JP2022173352A - Liquid medicine and liquid medicine container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide liquid medicine hardly causing a metal residue defect when brought into contact with a silicon substrate or a silicon substrate with a silicon oxide film, and a liquid medicine container.

SOLUTION: Liquid medicine contains an organic solvent and a metallic component. The metallic component contains titanium oxide particles and titanium ions. A mass ratio of content of the titanium oxide particles to that of the titanium ions is 10⁰ to 10¹².

SELECTED DRAWING: None

COPYRIGHT: (C)2023,JPO&INPIT

Description

TECHNICAL FIELD The present invention relates to a chemical liquid and a chemical liquid container.

Pre-wet liquid, resist liquid (composition for forming resist film), developer, rinse liquid, remover, chemical mechanical polishing (CMP) during manufacturing of semiconductor devices by wiring formation process including photolithography A chemical solution containing water and/or an organic solvent is used as a slurry, a cleaning solution after CMP, or a diluted solution thereof.
2. Description of the Related Art In recent years, advances in photolithography technology have led to finer patterns. As a technique for pattern miniaturization, pattern formation using ultraviolet rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet rays), etc., as exposure light sources has been attempted.
With the miniaturization of patterns to be formed, the above-mentioned chemicals used in this process are required to have further defect suppressing properties.

As a chemical solution used for conventional pattern formation, Patent Document 1 describes a method for producing an organic processing solution for patterning a chemically amplified resist film that can reduce the generation of particles in a pattern formation technique (paragraph [0010] )” is disclosed.

JP 2015-084122 A

On the other hand, in recent years, when a silicon substrate or a silicon substrate with a silicon oxide film (a silicon substrate whose surface is covered with a silicon oxide film) is brought into contact with a chemical solution, a metal residue is formed on the silicon substrate or the silicon substrate with a silicon oxide film. There is a demand for a chemical solution that is less likely to cause defects.
An object of the present invention is to provide a chemical solution that hardly causes metal residue defects when brought into contact with a silicon substrate or a silicon substrate with a silicon oxide film.
Another object of the present invention is to provide a chemical container.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that the above problems can be solved by the following configuration.

(1) A chemical solution containing an organic solvent and a metal component,
The metal component contains titanium oxide particles and titanium ions,
A chemical solution in which the mass ratio of the content of titanium oxide particles to the content of titanium ions is 10 ⁰ to 10 ¹² .
(2) The chemical solution according to (1), wherein the content of titanium ions is 0.10 to 100 ppt by mass with respect to the total mass of the chemical solution.
(3) The chemical solution according to (1) or (2), wherein the content of the titanium oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of the titanium component in the metal component.
(4) The chemical solution according to any one of (1) to (3), wherein the proportion of titanium oxide particles having a particle size of 0.5 to 17 nm is 60% by mass or more and less than 98% by mass.
(5) the metal component contains iron ions,
The chemical solution according to any one of (1) to (4), wherein the content of iron ions is 0.10 to 100 ppt by mass with respect to the total mass of the chemical solution.
(6) the metal component contains iron oxide particles,
The chemical solution according to any one of (1) to (5), wherein the content of the iron oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of the iron component in the metal component.
(7) the metal component contains iron oxide particles,
The chemical solution according to any one of (1) to (6), wherein the proportion of iron oxide particles having a particle size of 0.5 to 17 nm is 60% by mass or more and less than 98% by mass.
(8) the metal component contains iron oxide particles and iron ions,
The chemical solution according to any one of (1) to (7), wherein the mass ratio of the content of iron oxide particles to the content of iron ions is 10 ⁰ to 10 ¹² .
(9) the metal component contains aluminum ions,
The chemical solution according to any one of (1) to (8), wherein the content of aluminum ions is 0.10 to 100 mass ppt with respect to the total mass of the chemical solution.
(10) the metal component contains aluminum oxide particles,
The chemical solution according to any one of (1) to (9), wherein the content of the aluminum oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of the aluminum component in the metal component.
(11) the metal component contains aluminum oxide particles,
The chemical solution according to any one of (1) to (10), wherein the proportion of aluminum oxide particles having a particle size of 0.5 to 17 nm is 60% by mass or more and less than 98% by mass.
(12) the metal component contains aluminum oxide particles and aluminum ions,
The chemical solution according to any one of (1) to (11), wherein the mass ratio of the content of aluminum oxide particles to the content of aluminum ions is 10 ⁰ to 10 ¹² .
(13) the metal component contains copper oxide particles,
The chemical solution according to any one of (1) to (12), wherein the content of the copper oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of the copper component in the metal component.
(14) the metal component contains copper oxide particles,
The chemical solution according to any one of (1) to (13), wherein the proportion of copper oxide particles having a particle size of 0.5 to 17 nm is 60% by mass or more and less than 98% by mass.
(15) the metal component contains copper oxide particles and copper ions,
The chemical solution according to any one of (1) to (14), wherein the mass ratio of the content of copper oxide particles to the content of copper ions is 10 ⁰ to 10 ¹² .
(16) further contains organic impurities,
The chemical solution according to any one of (1) to (15), wherein the content of organic impurities is 1000 to 100000 ppt by mass with respect to the total mass of the chemical solution.
(17) The chemical solution according to any one of (1) to (16), wherein the content of water relative to the total mass of the chemical solution is 500 mass ppb or less.
(18) The organic solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, propylene carbonate, isopropanol, 4-methyl-2-pentanol, butyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl. Ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone , 2-heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether, and undecane.
(19) A drug solution container comprising a container and the drug solution according to any one of (1) to (18) contained in the container.

According to the present invention, it is possible to provide a chemical solution that hardly causes metal residue defects when brought into contact with a silicon substrate or a silicon substrate with a silicon oxide film.
Further, according to the present invention, a drug container can be provided.

The present invention will be described in detail below.
Although the description of the constituent elements described below may be made based on representative embodiments of the present invention, the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
In the present invention, "ppm" means "parts-per-million (10 ^-6 )", "ppb" means "parts-per-billion (10 ^-9 )", and "ppt" means means "parts-per-trillion (10 ^-12 )" and "ppq" means "parts-per-quadrillion (10 ^-15 )".
In addition, in the notation of a group (atom group) in the present invention, the notation that does not describe substituted or unsubstituted refers to a group containing a substituent as well as a group not having a substituent within a range that does not impair the effect of the present invention. also includes For example, the term "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group containing a substituent (substituted hydrocarbon group). This point is the same for each compound.
Moreover, the "radiation" in the present invention means, for example, deep ultraviolet rays, extreme ultraviolet rays (EUV), X-rays, electron beams, or the like. Moreover, in the present invention, light means actinic rays or radiation. Unless otherwise specified, the term "exposure" in the present invention includes not only exposure with far ultraviolet rays, X-rays, EUV, etc., but also drawing with particle beams such as electron beams and ion beams.

Although the mechanism by which the liquid medicine of the present invention solves the above problems is not necessarily clear, the present inventors speculate as follows about the mechanism. In addition, the following mechanism is speculation, and even if the effect of the present invention is obtained by a different mechanism, it is included in the scope of the present invention.
When the chemical solution contains titanium oxide particles and titanium ions, the present inventors have determined that the mass ratio (mass of titanium oxide particles/mass of oxide ions) determines whether a silicon substrate or a silicon substrate with a silicon oxide film (these are hereinafter referred to as silicon substrates). (also collectively referred to as a “specific substrate”) have different susceptibility to the occurrence of metal residue defects (residues derived from metal components). More specifically, when the mass ratio is too large, in other words, when the proportion of titanium oxide particles is too high, it is believed that metal residue defects derived from titanium oxide particles tend to increase on the specific substrate. Further, when the mass ratio is too small, in other words, when the proportion of titanium ions is too high, oxidation-reduction reactions with other metal ions less noble than titanium ions tend to proceed, resulting in particles of other metals. (for example, oxide particles of other metals) increase, and metal residue defects tend to increase on the specific substrate.

