at least one of Fe, Ni, or Cr was counted during the above-mentioned heated time-dependent defect evaluation. The evaluation criteria are shown below. • Evaluation criteria A: 1 or less B: More than 1, less than 5 C: More than 5 pieces, less than 10 pieces D: More than 10 pieces, less than 20 pieces E: More than 20 pieces

[0127] 〔developing〕 <Formation of resist film, pattern formation (development)> A 12-inch silicon wafer was coated with the underlayer film formation composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. On top of this, the aforementioned resist composition R-1 was coated and baked (PB) at 90°C for 60 seconds to form a resist film with a thickness of 35 nm. This resulted in the fabrication of a silicon wafer with a resist film. A silicon wafer having the obtained resist film was patterned using an EUV exposure system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A photomask with a line size of 14-25 nm and a line-to-space ratio of 1:1 was used as the rectil. After baking (PEB) at 100°C for 60 seconds, the wafer was developed by paddleding with the processing solution (developer) of the examples and comparative examples for 30 seconds, and the wafer was rotated at a speed of 4000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 28-50 nm.

[0128] <Evaluation Criteria> In the above <Formation of resist film, pattern formation (development)>, the exposure amount that reproduces a pattern with a line size of 14-25 nm and a line:space ratio of 1:1 is the optimal exposure amount for each line size (unit: mJ / cm²). 2 ) The critical resolution (the minimum line width at which lines and spaces are separated and resolved) at the optimal exposure level described above was defined as resolution (unit: nm). The evaluation criteria are as follows. In practical terms, an evaluation result of "C" or higher is preferable. A: Less than 18.0 nm B: 18.0nm or more and less than 19.0nm C: 19.0nm or more and less than 20.0nm D: 20.0nm or more and less than 21.0nm E:21.0nm or more

[0129] 〔rinse〕 <Formation of resist film, pattern formation (rinsing solution)> A silicon wafer having a resist film with a thickness of 35 nm was formed using the same procedure as described in the above-mentioned <Formation of resist film, pattern formation (development)> method. A silicon wafer having the obtained resist film was patterned using an EUV exposure system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). A photomask with a line size of 14-25 nm and a line-to-space ratio of 1:1 was used as the rectil. After baking (PEB) at 100°C for 60 seconds, the wafer was developed by paddle for 30 seconds with Fujifilm Electronic Materials' developer FN-DP001. The wafer was then rinsed for 10 seconds using the processing solution (rinse solution) from the examples and comparative examples while rotating at 1000 rpm, and then rotated at 3000 rpm for 30 seconds to obtain a line-and-space pattern with a pitch of 28-50 nm.

[0130] <Evaluation Criteria> In the above <Formation of resist film, pattern formation (rinsing solution)>, the exposure amount that reproduces a pattern with a line size of 14-25 nm and a line:space ratio of 1:1 is the optimal exposure amount for each line size (unit: mJ / cm²). 2 ) The critical resolution (the minimum line width at which lines and spaces are separated and resolved) at the optimal exposure level described above was defined as resolution (unit: nm). The evaluation criteria are as follows. In practical terms, an evaluation result of "C" or higher is preferable. A: Less than 18.0 nm B: 18.0nm or more and less than 19.0nm C: 19.0nm or more and less than 20.0nm D: 20.0nm or more and less than 21.0nm E:21.0nm or more

[0131] [Cleaning] Using the Lithius semiconductor manufacturing equipment manufactured by Tokyo Electron Corporation, Fujifilm Electronic Materials' developer solution FN-DP001 was applied to three silicon substrates with a diameter of 300 mm. The number of foreign particles on the substrates with a size of ≥0.17 μm before and after processing was counted using a KLA-Tencor SurfScan SP-5, and it was confirmed that the number was 50 or less per substrate. Then, 3.79 L of Fujifilm Wako Pure Chemical Industries, Ltd.'s butyl acetate reagent special grade was passed through the processing solution supply line to contaminate the piping. After that, 10 L of the processing solutions from the examples and comparative examples were passed through to wash the piping, and then 10 L of FN-DP001 was passed through again before substrate coating and foreign particle count measurement. The effect of the washing was evaluated by the increase in the number of foreign particles. <Evaluation Criteria> A: Less than 50 pieces B: More than 50 pieces, less than 200 pieces C: More than 200 pieces, less than 400 pieces D: More than 400 pieces, less than 1,000 pieces E: Over 1,000 pieces

