TW202347054A - Pattern forming method and method for manufacturing semiconductor device - Google Patents

Abstract

Provided are: a chemical solution which is less susceptible to causing metal residue defects when brought into contact with a silicon substrate or a silicon substrate equipped with a silicon oxide film; and a chemical solution container. This chemical solution is a chemical solution containing an organic solvent and a metal component, wherein the metal component contains titanium oxide particles and titanium ions, and the mass ratio of the titanium oxide particle content with respect to the titanium ion content falls within the range of 100 to 1012, inclusive.

Description

Pattern forming method and semiconductor element manufacturing method

The invention relates to a medicinal liquid and a medicinal liquid container.

When manufacturing semiconductor devices through wiring formation steps including photolithography, as prewetting liquid, photoresist liquid (photoresist film forming composition), developer, rinse liquid, stripping liquid, chemical mechanical polishing (CMP: Chemical Mechanical Polishing) slurry and cleaning fluid after CMP, or as a diluent thereof, a chemical solution containing water and/or an organic solvent can be used. In recent years, through the advancement of photolithography technology, the miniaturization of patterns has continued to develop. As a method of pattern miniaturization, pattern formation using ultraviolet, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), etc. as the exposure light source has been attempted. As the pattern to be formed becomes finer, the above-mentioned chemical liquid used in the process is required to have further defect suppression properties.

As a chemical solution used for conventional pattern formation, Patent Document 1 discloses a "method for producing an organic processing solution for pattern formation of a chemically amplified photoresist film that can reduce the generation of particles in pattern formation technology" ([0010] paragraph)". [Prior technical literature] [Patent Document]

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

On the other hand, in recent years, there has been a demand to make it more difficult to generate metal on a silicon substrate or a silicon substrate with a silicon oxide film (a silicon substrate whose surface is covered with a silicon oxide film) when it comes into contact with a chemical solution. Residue defective liquid medicine. An object of the present invention is to provide a chemical solution that is less likely to generate metal residue defects when in contact with a silicon substrate or a silicon substrate with a silicon oxide film. Furthermore, another object of the present invention is to provide a medical solution container.

In order to solve the above-mentioned problems, the present inventors conducted intensive research and found that the above-mentioned problems can be solved by the following structure.

(1) A medical solution containing an organic solvent and a metal component, wherein the metal component contains titanium oxide particles and titanium ions, and the mass ratio of the content of titanium oxide particles to the content of titanium ions is 10 ⁰ to 10 ¹² . (2) The medical solution as described in (1), wherein the content of titanium ions is 0.10 to 100 ppt by mass relative to the total mass of the medical solution. (3) The chemical solution according to (1) or (2), wherein the content of the titanium oxide particles is 5 mass % or more and less than 99 mass % relative to the titanium component in the metal component. (4) The chemical solution according to any one of (1) to (3), wherein the proportion of particles having a particle diameter of 0.5 to 17 nm among the titanium oxide particles is 60 mass % or more and less than 98 mass %. (5) The medical solution according to any one of (1) to (4), wherein the metal component contains iron ions, and the content of iron ions is 0.10 to 100 ppt by mass relative to the total mass of the medical solution. (6) The chemical solution according to any one of (1) to (5), wherein the metal component contains iron oxide particles, and the content of the iron oxide particles is 5 mass % or more relative to the content of the iron component in the metal component, and Less than 99% by mass. (7) The chemical solution according to any one of (1) to (6), wherein the metal component contains iron oxide particles, and the proportion of the iron oxide particles as particles with a particle diameter of 0.5 to 17 nm is 60 mass % or more And less than 98% by mass. (8) The medical solution according to any one of (1) to (7), wherein the metal component contains iron oxide particles and iron ions, and the mass ratio of the iron oxide particle content to the iron ion content is 10 ⁰ to 10 ¹² . (9) The medical solution according to any one of (1) to (8), wherein the metal component contains aluminum ions, and the content of aluminum ions is 0.10 to 100 ppt by mass relative to the total mass of the medical solution. (10) The chemical solution according to any one of (1) to (9), wherein the metal component contains alumina particles, and the content of the alumina particles is 5 mass % or more relative to the content of the aluminum component in the metal component, and Less than 99% by mass. (11) The chemical solution according to any one of (1) to (10), wherein the metal component contains alumina particles, and the proportion of the alumina particles as particles with a particle diameter of 0.5 to 17 nm is 60 mass % or more And less than 98% by mass. (12) The medical solution according to any one of (1) to (11), wherein the metal component contains alumina particles and aluminum ions, and the mass ratio of the content of alumina particles to the content of aluminum ions is 10 ⁰ to 10 ¹² . (13) The chemical solution according to any one of (1) to (12), wherein the metal component contains copper oxide particles, and the content of the copper oxide particles is 5 mass % or more relative to the content of the copper component in the metal component, and Less than 99% by mass. (14) The chemical solution according to any one of (1) to (13), wherein the metal component contains copper oxide particles, and the proportion of the copper oxide particles as particles with a particle diameter of 0.5 to 17 nm is 60 mass % or more And less than 98% by mass. (15) The medical solution as described in any one of (1) to (14), wherein the metal component contains copper oxide particles and copper ions, and the mass ratio of the content of copper oxide particles to the content of copper ions is 10 ⁰ to 10 ¹² . (16) The medical solution according to any one of (1) to (15), which further contains organic impurities, and the content of the organic impurities is 1,000 to 100,000 ppt by mass relative to the total mass of the medical solution. (17) The chemical solution according to any one of (1) to (16), wherein the water content relative to the total mass of the chemical solution is 500 ppb by mass or less. (18) The medicinal solution according to any one of (1) to (17), wherein the organic solvent is selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, and carbonic acid. Propylene glycol, isopropyl alcohol, 4-methyl-2-pentanol, butyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, dibutyl acetate Isoamyl ether, isopentyl acetate, dimethyl styrene, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, cyclobutane, cycloheptanone, 2-Heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether and undecane. (19) A medical solution container containing a container and the medical solution according to any one of (1) to (18) contained in the container. [Effects of the invention]

According to the present invention, it is possible to provide a chemical solution that is less likely to generate metal residue defects when in contact with a silicon substrate or a silicon substrate with a silicon oxide film. Furthermore, according to the present invention, a medical solution container can be provided.

Hereinafter, the present invention will be described in detail. The description of the structural elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In addition, in this specification, the numerical range expressed using "～" means the range including the numerical value described before and after "～" as a lower limit value and an upper limit value. In addition, in the present invention, "ppm" means "parts-per-million: one part per million (10 ^-6 )", and "ppb" means "parts-per-billion: one part per billion (10 ^{- 9} )", "ppt" refers to "parts-per-trillion: one part per trillion (10 ^-12 )", "ppq" refers to "parts-per-quadrillion: one part per trillion (10 ^-15 )"". Furthermore, among the labels for groups (atomic groups) in the present invention, labels indicating unsubstitution and unsubstitution include not only groups without substituents but also groups containing substituents within the scope that does not impair the effects of the present invention. of the group. For example, the term "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). In this regard, the same applies to each compound. In addition, the "radiation" in the present invention refers to, for example, far ultraviolet rays, extreme ultraviolet (EUV; Extreme ultraviolet), X-rays or electron beams. In addition, "light" in the present invention means actinic rays or radiation. "Exposure" in the present invention includes not only exposure using far ultraviolet rays, X-rays, EUV, etc., but also drawing using particle beams such as electron beams or ion beams, unless otherwise specified.

Although the mechanism by which the above-mentioned problems are solved by the medicinal solution of the present invention is not necessarily clear, the inventors speculate as follows regarding the mechanism. In addition, the following mechanisms are speculations, and even when the effects of the present invention are obtained by different mechanisms, they are included in the scope of the present invention. The inventors of the present invention have found that when a chemical solution contains titanium oxide particles and titanium ions, based on their mass ratio (mass of titanium oxide particles/mass of titanium ions), on a silicon substrate or a silicon substrate with a silicon oxide film (hereinafter, The degree to which metal residue defects (residues derived from metal components) are likely to occur on these substrates (also collectively referred to as "specific substrates") varies. More specifically, it is considered that when the mass ratio is too large, in other words, when the ratio of titanium oxide particles is too high, metal residue defects derived from titanium oxide particles tend to increase on a specific substrate. Furthermore, it is considered that when the above mass ratio is too small, in other words, when the ratio of titanium ions is too high, redox reactions are likely to proceed with other metal ions belonging to base metals lower than titanium ions, and particles of other metals (such as , oxide particles of other metals) increase, and metal residue defects tend to increase on a specific substrate.

The medical solution of the present invention is a medical solution containing an organic solvent and a metal component. The metal component contains titanium oxide particles and titanium ions. The mass ratio of the content of titanium oxide particles to the content of titanium ions is 10 ⁰ to 10 ¹² . Hereinafter, the components contained in the medicinal solution of the present invention will be described in detail.

＜Organic solvent＞ The medical solution of the present invention (hereinafter also simply referred to as "medical solution") contains an organic solvent. In this specification, the organic solvent refers to a liquid organic compound containing each component in a content exceeding 10,000 ppm by mass relative to the total mass of the above-mentioned chemical solution. That is, in this specification, a liquid organic compound contained in an amount exceeding 10,000 ppm by mass relative to the total mass of the chemical solution is equivalent to an organic solvent. In addition, in this specification, the term "liquid state" means a liquid at 25° C. and atmospheric pressure.

The content of the organic solvent in the medicinal solution is not particularly limited, but relative to the total mass of the medicinal solution, it is preferably 98.0 mass % or more, more preferably 99.0 mass % or more, further preferably 99.90 mass % or more, and more than 99.90 mass % is still more preferred. 99.95% by mass is particularly preferred. The upper limit is less than 100% by mass. One type of organic solvent may be used alone, or two or more types may be used. When two or more organic solvents are used, the total content is preferably within the above range.

The type of organic solvent is not particularly limited, and known organic solvents can be used. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxy propionate, and cyclic lactone. (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, alkyl pyruvate, dioxane Base terine, cyclic terine, dialkyl ether, monohydric alcohol, ethylene glycol, alkyl acetate, and N-alkyl pyrrolidone, etc.

Regarding the organic solvent, for example, it is selected from the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), Isopropyl alcohol (IPA), 4-methyl-2-pentanol (MIBC), butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ- Butyrolactone, diisoamyl ether, isopentyl acetate, dimethyl styrene, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethyl carbonate, cyclobutane More than one kind from the group consisting of cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, isopentyl ether and undecane is preferred. Examples of using two or more organic solvents include the combined use of PGMEA and PGME, and the combined use of PGMEA and PC. In addition, the type and content of the organic solvent in the medical solution can be measured using a gas chromatography mass spectrometer.

＜Metal Components＞ The liquid medicine contains metal components. The metal component is composed of metal-containing particles and metal ions. For example, when it is called the content of the metal component, it means the total content of the metal-containing particles and metal ions. The metal-containing particles only need to contain metal atoms, and examples thereof include metal oxide particles, metal nitride particles, and metal particles. In addition, metal particles refer to particles composed of metal.

The metal component contained in the medicinal solution contains titanium oxide particles and titanium ions. The mass ratio of the content of titanium oxide particles to the content of titanium ions is 10 ⁰ to 10 ¹² . From the perspective that metal residue defects or composite residue defects described below are difficult to occur on a silicon substrate or a silicon oxide film, the above mass ratio 10 ¹ to 10 ¹⁰ is preferred, 10 ² to 10 ¹⁰ is more preferred, 10 ³ to 10 ⁸ is further preferred, and 10 ³ to 10 ⁷ is particularly preferred.

The content of titanium ions is not particularly limited, but is mostly 0.01 to 150 ppt by mass. Among them, from the perspective that metal residue defects or composite residue defects described below are difficult to occur on a silicon substrate or a silicon oxide film, the content of titanium ions relative to the total mass of the chemical solution is 0.10 to 100 ppt by mass, and 1.0 is preferred. ~70 quality ppt is better.

The content of the titanium oxide particles is not particularly limited, but is often 1 mass % or more and less than 100 mass % relative to the titanium component in the metal component. Among them, the content of the titanium oxide particles relative to the content of the titanium component in the metal component is 5 mass % or more and Less than 99 mass % is preferred, and 30 to 90 mass % is more preferred. The titanium component refers to a component containing titanium atoms, and examples include titanium-containing particles and titanium ions. For example, when it is called the content of the titanium component, it means the total content of the titanium-containing particles and titanium ions. The titanium-containing particles only need to contain titanium atoms, and examples thereof include titanium oxide particles, titanium nitride particles, and titanium particles. In addition, titanium particles refer to particles composed of metallic titanium.

Among the titanium oxide particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is not particularly limited, but is usually 40 mass % or more and less than 100 mass %. Among them, in terms of making it difficult for metal residue defects or composite residue defects to be described later to occur on a silicon substrate or a silicon oxide film, the proportion of particles with a particle diameter of 0.5 to 17 nm among the titanium oxide particles is 60 mass % or more Less than 98% by mass is preferred, and 60 to 95% by mass is even more preferred.

The metal component contained in the medicinal solution may also contain iron ions. The content of iron ions is not particularly limited, but is usually 0.01 to 200 ppt by mass relative to the total mass of the chemical solution. Among them, from the perspective that metal residue defects or composite residue defects described below are difficult to occur on a silicon substrate or a silicon oxide film, the content of iron ions relative to the total mass of the chemical solution is preferably 0.1 to 100 ppt by mass, and 1.0 ~90 quality ppt is better.