The chemical solution of the present invention 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 content of titanium oxide particles with respect to the content of titanium ions is The mass ratio is 10 ⁰ to 10 ¹² .
The components contained in the liquid medicine of the present invention are described in detail below.

<Organic solvent>
The chemical solution of the present invention (hereinafter also simply referred to as "chemical solution") contains an organic solvent.
In this specification, the organic solvent is intended to be a liquid organic compound contained in a content exceeding 10000 ppm by mass per component with respect to the total mass of the chemical solution. That is, in the present specification, a liquid organic compound contained in an amount exceeding 10000 ppm by mass with respect to the total mass of the chemical corresponds to an organic solvent.
In addition, the term “liquid” as used herein means liquid at 25° C. under atmospheric pressure.

The content of the organic solvent in the chemical solution is not particularly limited, but is preferably 98.0% by mass or more, more preferably more than 99.0% by mass, and more preferably 99.90% by mass or more, relative to the total mass of the chemical solution. Preferably, more than 99.95% by weight is particularly preferred. The upper limit is less than 100% by mass.
An organic solvent may be used individually by 1 type, or may use 2 or more types. 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. Organic solvents include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, lactic acid alkyl esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), and monoketone compounds which may have a ring. (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, dialkyl sulfoxides, cyclic sulfones, dialkyl ethers, monohydric alcohols, glycols, alkyl acetates, and N-alkylpyrrolidones. .

Organic solvents include, for example, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone (CHN), ethyl lactate (EL), propylene carbonate (PC), isopropanol (IPA), 4-methyl-2 -pentanol (MIBC), butyl acetate (nBA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N- One selected from the group consisting of methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, 2-heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether, and undecane. The above is preferable.
Examples of using two or more organic solvents include combined use of PGMEA and PGME and combined use of PGMEA and PC.
The type and content of the organic solvent in the chemical can be measured using a gas chromatograph-mass spectrometer.

<Metal component>
The chemical contains metal components.
The metal component is composed of metal-containing particles and metal ions. For example, the content of the metal component indicates the total content of the metal-containing particles and metal ions.
The metal-containing particles may contain metal atoms, and examples thereof include metal oxide particles, metal nitride particles, and metal particles. In addition, metal particles mean particles made of metal.

The metal component contained in the chemical 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 , and metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or silicon oxide film. The mass ratio is preferably 10 ¹ to 10 ¹⁰ , more preferably 10 ² to 10 ¹⁰ , still more preferably 10 ³ to 10 ⁸ , and particularly preferably 10 ³ to 10 ⁷ .

The content of titanium ions is not particularly limited, and is often 0.01 to 150 mass ppt. Among them, the content of titanium ions is 0.10 to 100 mass ppt with respect to the total mass of the chemical, in that metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or silicon oxide film. is preferred, and 1.0 to 70 mass ppt is more preferred.

The content of the titanium oxide particles is not particularly limited, and is often 1% by mass or more and less than 100% by mass with respect to the content of the titanium component in the metal component. Above all, the content of the titanium oxide particles is less than the content of the titanium component in the metal component, because it is more difficult for metal residue defects or composite residue defects, which will be described later, to occur on the silicon substrate or on the silicon oxide film. 5% by mass or more and less than 99% by mass is preferable, and 30 to 90% by mass is more preferable.
The titanium component is a component containing titanium atoms, and includes titanium-containing particles and titanium ions. For example, the content of the titanium component indicates the total content of the titanium-containing particles and titanium ions.
Titanium-containing particles may contain titanium atoms, and examples thereof include titanium oxide particles, titanium nitride particles, and titanium particles. Titanium particles mean particles made of metallic titanium.

Among the titanium oxide particles, the proportion of particles having a particle size of 0.5 to 17 nm is not particularly limited, and is often 40% by mass or more and less than 100% by mass. In particular, the ratio of particles having a particle size of 0.5 to 17 nm among the titanium oxide particles is 60, because metal residue defects or composite residue defects, which will be described later, are less likely to occur on the silicon substrate or on the silicon oxide film. % by mass or more and less than 98% by mass is preferable, and 60 to 95% by mass is more preferable.

The metal component contained in the chemical solution may contain iron ions.
The content of iron ions is not particularly limited, and is often 0.01 to 200 ppt by mass with respect to the total mass of the chemical solution. Above all, the content of iron ions is 0.1 to 100 mass ppt with respect to the total mass of the chemical, in that metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or silicon oxide film. is preferred, and 1.0 to 90 mass ppt is more preferred.

The metal component contained in the chemical solution may contain iron oxide particles.
The content of the iron oxide particles is not particularly limited, and is often 1% by mass or more and less than 100% by mass with respect to the content of the iron component in the metal component. Among them, the content of iron oxide particles is less likely to occur on a silicon substrate or on a silicon oxide film, or a composite residue defect described later. 5% by mass or more and less than 99% by mass is preferable, and 10 to 95% by mass is more preferable.
The iron component is a component containing iron atoms, and includes iron-containing particles and iron ions. For example, the content of the iron component indicates the total content of the iron-containing particles and iron ions.
The iron-containing particles may contain iron atoms, and examples thereof include iron oxide particles, iron nitride particles, and iron particles. The iron particles mean particles made of metallic iron.

Among the iron oxide particles, the proportion of particles having a particle size of 0.5 to 17 nm is not particularly limited, and is often 40% by mass or more and less than 100% by mass. Above all, the ratio of particles having a particle size of 0.5 to 17 nm among the iron oxide particles is 60, because metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or on the silicon oxide film. % by mass or more and less than 98% by mass is preferable, and 60 to 95% by mass is more preferable.

The mass ratio of the content of iron oxide particles to the content of iron ions in the chemical solution is not particularly limited, and is often 10 ⁻² to 10 ¹⁴ . Above all, the mass ratio is preferably 10 ⁰ to 10 ¹² , more preferably 10 ² to 10 ¹⁰ , in that metal residue defects or composite residue defects, which will be described later, are less likely to occur on the silicon substrate or on the silicon oxide film. , 10 ³ to 10 ⁸ are more preferred, and 10 ³ to 10 ⁷ are particularly preferred.

The metal component contained in the chemical solution may contain aluminum ions.
The content of aluminum ions is not particularly limited, and is often 0.01 to 200 ppt by mass with respect to the total mass of the chemical solution. Above all, the content of aluminum ions is 0.1 to 100 mass ppt with respect to the total mass of the chemical, in that metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or silicon oxide film. is preferred, and 1.0 to 90 mass ppt is more preferred.

The metal component contained in the chemical solution may contain aluminum oxide particles.
The content of the aluminum oxide particles is not particularly limited, and is often 1% by mass or more and less than 100% by mass with respect to the content of the aluminum component in the metal component. Above all, the content of aluminum oxide particles is less likely to occur on a silicon substrate or on a silicon oxide film. 5% by mass or more and less than 99% by mass is preferable, and 10 to 95% by mass is more preferable.
The aluminum component is a component containing aluminum atoms and includes aluminum-containing particles and aluminum ions. For example, the content of the aluminum component indicates the total content of the aluminum-containing particles and aluminum ions.
Aluminum-containing particles may contain aluminum atoms, and examples thereof include aluminum oxide particles, aluminum nitride particles, and aluminum particles. The aluminum particles mean particles made of metal aluminum.