[0132] The results of the above evaluation tests are shown in the table below. Note that in each table, entries such as "5.0E-08", "1.7E+01", and "1.3E+00" are abbreviations of the exponential notation. For example, "5.0E-08" is equivalent to "65.0 × 10 -8 "1.7E+01" is "1.7×10 1 "1.3E+00" means "1.3". Furthermore, in each table, "combined hydrocarbon solvent" refers to the hydrocarbon solvent used in conjunction with the "hydrocarbon solvent." Furthermore, in each table, if two components are listed in the "Specific Acid Component" column, it means that both components were used in combination, and the content listed represents the sum of the two components. For example, "Formic Acid / Acetic Acid" means that formic acid and acetic acid were used in combination. Furthermore, in each table, if two components are listed in the "ester-based solvent" column, it means that both were used in combination, and the content of each component is indicated separately. For example, "isoamyl formate / butyl acetate" means that isoamyl formate and butyl acetate were used in combination, and "30 / 59" means that 30% by mass of isoamyl formate and 59% by mass of butyl acetate were used.

[0133] [Table 1]

[0134] [Table 2]

[0135] [Table 3]

[0136] [Table 4]

[0137] [Table 5]

[0138] [Table 6]

[0139] [Table 7]

[0140] [Table 8]

[0141] [Table 9]

[0142] [Table 10]

[0143] [Table 11]

[0144] [Table 12]

[0145] [Table 13]

[0146] [Table 14]

[0147] As shown in Table 1, it was demonstrated that using the processing solution of the example suppresses the occurrence of defects when applied to the surface to be coated, and also suppresses the occurrence of defects on the surface to be coated when used after being housed in a container with a metal inner wall (Example).

[0148] In a comparison of Examples 5 to 10, it was shown that when the content of specific acid components was within the range of 5 to 50 ppm by mass (Examples 5 to 7), various performance characteristics were superior.

[0149] From a comparison between Example 6 and Example 11, the mass ratio of the acid component to the aromatic hydrocarbon was 1.0 × 10⁻⁶. -3 When the value is ~50 (Example 6), it was shown that various performance characteristics are superior.

[0150] From the comparison between Example 6 and Examples 14 to 16, it was shown that if the water content is 1 to 1000 mass ppm with respect to the total mass of the treatment liquid (Examples 6, 14, and 15), the occurrence of defects when the treatment liquid is used after heating can be more effectively suppressed.

[0151] From the comparison between Example 6 and Examples 17 to 19, it was shown that if the content of the sulfur-containing compound is 0.01 to 10 mass ppm with respect to the total mass of the treatment liquid (Examples 6, 17, and 18), the occurrence of defects when the treatment liquid is heated after being stored in a container with a metal inner wall surface and then used can be more effectively suppressed.

[0152] From the comparison between Example 40 and Example 20, it was shown that if the content of the aromatic hydrocarbon is 1 to 2000 mass ppm with respect to the total mass of the treatment liquid (Example 40), various performances are more excellent.

[0153] From the comparison between Example 6 and Example 21, it was shown that if the alcohol content is 1 to 5000 mass ppm with respect to the total mass of the treatment liquid (Example 6), various performances are more excellent.

[0154] From the comparison between Example 6 and Example 22, it was shown that if the content of the specific metal element is 0.03 to 100 mass ppt with respect to the total mass of the treatment liquid (Example 6), various performances are more excellent.