The metal component contained in the medical solution may also contain iron oxide particles. The content of the iron oxide particles is not particularly limited, but is often 1% by mass or more and less than 100% by mass relative to the content of the iron component in the metal component. Among them, the content of the iron oxide particles relative to the content of the iron component in the metal component is 5 mass % or more and Less than 99 mass % is preferred, and 10 to 95 mass % is more preferred. The iron component refers to a component containing iron atoms, and examples thereof include iron-containing particles and iron ions. For example, when it is called the content of the iron component, it means the total content of iron-containing particles and iron ions. The iron-containing particles only need to contain iron atoms, and examples thereof include iron oxide particles, iron nitride particles, and iron particles. In addition, iron particles refer to particles composed of metallic iron.

Among the iron oxide particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is not particularly limited, but is usually 40 mass% or more and less than 100 mass%. Among them, the proportion of iron oxide particles as particles with a particle diameter of 0.5 to 17 nm is 60 mass % or more, since metal residue defects or composite residue defects described below are less likely to occur on a silicon substrate or a silicon oxide film. It is more preferable that it is less than 98 mass %, and it is more preferable that it is 60 to 95 mass %.

The mass ratio of the content of iron oxide particles to the content of iron ions in the medical solution is not particularly limited, but is usually 10 ^-2 to 10 ¹⁴ . Among them, the above mass ratio is preferably 10 ⁰ to 10 ¹² , and more preferably 10 ² to 10 ¹⁰ , in terms of making it difficult for metal residue defects or composite residue defects to be described later to occur on a silicon substrate or a silicon oxide film. , 10 ³ to 10 ⁸ are further preferred, and 10 ³ to 10 ⁷ are particularly preferred.

The metal component contained in the medical solution may also contain aluminum ions. The content of aluminum ions is not particularly limited, but is usually 0.01 to 200 ppt by mass relative to the total mass of the chemical solution. Among them, from the perspective that metal residue defects or composite residue defects described below are difficult to occur on a silicon substrate or a silicon oxide film, the content of aluminum ions relative to the total mass of the chemical solution is preferably 0.1 to 100 ppt by mass, and 1.0 ~90 quality ppt is better.

The metal component contained in the medical solution may also contain aluminum oxide particles. The content of the alumina particles is not particularly limited, but is often 1% by mass or more and less than 100% by mass relative to the content of the aluminum component in the metal component. Among them, the content of the alumina particles relative to the content of the aluminum component in the metal component is 5 mass % or more and Less than 99 mass % is preferred, and 10 to 95 mass % is more preferred. The aluminum component means a component containing aluminum atoms, and examples thereof include aluminum-containing particles and aluminum ions. For example, when it is called the content of the aluminum component, it means the total content of the aluminum-containing particles and aluminum ions. The aluminum-containing particles only need to contain aluminum atoms, and examples thereof include aluminum oxide particles, aluminum nitride particles, and aluminum particles. In addition, aluminum particles refer to particles composed of metallic aluminum.

Among the alumina particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is not particularly limited, but is usually 40 mass% or more and less than 100 mass%. Among them, in terms of making it difficult for metal residue defects or composite residue defects to be described later to occur on a silicon substrate or a silicon oxide film, the proportion of particles with a particle size of 0.5 to 17 nm among the alumina particles is 60 mass % or more It is more preferable that it is less than 98 mass %, and it is more preferable that it is 60 to 95 mass %.

The mass ratio of the content of aluminum oxide particles to the content of aluminum ions in the chemical solution is not particularly limited, but is usually 10 ^-2 to 10 ¹⁴ . Among them, the above mass ratio is preferably 10 ⁰ to 10 ¹² , and more preferably 10 ² to 10 ¹⁰ , in terms of making it difficult for metal residue defects or composite residue defects to be described later to occur on a silicon substrate or a silicon oxide film. , 10 ³ to 10 ⁸ are further preferred, and 10 ³ to 10 ⁷ are particularly preferred.

The metal component contained in the medical solution may also contain components of other metal atoms in addition to those mentioned above. Examples of other metal atoms include Na (sodium), K (potassium), Ca (calcium), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Cr (chromium), Ni (Nickel) and Zr (Zirconium).

The metal component contained in the medicinal solution may also contain copper oxide particles. The content of copper oxide particles is not particularly limited, but is often 1 mass % or more and less than 100 mass % relative to the copper component in the metal component. Among them, the content of the copper oxide particles relative to the content of the copper component in the metal component is 5 mass % or more and Less than 99 mass % is preferred, and 10 to 95 mass % is more preferred. The copper component refers to a component containing copper atoms, and examples include copper-containing particles and copper ions. For example, when it is called the content of the copper component, it means the total content of the copper-containing particles and copper ions. The copper-containing particles only need to contain copper atoms, and examples thereof include copper oxide particles, copper nitride particles, and copper particles. In addition, the copper particles refer to particles composed of metallic copper.

Among the copper oxide particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is not particularly limited, but is usually 40 mass% or more and less than 100 mass%. Among them, in terms of making it difficult for metal residue defects or composite residue defects to be described later to occur on a silicon substrate or a silicon oxide film, the proportion of particles with a particle size of 0.5 to 17 nm among the copper oxide particles is 60 mass % or more It is more preferable that it is less than 98 mass %, and it is more preferable that it is 60 to 95 mass %.

The mass ratio of the content of copper oxide particles to the content of copper ions in the medicinal solution is not particularly limited, but is usually 10 ^-2 to 10 ¹⁴ . Among them, the above mass ratio is preferably 10 ⁰ to 10 ¹² , and more preferably 10 ² to 10 ¹⁰ , in terms of making it difficult for metal residue defects or composite residue defects to be described later to occur on a silicon substrate or a silicon oxide film. , 10 ³ to 10 ⁸ are further preferred, and 10 ³ to 10 ⁷ are particularly preferred.

The metal component may be a metal component that is inevitably contained in each component (raw material) contained in the chemical liquid, or may be a metal component that is inevitably contained when the treatment liquid is manufactured, stored, and/or transferred, or it may be a metal component that is inevitably contained in the chemical liquid. Can be added intentionally.

The content of the metal component is not particularly limited, but from the viewpoint that metal residue defects or composite residue defects described below are difficult to occur on a silicon substrate or a silicon oxide film, it is 10 to 500,000 ppt by mass relative to the total mass of the chemical solution. For better.

In addition, the types and contents of metal ions and metal-containing particles in the medical solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). Here, the so-called SP-ICP-MS method uses the same equipment as the normal ICP-MS method (inductively coupled plasma mass spectrometry), but only the data analysis is different. Data analysis by the SP-ICP-MS method can be performed using commercially available software. In ICP-MS, the content of the metal component to be measured is measured regardless of its existing form. Therefore, the total mass of the metal-containing particles and metal ions to be measured is determined as the content of the metal component.

On the other hand, the SP-ICP-MS method can measure the content of metal-containing particles. Therefore, by subtracting the content of metal-containing particles from the content of metal components in the sample, the content of metal ions in the sample can be calculated. An example of an apparatus for the SP-ICP-MS method is the Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies. Measurement was performed by the method described in the Examples. As devices other than the above, in addition to NexION350S manufactured by PerkinElmer Co., Ltd., Agilent 8900 manufactured by Agilent Technologies can also be used.

In addition, since metal-containing particles of 10 nm or less cannot be measured by SP-ICP-MS, the method described in paragraphs 0015 to 0067 of Japanese Patent Application Laid-Open No. 2009-188333 (hereinafter also referred to as "specific method") was used. ".). Here, a specific method is used to count the number of particles remaining in the range of 0.5 to 10 nm on the substrate, and the SNP-ICP-MS conversion value derived from 20 nm particles is used for the counting. Among them, since the conversion value of each metal is different, the conversion is performed separately for each metal. The specific conversion method is as follows. For example, in SNP-ICP-MS, the number of 20 nm titanium oxide particles in the chemical solution is 10, and the number of 20 nm titanium oxide particles remaining on the substrate calculated by a specific method is 1. , the converted value becomes 10. That is, when the number of 1 nm titanium oxide particles that can be confirmed by a specific method is 100, it is calculated as 1000 particles (100 particles × 10) in the chemical solution based on 10 times the conversion value. The number of particles below 10 nm in the present invention is estimated based on this conversion method for any metal.

＜Organic impurities＞ The medicinal solution may also contain organic impurities. The content of organic impurities in the chemical solution is not particularly limited, but in order to make it more difficult to produce the stain residue defect described below on the silicon substrate, 1,000 to 100,000 ppt by mass relative to the total mass of the chemical solution is preferred. In addition, organic impurities refer to organic compounds that are different from organic solvents and are contained in a content of 10,000 mass ppm or less relative to the total mass of the organic solvent. That is, in this specification, an organic compound contained in a content of 10,000 mass ppm or less with respect to the total mass of the above-mentioned organic solvent corresponds to an organic impurity and does not correspond to an organic solvent. Most of the organic impurities are mixed into or added to the medical solution during the process of purifying the object to be purified to obtain the medical solution. Examples of the organic impurities include plasticizers, antioxidants, and compounds derived from these (typically decomposition products).

＜Water＞ The medicinal solution may contain water. Water is not included in the above mentioned organic impurities. The water is not particularly limited, and for example, distilled water, ion-exchanged water, pure water, etc. can be used. Water may be added to the medicinal solution or may be inadvertently mixed into the medicinal solution during the manufacturing step of the medicinal solution. Examples of unintentional mixing during the manufacturing step of the medical solution include the case where water is contained in the raw materials (for example, organic solvents) used when manufacturing the medical solution, and mixing during the manufacturing step of the medical solution (such as , pollution) water conditions, etc., but are not limited to the above.

The water content in the chemical solution is not particularly limited, but it is preferably 2.0 mass % or less, and more preferably 500 mass ppb or less based on the total mass of the chemical solution. The lower limit is not particularly limited, but an example is 0 mass %. The water content in the chemical solution refers to the moisture content measured using a device based on the Karl Fischer moisture measuring method as the measuring principle.

＜Use of liquid medicine＞ The chemical solution of the present invention is preferably used in the manufacture of semiconductor devices. Among them, it is preferable to use the chemical solution of the present invention to manufacture semiconductor wafers. Specifically, in the manufacturing steps of semiconductor elements including lithography steps, etching steps, ion implantation steps, and stripping steps, it is used to process organic matter after completing each step or before moving to the next step. Specifically, , preferably used as prewetting fluid, developer fluid, rinse fluid and grinding fluid, etc. In addition, the chemical solution can also be used as a diluent of the resin contained in the composition for forming a photoresist film (in other words, as a solvent).

In addition, the above-mentioned chemical solution can be used for purposes other than the manufacture of semiconductor devices, and can also be used as a developer and rinse solution such as polyimide, resist for sensors, and resist for lenses. In addition, the above-mentioned chemical liquid can also be used as a solvent for medical purposes or cleaning purposes. For example, it can be suitably used for cleaning pipes, containers, substrates (for example, wafers, glass, etc.). As the above-mentioned cleaning purpose, it is also preferable to use it as a cleaning liquid (pipe cleaning liquid, container cleaning liquid, etc.) for cleaning pipes and containers that are in contact with the above-mentioned prewet liquid and other liquids.

Among them, the chemical solution can be preferably used in a prewet solution, a developer solution, a rinse solution, a polishing solution, and a composition for forming a photoresist film. Among them, when used in pre-wet fluid, developer fluid and rinse fluid, it can achieve better results. In particular, when the exposure light source is set to EUV, it exhibits even better effects when used in pre-wet liquids, developers, and rinse liquids. Furthermore, when applied to a pipe cleaning liquid used in pipes for transferring such liquids, a more excellent effect is exerted.

＜Method of manufacturing liquid medicine＞ There is no particular limitation on the method for producing the above-mentioned chemical solution, and a known production method can be used. Among them, in order to obtain a more excellent effect of the present invention, it is preferable that the method for producing a medicinal solution has a filtration step of filtering a purified substance containing an organic solvent using a filter to obtain a medicinal solution.

The purified substance used in the filtration step can be purchased by purchasing, etc., or can be obtained by reacting raw materials. As a purified product, it is preferable that the content of impurities is small. Examples of commercially available products of such purified products include commercially available products called "high-purity grade products."

The method of reacting raw materials to obtain a purified product (typically, a purified product containing an organic solvent) is not particularly limited, and a known method can be used. For example, there is a method of obtaining an organic solvent by reacting one or a plurality of raw materials in the presence of a catalyst. More specifically, examples include a method of reacting acetic acid and n-butanol in the presence of sulfuric acid to obtain butyl acetate; and a method of reacting ethylene, oxygen and water in the presence of Al(C ₂ H ₅ ) ₃ The method of obtaining 1-hexanol is to react cis-4-methyl-2-pentene in the presence of Ipc ₂ BH (Diisopinocampheylborane) to obtain 4-methyl- The method of 2-pentanol; the method of reacting propylene oxide, methanol and acetic acid in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); the oxidation of acetone and hydrogen in copper oxide A method of reacting in the presence of zinc-aluminum oxide to obtain IPA (isopropyl alcohol: isopropyl alcohol); a method of reacting lactic acid and ethanol to obtain ethyl lactate; etc.

(Filtering step) The method for producing a medicinal solution of the present invention preferably includes a filtration step of filtering the above-mentioned purified substance using a filter to obtain a medicinal solution. There is no particular limitation on the method of filtering the object to be purified using a filter. However, the method is to pass (liquid through) the object to be purified under pressure or unpressurization and has a housing and a filter element housed in the housing. The unit is better.

•Filter pore diameter The pore diameter of the filter is not particularly limited, and a filter having a pore diameter generally used for filtration of a substance to be purified can be used. Among them, from the perspective of making it easier to control the number of particles (metal particles, etc.) contained in the chemical solution within a desired range, the pore diameter of the filter is preferably 200 nm or less, and more preferably 20 nm or less. , 10 nm or less is further preferred, and 5 nm or less is particularly preferred. The lower limit value is not particularly limited, but from the viewpoint of productivity, it is generally preferably 1 nm or more. In addition, in this specification, the pore size of the filter refers to the pore size determined by the bubble point of isopropyl alcohol (IPA).