Among the aluminum oxide particles, the proportion of particles having a particle size of 0.5 to 17 nm is not particularly limited, and is often 40% by mass or more and less than 100% by mass. In particular, the ratio of particles with a particle size of 0.5 to 17 nm among the aluminum oxide particles is 60, because metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or on the silicon oxide film. % by mass or more and less than 98% by mass is preferable, and 60 to 95% by mass is more preferable.

The mass ratio of the content of aluminum oxide particles to the content of aluminum ions in the chemical solution is not particularly limited, and is often 10 ⁻² to 10 ¹⁴ . Above all, the mass ratio is preferably 10 ⁰ to 10 ¹² , more preferably 10 ² to 10 ¹⁰ , in that metal residue defects or composite residue defects, which will be described later, are less likely to occur on the silicon substrate or on the silicon oxide film. , 10 ³ to 10 ⁸ are more preferred, and 10 ³ to 10 ⁷ are particularly preferred.

The metal component contained in the chemical solution may contain other metal atom components than 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 chemical solution may contain copper oxide particles.
The content of the copper oxide particles is not particularly limited, and is often 1% by mass or more and less than 100% by mass with respect to the content of the copper component in the metal component. Above all, the content of the copper oxide particles is less likely to occur on the silicon substrate or on the silicon oxide film, and the content of the copper oxide particles with respect to the content of the copper component in the metal component is 5% by mass or more and less than 99% by mass is preferable, and 10 to 95% by mass is more preferable.
The copper component is a component containing copper atoms, and includes copper-containing particles and copper ions. For example, the content of the copper component indicates the total content of the copper-containing particles and copper ions.
The copper-containing particles may contain copper atoms, and examples thereof include copper oxide particles, copper nitride particles, and copper particles. In addition, a copper particle means the particle|grain which consists of metallic copper.

Among the copper oxide particles, the proportion of particles having a particle size of 0.5 to 17 nm is not particularly limited, and is often 40% by mass or more and less than 100% by mass. Above all, the ratio of particles with a particle size of 0.5 to 17 nm among the copper oxide particles is 60, in that metal residue defects or composite residue defects described later are less likely to occur on the silicon substrate or on the silicon oxide film. % by mass or more and less than 98% by mass is preferable, and 60 to 95% by mass is more preferable.

The mass ratio of the content of copper oxide particles to the content of copper ions in the chemical solution is not particularly limited, and is often 10 ⁻² to 10 ¹⁴ . Above all, the mass ratio is preferably 10 ⁰ to 10 ¹² , more preferably 10 ² to 10 ¹⁰ , in that metal residue defects or composite residue defects, which will be described later, are less likely to occur on the silicon substrate or on the silicon oxide film. , 10 ³ to 10 ⁸ are more 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 a metal component that is inevitably contained during the production, storage and/or transfer of the treatment liquid. may be intentionally added.

Although the content of the metal component is not particularly limited, it is 10 to 500,000 mass with respect to the total mass of the chemical in that metal residue defects or composite residue defects, which will be described later, are less likely to occur on the silicon substrate or on the silicon oxide film. ppt is preferred.

The types and contents of metal ions and metal-containing particles in the chemical solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry).
Here, the SP-ICP-MS method uses the same equipment as the normal ICP-MS method (inductively coupled plasma mass spectrometry), and differs only in data analysis. Data analysis of the SP-ICP-MS method can be performed with commercially available software.
In the ICP-MS method, the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal-containing particles to be measured and the metal ions is quantified 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, the content of metal ions in the sample can be calculated by subtracting the content of the metal-containing particles from the content of the metal components in the sample.
An apparatus for the SP-ICP-MS method includes, for example, Agilent 8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, which is described in the Examples. It can be measured by the method described. Other devices than the above include NexION350S manufactured by PerkinElmer, and Agilent 8900 manufactured by Agilent Technologies.

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 JP-A-2009-188333 (hereinafter also referred to as "specific method") is used.
Here, the number of particles of 0.5 to 10 nm remaining on the substrate is counted by a specific method, and the count is converted from SNP-ICP-MS of particles of 20 nm. Since the conversion value differs for each metal, this conversion is performed for each metal.
The specific method of conversion is as follows.
For example, when the number of 20 nm titanium oxide particles in the chemical solution is 10 by SNP-ICP-MS, and the number of 20 nm titanium oxide particles remaining on the substrate calculated by the specific method is 1, the converted value becomes 10. That is, when the number of 1 nm titanium oxide particles confirmed by the specific method is 100, the number in the chemical solution is calculated as 1000 (100 x 10) based on 10 times the converted value. The number of particles of 10 nm or less in the present invention is estimated by this conversion method for any metal.

<Organic impurities>
The chemical liquid may contain organic impurities.
Although the content of the organic impurities in the chemical is not particularly limited, it is preferably 1000 to 100000 ppt by mass with respect to the total mass of the chemical, from the viewpoint that stain-like residue defects, which will be described later, are less likely to occur on the silicon substrate.
The term "organic impurities" means an organic compound different from the organic solvent and contained in a content of 10000 ppm by mass or less with respect to the total mass of the organic solvent. In other words, in this specification, organic compounds contained in a content of 10000 ppm by mass or less with respect to the total mass of the organic solvent correspond to organic impurities and not to organic solvents.
Organic impurities are often mixed with or added to a chemical solution during the process of obtaining a chemical solution by purifying an object to be purified. Such organic impurities include, for example, plasticizers, antioxidants, and compounds derived therefrom (typically decomposition products).

<Water>
The chemical solution may contain water. Water is not included in the above organic impurities.
Water is not particularly limited, and for example, distilled water, ion-exchanged water, and pure water can be used.
Water may be added to the chemical solution, or may be unintentionally mixed into the chemical solution during the manufacturing process of the chemical solution. Examples of cases where water is unintentionally mixed in the manufacturing process of a chemical solution include, for example, when water is contained in a raw material (e.g., organic solvent) used in manufacturing the chemical solution, and when water is mixed in the manufacturing process of the chemical solution ( For example, contamination), etc., but not limited to the above.

Although the content of water in the chemical solution is not particularly limited, it is preferably 2.0 mass % or less, more preferably 500 mass ppb or less, relative to the total mass of the chemical solution. Although the lower limit is not particularly limited, it may be 0% by mass. The water content in the chemical solution means the water content measured using an apparatus based on the Karl Fischer moisture measurement method.

<Application of chemical solution>
The chemical solution of the present invention is preferably used for manufacturing semiconductor devices. Among them, it is preferable to manufacture a semiconductor chip using the chemical solution of the present invention.
Specifically, in a semiconductor device manufacturing process including a lithography process, an etching process, an ion implantation process, a peeling process, etc., the organic matter is treated after each process or before moving to the next process. Specifically, it is suitably used as a pre-wet liquid, developer, rinse liquid, polishing liquid, and the like.
Alternatively, the chemical solution may be used as a diluent or the like (in other words, a solvent) for the resin contained in the composition for forming a resist film.

In addition, the above-described chemical solution can be used for applications other than the manufacture of semiconductor devices, and can also be used as a developing solution for polyimide, a sensor resist, a lens resist, and the like, and a rinse solution.
In addition, the chemical solution can also be used as a solvent for medical use or cleaning use. For example, it can be suitably used for cleaning pipes, containers, substrates (for example, wafers, glass, etc.).
As the cleaning application, it is also preferable to use it as a cleaning liquid (pipe cleaning liquid, container cleaning liquid, etc.) for cleaning pipes, containers, etc. in contact with liquids such as the above-mentioned pre-wet liquids.