[0155] In contrast, when using the treatment liquid of the comparative example, it was shown that the occurrence of defects is not sufficiently suppressed when applied on the coated surface, or the occurrence of defects on the coated surface is not sufficiently suppressed when used after being stored in a container with a metal inner wall surface (comparative example).

[0156] <KrF exposure> A silicon wafer having a resist film was fabricated using the underlying DUV44 film (manufactured by Brewer Science) and the following resist composition R-2. Pattern irradiation was performed on this wafer using a KrF excimer laser scanner (ASML, PAS5500 / 850) (NA0.80). As rectification, a 6% halftone mask with a line width of 100 nm on the wafer and a line:space ratio of 1:1 was used to form a pattern with a line width of 100 nm. Otherwise, the processing solution (developer) for the examples and comparative examples was evaluated in the same manner as described in <Formation of resist film, pattern formation (development)> above. As a result, the same results as those described above for <formation of resist film, pattern formation (development)> were obtained.

[0157] (Preparation of resist composition R-2) The following components were mixed to prepare a mixture. • Polymer 2: 85 parts by mass • Photoacid generator 12 parts by mass • Acid diffusion control agent: 3 parts by mass • Propylene glycol monomethyl ether acetate 3430 parts by mass • Propylene glycol monomethyl ether 1470 parts by mass

[0158] Polymer 2 is a polymer having the following three repeating units, with a weight-average molecular weight of 10,000 and a dispersion degree (Mw / Mn) of 1.56. The molar ratio of each repeating unit was 3:2:5 from left to right.

[0159] [ka]

[0160] Photoacid generator (see structural formula below)

[0161] [ka]

[0162] Acid diffusion control agent (hereinafter, refer to the structural formula)

[0163] [Chemical formula]

[0164] Next, the obtained mixed solution was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resist composition R-2.

[0165] [ArF exposure] A silicon wafer having a resist film was fabricated using the lower layer film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) and the following resist composition R-3. Pattern irradiation was performed thereon using an ArF excimer laser immersion scanner (XT1700i manufactured by ASML, NA 1.20, Dipole, outer sigma 0.900, inner sigma 0.700, Y deflection). As the reticle, a 6% halftone mask having a line width of 50 nm in terms of the dimensions on the wafer and a line:space = 1:1 was used to form a pattern with a line width of 50 nm. Otherwise, the processing liquids (developer solutions) of the examples and comparative examples were evaluated in the same manner as in the above [Formation of resist film, pattern formation (development)]. As a result, the same results as in the above [Formation of resist film, pattern formation (development)] were obtained.

[0166] (Preparation of resist composition R-3) The following components were mixed to prepare a mixed solution. · 80 parts by mass of Polymer 3 · 15 parts by mass of photoacid generator · 5 parts by mass of acid diffusion control agent · 3430 parts by mass of propylene glycol monomethyl ether acetate · 1470 parts by mass of propylene glycol monomethyl ether

[0167] Polymer 3 is a polymer having the following three repeating units, and the weight average molecular weight is The value was 7800, and the degree of dispersion (Mw / Mn) was 1.51. The molar ratios of each repeating unit were 3:1:6 from left to right.

[0168] [ka]

[0169] Photoacid generator (see structural formula below)

[0170] [ka]

[0171] Acid diffusion control agent (see structural formula below)

[0172] [ka]

[0173] Next, the mixture obtained above is fed into a polyethylene film having a pore size of 0.03 μm. The resist composition R-3 was prepared by filtering through a filter.

[0174] <Electron beam exposure> A silicon wafer having a resist film was fabricated using the underlying film DUV44 (manufactured by Brewer Science) and the resist composition R-4 described below. Pattern irradiation was then performed using an electron beam lithography system (EBM-9000, manufactured by Newflare Technology Co., Ltd., accelerating voltage 50kV). A pattern with a line width of 75nm and a line:space ratio of 1:1 was formed on the wafer. Otherwise, the processing solutions (developers) for the examples and comparative examples were evaluated in the same manner as described in <Formation of resist film, pattern formation (development)> above. As a result, the same results as those described above for <formation of resist film, pattern formation (development)> were obtained.