If the pore diameter of the filter is 5.0 nm or less, it is preferable in terms of making it easier to control the number of particles contained in the chemical solution. Hereinafter, a filter with a pore diameter of 5.0 nm or less will also be referred to as a "micropore filter." In addition, micropore filters can be used alone or together with filters with other pore diameters. Among them, in terms of better productivity, it is preferable to use it with a filter having a larger pore diameter. That is, when using two or more filters, it is preferable that the pore diameter of at least one filter is 5.0 nm or less. In this case, if the object to be purified and previously filtered through a filter having a larger pore diameter passes through the fine pore diameter filter, clogging of the fine pore diameter filter can be prevented. That is, as the pore diameter of the filter, when one filter is used, the pore diameter is preferably 5.0 nm or less, and when two or more filters are used, the minimum pore diameter is The pore diameter of the filter is preferably 5.0 nm or less.

There is no particular limitation on the form in which two or more filters having different pore diameters are used sequentially. However, one example is a method of sequentially arranging the already described filter units along a pipeline that transports the object to be purified. At this time, if the flow rate of the purified substance per unit time is to be constant as a whole in the pipeline, a filter with a smaller pore diameter may be subjected to a higher pressure than a filter with a larger pore diameter. More pressure. In this case, a pressure regulating valve, a damper, etc. are arranged between the filters to keep the pressure applied to the filter with a small pore diameter constant, or the same filters are arranged side by side along the pipeline. It is better to use a filter unit to increase the filtering area. In this way, the number of particles in the chemical solution can be controlled more stably.

•Filter material The material of the filter is not particularly limited, and known materials can be used as the material of the filter. Specifically, in the case of resin, polyamides such as nylon (for example, 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; Polyamide imide; poly(meth)acrylate; polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propylene copolymer, ethylene·tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer , polyfluorocarbons such as polychlorotrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride; polyvinyl alcohol; polyester; cellulose; cellulose acetate, etc. Among them, in terms of having more excellent solvent resistance and the obtained chemical solution having more excellent defect suppression properties, it is selected from the group consisting of nylon (among them, 6,6-nylon is preferred), polyolefin (among them, , polyethylene is preferred), poly(meth)acrylate and polyfluorocarbon (of which polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) are preferred.) At least one type is preferred. These polymers can be used individually or in combination of 2 or more types. In addition to resin, diatomaceous earth, glass, etc. may also be used. In addition, polymers (nylon) obtained by graft copolymerizing polyolefins (UPE (ultra-high molecular weight polyethylene), etc. to be described later) and polyamides (for example, nylons such as nylon-6 or nylon-6,6) can also be used. Grafted UPE, etc.) as the filter material.

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

Plasma treatment makes the surface of the filter hydrophilic and is therefore preferred. The water contact angle on the surface of the filter that has been hydrophilized as a result of plasma treatment is not particularly limited, but the static contact angle measured by the contact angle at 25°C is preferably 60° or less, and 50° or less. Better still, 30° or less is even better.

As a chemical modification treatment, a method of introducing an ion exchange group into the filter is preferred. That is, as a filter, a filter having an ion exchange group is preferable. Examples of the ion exchange group include a cation exchange group and an anion exchange group. Examples of the cation exchange group include a sulfonic acid group, a carboxyl group, a phosphate group, and the like. Examples of an anion exchange group include a quaternary ammonium group and the like. The method of introducing an ion exchange group into the filter is not particularly limited, but a typical method of grafting is to react a compound containing an ion exchange group and a polymerizable group with the filter.

The introduction method of the ion exchange group is not particularly limited, but the filter is irradiated with ionizing radiation (α rays, β rays, γ rays, X rays, electron beams, etc.) to generate active moieties (free radicals). The irradiated filter is immersed in a solution containing a monomer, and the monomer and the filter are graft-polymerized. As a result, the polymer obtained by polymerizing the monomer is grafted with the filter. The produced polymer can be brought into contact with a compound containing an anion exchange group or a cation exchange group to introduce the ion exchange group into the polymer.

Furthermore, the filter may be composed of a combination of woven fabric or nonwoven fabric having an ion exchange group formed by radiation graft polymerization and conventional glass wool, woven fabric, or nonwoven fabric filter materials.

If a filter having an ion exchange group is used, it is easier to control the content of metal-containing particles and metal ions in the chemical solution within a desired range. The material constituting the filter having an ion exchange group is not particularly limited, but examples thereof include materials in which ion exchange groups are introduced into polyfluorocarbons and polyolefins, and materials in which ion exchange groups are introduced into polyfluorocarbons. The material is better. The pore diameter of the filter having an ion exchange group is not particularly limited, but 1 to 30 nm is preferred, and 5 to 20 nm is more preferred. The filter with an ion exchange base can double as the filter with the smallest pore diameter as described above, or can be used separately from the filter with the smallest pore diameter. Among them, in order to obtain a more excellent effect of the present invention, it is preferable to use a filter having an ion exchange group and a filter having the smallest pore diameter without an ion exchange group in the filtration step. The material of the filter having the smallest pore diameter described above is not particularly limited, but in terms of solvent resistance and the like, usually at least one selected from the group consisting of polyfluorocarbons and polyolefins is used. One type is preferred, and polyolefin is even more preferred.

Therefore, as the filter used in the filtration step, two or more types of filters of different materials can be used. For example, a filter selected from the group consisting of polyolefin, polyfluorocarbon, and polyamide, and an ion exchange group introduced into the filter can be used. Two or more types of filters in the same material group.

•Filter pore structure The pore structure of the filter is not particularly limited and can be appropriately selected depending on the components in the object to be purified. In this specification, the pore structure of the filter refers to the pore diameter distribution, the position distribution of the pores in the filter, the shape of the pores, etc., and can typically be controlled by a manufacturing method of the filter. For example, a porous membrane can be obtained by sintering powder of a resin or the like, and a fiber membrane can be obtained by forming it by methods such as electrospinning, electroblowing, and meltblowing. The pore structures of these are respectively different.

"Porous membrane" refers to a membrane that retains components in the object to be purified, such as gels, particles, colloids, cells, and oligomers, but allows components that are substantially smaller than the pores to pass through the pores. Sometimes the retention of components in the purified object based on a porous membrane depends on operating conditions, such as surface speed, use of surfactants, pH and combinations thereof, and may also depend on the pore size, structure and should be used of the porous membrane. The size and structure of the particles to be removed (hard particles or gel, etc.).

When the object to be purified contains negatively charged particles, the polyamide filter functions as a non-sieve membrane in order to remove such particles. Typical non-sieve membranes include nylon membranes such as nylon-6 membrane and nylon-6,6 membrane, but are not limited to these. In addition, the retention mechanism based on "non-sieve" used in this specification refers to retention by mechanisms such as obstruction, diffusion, and adsorption that are not related to the pressure drop of the filter or the pore size.

Non-sieve holding includes holding mechanisms such as obstruction, diffusion, and adsorption that remove removal target particles in the object to be purified regardless of the pressure drop of the filter or the pore size of the filter. The adsorption of particles on the filter surface can be mediated, for example, by van der Waals and electrostatic forces between molecules. Particles moving in the non-sieve membrane layer with the serpentine-like passages have a hindering effect when they cannot change direction quickly enough to avoid contact with the non-sieve membrane. Particle transport based on diffusion is formed by a certain probability of collision between particles and filter materials, mainly caused by the random motion or Brownian motion of small particles. The non-sieve retention mechanism can become active when there are no repulsive forces between the particles and the filter.

UPE (ultra high molecular weight polyethylene) filters are typically mesh membranes. Screen membrane mainly refers to a membrane that captures particles through a screen holding mechanism or a membrane that is optimized to capture particles through a screen holding mechanism. Typical examples of sieve membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes. In addition, the "sieve holding mechanism" refers to the result of holding particles to be removed larger than the pore size of the porous membrane. The screen retention force can be improved by forming a filter cake (aggregation of particles to be removed on the surface of the membrane). The filter cake effectively functions as a secondary filter.

The material of the fiber membrane is not particularly limited as long as it is a polymer capable of forming a fiber membrane. Examples of the polymer include polyamide and the like. Examples of polyamide include nylon 6, nylon 6,6, and the like. As the polymer forming the fiber membrane, poly(ether ether) may be used. When the fiber membrane is located on the primary side of the porous membrane, the surface energy of the fiber membrane is preferably higher than the polymer material of the porous membrane located on the secondary side. An example of such a combination is a case where the material of the fiber membrane is nylon and the porous membrane is polyethylene (UPE).

There is no particular limitation on the method for producing the fiber membrane, and a known method can be used. Examples of methods for producing fiber membranes include electrospinning, electroblowing, melt blowing, and the like.

The pore structure of the porous membrane (for example, a porous membrane containing UPE, PTFE, etc.) is not particularly limited. Examples of the shape of the pores include lace-like, string-like, node-like, and the like. The size distribution of pores in the porous film and the position distribution in the film are not particularly limited. The size distribution can be smaller and the distribution position in the film symmetrical. In addition, the size distribution may be larger, and the distribution position in the membrane may be asymmetric (the above-mentioned membrane is also called an "asymmetric porous membrane."). In asymmetric porous membranes, the size of the pores changes within the membrane, typically with the pore size becoming larger from one surface of the membrane to the other surface of the membrane. At this time, the surface on the side with large pores and many pores is called the "open side", and the surface on the side with small pores and many pores is called the "tite side". An example of an asymmetric porous membrane is a membrane in which the size of the pores is smallest at a certain position within the thickness of the membrane (this is also called an "hourglass shape").

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

The porous membrane can contain thermoplastic polymers such as PESU (polyether styrene), PFA (copolymer of perfluoroalkoxyalkane, tetrafluoroethylene and perfluoroalkoxyalkane), polyamide and polyolefin, and can also contain PTFE, etc. Among them, as the material of the porous membrane, ultra-high molecular weight polyethylene is preferred. Ultra-high molecular weight polyethylene refers to thermoplastic polyethylene with extremely long chains, with a molecular weight of one million or more, typically 2 to 6 million.

As the filter used in the filtration step, two or more types of filters with different pore structures may be used, or a porous membrane and a fiber membrane may be used in combination. Specific examples include a method using a nylon fiber membrane filter and a UPE porous membrane filter.

Also, regarding the filter, it is best to wash it thoroughly before use. When an uncleaned filter (or a filter that has not been adequately cleaned) is used, impurities contained in the filter can easily enter the chemical solution.

As described above, the filtration step in the embodiment of the present invention may be to pass the object to be purified through at least one different filter selected from the group consisting of filter material, pore diameter, and pore structure. multi-stage filtering steps. Furthermore, the object to be purified may be passed through the same filter a plurality of times, or the object to be purified may be passed through the same type of filter a plurality of times.

In addition, after preparing the chemical solution of the present invention, it is preferable to use a filter (metal component removal filter) that can selectively remove metal components (especially metal ions) such as "Purasol SN 200nm" .

The material for the wetted part of the purification device used in the filtration step (referring to the inner wall surface that may come into contact with the object to be purified and the chemical solution) is not particularly limited, but it must be selected from non-metallic materials (fluorine-based materials). It is preferable to form at least one of the group consisting of electrolytically ground metal materials (stainless steel, etc.) (hereinafter, these will also be collectively referred to as "corrosion-resistant materials".). For example, the liquid contact part of the production tank is formed of a corrosion-resistant material. The production tank itself is formed of a corrosion-resistant material, or the inner wall surface of the production tank is covered with a corrosion-resistant material.

There are no particular limitations on the non-metallic material, and known materials can be used. Examples of the non-metal material include polyethylene resins, polypropylene resins, polyethylene-polypropylene resins, and fluorine-based resins (eg, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether). Copolymer resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, chlorotrifluoroethylene-ethylene copolymer resin, vinylidene fluoride resin, chlorotrifluoroethylene copolymer resin and vinyl fluoride resin, etc.), but is not limited to this.

The metal material is not particularly limited, and known materials can be used. Examples of the metal material include metal materials in which the total content of chromium and nickel exceeds 25% by mass based on the total mass of the metal material. Among them, 30% by mass or more is more preferred. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less. Examples of metal materials include stainless steel, nickel-chromium alloy, and the like.

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

The nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy with a nickel content of 40 to 75 mass% and a chromium content of 1 to 30 mass% is preferred. Examples of nickel-chromium alloys include Hoechst alloy (product name, the same below), Monel alloy (product name, the same below), and Inconel alloy (product name, the same below). More specifically, Hoechst Alloy C-276 (Ni content: 63 mass%, Cr content: 16 mass%), Hoechst Alloy-C (Ni content: 60 mass%, Cr content: 17 mass%) %) and Hoechst Alloy C-22 (Ni content: 61 mass%, Cr content: 22 mass%). In addition, in addition to the above-mentioned alloys, the nickel-chromium alloy may also contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc. as needed.

The method of electrolytic polishing of metal materials is not particularly limited, and known methods can be used. For example, the methods described in paragraphs [0011] to [0014] of Japanese Patent Application Laid-Open No. 2015-227501 and paragraphs [0036] to [0042] of Japanese Patent Application Laid-Open No. 2008-264929 can be used.

Regarding metal materials, it is presumed that the chromium content in the passivation layer on the surface becomes larger than the chromium content in the matrix due to electrolytic polishing. Therefore, it is presumed that if a purification device in which the liquid contact part is made of an electrolytically polished metal material is used, the metal-containing particles will be less likely to flow out into the liquid to be purified. In addition, metal materials can also be polished. The polishing method is not particularly limited, and a known method can be used. The size of the abrasive grains used for fine polishing is not particularly limited, but since the unevenness on the surface of the metal material tends to become smaller, #400 or less is preferred. In addition, polishing is preferably performed before electrolytic polishing.