Among them, the chemical liquid is preferably used for the prewet liquid, the developer, the rinse liquid, the polishing liquid, and the composition for forming a resist film. Above all, when applied to a prewet liquid, a developer, and a rinse liquid, more excellent effects are exhibited. In particular, when the exposure light source is EUV, when applied to a pre-wet liquid, a developer, and a rinse liquid, more excellent effects are exhibited. Further, when applied to a pipe cleaning liquid used for pipes used for transferring these liquids, more excellent effects are exhibited.

<Method for producing chemical solution>
The method for producing the chemical solution is not particularly limited, and known production methods can be used. Above all, in order to obtain a chemical solution exhibiting the superior effects of the present invention, the method for producing a chemical solution has a filtration step of obtaining a chemical solution by filtering a substance to be purified containing an organic solvent using a filter. preferable.

The substance to be purified used in the filtration step may be procured by purchase or the like, or may be obtained by reacting raw materials. It is preferable that the material to be purified has a low impurity content. Commercially available products of such substances to be purified include, for example, commercial products called “high-purity grade products”.

The method of reacting raw materials to obtain a substance to be purified (typically a substance to be purified containing an organic solvent) is not particularly limited, and known methods can be used. For example, there is a method of obtaining an organic solvent by reacting one or more raw materials in the presence of a catalyst.
More specifically, for example, a method of reacting acetic acid and n-butanol in the presence of sulfuric acid to obtain butyl acetate; reacting ethylene, oxygen, and water in the presence of Al(C ₂ H ₅ ) ₃ a method of obtaining 1-hexanol; a method of reacting cis-4-methyl-2-pentene in the presence of Ipc2BH (Diisopinocampheylborane) to obtain 4-methyl-2-pentanol; propylene oxide, methanol, and acetic acid is reacted in the presence of sulfuric acid to obtain PGMEA (propylene glycol 1-monomethyl ether 2-acetate); acetone and hydrogen are reacted in the presence of copper oxide-zinc oxide-aluminum oxide to obtain IPA (isopropyl a method of obtaining alcohol); a method of reacting lactic acid and ethanol to obtain ethyl lactate; and the like.

(Filtration process)
The method for producing a chemical solution of the present invention preferably includes a filtering step of filtering the substance to be purified using a filter to obtain a chemical solution. The method of filtering the substance to be purified using a filter is not particularly limited, but the substance to be purified is passed through a filter unit having a housing and a filter cartridge housed in the housing under pressure or without pressure ( It is preferable to allow the liquid to pass through.

Pore size of filter The pore size of the filter is not particularly limited, and a filter having a pore size commonly used for filtering substances to be purified can be used. Among them, the pore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, even more preferably 10 nm or less, and 5 nm or less, in that the number of particles (metal particles, etc.) contained in the chemical solution can be easily controlled within a desired range. is particularly preferred. The lower limit is not particularly limited, but generally 1 nm or more is preferable from the viewpoint of productivity.
In this specification, the pore size of the filter means the pore size determined by the bubble point of isopropanol (IPA).

It is preferable that the pore size of the filter is 5.0 nm or less, since the number of particles contained in the chemical solution can be more easily controlled. Hereinafter, a filter with a pore size of 5.0 nm or less is also referred to as a "micropore size filter".
The fine pore size filter may be used alone, or may be used together with filters having other pore sizes. Among them, it is preferable to use a filter having a larger pore size from the viewpoint of better productivity. That is, when two or more filters are used, the pore size of at least one filter is preferably 5.0 nm or less. In this case, clogging of the micropore filter can be prevented by allowing the substance to be purified, which has been previously filtered through a filter having a larger pore size, to pass through the micropore filter.
That is, when one filter is used, the pore size of the filter is preferably 5.0 nm or less, and when two or more filters are used, the filter having the smallest pore size has a pore size of 5.0 nm. The following are preferred.

The mode of using two or more filters with different pore sizes in sequence is not particularly limited, but a method of sequentially arranging the already-described filter units along the pipeline through which the substance to be purified is transferred can be mentioned. At this time, when trying to keep the flow rate of the material to be purified constant throughout the pipeline, a filter with a smaller pore size may be subject to a higher pressure than a filter with a larger pore size. . In this case, a pressure regulating valve, a damper, or the like is placed between the filters to keep the pressure applied to the filter having a small pore size constant, and a filter unit containing the same filter is placed along the pipeline. It is preferable to increase the filtration area by, for example, arranging them in parallel. By doing so, the number of particles in the chemical solution can be controlled more stably.

- Filter material The material for the filter is not particularly limited, and known materials for the filter can be used. Specifically, when it is a resin, polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; Polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl such as polyvinyl fluoride fluorocarbon; polyvinyl alcohol; polyester; cellulose; cellulose acetate and the like.
Among them, nylon (among them, 6,6-nylon is preferable), polyolefin (among them, polyethylene is preferable), poly At least one selected from the group consisting of (meth)acrylates and polyfluorocarbons (among them, polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) are preferred) is preferred. These polymers can be used individually or in combination of 2 or more types.
In addition to resin, diatomaceous earth, glass, and the like may also be used.
In addition, a polymer (nylon graft UPE, etc.) obtained by graft copolymerizing polyamide (for example, nylon-6 or nylon such as nylon-6,6) to polyolefin (UPE (ultra-high molecular weight polyethylene), etc., described later) is used as a filter. It may be used as a material for

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

Plasma treatment is preferred because the surface of the filter is rendered hydrophilic. The water contact angle on the surface of the filter hydrophilized by plasma treatment is not particularly limited, but the static contact angle at 25° C. measured with a contact angle meter is preferably 60° or less, more preferably 50° or less. 30° or less is more preferable.

As the chemical modification treatment, a method of introducing an ion exchange group into the filter is preferred.
That is, the filter is preferably a filter having ion exchange groups.
Examples of ion-exchange groups include cation-exchange groups and anion-exchange groups. Examples of cation-exchange groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Examples of anion-exchange groups include quaternary ammonium groups. mentioned. The method of introducing the ion exchange group into the filter is not particularly limited, but typically includes a method of grafting by reacting a compound containing an ion exchange group and a polymerizable group with the filter.

The method for introducing ion exchange groups 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 (radicals). The irradiated filter is immersed in a monomer-containing solution to graft polymerize the monomer onto the filter. As a result, the polymer obtained by polymerizing this monomer is grafted onto the filter. The resulting polymer can be catalytically reacted with a compound containing anion-exchange or cation-exchange groups to introduce ion-exchange groups into the polymer.

Moreover, the filter may have a structure in which a woven fabric or nonwoven fabric having ion exchange groups formed by radiation graft polymerization is combined with a conventional filter material of glass wool, woven fabric or nonwoven fabric.

The use of a filter having ion exchange groups makes it easier to control the contents of the metal-containing particles and metal ions in the chemical solution within a desired range. The material constituting the filter having ion-exchange groups is not particularly limited, but examples thereof include polyfluorocarbons and materials obtained by introducing ion-exchange groups into polyolefin. Materials obtained by introducing ion-exchange groups into polyfluorocarbon are more preferable.
Although the pore size of the filter having ion exchange groups is not particularly limited, it is preferably 1 to 30 nm, more preferably 5 to 20 nm. The filter having ion-exchange groups may also serve as the filter having the smallest pore size already described, or may be used separately from the filter having the smallest pore size. Among them, the filtration step uses a filter having an ion-exchange group and a filter having no ion-exchange group and having a minimum pore size, in order to obtain a chemical solution exhibiting a more excellent effect of the present invention. is preferred.
The material of the filter having the smallest pore size already described is not particularly limited, but from the viewpoint of solvent resistance and the like, in general, at least one selected from the group consisting of polyfluorocarbons and polyolefins is preferable, and polyolefin is more preferred.