[0175] (Preparation of resist composition R-4) The following components were mixed to prepare a mixture. • Polymer 4 70 parts by mass • Photoacid generator 20 parts by mass • Acid diffusion control agent 10 parts by mass • Propylene glycol monomethyl ether acetate 3430 parts by mass • Propylene glycol monomethyl ether 1470 parts by mass

[0176] Polymer 4 is a polymer having the following three repeating units, with a weight-average molecular weight of 11,000 and a dispersion degree (Mw / Mn) of 1.62. The molar ratio of each repeating unit was 2:1:1:6 from left to right.

[0177] [ka]

[0178] Photoacid generator (see structural formula below)

[0179] [ka]

[0180] Acid diffusion control agent (see structural formula below)

[0181] [ka]

[0182] Next, the mixture obtained above was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare resist composition R-4.

Claims

1. Aliphatic hydrocarbon solvents, At least one acid component selected from the group consisting of carboxylic acids having 1 to 3 carbon atoms in the hydrocarbon group bonded to the carboxyl group, and formic acid, A processing solution comprising a metal impurity containing at least one metal element selected from the group consisting of Fe, Ni, and Cr, The mass ratio of the content of the metal element to the content of the acid component is 1.0 × 10 －９ ~3.0 x 10 －５ And, A processing solution used as a developer, rinse solution, pre-wetting solution, or washing solution.

2. The treatment liquid according to claim 1, wherein the content of the metal element is 0.03 to 100 ppt by mass with respect to the total mass of the treatment liquid.

3. The treatment solution according to claim 1, wherein the content of the acid component is 1 to 2000 ppm by mass with respect to the total mass of the treatment solution.

4. The aforementioned acid component includes acetic acid, The treatment solution according to claim 1, wherein the content of acetic acid is 5 to 50 ppm by mass with respect to the total mass of the treatment solution.

5. The treatment solution according to claim 1, wherein the content of the aliphatic hydrocarbon solvent is 2 to 70% by mass with respect to the total mass of the treatment solution.

6. The treatment solution according to claim 1, wherein the aliphatic hydrocarbon solvent comprises at least one selected from the group consisting of nonane, decane, undecane, dodecane, and methyldecane.

7. The treatment solution according to claim 1, further comprising aromatic hydrocarbons.

8. The mass ratio of the content of the acid component to the content of the aromatic hydrocarbon is 1.0 × 10 －３ The processing solution according to claim 7, wherein the value is 5.

9. The treatment solution according to claim 7, wherein the content of the aromatic hydrocarbon is 1 to 2000 ppm by mass with respect to the total mass of the treatment solution.

10. The treatment solution according to claim 1, further comprising an ester-based solvent.

11. The treatment solution according to claim 10, wherein the content of the ester solvent is 30 to 99% by mass with respect to the total mass of the treatment solution.

12. The treatment solution according to claim 10, wherein the ester solvent contains butyl acetate.

13. It absorbs more water, The treatment liquid according to claim 1, wherein the water content is 1 to 1,000 ppm by mass with respect to the total mass of the treatment liquid.

14. It further contains sulfur-containing compounds, The treatment solution according to claim 1, wherein the content of the sulfur-containing compound is 0.01 to 10 ppm by mass with respect to the total mass of the treatment solution.

15. It also contains alcohol, The treatment solution according to claim 1, wherein the alcohol content is 1 to 5,000 ppm by mass with respect to the total mass of the treatment solution.

16. The processing solution according to claim 1, used as a developer for a negative-type resist film exposed to extreme ultraviolet light.

17. A processing liquid container comprising a container and a processing liquid according to any one of claims 1 to 16 contained within the container.

18. The liquid treatment container according to claim 17, wherein at least a portion of the liquid-contacting part of the container is made of metal.

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