(additional steps) The method of producing a medical solution may include steps other than the filtration step. Examples of steps other than the filtration step include a distillation step, a reaction step, a static removal step, and the like.

(distillation step) The distillation step is a step of distilling a purified substance containing an organic solvent to obtain a distilled purified substance. There is no particular limitation on the method of distilling the object to be purified, and a known method can be used. Typically, there is a method in which a distillation column is disposed on the primary side of the purification device used in the filtration step, and the distilled purified product is introduced into a production tank. At this time, the liquid contact part of the distillation tower is not particularly limited, but it is preferably formed of the corrosion-resistant material as described above.

(reaction steps) The reaction step is a step of reacting raw materials to produce a purified product containing an organic solvent as a reactant. There is no particular limitation on the method for producing the purified product, and a known method can be used. Typically, a reaction tank is disposed on the primary side of a production tank (or distillation column) of a purification device used in the filtration step, and a reactant is introduced into the production tank (or distillation column). At this time, the liquid contact part of the manufacturing tank is not particularly limited, but it is preferably formed of the corrosion-resistant material as described above.

(Electrification removal step) The destaticizing step is a step of decharging the object to be purified to reduce the charging potential of the object to be purified. There is no particular limitation on the static elimination method, and a known static elimination method can be used. An example of the method of removing electricity is a method of bringing the object to be purified into contact with a conductive material. The contact time for bringing the object to be purified into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and further preferably 0.01 to 0.1 seconds. Examples of conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon. An example of a method for bringing the object to be purified into contact with a conductive material is to arrange a grounded mesh made of a conductive material in a pipeline and allow the object to be purified to pass therethrough.

Regarding the purification of the object to be purified, it is preferable to perform all the opening of the accompanying container, cleaning of the container and equipment, storage of the solution, and analysis in a clean room. The clean room is preferably a clean room with a cleanliness level of level 4 or above specified in the international standard ISO14644-1:2015 stipulated by the International Organization for Standardization. Specifically, it is more preferable that it satisfies any one of ISO level 1, ISO level 2, ISO level 3, and ISO level 4, it is more preferred that it satisfies ISO level 1 or ISO level 2, and it is still more preferred that it satisfies ISO level 1.

The storage temperature of the medical solution is not particularly limited. However, since impurities and the like contained in a small amount in the medical solution are difficult to dissolve and, as a result, more excellent effects of the present invention can be obtained, the storage temperature is 4°C or higher. For better.

＜Medical liquid container＞ The medicinal solution produced by the above purification method can be stored in a container until use. Such a container and the medical solution contained in the container are collectively referred to as a medical solution container. Take out the medicinal solution from the stored medicinal solution container and use it.

As a container for storing the above-mentioned chemical solution, for semiconductor device manufacturing purposes, it is preferable that the cleanliness inside the container is high and the elution of impurities is small. Specific examples of containers that can be used include the "Clean Bottle" series manufactured by AICELLO CHEMICAL CO., LTD. and the "Pure Bottle" manufactured by KODAMA PLASTICS CO., LTD., but are not limited thereto. .

As a container, a multi-layer bottle with a 6-layer structure based on 6 types of resins or a multi-layer bottle with a 7-layer structure based on 6 types of resins are used for the purpose of preventing the mixing (contamination) of impurities into the medicinal solution. It is also better. Examples of such containers include those described in Japanese Patent Application Laid-Open No. 2015-123351.

The liquid-contacting part of the container may be made of the corrosion-resistant material already described (preferably electrolytically ground stainless steel or fluorine-based resin) or glass. In order to obtain more excellent effects of the present invention, it is preferable that more than 90% of the area of the liquid contact part is formed of the above-mentioned material, and it is even more preferable that the entire liquid contact part is formed of the above-mentioned material.

The porosity of the chemical liquid container in the container is preferably 2 to 80 volume %, more preferably 2 to 50 volume %, and still more preferably 5 to 30 volume %. In addition, the above-mentioned porosity is calculated based on equation (1). Formula (1): Porosity = {1-(Volume of the liquid in the container/Volume of the container)}×100 The volume of the container mentioned above has the same meaning as the internal volume (capacity) of the container. By setting the porosity within this range, storage stability can be ensured by limiting contamination by impurities and the like. [Example]

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

In addition, when preparing the chemical solutions of Examples and Comparative Examples, container handling, preparation, filling, storage, and analysis and measurement of the chemical solution were all performed in a clean room that satisfies ISO Class 2 or 1.

(filter) As filters, the following filters were used. • "Purasol SN200nm": UPE membrane (material) manufactured by Entegris, Inc., pore diameter is 200nm •"PP 200nm": Polypropylene filter, manufactured by Entegris, Inc., pore size is 200nm •"Purasol SP200nm": UPE membrane (material) manufactured by Entegris, Inc., pore diameter 200nm • "Octolex 5nm": Nylon filter grafted from UPE, manufactured by Entegris, Inc., pore size is 5nm •"IEX 15nm": Ion exchange resin filter, manufactured by Entegris, Inc., pore size is 15nm •"IEX 16nm": Ion exchange resin filter, manufactured by Entegris, Inc., pore size is 16nm •"IEX 50nm": Ion exchange resin filter, manufactured by Entegris, Inc., pore size is 50nm •"IEX 200nm": Ion exchange resin filter, manufactured by Entegris, Inc., pore size is 200nm • "PTFE 5nm": polytetrafluoroethylene filter, manufactured by Entegris, Inc., pore size 5nm • “PTFE 7nm”: polytetrafluoroethylene filter, manufactured by Entegris, Inc., pore size 7nm • “PTFE 10nm”: polytetrafluoroethylene filter, manufactured by Entegris, Inc., pore size 10nm • “PTFE 20nm”: polytetrafluoroethylene filter, manufactured by Entegris, Inc., pore size 20nm •“Nylon 5nm”: Nylon filter, manufactured by Pall Company, pore size is 5nm •"UPE 1nm": ultra-high molecular weight polyethylene filter, manufactured by Pall Company, pore size 1nm •"UPE 3nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall Company, with a pore size of 3nm •"UPE 5nm": Ultra-high molecular weight polyethylene filter, manufactured by Pall Company, with a pore size of 5nm

＜Purified substance＞ In order to produce the chemical solutions of Examples and Comparative Examples, the following organic solvents were used as purified substances. •CyHe: cyclohexanone •PGMEA: propylene glycol monomethyl ether acetate •MIBC: 4-methyl-2-pentanol •nBA: butyl acetate •EL: Ethyl lactate •PC: propylene carbonate •IPA: Isopropyl alcohol •PGMEE: propylene glycol monoethyl ether •PGMPE: propylene glycol monopropyl ether •CPN: cyclopentanone In addition, "raw materials 1" to "raw materials 8" in the table indicate that the organic solvents used in each example and comparative example were purchased from the following manufacturers. "Raw material 1": Honeywell Company "Raw material 2": Toyo Gosei Co.,Ltd. "Raw material 3": KH Neochem Co.,Ltd. "Raw Material 4": SHOWA DENKO K.K. "Raw material 5": KH Neochem Co.,Ltd. "Raw material 6": SANWAYUKA INDUSTRY CORPORATION "Raw material 7": CCP Company "Raw material 8": BASF Company

＜Container＞ As a container for containing the medical solution, the following containers were used. •EP-SUS: A container with the wetted part made of electrolytically ground stainless steel •PFA: Containers whose wetted parts are coated with perfluoroalkoxyalkanes In addition, the filling rate of the chemical solution in each container was 95% by volume (the porosity was 5% by volume). The filling rate is calculated by the following formula. Filling rate = (volume of medicinal solution in the container/container volume of the container) × 100

＜Purification steps＞ One of the above-mentioned objects to be purified was selected, and the distillation purification treatment described in Table 1 was performed. In addition, "-1" in the "Distillation Purification" column in the table indicates that vacuum distillation using a distillation column (number of theoretical plates: 15 plates) was performed, and "-2" indicates that distillation was performed twice. For vacuum distillation of a column (number of theoretical plates: 30 plates), "Y-3" means that vacuum distillation using a distillation column (number of theoretical plates: 8 plates) was performed.

Next, the purified substance that has been distilled and purified is stored in a storage tank. The purified substance stored in the storage tank is sequentially passed through the filters 1 to 5 listed in Table 1 to be filtered and stored in the storage tank. Next, the following circulation filtration process was performed: the purified substances stored in the storage tank were filtered using filters 6 to 7 listed in Table 1, and the purified substances filtered by filter 7 were filtered in the filter. The upstream side of 6 is circulated, and filters 6 to 7 are used for filtration again. After the circulating filtration process, the chemical solution is stored in a container. In addition, regarding Examples 85 to 88, water was added to the chemical solution so that the water content became a predetermined value.

In addition, in the above series of purification processes, the liquid contact parts of various devices (for example, distillation towers, piping, storage tanks, etc.) that come into contact with the object to be purified are made of electrolytically polished stainless steel.

The contents of organic components and metal components in the chemical solution were measured by the method shown below.

＜Content of metal components＞ The content of metal components (metal ions, metal-containing particles) in the chemical solution was measured using ICP-MS and SP-ICP-MS. Regarding the equipment, the following equipment was used. •Manufacturer: PerkinElmer Co.,Ltd. •Model: NexION350S The following analysis software was used in the analysis. •"SP-ICP-MS" dedicated Syngistix nano application module •Syngistix for ICP-MS software However, since metal-containing particles below 10 nm cannot be measured in SP-ICP-MS, the specific method described above was used.

＜Content of organic impurities＞ The contents of organic impurities in various chemical solutions were analyzed using a gas chromatography mass spectrometry (GC/MS) device (manufactured by Agilent, GC: 7890B, MS: 5977B EI/CI MSD K.K.).

<Test> [Pre-wetting liquid or rinsing liquid] The defect-inhibiting properties of the produced chemicals when used as pre-wetting liquid or rinsing liquid were evaluated by the method shown below. First, the chemical liquid is rotated and discharged onto a silicon substrate with a diameter of 300 mm or a silicon substrate with a silicon oxide film (a silicon substrate whose surface is covered with a silicon oxide film) with a diameter of 300 mm. While rotating the substrate, 0.5 cc of each drug is added. The liquid is discharged onto the surface of the substrate. Then, the substrate was spin-dried. Next, the number of defects existing on the substrate after the chemical solution was applied was measured using a wafer inspection device "SP-5" manufactured by KLA-Tencor Corporation (this was set as a measured value). Next, EDAX (energy-dispersive X-ray spectroscopy) is used to classify the types of defects into metal residue defects, composite residue defects, and stain residue defects. Metal residue defects refer to residues originating from metal components, composite residue defects refer to residues originating from a complex of organic matter and metal components, and stain residue defects refer to residues originating from organic matter. In addition, as long as both "metal residue on Si" and "metal residue on _SiO2 " are "D" or above, it is preferably used as a prewetting liquid or a rinse liquid.

＜Individual evaluation (metal residue defects, composite residue defects, stain residue defects)＞ A: The corresponding number of defects is less than 20/substrate. B: The corresponding number of defects is greater than 20/substrate and less than 50/substrate. C: The corresponding number of defects is greater than 50/substrate and less than 100/substrate. D: The corresponding number of defects is greater than 100/substrate and less than 150/substrate. E: The corresponding number of defects is greater than 150/substrate.

[Developer] The use of the produced chemical solution as a developer was evaluated by the method shown below. First, a photoresist pattern is formed by the operation shown below. Coat the photosensitive radiation or radiation-sensitive resin composition described below on a 300 mm diameter silicon substrate or a 300 mm diameter silicon substrate with a silicon oxide film, and pre-bake (PB) at 100°C for 60 seconds. Thus, a photoresist film with a film thickness of 150 nm was formed.

(Photosensitive radiation or radiation-sensitive resin composition) Acid-decomposable resin (resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical value described in each repeating unit represents mol%.): 100 parts by mass

[Chemical 1]

Photoacid generator shown below: 8 parts by mass

[Chemicalization 2]

The quenching agent shown below: 5 parts by mass (the mass ratio is 0.1:0.3:0.3:0.2 from the left.). In addition, among the quenching agents described below, the weight average molecular weight (Mw) of the polymer type quenching agent is 5,000. In addition, the numerical value described in each repeating unit represents the molar ratio.

[Chemical 3]

Hydrophobic resin shown below: 4 parts by mass (mass ratio from left to right is 0.5:0.5.). Among the hydrophobic resins described below, the hydrophobic resin on the left has a weight average molecular weight (Mw) of 7,000, and the hydrophobic resin on the right has a weight average molecular weight (Mw) of 8,000. In addition, in each hydrophobic resin, the numerical value described in each repeating unit represents a molar ratio.

[Chemical 4]

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

The wafer with the photoresist film formed on it was pattern-exposed using an ArF excimer laser scanner (Numerical Aperture (numerical aperture): 0.75) at 25 mJ/cm ² . Then, it was heated at 120°C for 60 seconds. Next, liquid development was performed for 30 seconds using each developing solution (chemical solution). Next, the wafer was rotated at 4000 rpm for 30 seconds to form a negative photoresist pattern. After that, the obtained negative photoresist pattern was heated at 200°C for 300 seconds. Through the above steps, an L/S pattern with a line/space ratio of 1:1 was obtained (average pattern width: 45 nm). In the space portion of the obtained sample, the presence or absence of the above-mentioned metal residue defects, composite residue defects, and stain residue defects was evaluated based on the above method.