Therefore, as the filter used in the filtration step, two or more filters made of different materials may be used. Two or more selected from the group consisting of may be used.

Pore structure of filter The pore structure of the filter is not particularly limited, and may be appropriately selected according to the components in the substance to be purified. As used herein, the pore structure of a filter means the pore size distribution, the positional distribution of pores in the filter, the shape of the pores, etc., and is typically controlled by the manufacturing method of the filter. It is possible.
For example, a porous membrane can be obtained by sintering a powder such as a resin, and a fiber membrane can be obtained by electrospinning, electroblowing, meltblowing, or the like. These have different pore structures.

A "porous membrane" is a membrane that retains components in an object to be purified, such as gels, particles, colloids, cells, and poly-oligomers, but allows components that are substantially smaller than the pores to pass through the pores. means Retention of components in the material to be purified by porous membranes can depend on operating conditions such as surface velocity, use of surfactants, pH, and combinations thereof, and the pore size of the porous membrane, It can depend on the structure and the size and structure of the particles to be removed (hard particles or gels, etc.).

If the material to be purified contains negatively charged particles, a polyamide filter acts as a non-sieving membrane for the removal of such particles. Typical non-sieving membranes include, but are not limited to, nylon membranes such as nylon-6 membranes and nylon-6,6 membranes.
As used herein, "non-sieving" retention mechanisms refer to retention that occurs through mechanisms such as obstruction, diffusion and adsorption that are not related to filter pressure drop or pore size.

Non-sieving retention includes retention mechanisms such as hindrance, diffusion and adsorption that remove particles of interest in the product to be purified regardless of filter pressure drop or filter pore size. Adsorption of particles to the filter surface can be mediated, for example, by intermolecular van der Waals and electrostatic forces. A jamming effect occurs when particles traveling in a non-sieving membrane layer with a tortuous path are not able to change direction fast enough to avoid contact with the non-sieving membrane. Particle transport by diffusion results primarily from random or Brownian motion of small particles, which creates a certain probability of particles colliding with the filter media. Non-sieve retention mechanisms can be active when there is no repulsive force between the particles and the filter.

UPE (ultra high molecular weight polyethylene) filters are typically sieve membranes. Sieve membrane means a membrane that traps particles primarily via a sieve retention mechanism or a membrane that is optimized for trapping particles via a sieve retention mechanism.
Typical examples of sieve membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.
In addition, the "sieve retention mechanism" refers to the retention of the result due to the particles to be removed being larger than the pore diameter of the porous membrane. Sieve retention is enhanced by forming a filter cake (a clump of particles to be removed on the surface of the membrane). The filter cake effectively performs the function of 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 polymers include polyamides. Polyamides include, for example, nylon 6 and nylon 6,6. The polymer forming the fiber membrane may be poly(ethersulfone). When the fiber membrane is on the primary side of the porous membrane, the surface energy of the fiber membrane is preferably higher than the polymer from which the porous membrane is made on the secondary side. Such combinations include, for example, the fiber membrane material being nylon and the porous membrane being polyethylene (UPE).

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

The pore structure of the porous membrane (for example, a porous membrane containing UPE, PTFE, etc.) is not particularly limited, but examples of the shape of the pores include lace, string, and node. be done.
The size distribution of pores in the porous membrane and the distribution of their positions in the membrane are not particularly limited. The size distribution may be smaller and the distribution position in the membrane may be symmetrical. Moreover, the size distribution may be larger and the distribution position in the membrane may be asymmetrical (the above membrane is also referred to as an "asymmetric porous membrane"). In an asymmetric porous membrane, the pore size varies throughout the membrane, typically increasing in pore size from one surface of the membrane to the other surface of the membrane. At this time, the surface on the side with many pores with large pore diameters is called "open side", and the surface on the side with many pores with small pore diameters is also called "tight side".
An example of an asymmetric porous membrane is a membrane in which the pore size is minimized at a certain position within the thickness of the membrane (this is also referred to as an "hourglass shape").

Using an asymmetric porous membrane with larger sized pores on the primary side, in other words an open side on the primary side, can create a pre-filtration effect.

The porous membrane may comprise a thermoplastic polymer such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, copolymer of ethylene tetrafluoride and perfluoroalkoxyalkane), polyamide, and polyolefin. , polytetrafluoroethylene, and the like.
Among them, ultra-high molecular weight polyethylene is preferable as the material for the porous membrane. Ultra-high molecular weight polyethylene means a thermoplastic polyethylene with very long chains and preferably has a molecular weight of 1 million or more, typically 2-6 million.

As the filter used in the filtration step, two or more filters having different pore structures may be used, and a porous membrane filter and a fiber membrane filter may be used in combination. A specific example is a method using a nylon fiber membrane filter and a UPE porous membrane filter.

Moreover, it is preferable to wash the filter thoroughly before use.
If an unwashed filter (or a filter that has not been thoroughly washed) is used, the impurities contained in the filter are likely to be carried into the chemical solution.

As described above, in the filtration step according to the embodiment of the present invention, the substance to be purified is passed through two or more filters in which at least one selected from the group consisting of filter materials, pore sizes, and pore structures is different. It may be a multi-stage filtration process.
Moreover, the substance to be purified may be passed through the same filter a plurality of times, or may be passed through a plurality of filters of the same type.

When preparing the chemical solution of the present invention, it is preferable to use a filter (metal component removal filter) capable of selectively removing metal components (especially metal ions) such as "Purasol SN 200 nm".

The material of the wetted part of the refining device used in the filtration process (meaning the material to be purified and the inner wall surface that may come into contact with the chemical solution) is not particularly limited, but non-metallic materials (fluororesin etc.), and at least one selected from the group consisting of electrolytically polished metal materials (stainless steel, etc.) (hereinafter these are also collectively referred to as “corrosion resistant materials”). For example, when the wetted part of the manufacturing tank is made of a corrosion-resistant material, the manufacturing tank itself may be made of a corrosion-resistant material, or the inner wall surface of the manufacturing tank may be coated with a corrosion-resistant material. mentioned.

The nonmetallic material is not particularly limited, and known materials can be used.
Examples of non-metallic materials include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluororesin (e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene - Propylene hexafluoride copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene trifluoride chloride-ethylene copolymer resin, vinylidene fluoride resin, ethylene trifluoride chloride copolymer resin, and vinyl fluoride resin etc.), but is not limited thereto.

The metal material is not particularly limited, and known materials can be used.
Examples of metal materials include metal materials in which the total content of chromium and nickel is more than 25% by mass with respect to the total mass of the metal material, and more preferably 30% by mass or more. 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.
Metal materials include, for example, stainless steel and nickel-chromium alloys.

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

Nickel-chromium alloys are not particularly limited, and known nickel-chromium alloys can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable.
Examples of nickel-chromium alloys include Hastelloy (trade name, hereinafter the same), Monel (trade name, hereinafter the same), and Inconel (trade name, the same hereinafter). More specifically, Hastelloy C-276 (Ni content 63% by mass, Cr content 16% by mass), Hastelloy-C (Ni content 60% by mass, Cr content 17% by mass), and Hastelloy C- 22 (Ni content 61% by mass, Cr content 22% by mass).
In addition, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc. in addition to the alloys described above, if necessary.

A method for electropolishing a metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs [0011] to [0014] of JP-A-2015-227501 and paragraphs [0036] to [0042] of JP-A-2008-264929 can be used.