In addition, in each embodiment, the pressure difference between the filters is 0.01 to 0.03 MPa. In Table 1, "Application 1" in the "Application" column means that the above-mentioned test was carried out using the chemical liquid described in each example and comparative example as a prewetting liquid and a flushing liquid. "Use 2" in the "Application" column means that the chemical solution described in each Example and Comparative Example was used as a developer and the above-mentioned test was carried out. In addition, in the table, "Metal residue on Si" shows the evaluation results of metal residue defects on the silicon substrate, "Composite residue on Si" shows the evaluation results of the composite residue defects on the silicon substrate, ""Color stain residue on Si" shows the evaluation results of stain residue defects on silicon substrates, and "Metal residue on SiO ₂ " shows the evaluation results of metal residue defects on silicon substrates with silicon oxide films, " The evaluation results of composite residue defects on a silicon substrate with a silicon oxide film are shown in "Composite Residue on _SiO2 ".

in FIG. 1. The "Ti oxide particles/Ti ions" column indicates the mass ratio of the content of titanium oxide particles to the content of titanium ions. The "Ti ion amount (mass ppt)" column indicates the titanium ion content (mass ppt) relative to the total mass of the chemical solution. The "Fe oxide particles/Fe ions" column indicates the mass ratio of the content of iron oxide particles to the content of iron ions. The "Fe ion amount (mass ppt)" column indicates the iron ion content (mass ppt) relative to the total mass of the chemical solution. The column "Oxidized Al particles/Al ions" indicates the mass ratio of the content of aluminum oxide particles to the content of aluminum ions. The "Al ion amount (mass ppt)" column indicates the aluminum ion content (mass ppt) relative to the total mass of the chemical solution. The "Ti oxide particle ratio (mass %)" column indicates the content (mass %) of titanium oxide particles relative to the titanium component content in the metal component. The "Fe oxide particle ratio (mass %)" column indicates the content (mass %) of iron oxide particles relative to the content of the iron component in the metal component. The "Al oxide particle ratio (mass %)" column indicates the content of aluminum oxide particles (mass %) relative to the content of the aluminum component in the metal component. The column "Proportion of Ti oxide particles 0.5 to 17 nm (mass %)" indicates the proportion (mass %) of particles with a particle diameter of 0.5 to 17 nm among titanium oxide particles. The column "Proportion of 0.5-17 nm Fe oxide particles (mass %)" indicates the proportion (mass %) of particles with a particle diameter of 0.5 to 17 nm among the iron oxide particles. The "Proportion of 0.5-17 nm Al oxide particles (mass %)" column indicates the proportion (mass %) of particles with a particle diameter of 0.5 to 17 nm among the alumina particles. The "Oxidized Cu particle ratio (mass %)" column indicates the content (mass %) of copper oxide particles relative to the content of the copper component in the metal component. The "Proportion of 0.5-17 nm oxidized Cu particles (mass %)" column indicates the proportion (mass %) of particles with a particle diameter of 0.5 to 17 nm among the copper oxide particles. The "moisture content" column indicates the water content (mass ppb) in the chemical solution relative to the total mass of the chemical solution. In addition, in Table 1, "E+number" means "10 ^numbers ", for example. "3.5E+04" means "3.5×10 ⁴ ". In Table 1, ">99" means greater than 99. "<1" means less than 1. In Table 1, "<500 ppb" means less than 500 ppb by mass.

[Table 1] Table 1 [Part 1] ＜1＞ organic solvent use raw material Distillation and purification filter 1 Example 1 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 85 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 2 cH Purpose 1 Raw material 2 There is -1 Purasol SN 200nm Example 3 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 4 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 5 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 6 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 7 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 8 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 9 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 10 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 11 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 12 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 13 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 14 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 15 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 16 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 17 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 18 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 19 cH Purpose 1 Raw material 1 There is -1 Purasol SN 200nm Example 20 cH Purpose 1 Raw material 2 There are -2 Purasol SN 200nm Example 21 cH Purpose 1 Raw material 2 There are 3 Purasol SN 200nm Example 22 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 86 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 23 PGMEA Purpose 1 Raw material 4 There is -1 Purasol SN 200nm Example 24 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 25 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 26 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 27 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 28 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 29 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 30 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 31 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 32 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm

[Table 2] Table 1 [Part 1] ＜2＞ filter 2 filter 3 filter 4 filter 5 filter 6 filter 7 Example 1 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 85 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 2 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 3 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm UPE1nm Example 4 IEX 15nm PTFE 10nm Nylon 5nm UPE1nm UPE1nm Example 5 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm UPE1nm UPE1nm Example 6 IEX 15nm IEX 15nm PTFE 10nm PTFE 5nm Example 7 IEX 15nm IEX 15nm PTFE 10nm PTFE 7nm Example 8 IEX 15nm IEX 15nm PTFE 10nm PTFE 10nm Example 9 IEX 15nm Oktolex 5nm PTFE 10nm Nylon 5nm UPE3nm Example 10 IEX 15nm Nylon 5nm Nylon 5nm Nylon 5nm UPE3nm Example 11 IEX 15nm IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 12 IEX 15nm PTFE 10nm PTFE 7nm PTFE 5nm UPE3nm Example 13 IEX 15nm IEX 15nm Nylon 5nm Nylon 5nm UPE1nm Example 14 PTFE 10nm PTFE 10nm Nylon 5nm UPE3nm Example 15 IEX 15nm IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE1nm Example 16 IEX 15nm PTFE 5nm UPE3nm UPE1nm UPE1nm UPE1nm Example 17 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm Example 18 IEX 15nm IEX 15nm IEX 16nm Nylon 5nm Nylon 5nm UPE1nm Example 19 IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE3nm Example 20 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Example 21 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Example 22 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 86 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 23 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 24 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm UPE1nm Example 25 IEX 15nm PTFE 10nm Nylon 5nm UPE1nm UPE1nm Example 26 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm UPE1nm UPE1nm Example 27 IEX 15nm IEX 15nm PTFE 10nm PTFE 5nm Example 28 IEX 15nm IEX 15nm PTFE 10nm PTFE 7nm Example 29 IEX 15nm IEX 15nm PTFE 10nm PTFE 10nm Example 30 IEX 15nm Oktolex 5nm PTFE 10nm Nylon 5nm UPE3nm Example 31 IEX 15nm Nylon 5nm Nylon 5nm Nylon 5nm UPE3nm Example 32 IEX 15nm IEX 15nm PTFE 10nm Nylon 5nm UPE3nm

[table 3] Table 1 [Part 1] ＜3＞ liquid medicine Oxidized Ti particles/Ti ions Ti ion amount (mass ppt) Oxidized Fe particles/Fe ions Fe ion amount (mass ppt) Oxidized Al particles/Al ions Example 1 3.5E+04 15 5.1E+04 twenty two 7.4E+04 Example 85 3.5E+04 15 5.1E+04 twenty two 7.4E+04 Example 2 2.1E+02 12 3.1E+02 17 4.5E+02 Example 3 1.2E+01 8 1.7E+01 12 2.5E+01 Example 4 5.0E+00 1 7.3E+00 1 1.1E+01 Example 5 2.0E+00 1 6.7E-01 1 9.7E-01 Example 6 5.1E+06 8 7.4E+06 12 1.1E+07 Example 7 1.5E+09 32 2.2E+09 46 3.2E+09 Example 8 3.5E+11 51 1.7E+12 74 3.1E+12 Example 9 2.8E+04 13 6.7E-01 2 4.6E+04 Example 10 4.1E+04 12 5.1E+12 85 3.8E+04 Example 11 4.5E+04 15 4.7E+04 19 9.7E-01 Example 12 4.5E+04 15 6.5E+04 27 1.3E+13 Example 13 4.0E+00 0.08 5.8E+00 0.06 8.4E+00 Example 14 3.3E+10 113 4.7E+10 164 6.9E+10 Example 15 2.9E+04 16 4.3E+04 15 6.2E+04 Example 16 2.7E+04 12 3.8E+04 11 5.6E+04 Example 17 2.6E+03 13 3.7E+03 12 5.4E+03 Example 18 1.7E+03 9 2.5E+03 8 3.6E+03 Example 19 1.7E+03 9 2.5E+03 8 3.6E+03 Example 20 3.8E+04 16 5.5E+04 twenty three 8.0E+04 Example 21 4.1E+04 12 5.9E+04 17 8.6E+04 Example 22 3.3E+04 14 4.8E+04 twenty one 7.0E+04 Example 86 3.3E+04 14 4.8E+04 twenty one 7.0E+04 Example 23 2.0E+02 11 2.9E+02 17 4.2E+02 Example 24 1.1E+01 8 1.7E+01 11 2.4E+01 Example 25 4.8E+00 1 6.9E+00 1 1.0E+01 Example 26 1.9E+00 1 6.3E-01 1 9.2E-01 Example 27 4.8E+06 8 7.0E+06 11 1.0E+07 Example 28 1.5E+09 30 2.1E+09 44 3.1E+09 Example 29 3.3E+11 48 1.6E+12 70 2.9E+12 Example 30 2.7E+04 12 6.3E-01 2 4.3E+04 Example 31 3.9E+04 11 4.8E+12 81 3.6E+04 Example 32 4.3E+04 14 4.5E+04 18 9.2E-01

[Table 4] Table 1 [Part 1] ＜4＞ liquid medicine Al ion amount (mass ppt) Oxidized Cu particles/Cu ions Cu ion amount (mass ppt) Proportion of Ti oxide particles (mass %) Proportion of oxidized Fe particles (mass %) Proportion of oxidized Al particles (mass %) Proportion of oxidized Cu particles (mass %) Proportion of 0.5-17nm Ti oxide particles (mass %) Example 1 32 4.4E+05 27 90 81 90 81 90 Example 85 32 4.4E+05 27 90 81 90 81 90 Example 2 25 2.7E+03 twenty one 80 72 84 77 85 Example 3 8 1.5E+02 7 80 72 84 81 90 Example 4 9 6.3E+01 8 75 68 79 85 90 Example 5 2 5.8E-01 2 75 68 79 84 90 Example 6 35 6.4E+07 30 80 72 84 58 80 Example 7 69 1.9E+10 59 90 81 75 66 90 Example 8 102 1.8E+13 87 80 85 80 85 90 Example 9 26 2.7E+05 twenty two 90 45 90 45 84 Example 10 41 2.3E+05 35 90 90 90 90 78 Example 11 2 6.0E-01 2 90 81 95 81 66 Example 12 145 7.6E+13 123 90 81 98 81 85 Example 13 0.09 5.0E+01 0.08 98 88 95 72 95 Example 14 238 4.1E+11 202 90 85 80 85 85 Example 15 14 3.7E+05 12 20 18 twenty one 68 80 Example 16 10 3.3E+05 9 4 3 5 3 90 Example 17 11 3.2E+04 10 >99 >99 >99 >99 90 Example 18 8 2.1E+04 7 95 86 96 50 45 Example 19 8 2.1E+04 7 94 85 99 89 >99 Example 20 34 4.8E+05 29 90 81 90 81 90 Example 21 25 5.2E+05 twenty one 90 81 90 81 90 Example 22 30 4.2E+05 25 86 77 86 77 86 Example 86 30 4.2E+05 25 86 77 86 73 86 Example 23 twenty four 2.5E+03 20 74 67 78 71 79 Example 24 8 1.4E+02 6 74 67 78 75 84 Example 25 9 6.0E+01 7 70 63 73 79 84 Example 26 2 4.0E-01 2 70 63 73 78 84 Example 27 33 6.1E+07 28 74 67 78 54 74 Example 28 66 1.8E+10 56 84 75 70 61 84 Example 29 97 1.7E+13 82 74 79 74 79 84 Example 30 25 2.6E+05 twenty one 84 42 84 42 78 Example 31 39 2.1E+05 33 84 84 84 84 73 Example 32 2 5.5E-01 2 84 75 88 75 61

[table 5] Table 1 [Part 1] ＜5＞ liquid medicine fill container Proportion of 0.5-17nm Fe oxide particles (mass %) Proportion of 0.5-17 nm oxidized Al particles (mass %) Proportion of 0.5-17nm oxidized Cu particles (mass %) Moisture content Amount of organic impurities (mass ppt) Example 1 81 95 81 <500ppb 11330 EP-SUS Example 85 81 95 81 700 ppb 11330 EP-SUS Example 2 85 85 85 <500ppb 10987 EP-SUS Example 3 90 90 90 <500ppb 9613 EP-SUS Example 4 81 94 81 <500ppb 8583 EP-SUS Example 5 81 93 81 <500ppb 8240 EP-SUS Example 6 72 65 72 <500ppb 10987 EP-SUS Example 7 81 73 81 <500ppb 15450 EP-SUS Example 8 81 85 81 <500ppb 13047 EP-SUS Example 9 85 90 85 <500ppb 10987 EP-SUS Example 10 85 90 85 <500ppb 9613 EP-SUS Example 11 59 65 59 <500ppb 8583 EP-SUS Example 12 80 80 80 <500ppb 8927 EP-SUS Example 13 86 80 86 <500ppb 16480 EP-SUS Example 14 75 85 75 <500ppb 10643 PFA Example 15 80 75 80 <500ppb 10300 EP-SUS Example 16 85 80 85 <500ppb 9613 PFA Example 17 80 72 80 <500ppb 12017 EP-SUS Example 18 40 55 40 <500ppb 11673 EP-SUS Example 19 >99 >99 >99 <500ppb 10987 EP-SUS Example 20 90 90 90 <500ppb <1 EP-SUS Example 21 90 90 90 <500ppb 164800 EP-SUS Example 22 77 90 77 <500ppb 12733 EP-SUS Example 86 77 90 81 700ppb 12733 EP-SUS Example 23 79 79 79 <500ppb 13131 EP-SUS Example 24 84 84 84 <500ppb 15007 EP-SUS Example 25 75 87 75 <500ppb 16808 EP-SUS Example 26 75 86 75 <500ppb 17508 EP-SUS Example 27 67 60 67 <500ppb 13131 EP-SUS Example 28 75 68 75 <500ppb 9338 EP-SUS Example 29 75 79 75 <500ppb 11058 EP-SUS Example 30 79 84 79 <500ppb 13131 PFA Example 31 79 84 79 <500ppb 15007 EP-SUS Example 32 55 60 55 <500ppb 16808 PFA

[Table 6] Table 1 [Part 1] ＜6＞ Evaluation Metal residue on Si Complex residue on Si stain residue on Si Metal residue on _SiO2 Complex residue on _SiO2 Example 1 A A A A A Example 85 B A A B A Example 2 A A A A A Example 3 A B A A B Example 4 A C A A C Example 5 A D A A C Example 6 A A A B A Example 7 B B A C A Example 8 C B A D B Example 9 A B A A C Example 10 B A A D A Example 11 A B A A C Example 12 B A A D A Example 13 A D A A D Example 14 B C A B C Example 15 B A A A B Example 16 C B A B C Example 17 B D A D D Example 18 B B A C B Example 19 A C A D C Example 20 A A D A A Example 21 A A D A A Example 22 A A A A A Example 86 B A A B A Example 23 A A A A A Example 24 A B A A B Example 25 A C A A C Example 26 A D A A C Example 27 A A A B A Example 28 B B A C A Example 29 C B A D B Example 30 A B A A C Example 31 B A A D A Example 32 A B A A C

[Table 7] Table 1 [Part 2] ＜1＞ organic solvent use raw material Distillation and purification filter 1 Example 33 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 34 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 35 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 36 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 37 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 38 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 39 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 40 PGMEA Purpose 1 Raw material 3 There is -1 Purasol SN 200nm Example 41 PGMEA Purpose 1 Raw material 3 There are -2 Purasol SN 200nm Example 42 PGMEA Purpose 1 Raw material 3 There are 3 Purasol SN 200nm Example 43 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 87 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 44 MIBC Purpose 1 Raw material 6 There is -1 Purasol SP 200nm Example 45 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 46 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 47 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 48 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 49 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 50 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 51 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 52 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 53 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 54 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 55 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 56 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 57 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 58 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 59 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 60 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 61 MIBC Purpose 1 Raw material 5 There is -1 Purasol SP 200nm Example 62 MIBC Purpose 1 Raw material 6 There are -2 Purasol SP 200nm Example 63 MIBC Purpose 1 Raw material 6 There are 3 Purasol SP 200nm Comparative example 1 cH Purpose 1 Raw material 1 There is -1 PP 200nm Comparative example 2 cH Purpose 1 Raw material 1 There is -1 Purasol SP 200nm

[Table 8] Table 1 [Part 2] ＜2＞ filter 2 filter 3 filter 4 filter 5 filter 6 filter 7 Example 33 IEX 15nm PTFE 10nm PTFE 7nm PTFE 5nm UPE3nm Example 34 IEX 15nm IEX 15nm Nylon 5nm Nylon 5nm UPE1nm Example 35 PTFE 10nm PTFE 10nm Nylon 5nm UPE3nm Example 36 IEX 15nm IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE1nm Example 37 IEX 15nm PTFE 5nm UPE3nm UPE1nm UPE1nm UPE1nm Example 38 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm Example 39 IEX 15nm IEX 15nm IEX 16nm Nylon 5nm Nylon 5nm UPE1nm Example 40 IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE3nm Example 41 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Example 42 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Example 43 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 87 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 44 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 45 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm UPE1nm Example 46 IEX 15nm PTFE 10nm Nylon 5nm UPE1nm UPE1nm Example 47 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm UPE1nm UPE1nm Example 48 IEX 15nm IEX 15nm PTFE 10nm PTFE 5nm Example 49 IEX 15nm IEX 15nm PTFE 10nm PTFE 7nm Example 50 IEX 15nm IEX 15nm PTFE 10nm PTFE 10nm Example 51 IEX 15nm Oktolex 5nm PTFE 10nm Nylon 5nm UPE3nm Example 52 IEX 15nm Nylon 5nm Nylon 5nm Nylon 5nm UPE3nm Example 53 IEX 15nm IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 54 IEX 15nm PTFE 10nm PTFE 7nm PTFE 5nm UPE3nm Example 55 IEX 15nm IEX 15nm Nylon 5nm Nylon 5nm UPE1nm Example 56 PTFE 10nm PTFE 10nm Nylon 5nm UPE3nm Example 57 IEX 15nm IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE1nm Example 58 IEX 15nm PTFE 5nm UPE3nm UPE1nm UPE1nm UPE1nm Example 59 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm Example 60 IEX 15nm IEX 15nm IEX 16nm Nylon 5nm Nylon 5nm UPE1nm Example 61 IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE3nm Example 62 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Example 63 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Comparative example 1 PTFE 10nm PTFE 10nm PTFE 7nm PTFE 5nm UPE1nm UPE1nm Comparative example 2 IEX 15nm IEX 15nm PTFE 50nm PTFE 50nm UPE5nm

[Table 9] Table 1 [Part 2] ＜3＞ liquid medicine Oxidized Ti particles/Ti ions Ti ion amount (mass ppt) Oxidized Fe particles/Fe ions Fe ion amount (mass ppt) Oxidized Al particles/Al ions Example 33 4.3E+04 14 6.2E+04 26 1.2E+13 Example 34 3.8E+00 0.08 5.5E+00 0.06 8.0E+00 Example 35 3.1E+10 107.35 4.5E+10 156 6.5E+10 Example 36 2.8E+04 15 4.1E+04 14 5.9E+04 Example 37 2.5E+04 11 3.7E+04 11 5.3E+04 Example 38 2.4E+03 12 3.5E+03 11 5.1E+03 Example 39 1.7E+03 9 2.5E+03 8 3.6E+03 Example 40 1.7E+03 9 2.5E+03 8 3.6E+03 Example 41 3.8E+04 16 5.5E+04 twenty three 8.0E+04 Example 42 4.1E+04 12 5.9E+04 17 8.6E+04 Example 43 4.2E+04 18 6.0E+04 26 8.7E+04 Example 87 4.2E+04 18 6.0E+04 26 8.7E+04 Example 44 2.5E+02 14 3.7E+02 twenty one 5.3E+02 Example 45 1.4E+01 10 2.1E+01 14 3.0E+01 Example 46 5.9E+00 1 8.6E+00 2 1.2E+01 Example 47 2.4E+00 1 7.9E-01 2 7.8E-01 Example 48 6.1E+06 10 8.8E+06 14 1.3E+07 Example 49 1.8E+09 38 2.6E+09 55 3.8E+09 Example 50 4.2E+11 61 2.0E+12 88 3.6E+12 Example 51 3.3E+04 15 7.9E-01 2 5.4E+04 Example 52 4.9E+04 14 6.0E+12 101 4.5E+04 Example 53 5.3E+04 18 5.6E+04 twenty three 8.7E-01 Example 54 5.3E+04 18 7.7E+04 32 1.5E+13 Example 55 4.8E+00 0.08 6.9E+00 0.08 1.0E+01 Example 56 3.9E+10 134.19 5.6E+10 195 8.2E+10 Example 57 3.5E+04 19 5.1E+04 18 7.4E+04 Example 58 3.1E+04 14 4.6E+04 13 6.6E+04 Example 59 3.0E+03 15 4.4E+03 14 6.4E+03 Example 60 2.1E+03 11 3.1E+03 10 4.5E+03 Example 61 2.1E+03 11 3.1E+03 10 4.5E+03 Example 62 4.8E+04 20 6.9E+04 29 1.0E+05 Example 63 5.1E+04 15 7.4E+04 twenty two 1.1E+05 Comparative example 1 6.0E-01 twenty two 5.4E-01 32 4.9E-01 Comparative example 2 1.3E+12 18 1.2E+12 26 1.0E+12

[Table 10] Table 1 [Part 2] ＜4＞ liquid medicine Al ion amount (mass ppt) Oxidized Fe particles/Fe ions Fe ion amount (mass ppt) Proportion of Ti oxide particles (mass %) Proportion of oxidized Fe particles (mass %) Proportion of oxidized Al particles (mass %) Proportion of oxidized Cu particles (mass %) Proportion of 0.5-17nm Ti oxide particles (mass %) Example 33 138 7.2E+13 117 84 75 91 75 79 Example 34 0.09 4.8E+01 0.07 91 82 88 67 88 Example 35 226 3.9E+11 192 84 79 74 79 79 Example 36 13 3.5E+05 11 19 17 20 64 76 Example 37 10 3.2E+05 8 4 3 5 3 86 Example 38 11 3.1E+04 9 >99 >99 >99 >99 86 Example 39 8 2.1E+04 7 90 81 91 47 45 Example 40 8 2.1E+04 7 89 80 94 94 >99 Example 41 34 4.8E+05 29 90 90 90 90 90 Example 42 25 5.2E+05 twenty one 90 90 90 90 90 Example 43 37 5.2E+05 32 90 81 90 81 90 Example 87 37 5.2E+05 32 90 81 90 75 90 Example 44 30 3.2E+03 25 78 70 82 70 83 Example 45 10 1.8E+02 8 78 70 82 70 88 Example 46 11 7.5E+01 9 73 66 77 66 88 Example 47 2 4.7E-01 2 73 66 77 66 88 Example 48 42 7.6E+07 35 78 70 82 70 78 Example 49 82 2.3E+10 70 88 79 73 79 88 Example 50 121 2.2E+13 103 78 83 78 83 88 Example 51 31 3.2E+05 26 88 44 88 44 82 Example 52 49 2.7E+05 41 88 88 88 88 76 Example 53 2 5.2E-01 2 88 79 93 79 64 Example 54 172 9.0E+13 146 88 79 96 79 83 Example 55 0.08 6.0E+01 0.07 96 86 93 70 93 Example 56 282 4.9E+11 240 88 83 78 83 83 Example 57 16 4.4E+05 14 16 15 17 55 65 Example 58 12 4.0E+05 10 3 2 4 2 73 Example 59 13 3.8E+04 11 >99 >99 >99 >99 90 Example 60 10 2.7E+04 8 77 69 78 40 45 Example 61 10 2.7E+04 8 76 68 80 76 >99 Example 62 42 6.0E+05 36 80 86 79 86 90 Example 63 32 6.5E+05 27 85 78 80 78 90 Comparative example 1 47 2.9E+00 40 94 85 94 85 90 Comparative example 2 37 6.3E+12 32 82 74 86 74 90

[Table 11] Table 1 [Part 2] ＜5＞ liquid medicine fill container Proportion of 0.5-17nm Fe oxide particles (mass %) Proportion of 0.5-17 nm oxidized Al particles (mass %) Proportion of 0.5-17nm oxidized Cu particles (mass %) Moisture content Amount of organic impurities (mass ppt) Example 33 74 74 74 <500ppb 16161 EP-SUS Example 34 80 74 80 <500ppb 8754 EP-SUS Example 35 70 79 70 <500ppb 13555 EP-SUS Example 36 76 71 76 <500ppb 14007 EP-SUS Example 37 81 76 81 <500ppb 15007 EP-SUS Example 38 76 68 76 <500ppb 12006 EP-SUS Example 39 40 55 40 <500ppb 12359 EP-SUS Example 40 >99 >99 >99 <500ppb 13131 EP-SUS Example 41 90 90 90 <500ppb <1 EP-SUS Example 42 90 90 90 <500ppb 1521525 EP-SUS Example 43 81 95 81 <500ppb 11030 EP-SUS Example 87 81 95 83 600ppb 11030 EP-SUS Example 44 83 83 83 <500ppb 11375 EP-SUS Example 45 88 88 88 <500ppb 12999 EP-SUS Example 46 79 92 79 <500ppb 14559 EP-SUS Example 47 79 91 79 <500ppb 15166 EP-SUS Example 48 70 63 70 <500ppb 11375 EP-SUS Example 49 79 71 79 <500ppb 8089 EP-SUS Example 50 79 83 79 <500ppb 9579 EP-SUS Example 51 83 88 83 <500ppb 11375 PFA Example 52 83 88 83 <500ppb 12999 EP-SUS Example 53 58 63 58 <500ppb 14559 PFA Example 54 78 78 78 <500ppb 13999 PFA Example 55 83 78 83 <500ppb 7583 PFA Example 56 73 83 73 <500ppb 11741 PFA Example 57 65 61 65 <500ppb 12133 PFA Example 58 69 65 69 <500ppb 12999 PFA Example 59 80 72 80 <500ppb 10400 PFA Example 60 40 55 40 <500ppb 10705 PFA Example 61 >99 >99 >99 <500ppb 11375 PFA Example 62 90 90 90 <500ppb <1 PFA Example 63 90 90 90 <500ppb 1502701 PFA Comparative example 1 81 95 81 <500ppb 12825 EP-SUS Comparative example 2 81 95 81 <500ppb 10590 EP-SUS

[Table 12] Table 1 [Part 2] ＜6＞ Evaluation Metal residue on Si Complex residue on Si stain residue on Si Metal residue on _SiO2 Complex residue on _SiO2 Example 33 B A A D A Example 34 A D A A D Example 35 B C A B C Example 36 B A A A B Example 37 C B A B C Example 38 B D A D D Example 39 B B A C B Example 40 A C A D C Example 41 A A D A A Example 42 A A D A A Example 43 A A A A A Example 87 B A A B A Example 44 A A A A A Example 45 A B A A B Example 46 A C A A C Example 47 A D A A C Example 48 A A A B A Example 49 B B A C A Example 50 C B A D B Example 51 A B A A C Example 52 B A A D A Example 53 A B A A C Example 54 B A A D A Example 55 A D A A D Example 56 B C A B C Example 57 B A A A B Example 58 C B A B C Example 59 B D A D D Example 60 B B A C B Example 61 A C A D C Example 62 A A D A A Example 63 A A D A A Comparative example 1 E D A E C Comparative example 2 D E A E D