It is presumed that the metal material has a higher chromium content in the passivation layer on the surface than the chromium content in the matrix due to electropolishing. Therefore, it is presumed that the metal-containing particles are less likely to flow out into the material to be purified when a refining apparatus in which the liquid-contacting portion is formed of an electrolytically polished metal material is used.
Note that the metal material may be buffed. The buffing method is not particularly limited, and any known method can be used. The size of the abrasive grains used for the buffing finish is not particularly limited, but #400 or less is preferable in that the irregularities on the surface of the metal material are likely to be smaller. Buffing is preferably performed before electropolishing.

(Other processes)
The method for producing a chemical liquid may further include steps other than the filtering step. Processes other than the filtration process include, for example, a distillation process, a reaction process, and a static elimination process.

(Distillation process)
The distillation step is a step of distilling a substance to be purified containing an organic solvent to obtain a distilled substance to be purified. The method for distilling the substance to be purified is not particularly limited, and known methods can be used. Typically, there is a method of arranging a distillation column on the primary side of a refiner subjected to a filtration step and introducing the distilled material to be refined into a production tank.
At this time, the wetted portion of the distillation column is not particularly limited, but is preferably made of the corrosion-resistant material already described.

(Reaction step)
The reaction step is a step of reacting raw materials to produce a product to be purified containing an organic solvent as a reactant. The method for producing the substance to be purified is not particularly limited, and known methods can be used. Typically, there is a method of arranging a reaction tank on the primary side of a manufacturing tank (or distillation column) of a refiner subjected to a filtration step and introducing a reactant into the manufacturing tank (or distillation column).
At this time, the wetted portion of the production tank is not particularly limited, but is preferably made of the corrosion-resistant material already described.

(Static elimination process)
The static elimination step is a step of eliminating static electricity from the object to be purified to reduce the charge potential of the object to be purified.
The static elimination method is not particularly limited, and a known static elimination method can be used. Examples of the static elimination method include a method of bringing the object to be purified into contact with a conductive material.
The contact time for bringing the material to be purified into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and even more preferably 0.01 to 0.1 seconds. Conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon.
As a method for bringing the substance to be purified into contact with the conductive material, for example, there is a method of arranging a grounded mesh made of a conductive material inside the pipeline and passing the substance to be purified through the mesh.

It is preferable to carry out all the accompanying operations such as opening of containers, cleaning of containers and equipment, accommodation of solutions, and analysis in a clean room. The clean room is preferably a class 4 or higher clean room defined by the international standard ISO14644-1:2015 defined by the International Organization for Standardization. Specifically, it preferably satisfies any of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably satisfies ISO Class 1 or ISO Class 2, and satisfies ISO Class 1. is more preferred.

Although the storage temperature of the chemical solution is not particularly limited, the storage temperature is preferably 4° C. or higher in that trace amounts of impurities contained in the chemical solution are less likely to be eluted, and as a result, more excellent effects of the present invention can be obtained.

<Medicine container>
The drug solution produced by the above purification method may be put in a container and stored until use.
Such a container and the drug solution stored in the container are collectively referred to as a drug solution container. The drug solution is taken out from the stored drug solution container and used.

As for the container for storing the chemical solution, it is preferable that the container has a high degree of cleanliness and little elution of impurities for use in manufacturing semiconductor devices.
Examples of usable containers include, but are not limited to, the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd., and the "Pure Bottle" manufactured by Kodama Resin Industry.

For the container, a multi-layer bottle with a 6-layer structure made of 6 types of resin for the inner wall, or a multi-layer bottle with a 7-layer structure made of 6 types of resin, is used for the purpose of preventing contamination of the chemical solution. is also preferred. Examples of these containers include containers described in JP-A-2015-123351.

The liquid-contacting parts of this container may be the previously described corrosion-resistant material (preferably electropolished stainless steel or fluororesin) or glass. In order to obtain a better effect of the present invention, it is preferable that 90% or more of the area of the liquid contacting portion is made of the above material, and it is more preferable that the entire liquid contacting portion is made of the above material.

The porosity in the container of the drug solution container is preferably 2 to 80% by volume, more preferably 2 to 50% by volume, and even more preferably 5 to 30% by volume.
In addition, the said porosity is calculated according to Formula (1).
Formula (1): Porosity = {1-(volume of chemical solution in container/volume of container)} × 100
The container volume is synonymous with the internal volume (capacity) of the container.
By setting the porosity within this range, storage stability can be ensured by limiting contamination such as impurities.

The present invention will be described in more detail based on examples below. The materials, amounts used, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

Further, in preparing the chemical solutions of Examples and Comparative Examples, handling of the container, preparation, filling, storage and analysis of the chemical solution were all performed in a clean room satisfying ISO class 2 or 1.

(filter)
As filters, the following filters were used.
・ “Purasol SN 200 nm”: UPE membrane (material) manufactured by Entegris, pore size 200 nm
・ “PP 200 nm”: Polypropylene filter, manufactured by Entegris, pore size 200 nm
・ “Purasol SP 200 nm”: UPE membrane (material) manufactured by Entegris, pore size 200 nm
- "Octolex 5 nm": Nylon filter graft made by UPE, manufactured by Entegris, pore size 5 nm
・ “IEX 15 nm”: ion exchange resin filter, manufactured by Entegris, pore size 15 nm
・ “IEX 16 nm”: ion exchange resin filter, manufactured by Entegris, pore size 16 nm
- "IEX 50 nm": ion exchange resin filter, manufactured by Entegris, pore size 50 nm
- "IEX 200 nm": ion exchange resin filter, manufactured by Entegris, pore size 200 nm
・ “PTFE 5 nm”: polytetrafluoroethylene filter, manufactured by Entegris, pore size 5 nm
・ “PTFE 7 nm”: Polytetrafluoroethylene filter, manufactured by Entegris, pore size 7 nm
・ “PTFE 10 nm”: Polytetrafluoroethylene filter, manufactured by Entegris, pore size 10 nm
・ “PTFE 20 nm”: Polytetrafluoroethylene filter, manufactured by Entegris, pore size 20 nm
・ “Nylon 5 nm”: Nylon filter, manufactured by Pall, pore size 5 nm
・ “UPE 1 nm”: ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 1 nm
・ “UPE 3 nm”: ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 3 nm
・ “UPE 5 nm”: ultra-high molecular weight polyethylene filter, manufactured by Pall, pore size 5 nm

<Substance to be refined>
The following organic solvents were used as substances to be purified for the production of chemical solutions of Examples and Comparative Examples.
・CyHe: cyclohexanone ・PGMEA: propylene glycol monomethyl ether acetate ・MIBC: 4-methyl-2-pentanol ・nBA: butyl acetate ・EL: ethyl lactate ・PC: propylene carbonate ・IPA: isopropanol ・PGMEE: propylene glycol monoethyl ether・PGMPE: propylene glycol monopropyl ether ・CPN: cyclopentanone In addition, for “raw materials 1” to “raw materials 8” in the table, the organic solvents used in each example and comparative example were purchased from the following manufacturers. represents something.
"Raw material 1": Honeywell
"Raw material 2": Toyo Gosei "Raw material 3": KH Neochem "Raw material 4": Showa Denko "Raw material 5": KH Neochem "Raw material 6": Sanwa Yuka Kogyo "Raw material 7": CCP
"Raw material 8": BASF

<Container>
The following container was used as a container for containing the chemical solution.
・EP-SUS: A container whose wetted part is made of stainless steel with electrolytic polishing ・PFA: A container whose wetted part is coated with perfluoroalkoxyalkane The filling rate of the chemical solution in each container is 95% by volume ( The porosity was 5% by volume).
The filling rate is obtained by the following formula.
Filling rate = (volume of chemical solution in container/container volume of container) x 100

<Purification procedure>
One of the substances to be purified was selected and subjected to the distillation purification treatment shown in Table 1.
In the table, "Yes-1" in the "Distillation purification" column indicates that vacuum distillation was performed using a distillation column (theoretical plate number: 15 plates), and "Yes-2" indicates a distillation column (theoretical plate number: 30 stages), and "Yes-3" means that vacuum distillation was performed using a distillation column (theoretical number of stages: 8 stages).

Next, the substance to be purified by distillation is stored in a storage tank, and the substance to be purified stored in the storage tank is passed through filters 1 to 5 shown in Table 1 in this order, filtered, and stored. stored in a tank.
Next, the substance to be purified stored in the storage tank is filtered by filters 6 to 7 shown in Table 1, and the substance to be purified after being filtered by filter 7 is circulated upstream of filter 6, and filtered again. A circulating filtration process was performed to filter through 6-7.
After the circulating filtration treatment, the chemical solution was placed in the container.
Incidentally, in Examples 85 to 88, water was added to the chemical so that the water content reached a predetermined value.

In the above-described series of purification processes, liquid-contacting parts of various devices (for example, distillation columns, pipes, storage tanks, etc.) with which the material to be purified comes into contact are made of electropolished stainless steel.

Contents of organic components and metal components in the chemical solution were measured by the methods described below.

<Content of metal component>
The content of metal components (metal ions, metal-containing particles) in the chemical solution was measured by a method using ICP-MS and SP-ICP-MS.
The following devices were used.
・Manufacturer: PerkinElmer
・Model: NexION350S
The following analysis software was used for the analysis.
・Syngistix nano application module dedicated to “SP-ICP-MS” ・Syngistix for ICP-MS software However, since metal-containing particles of 10 nm or less cannot be measured by SP-ICP-MS, the specific method described above was used.

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

<Test>
[Pre-wet liquid or rinse liquid]
By the method shown below, the produced chemical liquid was evaluated for defect suppression when used as a prewetting liquid or a rinse liquid.
First, a chemical solution is spun 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. 0.5 cc of each chemical was discharged. The substrate was then spun dry. Next, the number of defects existing on the substrate after the chemical solution was applied was measured using a wafer inspection apparatus "SP-5" manufactured by KLA-Tencor (this is the measured value).
Next, using EDAX (energy-dispersive X-ray spectroscopy), the types of defects were classified into metal residue defects, composite residue defects, and stain-like residue defects. A metal residue defect is a residue derived from a metal component, a composite residue defect is a residue derived from a composite of an organic substance and a metal component, and a spot-like residue defect is a residue derived from an organic substance.
If both "metal residue on Si" and "metal residue on _SiO2 " are "D" or higher, it can be suitably used as a pre-wet liquid or a rinse liquid.

<Individual evaluation (metal residue defect, compound residue defect, spot-like residue defect)>
A: The number of corresponding defects was 20 or less per substrate.
B: The number of corresponding defects exceeded 20/substrate and was 50/substrate or less.
C: The number of corresponding defects exceeded 50/substrate and was 100/substrate or less.
D: The number of corresponding defects exceeded 100/substrate and was 150/substrate or less.
E: The number of corresponding defects exceeded 150/substrate.

[Developer]
By the method shown below, the case where the manufactured chemical solution was used as a developing solution was evaluated.
First, a resist pattern was formed by the operation described below.
A silicon substrate with a diameter of 300 mm or a silicon substrate with a silicon oxide film with a diameter of 300 mm is coated with an actinic ray-sensitive or radiation-sensitive resin composition described later and pre-baked (PB) at 100 ° C. for 60 seconds. , a resist film having a thickness of 150 nm was formed.

(Actinic ray-sensitive 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 means mol %): 100 parts by mass

Photoacid generator shown below: 8 parts by mass

Quencher shown below: 5 parts by mass (mass ratio was 0.1:0.3:0.3:0.2 from left to right). Among the quenchers below, the polymer type quencher has a weight average molecular weight (Mw) of 5,000. Moreover, the numerical value described in each repeating unit means a molar ratio.

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

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

In each example, the pressure difference between the filters was 0.01 to 0.03 MPa.
In Table 1, "Use 1" in the "Use" column means that the above tests were performed using the chemical liquids described in each example and comparative example as the prewetting liquid and the rinse liquid. "Use 2" in the "Use" column means that the above test was performed using the chemical solution described in each example and comparative example as a developer.
In the table, "metal residue on Si" indicates evaluation results of metal residue defects on silicon substrates, and "composite residue on Si" indicates composite residue defects on silicon substrates. The evaluation results are shown, "Stain-like residue on Si" shows the evaluation result of stain-like residue defects on a silicon substrate, and "Metal residue on _SiO2 " shows the evaluation results of defects on a silicon substrate with a silicon oxide film. shows the evaluation results of metal residue defects in , and "composite residue on _SiO2 " shows the evaluation results of composite residue defects on a silicon substrate with a silicon oxide film.

In Table 1, the column "Ti oxide particles/Ti ions" represents the mass ratio of the content of titanium oxide particles to the content of titanium ions. The "Ti ion amount (mass ppt)" column represents the titanium ion content (mass ppt) with respect to the total mass of the chemical solution. The "Fe oxide particle/Fe ion" column represents the mass ratio of the content of iron oxide particles to the content of iron ions. The "Fe ion amount (mass ppt)" column represents the iron ion content (mass ppt) with respect to the total mass of the chemical solution. The "Al oxide particles/Al ions" column represents the mass ratio of the content of aluminum oxide particles to the content of aluminum ions. The "Al ion content (mass ppt)" column represents the aluminum ion content (mass ppt) with respect to the total mass of the chemical solution. The "Ti oxide particle ratio (% by mass)" column represents the content (% by mass) of titanium oxide particles with respect to the content of the titanium component in the metal component. The column "ratio of Fe oxide particles (% by mass)" represents the content (% by mass) of iron oxide particles with respect to the content of the iron component in the metal component. The "Al oxide particle ratio (% by mass)" column represents the content (% by mass) of the aluminum oxide particles with respect to the content of the aluminum component in the metal component. The column "ratio of Ti oxide particles of 0.5 to 17 nm (% by mass)" represents the ratio (% by mass) of particles having a particle size of 0.5 to 17 nm among the titanium oxide particles. The column "ratio of Fe oxide particles of 0.5 to 17 nm (% by mass)" represents the ratio (% by mass) of particles having a particle size of 0.5 to 17 nm among the iron oxide particles. The column "ratio of Al oxide particles of 0.5 to 17 nm (% by mass)" represents the ratio (% by mass) of particles having a particle size of 0.5 to 17 nm among the aluminum oxide particles. The "Cu oxide particle ratio (% by mass)" column represents the content (% by mass) of the copper oxide particles with respect to the content of the copper component in the metal component. The column "ratio of Cu oxide particles of 0.5 to 17 nm (% by mass)" represents the ratio (% by mass) of particles having a particle size of 0.5 to 17 nm among the copper oxide particles. The "water content" column represents the water content (mass ppb) in the chemical solution relative to the total mass of the chemical solution.
Also, in Table 1, "E+number" represents "10 ^numbers ", and for example, "3.5E+04" represents "3.5×10 ⁴ ".
In Table 1, ">99" represents greater than 99. "<1" represents less than one.
In Table 1, "<500 ppb" represents less than 500 mass ppb.