[Table 13] Table 1 [Part 3] ＜1＞ organic solvent use raw material Distillation and purification filter 1 Example 64 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 88 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 65 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 66 nBA Purpose 2 Ingredients 8 There is -1 Purasol SP 200nm Example 67 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 68 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 69 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 70 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 71 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 72 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 73 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 74 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 75 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 76 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 77 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 78 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 79 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 80 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 81 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 82 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm Example 83 nBA Purpose 2 Ingredients 8 There are -2 Purasol SP 200nm Example 84 nBA Purpose 2 Ingredients 8 There are 3 Purasol SP 200nm Comparative example 3 nBA Purpose 2 Raw material 7 There is -1 PP 200nm Comparative example 4 nBA Purpose 2 Raw material 7 There is -1 Purasol SP 200nm

[Table 14] Table 1 [Part 3] ＜2＞ filter 2 filter 3 filter 4 filter 5 filter 6 filter 7 Example 64 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 88 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 65 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 66 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm UPE1nm Example 67 IEX 15nm PTFE 10nm Nylon 5nm UPE1nm UPE1nm Example 68 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm UPE1nm UPE1nm Example 69 IEX 15nm IEX 15nm PTFE 10nm PTFE 5nm Example 70 IEX 15nm IEX 15nm PTFE 10nm PTFE 7nm Example 71 IEX 15nm IEX 15nm PTFE 10nm PTFE 10nm Example 72 IEX 15nm Oktolex 5nm PTFE 10nm Nylon 5nm UPE3nm Example 73 IEX 15nm Nylon 5nm Nylon 5nm Nylon 5nm UPE3nm Example 74 IEX 15nm IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 75 IEX 15nm PTFE 10nm PTFE 7nm PTFE 5nm UPE3nm Example 76 IEX 15nm IEX 15nm Nylon 5nm Nylon 5nm UPE1nm Example 77 PTFE 10nm PTFE 10nm Nylon 5nm UPE3nm Example 78 IEX 15nm IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE1nm Example 79 IEX 15nm PTFE 5nm UPE3nm UPE1nm UPE1nm UPE1nm Example 80 IEX 15nm PTFE 10nm PTFE 5nm Nylon 5nm Example 81 IEX 15nm IEX 15nm IEX 16nm Nylon 5nm Nylon 5nm UPE1nm Example 82 IEX 15nm PTFE 10nm UPE3nm UPE3nm UPE3nm Example 83 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Example 84 IEX 15nm PTFE 10nm Nylon 5nm UPE5nm UPE3nm Comparative example 3 PTFE 10nm PTFE 10nm PTFE 7nm PTFE 5nm UPE1nm UPE1nm Comparative example 4 IEX 15nm IEX 15nm PTFE 50nm PTFE 50nm UPE5nm

[Table 15] Table 1 [Part 3] ＜3＞ liquid medicine Oxidized Ti particles/Ti ions Ti ion amount (mass ppt) Oxidized Fe particles/Fe ions Fe ion amount (mass ppt) Oxidized Al particles/Al ions Example 64 3.4E+04 15 4.9E+04 twenty one 7.1E+04 Example 88 3.4E+04 15 4.9E+04 twenty one 7.1E+04 Example 65 2.1E+02 12 3.0E+02 17 4.3E+02 Example 66 1.2E+01 8 1.7E+01 11 2.4E+01 Example 67 4.9E+00 1 7.0E+00 1 1.0E+01 Example 68 1.9E+00 1 6.5E-01 1 9.4E-01 Example 69 4.9E+06 8 7.2E+06 11 1.0E+07 Example 70 1.5E+09 31 2.2E+09 45 3.1E+09 Example 71 3.4E+11 49 1.6E+12 72 3.0E+12 Example 72 2.7E+04 13 6.5E-01 2 4.4E+04 Example 73 4.0E+04 12 4.9E+12 82 3.6E+04 Example 74 4.4E+04 15 4.6E+04 18 9.4E-01 Example 75 4.4E+04 15 6.3E+04 26 1.2E+13 Example 76 3.9E+00 0.08 5.6E+00 0.06 8.2E+00 Example 77 3.2E+10 109.61 4.6E+10 159 6.7E+10 Example 78 2.9E+04 16 4.1E+04 14 6.0E+04 Example 79 2.6E+04 12 3.7E+04 11 5.4E+04 Example 80 2.5E+03 13 3.6E+03 12 5.2E+03 Example 81 1.6E+03 9 2.4E+03 8 3.5E+03 Example 82 1.6E+03 9 2.4E+03 8 3.5E+03 Example 83 3.7E+04 16 5.3E+04 twenty three 7.7E+04 Example 84 4.0E+04 12 5.8E+04 17 8.4E+04 Comparative example 3 6.0E-01 18 5.4E-01 26 4.9E-01 Comparative example 4 1.3E+12 15 1.2E+12 twenty one 1.0E+12

[Table 16] Table 1 [Part 3] ＜4＞ liquid medicine Al ion amount (mass ppt) Oxidized Fe particles/Fe ions Fe ion amount (mass ppt) Proportion of Ti oxide particles (mass %) Proportion of oxidized Fe particles (mass %) Proportion of oxidized Al particles (mass %) Proportion of oxidized Cu particles (mass %) Proportion of 0.5-17nm Ti oxide particles (mass %) Example 64 31 4.3E+05 26 86 77 86 77 86 Example 88 31 4.3E+05 26 86 77 86 73 86 Example 65 twenty four 2.6E+03 twenty one 76 80 80 80 81 Example 66 8 1.5E+02 7 76 68 80 77 86 Example 67 9 6.1E+01 7 71 64 75 80 86 Example 68 2 8.0E-01 2 71 64 75 80 86 Example 69 34 6.2E+07 29 76 68 80 55 76 Example 70 67 1.9E+10 57 86 77 71 62 86 Example 71 99 1.8E+13 84 76 81 76 81 86 Example 72 25 2.7E+05 twenty one 86 43 86 43 80 Example 73 40 2.2E+05 34 86 86 86 86 74 Example 74 2 5.6E+00 2 86 77 90 77 63 Example 75 141 7.3E+13 120 86 77 93 77 81 Example 76 0.09 4.9E+01 0.08 93 84 90 68 90 Example 77 230 4.0E+11 196 86 81 76 81 81 Example 78 13 3.6E+05 11 20 18 twenty one 18 80 Example 79 10 3.2E+05 9 4 3 5 3 90 Example 80 11 3.1E+04 9 >99 >99 >99 >99 90 Example 81 8 2.1E+04 6 90 81 91 47 45 Example 82 8 2.1E+04 6 89 80 94 89 >99 Example 83 33 4.6E+05 28 86 77 86 77 86 Example 84 twenty four 5.0E+05 twenty one 86 77 86 77 86 Comparative example 3 1 2.9E+00 1 81 73 81 73 81 Comparative example 4 1 6.3E+12 1 71 64 74 68 75

[Table 17] Table 1 [Part 3] ＜5＞ liquid medicine fill container Proportion of 0.5-17nm Fe oxide particles (mass %) Proportion of 0.5-17nm oxidized Al particles (mass %) Proportion of 0.5-17nm oxidized Cu particles (mass %) Moisture content Amount of organic impurities (mass ppt) Example 64 77 90 77 <500ppb 18317 EP-SUS Example 88 77 90 81 750 ppb 18317 EP-SUS Example 65 81 81 81 <500ppb 18488 EP-SUS Example 66 86 86 86 <500ppb 23110 EP-SUS Example 67 77 89 77 <500ppb 27733 EP-SUS Example 68 77 88 77 <500ppb 33279 EP-SUS Example 69 68 62 68 <500ppb 33279 EP-SUS Example 70 77 69 77 <500ppb 33279 EP-SUS Example 71 77 81 77 <500ppb 31713 EP-SUS Example 72 81 86 81 <500ppb 23880 EP-SUS Example 73 81 86 81 <500ppb 22553 EP-SUS Example 74 56 62 56 <500ppb 16539 EP-SUS Example 75 76 76 76 <500ppb 16335 EP-SUS Example 76 81 76 81 <500ppb 15835 EP-SUS Example 77 71 81 71 <500ppb 13972 EP-SUS Example 78 80 75 80 <500ppb 17008 EP-SUS Example 79 85 80 85 <500ppb 18631 PFA Example 80 80 72 80 <500ppb 17568 EP-SUS Example 81 40 55 40 <500ppb 28693 EP-SUS Example 82 >99 >99 >99 <500ppb 23984 EP-SUS Example 83 86 86 86 <500ppb <1 EP-SUS Example 84 86 86 86 <500ppb 1451800 EP-SUS Comparative example 3 73 86 73 <500ppb 21980 EP-SUS Comparative example 4 75 75 75 <500ppb 17401 EP-SUS

[Table 18] Table 1 [Part 3] ＜6＞ Evaluation Metal residue on Si Complex residue on Si stain residue on Si Metal residue on _SiO2 Complex residue on _SiO2 Example 64 A A A A A Example 88 B A A B A Example 65 A A A A A Example 66 A B A A B Example 67 A C A A C Example 68 A C A A D Example 69 B A A A A Example 70 C A A B A Example 71 D B A C B Example 72 A C A A B Example 73 D A A B A Example 74 A C A A B Example 75 D A A B A Example 76 A D A A D Example 77 B C A B C Example 78 A B A B A Example 79 B C A C B Example 80 D D A B D Example 81 C B A B B Example 82 D C A A C Example 83 A A D A A Example 84 A A D A A Comparative example 3 E C A E D Comparative example 4 E D A D E

[Table 19] Table 1 [Part 4] <1> organic solvent use raw material Distillation and purification filter 1 Example 89 EL Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 90 PC Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 91 IPA Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 92 PGMEE Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 93 PGMPE Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 94 Methyl methoxypropionate Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 95 CPN Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 96 γ-butyrolactone Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 97 Diisoamyl ether Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 98 Isoamyl acetate Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 99 DMSO Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 100 N-methylpyrrolidone Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 101 diethylene glycol Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 102 Ethylene glycol Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 103 dipropylene glycol Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 104 propylene glycol Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 105 Ethylene carbonate Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 106 cyclotenine Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 107 Cycloheptanone Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 108 2-Heptanone Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 109 Butyl butyrate Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 110 Isobutyl isobutyrate Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 111 Isoamyl ether Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm Example 112 undecane Purpose 1 Ingredients 8 There is -1 Purasol SP 200nm

[Table 20] Table 1 [Part 4] ＜2＞ filter 2 filter 3 filter 4 filter 5 filter 6 filter 7 Example 89 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 90 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 91 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 92 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 93 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 94 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 95 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 96 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 97 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 98 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 99 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 100 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 101 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 102 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 103 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 104 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 105 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 106 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 107 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 108 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 109 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 110 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 111 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm Example 112 IEX 15nm PTFE 10nm Nylon 5nm UPE3nm

[Table 21] Table 1 [Part 4] ＜3＞ liquid medicine Oxidized Ti particles/Ti ions Ti ion amount (mass ppt) Oxidized Fe particles/Fe ions Fe ion amount (mass ppt) Oxidized Al particles/Al ions Example 89 3.3E+04 15 3.9E+04 twenty one 7.1E+04 Example 90 3.8E+04 17 4.6E+04 twenty three 7.1E+04 Example 91 3.3E+04 15 3.9E+04 twenty one 7.1E+04 Example 92 3.6E+04 16 4.3E+04 twenty two 7.1E+04 Example 93 3.3E+04 15 3.9E+04 twenty one 7.1E+04 Example 94 3.2E+04 14 3.8E+04 20 7.1E+04 Example 95 2.9E+04 13 3.5E+04 19 7.1E+04 Example 96 2.7E+04 12 3.2E+04 18 7.1E+04 Example 97 3.4E+04 15 4.1E+04 twenty one 7.1E+04 Example 98 3.8E+04 17 4.6E+04 twenty three 7.1E+04 Example 99 4.1E+04 18 4.9E+04 twenty four 7.1E+04 Example 100 4.3E+04 19 5.1E+04 25 7.1E+04 Example 101 3.2E+04 14 3.8E+04 20 7.1E+04 Example 102 2.9E+04 13 3.5E+04 19 7.1E+04 Example 103 3.8E+04 17 4.6E+04 twenty three 7.1E+04 Example 104 3.2E+04 14 3.8E+04 20 7.1E+04 Example 105 3.2E+04 14 3.8E+04 20 7.1E+04 Example 106 3.4E+04 15 4.1E+04 twenty one 7.1E+04 Example 107 4.1E+04 18 4.9E+04 twenty four 7.1E+04 Example 108 3.4E+04 15 4.1E+04 twenty one 7.1E+04 Example 109 3.2E+04 14 3.8E+04 20 7.1E+04 Example 110 3.4E+04 15 4.1E+04 twenty one 7.1E+04 Example 111 3.6E+04 16 4.3E+04 twenty two 7.1E+04 Example 112 2.9E+04 13 3.5E+04 19 7.1E+04

[Table 22] Table 1 [Part 4] ＜4＞ liquid medicine Al ion amount (mass ppt) Oxidized Fe particles/Fe ions Fe ion amount (mass ppt) Proportion of Ti oxide particles (mass %) Proportion of oxidized Fe particles (mass %) Proportion of oxidized Al particles (mass %) Proportion of oxidized Cu particles (mass %) Proportion of 0.5-17nm Ti oxide particles (mass %) Example 89 29 3.9E+04 twenty one 89 79 89 82 94 Example 90 32 4.6E+04 twenty three 92 82 92 85 97 Example 91 29 3.9E+04 twenty one 89 79 89 82 94 Example 92 31 4.3E+04 twenty two 91 81 91 84 96 Example 93 29 3.9E+04 twenty one 89 79 89 82 94 Example 94 28 3.8E+04 20 88 78 88 81 93 Example 95 27 3.5E+04 19 87 77 87 80 92 Example 96 25 3.2E+04 18 85 75 85 78 90 Example 97 29 4.1E+04 twenty one 89 79 89 82 94 Example 98 32 4.6E+04 twenty three 92 82 92 85 97 Example 99 34 4.9E+04 twenty four 94 84 94 87 98 Example 100 35 5.1E+04 25 95 85 95 88 95 Example 101 28 3.8E+04 20 88 78 88 81 93 Example 102 27 3.5E+04 19 87 77 87 80 92 Example 103 32 4.6E+04 twenty three 92 82 92 85 97 Example 104 28 3.8E+04 20 88 78 88 81 93 Example 105 28 3.8E+04 20 88 78 88 81 93 Example 106 29 4.1E+04 twenty one 89 79 89 82 94 Example 107 34 4.9E+04 twenty four 94 84 94 87 99 Example 108 29 4.1E+04 twenty one 89 79 89 82 94 Example 109 28 3.8E+04 20 88 78 88 81 93 Example 110 29 4.1E+04 twenty one 89 79 89 82 94 Example 111 31 4.3E+04 twenty two 91 81 91 84 96 Example 112 27 3.5E+04 19 87 77 87 80 92

[Table 23] Table 1 [Part 4] ＜5＞ liquid medicine fill container Proportion of 0.5-17nm Fe oxide particles (mass %) Proportion of 0.5-17nm oxidized Al particles (mass %) Proportion of 0.5-17nm oxidized Cu particles (mass %) Moisture content Amount of organic impurities (mass ppt) Example 89 76 93 93 21098 <500ppb EP-SUS Example 90 79 96 96 21870 <500ppb EP-SUS Example 91 76 93 93 21098 <500ppb EP-SUS Example 92 78 95 95 21555 <500ppb EP-SUS Example 93 76 93 93 21098 <500ppb EP-SUS Example 94 75 92 92 20925 <500ppb EP-SUS Example 95 74 91 91 20610 <500ppb EP-SUS Example 96 72 89 89 20295 <500ppb EP-SUS Example 97 76 93 93 21240 <500ppb EP-SUS Example 98 79 96 96 21870 <500ppb EP-SUS Example 99 81 97 97 22050 <500ppb EP-SUS Example 100 82 94 94 21375 <500ppb EP-SUS Example 101 75 92 92 20925 <500ppb EP-SUS Example 102 74 91 91 20610 <500ppb EP-SUS Example 103 79 96 96 21870 <500ppb EP-SUS Example 104 75 92 92 20925 <500ppb EP-SUS Example 105 75 92 92 20925 <500ppb EP-SUS Example 106 76 93 93 21240 <500ppb EP-SUS Example 107 81 98 98 22185 <500ppb EP-SUS Example 108 76 93 93 21240 <500ppb EP-SUS Example 109 75 92 92 20925 <500ppb EP-SUS Example 110 76 93 93 21240 <500ppb EP-SUS Example 111 78 95 95 21555 <500ppb EP-SUS Example 112 74 91 91 20610 <500ppb EP-SUS

[Table 24] Table 1 [Part 4] ＜6＞ liquid medicine Metal residue on Si Complex residue on Si stain residue on Si Metal residue on _SiO2 Complex residue on _SiO2 Example 89 A A A A A Example 90 A A A A A Example 91 A A A A A Example 92 A A A A A Example 93 A A A A A Example 94 A A A A A Example 95 A A A A A Example 96 A A A A A Example 97 A A A A A Example 98 A A A A A Example 99 A A A A A Example 100 A A A A A Example 101 A A A A A Example 102 A A A A A Example 103 A A A A A Example 104 A A A A A Example 105 A A A A A Example 106 A A A A A Example 107 A A A A A Example 108 A A A A A Example 109 A A A A A Example 110 A A A A A Example 111 A A A A A Example 112 A A A A A

In Table 1, the data of each Example and Comparative Example are shown in Table 1 [Part 1] <1> to <6>, Table 1 [Part 2] <1> to <6>, Table 1 [Part 3] <1 ＞～＜6＞ and each row of Table 1 [Part 4]＜1＞～＜6>. For example, in Example 1, as shown in Table 1 [Part 1] <1>, CyHe is used as the organic solvent, as shown in Table 1 [Part 1] <2>, and the filter 2 is "IEX 15nm", as shown in Table 1 As shown in 1 [Part 1]＜3＞, the oxidized Ti particles/Ti ions in the chemical solution are 3.5E+04, as shown in Table 1 [Part 1]＜4＞, and the amount of Al ions is 32 mass ppt, as shown in the table As shown in 1 [Part 1] <5>, the proportion of 0.5-17 nm Fe oxide particles is 81 mass %. As shown in Table 1 [Part 1] <6>, the "metal residue on Si" is "A". The same applies to other Examples and Comparative Examples.

From the results shown in the table, it was confirmed that the chemical solution of the present invention can obtain the intended effect. In particular, from the comparison of Examples 1 to 8, it was confirmed that when the mass ratio of the titanium oxide particle content to the titanium ion content is 10 ¹ to 10 ¹⁰ , the effect is more excellent. Furthermore, from Examples 9 and 10, it was confirmed that when the mass ratio of the content of iron oxide particles to the content of iron ions is 10 ⁰ to 10 ¹² , the effect is more excellent. Furthermore, from Examples 11 and 12, it was confirmed that when the mass ratio of the content of alumina particles to the content of aluminum ions is 10 ⁰ to 10 ¹² , the effect is more excellent. Furthermore, from Examples 13 and 14 (34 and 35, 55 and 56, 76 and 77), it was confirmed that the content of titanium ions (or iron ions, aluminum ions) was 0.10 to 100 ppt by mass relative to the total mass of the chemical solution. down, the effect is better. Furthermore, from Examples 16 and 17 (37 and 38, 58 and 59, 79 and 80), it was confirmed that the content of titanium oxide particles (or iron oxide particles, aluminum oxide particles) relative to the content of the titanium component in the metal component is When the content is 5% by mass or more and less than 99% by mass, the effect is even better. Furthermore, from Examples 18 and 19 (39 and 40, 60 and 61, 81 and 82), it was confirmed that the proportion of particles with a particle diameter of 0.5 to 17 nm in titanium oxide particles (or iron oxide particles, aluminum oxide particles) When it is 60 mass % or more and less than 98 mass %, the effect will be more excellent. Furthermore, from Examples 20 and 21 (41 and 42, 62 and 63, 83 and 84), it was confirmed that when the content of organic impurities is 1,000 to 100,000 ppt by mass relative to the total mass of the chemical solution, the effect is more excellent.

After cleaning the container (EP-SUS) and various devices used in the <Purification Step> using the chemical solution (100L) of Example 22, the separately prepared chemical solution of Example 22 was allowed to flow through the above-mentioned cleaned device and recovered in the cleaned container, thereby obtaining solution A in the container. In addition, the chemical solution (100L) of Example 38 was used, and after cleaning the container (EP-SUS) and various devices used in the <purification step>, the separately prepared chemical solution of Example 22 was passed through the above process. Clean the device and recover it in the cleaned container, thereby obtaining solution B in the container. Solution A and solution B were used to evaluate "metal residue defects on Si", and solution A was found to be more favorable.

<Example (EUV exposure)> First, each component was mixed with the following composition, and the photoresist composition 1 was obtained. •Resin (A-1): 0.77g •Photoacid generator (B-1): 0.03g •Basic compound (E-3): 0.03g •PGMEA (commercially available, high purity grade): 67.5g •Ethyl lactate (commercially available, high purity grade): 75g

•Resin (A-1) As the resin (A-1), the following resins were used.

[Chemistry 5]

•Photoacid generator (B-1) As the photoacid generator (B-1), the following compounds were used.

[Chemical 6]

•Basic compounds (E-3) As the basic compound (E-3), the following compounds were used.

[Chemical 7]

(Pattern formation and evaluation) First, the photoresist composition 1 is coated on a silicon wafer with a diameter of 300 mm, and baked (PB: Prebake) at 100°C for 60 seconds to form a photoresist film with a film thickness of 30 nm.

This photoresist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA0.33, Dipole (dipole) 90°, outer sigma 0.87, inner sigma 0.35). Then, heat (PEB: Post Exposure Bake) at 85°C for 60 seconds. Next, a developer (manufactured by butyl acetate/FETW) was sprayed by the spray coating method for 30 seconds and developed, and a rinse liquid was sprayed on the silicon wafer by the spin coating method for 20 seconds and rinsed. Next, the silicon wafer was rotated at 2000 rpm for 40 seconds to form a line and space pattern with a space width of 20 nm and a pattern line width of 15 nm. As the above-mentioned rinse liquid, the chemical liquid used in the above-mentioned Example 44 was used. In addition, as a result of conducting various evaluations as described above, the desired effects in the same direction as Table 1 were obtained.

Claims (20)

A pattern forming method, including: a photoresist film forming step, using a photosensitive radioactive or radiation-sensitive resin composition to form a photoresist film; an exposure step, exposing the photoresist film; and a developing step, using a chemical solution to The exposed photoresist film is developed. The chemical solution contains an organic solvent and a metal component. The metal component contains titanium oxide particles and titanium ions. The mass ratio of the content of the titanium oxide particles to the content of the titanium ions is 10 ⁰ to 10 ^12. The titanium ion content is 0.10 to 100 mass ppt relative to the total mass of the chemical solution, and the titanium oxide particle content is 5 mass% or more and less than 99 mass% relative to the titanium component in the metal component. A pattern forming method, including: a photoresist film forming step, using a photosensitive radioactive or radiation-sensitive resin composition to form a photoresist film; an exposure step, exposing the photoresist film; and a developing step, using a chemical solution to The exposed photoresist film is developed. The chemical solution contains an organic solvent and a metal component. The metal component contains titanium oxide particles and titanium ions. The mass ratio of the content of the titanium oxide particles to the content of the titanium ions is 10 ⁰ to 10 ^12. The content of the titanium ions is 0.10 to 100 ppt by mass relative to the total mass of the chemical solution. A pattern forming method, including: a photoresist film forming step, using a photosensitive radioactive or radiation-sensitive resin composition to form a photoresist film; an exposure step, exposing the photoresist film; and a developing step, using a chemical solution to The exposed photoresist film is developed. The chemical solution contains an organic solvent and a metal component. The metal component contains titanium oxide particles and titanium ions. The mass ratio of the content of the titanium oxide particles to the content of the titanium ions is 10 ⁰ to 10 ^12. The content of the titanium oxide particles is 5 mass% or more and less than 99 mass% relative to the titanium component in the metal component. The pattern forming method according to any one of claims 1 to 3, wherein In this exposure step, the photoresist film is exposed to EUV. The pattern forming method according to any one of claims 1 to 3, wherein Among the titanium oxide particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is 60 mass% or more and less than 98 mass%. The pattern forming method according to any one of claims 1 to 3, wherein This metal component contains iron ions, The content of the iron ions is 0.10 to 100 ppt by mass relative to the total mass of the chemical solution. The pattern forming method according to any one of claims 1 to 3, wherein The metal component contains iron oxide particles, The content of the iron oxide particles is 5% by mass or more and less than 99% by mass relative to the content of the iron component in the metal component. The pattern forming method according to any one of claims 1 to 3, wherein The metal component contains iron oxide particles, Among the iron oxide particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is 60 mass% or more and less than 98 mass%. The pattern forming method according to any one of claims 1 to 3, wherein the metal component contains iron oxide particles and iron ions, and the mass ratio of the content of the iron oxide particles to the content of the iron ions is 10 ⁰ to 10 ¹² . The pattern forming method according to any one of claims 1 to 3, wherein This metal component contains aluminum ions, The content of the aluminum ions is 0.10 to 100 ppt by mass relative to the total mass of the chemical solution. The pattern forming method according to any one of claims 1 to 3, wherein The metal component contains aluminum oxide particles, The content of the alumina particles is 5% by mass or more and less than 99% by mass relative to the content of the aluminum component in the metal component. The pattern forming method according to any one of claims 1 to 3, wherein The metal component contains aluminum oxide particles, Among the alumina particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is 60 mass% or more and less than 98 mass%. The pattern forming method according to any one of claims 1 to 3, wherein the metal component contains alumina particles and aluminum ions, and the mass ratio of the content of the alumina particles to the content of the aluminum ions is 10 ⁰ to 10 ¹² . The pattern forming method according to any one of claims 1 to 3, wherein The metal component contains copper oxide particles, The content of the copper oxide particles is 5% by mass or more and less than 99% by mass relative to the content of the copper component in the metal component. The pattern forming method according to any one of claims 1 to 3, wherein The metal component contains copper oxide particles, In the copper oxide particles, the proportion of particles having a particle diameter of 0.5 to 17 nm is 60 mass% or more and less than 98 mass%. The pattern forming method according to any one of claims 1 to 3, wherein the metal component contains copper oxide particles and copper ions, and the mass ratio of the content of the copper oxide particles to the content of the copper ions is 10 ⁰ to 10 ¹² . The pattern forming method according to any one of claims 1 to 3, wherein, The medicinal solution also contains organic impurities, The content of the organic impurities is 1,000 to 100,000 mass ppt relative to the total mass of the chemical liquid. The pattern forming method according to any one of claims 1 to 3, wherein The water content relative to the total mass of the chemical solution is 500 ppb by mass or less. The pattern forming method according to any one of claims 1 to 3, wherein The organic solvent contains propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, propylene carbonate, isopropyl alcohol, 4-methyl-2-pentanol, butyl acetate. , Propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isopentyl acetate, dimethyl styrene, N-methylpyrrolidine Ketone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, cyclobutanone, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether And one or more species from the group of undecane. A method of manufacturing a semiconductor element, including the pattern forming method according to any one of claims 1 to 19.