In Table 1, the data related to each example and comparative example are Table 1 [Part 1] <1> to <6>, Table 1 [Part 2] <1> to <6>, Table 1 [Part 3] <1> to <6> and Table 1 [Part 4] <1> to <6>.
For example, in Example 1, as shown in Table 1 [Part 1] <1>, CyHe was used as the organic solvent, and as shown in Table 1 [Part 1] <2>, the filter 2 was "IEX 15 nm ”, and as shown in Table 1 [Part 1] <3>, the Ti oxide particle / Ti ion in the chemical solution is 3.5E + 04, and as shown in Table 1 [Part 1] <4>, Al ion The amount is 32 mass ppt, and as shown in Table 1 [Part 1] <5>, the proportion of 0.5-17 nm Fe oxide particles is 81 mass%, and Table 1 [Part 1] <6> As shown, "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 provide a predetermined effect.
In particular, from the comparison of Examples 1 to 8, it was confirmed that when the mass ratio of the content of titanium oxide particles to the content of titanium ions is 10 ¹ to 10 ¹⁰ , the effect is more excellent.
Further, 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.
Moreover, from Examples 11 and 12, it was confirmed that when the mass ratio of the content of aluminum oxide particles to the content of aluminum ions was 10 ⁰ to 10 ¹² , the effect was more excellent.
Further, from Examples 13 and 14 (34 and 35, 55 and 56, 76 and 77), the content of titanium ions (or iron ions, aluminum ions) is 0.10 to 100 with respect to the total mass of the chemical solution. It was confirmed that the effect is more excellent when the mass is ppt.
Further, from Examples 16 and 17 (37 and 38, 58 and 59, 79 and 80), the content of titanium oxide particles (or iron oxide particles, aluminum oxide particles) On the other hand, when it is 5% by mass or more and less than 99% by mass, it was confirmed that the effect is more excellent.
Further, from Examples 18 and 19 (39 and 40, 60 and 61, 81 and 82), among titanium oxide particles (or iron oxide particles, aluminum oxide particles), particles having a particle size of 0.5 to 17 nm It was confirmed that the effect is more excellent when the ratio is 60% by mass or more and less than 98% by mass.
In addition, from Examples 20 and 21 (41 and 42, 62 and 63, 83 and 84), the effect is more excellent when the content of organic impurities is 1000 to 100000 mass ppt with respect to the total mass of the chemical solution. was confirmed.

After washing the container (EP-SUS) and various devices used in <purification procedure> using the chemical solution (100 L) of Example 22, the separately prepared chemical solution of Example 22 was poured into the cleaned device, Collected in a washed container to obtain a solution A in the container.
In addition, after washing the container (EP-SUS) and various devices used in <purification procedure> using the chemical solution (100 L) of Example 38, the separately prepared chemical solution of Example 22 was poured into the cleaned device. and collected in a washed container to obtain a solution B in the container.
When the evaluation of "metal residue defects on Si" was performed using solution A and solution B, better results were obtained with solution A.

<Example (EUV exposure)>
First, a resist composition 1 was obtained by mixing each component with the following composition.
・Resin (A-1): 0.77 g
- Photoacid generator (B-1): 0.03 g
- Basic compound (E-3): 0.03 g
・ PGMEA (commercial product, high purity grade): 67.5 g
・ Ethyl lactate (commercially available, high purity grade): 75 g

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

・Photoacid generator (B-1)
The following compounds were used as the photoacid generator (B-1).

・Basic compound (E-3)
The following compounds were used as the basic compound (E-3).

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

This resist film was exposed through a reflective mask using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 90°, outer sigma 0.87, inner sigma 0.35). Then, it was heated at 85° C. for 60 seconds (PEB: Post Exposure Bake). Next, a developing solution (butyl acetate/manufactured by FETW) was sprayed for 30 seconds by a spray method for development, and a rinse solution was discharged onto the silicon wafer for 20 seconds by a spin coating method for rinsing. Subsequently, the silicon wafer was rotated at a rotational speed of 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 rinsing liquid, the chemicals used in Example 44 were used. In addition, when the various evaluations described above were carried out, desired effects with the same tendencies as in Table 1 were obtained.

Claims (19)

A chemical solution containing an organic solvent and a metal component,
The metal component contains titanium oxide particles and titanium ions,
A chemical solution, wherein the mass ratio of the content of the titanium oxide particles to the content of the titanium ions is 10 ⁰ to 10 ¹² . 2. The chemical solution according to claim 1, wherein the content of said titanium ions is 0.10 to 100 mass ppt with respect to the total mass of said chemical solution. 3. The chemical solution according to claim 1, wherein the content of said titanium oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of said titanium component in said metal component. The chemical solution according to any one of claims 1 to 3, wherein the titanium oxide particles have a particle size of 0.5 to 17 nm in a proportion of 60% by mass or more and less than 98% by mass. The metal component contains iron ions,
The chemical solution according to any one of claims 1 to 4, wherein the iron ion content is 0.10 to 100 mass ppt with respect to the total mass of the chemical solution. The metal component contains iron oxide particles,
The chemical solution according to any one of claims 1 to 5, wherein the content of the iron oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of the iron component in the metal component. The metal component contains iron oxide particles,
The chemical solution according to any one of claims 1 to 6, wherein the proportion of particles having a particle size of 0.5 to 17 nm among the iron oxide particles is 60% by mass or more and less than 98% by mass. The metal component contains iron oxide particles and iron ions,
The chemical solution according to any one of claims 1 to 7, wherein the mass ratio of the iron oxide particle content to the iron ion content is 10 ⁰ to 10 ¹² . The metal component contains aluminum ions,
The chemical solution according to any one of claims 1 to 8, wherein the aluminum ion content is 0.10 to 100 mass ppt with respect to the total mass of the chemical solution. The metal component contains aluminum oxide particles,
The chemical solution according to any one of claims 1 to 9, wherein the content of the aluminum oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of the aluminum component in the metal component. The metal component contains aluminum oxide particles,
The chemical solution according to any one of claims 1 to 10, wherein the proportion of particles having a particle size of 0.5 to 17 nm among the aluminum oxide particles is 60% by mass or more and less than 98% by mass. The metal component contains aluminum oxide particles and aluminum ions,
The chemical solution according to any one of claims 1 to 11, wherein the mass ratio of the content of the aluminum oxide particles to the content of the aluminum ions is 10 ⁰ to 10 ¹² . The metal component contains copper oxide particles,
The chemical solution according to any one of claims 1 to 12, wherein the content of the copper oxide particles is 5% by mass or more and less than 99% by mass with respect to the content of the copper component in the metal component. The metal component contains copper oxide particles,
The chemical solution according to any one of claims 1 to 13, wherein the proportion of particles having a particle size of 0.5 to 17 nm among the copper oxide particles is 60% by mass or more and less than 98% by mass. The metal component contains copper oxide particles and copper ions,
The chemical solution according to any one of claims 1 to 14, wherein the mass ratio of the content of the copper oxide particles to the content of the copper ions is 10 ⁰ to 10 ¹² . Furthermore, it contains organic impurities,
The chemical solution according to any one of claims 1 to 15, wherein the content of said organic impurities is 1000 to 100000 ppt by mass with respect to the total mass of said chemical solution. The chemical solution according to any one of claims 1 to 16, wherein the content of water with respect to the total mass of the chemical solution is 500 mass ppb or less. The organic solvent is propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, propylene carbonate, isopropanol, 4-methyl-2-pentanol, butyl acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, Methyl methoxypropionate, cyclopentanone, γ-butyrolactone, diisoamyl ether, isoamyl acetate, dimethyl sulfoxide, N-methylpyrrolidone, diethylene glycol, ethylene glycol, dipropylene glycol, propylene glycol, ethylene carbonate, sulfolane, cycloheptanone, 2 -Heptanone, butyl butyrate, isobutyl isobutyrate, isoamyl ether, and one or more selected from the group consisting of undecane, according to any one of claims 1 to 17. A drug solution container comprising a container and the drug solution according to any one of claims 1 to 18 contained in the container.